Browsing by Author "Niraj Kumar Vishwakarma"

Now showing 1 - 18 of 18

Effects of tacticity and molecular weight of poly(N -isopropylacrylamide) on its glass transition temperature
(2011) Chandra Sekhar Biswas; Vijay Kumar Patel; Niraj Kumar Vishwakarma; Vimal K. Tiwari; Biswajit Maiti; Pralay Maiti; Masami Kamigaito; Yoshio Okamoto; Biswajit Ray
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) = 47-88%]] was successfully synthesized using the reversible addition-fragmentation chain transfer (RAFT) polymerization method in the presence of different concentrations of Y(OTf)3 Lewis acid. Measurement of the glass transition temperature (Tg) of this high molecular weight isotactic PNIPAM series and the low molecular weight PNIPAM series (Mn = 3.5 × - 104 to 4.0 × - 104 g mol-1, PDI = 1.2-1.3) having different isotacticity [meso diad (m) = 45-72%)] reported earlier by us (Ray et al. Polym. J. 2005, 37, 234) showed that Tg of PNIPAM decreases with increase in its meso diad content (m %) and decrease in its molecular weight. © 2011 American Chemical Society.
Erratum: Nanochannel conduction in piezoelectric polymeric membrane using swift heavy ions and nanoclay(RSC Advances(2013) 3 (6147–6159) DOI: 10.1039/C3RA23176C)
(Royal Society of Chemistry, 2013) Karun Kumar Jana; Niraj Kumar Vishwakarma; Biswajit Ray; Saif A. Khan; Devesh K. Avasthi; Manjusri Misra; Pralay Maiti
The authors regret a mistake in Fig. 1a and in the caption of Fig. 1a. Fig. 1a shows SEM images of PVDF and NH surfaces after etching at different fluences. In Fig. 1a of the original manuscript, the panel for PVDF after etching at 1 x 106fluences incorrectly showed a zoomed in section of the panel of PVDF after etching at 1 x 105fluences. © 2022 Royal Society of Chemistry. All rights reserved.
In Vitro Anticancer Drug Delivery Using Amphiphilic Poly(N-vinylpyrrolidone)-b-Polyketal-b-Poly(N-vinylpyrrolidone) Block Copolymer as Micellar Nanocarrier
(Wiley-Blackwell, 2018) Kheyanath Mitra; Sumit Kumar Hira; Shikha Singh; Niraj Kumar Vishwakarma; Sambhav Vishwakarma; Uttam Gupta; Partha Pratim Manna; Biswajit Ray
We have first synthesized acid-degradable alkyne-terminated aliphatic polyketal and thereof synthesized novel pH-responsive double hydrophilic amphiphilic block copolymer of poly(N-vinyl pyrrolidone) (PNVP) and aliphatic polyketal (PK) (PNVP-b-PK-b-PNVP via click chemistry upon reaction with azide-terminated PNVP. Formation of block copolymer is confirmed by proton nuclear magnetic resonance, gel permeation chromatography, thermogravimetry, differential scanning calorimetry, and fluorescence spectroscopy techniques. pH-dependent degradation study of the block copolymer shows faster degradation at lower pH. Transmission electron microscopy (TEM) has revealed the formation of tiny (∼3.8 nm) micellar nanoparticles. Loading of the anticancer drugs doxorubicin (Dox) and imatinib in the micelle is confirmed from UV-Visible, and TEM studies. Drug release study from drug-loaded micelles has shown that imatinib is being released faster than Dox and both systems have shown higher load release at acidic pH of 6.4. Doxorubicin- and imatinib- loaded micelles demonstrate significant tumoricidal properties against parental and drug resistant human erythroleukemia K-562 and Dalton's lymphoma cells with respect to enhanced cellular uptake, cytotoxicity and growth inhibition. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Nanochannel conduction in piezoelectric polymeric membrane using swift heavy ions and nanoclay
(Royal Society of Chemistry, 2013) Karun Kumar Jana; Niraj Kumar Vishwakarma; Biswajit Ray; Saif A. Khan; Devesh K. Avasthi; Manjusri Misra; Pralay Maiti
A poly(vinylidene fluoride) nanohybrid membrane has been prepared using high energy swift heavy ions (SHI) followed by chemical functionalization. Through-channels were generated by selective etching of the amorphous latent track created during irradiation of SHI, whose average dimensions are varied from 52 nm in pure PVDF to 40 nm for the nanohybrid in the presence of nanoclay, indicating suitable membrane formation using the nanohybrid, as compared to pure PVDF. The nanochannels were suitably grafted with conducting polymer (pyrrole) using the active free radicals caused by SHI irradiation. Spectroscopic and gel permeation chromatographic experiments have been performed to understand the effect of irradiation on filled polymer and subsequent functionalization. Doping and sulphonation on the grafted species has been done to introduce a variety of functionalities. The effect of fluence on the channel width and functionalization study indicates a larger diameter of the channels and formation of a greater ionomer at higher fluence, leading to enhancement of the bulk electrical conductivity up to 10-3 S cm-1 (12 orders higher in magnitude than pure PVDF). The activation energy of the modified nanohybrid membrane is calculated to be 26.9 kJ mol-1, compared to 10.6 kJ mol-1 of pure PVDF, indicating superior stability of the nanohybrid membrane at higher temperature as compared to pure PVDF or functionalized PVDF under similar conditions. The nanohybrid conducting membrane produces a current of 46 nA compared to a value of almost zero for pristine PVDF or NH measured through I-V characteristic curves against a bias voltage of 10 V, making the nanohybrid suitable for electrochemical applications. © 2013 The Royal Society of Chemistry.
(S)-2-(Ethyl propionate)-(O-ethyl xanthate) and (S)-2-(ethyl isobutyrate)-(O-ethyl xanthate)-mediated RAFT polymerization of N-vinylpyrrolidone
(2010) Vijay Kumar Patel; Avnish Kumar Mishra; Niraj Kumar Vishwakarma; Chandra Sekhar Biswas; Biswajit Ray
(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 (Mn) 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 by1H 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 heterochain extension experiment involving synthesis of poly(NVP)-b-polystyrene amphiphilic diblock copolymer. © Springer-Verlag 2009.
(S)-2-(ethyl propionate)-(O-ethyl xanthate)- and (S)-2-(Ethyl isobutyrate)-(O-ethyl xanthate)-mediated RAFT polymerization of vinyl acetate
(2012) Vijay Kumar Patel; Niraj Kumar Vishwakarma; Avnish Kumar Mishra; Chandra Sekhar Biswas; Biswajit Ray
(S)-2-(Ethyl propionate)-(O-ethyl xanthate) (X1) and (S)-2-(Ethyl isobutyrate)-(O-ethyl xanthate) (X2) were used as the reversible addition-fragmentation chain transfer (RAFT) agents for the radical polymerization of vinyl acetate (VAc). The former showed the better chain transfer ability in the polymerization at 60°C. Kinetic study with both RAFT agents showed pseudo-first order kinetics up to around 85% monomer conversion. Molecular weight of the resulting polymer increased linearly with increase in the monomer conversion up to around 85%. The observed molecular weights calculated from 1H-NMR spectrum [M n(NMR)] are close to the corresponding theoretical molecular weights [M n(theor)]. The corresponding polydispersity index (PDI) of the resulting polymers remained almost constant at around 1.2 up to ∼ 65% monomer conversion and then increased gradually with the further increase in the monomer conversion. Chain-end analysis of the resulting polymers by 1H-NMR showed clearly that polymerization started with the radical forming out of the xanthate mediator. The negligible homo-chain extension and the hetero-chain extension involving synthesis of poly(VAc)-b-poly(NVP) diblock copolymer were occurred. © 2012 Wiley Periodicals, Inc.
Synthesis and characterization of porous poly(N-isopropylacrylamide) hydrogels prepared in ethanol-water mixtures
(2011) Chandra Sekhar Biswas; Vijay Kumar Patel; Niraj Kumar Vishwakarma; Avnish Kumar Mishra; Biswajit Ray
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 â X0.68 > X 0.48 > 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 > X 0.04 > X0. The reswelling rates of these hydrogels decreased in the following order: X0 > X0.04 â X0.48 > X0.09 â 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.
Synthesis and characterization of stereocontrolled poly(N -isopropylacrylamide) hydrogel prepared in the presence of Y(OTf)3 lewis acid
(2010) Chandra Sekhar Biswas; Vijay Kumar Patel; Niraj Kumar Vishwakarma; Avnish Kumar Mishra; Satyen Saha; Biswajit Ray
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. © 2010 American Chemical Society.
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
(2012) Chandra Sekhar Biswas; Niraj Kumar Vishwakarma; Vijay Kumar Patel; Avnish Kumar Mishra; Satyen Saha; Biswajit Ray
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. © 2012 American Chemical Society.
Synthesis of ABA-type double hydrophilic amphiphilic PU-based block copolymers of poly(N-Vinylpyrrolidone) and poly(N-isopropylacrylamide) via click chemistry
(Bellwether Publishing, Ltd., 2021) Niraj Kumar Vishwakarma; Vijay Kumar Patel; Payel Mitra; K. Ramesh; Kheyanath Mitra; Sambhav Vishwakarma; Krishnendu Acharya; Nira Misra; Pralay Maiti; Biswajit Ray
Double hydrophilic ABA-type amphiphilic polyurethane (PU)-based poly(N-vinylpyrrolidone) (PNVP)-b-PU-b-PNVP and poly(N-isopropylacrylamide) (PNIPAM)-b-PU-b-PNIPAM triblock copolymers have successfully been synthesized via the combination of the step-growth polymerization, reversible addition-fragmentation chain transfer (RAFT) polymerization and azide-alkyne click reaction. All polymers are characterized by 1H NMR, FTIR, and gel permeation chromatography. The cmcs of PNVP-b-PU-b-PNVP block copolymers increase with increase in PNVP block length: 0.0019 mg/mL for PNVP39-b-PU-b-PNVP39 and 0.005 mg/mL for PNVP68-b-PU-b-PNVP68. The iron-chelating ability and the reducing power of PNVP68-b-PU-b-PNVP68 are superior to that of PNVP owing to the presence of urethane moiety of PU block in copolymer. The LCST of PNIPAM-b-PU-b-PNIPAM are lower than that of PNIPAM (33 °C): 23.5 and 25.5 °C for PNIPAM42-b-PU-b-PNIPAM42 and PNIPAM66-b-PU-b-PNIPAM66, respectively. © 2020 Taylor & Francis Group, LLC.
Synthesis of alkyne-terminated xanthate RAFT agents and their uses for the controlled radical polymerization of N-vinylpyrrolidone and the synthesis of its block copolymer using click chemistry
(2013) Vijay Kumar Patel; Niraj Kumar Vishwakarma; Avnish Kumar Mishra; Chandra Sekhar Biswas; Pralay Maiti; Biswajit Ray
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) (X 4) 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 Copyright © 2012 Wiley Periodicals, Inc.
Synthesis of fluorescence poly(N -vinylpyrrolidone) via click chemistry using azide-terminated xanthate mediator (S)-2-(4-azidobutyl propionate)-(O -ethyl xanthate)
(Taylor and Francis Inc., 2016) Vijay Kumar Patel; Niraj Kumar Vishwakarma; Shikha Singh; Kheyanath Mitra; K. Ramesh; Nira Mishra; Biswajit Ray
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. © 2016 Copyright Taylor & Francis Group, LLC.
Synthesis of well-defined amphiphilic poly(d,l-lactide)-b-poly(N- vinylpyrrolidone) block copolymers using ROP and xanthate-mediated RAFT polymerization
(Elsevier Ltd, 2012) K. Ramesh; Avnish Kumar Mishra; Vijay Kumar Patel; Niraj Kumar Vishwakarma; Chandra Sekhar Biswas; Tapas Kumar Paira; Tarun Kumar Mandal; Pralay Maiti; Nira Misra; Biswajit Ray
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 1H NMR spectroscopy and GPC. Spherical micelles of ∼30.2 nm diameter were formed from the aqueous solution of amphiphilic diblock copolymer PDLLA42-b-PNVP63 as revealed by TEM and supported by 1H 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 (Rh) 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. © 2012 Elsevier Ltd. All rights reserved.
Synthesis of well-defined amphiphilic poly(ε-caprolactone)-b-poly(N- vinylpyrrolidone) block copolymers via the combination of ROP and xanthate-mediated RAFT polymerization
(2011) Avnish Kumar Mishra; Vijay Kumar Patel; Niraj Kumar Vishwakarma; Chandra Sekhar Biswas; Manoj Raula; Arvind Misra; Tarun Kumar Mandal; Biswajit Ray
Well-defined amphiphilic poly(ε-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(ε-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 NMR spectroscopy, and light scattering. The critical micellar concentrations were determined by fluorescence spectroscopy using pyrene as probe. The critical micelle concentration (cmc) value of the block copolymers increases with the increase in the chain length of PNVP block. The overall hydrodynamic radius (Rh) of the micelles remains almost constant over the concentration range above the cmc value and over the angles of scattering measurement. © 2011 American Chemical Society.
Synthesis, characterization, and application of novel amphiphilic poly(D-gluconamidoethyl methacrylate)-b-polyurethane-b-poly(D-gluconamidoethyl methacrylate) triblock copolymers
(2013) Niraj Kumar Vishwakarma; Avnish Kumar Mishra; Abhinay Mishra; Tapas Paira; Vijay Kumar Patel; Chandra Sekhar Biswas; Tarun Kumar Mandal; Pralay Maiti; Biswajit Ray
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.
Synthesis, characterization, and drug release properties of poly(N-isopropylacrylamide) gels prepared in methanol-water cononsolvent medium
(2012) Chandra Sekhar Biswas; Vijay Kumar Patel; Niraj Kumar Vishwakarma; Avnish Kumar Mishra; Rajasekhar Bhimireddi; Ramanand Rai; Biswajit Ray
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: X 0.43>X 0.21>X 0.76 ≈ X 0.57>X 0.31>X 0.13>X 0.06>X 0, where X m denotes a gel prepared in a methanol-water mixture with m mole fraction of methanol (x m). 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 x m values at 20°C passed through a minimum in the cononsolvency zone. The deswelling rates of the hydrogels decreased in the following order: X 0.43> X 0.31> X 0.21> X 0.57> X 0.76 â≈ X 0.13> X 0.06> X 0. The reswelling rates of these hydrogels decreased in the following order: X 0> X 0.31> X 0.06 ≈ X 0.13 > X 0.76> X 0.57> X 0.21> X 0.43. 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.
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
(Springer Verlag, 2014) Avnish Kumar Mishra; Niraj Kumar Vishwakarma; Vijay Kumar Patel; Chandra Sekhar Biswas; Tapas Kumar Paira; Tarun Kumar Mandal; Pralay Maiti; Biswajit Ray
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. © 2014 Springer-Verlag.
Tadpole-shaped β-cyclodextrin-tagged poly(N-vinylpyrrolidone): Synthesis, characterization and studies of its complexation with phenolphthalein and anti tumor activities
(Royal Society of Chemistry, 2015) Niraj Kumar Vishwakarma; Vijay Kumar Patel; Sumit Kumar Hira; K. Ramesh; Prateek Srivastava; Kheyanath Mitra; Shikha Singh; Dipankar Chattopadhyay; Pralay Maiti; Nira Misra; Partha Pratim Manna; Biswajit Ray
Tadpole-shaped β-cyclodextrin-tagged poly(N-vinylpyrrolidone) (β-CD-PNVP) has been synthesised via the click reaction of alkyne-terminated PNVP and azide-functionalized β-CD. The formed polymer is characterized by 1H NMR, FTIR, and TGA study. The complexing ability of such a polymer with phenolphthalein is considerably lower with respect to that with β-CD alone. Doxorubicin (DOX)-loaded β-CD-PNVP (DOX-β-CD-PNVP) exhibits higher tumoricidal activity against a panel of tumor cell lines derived from sarcoma (U2-OS) and carcinomas (MCF-7 and HEPG2), causing significant lysis of tumor cells compared to free DOX. The formulation also demonstrates significantly higher uptake by the tumor cells and enhances apoptosis compared to free DOX. This journal is © The Royal Society of Chemistry.