Search

Systematic molecular dynamics simulations, along with dielectric measurements on poly(vinyl methyl ether)/polystyrene blends, are performed to investigate the topological effect on the effective lo...

Isotactic poly (N-isopropylacrylamides) (PNIPAMs) with a wide range of tacticity exhibit upper critical solution temperature (USCT) type phase transition in an ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([BMIM][TFSI]). The phase transition temperature becomes higher with increasing isotacticity, since more amide groups are aligned along the same side of backbones to form stronger intramolecular hydrogen bonding. Phase diagrams of highly isotactic PNIPAMs show prominent UCST peaks at low concentrations, similar with the typical polymer solution, which implies the dissolution of isotactic PNIPAMs is dominated by the entropy-driven effect. The increase in phase transition temperature with molecular weight is also from the entropic reason. The phenomena above reveal that the phase transition behavior of PNIPAMs in ionic liquids is highly influenced by tacticity effect.

In the present study, rapid and highly efficient solid-state synthesis strategy has been successfully employed for the synthesis of zinc oxide nanoparticles (ZnO NPs). Herein, prepared ZnO NPs are characterized and used for the fabrication of highly sensitive, selective, and accountable gas sensors. Structural elucidation, surface composition, and morphological investigations of as-synthesized ZnO NPs respectively, are carried out using X-ray diffraction, Raman spectroscopy, energy dispersive X-ray spectroscopy, scanning electron microscopy, transmission electron microscopy, and selected area electron diffraction measurement techniques. The gas sensing properties of ZnO NPs studied at various operating temperatures and towards different oxidizing and reducing gases demonstrated the ability of ZnO to detect hazardous chlorine (Cl2) gas (optimum @ 200 °C) with rapid response and recovery times. In addition, ZnO sensor film has detected the low 5 ppm concentration of Cl2 with reasonable response of 199% with outstanding repeatability and stability in response. The variation of ZnO response with respect to different Cl2 concentrations has systematically been investigated and explored. Finally, the plausible sensing mechanism of ZnO with Cl2 gas molecules has been proposed using energy band model diagram.

The synthesis of amphiphilic block-copolymers of poly(N-isopropylacrylamide) (PNIPAM) and poly(N-acryloyl- l -phenylalanine methyl ester) (PNALPA) by RAFT polymerization is reported. The polymers were characterized by proton NMR (1H NMR), gel permeation chromatography (GPC), powder X-ray diffraction (XRD), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) to understand their structure-property relationships. All synthesized polymers show pH triggered release at acidic (pH 5) and biological pH (pH 7.4). Critical micellar concentration also varied systematically depending on the amphiphilic nature of the polymers. Biocompatibilities of the polymers are also determined to check their suitability for biomedical applications.

Here, we report on the effect of functional copolymer poly(N-isopropylacrylamide-co-4-vinyl-phenylboronic acid) (NIBA) on the rheology and network structure formed by sodium alginate (SA) through linear and nonlinear viscoelasticity measurements. The hydrogel moduli at pH 3 increased with increasing NIBA addition, while the yield point decreased. Furthermore, these hydrogels showed strain-softening behavior, weak G″-overshoot marking the onset of nonlinearity, and good self-healing properties after large deformation. The zero-strain nonlinearity parameter (Q0) was found to be more sensitive to NIBA-addition than the linear viscoelastic properties. The blends showed a clear peak in the startup test except for SA alone and the peak intensity increased with increasing NIBA-concentration. Finally, based on all data, gelation mechanism and interaction of SA and NIBA will be clarified.

Some physical properties of high molecular weight linear poly(N-isopropylacrylamide)s (PNIPAM) having different isotacticities (m, meso dyad = 47, 62, 68, 81, and 88 %) have been studied. The solubility of these polymers in different solvents varied with their isotacticity. Thermal degradation of higher isotactic polymer started slightly earlier. Cloud point of these polymers in water gradually decreased with increase in m up to 68 %. Surface tension of these polymers in N,N-dimethylformamide (DMF) was slightly lower than DMF and almost independent of their isotacticity in the temperature range of 20–60 °C. But it decreased linearly with the increase in temperature. Moreover, for all polymers, it decreased very slightly with the increase in their concentrations in the range of 0.001–0.01 % (w/v). Viscosity of these polymers in DMF increased with (i) the increase in the concentration range of 1–5 % (w/v), (ii) the increase in their m values, and (iii) the decrease in the temperature in the range of 20–60 oC.

Well-defined linear dihydrophilic amphiphilic ABA-type triblock copolymers of e-caprolactone (CL) and N-isopropylacrylamide (NIPAAm) have successfully been synthesized with a high yield by combining the ring opening polymerization (ROP) and xanthate-mediated reversible addition-fragmentation chain transfer (RAFT) polymerization methods. The resulted block copolymer shows the formation of micelles in water as supported by light scattering. The critical micelle concentration (cmc) value of the micelle increases with the increase in the chain length of the poly (N-isopropylacrylamide) (PNIPAAm) block. Cloud point of the block copolymers decreases with the decrease in the PNIPAAm chain length. The TGA analysis shows a one-step degradation and a lower thermal stability of the triblock copolymer than the PNIPAAm. The DSC analysis of the triblock copolymer shows the lowering of glass transition temperature (T g), and melting temperature (T m) peaks possibly due to the partial miscibility of the poly (e-caprolactone) (PCL) block with the amorphous PNIPAAm block through the interaction of ester groups of PCL with the amide groups of PNIPAAm. The XRD pattern of the triblock copolymer shows a broad peak due to the suppression of the crystallization of PCL block owing to the mixing of PNIPAAm block with the PCL block.

Well-defined amphiphilic poly( d , l -lactide)- b -poly( N -vinylpyrrolidone) (PDLLA- b -PNVP) block copolymers were successfully prepared using ring-opening polymerization (ROP) and xanthate-mediated reversible addition-fragmentation chain transfer (RAFT) polymerization. Synthesized PDLLA- b -PNVP block copolymers were characterized by 1 H NMR spectroscopy and GPC. Spherical micelles of ∼30.2 nm diameter were formed from the aqueous solution of amphiphilic diblock copolymer PDLLA 42 - b -PNVP 63 as revealed by TEM and supported by 1 H NMR and light scattering. The critical micelle concentration value of the block copolymers, determined by fluorescence spectroscopy using pyrene as probe, increased with the increase in the chain length of PNVP block. The average hydrodynamic radius ( R h ) of the micelles remained almost constant above the cmc value over the angles of scattering measurement. Thermal properties of these block copolymers were studied by TGA, DTA and DSC. Crystalline properties of these block copolymers were studied by WXRD.

Two new alkyne-terminated xanthate reversible addition-fragmentation chain-transfer (RAFT) agents: (S)-2-(Propynyl propionate)-(O-ethyl xanthate) (X3) and (S)-2-(Propynyl isobutyrate)-(O-ethyl xanthate) (X4) were synthesized and characterized and used for the controlled radical polymerization of N-vinylpyrrolidone (NVP). X3 showed better chain transfer ability in the polymerization at 60°C. Molecular weight of the resulted polymer increased linearly with the increase in monomer loading. Kinetics study with X3 showed the pseudo-first order kinetics up to 67% monomer conversion. Molecular weight (Mn) of the resulting polymer increased linearly with the increase in the monomer conversion up to around 67%. With the increase in the monomer conversion, polydispersity of the corresponding poly(NVP)s initially decreased from 1.34 to 1.32 and then increased gradually to 1.58. Chain-end analysis of the resulting polymer by 1H-NMR and FTIR showed clearly that polymerization started with radical forming out of xanthate RAFT agent. Living nature of the polymerization was also confirmed from the successful homo-chain extension experiment and the hetero-chain extension experiment involving synthesis of poly(NVP)-b-polystyrene amphiphilic diblock copolymer. Formed alkyne-terminated poly(NVP) also allowed easy conjugation to azide-terminated polystyrene by click chemistry to prepare well-defined poly(NVP)-b-polystyrene block copolymers. Resulting polymers were characterized by GPC, 1H-NMR, FTIR, and thermal study. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

S)-2-(Ethyl propionate)-(O-ethyl xanthate) (X1) and the newly syn- thesized (S)-2-(ethyl isobutyrate)-(O-ethyl xanthate) (X2) were used as the revers- ible addition-fragmentation chain transfer (RAFT) agents for the radical polymerization of N-vinylpyrrolidone (NVP). The former showed the better chain transfer ability in the polymerization at 60 C. Kinetics study with X1 shows the psuedo-first order kinetics upto 45% monomer conversion. Molecular weight (Mn) of the resulted polymer increases linearly with increase in the monomer conversion upto around 45%. Polydispersity of the corresponding poly(NVP)s increase grad- ually from 1.2 to 1.9 with increase in the monomer conversion. Chain-end analysis of the resulted polymer by 1 H NMR shows clearly that polymerization started with radical forming out of xanthate mediator. Living nature of the polymerization was confirmed from the successful homo chain extension experiment and also the het- ero-chain extension experiment involving synthesis of poly(NVP)-b-polystyrene amphiphilic diblock copolymer.

Poly(N-isopropylacrylamide) (PNIPAM) hydrogels were simply prepared by free radical polymerization in different methanol–water mixture. A scanning electron microscopy study revealed that the freeze-dried hydrogels were macroporous. The swelling ratios in water at 20°C of the resulting hydrogels followed the order: X0.43>X0.21>X0.76 ≈ X0.57>X0.31>X0.13>X0.06>X0, where Xm denotes a gel prepared in a methanol–water mixture with m mole fraction of methanol (xm). Below the lower critical solution temperature, the swelling ratio values of all of the hydrogels gradually decreased with the increase in the temperature. The complete collapse of the PNIPAM chain of all the gels occurred at about 38°C, whereas the same was observed at about 35°C for the conventional gel prepared in water. The swelling ratio values of all the PNIPAM gels in the methanol–water mixtures with different xm values at 20°C passed through a minimum in the cononsolvency zone. The deswelling rates of the hydrogels decreased in the following order: X0.43> X0.31> X0.21> X0.57> X0.76 ≈ X0.13> X0.06> X0. The reswelling rates of these hydrogels decreased in the following order: X0> X0.31> X0.06 ≈ X0.13 > X0.76> X0.57> X0.21> X0.43. The release rates of the Tramadol Hydrochloride drug at 37°C from the drug-loaded hydrogels were almost same for all of the hydrogels. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Well-defined amphiphilic poly(e-caprolactone)-b-poly(N-vinylpyrrolidone) (PCL-b-PNVP) block copolymers were successfully prepared via the combination of ring-opening polymerization (ROP) and xanthate-mediated reversible addition−fragmentation chain transfer (RAFT) polymerization. Well-defined poly(e-caprolactone) (PCL−OH) was synthesized by ROP in bulk at 110 °C using benzyl alcohol as initiator and stannous octate [Sn(Oct)2] as catalyst . The −OH end group was then converted into its corresponding xanthate (PCL−X) via the conversion to its corresponding bromide (PCL−Br). These are verified by 1H NMR spectroscopy. PCL-b-PNVP block copolymers were synthesized via RAFT polymerization in tetrahydrofuran (THF) at 80 °C using PCL−X as macro-chain transfer agent and characterized by 1H NMR spectroscopy and gel permeation chromatography (GPC). The amphiphilic diblock copolymer PCL63-b-PNVP90 forms spherical micelles of ∼34 nm diameter in water as shown by transmission electron microscopy (TEM), supported by 1H N...

Poly(N-isopropylacrylamide) (PNIPAM) hydrogels were prepared by free-radical polymerization in different ethanol–water mixtures. A scanning electron microscopy study revealed that the resulting hydrogels were macroporous. The swelling ratios of the resultant hydrogels in water at 20°C followed this order: X0.34 ≈ X0.68 > X0.48 > X0.09 > X0.04 > X0, where Xa denotes a gel prepared in an ethanol–water solvent mixture with an ethanol molar fraction of a. Below the lower critical solution temperature, the swelling ratio values of all of the hydrogels gradually decreased with increasing temperature. The complete collapse of the PNIPAM chain of all of these gels occurred at about 38°C, whereas the same was observed at about 35°C for the conventional gel prepared in water. The swelling ratio values of all of the PNIPAM gels with different molar fractions of ethanol at 20°C passed through a minimum in the cononsolvency zone. The deswelling rates of the hydrogels decreased in the following order: X0.34 > X0.48 > X0.68 > X 0.09 > X0.04 > X0. The reswelling rates of these hydrogels decreased in the following order: X0 > X0.04 ≈ X0.48 > X0.09 ≈ X0.68 > X 0.34. The freeze-drying process decreased the swelling ratios but increased the deswelling and reswelling properties of the PNIPAM gels. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

(S)-2-(Ethyl propionate)-(O-ethyl xanthate) (X1) and the newly synthesized (S)-2-(ethyl isobutyrate)-(O-ethyl xanthate) (X2) were used as the reversible addition-fragmentation chain transfer (RAFT) agents for the radical polymerization of N-vinylpyrrolidone (NVP). The former showed the better chain transfer ability in the polymerization at 60 °C. Kinetics study with X1 shows the psuedo-first order kinetics upto 45% monomer conversion. Molecular weight (M n) of the resulted polymer increases linearly with increase in the monomer conversion upto around 45%. Polydispersity of the corresponding poly(NVP)s increase gradually from 1.2 to 1.9 with increase in the monomer conversion. Chain-end analysis of the resulted polymer by 1H NMR shows clearly that polymerization started with radical forming out of xanthate mediator. Living nature of the polymerization was confirmed from the successful homo chain extension experiment and also the hetero-chain extension experiment involving synthesis of poly(NVP)-b-polystyrene amphiphilic diblock copolymer.

Two series of macroporous poly(N-ethylacrylamide) (PNEAM) gels are synthesized in different composition of methanol-water mixtures (x(m)=0, 0.06, 0.13, 0.21, 0.31, and 0.43; where x(m)=mole fraction of methanol) in presence as well as in the absence of 0.1M Y(OTf)(3) Lewis acid as additive. The gels synthesized in the absence of Lewis acid are atactic and in the presence of the same are isotactic. Synthesis of the corresponding linear PNEAM homopolymers shows that, the isotacticity (meso dyad, %) of the resulted polymers increases for the gels prepared in the presence of Lewis acid (LA) and remains constant for the gel prepared in the absence of LA, respectively, with the increase in the concentration of the synthesis solvent methanol. SEM micrographs reveal that, the hydrogels synthesized in the presence of LA are more porous than the gels prepared in the absence of LA. Swelling ratio of all the hydrogels decreases with the increase in the temperature and LA gels show higher swelling ratio values than non LA gels (NLA). Deswelling rate of the hydrogels prepared in methanol-water mixture in presence of LA is faster than the hydrogels prepared in absence of LA. Moreover, reswelling rate increases with increase in the isotacticity of the PNEAM segment in the gel. All these results have been explained on the basis of the formation of highly porous hydrogels with higher isotactic PNEAM chain segment in the presence of LA in methanol-water mixtures. (c) 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41668.

Random copolymer hydrogels of N-isopropylacrylamide and N-ethylacrylamide (NEAM) were prepared using different monomer compositions in 1:1 methanol–water mixtures. The samples were characterized by cononsolvency study in methanol-water mixtures at various temperatures, swelling properties measurements, scanning electron microscopy. With changing ratio of the monomers in the reaction mixture, the thermal, morphological and swelling properties, varied significantly. The change in the properties with monomer composition variation are interpreted based on the different thermoresponsive characteristics and interactions of gels of N-isopropylacrylamide and NEAM (homo- and copolymer gels) in water and different methanol-water mixtures, their variable compositions in the synthesis mixtures, and their morphologies. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45176.

A series of high molecular weight poly(N-isopropylacrylamide) (PNIPAM)s with low polydispersity (Mn = 7.0 × 104 to 10.2× 104 g mol–1, PDI = 1.23–1.35) having different isotacticity [meso diad (m) =...

WOS: 000347696100012, Macroporous poly(N-ethylacrylamide) (PNEAM) hydrogels have been prepared in a methanol-water (1:1, v/v) mixture in the presence of 0, 0.05, 0.1, 0.15, and 0.2 M yttrium trifluoromethanesulfonate [Y(OTf)(3)] Lewis acid (LA) concentrations. SEM micrographs show that the resulted hydrogels are highly porous. Swelling ratios of all the hydrogels in water decrease with the increase in the temperature, and the hydrogels show lower critical solution temperature (LCST) volume phase transition at around 75 A degrees C. LCST of PNEAM homopolymers gradually increases with the increase in the isotacticity of the polymers. Moreover, the hydrogels show cononsolvency in different methanol-water mixtures at 50 A degrees C. Deswelling rate of the hydrogels prepared in the presence of LA is higher than the gel prepared in the absence of LA and this rate increases with increase in the LA concentration. The reswelling rate of the hydrogels also follows the same order, that is reswelling rate also increases with the increase in the LA loading in the gels. All these results are explained on the basis of the formation of the highly porous hydrogels with a higher isotactic PNEAM chain segment in a methanol-water mixture in the presence of LA., TUBITAK, Government of TurkeyTurkiye Bilimsel ve Teknolojik Arastirma Kurumu (TUBITAK); TUBITAKTurkiye Bilimsel ve Teknolojik Arastirma Kurumu (TUBITAK) [211T016]; Bulent Ecevit University Research FundBulent Ecevit University [BEU-2012-10-03-13], We gratefully acknowledge the financial support from TUBITAK, Government of Turkey, through 2216 fellowship program for the foreign citizens (CSB). This work was also supported by both TUBITAK (grant no. 211T016) and the Bulent Ecevit University Research Fund (#BEU-2012-10-03-13). We personally thank Elvan Sulu for her technical assistance.

Novel amphiphilic ABA-type poly(D-gluconamidoethyl methacrylate)-b-polyurethane-b-poly(D-gluconamidoethyl methacrylate) (PGAMA-b-PU-b-PGAMA) tri-block copolymers were successfully synthesized via the combination of the step-growth and copper-catalyzed atom transfer radical polymerization (ATRP). Dihydroxy polyurethane (HO-PU-OH) was synthesized by the step-growth polymerization of hexamethylene diisocyanate with poly(tetramethylene glycol). PGAMA-b-PU-b-PGAMA block copolymers were synthesized via copper-catalyzed ATRP of GAMA in N, N-dimethyl formamide at 20°C in the presence of 2, 2′-bipyridyl using Br-PU-Br as macroinitiator and characterized by 1H-NMR spectroscopy and GPC. The resulting block copolymer forms spherical micelles in water as observed in TEM study, and also supported by 1H NMR spectroscopy and light scattering. Miceller size increases with increase in hydrophilic PGAMA chain length as revealed by DLS study. The critical micellar concentration values of the resulting block copolymers increased with the increase of the chain length of the PGAMA block. Thermal properties of these block copolymers were studied by thermo-gravimetric analysis, and differential scanning calorimetric study. Spherical Ag-nanoparticles were successfully synthesized using these block copolymers as stabilizer. The dimension of Ag nanoparticle was tailored by altering the chain length of the hydrophilic block of the copolymer. A mechanism has been proposed for the formation of stable and regulated Ag nanoparticle using various chain length of hydrophilic PGAMA block of the tri-block copolymer. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013