Hyperbranched Polymers: Advances From Synthesis To Applications

See discussions, stats, and author profiles for this publication at: https://www.researchgate.
net/publication/334064279
Hyperbranched polymers: advances from synthesis to applications
Article · January 2015
CITATIONS READS
142 1,143
4 authors, including:
Yaochen Zheng Sipei Li

Yantai University MIT
24 PUBLICATIONS 890 CITATIONS 26 PUBLICATIONS 532 CITATIONS
SEE PROFILE SEE PROFILE
Chao Gao
Zhejiang University
305 PUBLICATIONS 26,884 CITATIONS
SEE PROFILE
Some of the authors of this publication are also working on these related projects:
dielectric elastomer View project
Graphene fiber fabrics View project
All content following this page was uploaded by Sipei Li on 27 June 2019.
The user has requested enhancement of the downloaded file.

Chem Soc Rev
View Article Online
REVIEW ARTICLE View Journal | View Issue
Hyperbranched polymers: advances from

Published on 23 April 2015. Downloaded by Carnegie Mellon University on 6/27/2019 4:24:07 PM.
synthesis to applications
Cite this: Chem. Soc. Rev., 2015,
44, 4091
Yaochen Zheng,†ab Sipei Li,†a Zhulin Wenga and Chao Gao*a
Hyperbranched polymers (HPs) are highly branched three-dimensional (3D) macromolecules. Their globular
and dendritic architectures endow them with unique structures and properties such as abundant functional
groups, intramolecular cavities, low viscosity, and high solubility. HPs can be facilely synthesized via a
one-pot polymerization of traditional small molecular monomers or emerging macromonomers. The
great development in synthetic strategies, from click polymerization (i.e., copper-catalyzed azide–alkyne
cycloaddition, metal-free azide–alkyne cycloaddition, strain-promoted azide–alkyne cycloaddition, thiol–ene/
yne addition, Diels–Alder cycloaddition, Menschutkin reaction, and aza-Michael addition) to recently reported
multicomponent reactions, gives rise to diverse HPs with desirable functional/hetero-functional groups
and topologies such as segmented or sequential ones. Benefiting from tailorable structures and corre-
spondingly special properties, the achieved HPs have been widely applied in various fields such as light-
Received 8th January 2015 emitting materials, nanoscience and technology, supramolecular chemistry, biomaterials, hybrid materials
DOI: 10.1039/c4cs00528g and composites, coatings, adhesives, and modifiers. In this review, we mainly focus on the progress in
the structural control, synthesis, functionalization, and potential applications of both conventional and
www.rsc.org/csr segmented HPs reported over the last decade.
1. Introduction
The world is full of branching. From non-living to living objects,
a
MOE Key Laboratory of Macromolecular Synthesis and Functionalization, branching occurs anywhere and anytime, such as the Crab
Department of Polymer Science and Engineering, Zhejiang University, Nebula, forked lightning, river basins, trees, nervures, nerves,
Hangzhou 310027, P. R. China. E-mail: chaogao@zju.edu.cn; veins, and proteoglycan ranging from light-years to kilometers,
Tel: +86-0571-87952088
b
and to microscale and nanoscales (see Fig. 1). Hence, branch-
Department of Polymer Science and Engineering, College of Chemistry and
Chemical Engineering, Yantai University, 30 Qingquan Road, Yantai 264005,
ing is a general and important phenomenon that could result
P. R. China in faster and more efficient transfer, dissipation, and distribu-
† These authors contributed equally to this work. tion of energy and/or matter.1
Yaochen Zheng received his PhD Sipei Li was born in Zhejiang,

degree at Shanghai Jiao Tong China in 1989. He received his
University (2012). In 2013, he Bachelor’s degree (2011) from
joined Prof. Gao’s group in the Zhejiang University of Technology
Department of Polymer Science and his Master’s degree in polymer
and Engineering at Zhejiang chemistry (2014) from Zhejiang
University as a post-doctoral University with Prof. Chao Gao.
research fellow. His research He is currently a PhD student with
interests include hyperbranched Prof. Krzystof Matyjaszewski as
polymers, thiol–ene/–yne polymer- his supervisor at Carnegie Mellon
ization, and controlled radical University, USA. His research
polymerization. interests include hyperbranched
Yaochen Zheng Sipei Li polymers, atom transfer radical
polymerization (ATRP), gene
delivery, ionic liquids, etc.
This journal is © The Royal Society of Chemistry 2015 Chem. Soc. Rev., 2015, 44, 4091--4130 | 4091
View Article Online
Review Article Chem Soc Rev
acid (A2B2 type monomer) and glycerol (B3 type monomer).5

In 1952, using theoretical calculations, Flory predicted that
highly branched polymers could be successfully synthesized
by the polycondensation of an ABn (n Z 2) monomer without
the risk of gelation (Scheme 1a).6 Until the late 1980s, Kim
Fig. 1 Selected branching patterns observed in the universe and nature:
and Webster proposed the terminology of ‘‘hyperbranched
Crab Nebula (a), forked lightning (b), trees (c), nervures (d), vascular network polymers’’ as dendritic macromolecules with random branch-
(e). All images except c were obtained from the Internet. on-branch topology prepared by only a one-step polymeriza-
tion (Scheme 1b).7 Prior to Kim’s definition, Kricheldorf and
co-workers even prepared branched copolymers by a one-step

As the fourth subcategory of polymer structure following copolymerization of AB- and AB2-type monomers in 1982.8
linear, cross-linked, and chain-branched, dendritic polymers Afterwards, this area was more intensely explored, especially
have greatly evolved from theory to practice. over the last 25 years.
As one main subclass of dendritic polymers, HPs are a kind of As shown in Fig. 2, the number of published papers has
randomly branched molecules with a molecular size generally risen monotonously, bearing witness to the rapid development
ranging from several nanometers to dozens of nanometers. Another of HPs in synthesis, modification and their potential applica-
main subclass of dendritic polymers is dendrimers with regularly tions since 1990. The achievements can be summarized as the
branched and uniform structures. The differences among linear following major aspects: (1) synthesis: both polymer diversity
polymers, HPs, and dendrimers are listed in Table 1.2 Generally, and synthesis methodology are now highly developed; (2) char-
HPs possess irregular topology, functional groups at both the linear acterization: the degree of branching (DB) can now be deter-
and terminal units, low viscosity, and high solubility. mined accurately and controlled to some extent; (3) theory:
By far, all the reported synthesized HPs could fall within two the polymerization kinetics has been theorized and used to
main categories, namely compact HPs (CHPs) and segmented calculate the molecular parameters of HPs; (4) hyperbranched
HPs (SHPs).3,4 CHPs refer to the type of HPs with single or architecture: new highly branched structures are presented and
several repeating units between two branching points. A compact prepared; (5) surface modification: multifunctional surfaces
branching architecture and peripheral functional groups are ranging from nanoforests to polymer brushes are easily acces-
their typical features. SHPs are analogues of CHPs, with long sible; (6) nanotechnology: the use of HPs as new building
linear segments dispersed between every two branching points. elements, reactors, and templates of nanomaterials and nano-
Compared with CHPs, SHPs possess a sparsely branched frame- hybrids; (7) supramolecular self-assembly: representing new
work, and the reactive groups may locate on the periphery and building blocks, new assembly mechanisms, and new assembly
exist in the inner of the SHPs. objects; (8) other diverse applications: ranging from functional
In the early 20th century, Swedish chemist Jöns Jacob materials, biomaterials, and coatings to additives.1 All the
Berzelius first described the resin synthesized from tartaric progress has been well documented in the recently reported
Zhulin Weng obtained his Master’s Prof. Chao Gao received his PhD
degree from the Central China in 2001 from SJTU. Since 2003,
Normal University in 2005. He is he has worked with Prof. Sir
currently a PhD student with Prof. Harry Kroto at the University of
Chao Gao as his supervisor in the Sussex, UK, and then Prof. Axel
Department of Polymer Science H. E. Müller at Bayreuth Univer-
and Engineering at Zhejiang sity, Germany, as post-doc and as
University. His research interests an Alexander von Humboldt
include hyperbranched polymers, research fellow. In 2008, he
thiol–yne click polymerization, joined Zhejiang University, and
and polymer coloring. was promoted to full Professor.
His research interests include hyper-
Zhulin Weng Chao Gao branched polymers, graphene,
and click chemistry. He co-edited
the book Hyperbranched Polymers: Synthesis, Properties and
Applications (published by John, Wiley & Sons). He won an
award in 2013: Ten Pieces of News in Science and Technology in
China and the National Science Fund for Distinguished Young
Scholars. He has served as the Regional Editor of Colloid and
Polymer Science since 2013.
4092 | Chem. Soc. Rev., 2015, 44, 4091--4130 This journal is © The Royal Society of Chemistry 2015
View Article Online
Chem Soc Rev Review Article
Table 1 Comparison of HP with a linear polymer and dendrimer
Polymer Linear Hyperbranched Dendrimer
Structure
Topology 1D, linear 3D, irregular 3D, regular

Synthesis One-step, facile One-step, relatively facile Multi-step, laborious

Purification Precipitation Precipitation or classification Chromatography
Scaling-up Already, easy Already, easy Difficult
MW Discrepant Discrepant Identical
PDI 41.1 41.1 1.0 (o1.05)
DB 0 0.4–0.6 1.0
Entanglement Strong Weak Very weak or no
Viscosity High Low Very low
Solubility Low High High
Functional group At two ends At linear and terminal units On periphery (terminal units)
Reactivity Low High High
Strength High Low Very low
post-functionalizations), and the applications of both CHPs

and SHPs developed in the last decade.
2. Structure of HPs
2.1 DB
Highly branched is the important characteristic of HPs, which
makes them unique from linear macromolecules and cross-
Scheme 1 Flory’s theoretical model for the synthesis of HPs (a)6 and linked networks. Generally, DB is defined as the ratio of the
Kim–Webster’s hyperbranched polyphenylene prepared by the Suzuki molar fraction of branched and terminal units relative to that of
polycondensation of AB2-type monomer (b).7
the total possible branching sites. The HP made from AB2 type
monomers may contain dendritic (D), terminal (T), linear (L)
and initial (I) units (Fig. 3).
For the polycondensation of an AB2 type monomer, DB can
be calculated approximately from eqn (1):44–47
DþT
DB ¼ (1)
DþTþL
As a HP with a high degree of polymerization (DP), the number
of T approximates that of D. So, eqn (1) is simplified as,
2D 1
DB ¼ ¼ (2)
2D þ L 1 þ L=2D
Although the accurate number of structural units is not known,

DB can be indirectly derived from the ratio of L/D by NMR
measurements.
Fig. 2 Publication numbers during 1990 and 2014 with the topic of
‘‘hyperbranched polymers’’ searched by ISI Web of Science. Inset (left)
shows the publication contributions of the top ten states from 1990 to
2005; and inset (right) shows those from 2005 to 2014.
review articles9–43 and a monograph edited by Yan, Gao

and Frey.1
In this review, we focus on the structure control methods,
synthetic strategies (especially click polymerizations and click Fig. 3 Different units in HPs made from an AB2 type monomer.
View Article Online
With regard to the self-condensing vinyl polymerization of Furthermore, the indirect viscometry approach can be used
AB2 inimer-type monomers, the DB of HP largely depends on to evaluate the DB of HPs based on the Mark–Houwink equa-
the reactivity ratio (g) of two step reactions, which can be tion ([Z] = KMavis),4 since the relationship between the intrinsic
calculated by eqn (3).45,46 viscosity ([Z]) and the molecular weight (Mvis) of HPs is different
from that of linear polymers.
DB
2.2 MW
4 ðg 1Þ 1 e2z þ egz 1 g 2 þ 2egz ge2z
¼ MW and the polydispersity index (PDI) are two other significant
2
2 2z gz 2z
ðg 2Þ 1 1 ½ðg 1Þð1 e Þ þ e 1 ð2 e Þ parameters for HPs. Based on statistical and kinetic methods
g2
for HPs made by the polycondensation of ABg monomers, the
(3)
dependence of DP and PDI on conversion of the monomers are
summarized in Table 2.80,81 Obviously, PDI increases with the
where, g = kA–B 0 /kA–B; kA–B 0 and kA–B are the reaction rate
increasing conversion. Nevertheless, in experiments, the PDI
constants of A to B 0 and B groups (B 0 refers to the residual
could be narrowed by utilizing the techniques of: (i) a slow
functional group on the linear unit, see Fig. 3); and z is a
addition of monomers into the reaction system,82–86 (ii) copoly-
dummy variable. At the extreme, as g = 0, a linear polymer (DB = 0)
merization with core molecules,84–90 and (iii) classification by
is achieved; if g approaches infinity, DB will reach 1. As g = 1
dialysis or precipitation.1 It should also be mentioned that
(namely B and B 0 groups with equal reactivity), the dependence
the monomer/core ratio (g) has an effect on the PDI, since the
of the average value of DB on the conversion (x) of A group can
tendency for self-polycondensation of the monomers cannot be
be simply expressed by eqn (4):45,47
completely suppressed. As g o 100, PDI is lower than 1.3, while
2x when g 4 100, PDI becomes broader.40,84,89
DBg¼1 ¼ (4)
5x Yokozawa and colleagues successfully synthesized diverse HPs
with low PDIs (B1.13) and controlled MWs.91–96 They attributed
when the polycondensation approaches completion, that is, these to the improved reactivity of the terminal groups by the
x E 1, DB can reach 0.5—the maximum value for the case of condensation and considered the process of propagation to be
equal reactivity. carried out following a mechanism of controlled chain-growth
In experiments, DB could be altered or tuned to some polymerization.
extent40,48–52 via four major methods: (i) copolymerization of Similarly, due to the controllable chain propagation, living/
AB2 and AB monomers with different feed ratios;53 (ii) changing controlled polymerizations (such as anionic, cationic, and radical
the polymerization conditions such as temperature, feed ratio one) of AB2 or latent AB2 type monomers have been already utilized
of monomer to catalyst, and solvent,54–57 and the pressure of to prepare HPs with low PDI and controlled MWs.97,98
monomer;58,59 (iii) host–guest inclusion of AB2 or a multifunc- Typically, Brooks synthesized hyperbranched polyglycerol
tional monomer;60 and (iv) combination of the above ones. (HPG) with an ultrahigh number-average molecular weight (up to
To enhance DB, five methods have been tried: (i) increasing 700 000 g mol1) and a PDI of 1.1–1.4 by the emulsion anionic
the reactivity of the B 0 group;61 (ii) addition of core molecules;62 polymerization of glycidol.99
(iii) polycondensation of dendrons;63 (iv) post-modification of
the formed HPs to convert the linear units to dendritic ones;64 2.3 Topology
and (v) using a special catalyst.65 Through these techniques, Apart from the general compact/sparse branching structure of
DB could be clearly seen to be higher than 0.5 or may even CHPs/SHPs, some complex topologies have been designed and
approach 1 in some cases.65–71 Attentively, HPs still contain prepared to meet various potential applications.100,101 Generally,
many isomers with different MWs, even though DB is equal the complex topologies of HPs include two major types, namely,
to 1,65,66 which is different from dendrimers that have the linear–hyperbranched and hyperbranched–hyperbranched. Linear–
same MWs. hyperbranched polymers consist of both a linear moiety and a
Direct and indirect methods have been set up to measure the branched part, such as tadpole-like, dumbbell-like, mop-like, star-
DB of HPs. The direct methods include NMR measurements like, necklace-like, hyperbranched linear and hyperbranched cyclic
and degradation of the polymer units. In the NMR measure- ones (Fig. 4a–f). The hyperbranched–hyperbranched polymer is
ments, both 1D44 and 2D60,72 techniques have been employed. composed of different branched spheres or hemispheres, including
Sometimes model compounds are required in order to correctly branch-on-branch polymers, HP-cross-linked particles, and unsym-
assign the signals of the linear, dendritic, and terminal units metrical HPs (Fig. 4g–i).
and to accurately calculate the integral. For the heteroatom-
containing HPs, 15N, 19F, 29Si, and 31P NMR spectroscopies have
been applied to calculate the DBs.73–77 Table 2 DP and PDI of polymers synthesized from ABg type monomers
Other than the NMR spectroscopy, the degradable approach Monomer type g=1 gZ2
has also been directly used to detect the DB of HPs. Hawker78
Pn 1/(1 x) 1/(1 x)
and Wooley79 degraded HP into L, D and T subunits, which Pw (1 + x)/(1 x) (1 x2/g)/(1 x)2
could be accurately detected by chromatographic analysis. PDI 1+x (1 x2/g)/(1 x)
View Article Online

Fig. 4 HP-based complex polymeric structures.
3. Synthesis of CHPs SCVP was first invented by Fréchet in 1995,102 using an

3.1 Synthesis methodologies inimer (AB*) to construct HPs. Here, the A group represents a
vinyl moiety and the B* group refers to the initiating site. As the
Various synthesis methods have been proposed to access CHPs. polymerization starts, the formed dimer (A-b-a*-B*, similar to
In terms of the number of monomers used in the polymerization, the AB2 monomer) contains one vinyl group and two initiating
we classify them into four categories: single-monomer method- sites. Based on a broad variety of monomers, the SCVP approach
ology (SMM), double-monomer methodology (DMM), couple- greatly extended the amount and application of HPs.15,103–108
monomer methodology (CMM) and multi-component method- Moreover, if combined with controlled radical polymerizations,
ology (MCM) (Fig. 5). better controllability of the polymerization becomes accessible.
For SMM, only one type of monomers (ABn or latent ABn type) The free radical polymerization of divinyl monomers was reported
is used in the polymerization. The SMM generally includes six by Wang and co-workers.109 This strategy of vinyl oligomer
types of polymerization techniques: (1) the classic step-growth combination can overcome those shortcomings (such as low DB
ABn polycondensation, (2) self-condensing vinyl polymerization and yield) involved in other synthetic approaches.3,110 Using the
(SCVP), (3) self-condensing ring-opening polymerization (SCROP), kinetic theory to adjust the chain growth conditions, an HP with a
(4) proton-transfer polymerization, (5) chain-walking polymeriza- DB of 0.66 and numerous vinyl functional groups were synthe-
tion (CWP), and (6) dialkyne polycyclotrimerization. sized via the deactivation-enhanced atom transfer radical poly-
The step-growth ABn polycondensation is probably the most merization (DE-ATRP) of the multi-vinyl monomers using ethyl
widely employed method to prepare HPs. Generally, ‘‘n’’ equals 2. 2-bromoisobutyrate (EBriB), and copper(II) bromide/N,N,N0 ,N0 ,N00 -
If both B groups can react with the A group, it generates one branch pentamethyldiethylenetriamine (CuBr2/PMDETA) as the initiator
unit. If only one B group of AB2 monomer is reacted, it forms one and catalyst, respectively (Scheme 2).
linear segment. If none of the B groups is reacted, this unit becomes Via oxyanionic vinyl polymerization, commercially available
a terminal one. Despite there being no risk of gelation in such a hydroxyethyl methacrylate (HEMA) or poly(ethylene glycol) meth-
method, most of monomers need to be freshly synthesized. acrylate (PEG-MA) was applied as an inimer for the scalable
synthesis of HPs.111,112
Scheme 2 HPs with abundant vinyl groups synthesized by the approach

Fig. 5 Four types of synthesis methodologies for accessing CHPs. of a vinyl oligomer combination.109
View Article Online
Exclusively for hyperbranched polyethylenes or polyolefins,

the CWP is a great development in the field of transition-metal
catalyzed reaction. By finely tuning the catalyst and ethylene
pressure, Guan et al. discovered the topology of the product
could change from linear to a highly branched structure.133,134
The polycyclotrimerization of dialkynes was developed by
Tang’s group.135 Enlightened by the transition metal catalyzed
alkyne cyclotrimerization, Tang and co-workers successfully
synthesized soluble HPs under mild condition. They offered a
new synthetic route for hyperbranched conjugated polymers.

For DMM, the polycondensation of A2 and B3 type commercial
monomers is the most utilized approach to achieve HPs.136,137
Commonly, one needs to terminate the polymerization or add
end-capping molecules prior to the critical point of gelation.
The CMM approach was invented by Gao and Yan.3 Based on the
non-equal reactivity design of functional groups, it combines the
advantages of SMM and DMM. In particular, it can largely avoid
gelation by the direct polymerization of commercial monomers. For
example, to an AA0 + B0 B2 monomer pair (Fig. 5), in which group A0
is more reactive than A or B0 is more reactive than B, the faster
coupling between A0 and B0 groups predominantly gives rise to an
AB2-like intermediate (A-a0 b0 -B2) in situ at the early stage of reaction,
ensuring a subsequent smooth propagation in the manner of SMM.
The MCM employs three or more different monomers to
Scheme 3 Typical topologies of HPGs: linear-HPG block copolymer (a),115 prepare HPs in a one-pot process.138–145 The multicomponent
core–HPG shell type block-copolymer (b),116 linear-HPG block-copolymer
through hypergrafting of one block (c),117 and HPG-linear-HPG triblock
reaction (MCR) follows a step-growth reactive mechanism,
copolymer (d).120 giving the resulting HPs with a sequence-controlled architecture.
For a three-component system (Fig. 5), the reaction of group A and C
first generates the highly reactive group D, which subsequently
In 1999, Fréchet and Hedrick simultaneously reported the reacts with group B, affording the target HPs. Notably, group A
SCROP for CHPs.113,114 Frey reported the synthesis of HPG via cannot directly react with group B, group B cannot directly react
the anionic inimer mediated method,115–120 affording diverse with group C, and only the intermediate group D can trigger the
interesting topologies of HPGs (Scheme 3).115–117 Typically, the further polymerization.
hyperbranched–linear–hyperbranched triblock copolymer was Isocyanide-based (Passerini and Ugi reactions) and sulfoyl
composed of a linear poly(oxymethylene) block and double azide-based chemistries have been developed to synthesize HPs
HPG blocks. Firstly, bishydroxy-functional poly(oxymethylene) (Scheme 4).139 The first three-component reaction of amine,
was synthesized via the cationic ring-opening copolymerization aldehydes and hydrogen cyanide was used to synthesize amino
of trioxane and 1,3-dioxolane, exploiting formic acid as a acids.140 Later, multicomponent reactions were successfully
chain transfer agent. After hydrolysis of the formate groups, a used for the preparation of monomers,141 dendrimers,142 seg-
linear poly(oxymethylene) was obtained and served as a macro- mented HPs,139,140 and linear polymers,143 as well as for post-
initiator for the subsequent anionic ring-opening polymerization modifications.144,145
of glycidol. The hyperbranched–linear–hyperbranched copolymers Just recently, Li’s group reported MCM for HP synthesis.138
with PDIs of 1.31–2.01 and MWs of 6100–22 900 g mol1 As shown in Scheme 5, hexanedioic acid, hexane-1,6-dial, 1,6-
exhibited an adjustable degree of crystallization and hydro- diisocyanohexane and 10-undecenoic acid were copolymerized via
philicity.120 Yan reported the cationic SCROP of 3-methyl-3- a one-pot Passerini reaction. Through adjusting the feed ratio of
xetanemethanol to get HPs with different DBs and degree of
crystallization.118,119 Recently, several papers were published
elaborating the synthesis and corresponding performance
investigations of HPG.121–129
Moreover, Fréchet developed the proton transfer polymer-
ization for hyperbranched epoxy polymers by a nucleophilic
ring-opening reaction of an H-AB2 monomer.130 Zhu and Yan
synthesized thermo-responsive HPGs via a proton transfer
polymerization of vinyl and hetero-ring groups of glycidyl
methacrylate, which displayed a wide range of critical solution
temperatures from 0 to 100 1C.131,132 Scheme 4 Isocyanide- and sulfonyl azide-type MCRs.139
View Article Online

Scheme 5 Synthesis strategy of HPs with tuneable DB and DP values by Passerini MCM. Herein, the star mark represents the functional linear structure
(F). (Reproduced from ref. 138, with permission from Royal Society of Chemistry.)
the starting materials, gelation was effectively avoided. Moreover, radical-initiated click chemistries (Fig. 6). Cycloaddition click
the resulting topologies could be facilely tuned from the sequence chemistries include copper-catalyzed alkyne–azide cycloaddition
controlled linear structure to segmented hyperbranched ones. (CuAAC),167 metal-free alkyne–azide cycloaddition (MFAAC),168
strain-promoted cycloaddition (SPC)169 and Diels–Alder reaction.170
3.2 Synthesis by click polymerization Nucleophilic click chemistries include thiol-click chemistry (thiol–
To meet the increasing demands for sustainable and green epoxy reaction, thiol–isocyanate reaction, thiol–halogen reaction,
polymer chemistry, chemists have been seeking to develop and thiol-Michael addition)171,172 and amino-click chemistry
efficient chemical conjugation techniques featuring simplicity, (amino-epoxy ring-opening reaction173 and aza-Michael addi-
reaction robustness and high atom economy. In this process, a tion174). The recently reported Menschutkin quaternization can
number of classical or new chemistries have appeared and their be considered as belonging to the electrophilic click chemistry
usages have gradually matured. The chemistries involved include class,175 and thiol–ene/thiol–yne addition could be considered as
amidation,146 phosphation,147 etherification,148 esterification,149 being radical-initiated click chemistries.
transetherification,150 transesterification,151 the Knoevenagel reac- Click polymerization, coined by Qin and Tang, has brought
tion,152 Suzuki–Heck–Friedel–Crafts–Sonogashira coupling,153–156 about an influential revolution in both polymer synthesis and
hydrosilylation addition,157 nucleophilic substitution,158 nucleo- polymer post-modifications.176 The monomers employed for HPs
philic ring opening,159 electrophilic substitution,160 electrophilic through click polymerizations are summarized in Tables 3–5.
addition,161 blocked isocyanate ring opening,162 catalytic diene 3.2.1 CuAAC polymerization. The CuAAC-based AB2 approach
metathesis,163 and supramolecular coupling,164 etc. has been adopted to synthesize high-yield soluble azo-containing
In this odyssey of exploring efficient chemistries, the so-called HPs, using two types of azo-chromophore AB2 monomers (M1 and
click chemistry proposed by Sharpless clearly marks a turning M2 in Table 3).177,178 To avoid possible cross-linking of the
point,165 as it offers a new philosophy of material design and has polymer caused by the peripheral azido groups, similar mono-
inspired numerous efforts to look into the library of available alkynyl structures were introduced to end-cap the unreacted
reactions for developing more ‘‘click’’ or ‘‘click-like’’ chemistries.166 azido groups.178 A new AB2 monomer (M3) with fluoroaromatic
Up to now, click chemistries have made a great contribution to the groups was synthesized through the azo-coupling method.179
synthesis of HPs. Generally, click chemistry could be classified as HPs were prepared using the nonfluoro monomer M2 and the
three major types: cycloaddition, nucleophilic/electrophilic and fluoro monomer M3 via CuAAC chemistry, respectively. The
as-synthesized polymers were either end-capped with non-
fluoro mono-alkynyl azo chromophore or pentafluoroaromatic
mono-alkynyl azo chromophore via secondary CuAAC. The
fluoro-monomer decreased the chromophore loading density,
which is useful for non-linear optical (NLO) properties.
Coexisting in the ABx type monomer, alkynyl and azide
groups are reactive and can be consumed spontaneously during
their preparation and storage. The Ax + By approach can solve
this issue.180–184 A slow addition of M4 into the diluted solution
of M5 during A2 + B3 CuAAC polymerization afforded soluble
azobenzene-containing HPs with a Mw of 15 000 g mol1, DB of
0.57 and a yield of 65.5%.180 Compared with their linear analo-
gues, they exhibited a higher second-harmonic coefficient.181
Fig. 6 Various types of click reactions for the synthesis of HPs. Using M6 and M7, Qin and Tang prepared highly soluble and
View Article Online
Table 3 Monomers used for click polymerization for CHPs
Structure Type Ref. Structure Type Ref.
AB2 CB2
M1 177 M17 191
CuAAC Thiol–halogen/thiol–yne
AB2 A2
M2 178 M18 191

CuAAC Thiol–halogen/thiol–yne
AB2 A2
M3 179 M19 192
CuAAC Thiol–ene/thiol–yne
A2 CB2
M4 180 M20 192
CuAAC Thiol–ene/thiol–yne
B3 AB2
M5 180 M21 196
CuAAC Diels–Alder
A2 AB2
M6 182 M22 197
CuAAC Diels–Alder
B3 AB2
M7 182 M23 197
CuAAC Diels–Alder
A2 A2
M8 183 M24 199
CuAAC Diels–Alder
B4 B3
M9 183 M25 199
CuAAC Diels–Alder
AB2 A3
M10 176 M26 199
CuAAC Diels–Alder
AB2 B2
M11 185 M27 199
TAAC Diels–Alder
B3 Protected AB2
M12 186 M28 199
CuAAC Diels–Alder
View Article Online
Table 3 (continued)
A2 Protected A2B
M13 187 M29 199
CuAAC Diels–Alder
B3 A2
M14 187 M30 200
CuAAC Aza-Michael
AB2 B2
M15 189 M31 200
Thiol–ene Aza-Michael
AB2 CB2
M16 190 M32 201
Thiol–yne Aza-Michael
Table 4 Monomers and macromonomers for the synthesis of SHPs
Y-type macro
Macro B3
MM1 AB2 209 MM7 214
CuAAC
CuAAC
Seesaw-type Masked Y-type

MM2 macro AB2 210 MM8 macro AB2 215
CuAAC Thiol–bromo
Seesaw-type
Y-type macro AB2
MM3 macro AB2 211 MM9 216
Thiol–yne
CuAAC
Seesaw-type
Y-type macro AB2
MM4 macro AB2 212 MM10 208
Thiol–yne
CuAAC
Macro A2 Y-type macro AB2

MM5 213 MM11 217
CuAAC Thiol–yne
Macro A2 B3
MM6 214 M34 213
CuAAC CuAAC
processable HPs with a DB of B0.90, which can be used as (up to 7–10 days), implying that CuAAC was alkyne-sensitive.
aggregation-induced emission (AIE) materials.182–184 The con- Compared to copper catalyst [Cu(PPh3)3Br], the ruthenium catalyst
jugated HP with a Mw of 39 000 g mol1 was synthesized via the (Cp*Ru(PPh3)2Cl or [Cp*RuCl2]n) exhibited better substrate tolerance
CuAAC click polymerization of equally molar M8 and M9. Due and a higher catalytic activity and yield (483%).182 Moreover,
to the rigid hyperbranched structure, the HP exhibited a typical employing ruthenium complex as the catalyst produces regio-
aggregation-enhanced emission (AEE) effect. selective products to afford solely 1,5-regioregular HPs.
It is worth noting that the CuAAC polymerization of an 3.2.2 MFAAC polymerization. CuAAC has exhibited a high
electron-rich alkyne (such as M7) and azide was very slow reactive efficiency, having been widely applied to synthesize
View Article Online
Table 5 Click monomers for post-functionalizations
S1 CuAAC 246 S6 CuAAC 49
S2 CuAAC 246 S7 CuAAC 49

S3 Amine-epoxy 261 S8 CuAAC 49
S4 Menschutkin 49 S9 CuAAC 228
S5 Menschutkin 49 S10 Thiol–ene 228
AB2 Inimer
M35 238 M45 49
Transetherification RAFT-SCVP
AR Vinyl monomer
M36 238 M46 49
AB2 Vinyl monomer

M37 239 M47 63
AB2 Inimer
M38 240 M48 169
Transesterification ATR-SCVP
AB2 B3
M39 241 M49 228
Transesterification Transetherification
AB2 AB2
M40 149 M50 228
Esterification Transetherification
A1 & A2
Inimer
M41 242 M51 Chain-growth 262
AGET ATR-SCVP
polymerization
A1 & A2
A3–A3
M42 243 M52 Chain-growth 262
Polycyclotrimerization
polymerization
AB2 B3 (initiator)
M43 256 M53 263
Transesterification ROP
B2 (initiator) A3–A3
M44 258 M54 243
ROP Polycyclotrimerization
polymers. However, the involved metal ions are very difficult to can greatly improve their reactivity, making MFAAC polymeriza-
remove thoroughly, which limits the properties of the photo- tion possible. Introducing sulfone groups with their stronger
electric materials. Qin and Tang developed the MFAAC strategy electron withdrawing capability into the reactant makes it easier.
for conjugated HPs. Connecting alkynyl or azide groups with In a preliminary study, 3,5-bis(propargyloxy)benzyl azide
electron withdrawing groups, such as carboxyl, ether bonds, etc., (M10) was investigated for its polymerization behavior under
View Article Online
Cu-catalyzed or metal-free conditions.176 Because of its high 3.2.3 Thiol–ene polymerization. In general, silicon-containing
reactivity, M10 needs to be stored below 20 1C. The CuAAC HPs are prepared through hydrosilylation using a platinum catalyst.
polymerization gives polymers with a triazole ring of pure 1,4- However, the rigorous reacting conditions have so far limited their
isomer, while the MFAAC one affords products containing both applications. As an alternative approach, a photo-radical thiol–ene
the 1,4-isomer and 1,5-isomer. click polymerization was reported.189 Via the thiol–ene click
To avoid the metal ions involved appearing in the products, polymerization of M15, highly soluble silyl HPs were obtained,
researchers have also explored MFAAC polymerization between with a number-average molecular weight (Mn) of 3200 g mol1
azides and 1,2-disubstituted triple bonds. Therefore, a series of and a PDI of 1.78. The resulting polymer possesses a large
AB2 monomers (M11a, M11b and M11c) with two azido groups amount of allyl groups around the periphery, allowing for
and one 1,2-disubstituted triple bond were synthesized to probe the further functionalizations.
polymerizability. After optimization, the polymerization of M11a in 3.2.4 Thiol–yne polymerization. Thiol–yne polymerization is
bulk at 45 1C for several days and M11b in bulk at 60 1C for several one of the newest synthetic techniques for HPs. AB2 type thiol–yne
hours yielded soluble products. This result was in accordance with monomer M16 was reported by Perrier and co-workers.190 Initiated
the later report from Tang’s group, which demonstrated the effect by UV irradiation, thiol–yne polymerization was quickly carried out,
of the electron-withdrawing group on MFAAC.176,185 with a monomer conversion of 70% and 90% within 10 and 90 min.
Recently, it was demonstrated that electron-withdrawing The resulting hyperbranched polythioether had a DB of 1.0.
groups would be favorable for regioselective [1+3] dipolar Three major issues surround achieving the a-thiol-o-alkynyl
cycloaddition. M12a and M12b were used to carry out thermal AB2 type monomer for CHPs: (1) rare commercial supply; (2) difficult
alkyne–azide cycloaddition (TAAC) with M8 in DMF at 60 1C. synthesis; and (3) low yield.
Strong electron-withdrawing ester groups in the used alkyne Gao et al. developed the synthesis of AB2 type monomers via
could activate and proceed the A2 + B3 click polymerization even a thiol–halogen reaction using commercially available reactants
without the presence of a metal ionic catalyst.186 Bis(aroyl- in a one-pot manner. In an ice bath, the solution of M17 was
acetylene)s (M13a and M13b) and triazide (M14) were designed slowly added into the mixture of M18 and KOH to form the AB2 type
and prepared for hyperbranched poly(aroyltriazole)s. Contain- monomer (Scheme 6a). After the consecutive two-step thiol–yne
ing a large number of peripheral azido and alkynyl groups, the addition reaction triggered by the photoinitiator, 2,2-dimethoxy-2-
prepared film, when cut, could self-repair through TAAC at phenylacetophenone (DMPA), hyperbranched polythioethers
elevated temperature (Fig. 7).187 were achieved with a Mw of as high as 230 000 g mol1 and a
Nitrogen-rich HPs were prepared by the polycyclotrimeriza- DB of 0.68–0.82.191
tion of dinitriles in 1,2-dichlorobenzene at room temperature, As mentioned above, the preparation and storage of AB2 are
utilizing trifluoromethanesulfonic acid (CF3SO3H) as the difficult for thiol–yne click polymerization. Gao and co-workers
catalyst. Both Lewis and protonic acids are common catalysts
for the cyclotrimerization of aromatic nitriles. Since the catalytic
activity closely correlates with their strength, CF3SO3H with a strong
enough strength can accelerate cyclotrimerization effectively,
affording heteroatom-containing hyperbranched polytriazine
with a high DB (about 0.63) and in a high yield (B74.7%).188
Fig. 7 Synthesis route of hyperbranched poly(aroyltriazole). The as-prepared

film from hyperbranched poly(aroyltriazole) in a petri-dish (a); the half-cut film
(b); the self-healed film an overlapping width of 5 mm after heating (c); and the Scheme 6 CMM click polymerization based on sequential thiol–halogen/
self-healed and stripped film (d). (Reproduced from ref. 187, with permission thiol–yne click polymerization (a)191 and thiol–ene/thiol–yne click poly-
from Nature Publishing Group.) merization (b).192
View Article Online
3.2.6 Aza-Michael addition. The aza-Michael addition was

widely used to synthesize HPs prior to the concept of ‘‘click
chemistry’’. Because of its high reactivity, atom economy, and
high selectivity, recently, the aza-Michael addition has been
adopted as a kind of click reaction and has been employed to
prepare novel polymers. Generally, electron-withdrawing groups,
Fig. 8 All the click reactions of CMM for the synthesis of HPs. such as carboxyl and sulfone groups, joined to carbon–carbon
double bond (CQC) can greatly improve the reactivity of the aza-
Michael addition reaction between amine and CQC.
designed a CMM approach to split the AB2 monomer into two Aza-Michael addition is a typical CMM reaction.3 M30 (A2 type
parts, which could then selectively combine into an AB2 type monomer), M31 (B2 type monomer) and M32 (CB2 type monomer)
dimer. M19 (A2 monomer) and M20 (CB2 monomer) were employed have been used to carry out an aza-Michael addition.200,201 In the
to carry out the thiol–ene click chemistry for the AB2 type dimer, reaction, the secondary amino hydrogen is more reactive than the
as shown in Scheme 6b and Fig. 8.192 Then, AIBN was added to primary amino hydrogen. Therefore, during the early stages of
initiate the sequential thiol–yne click polymerization. The Mw of the polymerization, an A-ac-B2 type intermediate was formed,
the products ranged from 3400 to 105 000 g mol1, with a DB of which ensured the polymerization process without gelation.
0.76–0.91. The high DB was attributed to the greater ratio (about 3) Pan et al. reported that the topology of the polymer was
of the second addition of thiol to vinyl sulfide (r2) and the first one controlled by the reaction temperature during the aza-Michael
of thiol to alkyne (r1).193 addition of disulfide-containing diacrylate and N-methyl ethylene-
Similarly, employing the hydroxyl group-containing a-thiol- diamine (MEDA).202 If the reaction temperature is below 40 1C, the
o-alkyne AB2 type monomer, the sequential hetero-functional formed secondary amine is non-reactive, owing to a too high steric
HP with a Mw of 4800 g mol1 and a PDI of 1.27 was facilely hindrance. In this case, aza-Michael addition follows the A2 + B2
achieved via the step-growth polymerization initiated by the mechanism and results in a linear polymer. By elevating the tem-
free radical (Scheme 7).172 perature (beyond 48 1C), the formed secondary amine is activated
3.2.5 Diels–Alder cycloaddition. Initiated from the enlightening and the addition is carried out based on the A2 + B3 mechanism.
work of Stille et al.,194 the [2+4] Diels–Alder (DA) cycloaddition for Correspondingly, a highly branched structure is obtained.
HPs has gradually become popular.195 Three types of tetraphenyl Additionally, the thiol-Michael addition of tri(2-mercaptoethyl)
AB2 monomers (M21a–M21c) containing two dienophile func- amine (TMEA) and ethylene glycol diacrylate (EGDA) has been
tion and one diene function were synthesized.196 Repetitive used to synthesize hyperbranched poly(amine-ester)s (HPET) at
intermolecular DA reactions of M21a–M21c afforded poly(ethynyl)-, 50 1C.203 Tertiary aliphatic amine in the branching units greatly
poly(methylethyl)- and poly(phenylethynyl)-substituted hyper- restrains the fluorescence quenching.
branched polyphenylene. Their Mns ranged from 2500 to
25 100 g mol1, with a PDI of 1.66–6.85.
Utilizing the properties of high packing density and proces- 4. Synthesis of SHPs
sability, M22 and M23 carried out the polymerization within
4.1 Synthetic methodologies
the channel of the porous alumina membranes.197 The DB of
the hyperbranched polyphenylene could be regulated using an SHPs are the long chain analogues of CHPs. The farther distance
AB2/AB monomer pair.198 between the two branching units endows SHP with the sparser
Reactions between the derivatives of furan and maleimide structure. So far, two major synthetic routes toward SHPs have been
follow the mechanism of Diels–Alder cycloaddition. Due to the developed: macromonomer methodology via either the polymeriza-
facility of the synthesis of the furan or maleimide derivative, tion of AB2 type macromonomer204–206 or the copolymerization of
diverse HPs can be prepared via furan/maleimide Diels–Alder A2 + B3 type (macro)monomers and small-monomer methodology.
click polymerization, including A2 + B3 (M24 + M25) and A3 + B2 Perrier and co-workers employed RAFT polymerization to
(M26 + M27). Additionally, AB2 or A2B monomer was synthesized prepare macromonomers, such as poly(divinyl benzene).207 Two
from the retro-DA deprotection of M28 or M29. Typically, the direct synthetic strategies including ‘‘core outward’’ and ‘‘periphery
Mw of the obtained HPs ranged from 35 000 to 67 000 g mol1, inward’’ have been designed to build SHPs via chain step-growth/
with a PDI of 2.0–3.2.199 branching reactions.208
The biggest issue of macromonomer methodology for SHPs
is isolation of the residual macromonomers from products.
Adopting a highly efficient reaction, such as the robust click
polymerization, can easily achieve a 100% conversion of mono-
mers and could facilely solve this problem.
4.2 Synthesis by click polymerization

Scheme 7 Synthesis of sequential hetero-functional HPs via the step 4.2.1 CuAAC polymerization. The Y-type AB2 macromono-
growth thiol–yne polymerization.172 mers (MM1, in Table 4) synthesized by the ATRP of styrene
View Article Online
possessed Mns of 1000, 3300 and 7300 g mol1. They were

further used to carry out CuAAC polymerization, affording SHPs
with MWs of 82 000, 210 000 and 340 000 g mol1 and corres-
ponding PDIs of around 2. Interestingly, the macromonomer
with the lowest Mw generated the SHP with largest Mw.209 These
two reactive alkynyls are so close to each other within Y-type AB2
macromonomes. Once the first reaction is carried out, it will
generate great steric hindrance for the subsequent click reaction.
Hence, linear-units inevitably are involved in the resulting SHPs.
Compared to the Y-type AB2 macromonomer, the seesaw- Scheme 8 Synthesis of alternating multiblock SHPs via the bulk CuAAC
click polymerization of A2 and B3 macromonomer.214
type one has a reactive group (A) in the middle of the long chain
and two identical functional groups (B2) at both ends of the two
subchains. The specific structure of the seesaw-type AB2 macro- The obtained amphiphilic SHPs showed two melting tempera-
monomers affords linear-unit-free (or defect-free) SHPs, mak- tures, belonging to the PCL and PEG segments, respectively.214
ing this synthetic strategy more popular. The ATRP of styrene 4.2.2 Thiol–halogen substitutions. Macromonomers (MM8,
and the subsequent azidation of the bromo moieties generated PDI o 1.2) with dithiolbenzonate and bromoester groups were
MM2s (MWs of 4400, 10 000 and 18 000 g mol1) using 1,3- synthesized via RAFT polymerization.215 Hexylamine was applied
dibromomethyl-5-propargyloxy-benzene (DBMPB) as the difunc- as both the reduction agent and polymerization initiator, which
tional initiator.210 By CuAAC of MM2, SHPs were synthesized with can reduce trithiocarbonyl groups to thiols and can catalyze the
MWs of 900 000–1 400 000 g mol1 (determined by GPC-MALLS). thiol-bromo click chemistry simultaneously. The Mw of the resulting
The results indicated that 10–20% of the macromonomers under- SHPs measured by static light scattering was 64 000 g mol1, while
went an intrachain reaction and a longer sub-chain or higher measured by GPC, it was only 30 000 g mol1. The difference in the
MM2 concentration effectively reduced the cyclization. Intrachain Mw by different measurements indicates the obtained SHPs had a
clicking reactions (cyclizations) were evitable during the polymer- globular structure. The periphery of the resulting SHPs was covered
ization of seesaw-type AB2 macromonomers, especially as the with abundant bromo groups, which could be further modified via
average degree of the self-polycondensation was high. Therefore, click chemistry.
the achieved DB of the SHPs synthesized by them is larger than 4.2.3 Thiol–yne additions. The a-thiol-o-alkynyl polystyrene
that of SHPs made from Y-type AB2 macromonomers. (MM9) was formed via the aminolysis of alkyne-terminated
Another polystyrene seesaw-type macromonomer, MM3, was polystyrene trithiocarbonate (Mw = 787 000 g mol1, PDI = 1.07) in
synthesized by a similar strategy. The initial concentration of the presence of isopropyl amine. The thiol–yne click polymerization
MM3 has a more obvious influence than its Mw on the rate of of MM9 was initiated by 5 wt% DMPA (Scheme 9) under ultraviolet
the polycondensation. The structure of the resulting SHPs was irradiation (l = 365 nm). Within 180 min, 95% conversion was
open and loose, and was controlled by the reaction-limited achieved and the resulting hyperbranched polythioether had a
cluster–cluster aggregation mechanism.211 Mw of 42 000 g mol1.216,217
A macro-block-monomer (MM4) was synthesized via the The macro-block-monomer alkyne dimethyl acrylamide–
sequential ATRP of styrene and tert-butyl acrylate and by sub- styrene thiol (ADMAST, MM10) was prepared via the sequential
sequent azidation. The CuAAC polymerization of MM4 afforded RAFT polymerization of PYPBTC with dimethyl acrylamide
diblock SHPs, hyper-(PtBA-PS-PtBA)s. As the tert-butyl group and styrene, followed by aminolysis. The SHPs with a Mw of
was hydrolyzed into acrylic acid, the amphiphilic hyper-(PAA- 15 000 g mol1 and a PDI of 3.5 were synthesized using MM10
PS-PAA) was obtained. When dispersed in a poor solvent for PS, as the starting macromonomer.208
the amphiphilic SHP tended to undergo an intrachain folding To synthesize ionized SHPs, alkyne tert-butyl acrylate-styrene
of PS. When the concentration of SHP was 450 g L1, a thiol (AtBAST, MM11) was synthesized via the sequential RAFT
physical gel was formed.212 polymerization of tert-butyl acrylate and styrene, followed by an
By the CuAAC polymerization between A2 macromonomer
(MM5) and B3 monomer (M34), SHPs were synthesized with
MWs of 9000–12 000 g mol1. The resultant SHPs showed a
liquid crystalline characteristic of nematic phase and a fast
photo-response trans–cis isomerization with a rate constant in
the range of 0.7–1.4 102 and 7.0–2.5 105 s1.213
An A2 macromonomer + B3 macromonomer approach was
used to synthesize sequential multiblock SHPs (Scheme 8). The
A2 macromonomer (MM6) was synthesized by the esterification
of PEG diols and carboxylic azide. The B3 macromonomer
(MM7) was prepared via condensation between PCL triols and
carboxylic alkyne. Through bulk click polymerization, the SHP Scheme 9 Synthesis of HPs by the AB2-type macromonomer, a-thiol-o-
with a DP as high as 16 was achieved only in several minutes. alkynyl polystyrene (ATPST).
View Article Online
aminolysis reaction. The thiol–yne click polymerization of easily obtained and require several synthetic steps to prepare
MM11, followed by the selective hydrolysis of tert-butyl ester them. The development of novel synthetic strategies for the
groups affords SHPs with alternating poly(acrylic acid) and monomers and HPs in a facile manner still remains a very
polystyrene blocks (Mw of 37 000 g mol1 and PDI of 7.4). The formidable task.
PAA-PS SHPs showed a pH-dependence self-assembly in aqueous
solution. The size of the aggregates was 10 (in higher pH solution)
and 500 nm (in lower pH solution), respectively.217 5. Click post-functionalization
4.2.4 Epoxy-amine chemistry. The epoxy-amine addition
reaction is another kind of click chemistry. The primary amine Besides the development of synthesis routes, great progress in the
first undergoes an addition reaction with an epoxide group, functionalization of HPs has also been made. The modification of
generating a secondary amine, which is able to take place in a HPs is quite similar to the growth of leaves in a tree (Fig. 9).
further addition reaction with the second epoxide group. Functionalization of CHP only occurs on the periphery, since
Jiang and Yin prepared a series of amphiphilic hyper- its compact structure confines the external reactive molecules
branched poly(ether amine)s (HPEAs) via the epoxy-amine from access and further modification (Fig. 9a and b). This is
polymerization of B3 monomer (N-ethylethylenediamine) with just like densely branched trees, which mainly grow their leaves
two kinds of A2 monomers: poly(ethylene glycol) diglycidyl ether on outer twigs, because their internal parts receive less sunshine
(PEO-DE, Mn = 526 g mol1) and poly(propylene glycol) diglycidyl (Fig. 9e and f).222,223
ether (PPO-DE, Mn = 640 g mol1) (Scheme 10).218 Changing the feed In contrast, SHP has a sparser framework, thus providing more
ratio, HPEAs were obtained with a Mn of 10 000–18 000 g mol1, convenience for subsequent functionalizations (Fig. 9c and d),
a PDI of 1.3–2.2 and a DB of 0.52–0.62. The resulting HPs are just as a sparsely branched tree can grow leaves both at the
water-soluble and temperature-, pH-, and ionic strength-sensitive. peripheral and in the internal parts (Fig. 9g and h). As a result, it is
Their cloud-point temperature could be adjusted from 35 1C to possible to introduce a full-backbone modification for SHP.
100 1C by tuning the content of the PEO moieties, pH values Apart from the aforementioned click polymerizations for
and ionic strength. Additionally, based on the resultant HPEAs, HPs, this versatile approach has been widely utilized to modify
the subsequent modifications facilely afforded diverse novel their periphery, core, and simultaneously both the core and
materials.219–221 periphery. In this section, we mainly focus on click modifica-
Although various click reactions have been widely used for tions of both CHPs and SHPs that were synthesized by non-
the synthesis of HPs, the employed monomers are usually not click strategies (Fig. 10).
5.1 Functionalizations of the periphery

5.1.1 Functionalizations by the CuAAC approach. A successful
preparation of alkynyl- or azido-terminated HPs is the premise for
further functionalization through CuAAC. Generally, an alkynyl
group is introduced into the HPs by the esterification of hydroxyl
and alkynyl-containing acids in dichloromethane (DCM) or tetra-
hydrofuran (THF), while the azido group is achieved via the
nucleophilic substitution of halogen and sodium azide in dimethyl
Scheme 10 Synthesis of HPEA via the A2 + B3 protocol following the formamide (DMF). Then, by CuACC modification, the resulting
mechanism of epoxy-amine click polymerization.218 HPs can possess diverse specific functions.224–231
Fig. 9 (a) Densely branched tree. (b) CHP has a high steric congestion that hinders post-functionalization in the core. (c) Sparsely branched tree. (d) SHP
with the low steric congestion. (e) Sparsely branched tree with full scaffold leaves of different colors. (f) SHPs with full scaffold hetero functionality.
(g) Sparsely branched tree with abundant side-branches on the scaffold. (h) Compact functional dendritic molecular brush. (Reproduced from ref. 222
and 223, with permission from Royal Society of Chemistry.)
View Article Online
The (propargyl carbamate) ethyl disulfide ethyl 1-carbamide-

imidazole (S1) or 3-azidopropyl ester of carbonylimidazole (S2)
was applied to modify HPEI via conjugation between the imid-
azole ring and primary amine. The subsequent click reaction
between the obtained alkynyl- and the azido-HPEIs generated
disulfide-containing HPEI nanoparticles, which were able to bind
the plasmid DNA and showed a potential use as a gene vector.232
Incidentally, by the SCROP approach, the achieved HPGs
have been widely used in biochemistry and materials science,
due to their high DB, inert polyether scaffolds and abundant

hydroxyl groups. The alkynyl- or azido-terminated HPGs can be
Fig. 10 Functionalizations of the periphery, backbone and core, as well as further modified via CuAAC.233–241
the periphery of the HPs.
5.1.2 Functionalizations by thiol–ene addition. Both thiol–
ene addition (between thiol and vinyl groups) triggered by free
Alkynyl-terminated HPs were synthesized via the melt- radicals and thiol-Michael addition (between the thiol and
transetherification polymerization of the hydrophobic M35 and acrylate groups) activated by catalysts have been utilized to
the hydrophilic M36 (see Table 5). Afterwards, 1-azidomethylpyrene modify the periphery of HPs. Etherification and esterification
was attached to achieve HPs, forming the fluorescent polyether via are often used for the synthesis of unsaturated double bond- or
CuAAC chemistry.224 The similar process for the polymerization of thiol-terminated HPs or modifiers.
M37 or M38 was also reported.225,226 An alkene-terminal HP was made by the melt-transetherification
Alkynyl-ended core–shell type HPEs were made from M39.227 of M43. The HP could be further modified by benzylthiol,
When followed by the CuAAC modification of the azido-ended 2-mercaptoethanol, N-benzoyl cystine and hexadecyl thiol.242
long alkyl chain and peripheral alkynyl groups, amphiphilic star- Allyl-functional HPG was modified with monothiol-ended
like brushes were achieved, which could then be self-assembled PEG by thiol–ene click chemistry to form HPG-star-PEG.243
into Janus structures in aqueous solution. Via the copolymerziation of glycidol and 2,2 0 -dihydroxyethane
Azido-ended HPEs were prepared by a carbodiimide reac- disulfide (M44), followed by cleavage of the disulfide-containing
tion, followed by the polyesterification of M40.149 They were HPG, the generated monothiol-functional HPG could be used for
further modified into amphiphilic ones for loading small guest further modifications.244
molecules. In addition, the PEG-grafted-hyperbranched cyclo- Through a thiol-Michael addition, thio-glucose was attached
dextrin was also synthesized by CuAAC, and it exhibited inter- on to peripheral vinyl groups of the hyperbranched poly-
esting multi-guest encapsulation/release properties. (amine-ester), forming core–shell glycopolymers with strong
Voit et al. utilized the activator-generated electron transfer photoluminescence.245
(AGET) ATRP strategy to synthesize HPs, using M41 as the 5.1.3 Functionalizations by aza-Michael addition. To
inimer. Compared to the traditional ATRP, the AGET process obtain HPG with peripheral amino groups, Frey’s group
can be carried out under looser experimental conditions employed the three-step synthetic strategy.246 Firstly, a hydroxyl
and greatly simplifies the polymerization procedure. After the group was esterified with 4-tolunesulfonyl chloride, followed by
azidation, these abundant peripheral chloro groups were replaced azidation to transform the chlorine atoms into azido groups.
by azido groups, which further reacted with propargyl alcohol, Secondly, through the Staudinger reduction, azido groups were
resulting in hydroxyl-terminal HPs.228 reduced into primary amines. Finally, by the aza-Michael addi-
A new kind of HCPE with a long wave emitting property was tion between amine and N-isopropyl acrylamide, the resultant
synthesized using M42 as the reactant. The terminal amino HP was endowed with thermosensitivity.
groups introduced via CuAAC were further linked with the anti- 5.1.4 Functionalizations by amine-epoxy chemistry. Due to
HER2 antibody.229 The functionalized HCPE displayed targeted the presence of abundant amino functional groups, HPEIs could
cellular imaging at low cytotoxicity and good photostability. be directly modified via an amine-epoxy reaction. For example,
Via a condensation reaction between the peripheral primary 4-glycidol-2,2,6,6-tetrametylpiperidin-1-oxyl (S3) was attached onto
amino groups with 5-hexynoic acid or 10-undecynoic acid, the periphery of HPEIs. Subsequent modifications of PEO and
two kinds of alkynyl-terminated HPEIs were synthesized. The PS afforded the three-layer products. The onion-like HPs could
mono-(6-azido-6-desoxy)-b-cyclodextrin (CD-N3) was attached simultaneously deliver both polar and apolar guests.247
onto alkynyl-containing HPEIs, giving HPEI-(CH2)3-CD and
HPEI-(CH2)8-CD. Both of these showed stimuli-responsive con- 5.2 Functionalizations of the backbone
traction and expansion properties.230 Based on the host–guest Besides the peripheral modification of HPs, their backbones
interaction between adamantanes and cyclodextrins, two kinds can also be modified, affording various functions. For CHPs,
of adamantane-containing anthraquinone dyes were used to the densely branched framework makes the functionalization of
further modify HPEIs. In water, the functionalized HPEI can the core very difficult, indeed only about 70% of reactive sites
form nanoparticles, with an average diameter of 260 nm and in the compact core could be functionalized.222 On the contrary,
critical temperature of 26 1C.231 SHP possesses a sparser branching structure, giving a lower
View Article Online
steric hindrance. By combining the loose backbone architec- chemistries, including thiol–ene, CuAAC and Menschutkin
ture with orthogonal click chemistries, diverse functional quaternization click chemistries, afforded SHPs with hetero-
groups can be introduced into all the scaffolds. functionality of hydroxyl + alkene/carboxyl/alkyne/tertiary amine,
Gao et al. reported that as the bromine is linked with strong dual/triple hydroxyl, alkene/alkyne + azide, dual hydroxyl +
electron-withdrawing group(s) such as a carbonyl or sulfuryl alkene, etc., all at B100% conversion (Fig. 12).223
group, the Menschutkin reaction between bromine and tertiary
amino group can be quickly completed within several seconds 5.3 Functionalizations of the periphery and backbone
at 0 1C; whereas, without an electron-withdrawing group joined For more complex architectures and functions, both the core
to bromine, the addition reaction needs more than ten hours, and periphery of HPs can be modified. As shown in Fig. 13, a
even under heating conditions.223 Now, the Menschutkin click clickable inimer-containing HP was synthesized through SCVP
reaction has been successfully employed in the post-modification using 3-azido-2-(2-bromo-2-methylpropanoyloxy) propyl meth-
of tertiary amino group-containing SHPs. Various functional acrylate (M48) as the starting material.248 The pendant bromo
groups, including alkynyl, azido, carboxyl, hydroxyl, etc., have been and azido groups were used to initiate the second ATRP of MMA
introduced into scaffolds of SHP with 100% conversion.108,223 and the click reaction with the mono-alkynyl PEG (S6) chains in
The dimethyl amino group-containing SHP was facilely one-pot, respectively. The obtained HPs with the multihetero-arm
synthesized via the SCVP of the RAFT inimer (M45) and M46 displayed a unique dynamic self-assembly behavior.
in one-step.108 As shown by a kinetics study, both segments Based on the difference between the methoxy groups of M49
were regularly dispersed in the HP backbone. The dimethyl and the allyloxy groups of M50, clickable HPs with an alkynyl
amino groups were fully reacted with propargyl bromide (S4) or core and allyl shell result.249 Via CuAAC chemistry, the core was
azido bromide (S5) by Menschutkin click chemistry, forming conjugated with an azido acceptor molecule S9. The allyl shell
clickable SHPs (Fig. 11 and 12).108,223 was modified by a thiol donor molecule S10 through a thiol–
Moreover, azido-functional SHP was conjugated with S6, afford- ene addition.249 Carrying two different kinds of chromophores,
ing a hydrophilic dendritic molecular brush. Alkynyl SHP clicked the hetero-functional platform showed fluorescence resonance
with S7 or azido ATRP initiator (S8), afforded an amphiphilic energy transfer (FRET) from the periphery to the core.
hyperbranched polyelectrolyte or ATRP macroinitiator.108
The RAFT-SCVP approach has realized whole-scaffold epoxy 5.4 Functionalizations of the core
groups via the copolymerization between inimer M45 and Through the incorporation of clickable groups into the core
M47.222 Since the epoxy ring is highly reactive under the attack of star-like HPs, subsequent modifications can be carried out
of strong nucleophiles, such as sodium azide, this gives SHPs smoothly via click reactions. Here, DMF is a very suitable solvent,
with hetero-functionality of the hydroxyl + azide (Fig. 11).108 A due to its good chemical stability, high dissolving capacity, and
subsequent click functionalization via a collection of click moderate polarity.
Fig. 11 Synthesis of dimethyl amino SHPs and the subsequent click functionalization. (Reproduced from ref. 108, with permission from American
Chemical Society.)
View Article Online

Fig. 12 Hetero-functional group engineering of SHPs via click chemistry. (Reproduced from ref. 223, with permission from Royal Society of Chemistry.)
Using propargyl alcohol or M53 as the initiator, alkynyl-

functional HPG with a moderate Mw was synthesized via
SCROP.251 The azido-biotin, -fluorophore or -amine was then
used to functionalize the alkynyl-ended HPG, expanding its
application fields.252
By the alkynyl polycyclotrimerization of M54 and a sub-
sequent CuAAC modification, fluorescent hyperbranched conju-
gated polyelectrolyte (HCPE) was synthesized.229 The core of
HCPE was ionized via the addition of bromo and triethylamine.
With peripheral PEG brushes, the HCPE showed a double-
layered ingredient structure and good water-solubility, which
could be utilized for breast cancer cell imaging.
Compared with CuAAC modifications, the Menschutkin
reaction can give rise to a water soluble quaternary ammonium
salt core for polymer coloring or for other specific applications
(such as biomedicine). The tertiary amine-containing core can
Fig. 13 Clickable hyperbranched polymer synthesized from SCVP. (Repro- be reacted with methyl iodide or propargyl bromide to afford
duced from ref. 248, with permission from Royal Society of Chemistry.) amphiphilic HPs for coloring common polymers.253–258
The copolymerization of mono-alkynyl monomer (M51) 6. Potential applications of HPs

or diene monomer (M52) for HPs has been reported using a
cationic diphosphine-ligated Pd(II) as catalyst. The residual HPs display many useful features such as highly reactive groups,
alkynyls were dispersed randomly in the whole scaffold, yield- few chain entanglements, low or no crystallization, and so on,
ing clickable HPs. Mono-azido polystyrene was clicked onto the which endow them with a large free volume, tailor-made proper-
triple bond via CuAAC, forming the star-like polymer with a ties, high solubility in solvents, low viscosity, etc. Therefore, they
core–shell structure.250 have been utilized in fields ranging from photoelectric materials,
View Article Online

Fig. 14 Relationship between the structure and property of HPs and their major applications.
nanotechnology, biomedicine, composites, coatings, adhesives, available PEDOT/PSS. Compared to the traditional PEDOT/PSS,
modifiers, and so forth (Fig. 14). However, most of them remain HCuPc as a hole injection layer achieved a higher luminous
theoretical only, and so far only a few HPs are actual products, efficiency (1.92 cd A1) and brightness (13 000 cd m2). Further-
such as Boltornt (HPE, Perstorp Co., Sweden) and Lupasols more, organic solvent-soluble HCuPcs enable the fabrication of
(hyperbranched polyethylenimine, BASF Co., Germany). high quality PLEDs.
6.1.2 Non-linear optical materials. With donor–p–acceptor
6.1 Conjugated HPs chromophores, NLO materials play a significant role in latent
Compared to their linear counterparts, hyperbranched conju- electro-optic applications.268 For high performance NLO materials,
gated polymers (HCPs) have better solubility and processability. one of the daunting problems is how to eliminate intermolecular
Moreover, their highly branched and globular frameworks can dipole–dipole interactions. Such defects can be efficiently
prevent aggregation and reduce interchain actions. Therefore, restrained by building chromophores as the main-chain,269,270
HCPs are promising as photoelectric materials. side-chain271,272 and periphery273 of HPs.
6.1.1 Light-emitting materials. Driven by the requirement for To prevent undesired dipole–dipole interactions, direct poly-
unusual properties, many efforts have been devoted to designing condensation via the A2 + B4 route afforded soluble HPs with
and synthesizing HCPs in recent years. Among the diverse HCPs, isolation chromophores.269 According to the second harmonic
polyfluorines (PFs) are very important candidates for blue light- generation measurements, the d33 coefficients were 40.0 and
emitting diodes (LEDs) because of their desirable luminous inten- 73.6 pm V1 with F values of 0.11 and 0.13. Peripheral
sity.259–266 To reduce detrimental green emission and/or inherent chromophore-modified HPs can also reduce the dipole–dipole
ketonic defects, the incorporation of triazole,260 truxene,261,262 interactions. Although the chromophore content (about 20–23 wt%)
oxadiazole,264,265 or carbazole266 building units into the HPFs is lower than that of their linear counterparts, the d33 coefficients
has improved their electron transport abilities. are similar (up to 65 pm V1), which is attributed to their unique
Through Suzuki cross-coupling, a series of novel HPFs molecular architectures.274
were prepared with a Mn of 5500–9700 g mol1 and a PDI of Rigid groups, such as a three triazole ring formed by a click
1.86–4.45.261 The products were soluble in common organic reaction, can effectively reduce the molecular interchain aggre-
solvents, such as CHCl3, CH2Cl2, and toluene, and displayed good gations. Azo-chromophore-containing HP was synthesized via
thermal stability (Td 4 446 1C). Either in film or in chloroform click chemistry using AB2 type monomers.156,177 Detected by
solution, they exhibited absorption maxima at 349–378 nm. For the second harmonic generation, the resulting d33 coefficients
the LED with HPF as the emitting layer, the blue emission was up were 77.9 and 124.4 pm V1, which are ascribed to the sup-
to 212 cd m2 at about 19 V. pressed electrostatic interactions of the chromophore moieties
With hexaphenylbenzene as the core and 1,3,4-oxadiazole as caused by the rigid triazole rings.
the adjusted units, the obtained HCP acted as the active layer in Moreover, via chemosynthesis, high performance NLO
a two-layer PLED.265 It showed a maximum luminous efficiency materials can also be obtained by a macromolecular dopant
of 0.72 cd A1 and a brightness of 549 cd m2 at 16.5 V. strategy.275 A hyperbranched NLO oligomer (o-HP) (Mn of
To improve the device efficiency, a new hyperbranched 3300 g mol1) was synthesized and further used as a dopant
copper phthalocyanine (HCuPc) was synthesized by the self- agent. The o-HP was soluble in aprotic solvents such as DMF
condensation of 4,4 0 -oxybis(phthalonitrile).267 Here, HCuPc and NMP. As the specimen contained 15 wt% of o-HP, the d33
was used as a hole injection layer to replace the commercially reached 65 pm V1.276
View Article Online
6.2 HP-stabilized nanocrystals

Nanocrystals (NCs) include insulator, semiconductor and metal
crystals. They exhibit unique size-dependent physical or chemical
properties.277,278 Spontaneous aggregation among NC particles
leads to performance degradation. To restrain this, HPs are often
used as a stabilizer in the preparation of NCs because of their
specific three-dimensional structure, good solubility, and plenty
of intramolecular cavities. The influence of the HP architecture
on the synthesis of NCs mainly shows through in the following

three aspects: (i) their unique 3D structure can provide sufficient
hindrance and can efficiently suppress the tendency for the NCs
to aggregate; (ii) plenty of cavities in the HP templates confine
the free diffusion of NCs’ precursors, and hence are useful for
controlling the size of the NCs; and (iii) the terminal groups
endow the HPs with enough functionalized flexibility to facili-
tate the synthesis and the size control of NCs.
Based on the synthesis process of NCs, three approaches
have been developed: (i) HPs first, using HPs as stabilizers to
directly prepare NCs, (ii) ligand-exchange, achieving NCs with
surfactants or linear polymers as ligands, followed by a ligand-
replacing-step with appropriate HPs, and (iii) grafting or in situ
growth of HPs from the surfaces of premade NCs (Fig. 15).
Up to now, six major kinds of HPs were employed to prepare
NCs, namely HPAMAM,279–284 HPEI,285–295 HPG,296–305 HPE,306–309
HPAM310–312 and HPEO313 (Fig. 16). Using these HPs as stabili-
zers, a lot of semiconducting and metal NCs have been prepared Fig. 16 Schematic structures of classic HPs used as stabilizers to prepare NCs.
for many diverse applications.
6.2.1 Semiconducting nanocrystals. On top of just NLO
materials, semiconductor NCs, also called quantum dots (QDs),
have been used in optical devices, biosensors, and biological
imaging, etc. Compared with those organic materials, QDs have
better thermostability and longer service life.
Most of the QDs were synthesized by a HPs first strategy
(Fig. 15A).279–293,295–297 Hydroxyl-ended HPG (Mn 4 20 000 g mol1)
was directly used as the stabilizer to prepare QDs (Fig. 17). The
obtained QDs included ZnS, Ag2S, PbS, CuS and CdS.298 Due to the
role of HPG, various QDs displayed good solubility in water and
DMF. Moreover, the QDs showed low toxicity and good biocompati-
bility. Excluding unmodified HPGs, thioether-functionalized HPGs
could be employed to prepare CdS and CdSe QDs.299 Interestingly,
Fig. 17 Images of the aqueous solutions (left) and TEM images of HPG-
stabilized nanocrystals (right). (Reproduced from ref. 298, with permission
from American Chemical Society.)
the sizes of the resultant QDs depended on the molecular weights

of the modified HPGs.
Compared to the HPs first method, the ligand-exchange strategy
shows its superiority in size control of NCs, since the used NCs can
be pre-prepared. HPEI (MWs of 800 and 25 000 g mol1) exchanged
Fig. 15 Three methods for the synthesis of NCs: A ‘‘HPs first’’, B ‘‘ligand with hydrophobic surfactants of CdSe@ZnS QDs and can form
exchange’’ and C ‘‘NCs first’’. a very stable colloid in chloroform.296 Following the extraction
View Article Online
of QDs from the non-polar solution with water, HPEI-coated HPs are widely used due to their stronger interaction with metal
CdSe@ZnS with average diameters of 10.7 1.4 and 17.5 2.5 nm NCs.320–325 Based on the specific properties of the metallic
were afforded, respectively. elements themselves, the corresponding metal NCs have been
PEG-grafted HPEI (PEI-g-PEG) (Mn = 18 500 g mol1) was widely used as catalysts,320–323 disinfectants,324 sensors,325,326
utilized to load and stabilize CdSe/CdS/ZnS QDs (6.5 nm in and so on. Without the undesired aggregation, they exhibited
diameter) via a ligand-exchange strategy.314 The grafted PEG high catalytic activity and good reusability.
segment is crucial for reducing the cytotoxicity of PEI and for Ni NCs were facilely prepared using HPAMAM-grafted poly-
improving the stability of the QDs. vinylamine (PVAm)/SBA-15 as a stabilizer.320 The resulting
Compared with the aforementioned approaches, surface Ni@PAMAM-PVAm/SBA-15 NCs showed high catalytic efficiency in
chemical grafting on QDs is a more reliable way to stabilize the reduction of aromatic nitro compounds. Compared to PVAm/
NCs. Coating the QD with a protective shell can effectively SBA-15, it could cut the reaction time in half. In addition, Ni NCs
avoid fluorescence quenching or toxic metal ions being could be reused ten times without any obvious loss of activity.
released.295,302,303,315–321 Surface modified polyacrylonitrile fiber (PANF) by HPEI was
Up to now, several kinds of HPs, including HPG,319,320,324 applied as an in situ supporter to prepare Au NCs (3.0 nm in
PDMAEMA,320 HPEI,306,307 etc., have been successfully grafted diameter).321 The resulting Au@PANF-g-HPEI NC was an efficient
from the surfaces of preformed QDs. HPG-stabilized CdTe QDs heterogeneous catalyst for the reduction of 4-nitrophenol by
were prepared by an in situ surface-initiated ROP of glycidol. NaBH4. Interestingly, Au@PANF-g-HPEI with a lower HPEI con-
Compared to unmodified ones, the biocompatibility and stabi- tent performed better in catalytic rate, and could be recovered as
lity of the CdTe@HPGs were notably improved due to the HPG well as reused many times.
cladding layer.318 Hyperbranched polylysine reacted with stearoyl/palmitoyl
Multicarboxylic HPG-grafted SiO2@Fe3O4 magnetic hybrids chloride and glycidyl hexadecyl ether, respectively, to afford
were synthesized and used for the growth of various noble NCs, amphiphilic HPs. Using the resultant HPs with Mns of 9400–
such as Pt, Au, and Pd (with the average sizes of 4.8 0.5, 10 700 g mol1 and DBs of 0.50–0.54 as templates, various stable
6.0 0.6, and 4.0 0.4 nm, respectively) (Fig. 18).319 Their monometallic (Ag, Au, and Pd) NCs (about 5 nm in diameter) were
loading capacities of 0.296, 0.243 and 0.268 mmol g1 were synthesized in organic solvents for versatile applications.322
obtained, respectively, due to the amplification effect of HPG. Silver NCs were prepared using hyperbranched polyamine as
Moreover, these noble NCs could catalyze the reduction reac- the stabilizer via reduction. As confirmed by the biological
tions of 4-nitrophenol, alcohol oxidation, and the Heck reaction activity detections, silver NCs exhibited good antibacterial
with high catalytic activity and good reusability. HPG-stabilized activity against B. subtilis and S. aureus bacteria.324 An interest-
multifunctional magnetic hybrids possessed promising potential ing phenomenon is that the branching architectures of the HPs
applications in catalysis and biomaterial areas. have an effect on the antimicrobial activity.327
6.2.2 Metal nanocrystals. Similar to the synthesis of QDs, Water insoluble HPC was synthesized via ATRP-SCVP of
stable metal NCs can be prepared under the assistance of HPs. styrene and p-chloromethyl styrene.328 HPC was further utilized
Among the numerous available HPs, amine- or sulfur-containing as an in situ template for the preparation of Ag NCs. The Ag@HPC
NC (around 4–5 nm in diameter) exhibits excellent dispersion
and stability (in the absence of aggregation, even standing for
6 months). It is a promising electrochemical sensor because of
the good catalytic activity for the reduction of H2O2.
Self-assembled aggregations of HPs have been applied as
stabilizers for NCs.329–331 Hyperbranched poly(ethylene glycol)
monomethylether methacrylate (HPEGMA) was used to synthe-
size Au@HPEGMA NCs via a ligands-exchange approach.332 By
combining different Raman tag molecules with hybrid com-
plexes, they could be used as various surface enhanced Raman
scattering diagnostic probes for nanomedicine applications.
Incidentally, the DB of HP,328 the reactive temperature331
and the concentration of metal ion331,332 all have an effect on the
particle size of the NCs. Other than monometallic (Au, Ag, Pt, Pd,
and Ru) NCs, bimetallic (Au/Pt, Au/Pd, and Au/Ru) NCs323 and
smart HP-stabilized NCs246 (thermo- or pH-responsive one) have
also been easily achieved using the similar strategy.
Fig. 18 Preparation of NCs supported on HPG-functionalized magnetic 6.3 HP-based supramolecular self-assembly
hybrids (top); TEM images of Pt (a), Au (b), and Pd (c) nanoparticles on the
(HPG–COOH@SiO2)@Fe3O4 supports; and their applications for dye-loading
6.3.1 Self-assembly of amphiphilic HPs. Molecular self-
(d and e). (Reproduced from ref. 319, with permission from American assembly is a common phenomenon in nature. With a regular
Chemical Society.) molecular structure, surfactants, linear block copolymers and
View Article Online
dendrimers can self-assemble into well-organized supramolecular

objects.333,334 However, the mystery of the self-assembly of HPs was
not unveiled until 2004.335 The self-assembly of HPs was ignored
for a long time because of their irregular molecular structures.
If strong interactions originates from the hydrogen bonding, then
electrostatic attraction, or host–guest self-recognition can surpass
the effects of the molecular structure, and the self-assembly of HPs
will then be a spontaneous process.
As shown in Fig. 19, various morphologies have been formed
by the self-assembly of HPs, including micelles (0D),335–352

fibers or tubes (1D),335,352–359 vesicles or films (2D)360–367 and
networks (3D).368,369 Interestingly, HPs with a similar architec-
ture can self-assemble into entirely different topologies of nano-
objects. For instance, HPG-star-linear polymers with the same
core (HPG) but different peripheral linear polymer segments Fig. 20 Preparation, self-assembly, and disassembly of C18-b-HPG. (Repro-
duced from ref. 375 with permission from American Chemical Society.)
(such as PEO,334 PPO,342 PMDETA,344 etc.) will self-assemble into
diverse nanoparticles, from micelles to vesicles (0D–3D) (Fig. 19).
Today, the self-assembly of HPs is a key research focus, due and the cloudy dispersion became transparent again. After
to the developed synthesis methodology and their promising continuous stirring for 24 h in the dark, rod-like micelles
potential applications. appear again. Switched by UV light irradiation, this ‘‘smart’’
Although more complicated structures (such as alternating reversible assembly and disassembly transition has wide
multiblock copolymers,214 miktoarm polymer brushes,370 etc.), potential applications.375–379
amphiphilic hyperbranched copolymers (AHPs) have also been Just recently, the self-assembly of Janus HPs was developed by
synthesized. Based on the results of AFM and DLS measure- Zhou and Yan by the noncovalent coupling of the azobenzene
ments, their self-assembled morphologies were seen to mainly and the hyperbranched polyglycerol grafted b-CD (b-CD-g-HPG).
depend on the Mn (or volume fraction) of the block moieties, The Janus supramolecular object can be disassembled through
the type of solvent, and the concentration of AHP.214,370 UV light (l = 365 nm) irradiation.376
More recently, supramolecular self-assembly utilizing host– Self-assembly of the hydrophobic adamantane-ended long
guest molecular recognition interactions as the driving force alkyl chain and hydrophilic b-CD-g-HPG was carried out through
are attracting increasing attentions.371–376 Adamantine and adamantine (AD)/cyclodextrin (CD) host–guest interactions.
b-cyclodextrin (b-CD),371–374 as well as azobenzene and The unilamellar vesicles self-assembled by Cn-b-HPGs (n = 12,
a-CD,375,376 are the frequently used host–guest molecular pairs. 18 and 30) with excellent ductility that could then be readily
The self-assembly of HPG-azo and a-CD immediately occurs disassembled via the competitive host of b-CD (Fig. 20).375
after the addition of water into DMF solution. As demonstrated 6.3.2 Self-assembly of HPs for biomedical applications.
by AFM measurements, the complex showed a rod-like large Supramolecular complexes have displayed potential applications
micelle (about 540 nm in length and 127 nm in width). Irradiated in biomedical areas because of their biocompatibility and devisa-
by UV light at 365 nm for 30 min, the formed complexes collapsed ble molecular architectures. Hyperbranched polyethers, polyesters,
polyphosphates and polysaccharides can be used as candidates for
cytomimetic chemistry, drug delivery, gene transfection, anti-
microbial material, and in the bioimaging field.26,34,380
Compared with small molecular liposomes, the formed HP
vesicles (HPVs) display lower membrane fluidity and higher
stability. HPVs can form multivalent interactions among vesicles,
like the biomembrane does. Moreover, the size of HPVs is very
close to that of the cell, allowing directly observation through
optical or fluorescent microscopy. In 2005, Zhou and Yan
revealed membrane fusions initiated only by small perturbations
or by changing the osmotic pressure.381,382
Apart from cytomimetic chemistry, supramolecular aggre-
gates formed by HP self-assembly have been utilized to load
drugs. Compared with naked drugs, HP–drug complexes can
improve solubility and prolong service time. At the same time,
they can easily penetrate cell membranes and selectively accumu-
late, as well as be retained at tumor sites.33
Fig. 19 Various self-assembled structures from 0 to 3D by the HPs (a). 0D Recently, a diselenide-containing amphiphilic hyperbranched
(b–d), 1D (e, f), 2D (g), and 3D (h and i). phosphate (AHPP) (Mw = 6100 g mol1 and PDI = 1.7) was
View Article Online
synthesized.383 Diselenide segments in the backbone structure Haag et al. reported that the DB of AHPG had a significant
of the AHPP endowed it with the ability to inhibit the prolifera- effect on the Cload of dyes.392,411 As the DBs of AHPGs were in the
tion of cancer cells. In water, the AHPP could self-assemble into range of 0.45–0.50, the highest Cload (about 3 moldyes molAHPG1)
nanomicelles (around 50 nm in diameter) and could further was achieved. AHPG could only load anionic dyes, but was
encapsulate doxorubicin for combining therapies. inoperative to cationic dyes, owing to the lack of a strong enough
Haag and co-workers developed a series of HPGs for biomedicine core–dye interaction.
applications via conjugated drug molecules, supramolecular encap- To confirm the importance of the host–guest interaction
sulation, and the formation of a microgel.383–385 on Cload, partly396 or completely175,253 quaternized AHPs were
Additionally, HP–fluorescent dye complexes, multiple func- used to encapsulate anionic dyes such as fluorescein sodium
tional HPAMAMs and HCPEs were able to form stable nano- (FS), MO, CR, RB, etc. Hyperbranched poly(propargyl quaternary
micelles for bioimaging.385–388 ammonium methacrylate)-co-polystyrene (HPPrAM-co-PS) was
6.3.3 Supramolecular encapsulation of dyes. Due to the facilely prepared via RAFT-SCVP and the Menschutkin reaction.253
unique branched structure and numerous binding sites, amphi- With a hydrophilic core and hydrophobic shell (Fig. 21a), the
philic HPs (AHPs) have been applied as hosts to encapsulate Cloads of HPPrAM-co-PS (Mn = 24 200 g mol1) achieved 24.1 for
small molecule guests.389–395 The loading capability (Cload) of MO, 24.2 for RB, 238.4 for CR and 22.0 for FS.
AHPs is one of the most important parameters, which mainly Amphiphilic hyperbranched poly(quaternary ammonium salt)
depends on the following four factors: (i) molecular weight and (AHPQAS) was easily synthesized via successive click reactions
DB of the core, (ii) shell density, (iii) polarity gradient between
the core and shell, and (iv) the affinity between the core and
guest molecules. Although supramolecular encapsulation has
been successfully used in many fields, such as phase-transfer,
bioimaging, etc., here, we mainly focus on the encapsulation of
organic dyes and their further applications for polymer coloring.
In nature, the encapsulation of dyes by AHPs is a phase-
transfer process, caused by the self-aggregation behavior of
AHPs in solution. Two kinds of micelles, micelle and inverse
micelle, are involved. In polar solvents, the micelle composed
of a hydrophobic core and hydrophilic shell is capable of
encapsulating nonpolar dyes; while, in nonpolar solvents, the
inverse micelle consisting of a hydrophilic core and hydro-
phobic shell can encapsulate polar dye molecules.
The extraction technique was the common way to encapsu-
late dyes. Under mixing conditions, dye molecules pass through
the water–oil interface and enter the internal cavities of AHPs.
Polar HPs, such as HPG,389–394 HPEI,396–401 HPAMAM,402–404
HPSA403–405 and hyperbranched poly(ester amide)/poly(ester
amine),406,407 have been utilized as polar cores of AHPs for
the encapsulations.
Alkyl modified HPG was used as the host for the encapsula-
tion of water soluble dyes.389 Congo red (CR) and Rose Bengal
(RB) occurred irreversibly, transferring from an aqueous solution
into the chloroform phase by extraction of the AHPG. However,
the linear amphiphilic PGs did not work, owing to the lack of
sufficient space. This result confirms that the highly branched
structure is crucial during the encapsulation of dyes.408,409
Core–shell PEI-star-PLAs were synthesized by a ring opening
polymerization. It was found that Cload of dyes mainly depends
on the length of the PLA.338 The longer arms lead to a higher
Cloads, suggesting that the molecular weight of the core or shell
has an effect on the Cload.
In addition, an increasing polarity difference between the
core and shell can also lead to a high Cload. For the amphiphilic
palmityl-functionalized HPSA, the average Cloads of CR and
Fig. 21 Synthesis of HPTAM, HPTAM-co-PS and HPPrAM-co-PS via RAFT-
MO are 41.8 and 19.4, respectively.410 Valeryl- and nonanoyl- SCVP and subsequent modification by the Menschutkin reaction with propargyl
modified HPSAs with a lower polar difference displayed the bromide (a)253 and synthesis of the amphiphilic hyperbranched poly(quaternary
lower Cloads. ammonium salt) for dye-loading (b).254
View Article Online
(Fig. 21b). The resultant AHPs exhibit high Cloads of dyes and Staphylococcus epidermidis (1600 CFU cm2) could be killed by
good dyeing property for general polymers (such as PMMA QACs. Notably, its antimicrobial effect was persistent, as the QACs
and SBS). The average numbers of dyes trapped per AHPQAS were directly connected with the HPUA matrix by covalent bonds.
reached 4.8 for RB, and 0.5–0.6 for MO, methyl violet (MV), FS For bioimaging, HP–probe conjugates with good water-
and eosin Y (EY), respectively.254 The polymer–dye complexes solubility and available functional groups are good solutions
showed a good dyeing effect for PS and SBS. The color of the to problems such as low quantum yield and poor specificity.
dyeing membrane was very stable and uniform. Similar results Zhu and Yan grafted fluorescein isothiocyanate on the periphery
were also observed for amphiphilic POSSs.175 of HPSA through the reaction of isothiocyanate and a primary
As declared by Frey et al.,409 entrapped dyes cannot escape amino group.436,437 With low cytotoxicity and good serum-
from AHP–dye complexes unless the linkage connecting the compatibility, the HPSA–probe conjugate can be used for bio-
core and the shell is destroyed. So the dye-containing complex imaging or for tracking cells.428
exhibits sufficient stability and can further be applied to stain Star-like HPs, HCP–N-PEG and HCP–O-PEG, with a HCP core
common plastics,253–255 rubbers253,254 and fibers.256–258 and linear PEG arms showed a superior fluorescein response
Long-alkyl-chain modified hyperbranched aromatic poly- sensitivity over those of small fluorophores and could be used
esters (HAPs) were used as nanocarriers to load organic dyes.255 as drug carriers for tumor therapy (Fig. 22 and 23).438
HAP–dye complexes could be monodispersed in the polyolefin Degradable hyperbranched polyphosphates were developed
matrix. The dyed polypropylene and high-density polyethylene by Huang and Yan via the SCROP of a cyclic phosphate inimer,
displayed good coloring stability, which was testified by 2-(2-hydroxyethoxy)ethoxy-2-oxo-1,3,2-dioxaphospholane (HEEP),
extraction tests. at 60 1C 14 h in bulk without any catalyst (Scheme 11).439
Inspired by Voit,255 the alkyl chain-modified HPQA, Hybrane The resultant HPHEEP with a Mw of 5200 g mol1, a PDI of
PS2550, was employed to improve the dyeing quality of PP 1.75 (GPC) and a DB of 0.47 (on the basis of 31P NMR measure-
fibers.256 Additionally, by attaching HPAMAM to cotton fibers, ments) was a promising biomaterial, due to there being no potential
the stain fastness and the levelling properties of the fiber were heavy metal pollution involved.
obviously improved.257,258 In addition, through a sequential feeding strategy, a series of
biodegradable polyphosphates with various topologies (such as,
6.4 HPs for bioapplications linear, star and hyperbranched ones) were facilely synthesized
Section 6.3.2 summarizes the self-assembly of various AHPs for via successive SCROPs of different cyclic phosphates. These were
biomedical application, thus, in this section, we will focus on also promising candidates for drug carriers (Scheme 12).440–446
the bioapplications based on their bulk properties, mainly
including gene transfection, antibacterial/antifouling materials,
bioimaging, and drug delivery.333,412–433
As cationic HPs, such as PEI, mix with electronegative DNA, they
can form HP–DNA polyplexes for gene transfection. Compared
with viral vectors, HP–DNA polyplexes exhibited higher safety,
weaker immune responses, more facile synthesis, and easier
operation.423–429
Using a natural molecule, kanamycin, as the starting material,
hyperbranched kanamycin-containing polymer (HPKM) was
synthesized. In COS-7, the transfection activity of HPKM was
up to 4.4 108 RLU (mg protein)1, about 33-fold larger than
that of chitosan.423
Furthermore, cationic long-chain HPEGs were applied for gene
delivery.426 As evidenced by fluorescence microscopic analysis, the
polyplex could efficiently penetrate into cells, due to its lower charge
density. Furthermore, HPEHO-g-PDMAEMAs and PEI-g-HCPEs were
also able to improve gene transfection efficiency.428,429
Recently, HPs have also been widely used as antibacterial/
antifouling materials. With good biocompatibility and chemical
stability, HPGs are promising antifouling materials that can be
employed to prevent the attachment of proteins.434
By anchoring quaternary ammonium compounds (QACs)
onto HPUA, the resulting shape-adaptive coating was capable
of killing bacteria in a partially enveloping manner.435 Since the
Fig. 22 Synthesis of HCP–N-PEG and HCP–O-PEG conjugated copoly-
adhesion force between Staphylococcus epidermidis and QACs mers (a); self-assembly of conjugated copolymer and their endocytosis in
was strong enough, these QACs could quickly remove membrane tumor cells (b). (Reproduced from ref. 438 with permission from American
lipids and give rise to bacterial death. More than 99.99% of Chemical Society.)
View Article Online
good solubility, low viscosity and special rheological properties.

Their unique 3D architecture offers a large enough steric hindrance
to avoid aggregation of the nanoparticles. Therefore, HPs are good
dispersants and surface modifiers for nanoparticles.448
Due to the remarkable mechanical, thermal, and electrical
properties, carbon nanotubes (CNTs) can be used as extra
reinforcing additives to strengthen polymer matrices. However,
keeping CNTs full and stable in dispersion in a polymer matrix
is a big challenge, owing to the great surface property difference
between CNTs and the matrix. The direct grafting of HPs on CNT
can effectively solve this issue. Here, HPs act as the dispersant
for CNTs and the compatilizer for the matrix.449–458
Fig. 23 Time-dependent fluorescence microscopy images of MCF-7 cells with
the incubation time of 1 h (a row), 12 h (b row) and 32 h (c row). (Reproduced The growth of HPs onto CNTs will generate HP brushes or
from ref. 438 with permission from American Chemical Society.) molecular nanoforests to improve the dispersing stability of
CNTs. In this regard, a series of works on CNT-based polymer
brushes by in situ SCVP, SCROP, polycondensation or layer-by-
layer self-assembly techniques have been reported.449–453 Fig. 24
shows the synthesis of hyperbranched poly[3-ethyl-3-(hydroxy-
methyl)-oxetane]-grafted multiwalled carbon nanotubes (MWCNTs)
and the corresponding TEM images of the product.449 The polymer
layer cover was about 12.5 nm on the MWNT.
Hyperbranched poly(phenylene sulfide)-grafted MWNTs
(HPPS-g-MWNTs) were prepared via a two-step Friedel–Crafts
acylation reaction.454 Both the dispersibility and processability
of HPPS-g-MWNTs were enhanced significantly by the grafting
of HPPSs.
The incorporation of hydrophilic polymer grafted CNTs into
Scheme 11 Synthesis of HPHEEP via the SCROP of HEEP. the hydrophobic membrane can improve its surface hydrophi-
licity and protein resistance.455–457 Hyperbranched poly(amine-
ester)-modified MWNTs (HPAE-g-MWNTs) were employed to
prepare the HPAE-g-MWNT/PVDF nanohybrid membranes.457
Hydrophilic HPAE-g-MWNT covered the surface of the PVDF,
thereby reducing the water contact angle and protein adsorption.
Scheme 12 Selected topological structures of copolyphosphates. (Repro-

duced from ref. 440, with permission from American Chemical Society.)
A thin film of a hyperbranched glycoacrylate, poly(3-O-acryloyl-

a,b-D-glucopyranoside) (HPAGlc), was immobilized on a PTFE-like
fluorocarbon surface via low pressure plasma. The results of
protein adsorption, cell adhesion and proliferation measurements
indicated HPAGlc could control biointerfacial phenomena.447
6.5 Dispersion and surface modification by HPs Fig. 24 Synthetic route for HPG-g-MWCNTs and the corresponding TEM
images (a). The inset (b) shows the TEM image of the bent area of the
Because of the highly branched structure, fewer intermolecular functionalized CNT. The scale bar is 20 nm. (Reproduced from ref. 449
entanglements are involved in HPs, which endows them with with permission of the American Chemical Society.)
View Article Online
The flux recovery ratio of the PVDF membranes increased from more compact networks, which also benefit the barrier
82% to 95.7%, implying that the antifouling capability was performance.471–474
significantly enhanced. 6.6.4 HP–graphene oxide hybrids. In recent years, graphene
has attracted increasing attention and gained a rapid development
6.6 HP-based nanocomposites/hybrids because of its unique atom-thick 2D structure,475 excellent
Nanocomposites/hybrids exhibited better performances than performances and wide range of promising applications.476
other components because of their favorable synergetic effects.459,460 Compared to graphene, graphene oxide (GO) possesses plenty
HPs possess a low intrinsic viscosity, thus endowing the nano- available groups (hydroxyl and epoxide groups) at their sheet
composite/hybrids with good processability. Nanoparticles can edges,477 which facilitate further chemical modifications.
introduce some specific functions (such as flame retardancy, Furthermore, these functional groups endow GO sheets with
etc.) into the nanocomposites/hybrids and improve their mecha- strong hydrophilicity, which makes GO fully disperse in water
nical and thermal properties.459 or polar solvents (such as DMF).478 All these merits allow GO to
There are two main methods to prepare nanocomposites or be a good candidate for nanocomposites.
hybrids: (i) direct mixing of HPs with inorganic nanoparticles, Generally, HPs exhibit very poor strength, owing to their weak
and (ii) in situ polymerization in the presence of nanoparticles.460 entanglements. Therefore, HPs are rarely used as materials indi-
If HPs and nanoparticles were linked by covalent bonds, the vidually. Gao et al. employed HPG as binders and added them into
phase interface can be efficiently eliminated and the overall GO suspensions to develop a nacre-mimic continuous fiber via a
performances will be greatly enhanced. wet-spinning assembly strategy. With ‘‘brick-and-mortar’’ lamellar
6.6.1 HP-based nanosilica hybrids. The growth of HPs on a structures of alternating GO sheets and HPG binders, HPG–GO
nanosilica surface will generate stable HP–nanosilica hybrids. fibers exhibited excellent mechanical properties, high electrical
To accomplish this, first, spherical silica nanoparticles were conductivity and remarkable corrosion resistance.479
modified by 2-bromo-isobutyryl bromide to afford the initiator. Through a liquid crystal self-templating methodology, the
Second, the initiator was used to synthesize the HP–silica next generation of continuous nacre-mimics with ultrastrong
hybrids via in situ SCVP.461–465 and tough properties have been achieved.480,481 Hierarchically
The epoxy functionalized alkoxysilane was added into the assembled fibers exhibited the highest tensile strength (652 MPa),
mixture of the epoxy resin and the phenolic group-ended HPs.466 5 to 8 times as high as that of nacre (80–135 MPa), and excellent
After curing the epoxy groups by UV irradiation and the sol–gel ductility with a toughness of 18 MJ m3, 10 to 20 times greater
reaction of alkoxysilane, HP-toughened scratch-resistant hybrid than that of nacre (0.1–1.8 MJ m3). These outstanding mecha-
coatings were obtained. nical performances of GO–HPG fibers are ascribed to its hierar-
Via the amidation of amino groups, an ethoxysilyl moiety chically assembled structure and the uniform alignment of GO
was introduced into polyamic acid and 3-(triethoxysilyl) propyl sheets (Fig. 25).
succinic anhydride (TESSA).467 By the sol–gel reaction with Apart from the self-assembly induced by the hydrogen
tetraethoxysilane (TEOS) and a following imidation, polyimide– bonding interactions, another reliable approach is the grafting
silica hybrid films (with 40 and 50 wt% of silica) were prepared.
The resulting polyimide–silica films exhibited permselectivity for
CO2/CH4 separation.468
6.6.2 HP–POSS nanohybrids. Chlorine- or bromine-containing
polyhedral oligomeric silsesquioxane (POSS) nanoparticles can
react with the hydroxyl of HPI to afford POSS-modified HPI
nanohybrids. The hybrid layers possess low dielectric constants
(up to 2.54).469
POSS-containing hyperbranched polyethylenes (HPEs) were
synthesized via a chain walking copolymerization of ethylene
and acryloisobutyl–POSS.470 POSS moieties significantly reduce
the intrinsic viscosity and improve the thermal oxidative stability
of the products.
6.6.3 HP–clay nanocomposites. Clay, such as montmo-
rillonite, with a natural lamellar structure has been widely used
in organic–inorganic nanocomposites. Other than improving the
strength, flame retardation, thermotolerance, etc., introducing
layered nanoparticles into the matrix can greatly enhance the Fig. 25 Image of a 30 m long GO–HPG gel fibre (a, scale bar of 10 mm).
barrier property of the matrix, which mainly depends on the SEM images of a cross-section of a GO–HPG gel fibre (b and c, scale bars
of 250 nm and 3.0 mm, respectively); wet-spinning assembly of complex
content and dispersion of the layered montmorillonite.
LCs into nacre-mimetic fibres with hierarchical structures (d); typical stress–
The formed pathways efficiently retard the progress of diffu- strain curves for neat GO (1), GO–HPG (2), and GO–HPG–GA (3) fibres (e); the
sion molecules. Moreover, as HPs take part in cross-linking strain rate is 10% per minute (f). (Reproduced from ref. 480 with permission
reactions, their abundant functional groups can generate from Nature Publishing Group.)
View Article Online
of HPs onto GO nanosheets. Hyperbranched polysiloxane (HPS) Moisture-cured isocyanate-terminated HPUs were prepared
functionalized GOs were prepared via the in situ condensation via the addition of isocyanate (NCO) and the hydroxyl group
of trimethoxyl silicane and hydroxyl groups of GOs.482 The (OH) of HPG.491 The ratio of NCO/OH and the molecular weight
resulting HPS-g-GOs reacted with dicyclopentadiene bisphenol of HPG have a crucial effect on the mechanical and thermal
dicyanate ester resin to produce the novel PU composites. properties of the cured coating. Tensile strength, hydrophobility
Compared with the control PU, the impact and flexural strengths and the char residue value were enhanced with increasing the
of the HPS-g-GOs modified PUs were enhanced by 60% and 47%, NCO/OH ratio.
respectively. 6.7.3 Antifouling coatings. Conventional antifouling
The N-isopropylacrylamide (NIPAM) partially modified HPEI approaches are through releasing toxic metal ions or biocides
(HPEI-PNIPAM) was synthesized via a Michael addition, followed to inhibit the proliferation of organisms. This strategy may
by the epoxy-amide addition between the imino groups from bring about some undesired side effects, such as the released
HPEI and the epoxy groups from GO. PNIPAM moieties presented toxins are harmful to the environment. Because of the electro-
the thermosensitivity, indicating that the nanocomposite could be static repulsion and interfacial hydration effects, PEG can
used in biomedical or biosensor fields.483–486 inhibit protein and cell adsorption. Introducing PEG moieties
into coatings can endow them with a good biofouling preven-
6.7 HP-based coatings tion property.492–495
HPs possess highly branched structures, rendering especially HPEI was firstly coupled to a polydopamine-coated stainless
lower viscosity and good flow properties. Moreover, their irregular steel substrate. Using HPEI as a platform, various modifications
molecular structures can reduce the likelihood of crystallization, were carried out via the thiol–epoxy coupling, thiol–ene and
making them highly transparent. Consequently, HPs are suitable thiol-Michael addition.496 The resultant stainless steel-P(HEMA-
coating resins. So far, they have been widely used as UV-curable, b-SBMA) and stainless steel-PPEGMA surfaces can prevent
waterborne, and powder coatings, etc. bacterial adhesion.
6.7.1 UV-curable coatings. Compared with thermally acti- QACs have been used as a bactericide in a contact-killing
vated systems, UV-curable coatings can be cross-linked at lower manner.435 PVDF-g-PDMAEMA copolymers were synthesized,
temperature and have almost no emission of volatile organic followed by quaternization of propargyl bromide and the click
compounds. For heat-sensitive substrates (such as plastic and reaction of N3-HPG, to develop a microporous membrane, which
wood), UV-curable coatings will not cause substrate deforma- can inhibit bacterial growth and proliferation functions.497
tion, which is a big challenge to the heat curing systems. 6.7.4 Vegetable oil-based coatings. Vegetable oils (such as
Unsaturated double bond-terminated HPs are the main com- castor, soybean and palm oil) are renewable, ecologically safe
ponents in UV-curable coatings. With diverse backbones, HPs have and biodegradable materials that can be obtained from plant
been designed and synthesized for UV-curable flame retardant, seeds. They are general starting materials widely used in conven-
hydrophobic, powder and waterborne coatings.487–489 tional coatings. Via careful molecular design, vegetable oils or
Hyperbranched polyphosphate acrylates (HPPAs) were syn- their derivatives can be introduced into HPs, which may present
thesized via the Michael addition of tri(acryloyloxyethyl) phos- unique performance for end applications.498–500
phate (TAEP) and piperazine, and were exploited for UV-cured Two types of castor oil-based HPUs, MHPU and CHPU, were
coatings. The highest tensile strength (31.7 MPa) and elongation at prepared using castor oil/monoglyceride, 1,4-butane diol, PCL
break (2 folds that of cured TAEP) were obtained at a feed ratio of and TDI as reactants.498 The MHPUs exhibited higher tensile
HPPA and TAEP of 2 : 8. With the increasing content of HPPA (from strength, scratch hardness and gloss, as well as lower elonga-
0 to 20 wt%), the limiting oxygen index (LOI) values decreased from tion at break than those of CHPUs. Both of them showed good
47.0 to 34.0, illustrating that the TAEP has a dominant effect on thermal and dielectric properties.
the flame retardancy.487 Using similar synthetic protocols, hyper- N,N0 -Bis(2-hydroxy ethyl) castor oil fatty amide, maleic anhydride,
branched polyphosphonate acrylate (HBPPA)474 and melamine- phthalic anhydride and isophthalic were reacted with diethanol
based hyperbranched polyphosphonate acrylate (MHPA)475 amine to synthesize castor oil-based hyperbranched poly(ester
were also facilely synthesized. Both of them exhibited good amide)s (HPEAs).499 HPEA was employed to cross-link the epoxy
flame retardancy and UV-curing property. resin for thermosetting coatings. It presented desirable properties,
6.7.2 Protective coatings. One of major functions of a including adhesion strength, scratch hardness, impact strength
protective coating is to prevent metal substrates from corrosion and so on, making it useful for surface coatings. Additionally, the
or scratches. The protection performance and service life depend cross-linked coating was biodegradable due to incorporating the
on its cross-linked density. renewable and degradable castor oil moiety.
Hyperbranched poly(ester-urethane-urea) (HPEUU) was
used to make an anticorrosive coating using hydroxyl-ended 6.8 HP-based modifiers
HPEs (OH-HPEs) and isophorone di-isocyanate (IPDI) as the 6.8.1 Toughenings or reinforcings. The diglycidyl ether of
starting materials. Compared with their linear counterparts, bisphenol A (DGEBA) resins are very useful precursors of
their mechanical, durability and corrosion resistance proper- thermoset materials. The rigid aromatic ring involved in their
ties were improved significantly, due to the higher cross-linked molecular chain leads to intrinsic brittleness, which has limited
density.490 their application. With a large free volume, epoxy-functional
View Article Online
HPs have been exploited as modifiers to develop the toughness cross-linking of 3,4-epoxycyclohexylmethyl-3 0 ,4 0 -epoxycyclohexyl
of cured DGEBA resin.501,502 carboxylate epoxy resin, as indicated by the thermal- and photo-
The curable HERSS with a DB of 0.71–0.84 was employed to DSC detections.
prepare HERSS–DGEBA composites, which exhibited better 6.8.4 Hydrophobic modifiers. Fluoroalkyl- or silane-containing
mechanical properties in comparison with those of pure DGEBA HPs have been utilized as surface modifiers to regulate the surface
epoxy resins.487 The improvements of tensile, flexural and impact tension of polymer matrices, affording the hydrophobic surface.517
strengths were 76.4–88.6%, 25.3–36.0% and 78.4–92.1%, which Two classes of fluorocarbon-containing HPs (HPEFs/HPUFs) have
were attributed to the ‘‘sea-island’’ structure (3.62–4.75 mm in exhibited very low surface free energies (13.67–24.49 mJ m2).518
diameter) formed in the composites. The resulting low surface tensions mainly rely on the terminal
Reactive hyperbranched polyether (HPEE) was composed of short fluorinated chains. Cotton fabrics treated by HPEFs or
an aromatic skeleton and terminal epoxy groups.502 The modi- HPUFs presented high hydrophobicity. The static contact angles
fied DGEBA epoxy resin with 5 wt% HPEE showed a higher Tg were up to 1461 with water, 1221 with hexadecane and 1021 with
than that of a control sample. Although there was no phase decane, respectively.
separation involved, the properties of the cured HPEE/DGEBA 6.8.5 Low dielectric modifiers. Fluoro-terminated hyper-
were significantly improved because of the high reactivity, rigid branched poly(phenylene oxide)s (FHPPOs) with DBs of 0.53–0.63
backbone and large mole free volume of HPEE. were synthesized by self-condensation.158 The Tg of the product
Poly(styrene)-b-poly(e-caprolactone) (PSOH-b-PCL) with an reached 164 1C as Mn was 4 6800 g mol1. The low polarity
average DPn of PCL arms of 60 has been prepared by combining framework, plentiful number of fluorine-containing terminal
ATRP and ROP.100 PSOH-b-PCL could toughen cured epoxy groups and large free volume endowed the FHPPOs with good
resins by incorporating the linear PCL arms. dielectric properties. Incorporation of FHPPO into DGEBA/
Other than epoxy-functional HPs, hyperbranched poly- 2-ethyl-4-methylimidazole thermost could largely reduce the
imides,503,504 poly(amidoamine),505,506 poly(ester-amide),507,508 dielectric constant and water absorption. These results implied
and polyesters509–514 were also good tougheners or reinforcers that FHPPO was an effective low-k dielectric modifier.
for the cured DGEBA-based thermoset.
6.8.2 Thickening agents. Star-like hyperbranched waterborne 6.9 HP-based membranes
polyurethanes (HWPU) were composed of the hyperbranched core Up till now, HPs have been widely used as diverse membranes,
and the hydrophilic linear arms.515 The number of arms has an such as in nanofiltration membranes for water softening or water
effect on the thickening effect of HWPU; for instance, the treatment,519–523 proton exchange membranes for fuel cells,524–526
thickening effect of the HWPU with six arms was superior to gas separation membranes for chemical engineering527–530 and
those with four or twelve arms. Furthermore, with the same core, antifouling/antibacterial membranes for bioapplications,531–533 etc.
the thickening effect is relevant to the length of the hydrophilic Using 4-dimethylaminopyridine (DMAP) as the catalyst, tri-
chain and the hydrophobic terminal group content. mesoyl chloride (TMC) and hyperbranched polyesteramide (HPEA)
Hyperbranched poly(DVB-co-PDMS) was synthesized via the took part in an interfacial polymerization to generate a reverse
deactivation enhanced atom transfer polymerization (DE-ATRP) osmosis membrane.521 This composite membrane (thickness of
of PDMS and divinylbenzene (DVB). It has also been applied as B100 nm) exhibited a high salt rejection rate, e.g. Na2SO4 rejection
a thickening agent for silicon oils. Within the coating, cosmetic was up to 98% and NaCl and MgSO4 rejections were 492% with
and pharmaceutical fields, this viscosity-modifier has shown water fluxes of around about 30–40 L m2 h1 and a pressure of
well-controlled effects.516 0.6 MPa. Interestingly, the composite membrane could be used to
6.8.3 Curing accelerants. With a hyperbranched–linear– separate organic compounds, such as PEG200.
hyperbranched structure, the copolymer, HPH, was prepared Sulfonated star-hyperbranched polyimide (SHPI) membranes
by the condensation of 4,4-bis(4-hydroxyphenyl) valeric acid have also been synthesized for proton-transport.525 The electro-
and poly(ethylene glycol) in one-pot (Scheme 13).101 Because of chemical impedance spectroscopy (EIC) showed that the SHPI
the abundant peripheral phenolic hydroxyls, the addition of membrane exhibited high proton conductivity. At 80 1C and 98%
HPH in the epoxy and hardener mixture could accelerate the RH, the proton-transport rate reached 0.51 S cm1, which was
obviously superior to that of commercial Nafions. Moreover, the
proton conductivity of the amphiphilic SHPI membranes was
connected with the content of the sulfonated-HPI moiety,
because the proton-transport channels were formed by self-
assembly of the SHPIs.
A hybrid membrane composed of HPI/OH-HPI and silica was
used for the CO2/CH4 separation.530 The incorporation of silica
into the HPI/OH-HPI matrix enhanced significantly the gas per-
meability, which was ascribed to the larger free volume in the
membrane and the synergistic effect of HPI/OH-HPI and silica.
Introducing a hydrophilic polymer into hydrophobic membranes
Scheme 13 Schematic illustration of HPH. can greatly improve their antifouling property.531 The addition of
View Article Online
HPE-g-mPEG into poly(vinylidene fluoride) (PVDF) membranes 6.11 Other applications

by direct mixing allowed porous membranes to be obtained by 6.11.1 Shape memory materials. Shape memory polymers
a phase inversion process. The water soluble mPEG-modified (SMPs) are those materials that can maintain deformation in a
porous membranes exhibited a low water contact angle (491), temporary state and can recover their primal shapes as they are
and good antifouling and water flux recovery properties. subjected to specific external stimuli. This deformation and
In addition, HP-based membranes have been widely utilized recovery process corresponds to the reversible storage and release
in chemical engineering unit operations,534 such as in distilla- of entropy energy.
tion,535 extraction,536 absorption,537 and so on. Details about PCL-based HPUs,555 HPU–MWCNTs556 and HPU–GO557 have
these applications can be found in the recent review.533
served as advanced thermo-responsive SMPs.

6.11.2 Self-healing materials. Self-healing materials can
6.10 Chemosensors spontaneously heal injuries just as an organism does. This
Conjugated polymers are promising candidates for a chemo- advanced function of artificial polymers is attributed to the
sensor to detect nitroaromatic explosives such as, picric acid physical or chemical network formed. Imposing damage on it
(PA), 2,4,6-trinitrotoluene (TNT) and 2,4-dinitrotoluene (DNT), leads to the partial fracture of noncovalent bonds. On the contrary,
etc., because of their superior response and sensitivity to the injury healing process corresponds to the reconstruction of the
analytes.538–547 However, intrinsic self-aggregation caused by broken noncovalent or covalent bonds. Consequently, the dynamic
polymer chains and the induction of nitroaromatics will lead to physical/chemical networks play a crucial role in self-healing
emission quenching and the decay of sensitivity. materials.
HCPs have some intriguing features, compared to their Azide- and alkyne-ended hyperbranched poly(isobutylene)s
linear analogues: (i) high branching structures, endowing the (HPIBs, Mn = 25 200–35 400 g mol1, with B9 terminal groups)
HCPs with desired AEE activity and a signal amplification were employed to synthesize self-healing HPs via the CuAAC.558
effect;548–551 (ii) few entanglements among the polymer chains, Because of the high molecular mobility of HPIB chains (Tgs
greatly reducing the chances of the aforementioned autoaggre- of 60 to 70 1C), the product showed self-healing behavior
gation;1–3 (iii) numerous intramolecular cavities, affording high (Fig. 27).
binding capability to analytes,550–552 and (iv) a 3D architecture, 6.11.3 Elastomers. Generally, elastomers have low Tg, ultra-
making excitonic migration and interaction between HCP and the high molecular weights, and a suitable degree of cross-linking. A
analyte easier;553,554 In particular, hyperbranched poly(silole)s,538–540 low Tg endows the elastomer with a large deformability and the
polytriazoles,541,542 poly(tetraphenylethene),543,544 carbazole- modest degree of cross-linking makes its deformation restorable.
containing HPs545 and porous HCP nanoparticles546,547 have PUs have been widely used as elastomers. Introducing hydroxyl-
been used as chemosensors for the detection of nitroaromatics functional HPs into PU elastomers gives the products better mecha-
with superior sensitivity. For instance, tetraphenylethylene-based nical properties than those of their linear counterparts.559–561
HCP (HP-TPE-Cz) quenching could be clearly discerned at a 6.11.4 Adhesives. Adhesives serve as the important media
PA concentration as low as 0.33 ppm with a quenching constant to link up two or more objects. Good wettability, strong inter-
of 3.99 104 M1, due to its higher AIEE activity and signal facial interaction and high mechanical performances are essen-
amplification effect (Fig. 26).545 tial features of an adhesive.
Hyperbranched poly(triazole)s were used as adhesives and
have shown high adhesive strength at ambient temperature
(such as 16.49 1.21 MPa) and at 200 1C (7 times epoxy
adhesive 4006# and GY-1#) due to their abundant rigid aromatic
and triazole rings. Moreover, their strong polar triazole groups
give rise to large binding energy between the HP-based adhesive
and metal substrates.183
Fig. 26 Photoluminescence spectra of HP-TPE-Cz in a THF–water mixture

(1 : 9 v/v, 2.0 103 mg mL1) with different contents of PA (a); PA
concentration dependence of the intensity of HP-TPE-Cz in the THF–water
mixture, where I is the peak intensity and I0 is the peak intensity at [PA] =
0 mg mL1 (b); inset of (b): fluorescence images of HP-TPE-Cz specimens
adsorbed in filter papers before (left), and after being partially dipped into
toluene (middle) and after being partially dipped into a toluene solution of
PA (right). (Reproduced from ref. 545 with permission from Royal Society Fig. 27 Cross-linking hyperbranched azide- and alkyne-functionalized
of Chemistry.) PIBs by CuACC reaction at 20 1C.558
View Article Online
Moreover, HPG-based PUs and hyperbranched poly(dopamine-

co-acrylate)s have been used as non-toxic adhesives, possessing
promising application in biological fields.562,563
6.11.5 Printing inks. Similar to paints, besides good rheo-
logical properties, high quality printing ink should have a high
adhesive force, bright color and good color fastness.
Two classes of hydroxyl-ended HPEs, Boltornt P500 and
P1000, were firstly applied to modify the commercially available
printing ink Uranias.564 Both of the modified flexographic
printing inks by Boltornt P500 or P1000 showed better coloring

fastness, compared to the control sample.
6.11.6 Catalysts. Related contents of HP-stabilized transi-
tion metal complexes/catalysts were illustrated in Section 6.2.2.
Here, we introduce HPs directly used as catalysts.
Hyperbranched polyselenides can act as catalysts due to
their having a lot of diselenide groups on the skeleton.565
Diselenide groups show a glutathione peroxidase-like catalytic Fig. 28 Sulfur-rich HPs (SRHPs) used for battery materials. Structure of
property. Moreover, cobalt-containing poly [tris(4-ethynylphenyl)- SRHP (a), the good solubility of SRHPs in different organic solvents (b), and
cycle performance of Li–S cells using SRHPs as the cathode material (c).
amine] (HPTEPA) has already been used as an efficient catalyst for Insert shows the Li–S cell fabricated using SRHPs as the cathode material
the preparation of CNTs by the CVD approach.566 in Fig. 28c. (Reproduced from ref. 572, with permission from the Royal
6.11.7 CO2 capture materials. Amino groups can react with Society of Chemistry.)
CO2 forming the carbamate, whose chemical property is unstable.
The carbamate is easily decomposed at elevated temperature.
Based on the mechanism, amino-containing HPs can be applied and poly-(3,4-ethylenedioxythiophene) (PEDOT) to develop inter-
to CO2 capture materials. facial properties. The formed VHPSi layer could reduce the degra-
To improve the CO2 adsorption capability, amino-functionalized dation of the oxide film and lower the conductivity of the PEDOT
HPs are usually coated on the surface of mesoporous silica skeleton electrode. Consequently, the VHPSi-modified aluminum solid
to enlarge the effective contact area between the CO2 and amino electrolytic capacitor showed a high capacitance (410 mF) and a
groups.567–569 Amino-containing HPs have exhibited higher CO2 low equivalent series resistance (5.6 mO).
capture capacity and desorption efficiency than amino-containing
silane couplings modified mesoporous silica skeleton. 7. Conclusion and outlook
6.11.8 Microporous materials. Hyperbranched poly(phenylene
butadiynylene)s and poly(phenylene ethynylene)s with rigid This review has summarized the major developments in structure
skeletons were prepared via the Hay–Sonogashira coupling control, synthetic strategies, and functionalizations, as well as the
reaction.570 As the TGA measurement revealed, their thermal applications of CHPs and SHPs since 2004. Various robust click
degradation process displayed two stages. The first stage chemistries, including CuAAC, MFAAC, SPC, thiol–ene/yne addi-
(300–500 1C) was ascribed to the elimination of side chains tion, Menschutkin quaternization reaction, Diels–Alder cycloaddi-
and afforded microporous polymers (surface areas of about tion, Michael addition, etc., have been employed for the synthesis
800 m2 g1). The second stage (4900 1C) was attributed to the of HPs based on SMM, DMM, CMM and MCM in an orthogonal
degradation of the backbones. Correspondingly, microporous manner. The HPs can be further functionalized from their
carbon was formed (surface area of ca. 13 m2 g1). periphery to their core through these efficient click chemistries,
6.11.9 Battery materials. HPG was used to prepare the gel affording tailored structures and properties. Notably, function-
electrolyte for dye-sensitized solar cells (DSSCs).571 Increasing the alization of the core of the HPs, largely depends on their structures.
HPG content can enhance the open circuit voltage of DSSCs and With the loose framework and the lower steric hindrance, all the
improve the energy conversion efficiency (by up to 6.78% at 1 sun). scaffolds of SHPs were functionalized. On the contrary, the back-
Sulfur-rich HPs (SRHPs) were synthesized via the thiol–ene- bone functionalization of CHPs only reached around 70%, owing to
like addition of elemental sulfur and 1,3-diidopropenylbenzene their highly compact structures. HPs with highly branched struc-
in chloroform.572 Then, they were utilized as the cathode tures, abundant functional groups and unique properties have
materials in Li–S cells. Due to the need to avoid the possibility shown great potential for applications as light-emitting materials,
of involving elemental sulfur in the cathode material, the Li–S cell biomaterials, supramolecular chemistry, nanoscience and tech-
exhibited good battery properties, such as high initial capacities nology, hybrid materials and composites, coatings, adhesives,
(1247.6 mA h g1) and good cycle performance (167.2 mA h g1 and so on.
after 400 times), which outperformed pure sulfur (Fig. 28). Although large advances have been achieved in the past few
6.11.10 Supercapacitors. Vinyl-terminated hyperbranched decades, several major challenges still exist.
poly(siloxysilane)s (VHPSis) were synthesized via hydrosilyl- Firstly, how to precisely control the DB, chemical structures,
ation.573 VHPSis filled in the gap between the aluminum oxide MWs and PDIs of HPs? All these parameters are very important
View Article Online
for their performance and further applications. With regard to 8 H. R. Kricheldorf, Q. Z. Zang and G. Schwarz, Polymer,
linear polymers or dendrimers, their corresponding polymeri- 1982, 23, 1821.
zations can be well controlled. However, for HPs, the effective 9 Y. H. Kim and O. W. Webster, Polym. Prepr., 1988, 23, 1821.
control of these parameters is very difficult, since the chain 10 C. R. Yates and W. Hayes, Eur. Polym. J., 2004, 40, 1257.
propagation is intricate and elusive. 11 A. Hirao, M. Hayashi, S. Loykulnant, K. Sugiyama, S. W. Ryu,
Secondly, how to facilely introduce hetero-atoms (such as N, N. Haraguchi, A. Matsuo and T. Higashihara, Prog. Polym.
P, S, Se, etc.) and/or hetero-functional groups into HPs?574 Such Sci., 2005, 30, 111.
hetero-atoms/-functional groups-containing HPs have exhibited 12 B. D. Mather, K. Viswanathan, K. M. Miller and T. E. Long,
fascinating and unique performances. For instance, nitrogen- and Prog. Polym. Sci., 2006, 31, 487.
phosphorus-containing HPs are flame retardancy; sulfur- 13 D. K. Chattopadhyay and K. V. S. N. Raju, Prog. Polym. Sci.,
containing HPs possess a refractive index; and selenium- 2007, 32, 352.
containing HPs are promising candidates for biomaterials. 14 M. Marcos, R. Martı́n-Rapún, A. Omenat and J. L. Serrano,
However, more effective methods are required to easily intro- Chem. Soc. Rev., 2007, 36, 1889.
duce these designed hetero-atoms into HPs. 15 L. R. Hutchings, Soft Matter, 2008, 4, 2150.
Thirdly, how to successfully synthesize planar (2D) HPs? 16 S. H. Hwang, C. N. Moorefield and G. R. Newkome, Chem.
Although soluble linear (1D) and spherical (3D) macromolecules Soc. Rev., 2008, 37, 2543.
have been well developed, so far, no planar HPs have been 17 B. I. Voit and A. Lederer, Chem. Rev., 2009, 109, 5924.
reported. The synthesis and applications of 2D HPs may become 18 J. Peter, A. Khalyavina, J. Křı́ž and M. Bleha, Eur. Polym. J.,
a new research hotspot in the near future. 2009, 45, 1716.
Fourthly, how to facilely develop sequence-controlled HPs? 19 Y. F. Zhou and D. Y. Yan, Chem. Commun., 2009, 1172.
Just recently, the first hetero-functional sequence-controlled 20 M. Scholl, Z. Kadlecova and H. A. Klok, Prog. Polym. Sci.,
HP was synthesized via a thiol–yne polymerization.172 With 2009, 34, 24.
their unique architecture, novel HPs will attract more interest 21 M. Ouchi, T. Terashima and M. Sawamoto, Chem. Rev.,
and become part of the scientific mainstream. 2009, 109, 4963.
Fifthly, how to effectively apply these artificial HPs in the 22 A. Carlmark, C. Hawker, A. Hult and M. Malkoch, Chem.
service of humanity? Linear polymers have had a broad range of Soc. Rev., 2009, 38, 352.
uses since they first appeared; whereas their hyperbranched 23 R. M. England and S. Rimmer, Polym. Chem., 2010, 1, 1533.
analogue has few practical applications so far. Combining the 24 X. L. Zhang, Prog. Org. Coat., 2010, 69, 295.
relationship between the structure and property and making a 25 D. Wilms, S.-E. Stiriba and H. Frey, Acc. Chem. Res., 2010,
new breakthrough in synthetic methodology for HPs could 43, 129.
further promote the development of this subject. 26 M. Calderón, M. A. Quadir, S. K. Sharma and R. Haag, Adv.
Mater., 2010, 22, 190.
27 C. H. Li and Z. S. Bo, Polymer, 2010, 51, 4273.
Acknowledgements 28 R. M. England and S. Rimmer, Polym. Chem., 2010, 1, 1533.
29 X. Z. Hu, L. Zhou and C. Gao, Colloid Polym. Sci., 2011,
This work was supported by the National Natural Science Foun-
289, 1299.
dation of China (No. 21325417 and No. 51173162), Fundamental
30 F. Wurm and H. Frey, Prog. Polym. Sci., 2011, 36, 1.
Research Funds for the Central Universities (No. 2013XZZX003),
31 D. J. A. Cameron and M. P. Shaver, Chem. Soc. Rev., 2011,
and China Postdoctoral Science Foundation (2014M551724). The
40, 1761.
authors also thank Li Peng, Bo Zhao and Shengying Cai for the
32 E. Žagar and M. Žigon, Prog. Polym. Sci., 2011, 36, 53.
reference collections.
33 A. Gregory and M. H. Stenzel, Prog. Polym. Sci., 2012,
37, 38.
Notes and references 34 H. B. Jin, W. Huang, X. Y. Zhu, Y. F. Zhou and D. Y. Yan,
Chem. Soc. Rev., 2012, 41, 5986.
1 D. Y. Yan, C. Gao and H. Frey, Hyperbranched Polymers: 35 K. Kirkorian, A. Ellis and L. J. Twyman, Chem. Soc. Rev.,
Synthesis, Properties and Applications, A John Wiley and 2012, 41, 6138.
Sons Inc., Hoboken, New Jersy, 2011. 36 H. Frey, Nat. Mater., 2012, 359.
2 M. Adeli, Novel Polymers and Nanoscience, Transworld 37 Q. Zhu, F. Qiu, B. S. Zhu and X. Y. Zhu, RSC Adv., 2013,
Research Network, Kerala, 2008. 3, 2071.
3 C. Gao and D. Yan, Prog. Polym. Sci., 2004, 29, 183. 38 A. Carlmark, E. Malmström and M. Malkoch, Chem. Soc.
4 L. R. Hutchings, J. M. Dodds and S. J. Roberts-Bleming, Rev., 2013, 42, 5858.
Macromolecules, 2005, 38, 5970. 39 E. Moore, H. Thissen and N. H. Voelcker, Prog. Polym. Sci.,
5 R. H. kienle and A. G. Hovery, J. Am. Chem. Soc., 1929, 51, 509. 2013, 88, 213.
6 P. J. Flory, J. Am. Chem. Soc., 1952, 74, 2718. 40 Y. Segawa, T. Higashihara and M. Ueda, Polym. Chem.,
7 Y. H. Kim and O. W. Webster, J. Am. Chem. Soc., 1990, 2013, 4, 1746.
112, 4592. 41 Z. M. Dong and Z. B. Ye, Polym. Chem., 2012, 3, 286.
View Article Online
42 J. T. Sun, C. Y. Hong and C. Y. Pan, Polym. Chem., 2011, 73 G. Maier, C. Zech, B. Voit and H. Komber, Macromol. Chem.
2, 998. Phys., 1998, 199, 2655.
43 T. Satoh, Soft Matter, 2009, 5, 1972. 74 L. J. Hobson, A. M. Kenwright and W. J. Feast, Chem.
44 C. J. Hawker, R. Lee and J. M. J. Fréchet, J. Am. Chem. Soc., Commun., 1997, 1877.
1991, 113, 4583. 75 C. J. Hawker and F. Chu, Macromolecules, 1996, 29, 4370.
45 D. Y. Yan, A. H. E. Müller and K. Matyjaszewski, Macro- 76 K. Yoon and D. Y. Son, Macromolecules, 1999, 32, 5210.
molecules, 1997, 30, 7024. 77 S. Merino, L. Brauge, A. M. Caminade, J. P. Majoral,
46 A. H. E. Müller and D. Y. Yan, Macromolecules, 1997, D. Taton and Y. Gnanou, Chem. – Eur. J., 2001, 7, 3095.
30, 7015. 78 P. Kambouris and C. J. Hawker, J. Chem. Soc., Perkin Trans.
47 D. Hölter, A. Burgath and H. Frey, Acta Polym., 1997, 48, 30. 1, 1993, 2717.
48 X. Y. Zhu, Y. F. Zhou and D. Y. Yan, J. Polym. Sci., Part B: 79 D. H. Bolton and K. L. Wooley, J. Polym. Sci., Part A: Polym.
Polym. Phys., 2011, 49, 1277. Chem., 2002, 40, 823.
49 D. Schmaljohann and B. Voit, Macromol. Theory Simul., 80 Z. P. Zhou and D. Y. Yan, Chem. J. Chin. Univ., 1999, 20, 1978.
2003, 12, 679. 81 D. Y. Yan and Z. P. Zhou, Macromolecules, 1999, 32, 819.
50 S. Unal, Q. Lin, T. H. Mourey and T. E. Long, Macromolecules, 82 K. C. Cheng, T. H. Chuang, J. S. Chang, W. Guo and
2005, 38, 3246. W. F. Su, Macromolecules, 2005, 38, 8252.
51 S. Unal, C. Oguz, E. Yilgor, M. Gallivan, T. E. Long and 83 K. C. Cheng, Polymer, 2003, 44, 1259.
I. Yilgor, Polymer, 2005, 46, 4533. 84 A. Mock, A. Burgath, R. Hanselmann and H. Frey, Macro-
52 D. Hölter and H. Frey, Acta Polym., 1997, 48, 298. molecules, 2001, 34, 7692.
53 H. Frey and D. Hölter, Acta Polym., 1999, 50, 67. 85 P. Bharathi and J. S. Moore, Macromolecules, 2000, 33, 3212.
54 Y. Y. Mai, Y. F. Zhou, D. Y. Yan and H. W. Lv, Macro- 86 R. Hanselmann, D. Hölter and H. Frey, Macromolecules,
molecules, 2003, 36, 9667. 1998, 31, 3790.
55 D. Y. Yan, J. Hou, X. Y. Zhu, J. J. Kosman and H. S. Wu, 87 W. Radke, G. Litvinenko and A. H. E. Müller, Macromolecules,
Macromol. Rapid Commun., 2000, 21, 557. 1998, 31, 239.
56 M. W. Weimer, J. M. J. Fréchet and I. Gitsov, J. Polym. Sci., 88 D. Y. Yan, Z. P. Zhou and A. H. E. Müller, Macromolecules,
Part A: Polym. Chem., 1998, 36, 955. 1999, 32, 245.
57 Y. Segawa, T. Higashihara and M. Ueda, J. Am. Chem. Soc., 89 Z. P. Zhou and D. Y. Yan, Polymer, 2000, 41, 4549.
2010, 132, 11000. 90 G. I. Litvinenko and A. H. E. Müller, Macromolecules, 2002,
58 Z. Guan, Chem. – Asian J., 2010, 5, 1058. 35, 4577.
59 Z. Guan, P. M. Cotts, E. F. McCord and S. J. McLain, 91 T. Yokozawa, T. Asai, R. Sugi, S. Ishigooka and S. Hiraoka,
Science, 1999, 283, 2059. J. Am. Chem. Soc., 2000, 122, 8313.
60 L. Chen, X. Y. Zhu, D. Y. Yan, Y. Chen, Q. Chen and 92 T. Yokozawa, Y. Suzuki and S. Hiraoka, J. Am. Chem. Soc.,
Y. F. Yao, Angew. Chem., Int. Ed., 2006, 45, 87. 2001, 123, 9902.
61 J. Y. Wang and D. M. Johnson, Polym. Int., 2009, 58, 1234. 93 T. Yokozawa, D. Muroya, R. Sugi and A. Yokoyama, Macro-
62 W. Radke, G. Litvineko and A. H. E. Müller, Macromolecules, mol. Rapid Commun., 2005, 26, 979.
1998, 31, 239. 94 K. Iwashita, A. R. Sugi, A. Yokoyama, T. Furuyama,
63 Y. Ishida, A. C. F. Sun, M. Jikei and M. Kakimoto, Macro- M. Uchiyama and T. Yokozawa, J. Am. Chem. Soc., 2005,
molecules, 2000, 33, 2832. 127, 10172.
64 C. Lach and H. Frey, Macromolecules, 1998, 31, 2381. 95 A. Yokoyama and T. Yokozawa, J. Polym. Sci., Part A: Polym.
65 W. G. Huang, L. J. Shu and Z. S. Bo, J. Am. Chem. Soc., 2009, Chem., 2005, 43, 4109.
131, 10348. 96 A. Yokoyama, H. Suzuki, Y. Kubota, K. Ohuchi, H. Higashimura
66 B. Yao, J. Sun, A. Qin and B. Z. Tang, Chin. Sci. Bull., 2013, and T. Yokozawa, J. Am. Chem. Soc., 2007, 129, 7236.
58, 2711. 97 C. B. Zhang, Y. Zhou, Q. Liu, S. Li, S. Perrier and Y. L. Zhao,
67 M. Smet, E. Schacht and W. Dehaen, Angew. Chem., Int. Ed., Macromolecules, 2011, 44, 2034.
2002, 41, 4547. 98 Z. Shen, Y. Chen, E. Barriau and H. Frey, Macromol. Chem.
68 Y. Fu, C. Van Oosterwijck, A. Vandendriessche, A. Kowalczuk- Phys., 2006, 207, 57.
Bleja, X. Zhang, A. Dworak, W. Dehaen and M. Smet, 99 R. K. Kainthan, E. B. Muliawan, S. G. Hatzikiriakos and
Macromolecules, 2008, 41, 2388. D. E. Brooks, Macromolecules, 2006, 39, 7708.
69 W. Sinananwanich, T. Higashihara and M. Ueda, Macro- 100 M. Morell, D. Foix, A. Lederer, X. Ramis, B. Voit and
molecules, 2009, 42, 994. A. Serra, J. Polym. Sci., Part A: Polym. Chem., 2011, 49, 4639.
70 C. K. W. Jim, A. Qin, J. W. Y. Lam, J. Liu, M. Haeussler and 101 D. Foix, X. Ramis, M. Sangermano and A. Serra, J. Polym.
B. Z. Tang, Sci. China, Ser. B: Chem., 2008, 51, 705. Sci., Part A: Polym. Chem., 2012, 50, 1133.
71 S. Kono, W. Sinananwanich, Y. Shibasaki and M. Ueda, 102 J. M. J. Fréchet, M. Henmi, I. Gitsov, S. Aoshima, M. R.
Polym. J., 2007, 39, 1150. Leduc and R. B. Grubbs, Science, 1995, 269, 1080.
72 Z. F. Jia, H. Chen, X. Y. Zhu and D. Y. Yan, J. Am. Chem. 103 L. R. Hutchings, J. M. Dodds and S. J. Roberts-Bleming,
Soc., 2006, 128, 8144. Macromol. Symp., 2006, 240, 56.
View Article Online
104 L. R. Hutchings, J. M. Dodds, D. Rees, S. M. Kimani, 131 Z. F. Jia, G. L. Li, Q. Zhu, D. Y. Yan, X. Y. Zhu, H. Chen,
J. J. Wu and E. Smith, Macromolecules, 2009, 42, 8675. J. L. Wu, C. L. Tu and J. Sun, Chem. – Eur. J., 2009, 15, 7593.
105 J. M. Dodds and L. R. Hutchings, Macromol. Symp., 2010, 132 H. Chen, Z. F. Jia, D. Y. Yan and X. Y. Zhu, Macromol.
291–292, 26. Chem. Phys., 2007, 208, 1637.
106 J. M. Dodds, E. de Luca, L. R. Hutchings and N. Clarke, 133 Z. Guan, Chem. – Asian J., 2010, 5, 1058.
J. Polym. Sci., Part B: Polym. Phys., 2007, 45, 2762. 134 Z. Guan, P. M. Cotts, E. F. McCord and S. J. McLain,
107 N. Clarke, E. de Luca, J. M. Dodds, S. M. Kimani and Science, 1999, 283, 2059.
L. R. Hutchings, Eur. Polym. J., 2008, 44, 665. 135 K. Xu and B. Tang, Chin. J. Polym. Sci., 1999, 17, 397.
108 J. Han, S. Li, A. Tang and C. Gao, Macromolecules, 2012, 136 M. Jikei, S. H. Chon, M. Kakimoto, S. Kawauchi, T. Imase
45, 4966. and J. Watanabe, Macromolecules, 1999, 32, 2061.

109 T. Y. Zhao, Y. Zheng, J. Poly and W. X. Wang, Nat. 137 T. Emrick, H. T. Chang and J. M. J. Fréchet, Macromolecules,
Commun., 2013, 4, 1873. 1999, 32, 6380.
110 B. Voit, J. Polym. Sci., Part A: Polym. Chem., 2005, 43, 2679. 138 X. X. Deng, Y. Cui, F. S. Du and Z. C. Li, Polym. Chem., 2014,
111 Z. F. Jia and D. Y. Yan, J. Polym. Sci., Part A: Polym. Chem., 5, 3316.
2005, 43, 3502. 139 R. Kakuchi, Angew. Chem., Int. Ed., 2014, 53, 46.
112 Z. F. Jia, H. Chen, X. Y. Zhu and D. Y. Yan, J. Am. Chem. 140 S. Brauch, S. S. Van Berkel and B. Westmann, Chem. Soc.
Soc., 2006, 128, 8144. Rev., 2013, 42, 4948.
113 M. J. Liu, N. Vladimirov and J. M. J. Fréchet, Macromolecules, 141 O. Kreye, T. Toth and M. A. R. Meier, J. Am. Chem. Soc.,
1999, 32, 6881. 2011, 133, 1790.
114 M. Trollsås, P. Löwenhielm, V. Y. Lee, M. Möller, R. D. Miller 142 J. Lee, L. A. Spagnuolo and J. G. Rudick, Org. Lett., 2012,
and J. L. Hedrick, Macromolecules, 1999, 32, 9062. 14, 3292.
115 F. Wurm, J. Nieberle and H. Frey, Macromolecules, 2008, 143 I. Lee, H. Kim and T. Choi, J. Am. Chem. Soc., 2013, 135, 3760.
41, 1184. 144 R. Kakuchi and P. Theato, ACS Macro Lett., 2013, 2, 419.
116 E. Barriau, L. Pastor-Pérez, E. Berger-Nicoletti, A. F. M. 145 P. Punyacharoennon, S. Charuchinda and K. Srikulkit,
Kilbinger, J. Pérez-Prieto, H. Frey and S.-E. Stiriba, J. Polym. J. Appl. Polym. Sci., 2008, 110, 3336.
Sci., Part A: Polym. Chem., 2008, 46, 2049. 146 M. Hasanzadeh, T. Moieni and B. H. Moghadam, Adv.
117 E. Barriau, A. Garcı́a Marcos, H. Kautz and H. Frey, Macromol. Polym. Technol., 2013, 32, 21345.
Rapid Commun., 2005, 26, 862. 147 Q. Wang and W. Shi, Polym. Degrad. Stab., 2006, 91, 1289.
118 J. Hou, D. Y. Yan, X. Y. Zhu and Y. P. Fang, Chem. J. Chin. 148 P. Wen, X. Wang, W. Xing, X. Feng, B. Yu, Y. Shi, G. Tang,
Univ., 1999, 20, 1815. L. Song, Y. Hu and R. K. K. Yuen, Ind. Eng. Chem. Res.,
119 D. Y. Yan, J. Hou, X. Y. Zhu, J. J. Kosman and H. S. Wu, 2013, 52, 17015.
Macromol. Rapid Commun., 2000, 21, 557. 149 S. Santra, C. Kaittanis and J. M. Perez, Langmuir, 2010,
120 R. Klein, C. Schüll, E. Berger-Nicoletti, M. Haubs, K. Kurz 26, 5364.
and H. Frey, Macromolecules, 2013, 46, 8845. 150 G. C. Behera, A. Saha and S. Ramakrishnan, Macromolecules,
121 J. Geschwind and H. Frey, Macromolecules, 2013, 46, 3280. 2005, 38, 7695.
122 C. Schüll, H. Rabbel, F. Schmid and H. Frey, Macromolecules, 151 L. J. Twyman and Y. Ge, Chem. Commun., 2006, 1658.
2013, 46, 5823. 152 Z. Zhu, Z. Li, Y. Tan, Z. Li, Q. Li, Q. Zeng, C. Ye and J. Qin,
123 A. Goodwin and D. Baskaran, Macromolecules, 2012, Polymer, 2006, 47, 7881.
45, 9657. 153 M. Sun, J. Li, B. Li, Y. Fu and Z. Bo, Macromolecules, 2005,
124 A. Natalello, M. Werre, A. Alkan and H. Frey, Macromolecules, 38, 2651.
2013, 46, 8467. 154 S. J. Lim, D. Y. Seok, B. K. An, S. D. Jung and S. Y. Park,
125 C. Moers, L. Nuhn, M. Wissel, R. Stangenberg, M. Mondeshki, Macromolecules, 2006, 39, 9.
E. Berger-Nicoletti, A. Thomas, D. Schaeffel, K. Koynov, 155 I. K. Moon, C. S. Choi and N. Kim, Polymer, 2007, 48, 3461.
M. Klapper, R. Zentel and H. Frey, Macromolecules, 2013, 156 W. Wu, C. Ye, J. Qin and Z. Li, Polym. Chem., 2013, 4, 2361.
46, 9544. 157 M. Schlögl, S. Biethmueller, C. Troll, M. Möller and
126 A. Alkan, A. Natalello, M. Wagner, H. Frey and F. R. Wurm, B. Rieger, Macromolecules, 2004, 37, 4004.
Macromolecules, 2014, 47, 2242. 158 L. Luo, T. Qiu, Y. Meng, L. Guo, J. Yang, Z. Li, X. Cao and
127 C. Osterwinter, C. Schubert, C. Tonhauser, D. Wilms, X. Li, RSC Adv., 2013, 3, 14509.
H. Frey and C. Friedrich, Macromolecules, 2015, 48, 119. 159 H. Wang, Q. Wang, Z. Huang and W. Shi, Polym. Degrad.
128 J. Herzberger, D. Kurzbach, M. Werre, K. Fischer, Stab., 2007, 92, 1788.
D. Hinderberger and H. Frey, Macromolecules, 2014, 160 Y. Tamura, Y. Ito, Y. Segawa, T. Higashihara and M. Ueda,
47, 7679. Polym. Chem., 2011, 2, 1644.
129 L. Nuhn, C. Schüll, H. Frey and R. Zentel, Macromolecules, 161 J. Luston and J. Kronek, Polym. Eng. Sci., 2007, 1273.
2013, 46, 2892. 162 F. Xiang, M. Stuart, J. Vorenkamp, S. Roest, H. Timmer-
130 H. Chang and J. M. J. Fréchet, J. Am. Chem. Soc., 1999, Bosscha, M. C. Stuart, R. Fokkink and T. Loontjens, Macro-
121, 2313. molecules, 2013, 46, 4418.
View Article Online
163 I. A. Gorodetskaya, T. L. Choi and R. H. Grubbs, J. Am. 190 D. Konkolewicz, A. Gray-Weale and S. Perrier, J. Am. Chem.
Chem. Soc., 2007, 129, 12672. Soc., 2009, 131, 18075.
164 F. Huang and H. W. Gibson, J. Am. Chem. Soc., 2004, 191 J. Han, B. Zhao, Y. Gao, A. Tang and C. Gao, Polym. Chem.,
126, 14738. 2012, 3, 1918.
165 H. C. Kolb, M. G. Finn and K. B. Sharpless, Angew. Chem., 192 J. Han, B. Zhao, Y. Gao, A. Tang and C. Gao, Polym. Chem.,
Int. Ed., 2001, 40, 2004. 2011, 2, 2175.
166 C. Barner-Kowollik, F. E. Du Prez, P. Espeel, C. J. Hawker, 193 B. D. Fairbanks, E. A. Sims, K. S. Anseth and C. N.
T. Junkers, H. Schlaad and W. Van Camp, Angew. Chem., Bowman, Macromolecules, 2010, 43, 4113.
Int. Ed., 2011, 50, 60. 194 J. K. Stille, Makromol. Chem., 1972, 154, 49.
167 M. Meldal and C. W. Tornoe, Chem. Rev., 2008, 108, 2952. 195 B. Voit, S. Fleischmann, H. Komber, A. Scheed and
168 A. J. Michael, Prakt. Chem., 1893, 48, 94. K. Stumpe, Macromol. Symp., 2007, 254, 16.
169 N. J. Agard, J. A. Prescher and C. R. Bertozzi, J. Am. Chem. 196 F. Morgenroth and K. Mullen, Tetrahedron, 1997, 53, 15349.
Soc., 2004, 126, 15046. 197 L. Zhi, J. Wu, J. Li, M. Stepputat, U. Kolb and K. Mullen,
170 M. A. Tasdelen, Polym. Chem., 2011, 2, 2133. Adv. Mater., 2005, 17, 1492.
171 C. E. Hoyle, A. B. Lowe and C. N. Bowman, Chem. Soc. Rev., 198 K. Stumpe, H. Komber and B. Voit, Macromol. Chem. Phys.,
2010, 39, 1355. 2006, 207, 1825.
172 J. Han, Y. Zheng, B. Zhao, S. Li, Y. Zhang and C. Gao, Sci. 199 C. Vilela, A. J. D. Silvestre and A. Gandini, J. Polym. Sci.,
Rep., 2014, 4, 4387. Part A: Polym. Chem., 2013, 51, 2260.
173 A. E. vander Ende, E. J. Kravitz and E. Harth, J. Am. Chem. 200 C. Gao and D. Y. Yan, Macromolecules, 2001, 34, 156.
Soc., 2008, 130, 8706. 201 C. Gao and D. Y. Yan, Chem. Commun., 2001, 107.
174 D. Mather, K. Viswananthan, K. M. Miller and T. E. Long, 202 C. Y. Hong, Y. Z. You, D. C. Wu, Y. Liu and C. Y. Pan, J. Am.
Prog. Polym. Sci., 2006, 31, 487. Chem. Soc., 2007, 129, 5354.
175 J. Han, Y. Zheng, S. Zheng, S. Li, T. Hu, A. Tang and C. Gao, 203 M. Sun, C. Y. Hong and C. Y. Pan, J. Am. Chem. Soc., 2012,
Chem. Commun., 2014, 50, 8712. 134, 20581.
176 A. Qin, C. K. W. jin, W. Lu, J. W. Y. Lam, M. Haussler, 204 L. R. Hutchings and S. J. Roberts-Bleming, Macromolecules,
Y. Dong, H. H. Y. Sung, I. D. Williams, G. K. L. Wong, 2006, 39, 2144.
G. K. L. Wong and B. Z. Tang, Macromolecules, 2007, 205 S. All, A. Alh and B. Hazer, J. Appl. Polym. Sci., 2012,
40, 2308. 124, 536.
177 Z. Li, G. Yu, P. Hu, C. Ye, Y. Liu, J. Qin and Z. Li, 206 T. Ozturk and B. Hazer, J. Macromol. Sci., Part A: Pure Appl.
Macromolecules, 2009, 42, 1589. Chem., 2010, 47, 265.
178 Z. Li, W. Wu, G. Qiu, G. Yu, Y. Liu, Y. Liu, C. Ye, J. Qin and 207 M. L. Koh, D. Konkolewicz and S. Perrier, Macromolecules,
Z. Li, J. Polym. Sci., Part A: Polym. Chem., 2011, 49, 1977. 2011, 44, 2715.
179 W. Wu, Y. Fu, C. Wang, C. Ye, J. Qin and Z. Li, 208 D. Konkolewicz, M. J. Monteiro and S. Perrier, Macromole-
Chem. – Asian J., 2011, 6, 2787. cules, 2011, 44, 7067.
180 J. Xie, L. Hu, W. Shi, X. Deng, Z. Cao and Q. Shen, Polym. 209 L. Kong, M. Sun, H. Qiao and C. Pan, J. Polym. Sci., Part A:
Int., 2008, 57, 965. Polym. Chem., 2010, 48, 454.
181 J. Xie, L. Hu, W. Shi, X. Deng, Z. Cao and Q. Shen, J. Polym. 210 C. He, L. Li, W. He, W. Jiang and C. Wu, Macromolecules,
Sci., Part B: Polym. Phys., 2008, 46, 1140. 2011, 44, 6233.
182 A. Qin, J. W. Y. Lam, C. K. W. Jim, L. Zhang, J. Yan, 211 L. Li, C. He and C. Wu, Macromolecules, 2011, 44, 8195.
M. Haussler, J. Liu, Y. Dong, D. Liang, E. Chen, G. Jia and 212 L. Li, J. Zhou and C. Wu, Macromolecules, 2012, 45, 9391.
B. Z. Tang, Macromolecules, 2008, 41, 3808. 213 S. Pandey, S. P. Mishra, B. Koli, T. Kanai and A. B. Samui,
183 Y. Tang, C. K. W. Jim, Y. Liu, L. Ye, A. Qin, J. W. Y. Lam, J. Polym. Sci., Part A: Polym. Chem., 2012, 50, 2659.
C. Zhao and B. Z. Tang, ACS Appl. Mater. Interfaces, 2010, 2, 566. 214 J. Han, D. Zhu and C. Gao, Polym. Chem., 2013, 4, 542.
184 J. Wang, J. Mei, E. Zhao, Z. Song, A. Qin, J. Z. Sun and 215 J. Xu, L. Tao, C. Boyer, A. B. Love and T. P. Davis, Macro-
B. Z. Tang, Macromolecules, 2012, 45, 7692. molecules, 2010, 43, 20.
185 Q. Wang, H. Li, Q. Wei, J. Z. Sun, J. Wang, X. A. Zhang, 216 D. Konkolewicz, A. Gray-Weale and S. Perrier, J. Am. Chem.
A. Qin and B. Z. Tang, Polym. Chem., 2013, 4, 1396. Soc., 2009, 131, 18075.
186 H. Li, H. Wu, E. Zhao, J. Li, J. Z. Sun, A. Qin and B. Z. Tang, 217 D. Konkolewicz, C. K. Poon, A. Gray-Weale and S. Perrier,
Macromolecules, 2013, 46, 3907. Chem. Commun., 2011, 47, 239.
187 Q. Wei, J. Wang, X. Shen, X. A. Zhang, J. Z. Sun, A. Qin and 218 B. Yu, X. Jiang, G. Yin and J. Yin, J. Polym. Sci., Part A:
B. Z. Tang, Sci. Rep., 2013, 3, 1093. Polym. Chem., 2010, 48, 4252.
188 C. Y. K. Chan, J. W. Y. Lam, C. K. W. Jim, H. H. Y. Sung, 219 B. Yu, X. Jiang, R. Wang and J. Yin, Macromolecules, 2010,
I. D. Williams and B. Z. Tang, Macromolecules, 2013, 43, 10457.
46, 9494. 220 R. Wang, B. Yu, X. Jiang and J. Yin, Adv. Funct. Mater., 2012,
189 L. Xue, Z. Yang, D. Wang, Y. Wang, J. Zhang and S. Feng, 22, 2606.
J. Org. Chem., 2013, 732, 1. 221 B. Li, X. Jiang and J. Yin, J. Mater. Chem., 2012, 22, 17976.
View Article Online
222 S. Li, J. Han and C. Gao, Polym. Chem., 2013, 4, 1774. 252 K. Pu, K. Li, J. Shi and B. Liu, Chem. Mater., 2009, 21, 3816.
223 S. Li and C. Gao, Polym. Chem., 2013, 4, 4450. 253 Z. L. Weng, Y. C. Zheng, A. J. Tang and C. Gao, Aust.
224 A. Saha and S. Ramakrishnan, Macromolecules, 2009, 42, 4028. J. Chem., 2014, 67, 103.
225 A. Saha and S. Ramakrishnan, Macromolecules, 2009, 42, 4956. 254 A. Tang, J. Han, Z. Weng and C. Gao, Acta Polym. Sin., 2013,
226 S. G. Ramkumar, K. A. Amala Rose and S. Ramakrishnan, 1, 70.
J. Polym. Sci., Part A: Polym. Chem., 2010, 48, 3200. 255 D. Schmaljohann, P. Pötschke, R. Hässler, B. Voit, P. E.
227 A. Z. Samuel and S. Ramakrishnan, Macromolecules, 2012, Froehling, B. Mostert and J. A. Loontjens, Macromolecules,
45, 2348. 1999, 32, 6333.
228 U. Georgi, M. Erber, J. Standermann, M. Abulikemu, 256 S. M. Burkinshaw, P. E. Froehling and M. Mignanelli, Dyes
H. Komber, A. Lederer and B. Voit, J. Polym. Sci., Part A: Pigm., 2002, 53, 229.
Polym. Chem., 2010, 48, 2224. 257 F. Zhang, Y. Chen, H. Lin and Y. Lu, Color. Technol., 2007,
229 K. Pu, J. Shi, L. Cai, K. Li and B. Liu, Biomacromolecules, 123, 351.
2011, 12, 2966. 258 F. Zhang, Y. Chen, H. Lin, H. Wang and B. Zhao, Carbohydr.
230 I. Bohm and H. Ritter, Macromol. Chem. Phys., 2011, Polym., 2008, 74, 250.
212, 1080. 259 J. Li and Z. S. Bo, Macromolecules, 2004, 37, 2013.
231 I. Hohm, S. K. Kreth, H. Ritter, R. Branscheid and U. Kolb, 260 Y. Xin, G. A. Wen, W. J. Zeng, L. Zhao, X. R. Zhu, Q. L. Fan,
Macromol. Chem. Phys., 2012, 213, 243. J. C. Feng, L. H. Wang, W. Wei, B. Peng, Y. Cao and
232 X. Jiang, J. Liu, L. Xu and R. Zhuo, Macromol. Chem. Phys., W. Huang, Macromolecules, 2005, 38, 6755.
2011, 212, 64. 261 L. Tsai and Y. Chen, Macromolecules, 2007, 40, 2984.
233 C. Schull, T. Gieshoff and H. Frey, Polym. Chem., 2013, 4, 3730. 262 X. Y. Cao, X. H. Zhou, H. Zi and J. Pei, Macromolecules,
234 I. Papp, J. Dernedde, S. Enders and R. Hagg, Chem. Commun., 2004, 37, 8874.
2008, 5851. 263 Y. G. Wu, X. H. Hao, J. L. Wu, J. Jin and X. W. Ba,
235 L. Zhou, J. Geng, G. Wang, J. Liu and B. Liu, ACS Macro Macromolecules, 2010, 43, 731.
Lett., 2012, 1, 927. 264 G. L. Wu, Y. Yang, C. He, X. M. Chen and Y. F. Li,
236 M. Meise and R. Haag, ChemSusChem, 2008, 1, 637. Eur. Polym. J., 2008, 44, 4047.
237 M. Weinhart, D. Groger, S. Enders, J. Dernedde and 265 Z. A. Li, S. H. Ye, Y. Q. Liu, G. Yu, W. B. Wu, J. H. Qin and
R. Haag, Biomacromolecules, 2011, 12, 2502. Z. Li, J. Phys. Chem. B, 2010, 114, 9101.
238 I. N. Kurniasih, H. Liang, V. D. Moschwitzer, M. A. Quadir, 266 J. Liu, L. Yu, C. M. Zhong, R. F. He, W. Yang, H. B. Wu and
M. Radowski, J. P. Rabe and R. Haag, New J. Chem., 2012, Y. Cao, RSC Adv., 2012, 2, 689.
36, 371. 267 T.-W. Lee, Y. Kwon, J.-J. Park, L. Pu, T. Hayakawa and
239 L. Zhao, T. Chano, S. Morikawa, Y. Saito, A. Shiino, S. Shimizu, M. Kakimoto, Macromol. Rapid Commun., 2007, 28, 1657.
T. Maeda, T. Irie, S. Aonuma, H. Okabe, T. Kimura, T. Inubushi 268 Z. Li, Q. Li and J. G. Qin, Polym. Chem., 2011, 2, 2723.
and N. Komatsu, Adv. Funct. Mater., 2012, 22, 5107. 269 W. B. Wu, L. J. Huang, L. Xiao, Q. Huang, R. L. Tang, C. Ye,
240 G. Wang, C. Liu, M. Pan and J. Huang, J. Polym. Sci., Part A: J. G. Qin and Z. Li, RSC Adv., 2012, 2, 6520.
Polym. Chem., 2009, 47, 1308. 270 Z. Zhu, Z. Li, Y. Tan, Z. Li, Q. Li, Q. Zeng, C. Ye and J. Qin,
241 M. Pan, G. Wang, Y. Zhang and J. Huang, J. Polym. Sci., Part Polymer, 2006, 47, 7881.
A: Polym. Chem., 2010, 48, 5856. 271 Y. Bai, N. Song, J. P. Gao, X. Sun, X. Wang, G. Yu and
242 R. Roy and S. Ramakrishnan, J. Polym. Sci., Part A: Polym. Z. Y. Wang, J. Am. Chem. Soc., 2005, 127, 2060.
Chem., 2011, 49, 1735. 272 Z. Li, A. Qin, J. W. Y. Lam, Y. Dong, C. Ye, I. D. Williams
243 H. T. Pu, Q. Zhou and D. C. Wan, Chin. Chem. Lett., 2007, and B. Z. Tang, Macromolecules, 2006, 39, 1436.
18, 758. 273 A. Scarpaci, E. Blart, V. Montembault, L. Fontaine,
244 P. J. Yeh, R. K. Kainthan, Y. Zhou, M. Chiao and J. N. V. Rodriguez and F. Odobel, ACS Appl. Mater. Interfaces,
Kizhakkedathu, Langmuir, 2008, 24, 4907. 2009, 1, 1799.
245 M. Li, K. Neoh, R. Wang, B. Zong, J. Y. Tan and E. Kang, 274 A. Scarpaci, E. Blart, V. Montembault, L. Fontaine,
Eur. J. Pharm. Sci., 2013, 48, 111. V. Rodriguez and F. Odobel, Chem. Commun., 2009, 1825.
246 Y. Shen, M. Kuang, Z. Shen, J. Nieberle, H. Duan and 275 Y. W. Bai, N. H. Song, J. P. Gao, X. Sun, X. M. Wang,
H. Frey, Angew. Chem., Int. Ed., 2008, 47, 2227. G. M. Yu and Z. Y. Wang, J. Am. Chem. Soc., 2005, 127, 2060.
247 Y. Liang, D. Wan, X. Cai, M. Jin and H. Pu, J. Polym. Sci., 276 N. Song, L. Men, J. P. Gao, Y. Bai, A. Beaudin and
Part A: Polym. Chem., 2010, 48, 681. Z. Y. Wang, Chem. Mater., 2004, 16, 3708.
248 C. Gao and X. Zheng, Soft Matter, 2009, 5, 4788. 277 X. Hu, L. Zhou and C. Gao, Colloid Polym. Sci., 2011, 289, 1299.
249 S. Brauch, S. S. Van Berkel and B. Westmann, Chem. Soc. 278 Q. Zhu, F. Qiu, B. S. Zhu and X. Y. Zhu, RSC Adv., 2013,
Rev., 2013, 42, 4948. 3, 2071.
250 Z. Dong and Z. Ye, Macromolecules, 2012, 45, 5020. 279 N. Perignon, J. D. Marty, A. F. Mingotaud, M. Dumont,
251 A. Zill, A. L. Rutz, R. E. Kohman, A. M. Alkilany, C. J. I. R. Lattes and C. Mingotaud, Macromolecules, 2007, 40, 3034.
Murphy, H. Kong and S. C. Zimmerman, Chem. Commun., 280 S. Saliba, C. V. Serrano, J. Keilitz, M. L. Kahn, C. Mingotaud,
2011, 47, 1279. R. Haag and J. D. Marty, Chem. Mater., 2010, 22, 6301.
View Article Online
281 Y. Y. Sun, D. Wang, J. G. Gao, Z. Zheng and Q. J. Zhang, 309 H. L. Liang, D. M. Yu, Y. C. Xie, C. Min, J. Zhang and
J. Appl. Polym. Sci., 2007, 103, 3701. G. H. Hu, Polym. Eng. Sci., 2009, 49, 2189.
282 Y. Y. Sun, Y. Q. Liu, G. Z. Zhao and Q. J. Zhang, J. Appl. 310 O. Monticellia, S. Russoa, R. Campagna and B. Voit,
Polym. Sci., 2008, 107, 9. Polymer, 2005, 46, 3597.
283 Y. W. Zhang, H. S. Peng, W. Huang, Y. F. Zhou, X. H. Zhang 311 N. Kakati, S. S. Mahapatra and N. Karak, Pure Appl. Chem.,
and D. Y. Yan, J. Phys. Chem. C, 2008, 112, 2330. 2008, 45, 658.
284 L. J. Zhu, Y. F. Shi, C. L. Tu, R. B. Wang, Y. Pang, F. Qiu, 312 S. S. Mahapatra and N. Karak, Mater. Chem. Phys., 2008,
X. Y. Zhu, D. Y. Yan, L. He, C. Y. Jin and B. S. Zhu, 112, 1114.
Langmuir, 2010, 26, 8875. 313 T. V. Richter, F. Schuler, R. Thomann, R. Mülhaupt and
285 L. Tuchbreiter and S. Mecking, Macromol. Chem. Phys., S. Ludwigs, Macromol. Rapid Commun., 2009, 30, 579.
2007, 208, 1688. 314 H. W. Duan and S. M. Nie, J. Am. Chem. Soc., 2007, 129,
286 M. Gladitz, S. Reinemann and H. J. Radusch, Macromol. 3333.
Mater. Eng., 2009, 294, 178. 315 L. Zhou, C. Gao, X. Z. Hu and W. J. Xu, ACS Appl. Mater.
287 M. Krämer, N. Perignon, R. Haag, J. D. Marty, R. Thomann, Interfaces, 2010, 2, 1211.
N. L. Viguerie and C. Mingotaud, Macromolecules, 2005, 316 L. Zhou, C. Gao and W. J. Xu, ACS Appl. Mater. Interfaces,
38, 8308. 2010, 2, 1483.
288 J. Keilitz, M. R. Radowski, J. D. Marty, R. Haag, F. Gauffre 317 L. Zhou, C. Gao, W. J. Xu, X. Wang and Y. H. Xu, Biomacro-
and C. Mingotaud, Chem. Mater., 2008, 20, 2423. molecules, 2009, 10, 1865.
289 S. Moisan, V. Martinez, P. Weisbecker, F. Cansell, S. Mecking 318 Y. F. Shi, J. M. Du, L. Z. Zhou, X. T. Li, Y. H. Zhou, L. L. Li,
and C. Aymonier, J. Am. Chem. Soc., 2007, 129, 10602. X. X. Zang, X. Y. Zhang, F. C. Pan, H. H. Zhang, Z. Y. Wang
290 Y. F. Shi, C. L. Tu, R. B. Wang, J. Y. Wu, X. Y. Zhu and and X. Y. Zhu, J. Mater. Chem., 2012, 22, 355.
D. Y. Yan, Langmuir, 2008, 24, 11955. 319 L. Zhou, C. Gao and W. J. Xu, Langmuir, 2010, 26, 11217.
291 K. Kim, H. B. Lee, J. W. Lee, H. K. Park and K. S. Shin, 320 R. J. Kalbasi and F. Zamani, RSC Adv., 2014, 4, 7444.
Langmuir, 2008, 24, 7178. 321 M. L. Wang, T. T. Jiang, Y. Lu, H. J. Liu and Y. Chen,
292 V. Juttukonda, R. L. Paddock, J. E. Raymond, D. Denomme, J. Mater. Chem. A, 2013, 1, 5923.
A. E. Richardson, L. E. Slusher and B. D. Fahlman, J. Am. 322 C. H. Ho, M. Thiel, S. Celik, E. K. Odermatt, I. Berndt,
Chem. Soc., 2006, 128, 420. R. Thomann and J. C. Tiller, Polymer, 2012, 53, 4623.
293 I. Y. Goon, L. Lai, M. Lim, P. Munroe, J. J. Gooding and 323 S. S. Mahapatra and N. Karak, Mater. Chem. Phys., 2008,
R. Amal, Chem. Mater., 2009, 21, 673. 112, 1114.
294 T. Nann, Chem. Commun., 2005, 1735. 324 H. H. Nguyen, C. V. Serrano, P. Lavedan, D. Goudounèche,
295 L. Zhou, C. Gao and W. J. Xu, J. Mater. Chem., 2010, A.-F. Mingotaud, N. L. Viguerie and J.-D. Marty, Nanoscale,
20, 5675. 2014, 6, 3599.
296 Y. Chen, H. Frey, R. Thomann and S. E. Stiriba, Inorg. 325 Z. Yuan, N. Cai, Y. Du, Y. He and E. S. Yeung, Anal. Chem.,
Chim. Acta, 2006, 359, 1837. 2014, 86, 419.
297 Z. Shen, H. W. Duan and H. Frey, Adv. Mater., 2007, 326 R. B. Wang, L. Wang, L. Z. Zhou, Y. Su, F. Qiu, D. L. Wang,
19, 349. J. L. Wu, X. Y. Zhu and D. Y. Yan, J. Mater. Chem., 2012,
298 L. Zhou, C. Gao, X. Z. Hu and W. J. Xu, Chem. Mater., 2011, 22, 15227.
23, 1461. 327 L. Yao, W. Yang, J. Yang, L. He, J. Sun, R. Song, Z. Ma and
299 D. C. Wan, Q. Fu and J. L. Huang, J. Appl. Polym. Sci., 2006, W. Huang, Nanoscale, 2011, 3, 916.
102, 3679. 328 P. Dey, I. Blakey, K. J. Thurecht and P. M. Fredericks,
300 J. Keilitz, M. Schwarze, S. Nowag, R. Schomäcker and Langmuir, 2013, 29, 525.
R. Haag, ChemCatChem, 2010, 2, 863. 329 L. Ding, J. Qiu and Z. S. Zhu, Macromol. Rapid Commun.,
301 X. Y. Ding, H. W. Liu, W. F. Shi and M. Skrifvars, J. Appl. 2013, 34, 1635.
Polym. Sci., 2009, 112, 1209. 330 H. Q. Li, J. J. Cooper-White and I. Kim, Soft Matter, 2013,
302 L. Zhou, C. Gao and W. J. Xu, Langmuir, 2010, 26, 11217. 9, 5270.
303 L. Zhou, C. Gao and W. J. Xu, J. Mater. Chem., 2009, 331 B. Yu, X. S. Jiang and J. Yin, Chem. Commun., 2013,
19, 5655. 49, 603.
304 J. Keilitz, S. Nowag, J. D. Marty and R. Haag, Adv. Synth. 332 Y. F. Zhou and D. Y. Yan, Chem. Commun., 2009, 1172.
Catal., 2010, 352, 1503. 333 Y. F. Zhou, W. Huang, J. Y. Liu, X. Y. Zhu and D. Y. Yan,
305 H. Q. Li, J. K. Jo, L. D. Zhang, C. S. Ha, H. Suh and I. Kim, Adv. Mater., 2010, 22, 4567.
Langmuir, 2010, 26, 18442. 334 D. Y. Yan, Y. F. Zhou and J. Hou, Science, 2004, 303, 65.
306 X. Z. Wei, B. K. Zhu and Y. Y. Xu, Colloid Polym. Sci., 2005, 335 Y. Z. You, C. Y. Hong, C. Y. Pan and P. H. Wang, Adv.
284, 102. Mater., 2004, 16, 1953.
307 Y. B. Zhao, J. H. Zou and W. F. Shi, Mater. Lett., 2005, 59, 686. 336 M. Berna, D. Dalzoppo, G. Pasut, M. Manunta, L. Izzo, A. T.
308 Z. D. Zhu, L. Kai and Y. C. Wang, Mater. Chem. Phys., 2006, Jones, R. Duncan and F. M. Veronese, Biomacromolecules,
96, 447. 2006, 7, 146.
View Article Online
337 T. Satoh, M. Tamaki, Y. Kitajyo, T. Maeda, H. Ishihara, 362 M. H. Stenzel, C. Barner-Kowollik and T. P. Davis, J. Polym.
T. Imai, H. Kaga and T. Kakuchi, J. Polym. Sci., Part A: Sci., Part A: Polym. Chem., 2006, 44, 2363.
Polym. Chem., 2006, 44, 406. 363 Y. F. Zhou, D. Y. Yan, W. Y. Dong and Y. Tian, J. Phys.
338 M. Adeli and R. Haag, J. Polym. Sci., Part A: Polym. Chem., Chem. B, 2007, 111, 1262.
2006, 44, 5740. 364 Z. Q. Shi, Y. F. Zhou and D. Y. Yan, Macromol. Rapid
339 J. Xu, S. Z. Luo, W. F. Shi and S. Y. Liu, Langmuir, 2006, Commun., 2008, 29, 412.
22, 989. 365 B. Guo, Z. Q. Shi, Y. Yao, Y. F. Zhou and D. Y. Yan,
340 H. Y. Tian, X. S. Chen, H. Lin, C. Deng, P. B. Zhang, Y. Wei Langmuir, 2009, 25, 6622.
and X. B. Jing, Chem. – Eur. J., 2006, 12, 4305. 366 Z. P. Guo, Y. H. Li, H. Y. Tian, X. L. Zhuang, X. S. Chen and
341 W. Fieber, A. Herrmann, L. Ouali, M. Velazco, G. Kreutzer, X. B. Jing, Langmuir, 2009, 25, 9690.
H.-A. Klok, C. Ternat, C. J. G. Plummer, J.-A. E. Månson 367 N. M. Sangeetha and U. Maitra, Chem. Soc. Rev., 2005,
and H. Sommer, Macromolecules, 2007, 40, 5372. 34, 821.
342 Y. M. Zhou, K. Q. Jiang, Q. L. Song and S. Y. Liu, Langmuir, 368 Y. W. Zhang, W. Huang, Y. F. Zhou and D. Y. Yan, Chem.
2007, 23, 13076. Commun., 2007, 2587.
343 W. Y. Dong, Y. F. Zhou, D. Y. Yan, H. Q. Li and Y. Liu, Phys. 369 Y. Y. Mai, Y. F. Zhou and D. Y. Yan, Small, 2007, 3, 1170.
Chem. Chem. Phys., 2007, 9, 1255. 370 J. Y. Wu and C. Gao, Macromolecules, 2010, 43, 7139.
344 H. Y. Hong, Y. Y. Mai, Y. F. Zhou, D. Y. Yan and J. Cui, 371 C. Moers, L. Nuhn, M. Wissel, R. Stangenberg, M. Mondeshki,
Macromol. Rapid Commun., 2007, 28, 591. E. Berger-Nicoletti, A. Thomas, D. Schaeffel, K. Koynov,
345 M. R. Radowski, A. Shukla, H. von Berlepsch, C. Böttcher, M. Klapper, R. Zentel and H. Frey, Macromolecules, 2013,
G. Pickaert, H. Rehage and R. Haag, Angew. Chem., Int. Ed., 46, 9544.
2007, 46, 1265. 372 Y. Han and C. Gao, Sci. China: Chem., 2010, 53, 2461.
346 R. K. Kainthan, C. Mugabe, H. M. Burt and D. E. Brooks, 373 B. B. Jiang, W. Tao, X. Lu, Y. Liu, H. B. Jin, Y. Pang,
Biomacromolecules, 2008, 9, 886. X. Y. Sun, D. Y. Yan and Y. F. Zhou, Macromol. Rapid
347 Y. Lin, X. H. Liu, Z. M. Dong, B. X. Li, X. S. Chen and Commun., 2012, 33, 767.
Y. S. Li, Biomacromolecules, 2008, 9, 2629. 374 H. B. Jin, Y. Liu, Y. L. Zheng, W. Huang, Y. F. Zhou and
348 S. Chen, X. Z. Zhang, S. X. Cheng, R. X. Zhuo and Z. W. Gu, D. Y. Yan, Langmuir, 2012, 28, 2066.
Biomacromolecules, 2008, 9, 2578. 375 W. Tao, Y. Liu, B. B. Jiang, S. Yu, W. Huang, Y. F. Zhou and
349 K. Ranganathan, R. Deng, R. K. Kainthan, C. Wu, D. E. D. Y. Yan, J. Am. Chem. Soc., 2012, 134, 762.
Brooks and J. N. Kizhakkedathu, Macromolecules, 2008, 376 Y. Han, C. Gao and X. H. He, Sci. China: Chem., 2012,
41, 4226. 55, 604.
350 H. X. Cheng, S. G. Wang, J. T. Yang, Y. F. Zhou and 377 Y. Liu, C. Y. Yu, H. B. Jin, B. B. Jiang, X. Y. Zhu, Y. F. Zhou,
D. Y. Yan, J. Colloid Interface Sci., 2009, 337, 278. Z. Y. Lu and D. Y. Yan, J. Am. Chem. Soc., 2013, 135, 4765.
351 E. Burakowska, S. C. Zimmerman and R. Haag, Small, 378 S. Zhai, H. Y. Hong, Y. F. Zhou and D. Y. Yan, Sci. China:
2009, 5, 2199. Chem., 2010, 53, 1114.
352 M. Prabaharan, J. J. Grailer, S. Pilla, D. A. Steeber and 379 J. X. Zhang and P. X. Ma, Angew. Chem., Int. Ed., 2009,
S. Q. Gong, Biomaterials, 2009, 30, 3009. 48, 964.
353 S. Peleshanko and V. V. Tsukruk, Prog. Polym. Sci., 2008, 380 D. L. Wang, H. Y. Chen, Y. Su, F. Qiu, L. J. Zhu, X. Y. Huan,
33, 523. B. S. Zhu, D. Y. Yan, F. L. Guo and X. Y. Zhu, Polym. Chem.,
354 M. Ornatska, S. Peleshanko, K. L. Genson, B. Rybak, 2013, 4, 85.
K. N. Bergman and V. V. Tsukruk, J. Am. Chem. Soc., 381 Y. F. Zhou and D. Y. Yan, J. Am. Chem. Soc., 2005,
2004, 126, 9675. 127, 10468.
355 M. Ornatska, K. N. Bergman, B. Rybak, S. Peleshanko and 382 Y. F. Zhou and D. Y. Yan, Angew. Chem., Int. Ed., 2005,
V. V. Tsukruk, Angew. Chem., Int. Ed., 2004, 43, 5246. 44, 3223.
356 X. Y. Zhu, L. Chen, D. Y. Yan, Q. Chen, Y. F. Yao, Y. Xiao, 383 J. Y. Liu, Y. Pang, J. Chen, P. Huang, W. Huang, X. Y. Zhu
J. Hou and J. Y. Li, Langmuir, 2004, 20, 484. and D. Y. Yan, Biomaterials, 2012, 33, 7765.
357 M. Ornatska, K. N. Bergman, M. Goodman, S. Peleshanko, 384 M. Calderón, P. Welker, K. Licha, I. Fichtner, R. Graeser,
V. V. Shevchenko and V. V. Tsukruk, Polymer, 2006, R. Haag and F. Kratz, J. Controlled Release, 2011, 151, 295.
47, 8137. 385 J. Khandare, A. Mohr, M. Calderón, P. Welker, K. Licha and
358 J. Mao, P. H. Ni, Y. Y. Mai and D. Y. Yan, Langmuir, 2007, R. Haag, Biomaterials, 2010, 31, 4268.
23, 5127. 386 M. A. Quadir and R. Haag, J. Controlled Release, 2012, 161, 484.
359 Y. F. Zhou and D. Y. Yan, Angew. Chem., Int. Ed., 2004, 387 W. Yang, C. Y. Pan, X. Q. Liu and J. Wang, Biomacromolecules,
43, 4896. 2011, 12, 1523.
360 J. H. Zou, X. D. Ye and W. F. Shi, Macromol. Rapid 388 G. X. Feng, J. Liang and B. Liu, Macromol. Rapid Commun.,
Commun., 2005, 26, 1741. 2013, 34, 705.
361 S. Peleshanko, R. Gunawidjaja, S. Petrash and V. V. Tsukruk, 389 Q. Zhu, F. Qiu, B. S. Zhu and X. Y. Zhu, RSC Adv., 2013,
Macromolecules, 2006, 39, 4756. 3, 2071.
View Article Online
390 A. Sunder, M. Kramer, R. Hanselmann, R. Mulhaupt and 419 C. Lin, Z. Y. Zhong, M. C. Lok, X. L. Jiang, W. E. Hennink,
H. Frey, Angew. Chem., Int. Ed., 1999, 38, 3552. J. Feijen and J. F. J. Engbersen, Bioconjugate Chem., 2007,
391 D. Wilms, S. Stiriba and H. Frey, Acc. Chem. Res., 2010, 18, 138.
43, 129. 420 Y. Chen, L. Z. Zhou, Y. Pang, W. Huang, F. Qiu, X. L. Jiang,
392 M. Kramer, J. Stumby, H. Turk, S. Krause, A. Komp, X. Y. Zhu, D. Y. Yan and Q. Chen, Bioconjugate Chem., 2011,
L. Delineau, S. Prokhorova, H. Kautz and R. Haag, Angew. 22, 1162.
Chem., Int. Ed., 2002, 41, 4252. 421 Y. Ping, D. C. Wu, J. N. Kumar, W. R. Cheng, C. L. Lay and
393 M. Slagt, S. Stiriba, J. Robertus, K. Gebbink, H. Kautz, Y. Liu, Biomacromolecules, 2013, 14, 2083.
H. Frey and G. Koten, Macromolecules, 2002, 35, 5734. 422 J. Chen, C. Wu and D. Oupicky, Biomacromolecules, 2009,
394 H. Turk, A. Shukla, P. Cristina, A. Rodrigues, H. Rehage 10, 2921.

and R. Haag, Chem. – Eur. J., 2007, 13, 4187. 423 X. Wang, Y. J. He, J. Y. Wu, C. Gao and Y. H. Xu,
395 L. Tziveleka, C. Kontoyianni, Z. Sideratou, D. Tsiourvas Biomacromolecules, 2010, 11, 245.
and C. Paleos, Macromol. Biosci., 2006, 6, 161. 424 Y. Ren, X. Jiang, D. Pan and H. Q. Mao, Biomacromolecules,
396 J. Han and C. Gao, Curr. Org. Chem., 2011, 15, 2. 2010, 11, 3432.
397 Y. Chen, Z. Shen, L. Perez, H. Frey and S. Stiriba, Macro- 425 B. Newland, H. Y. Tai, Y. Zheng, D. Velasco, A. D. Luca,
molecules, 2005, 38, 227. S. M. Howdle, C. Alexander, W. X. Wang and A. Pandit,
398 H. Liu, Y. Chen, D. Zhu, Z. Shen and S. Stiriba, React. Funct. Chem. Commun., 2010, 46, 4698.
Polym., 2007, 67, 383. 426 M. S. Chen, J. L. Wu, L. Z. Zhou, C. Y. Jin, C. L. Tu,
399 Y. Chen, Z. Shen, H. Frey, J. Prietob and S. Stiriba, Chem. B. S. Zhu, F. Wu, Q. Zhu, X. Y. Zhu and D. Y. Yan, Polym.
Commun., 2005, 755. Chem., 2011, 2, 2674.
400 H. Liu, Z. Shen, S. Stiriba, Y. Chen, W. Zhang and H. Liu, 427 C. L. Tu, N. Li, L. J. Zhu, L. Z. Zhou, Y. Su, P. Y. Li and
J. Polym. Sci., Part A: Polym. Chem., 2006, 44, 4165. X. Y. Zhu, Polym. Chem., 2013, 4, 393.
401 H. Tian, X. Chen, H. Lin, C. Deng, P. Zhang, Y. Wei and 428 S. R. Yu, J. X. Chen, R. J. Dong, Y. Su, B. Ji, Y. F. Zhou,
X. Jing, Chem. – Eur. J., 2006, 12, 4305. X. Y. Zhu and D. Y. Yan, Polym. Chem., 2012, 3, 3324.
402 D. Wan, J. Yuan and H. Pu, Macromolecules, 2009, 42, 1533. 429 G. Wang, H. Yin, J. C. Y. Ng, L. P. Cai, J. Li, B. Z. Tang and
403 C. H. Liu, C. Gao and D. Y. Yan, Chem. Res. Chin. Univ., B. Liu, Polym. Chem., 2013, 4, 5297.
2005, 21, 345. 430 L. Tao, J. Q. Liu, B. H. Tan and T. P. Davis, Macromolecules,
404 C. H. Liu, C. Gao and D. Y. Yan, Macromolecules, 2006, 2009, 42, 4960.
39, 8102. 431 Z. Kadlecova, Y. Rajendra, M. Matasci, L. Baldi, D. L.
405 J. Wu, C. H. Liu and C. Gao, Open Macromol. J., 2009, 3, 12. Hacker, F. M. Wurm and H. A. Klok, J. Controlled Release,
406 C. H. Liu, C. Gao, H. Zeng and D. Y. Yan, Chem. J. Chin. 2013, 169, 276.
Univ., 2005, 26, 1941. 432 W. Saiyin, D. L. Wang, L. L. Li, L. J. Zhu, B. Liu, L. J. Sheng,
407 Y. Lin, X. Liu, Z. Dong, B. Li, X. Chen and Y. Li, Biomacro- Y. W. Li, B. S. Zhu, L. M. Mao, G. L. Li and X. Y. Zhu, Mol.
molecules, 2008, 9, 2629. Pharmaceutics, 2014, 11, 1662.
408 L. Tang, Y. Fang and X. Tang, J. Polym. Sci., Part A: Polym. 433 S. R. Yu, R. J. Dong, J. X. Chen, F. Chen, W. F. Jiang,
Chem., 2005, 43, 2921. Y. F. Zhou, X. Y. Zhu and D. Y. Yan, Biomacromolecules,
409 S. Stiriba, H. Kautz and H. Frey, J. Am. Chem. Soc., 2002, 2014, 15, 1828.
124, 9698. 434 C. Siegers, M. Biesalski and R. Haag, Chem. – Eur. J., 2004,
410 C. H. Liu, C. Gao and D. Y. Yan, Macromolecules, 2006, 10, 2831.
39, 8102. 435 L. A. T. W. Asri, M. Crismaru, S. Roest, Y. Chen, O. Ivashenko,
411 A. Bernaby, M. Kramer, B. Olah and R. Haag, Chem. – Eur. J., P. Rudolf, J. C. Tiller, H. C. van der Mei, T. J. A. Loontjens and
2004, 10, 2822. H. J. Busscher, Adv. Funct. Mater., 2014, 24, 346.
412 Y. Nakayama, Acc. Chem. Res., 2012, 45, 994. 436 S. Y. Chen, Z. H. Tan, N. Li, R. B. Wang, L. He, Y. F. Shi,
413 R. B. Wang, L. Z. Zhou, Y. F. Zhou, G. L. Li, X. Y. Zhu, L. Jiang, P. Y. Li and X. Y. Zhu, Macromol. Biosci., 2011, 11, 828.
H. C. Gu, X. L. Jiang, H. Q. Li, J. L. Wu, L. He, X. Q. Guo, 437 S. Y. Chen, G. M. Sun, L. Jiang, N. Li, P. Y. Li and X. Y. Zhu,
B. S. Zhu and D. Y. Yan, Biomacromolecules, 2010, 11, 489. Chem. J. Chin. Univ., 2009, 30, 825.
414 M. Ahmed and R. Narain, Biomaterials, 2012, 33, 3990. 438 F. Qiu, D. L. Wang, Q. Zhu, L. J. Zhu, G. S. Tong, Y. F. Lu,
415 S. Höbel, A. Loos, D. Appelhans, S. Schwarz, J. Seidel, D. Y. Yan and X. Y. Zhu, Biomacromolecules, 2014, 15, 1355.
B. Voit and A. Aigner, J. Controlled Release, 2011, 149, 146. 439 J. Y. Liu, W. Huang, Y. F. Zhou and D. Y. Yan, Macro-
416 J. L. Xia, L. Chen, J. Chen, H. Y. Tian, F. F. Li, X. J. Zhu, molecules, 2009, 42, 4394.
G. Li and X. S. Chen, Macromol. Biosci., 2011, 11, 211. 440 J. Y. Liu, Y. Pang, W. Huang, X. Zhai, X. Y. Zhu, Y. F. Zhou
417 W. Fischer, M. A. Quadir, A. Barnard, D. K. Smith and and D. Y. Yan, Macromolecules, 2010, 43, 8416.
R. Haag, Macromol. Biosci., 2011, 11, 1736. 441 J. Y. Liu, W. Huang, Y. Pang, X. Y. Zhu, Y. F. Zhou and
418 J. H. Tan, N. A. J. McMillan, E. Payne, C. Alexander, D. Y. Yan, Langmuir, 2010, 26, 10585.
F. Heath, A. K. Whittaker and K. J. Thurecht, J. Polym. 442 J. Y. Liu, Y. Pang, Z. Y. Zhu, D. L. Wang, C. T. Li, W. Huang,
Sci., Part A: Polym. Chem., 2012, 50, 2585. X. Y. Zhu and D. Y. Yan, Biomacromolecules, 2013, 14, 1627.
View Article Online
443 J. Y. Liu, Y. Pang, W. Huang, X. H. Huang, L. L. Meng, 470 J. L. Wang, Z. B. Ye and H. Joly, Macromolecules, 2007,
X. Y. Zhu, Y. F. Zhou and D. Y. Yan, Biomacromolecules, 40, 6150.
2011, 12, 1567. 471 P. K. Maji, N. K. Das and A. K. Bhowmick, Polymer, 2010,
444 J. Y. Liu, W. Huang, Y. Pang, X. Y. Zhu, Y. F. Zhou and 51, 1100.
D. Y. Yan, Biomacromolecules, 2010, 11, 1564. 472 L. Fogelström, E. Malmström, M. Johansson and A. Hult,
445 J. Y. Liu, Y. Pang, W. Huang, X. Y. Zhu, Y. F. Zhou and ACS Appl. Mater. Interfaces, 2010, 2, 1679.
D. Y. Yan, Biomaterials, 2010, 31, 1334. 473 J. J. Decker, S. N. Chvalun and S. Nazarenko, Polymer, 2011,
446 J. Y. Liu, W. Huang, Y. Pang, X. Y. Zhu, Y. F. Zhou and 52, 3943.
D. Y. Yan, Biomaterials, 2010, 31, 5643. 474 S. Fotiadou, C. Karageorgaki, K. Chrissopoulou, K. Karatasos,
447 V. Geiser, Y. Leterrier and J.-A. E. Månson, Macromolecules, I. Tanis, D. Tragoudaras, B. Frick and S. H. Anastasiadis,
2010, 43, 7705. Macromolecules, 2013, 46, 2842.
448 R. Ruggerone, V. Geiser, S. D. Vacche, Y. Leterrier and 475 K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang,
J.-A. E. Månson, Macromolecules, 2010, 43, 10490. Y. Zhang, S. V. Dubonos, I. V. Grigorieva and A. A. Firsov,
449 Y. Y. Xu, C. Gao, H. Kong, D. Y. Yan, Y. Z. Jin and P. C. P. Science, 2004, 306, 666.
Watts, Macromolecules, 2004, 37, 8846. 476 A. K. Geim and K. S. Novoselov, Nat. Mater., 2007, 6, 183.
450 C. Gao, Y. Z. Jin, H. Kong, R. L. D. Whitby, S. F. A. Acqah, 477 H. He, J. Klinowski, M. Forster and A. Lerf, Chem. Phys.
G. Y. Chen, H. Qian, A. Hartschuh, S. R. P. Silva, S. Henley, Lett., 1998, 287, 53.
P. Fearon, H. W. Kroto and D. R. M. Walton, J. Phys. Chem. 478 M. Hirata, T. Gotou and M. Ohba, Carbon, 2005, 43, 503.
B, 2005, 109, 11925. 479 X. Z. Hu, Z. Xu and C. Gao, Sci. Rep., 2012, 2, 767.
451 C. Gao, S. Muthukrishnan, W. Li, J. Yuan, Y. Xu and 480 X. Z. Hu, Z. Xu, Z. Liu and C. Gao, Sci. Rep., 2013, 3, 3274.
A. H. E. Müller, Macromolecules, 2007, 40, 1803. 481 Z. Xu and C. Gao, Acc. Chem. Res., 2014, 47, 1267.
452 H. Kong, P. Luo, C. Gao and D. Y. Yan, Polymer, 2005, 482 M. M. Zhang, H. X. Yan, C. Gong and F. F. Zhang,
46, 2472. J. Compos. Mater., 2015, 49, 939.
453 I. Y. Jeon, H. J. Lee, Y. S. Choi, L. S. Tan and J. B. Baek, 483 Y. Liu, W. L. Li, L. Hou and P. Y. Wu, RSC Adv., 2014,
Macromolecules, 2008, 41, 7423. 4, 24263.
454 D. H. Wang, P. Mirau, B. Li, C. Y. Li, J. B. Baek and 484 S. Thakur and N. Karak, ACS Sustainable Chem. Eng., 2014,
L. S. Tan, Chem. Mater., 2008, 20, 1502. 2, 1195.
455 X. Y. Zhao, J. Ma, Z. H. Wang, G. Wen, J. Jiang, F. M. Shi 485 G. Cruz, H. Schüle, J. Losada, M. P. Garcı́a-Armada, H. Frey,
and L. X. Sheng, Desalination, 2012, 303, 29. B. Alonso and C. M. Casado, Eur. J. Inorg. Chem., 2013, 44.
456 P. Daraei, S. S. Madaeni, N. Ghaemi, M. A. Khadivi, 486 J. Kong, M. Kong, X. Zhang, L. Chen and L. An, ACS Appl.
B. Astinchap and R. Moradian, J. Membr. Sci., 2013, 444, 184. Mater. Interfaces, 2013, 5, 10367.
457 J. X. Zhang, Y. P. Zheng, P. Y. Yu, S. Mo and R. M. Wang, 487 D. H. Zhang, E. B. Liang, T. C. Li, S. F. Chen, J. H. Zhang,
Polymer, 2009, 50, 2953. X. J. Cheng, J. L. Zhou and A. Q. Zhang, RSC Adv., 2013,
458 S. S. Mahapatra, S. K. Yadav, H. J. Yoo and J. W. Cho, 3, 3095.
J. Mater. Chem., 2011, 21, 7686. 488 H. L. Wang, S. P. Xu and W. F. Shi, Prog. Org. Coat., 2009,
459 F. Caruso, Adv. Mater., 2001, 13, 11. 65, 417.
460 M. A. Hood, M. Mari and R. Muñoz-Espı́, Materials, 2014, 489 X. F. Wang, B. B. Wang, W. Y. Xing, G. Tang, J. Zhan,
7, 4057. W. Yang, L. Song and Y. Hu, Prog. Org. Coat., 2014, 77, 94.
461 H. Mori, D. C. Seng, M. Zhang and A. H. E. Müller, Langmuir, 490 R. S. Mishra and A. S. Khanna, Prog. Org. Coat., 2011,
2002, 18, 3682. 72, 769.
462 H. Mori, D. C. Seng, M. Zhang and A. H. E. Müller, Prog. 491 A. K. Mishra, R. Narayan and K. V. S. N. Raju, Prog. Org.
Colloid Polym. Sci., 2004, 126, 40. Coat., 2012, 74, 491.
463 E. Labalme, G. David, P. Buvat, J. Bigarre and T. Boucheteau, 492 M. D. Dimitriou, Z. L. Zhou, H. S. Yoo, K. L. Killops, J. A.
J. Polym. Sci., Part A: Polym. Chem., 2012, 50, 1308. Finlay, G. Cone, H. S. Sundaram, N. A. Lynd, K. P. Barteau,
464 H. Gao, D. Yorifuji, Z. H. Jiang and S. Ando, Polymer, 2014, L. M. Campos, D. A. Fischer, M. E. Callow, J. A. Callow,
55, 2848. C. K. Ober, C. J. Hawker and E. J. Kramer, Langmuir, 2011,
465 X. L. Hu, G. M. Hou, M. Q. Zhang, M. Z. Rong, W. H. Ruan 27, 13762.
and E. P. Giannelis, J. Mater. Chem., 2012, 22, 18961. 493 C. S. Gudipati, J. A. Finlay, J. A. Callow, M. E. Callow and
466 M. Sangermanoa, M. Messori, M. M. Galleco, G. Rizza and K. L. Wooley, Langmuir, 2005, 21, 3044.
B. Voit, Polymer, 2009, 50, 5647. 494 Y. P. Wang, D. E. Betts, J. A. Finlay, L. Brewer, M. E. Callow,
467 Y. Shiina and A. Morikawa, React. Funct. Polym., 2011, J. A. Callow, D. E. Wendt and J. M. DeSimone, Macromolecules,
71, 85. 2011, 44, 878.
468 M. Miki, H. Horiuchi and Y. Yamada, Polymers, 2013, 495 P. M. Imbesi, C. Fidge, J. E. Raymond, S. I. Cauët and
5, 1362. K. L. Wooley, ACS Macro Lett., 2012, 1, 473.
469 B. Somboonsub, S. Thongyai and P. Praserthdam, J. Appl. 496 W. J. Yang, K. G. Neoh, E. T. Kang, S. L.-M. Teo and
Polym. Sci., 2009, 114, 3292. D. Rittschof, Polym. Chem., 2013, 4, 3105.
View Article Online
497 Y. H. Zhao, Y. L. Qian, D. X. Pang, B. K. Zhu and Y. Y. Xu, 524 S. J. Grunzinger, M. Watanabe, K. Fukagawa, R. Kikuchi,
J. Membr. Sci., 2007, 304, 138. Y. Tominaga, T. Hayakawa and M. Kakimoto, J. Power
498 S. Thakur and N. Karak, Prog. Org. Coat., 2013, 76, 157. Sources, 2008, 175, 120.
499 S. Pramanik, R. Konwarh, K. Sagar, B. K. Konwar and 525 T. Suda, K. Yamazaki and H. Kawakami, J. Power Sources,
N. Karak, Prog. Org. Coat., 2013, 76, 689. 2010, 195, 4641.
500 G. Cheng, B. W. Greenland, C. Lampard, N. Williams, 526 M. Kakimoto, S. J. Grunzinger and T. Hayakawa, Polym. J.,
M. S. Bahra and W. Hayes, J. Polym. Sci., Part A: Polym. 2010, 42, 697.
Chem., 2013, 51, 3964. 527 H. Gao, D. Wang, W. Jiang, S. W. Guan and Z. H. Jiang,
501 D. H. Zhang, E. B. Liang, T. C. Li, S. F. Chen, J. H. Zhang, J. Appl. Polym. Sci., 2008, 109, 2341.
X. J. Cheng, J. L. Zhou and A. Q. Zhang, RSC Adv., 2013, 528 T. Suzuki, Y. Yamada and K. Itahashi, J. Appl. Polym. Sci.,
3, 9522. 2008, 109, 813.
502 L. J. Luo, Y. Meng, T. Qiu and X. Y. Li, J. Appl. Polym. Sci., 529 T. Suzuki and Y. Yamada, J. Membr. Sci., 2012, 417–418, 193.
2013, 130, 1064. 530 T. Suzuki, M. Miki and Y. Yamada, Eur. Polym. J., 2012,
503 X. Fernández-Francos, D. Santiago, F. Ferrando, X. Ramis, 48, 1504.
J. M. Salla, À. Serra and M. Sangermano, J. Polym. Sci., Part B: 531 Y. H. Zhao, B. K. Zhu, L. Kong and Y. Y. Xu, Langmuir,
Polym. Phys., 2012, 50, 1489. 2007, 23, 5779.
504 C. Acebo, X. Fernández-Francos, F. Ferrando, À. Serra, 532 I. Böhm, K. Isenbügel, H. Ritter, R. Branscheid and
J. M. Salla and X. Ramis, React. Funct. Polym., 2013, U. Kolb, Angew. Chem., 2011, 123, 8042.
73, 431. 533 T. Cai, W. J. Yang, K. G. Neoh and E. T. Kang, Ind. Eng.
505 H. A. Essawy, H. A. Mohamed and N. H. Elsayed, J. Appl. Chem. Res., 2012, 51, 15962.
Polym. Sci., 2013, 127, 4505. 534 M. Seiler, Fluid Phase Equilib., 2006, 241, 155.
506 M. Morell, X. Fernández-Francos, X. Ramis and A. Serra, 535 M. Seiler, D. Köhler and W. Arlt, Sep. Purif. Technol., 2003,
Macromol. Chem. Phys., 2010, 211, 1879. 30, 179.
507 M. Morella, M. Erber, X. Ramis, F. Ferrando, B. Voit and 536 M. Arkas, L. Eleades, C. M. Paleos and D. Tsiourvas, J. Appl.
A. Serra, Eur. Polym. J., 2010, 46, 1498. Polym. Sci., 2005, 97, 2299.
508 M. Morella, X. Ramis, F. Ferrando, Y. F. Yu and A. Serra, 537 H. C. Chao and J. E. Hanson, J. Sep. Sci., 2002, 25, 345.
Polymer, 2009, 50, 5374. 538 C. Y. K. Chan, J. W. Y. Lam, C. K. W. Jim, H. H. Y. Sung,
509 M. Floresa, X. r. Fernández-Francos, F. Ferrando, X. Ramis I. D. Williams and B. Z. Tang, Macromolecules, 2013,
and À. Serra, Polymer, 2012, 53, 5232. 46, 9494.
510 T. Li, H. J. Qin, Y. Liu, X. H. Zhong, Y. F. Yu and A. Serra, 539 J. Liu, Y. Zhong, J. W. Y. Lam, P. Lu, Y. Hong, Y. Yu, Y. Yue,
Polymer, 2012, 53, 5864. M. Faisal, H. H. Y. Sung, I. D. Williams, K. Sing Wong and
511 C. Acebo, A. Picardi, X. Fernández-Francos, S. D. la Flor, B. Z. Tang, Macromolecules, 2010, 43, 4921.
X. Ramis and À. Serra, Prog. Org. Coat., 2014, 77, 1288. 540 W. Shu, C. Guan, W. Guo, C. Wang and Y. Shen, J. Mater.
512 D. H. Zhang and D. M. Jia, J. Appl. Polym. Sci., 2006, Chem., 2012, 22, 3075.
101, 2504. 541 J. Wang, J. Mei, W. Yuan, P. Lu, A. Qin, J. Sun, Y. Ma and
513 A. Tomuta, F. Ferrando, À. Serra and X. Ramis, React. B. Z. Tang, J. Mater. Chem., 2011, 21, 4056.
Funct. Polym., 2012, 72, 556. 542 J. Wang, J. Mei, E. Zhao, Z. Song, A. Qin, J. Z. Sun and
514 M. Flores, X. Fernández-Francos, X. Ramis and A. Serra, B. Z. Tang, Macromolecules, 2012, 45, 7692.
Thermochim. Acta, 2012, 544, 17. 543 R. Hu, J. W. Y. Lam, J. Liu, H. H. Y. Sung, I. D. Williams,
515 Y. L. Lin, Y. Zhou, C. X. Xu, A. D. Xie, M. H. Yang, S. Yang Z. Yue, K. S. Wong, M. M. F. Yuen and B. Z. Tang, Polym.
and H. X. Chen, Prog. Org. Coat., 2013, 76, 1302. Chem., 2012, 3, 1481.
516 Y. Zheng, K. J. Thurecht and W. X. Wang, J. Polym. Sci., Part A: 544 W. Wu, S. Ye, G. Yu, Y. Liu, J. Qin and Z. Li, Macromol.
Polym. Chem., 2012, 50, 629. Rapid Commun., 2012, 33, 164.
517 M. Haraguchia, T. Hiraic, M. Ozawaa, K. Miyajia and 545 W. Wu, S. Ye, L. Huang, L. Xiao, Y. Fu, Q. Huang, G. Yu,
K. Tanaka, Appl. Surf. Sci., 2013, 266, 235. Y. Liu, J. Qin, Q. Li and Z. Li, J. Mater. Chem., 2012,
518 W. Y. Tang, Y. G. Huang, W. D. Meng and F. L. Qing, 22, 6374.
Eur. Polym. J., 2010, 46, 506. 546 L. Sun, Z. Liang, J. Yu and R. Xu, Polym. Chem., 2013,
519 X. Z. Wei, L. P. Zhu, H. Y. Deng, Y. Y. Xu, B. K. Zhu and 4, 1932.
Z. M. Huang, J. Membr. Sci., 2008, 323, 278. 547 X. Wu, H. Li, B. Xu, H. Tong and L. Wang, Polym. Chem.,
520 X. Z. Wei, X. Kong, J. Yang, G. L. Zhang, J. Y. Chen and 2014, 5, 4521.
J. D. Wang, J. Membr. Sci., 2013, 440, 67. 548 S. Yamaguchi, K. Goto and K. Tamao, Angew. Chem., Int. Ed.,
521 J. X. Qin, S. S. Lin, S. Q. Song, L. Zhang and H. L. Chen, ACS 2000, 39, 1695.
Appl. Mater. Interfaces, 2013, 5, 6649. 549 A. Qin, L. Tang, J. W. Y. Lam, C. K. W. Jim, Y. Yu, H. Zhao,
522 S. P. Sun, T. A. Hatton and T. S. Chung, Environ. Sci. J. Z. Sun and B. Z. Tang, Adv. Funct. Mater., 2009, 19, 1891.
Technol., 2011, 45, 4003. 550 A. Qin, J. W. Y. Lam and B. Z. Tang, Chem. Soc. Rev., 2010,
523 H. Yoo and S.-Y. Kwak, J. Membr. Sci., 2013, 448, 125. 39, 2522.
View Article Online
551 P. Lu, J. W. Y. Lam, J. Liu, C. K. W. Jim, W. Yuan, N. Xie, 564 Z. Źo1ek-Tryznowska and J. Izdebska, Dyes Pigm., 2013,
Y. Zhong, Q. Hu, K. S. Wong, K. K. L. Cheuk and B. Z. Tang, 96, 602.
Macromol. Rapid Commun., 2010, 31, 834. 565 H. P. Xu, J. Gao, Y. P. Wang, Z. Q. Wang, M. Smet,
552 J. C. Sanchez, S. A. Urbas, S. J. Toal, A. G. DiPasquale, W. Dehaenb and X. Zhang, Chem. Commun., 2006, 796.
A. L. Rheingold and W. C. Trogler, Macromolecules, 2008, 566 M. Häußler, J. W. Y. Lam, A. J. Qin, K. K. C. Tse, M. K. S. Li,
41, 1237. J. Z. Liu, C. K. W. Jim, P. Gao and B. Z. Tang, Chem.
553 D. Tyler McQuade, A. E. Pullen and T. M. Swager, Chem. Commun., 2007, 2584.
Rev., 2000, 100, 2537. 567 J. H. Drese, S. Choi, R. P. Lively, W. J. Koros, D. J. Fauth,
554 S. W. Thomas III, G. D. Joly and T. M. Swager, Chem. Rev., M. L. Gray and C. W. Jones, Adv. Funct. Mater., 2009, 19,
2007, 107, 1339. 3821.

555 C. Sivakumar and A. S. Nasar, Eur. Polym. J., 2009, 45, 2329. 568 P. López-Aranguren, L. F. Vega and C. Domingo, Chem.
556 H. Deka, N. Karak, R. D. Kalita and A. K. Buragohain, Commun., 2013, 49, 11776.
Carbon, 2010, 48, 2013. 569 H. K. He, M. J. Zhong, D. Konkolewicz, K. Yacatto,
557 S. Thakur and N. Karak, RSC Adv., 2013, 3, 9476. T. Rappold, G. Sugar, N. E. David and K. Matyjaszewski,
558 D. Döhler, P. Zare and W. H. Binder, Polym. Chem., 2014, J. Mater. Chem. A, 2013, 1, 6810.
5, 992. 570 N. Kobayashi and M. Kijima, J. Mater. Chem., 2007,
559 A. S. Nasar, M. Jikei and M. Kakimoto, Eur. Polym. J., 2003, 17, 4289.
39, 1201. 571 C. H. Ahn, J.-D. Jeon and S.-Y. Kwak, J. Ind. Eng. Chem.,
560 J. Zhang and C. P. Hu, Eur. Polym. J., 2008, 44, 3708. 2012, 18, 2184.
561 S. S. Mahapatra, S. K. Yadav and J. W. Cho, React. Funct. 572 Y. Y. Wei, X. Li, Z. Xu, H. Y. Sun, Y. C. Zheng, L. Peng,
Polym., 2012, 72, 227. Z. Liu, C. Gao and M. X. Gao, Polym. Chem., 2015, 6, 973.
562 M. Ł. Mamiński, P. G. Parzuchowski, A. Trojanowska and 573 K. Nogami, K. Sakamoto, T. Hayakawa and M. Kakimoto,
S. Dziewulski, Biomass Bioenergy, 2011, 35, 4461. J. Power Sources, 2007, 166, 584.
563 H. Zhang, L. P. Bré, T. Y. Zhao, Y. Zheng, B. Newland and 574 B. Zhao, Y. C. Zheng, Z. L. Weng, S. Y. Cai and C. Gao,
W. X. Wang, Biomaterials, 2014, 35, 711. Polym. Chem., DOI: 10.1039/C5PY00307E.
View publication stats

Hyperbranched Polymers: Advances From Synthesis To Applications

Uploaded by

Copyright:

Available Formats

Hyperbranched Polymers: Advances From Synthesis To Applications

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Hyperbranched Polymers: Advances From Synthesis To Applications

Uploaded by

Copyright:

Available Formats

See discussions, stats, and author profiles for this publication at: https://www.researchgate.

Hyperbranched polymers: advances from synthesis to applications

Article · January 2015

Yaochen Zheng Sipei Li

SEE PROFILE SEE PROFILE

dielectric elastomer View project

Graphene fiber fabrics View project

The user has requested enhancement of the downloaded file.

Hyperbranched polymers: advances from

Yaochen Zheng received his PhD Sipei Li was born in Zhejiang,

Review Article Chem Soc Rev

acid (A2B2 type monomer) and glycerol (B3 type monomer).5

co-workers even prepared branched copolymers by a one-step

Chem Soc Rev Review Article

Table 1 Comparison of HP with a linear polymer and dendrimer

Polymer Linear Hyperbranched Dendrimer

Topology 1D, linear 3D, irregular 3D, regular

Synthesis One-step, facile One-step, relatively facile Multi-step, laborious

post-functionalizations), and the applications of both CHPs

Although the accurate number of structural units is not known,

review articles9–43 and a monograph edited by Yan, Gao

Review Article Chem Soc Rev

Chem Soc Rev Review Article

Fig. 4 HP-based complex polymeric structures.

3. Synthesis of CHPs SCVP was first invented by Fréchet in 1995,102 using an

Scheme 2 HPs with abundant vinyl groups synthesized by the approach

Review Article Chem Soc Rev

Exclusively for hyperbranched polyethylenes or polyolefins,

new synthetic route for hyperbranched conjugated polymers.

Chem Soc Rev Review Article

Review Article Chem Soc Rev

Table 3 Monomers used for click polymerization for CHPs

Structure Type Ref. Structure Type Ref.

M2 178 M18 191

Chem Soc Rev Review Article

Structure Type Ref. Structure Type Ref.

Table 4 Monomers and macromonomers for the synthesis of SHPs

Structure Type Ref. Structure Type Ref.

Seesaw-type Masked Y-type

Macro A2 Y-type macro AB2

Review Article Chem Soc Rev

Table 5 Click monomers for post-functionalizations

Structure Type Ref. Structure Type Ref.

S1 CuAAC 246 S6 CuAAC 49

S2 CuAAC 246 S7 CuAAC 49

S3 Amine-epoxy 261 S8 CuAAC 49

S4 Menschutkin 49 S9 CuAAC 228

S5 Menschutkin 49 S10 Thiol–ene 228

AB2 Vinyl monomer

Chem Soc Rev Review Article

Fig. 7 Synthesis route of hyperbranched poly(aroyltriazole). The as-prepared

Review Article Chem Soc Rev

3.2.6 Aza-Michael addition. The aza-Michael addition was

4.2 Synthesis by click polymerization

Chem Soc Rev Review Article

possessed Mns of 1000, 3300 and 7300 g mol1. They were

Review Article Chem Soc Rev

5.1 Functionalizations of the periphery

Chem Soc Rev Review Article