Vijay Kumar Patel

Synthesis and Characterization of Stereocontrolled Poly(N-isopropylacrylamide) Hydrogel Prepared in the Presence of Y(OTf)3 Lewis Acid

Macroporous poly(N-isopropylacrylamide) (PNIPAM) hydrogels have been prepared in methanol-water (1:1, v/v) mixture in the presence of 0, 0.05, 0.1, 0.15, and 0.2 M Y(OTf)(3) Lewis acid concentrations. Synthesis of the corresponding linear PNIPAM homopolymers in the absence of a cross-linker keeping all other conditions the same shows that the isotacticity (meso dyad, %) and the cloud point temperature of the resulted in polymers increases and decreases, respectively, with the increase in the concentration of the Lewis acid. SEM micrographs reveal that the resulted hydrogels are highly porous. Swelling ratios of all the hydrogels in water decrease with the increase in the temperature. Moreover, swelling ratios of all the hydrogels in different methanol-water mixtures pass through a minimum in the co-nonsolvency zone, and the co-nonsolvency zone shifts toward the lower methanol-content solvent mixture with gradual increase in the Lewis acid concentration. Deswelling rate of the hydrogel prepared in methanol-water (1:1, v/v) mixture is much faster than that of the conventional hydrogel prepared in water. Moreover, the deswelling rate slightly increases with the hydrogels prepared with the increasing concentrations of Lewis acid. But, the reswelling rate of the hydrogels follows almost the reverse order. All these results have been explained on the basis of the formation of highly porous hydrogels with higher isotactic PNIPAM chain segment owing to the faster polymerization rate in the methanol-water mixture in the presence of Lewis acid and the co-nonsolvency behavior of the methanol-water (1:1, v/v) mixture toward PNIPAM chain segment in the PNIPAM hydrogel.

Synthesis and study of the properties of stereocontrolled poly(N-isopropylacrylamide) gel and its linear homopolymer prepared in the presence of a Y(OTf)3 Lewis acid: effect of the composition of methanol-water mixtures as synthesis media.

Poly(N-isopropylacrylamide) (PNIPAM) hydrogels and the corresponding linear homopolymers were synthesized in different methanol-water mixtures (x(m) = 0, 0.13, 0.21, 0.31, 0.43, 0.57, and 0.76, where x(m) is the mole fraction of methanol) in the presence of 0.1 M Y(OTf)(3) Lewis acid. The isotacticity (meso dyad (m), %) and cloud-point temperature of these homopolymers were gradually increased and decreased, respectively, with the increase in the x(m) values of the synthesis solvent mixtures. Moreover, the corresponding linear PNIPAM homopolymers prepared in the absence of Y(OTf)(3) showed an almost constant isotacticity of m = 45% and a cloud-point temperature of 33.0 °C. A SEM study revealed that the resulting hydrogels were highly porous except for the gels prepared at x(m) = 0 and 0.76. The swelling ratios of these hydrogels in water at different temperatures and in different methanol-water mixtures at 20 °C and the deswelling rate and the reswelling rate of these hydrogels were studied. All of these swelling results were compared with that of the corresponding gels prepared in the absence of a Lewis acid (Biswas, C. S.; Patel, V. K.; Vishwakarma, N. K.; Mishra, A. K.; Bhimireddi, R.; Rai, R.; Ray, B. J. Appl. Polym. Sci.2012, DOI: 10.1002/app.36318) and explained on the basis of the porosity of the gel, the state of aggregation and isotacticity of the PNIPAM chain segment, and the cononsolvency of the methanol-water mixture toward the PNIPAM chain segment.

Interaction of imidazolium based ionic liquids with Triton X-100 micelles: investigating the role of the counter ion and chain length

The micellar characteristics of an aqueous solution of the polyoxyethylene based alkyl aryl type non-ionic surfactant Triton X-100 (TX-100) in the presence of several 1-alkyl-3-methylimidazolium (Cnmim+) based non-amphiphilic, amphiphilic and biamphiphilic ionic liquids (ILs) varying in the alkyl chain length of the cation (C4–C10) and different anions viz. chloride [Cl−], tetrafluoroborate [BF4−], trifluoromethanesulfonate [CF3SO3−], hexaflurophosphate [PF6−] and octylsuphate [C8SO4−] have been systematically investigated by cloud point (CP), viscosity, dynamic light scattering (DLS), nuclear magnetic resonance (NMR), fluorescence and small-angle neutron scattering (SANS) measurements. These ILs interact with TX-100 micelles on account of their hydrophobicity; ILs with a hydrophilic counter ion (Cl−) favour demicellization, increase CP, decrease the solution viscosity and apparent hydrodynamic diameter (Dh) of micelle, whereas ILs with a hydrophobic counter ion (PF6−) increase the solution viscosity and exhibit micellar growth. SANS data on the size/shape of TX-100 micelles in the presence of different ILs are reported to provide information on microstructural changes in the micelles. The location of ILs, which has a dominating effect on the structure of the micelles, was evaluated using fluorescence and 1H NMR studies, and these results are discussed in terms of the insertion of the ILs in TX-100 micelles. IL molecules with long alkyl chains penetrate deeper in the TX-100 micelles. The present study provides useful information on tuning the solution characteristics of TX-100 in the presence of ILs that may have industrial applications.

1-Hexanol triggered structural characterization of the worm-like micelle to vesicle transitions in cetyltrimethylammonium tosylate solutions

The cationic surfactant cetyltrimethylammonium tosylate (CTAT) forms highly viscous/viscoelastic solutions and worm-like micelles at relatively low concentrations. The effect of 1-alkanols with short to long alkyl chains viz. ethanol, 1-butanol, 1-hexanol and 1-octanol on CTAT micelles was examined. In particular, a detailed study on the effect of 1-hexanol was carried out by viscosity, cryogenic transmission electron microscopy (cryo-TEM), nuclear magnetic resonance (NMR) and small-angle neutron scattering (SANS) to observe microstructural changes in CTAT micelles. 1-Hexanol displays a distinct interaction with CTAT micelles strongly dependent on CTAT concentration. Up to a certain critical CTAT concentration, 1-hexanol molecules penetrate into the micelles and show growth. Characterization by direct cryo-TEM imaging implies that upon progressive addition of 1-hexanol, worm-like CTAT micelles first grow and finally transform into vesicles. The course of vesicle formation was followed by SANS measurements. The site of 1-hexanol in the micelles close to the palisade layer was evaluated using 2D NMR. This study devotes a fundamental knowledge for controlling the shape and size of worm-like micelles that find many industrial applications particularly in personal- and home-care products.

Synthesis, characterization, and solution behavior of well-defined double hydrophilic linear amphiphilic poly ( N -isopropylacrylamide)- b -poly ( ε -caprolactone)- b -poly ( N -isopropylacrylamide) triblock copolymers

Well-defined linear dihydrophilic amphiphilic ABA-type triblock copolymers of ε-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 (Tg), and melting temperature (Tm) peaks possibly due to the partial miscibility of the poly (ε-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.

Synthesis of fluorescence poly(N-vinylpyrrolidone) via click chemistry using azide-terminated xanthate mediator (S)-2-(4-azidobutyl propionate)-(O-ethyl xanthate)

ABSTRACT Azide-terminated xanthate RAFT agent (S)-2-(4-azidobutyl propionate)-(O-ethyl xanthate) has been synthesized and used for the controlled radical polymerization of N-vinylpyrrolidone (NVP). Kinetics study showed the pesudo first-order kinetics along with gradual increase in molecular weight (Mn) of the resulted polymer up to 69% conversion. Chain-end analysis of the resulted polymer by 1H NMR showed the presence of the fragments of xanthate mediator at both chain ends. Successful chain extension has also been performed via the click reaction of alkyne-terminated PNVP with azide-terminated PNVP. Moreover, fluorescence pyrene-tagged PNVP has successfully been made via the click reaction of alkyne-functionalized pyrene with azide-terminated PNVP. GRAPHICAL ABSTRACT