Ivan Gitsov
The State University of New York, Chemistry, Faculty Member
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ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full... more
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
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ABSTRACT Novel linear–dendritic super-H block copolymers are prepared by multistage synthetic process involving “living” polymerizations.
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This study reports the first attempt to employ a potassium–graphite intercalation compound (KC24) as an initiator for the one-pot synthesis of a multi-block copolymer. The results obtained show that KC24 successfully initiated the... more
This study reports the first attempt to employ a potassium–graphite intercalation compound (KC24) as an initiator for the one-pot synthesis of a multi-block copolymer. The results obtained show that KC24 successfully initiated the copolymerization, leading to a copolymer consisting of poly(styrene), poly(methyl methacrylate) and poly(ethylene oxide) blocks. When all three comonomers were introduced simultaneously or in a specific sequence, the resulting copolymers had molecular masses in the range between 170,000 Da and 280,000 Da. Their composition was investigated by size-exclusion chromatography with triple detection (dRI/UV/IR) and 1H-NMR. The analyses indicated that all copolymers were enriched in methyl methacrylate (50–66 mol%) despite the fact that the comonomers were added in equimolar amounts. Due to the layered structure of the initiator, the polymerization took place in the graphite interlayer spaces and lead to extensive delamination, indicating at the potential to prod...
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In this paper, we describe a novel method for preparation of polymer composites with homogeneous dispersion of natural fibers in the polymer matrix. In our approach, Williamson ether synthesis is used to chemically modify cellulose with... more
In this paper, we describe a novel method for preparation of polymer composites with homogeneous dispersion of natural fibers in the polymer matrix. In our approach, Williamson ether synthesis is used to chemically modify cellulose with polymerizable styrene moieties and transform it into a novel multifunctional cellu-mer that can be further crosslinked by copolymerization with styrene. Reactions with model compounds (cellobiose and cellotriose) successfully confirm the viability of the new strategy. The same approach is used to transform commercially available cellulose nanofibrils (CNFs) of various sizes: Sigmacell and Technocell™ 40, 90 and 150. The styrene-functionalized cellulose oligomers and CNFs are then mixed with styrene and copolymerized in bulk at 65 °C with 2,2′-azobisisobutyronitrile as initiator. The resulting composites are in a form of semi-interpenetrating networks (s-IPN), where poly(styrene) chains are either crosslinked with the uniformly dispersed cellulosic co...
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This study reports the first enzymatic synthesis leading to several oligomer analogues of poly[3-(3,4-dihydroxyphenyl)glyceric acid]. This biopolymer, extracted from plants of the Boraginaceae family has shown a wide spectrum of... more
This study reports the first enzymatic synthesis leading to several oligomer analogues of poly[3-(3,4-dihydroxyphenyl)glyceric acid]. This biopolymer, extracted from plants of the Boraginaceae family has shown a wide spectrum of pharmacological properties, including antimicrobial activity. Enzymatic ring opening polymerization of 2-methoxycarbonyl-3-(3,4-dibenzyloxyphenyl)oxirane (MDBPO) using lipase from Candida rugosa leads to formation of poly[2-methoxycarbonyl-3-(3,4-dibenzyloxyphenyl)oxirane] (PMDBPO), with a degree of polymerization up to 5. Catalytic debenzylation of PMDBPO using H2 on Pd/C yields poly[2-methoxycarbonyl-3-(3,4-dihydroxyphenyl)oxirane] (PMDHPO) without loss in molecular mass. Antibacterial assessment of natural polyethers from different species of Boraginaceae family Symhytum asperum, S. caucasicum,S. grandiflorum, Anchusa italica, Cynoglossum officinale, and synthetic polymers, poly[2-methoxycarbonyl-3-(3,4-dimethoxyphenyl)oxirane (PMDMPO) and PMDHPO, reveals...
Research Interests: Chemistry, Medicine, Polymerization, Pharmaceutics, Oligomer, and 3 moreBoraginaceae, Antimicrobial, and ROMP
This paper reports the creation of hydroxyapatite/polyester nanografts by “graft-from” polymerization of d,l-lactide with [Ca5(OH)(PO4)3]2 as the initiator and tin(II)-2-ethylhexanoate as the catalyst. Model polymerizations were performed... more
This paper reports the creation of hydroxyapatite/polyester nanografts by “graft-from” polymerization of d,l-lactide with [Ca5(OH)(PO4)3]2 as the initiator and tin(II)-2-ethylhexanoate as the catalyst. Model polymerizations were performed with cyclooctanol as initiator to confirm the grafting on the surface of the hydroxyapatite nanocrystals. Polymers with the highest molecular mass (Mn) between 4250 Da (cyclooctanol) and 6100 Da (hydroxyapatite) were produced. In both cases the molecular mass distributions of the polymers formed were monomodal. The materials obtained were characterized by size-exclusion chromatography, NMR and FT-IR spectroscopy, and thermal methods. Their suitability as additives for commercial bone cement (Simplex P Speedset, Stryker Orthopaedics) has been confirmed by thermal analysis techniques and mechanical testing. The results obtained show that addition of the hydroxyapatite/ polyester nanografts improved both thermal and mechanical properties of the bone c...
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Herewith we report the first attempt towards non-covalent immobilization of Trametes versicolor laccase on neat and magnetically responsive highly porous polyamide 6 (PA6) microparticles and their application for catechol oxidation. Four... more
Herewith we report the first attempt towards non-covalent immobilization of Trametes versicolor laccase on neat and magnetically responsive highly porous polyamide 6 (PA6) microparticles and their application for catechol oxidation. Four polyamide supports, namely neat PA6 and such carrying Fe, phosphate-coated Fe and Fe3O4 cores were synthesized in suspension by activated anionic ring-opening polymerization (AAROP) of ε-caprolactam (ECL). Enzyme adsorption efficiency up to 92% was achieved in the immobilization process. All empty supports and PA6 laccase complexes were characterized by spectral and synchrotron WAXS/SAXS analyses. The activity of the immobilized laccase was evaluated using 2,2’-Azino-bis-(3- ethylbenzothiazoline-6-sulfonic acid (ABTS) and compared to the native enzyme. The PA6 laccase conjugates displayed up to 105% relative activity at room temperature, pH 4, 40 °C and 20 mM ionic strength (citrate buffer). The kinetic parameters of the ABTS oxidation were also det...
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Abstract The interaction of poly[2,2-bis(4-hydroxyphenyl)propanecarbonate] (PC) with phosphonic acid dialkyl esters [(RO) 2 P(O)H, where R CH 3 or CH 3 CH 2 ] or with phosphoric acid triethyl ester (CH 3 CH 2 O) 3 P(O) was studied.... more
Abstract The interaction of poly[2,2-bis(4-hydroxyphenyl)propanecarbonate] (PC) with phosphonic acid dialkyl esters [(RO) 2 P(O)H, where R CH 3 or CH 3 CH 2 ] or with phosphoric acid triethyl ester (CH 3 CH 2 O) 3 P(O) was studied. Treatment of PC pellets with phosphonic acid dialkyl esters at 160°C or with triethyl phosphate at 180°C yielded phosphorus-containing oligocarbonates. The structure of the phosphorus-containing oligocarbonates was studied by 31 P NMR, 1 H NMR and 13 C NMR spectroscopy.
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This study targets the synthesis of novel semi-interpenetrating networks and amphiphilic conetworks, where hydrophilic soft matter (Gellan Gum, GG) was combined with hydrophobic rigid poly(styrene), PSt. To achieve that, GG was chemically... more
This study targets the synthesis of novel semi-interpenetrating networks and amphiphilic conetworks, where hydrophilic soft matter (Gellan Gum, GG) was combined with hydrophobic rigid poly(styrene), PSt. To achieve that, GG was chemically modified with 4-vinyl benzyl chloride to form a reactive macromonomer with multiple double bonds. These double bonds were used in a copolymerization with styrene to initially form semi-interpenetrating networks (SIPNs) where linear PSt was intertwined within the GG-PSt conetwork. The interpenetrating linear PSt and unreacted styrene were extracted over 3 consecutive days with yields 18–24%. After the extraction, the resulting conetworks (yields 76–82%) were able to swell both in organic and aqueous media. Thermo-mechanical tests (thermal gravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis) and rheology indicated that both SIPNs and conteworks had, in most cases, improved thermal and mechanical properties compare...
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A key challenge to the creation of chemically responsive electro-functionality of nonconductive, hydrophobic, and free-contacted textile or fibrous network materials is how to impart the 3D structure with functional filaments to enable... more
A key challenge to the creation of chemically responsive electro-functionality of nonconductive, hydrophobic, and free-contacted textile or fibrous network materials is how to impart the 3D structure with functional filaments to enable responsive structure sensitivity, which is critical in establishing the fibrous platform technology for sensor applications. We demonstrate this capability using an electrospun polymeric fibrous substrate embedded with nano-filaments defined by size-tunable gold nanoparticles and structurally sensitive dendrons as crosslinkers. The resulting interparticle properties strongly depend on the assembly of the nano-filaments, enabling an interface with high structure sensitivity to molecular interactions. This is demonstrated with chemiresistive responses to vaporous alcohol molecules with different chain lengths and isomers, which is critical in breath and sweat sensing involving a high-moisture or -humidity background. The sensitivity scales with the chain length and varies with their isomers. This approach harnesses the multifunctional tunability of the nano-filaments in a sensor array format, showing high structure sensitivity to the alcohol molecules with different chain lengths and isomers. The high structure sensitivity and its implications for a paradigm shift in the design of textile sensor arrays for multiplexing human performance monitoring via breath or sweat sensing and environmental monitoring of air quality are also discussed.
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This talk will present and discuss an enzyme-catalyzed “green” synthesis of unnatural poly(amino acid)s and their dendronized analogues. It will be shown how DL-tyrosine could be polymerized under environmentally friendly conditions using... more
This talk will present and discuss an enzyme-catalyzed “green” synthesis of unnatural poly(amino acid)s and their dendronized analogues. It will be shown how DL-tyrosine could be polymerized under environmentally friendly conditions using linear-dendritic laccase complexes as initiators and water as solvent. The influence of the dendron generation in the linear-dendritic copolymers, the monomer concentration, time and temperature on the polymers yields and molecular masses will be discussed along with the structure of the poly(tyrosine) as investigated by NMR, FT-IR and MALDI-TOF. The synthesis of dendritic tyrosine monomers of different generations will also be presented. The materials formed by both polymerizations are completely water-soluble and behave either as typical poly(zwitterions) or like macro-amphiphiles, changing charge, size and shape with the medium pH and generation of the dendritic side groups. Potential biomedical applications will be outlined.
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This study reports the first enzyme-mediated polymerization of dendritic macromonomers. The enzyme substrates are prepared by "click" conjugation between tyrosine and hydrophilic triethylene glycol (TrEG)-based dendrons of three... more
This study reports the first enzyme-mediated polymerization of dendritic macromonomers. The enzyme substrates are prepared by "click" conjugation between tyrosine and hydrophilic triethylene glycol (TrEG)-based dendrons of three generations (G1, G2, and G3). The resulting enzyme-polymerizable dendrons are defect-free as revealed by mass spectrometry, size-exclusion chromatography, and spectroscopic techniques. The phenol-containing macromonomers are water soluble and their polymerizations into dendronized polymers (denpols) are catalyzed by laccase (an oxidoreductase) under benign conditions (45 °C and aqueous medium at pH = 4.0) with copolymer yields between 30 and 40%. The resulting denpols consist of unnatural poly(tyrosine) backbones and dendritic poly(ether-ester) side chains and have molecular masses up to ∼13 000 Da (generation 1), ∼20 000 Da (generation 2), and ∼36 000 Da (generation 3) determined by matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) analyses. They display amphiphilic properties and self-assemble in aqueous solutions to form aggregates with generation-dependent morphologies.
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This study reports a new strategy for enzyme immobilization based on passive immobilization in neat and magnetically responsive polyamide 4 (PA4) highly porous particles. The microsized particulate supports were synthesized by... more
This study reports a new strategy for enzyme immobilization based on passive immobilization in neat and magnetically responsive polyamide 4 (PA4) highly porous particles. The microsized particulate supports were synthesized by low-temperature activated anionic ring-opening polymerization. The enzyme of choice was laccase from Trametes versicolor and was immobilized by either adsorption on prefabricated PA4 microparticles (PA4@iL) or by physical in situ entrapment during the PA4 synthesis (PA4@eL). The surface topography of all PA4 particulate supports and laccase conjugates, as well as their chemical and physical structure, were studied by microscopic, spectral, thermal, and synchrotron WAXS/SAXS methods. The laccase content and activity in each conjugate were determined by complementary spectral and enzyme activity measurements. PA4@eL samples displayed >93% enzyme retention after five incubation cycles in an aqueous medium, and the PA4@iL series retained ca. 60% of the laccase....
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Terpolymers of methyl methacrylate with methacrylic acid and methacryloyl chloride [poly(MMA-MAA-MAC)] were synthesized with high yields by slow radical polymerization. The influence of the temperature of prebaking on the changes in the... more
Terpolymers of methyl methacrylate with methacrylic acid and methacryloyl chloride [poly(MMA-MAA-MAC)] were synthesized with high yields by slow radical polymerization. The influence of the temperature of prebaking on the changes in the chemical composition and the molecular weight characteristics of poly(MMA-5%MAA-5%MAC) was studied by infrared spectroscopy and gel permeation chromatography. It was found that resists containing terpolymer with molecular weight (Mw) of 41,000, which were prebaked at 100°C, were able to produce high contrast images (γ = 3.3) at doses of 16 μC/cm2.
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In this article, we report the solution self-assembly of a series of amphiphilic linear–dendritic block copolymers (LDBCs), which are composed of hydrophilic dendritic poly(ether-ester), PEE, blocks based on... more
In this article, we report the solution self-assembly of a series of amphiphilic linear–dendritic block copolymers (LDBCs), which are composed of hydrophilic dendritic poly(ether-ester), PEE, blocks based on 2,2-bis(hydroxymethyl)propionic acid and hydrophobic linear poly(styrene), PSt, blocks. The investigated LDBCs have narrow dispersity with three PEE generations (1–3) and a broad range of PSt molecular masses and are produced by dendron-initiated atom transfer radical polymerization of styrene followed by deprotection of the peripheral dendron hydroxyl groups. The solution self-assembly of the copolymers is performed by slowly adding water to the polymer solution in tetrahydrofuran (THF) as the common solvent for both blocks of the copolymers. The morphologies of the supramolecular assemblies are preserved either by diluting their dispersion by excess of water or by THF evaporation. It is found that the micellar morphology (sphere, wormlike, and/or vesicle) depends on the hydrophilic block fraction (F...
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A process for the separation of styrene oligomers and polymers by size and composition using a novel separation medium has been demonstrated. The process involves precipitation of the macromolecules on the molded macroporous rod columns,... more
A process for the separation of styrene oligomers and polymers by size and composition using a novel separation medium has been demonstrated. The process involves precipitation of the macromolecules on the molded macroporous rod columns, followed by progressive elution utilizing a simple gradient of the mobile phase. Molded macroporous rod columns are ideally suited for this technique because convection through the large pores of the rod enhances the mass transport of large analyte molecules and accelerates the separation process. Styrene oligomers and polymers are separated in a 50-mm x 8-mm-i.d. column using a solvent gradient composed of a poor solvent such as water, methanol, or acetonitrile and increasing amounts of a good solvent, tetrahydrofuran. Excellent separations are obtained, demonstrating that precipitation-redissolution can be a suitable alternate to size exclusion chromatography (SEC) of some polymers. Compared to SEC, the gradient elution separation can be achieved at higher flow rates in a much shorter time. Precipitation-redissolution with gradient elution can also be used for the separation of copolymers, for which the process is controlled not only by molecular weight but also by the composition of the copolymers.