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Bulk and transparent supramolecular glass from

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evaporation-induced noncovalent polymerization

Cite this: Mater. Horiz., 2023,
10, 5152 of nucleosides†
Received 3rd August 2023,
Accepted 4th September 2023 Shuanggen Wu,ab Changyong Cai,a Xunqiu Wang,b Qiao Zhang,a Zhijian Tan, *c
Fenfang Lid and Shengyi Dong *a
DOI: 10.1039/d3mh01220d

rsc.li/materials-horizons

Understanding the nature of glass is one of the most important

challenges in chemistry, physics, and materials science. In this New concepts
study, transparent bulk supramolecular glasses with excellent opti- Despite the long history and wide applications of glass, the mechanism of
cal behaviors and good mechanical properties were fabricated via its formation is still controversial. Understanding the structure of glass is
one of the most critical questions in materials science, chemistry, and
the non-covalent polymerization of nucleosides. Hydrogen bond-
physics. In this research, low-molecular-weight bulk supramolecular
ing is the main driving force in the formation of bulk supramole- glasses were prepared through the non-covalent polymerization of
cular glasses. The directional and saturated character of hydrogen nucleosides. Supramolecular glasses exhibit excellent optical and
bonding enables the formation of a short-range ordered structure, mechanical properties comparable to those of some synthetic glasses.
while the weak nature and reversibility of hydrogen bonds allow for In the formation of a supramolecular glass, hydrogen bonding is the
main driving force. The directional and saturated character of hydrogen
the asymmetric and random connections of the short-range
bonds results in the formation of short-range ordered structures during
ordered structure into a long-range disordered network. Various supramolecular polymerization, while the weak and reversible nature of
relaxations, including b, c, and d relaxations, are observed at hydrogen bonding enables asymmetric and random connection of short-
temperatures below the glass transition temperature, demonstrat- range ordered structures to a long-range disordered network. This study
ing the metastable nature of bulk supramolecular glasses. This highlights the importance of solvent evaporation and a rapid cooling
process in determining the amorphous and thermodynamically
investigation offers supramolecular insights into the nature of glass
metastable characteristics of supramolecular glasses. The development
materials. of BSGs provides a supramolecular view on the nature of glass.

in a metastable state.10–12 Despite the long history and wide

Introduction applications of glass, the mechanism of its formation is still
controversial.13–15 Understanding the structure of glass is one
Similar to artificial polymeric materials, glass is commonly of the most critical questions in materials science, chemistry,
used in daily life and industrial production.1,2 However, glass and physics.16–18
has a longer history, and man-made glass was first fabricated in DNA behaves as an anisotropic polymorphic polymer, particu-
approximately 1500 BC in Eastern Mesopotamia and Egypt.3,4 larly with regards its three-dimensional spatial configuration.19–21
In the past 3500 years, numerous developments have been But basically, a long DNA rod can be defined as an isotropic
made in glass, which is still in great demand nowadays.5–9 homogeneous chain from the view of its average mechanical and
Glass is recognized to be a typical isotropic material that exists physicochemical properties.22–25 Inspired by the molecular struc-
a
ture of DNA (and RNA, in some examples), nucleosides have been
College of Chemistry and Chemical Engineering, Hunan University, Changsha
used to construct artificial isotropic assemblies at micro- and
410082, Hunan, P. R. China. E-mail: dongsy@hnu.edu.cn
b
School of Chemical Engineering, Zhengzhou University, Zhengzhou, 450001, mesoscopic scales.26–28
P. R. China In this study, transparent bulk supramolecular glasses
c
Institute of Bast Fiber Crops, Chinese Academy of Agricultural Sciences, Changsha (BSGs) were prepared via the non-covalent polymerization of
410205, Hunan, P. R. China. E-mail: tanzhijian@caas.cn nucleosides. Isotropic, long-range disordered, and short-range
d
College of Chemistry and Chemical Engineering, Central South University,
ordered structures, along with their metastable states and relaxa-
Changsha 410083, Hunan, P. R. China
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/ tions, were identified in BSGs. To study the formation mecha-
10.1039/d3mh01220d nism and microstructure of BSGs, a combined experimental and

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theoretical investigation was conducted. This study provides a absorptions in the visible region and strong absorptions in the
supramolecular perspective on understanding the nature of glass. UV and IR regions (Fig. 1c), indicating the potential of BSGs as
anti-UV/IR glasses. These results are consistent with the macro-
scopic behavior of BSGs. In addition, the refractive indices of
Results and discussion UD and TD are 1.53 and 1.51, respectively (Fig. 1d). These
observations manifest that BSGs display excellent optical prop-
Preparation and optical properties of the BSGs erties, which are comparable with those of modern inorganic
Two BSGs, uridine/20 -deoxyadenosine (UD) and thymidine/20 - glasses.30
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deoxyadenosine (TD), were constructed according to the solution– In addition to the optical properties, density and contact
evaporation method.29 With the fabrication of UD as an example angle are important glass parameters. UD and TD have densi-
(Fig. 1a), uridine (U, 0.01 mol) and 20 -deoxyadenosine (D, 0.01 mol) ties of 1.47 and 1.41 g cm3, respectively, which are only 56–
were first dissolved in deionized water (10 mL). The aqueous 59% of that of man-made glass (2.5 g cm3), showing the
solution was heated in an oven at 100 1C, and then the crude potential of BSGs as light-weight optical materials (Fig. 1e).30
product was placed under vacuum at 25 1C to yield UD as a BSG. The contact angles of UD and TD with water are 35.5 and 32.61,
UD and TD are transparent materials. As shown in Fig. 1a, a respectively, demonstrating their hydrophilic nature (Fig. 1f
colorful print covered by a piece of UD (0.5 cm thick) is easily and Fig. S1, ESI†). A detailed comparison of BSGs and inorganic
and clearly identifiable by the naked eye. Transmittance tests glass is presented in Fig. 1d–f.
confirm the good transparency of BSGs (Fig. 1b). UD and TD
exhibit the transmittance of 89.4% and 88.6%, respectively.30
No obvious changes in the transmittances of TD and UD were Morphologies and mechanical properties of BSGs
observed when the measurements were carried out at low Next, attention was focused on the surface morphology and
humidity. Due to the good water solubility of nucleosides, BSGs mechanical behavior of BSGs. No fractures or cracks are
are not stable in water or highly humid environments.31–33 observed in BSGs either with the naked eye or via an optical
The optical properties of UD and TD were studied comprehen- microscope (Fig. 1a and Fig. S2, ESI†). The results of scanning
sively. The solid-state UV/Vis spectra of UD and TD show poor electron microscopy (SEM) and atomic force microscopy (AFM)

Fig. 1 Preparation and properties of BSGs. (a) Preparation method of BSGs (UD). (b) Transmittance spectra of BSGs with the thickness of 2.0 mm.
(c) Solid-state UV/Vis spectra of BSGs. (d–f) Physical properties of BSGs. (g) AFM image of TD.

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reveal smooth microscopic surfaces of UD and TD (Fig. 1g and temperature-resistance (Fig. 2f, g and Fig. S6, ESI†). Moreover,
Fig. S3, S4, ESI†). For example, the roughness of TD is approxi- the long-term structural stabilities of the BSGs were further
mately 1.3 nm, which is lower than that of common optical confirmed by time-dependent 1H NMR spectra. No obvious
glass (6.0 nm). changes in 1H NMR spectra of the BSGs were observed after
UD and TD exhibit good mechanical properties under 30 days (Fig. S7 and S8, ESI†), demonstrating that no covalent
ambient conditions. Macroscopic weight loading tests demon- interactions occurred in the BSGs. Meanwhile, the BSGs exhibit
strate the good mechanical strengths of BSGs. No deformations good optical and mechanical stabilities in low-polarity solvents
or ruptures are observed, when a piece of UD is hung or covered (toluene, dichloromethane, and chloroform) (Fig. S9, S10 and
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by a weight of 500 g (Fig. 2a). During the nanoindentation tests, Tables S3, S4, ESI†). What is more, the compressive strengths of
elastic moduli of 4.50  0.49 and 5.87  0.47 GPa are observed UD and TD are 3.3 and 2.6 MPa, respectively, indicating their
for UD and TD, respectively, which are comparable with those good hardness (Fig. 2h). The Shore hardnesses of UD and TD
of some artificial tough materials (Fig. 2c and Table S1, are 36 and 32 HD, respectively, which are lower than that of
ESI†).34–37 Storage moduli of BSGs over 107 Pa are obtained polymethyl methacrylate (PMMA, 49 HD). Although UD and TD
from the dynamic thermomechanical analysis tests (Fig. 2d and are tough under ambient conditions, at high temperatures,
Fig. S5, ESI†). Furthermore, UD and TD display good tensile they behave as soft materials, which can be easily processed.
and compressive strengths. As shown in Fig. 2e, UD and TD UD and TD of various sizes (410  10  1 or o0.1  0.1 
show tensile strengths of 1.24 and 1.27 MPa, respectively. The 0.05 cm3) and shapes (cylindrical, square, and circular) can be
tensile elastic moduli and compressive elastic moduli of TD are fabricated using the hot-forming method. Meanwhile, long and
4.94  0.32 and 58.7  3.11 MPa, respectively. The above flexible glass fibers with a diameter of 10 mm are successfully
information indicates that UD and TD belong to stiff materials cast from the molten BSGs, as shown in Fig. 2b. Temperature-
(Table S2, ESI†). Time- and temperature-dependent tensile tests dependent rheological tests clearly confirm the effect of heating
demonstrate that UD and TD have long-term stability and low- on the processing of BSGs (Fig. S12, ESI†).

Fig. 2 Mechanical properties of BSGs. (a) Macroscopic stretching behavior of UD. (b) Glass fibers of UD. (c) Nanoindentation load–displacement curve
of BSGs. (d) Temperature-dependent storage modulus, loss modulus, and tan d of UD. (e) Tensile strength–displacement curve of BSGs. (f) Time-
dependent tensile stress of BSGs. (g) Temperature-dependent tensile stress of BSGs. (h) Compressive strength–strain curve of BSGs.

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Driving force of BSGs Glass nature of BSGs

The driving force is one of the most important intrinsic features The typical nature of glass that distinguishes it from other
of supramolecular polymerization, and is closely related to the natural or artificial materials is the inner structural character-
glass-like nature of the BSGs.34,38 There is no new covalent istics: long-range disorder, short-range order, thermodynamic
bond formation in the BSGs, because neither new peaks nor metastability, and isotropic structure.15 Thus, the investigation
obvious chemical shifts are observed in their solution-state was shifted to study the formation mechanism and intrinsic
1
H NMR spectra (Fig. 3a and Fig. S13–S16, ESI†). This observation nature of the BSGs. The powder X-ray diffraction data of the UD
indicates that the driving force of BSGs may be attributed to non- and TD samples demonstrate that the BSGs are amorphous
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covalent interactions.39 Broad and intense bands (at approxi- (Fig. S23, ESI†). No diffraction peaks are observed in the small-
mately 2950 and 3104 cm1) and obvious band shifts (i.e. from angle X-ray scattering (SAXS) spectra, indicating the lack of
1656 to 1674 cm1, for the amide group in U) are observed in an ordered periodic structure in the BSGs at the mesoscopic
Raman spectrum of UD, suggesting the formation of intermole- scale (Fig. 4a). X-ray photoelectron spectroscopic (XPS) results
cular hydrogen bonds therein (Fig. 3b and Fig. S17, ESI†). further support the isotropic nature of the BSGs (Fig. 4b and
Similar observations are made in the Fourier transform Fig. S24, S25, ESI†). Similar binding energies and intensities
infrared (FT-IR) spectra of the BSGs (Fig. S18, ESI†). Two- were observed at different depths in the BSGs. Simulations
dimensional infrared correction spectroscopy was used to of Young’s moduli of the BSGs at different directions produce
investigate the subtle hydrogen bonds and temperature- similar results (Tables S8 and S9, ESI†). For example, UD exhibits
dependent molecular movements in the BSGs (Fig. 3c and Young’s moduli of 7.68 (X), 7.84 (Y), and 8.02 (Z) GPa, manifest-
Fig. S19, S20, ESI†).36,40 With UD as an example, according to ing its isotropic state. In addition, the refractive-index values
Noda’s rule, the order of the signal intensity change was obtained at random positions in the BSGs are the same. UD and
determined to be 1641 4 1679 4 1652 cm1, manifesting that TD show glass transition temperatures (Tg) of 56 and 62 1C,
the free amide group is more sensitive to elevated temperature respectively, which are considerably lower than that of man-
than the hydrogen-bonded amide group. The hydrogen bonded made optical glass or metal glass (Fig. 4c and d).30 The low Tg
structures in the BSGs were further confirmed via density values may be ascribed to the high fractional free volume of
functional theory simulations (Fig. 3d and Fig. S21, S22, BSG (8–9%) (Fig. 4e–g and Tables S10, S11, ESI†). Meanwhile,
Table S7, ESI†). during reversible heating–cooling cycles, the BSGs exhibit glass

Fig. 3 Driving force of BSGs. (a) Solution-state 1H NMR spectra (400 MHz, D2O, room temperature) of UD, D, and U. (b) Raman spectra of UD, D, and U.
(c) Synchronous correlation spectra (left) and asynchronous correlation spectra (right) of UD from 20 to 100 1C. (d) The IGM isosurfaces for the
interaction between U and D (molar ratio 1 : 1). The color bar shows that blue, green, and red represent strong attraction interactions (hydrogen bonding),
van der Waals interactions, and strong nonbonded overlap, respectively.

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Fig. 4 Glass nature of BSGs. (a) SAXS spectra of BSGs. (b) Wide-scan XPS spectra of UD after different etching times. (c) DSC spectra of UD. (d) DSC
spectra of TD. (e) Fraction of free volume of complex containing T + D + 3 wt% water at 298.0 K. (f) Fraction of free volume of complex containing U + D
+ 3 wt% water. (g) Configuration of molecular models of a complex containing T (fuchsia) + D (purple) + 3 wt% water at 298.0 K. (h) Radial distribution
function (RDF) of the U/D/water composite at room temperature. (i) Radial distribution function (RDF) of the T/D/water composite at room temperature.

transition behavior similar to that of synthetic optical glass or yielding the thermodynamically metastable BSGs. Rheological
metal glass, demonstrating the structural reversibility of the experiments provide detailed information (Fig. 5b).29 With a
BSGs. The low Tg values of UD and TD enable an investigation decrease in the testing temperature from 120 to 20 1C, the
of their glass nature under mild conditions. viscosities of the BSGs decrease considerably. At 20, 100,
Coexisting long-range disorder and short-range order char- and 120 1C, UD shows viscosities of 2.10  108, 384.27, and
acterize the structure of glass.15 UD and TD have this feature, as 8.44 Pa s, respectively, demonstrating that the viscosity of UD at
confirmed via radial distribution function (RDF) characteriza- 20 1C is more than 107 times its viscosity at 120 1C. Such a
tion. No prominent peaks are observed in the RDF spectra of significant change in viscosity results in the formation of a
the BSGs when the distance is more than 4 Å (Fig. 4h and i), metastable BSG. In a control experiment, single crystals were
indicating the absence of ordered structures at the long-range obtained when a UD aqueous solution was slowly evaporated
scale. In contrast, peaks assigned to intermolecular non- (Fig. S26, ESI†). This result indicates that in the low tempera-
covalent bonds are found at distances less than 4 Å, suggesting ture range, the high viscosities of the BSGs hinder the crystal-
the existence of short-range ordered structures in the BSGs.15 lization abilities of the nucleosides, thus maintaining their
The simultaneous appearance of isotropic, long-range dis- metastable states.
order, and short-range order is directly related to the chemical
structure and rapid annealing treatment of the BSGs. In DNA, Relaxations in the BSGs
base pairs apply self-sorted molecular recognition patterns.20 Relaxations are intrinsic and universal in natural/artificial glass
However, in the fabrication of BSGs, UD or TD is first heated to and are crucial for its glass transition behavior, mechanical
form a liquid with low viscosity and high mobility, as shown in properties, and stability.14 Herein, broadband dielectric
Fig. 5a. Subsequently, the liquid-type BSG is rapidly cooled to spectroscopy was applied to study the relaxation of the BSGs,
yield a compact solid, during which versatile hydrogen bonds because dielectric spectroscopy has various advantages, includ-
are formed and the dynamical recognition motifs are frozen, ing high sensitivity and a wide temperature range.39 Three

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Fig. 5 Thermodynamically metastable state of the BSGs. (a) Volume change with transforming from solution to crystal or BSGs. (b) G 0 , G00 and |Z*| value
of UD in reversible temperature-dependent rheological tests. (c) Average relaxation time as a function of temperature for relaxation processes in the
BSGs. Solid lines represent Arrhenius fitting for b-, g-, and d-relaxation. (d) Activation energies (Ea) of the BSGs for b-, g-, and d-relaxation.

distinguishable relaxation processes (b, g, and d) occur at formation of ordered and disordered structures.42 In the for-
temperatures below Tg. To quantitatively analyze these relaxa- mation of common inorganic glass, the importance of metal,
tions, the dielectric loss spectra were fitted using a combi- covalent, and ionic bonds outweighs that of hydrogen bonds
nation of the Havriliak–Negami function and a conductivity and van der Waals forces. Therefore, the coexistence of short-
term. b and g relaxations are the slowest and fastest processes range ordered and long-range disordered structures is directly
in supramolecular polymerization (for TD at 23.0 1C, the governed by the synergistic effect of metal, covalent, and
relaxation time required for the b and g processes are 5.03 ionic bonds.
and 2.35  105 s), respectively, indicating a greater mobility of In the formation of a BSG, hydrogen bonding is the main
the functional groups on the glass surface than those in the driving force. The directional and saturated character of hydro-
glass interior (Fig. 5c). Relaxations in the BSGs have a promi- gen bonds results in the formation of short-range ordered
nent temperature dependence, with b relaxation occurring at structures during supramolecular polymerization, while the
higher temperatures. The activation energies (Ea) of the b, g, weak and reversible nature of hydrogen bonding enables
and d relaxations were calculated using the Arrhenius equation asymmetric and random connection of short-range ordered
and are equal to 4.59, 3.61, and 0.84 kJ mol1, respectively, structures to a long-range disordered network. Compared to
in TD (Fig. 5d). The Ea values of the relaxation of UD and TD silicate or metallic glass, BSGs exhibit lower annealing and
(o5.0 kcal mol1) are considerably lower than those of artificial glass transition temperatures; thus, their glassy nature can be
glass materials because of the absence of covalently linked easily studied.34,43,44 The low-molecular-weight BSGs enable
polymeric structures.36,40 These results demonstrate that the more choices for characterization. For example, solution-state
1
segmental motion occurs easily even at temperatures below Tg, H NMR spectroscopy can be used to study the driving forces in
because of the metastability of the BSGs. BSGs.45

Discussion Conclusions
The definition of glass has never been established. In fact, it In conclusion, BSGs were fabricated via the non-covalent poly-
continuously changes over time. Intuitively, glass is a transpar- merization of low-molecular-weight nucleosides. BSGs exhibit
ent material with desirable optical properties. In addition to excellent optical and mechanical properties comparable to
traditional inorganic glass, a variety of new glass materials, those of some synthetic glasses. They display distinguished
including metal–organic framework glass and metallic glass, features on various scales. Macroscopically, the structures of
have been fabricated.7,41 It has been found that glass vitrifica- BSGs are random, long-range disordered, and isotropic; how-
tion is a highly complex thermodynamic process involving the ever, BSGs exhibit short-range order and anisotropic molecular

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organization patterns in a limited and localized scale. Solvent 106 Hz at each temperature from 40 to 80 1C with a 3 1C
evaporation and rapid cooling during the preparation process interval.33
determine the amorphous and thermodynamically metastable The Havriliak and Negami (H–N) function is employed to
characteristics of BSGs. Various relaxations in BSGs are analyze the dielectric spectra. The complex dielectric permittiv-
assigned to the local molecular motions in isolated regions of ity (e*) data as a function of frequency can be described by the
the structures. The development of BSGs from nucleosides following equation:
provides a supramolecular view of the nature of glass. De
e ¼ e1 þ
½1 þ ðiotHN Þa b
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where eN is the high-frequency limit of e 0 , De is the relaxation

Experiment section
strength, and tHN is the characteristic relaxation time. The a
Materials and methods and b parameters (0 o a, ab r 1) are defined as the symme-
All materials and reagents were commercially obtained and trical and asymmetrical broadening of the loss peak.
used without further purification. Contact angle measurements The relationship between tmax and temperature can be
were determined on an XG-CAM Contact Angle Meter. Optical described by Arrhenius functions:
microscope images were obtained on a NIKON Ti-E optical  
Ea
microscope. Atomic force microscopy (AFM) images were tmax ¼ t0 exp
RT
obtained on a Bruker Dimension Icon AFM. Nanoindentation
measurements were performed on a Hysitron TI-950 Nano where Ea is the activation energy and t0 is a constant.
Indenter. Dynamic thermomechanical analysis (DMA) was car-
Density functional theory (DFT) calculation
ried out on a Q800 (TA instrument) using tension mode.
Rheology measurements were performed on an Anton Paar To study the intermolecular interaction, 200 sets of configura-
MCR 92. The laminator model PP15 was chosen with a dia- tions were generated using a random method, and then these
meter of 15 mm with the gap at 0.5 mm. Solution-state 1H NMR configurations were optimized by using the PM6-DH+ method.
spectra were collected on a Bruker-AV400 with TMS or residual Finally, the optimal configuration was obtained through using
solvent as the internal standard. Raman spectra were recorded MOPAC 2016 software and used for DFT calculation.46
on a Renishaw inVia Raman Spectrometer with an excited All calculations were performed by using the Gaussian16
wavelength of 514 nm. Fourier transform infrared (FT-IR) software with the M06-2X functional. Crimme’s D3 dispersion
spectra were collected on a Bruker Vertex 70 FTIR spectro- correction was used for improving the calculation accuracy. The
photometer. Temperature-dependent FTIR spectra were 6-311g(d) basis set was used to optimize the geometry. The
recorded on a SHIMADZU IRAffinity-1S from 20 to 100 1C at nature of noncovalent interaction was investigated by using the
1 1C min1. The data were processed by 2DCS software and IGM (Independent Gradient Model) method through Multiwfn
generated the generalized 2D correlation spectra. Powder X-ray software. The IGM diagram was rendered by VMD (Visual
diffraction (PXRD) data were collected on a Bruker D8 Molecular Dynamics).29
ADVANCE. X-ray photoelectron spectroscopy (XPS) analysis The binding energy between compound A and compound B
was performed on Thermo escalab 250Xi X-ray photoelectron was calculated by the following formula:
spectrometer. Transparency and solid UV/Vis spectra were
Ebinding = Etotal  (EpartA + EpartB)
collected on a SHIMADZU UV-3600 spectrometer. Refractive
index was recorded on Digital Gem Refractometer. Density was Ebinding represents the binding energy between compound A
determined on an AccuPyc II 1340. Tensile and compressive and compound B; Etotal represents the total energy of the
strength measurements were performed on a HY-0580 Electro- system containing compound A and compound B; EpartA repre-
nic tensile testing machine. Small angle X-ray scattering (SAXS) sents the energy of compound A; EpartB represents the energy of
spectra were recorded on an Anton Paar SAXS mc2 using Cu Ka compound B.
radiation (l = 0.154 nm). Differential scanning calorimeter
(DSC) measurements were carried out using a TAQ200 with a Molecular dynamic (MS) calculation
heating rate of 10 1C min1 from 80 to 120 1C, and the cooling To further explore the formation of BSGs, molecular dynamics
rate was 10 1C min1 from 120 to 80 1C in a nitrogen simulations at an atomic level were carried out in the commer-
atmosphere. A Shore hardness test was performed by a Shore cial platform Materials Studio (V.8.0, Accerlys, San Diego,
hardness test instrument. USA).47 Firstly, the molecular model was created by using an
amorphous cell construction module, and its configuration was
optimized by using the COMPASS force field to find the mini-
Broadband dielectric measurements and analyses mum global energy configuration. An energy convergence
Broadband dielectric measurements were performed through a criterion of 105 kcal mol1 and force convergence criterion
Novocontrol Concept 80 system with Alpha impedance analyzer of 104 kcal mol1 Å1 were used in this process. Secondly, the
and Quatro Novocontrol Cryo-system temperature control. Fre- molecular model was annealed for 5-cycles under constant
quency sweep mode was used with a frequency range of 101 to temperature and constant volume (NVT ensemble) from 200

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