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Lower Critical Solution Temperature (lower + critical_solution_temperature)
Selected AbstractsSalt-Induced Depression of Lower Critical Solution Temperature in a Surface-Grafted Neutral Thermoresponsive PolymerMACROMOLECULAR RAPID COMMUNICATIONS, Issue 9 2006Young K. Jhon Abstract Summary: Quartz crystal microbalance with dissipation monitoring (QCM-D) is employed to determine the effect of salt on the volume phase transition of thermoresponsive polymer brushes. Changes in mass and viscoelasticity of poly(N -isopropylacrylamide) (PNIPAM) layers grafted from a QCM-D crystal are measured as a function of temperature, upon contact with aqueous solutions of varying salt concentrations. The phase-transition temperature of PNIPAM brushes, TC,graft, quantified from the QCM-D measurements is found to decrease as the concentration of salt is increased. This phenomenon is explained by the tendency of salt ions to affect the structure of water molecules (Hofmeister effect). However, in contrast to the linear decrease in phase-transition temperature upon increasing salt concentration observed for free PNIPAM, the trend in TC,graft for PNIPAM brushes is distinctively non-linear. Schematic representation of the effect of salt concentration on the phase transition behavior of thermoresponsive polymer brushes. [source] Accurate Prediction of , (Lower Critical Solution Temperature) in Polymer Solutions Based on 3D Descriptors and Artificial Neural NetworksMACROMOLECULAR THEORY AND SIMULATIONS, Issue 2-3 2008Jie Xu Abstract Quantitative structure-property relationships were studied between descriptors representing the three-dimensional structures of molecules and , (LCST, lower critical solution temperature) in polymer solutions with a database of 169 data containing 12 polymers and 67 solvents. Feed-forward artificial neural networks (ANNs) combined with stepwise multilinear regression analysis (MLRA) were used to develop the models. With ANNs, the squared correlation coefficient (R2) for , (LCST) of the training set of 112 systems is 0.9625, the standard error of estimation (SEE) is 13.43 K, and the mean relative error (MRE) is 1.99%; in prediction of , (LCST) using the test set of 57 systems, the MRE is 2.26%. With MLRA, the MREs for the training and test sets are 4.02% (R2,=,0.8739, SEE,=,25.88 K) and 5.05%, respectively. [source] Hybrid Polymerization of Vinyl and Hetero-Ring Groups of Glycidyl Methacrylate Resulting in Thermoresponsive Hyperbranched Polymers Displaying a Wide Range of Lower Critical Solution TemperaturesCHEMISTRY - A EUROPEAN JOURNAL, Issue 31 2009Zhifeng Jia Dr. Abstract Hybrid polymerization of glycidyl methacrylate (GMA) with potassium hydride (KH) and various oligo(ethylene glycol)s as the initiating system, in which both vinyl polymerization and ring-opening polymerization occur simultaneously, generates hyperbranched poly(ether-ester)s. The reaction process has been followed by an in situ nuclear magnetic resonance technique. The experimental results indicate that both the vinyl and epoxy groups of GMA undergo polymerization, with the reactivity of the latter being much higher than that of the former. Interestingly, the resulting hyperbranched polymers exhibit a sharp phase transition in water at the lower critical solution temperature (LCST). Significantly, the LCST values can be accurately controlled from 0 to 100,°C by changing the hydrophilic/hydrophobic balance of GMA and various oligo(ethylene glycol)s or by modification of the precursor polymer through acetylation. This novel stimuli-responsive hyperbranched polymer is a promising candidate for a new generation of commercially viable thermoresponsive polymers following on from the widely used poly(N- isopropylacrylamide) (PNIPAM). [source] Lower critical solution temperatures of thermo-responsive poly(N -isopropylacrylamide) copolymers with racemate or single enantiomer groupsPOLYMER INTERNATIONAL, Issue 2 2009Peng-Fei Li Abstract BACKGROUND: Thermo-responsive copolymers with racemate or single enantiomer groups are attracting increasing attention due to their fascinating functional properties and potential applications. However, there is a lack of systematic information about the lower critical solution temperature (LCST) of poly(N -isopropylacrylamide)-based thermo-responsive chiral recognition systems. In this study, a series of thermo-responsive chiral recognition copolymers, poly[(N -isopropylacrylamide)- co -(N -(S)- sec -butylacrylamide)] (PN- S -B) and poly[(N -isopropylacrylamide)- co -(N -(R,S)- sec -butylacrylamide)] (PN- R,S -B), with different molar compositions, were prepared. The effects of heating and cooling processes, optical activity and amount of chiral recognition groups in the copolymers on the LCSTs of the prepared copolymers were systematically studied. RESULTS: LCST hysteresis phenomena are found in the phase transition processes of PN- S -B and PN- R,S -B copolymers in a heating and cooling cycle. The LCSTs of PN- S -B and PN- R,S -B during the heating process are higher than those during the cooling process. With similar molar ratios of N -isopropylacrylamide groups in the copolymers, the LCST of the copolymer containing a single enantiomer (PN- S -B) is lower than that of the copolymer containing racemate (PN- R,S -B) due to the steric structural difference. The LCSTs of PN- R,S -B copolymers are in inverse proportion to the molar contents of the hydrophobic R,S -B moieties in these copolymers. CONCLUSION: The results provide valuable guidance for designing and fabricating thermo-responsive chiral recognition systems with desired LCSTs. Copyright © 2008 Society of Chemical Industry [source] Preparation and Characterization of a pH- and Thermally Responsive Poly(N -isopropylacrylamide- co -acrylic acid)/Porous SiO2 HybridADVANCED FUNCTIONAL MATERIALS, Issue 5 2010Loren A. Perelman Abstract A multifunctional nanohybrid composed of a pH- and thermoresponsive hydrogel, poly(N -isopropylacrylamide- co -acrylic acid) [poly(NIPAM- co -AAc)], is synthesized in situ within the mesopores of an oxidized porous Si template. The hybrid is characterized by electron microscopy and by thin film optical interference spectroscopy. The optical reflectivity spectrum of the hybrid displays Fabry,Pérot fringes characteristic of thin film optical interference, enabling direct, real-time observation of the pH-induced swelling, and volume phase transitions associated with the confined poly(NIPAM- co -AAc) hydrogel. The optical response correlates to the percentage of AAc contained within the hydrogel, with a maximum change observed for samples containing 20% AAc. The swelling kinetics of the hydrogel are significantly altered due to the nanoscale confinement, displaying a more rapid response to pH or heating stimuli relative to bulk polymer films. The inclusion of AAc dramatically alters the thermoresponsiveness of the hybrid at pH 7, effectively eliminating the lower critical solution temperature (LCST). The observed changes in the optical reflectivity spectrum are interpreted in terms of changes in the dielectric composition and morphology of the hybrids. [source] A Thermoresponsive Membrane for Chiral Resolution,ADVANCED FUNCTIONAL MATERIALS, Issue 4 2008Mei Yang Abstract A novel thermoresponsive membrane for chiral resolution with high performance has been developed. The membrane exhibits chiral selectivity based on molecular recognition of beta-cyclodextrin (, -CD) and thermosensitivity based on the phase transition of poly(N -isopropylacrylamide) (PNIPAM). Linear PNIPAM chains were grafted onto porous nylon-6 membrane substrates by using a plasma-graft pore-filling polymerization method; the chains thus acted as microenvironmental adjustors for , -CD molecules. , -CD moieties were introduced into the linear PNIPAM chains by a chemical grafting polymerization method and acted as chiral selectors. The phase transition of grafted PNIPAM chains affects the microenvironment of , -CD molecules and, thus, the association between , -CD and guest molecules. The chiral selectivity of the prepared thermoresponsive membranes in chiral resolution operated at temperature below the lower critical solution temperature (LCST) of PNIPAM is higher than that of membranes with no thermosensitivity. Furthermore, the decomplexation ratio of enantiomer-loaded thermoresponsive membranes in decomplexation at temperatures above the LCST is much higher than that of membranes with no thermosensitivity. Thus, by simply changing the operation temperature, high, selective chiral resolution and efficient membrane regeneration are achieved. The proposed membrane provides a new and efficient way to solve the difficult decomplexation problem of chiral solid membranes, which is highly attractive for chiral resolution. [source] Thermally Responsive Biomineralization on Biodegradable Substrates,ADVANCED FUNCTIONAL MATERIALS, Issue 16 2007J. Shi Abstract Biomineralization offers an elegant example of how nature can design complex, hierarchical, and structurally/morphologically controllable materials. In this work, the surface of bioactive substrates prepared from poly(L -lactic acid) and reinforced with Bioglass are modified by the graft polymerization of poly(N -isopropylacrylamide), (PNIPAAm) after plasma activation. It is found that such treatment, together with temperature, could trigger the formation of apatite on the biodegradable substrate upon immersion in simulated body fluid above the PNIPAAm lower critical solution temperature (LCST); in contrast, no apatite is formed at room temperature. A control experiment on a material that is not subjected to surface treatment does not show any evidence of mineral deposition at the two analyzed temperatures. This "smart" biomineralization concept is combined with patterning methodologies to control the microstructure of the surface onto which PNIPAAm is grafted. In this case, the apatite is formed at 37,°C in the modified regions. We suggest that this concept could be extended in the biomimetic production of other minerals, where it would be triggered by another kind of stimulus (e.g., pH or ionic strength) in substrates with more complex geometries. [source] A Novel Approach to Observing Synergy Effects of PHSRN on Integrin,RGD Binding Using Intelligent Surfaces,ADVANCED MATERIALS, Issue 16 2008Mitsuhiro Ebara A novel assay for measuring time-dependant ligand-receptor affinity changes is developed based on a peptide-immobilized temperature-responsive surface, as schematically illustrated in the figure. The grafted thermoresponsive polymer acts as an "on-off" switch for mediating integrin,peptide bonding. At temperatures above and below the lower critical solution temperature (LCST), the peptides are accessible and shielded from integrin access, respectively. [source] Synthesis and characterization of temperature-sensitive block copolymers from poly(N -isopropylacrylamide) and 4-methyl-,-caprolactone or 4-phenyl-,-caprolactoneJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2010Ren-Shen Lee Abstract This study synthesizes thermally sensitive block copolymers poly(N -isopropylacrylamide)- b -poly(4-methyl-,-caprolactone) (PNIPA- b -PMCL) and poly(N -isopropylacrylamide)- b -poly(4-phenyl-,-caprolactone) (PNIPA- b -PBCL) by ring-opening polymerization of 4-methyl-,-caprolactone (MCL) or 4-phenyl-,-caprolactone (BCL) initiated from hydroxy-terminated poly(N -isopropylacrylamide) (PNIPA) as the macroinitiator in the presence of SnOct2 as the catalyst. This research prepares a PNIPA bearing a single terminal hydroxyl group by telomerization using 2-hydroxyethanethiol (ME) as a chain-transfer agent. These copolymers are characterized by differential scanning calorimetry (DSC), 1H-NMR, FTIR, and gel permeation chromatography (GPC). The thermal properties (Tg) of diblock copolymers depend on polymer compositions. Incorporating larger amount of MCL or BCL into the macromolecular backbone decreases Tg. Their solutions show transparent below a lower critical solution temperature (LCST) and opaque above the LCST. LCST values for the PNIPA- b -PMCL aqueous solution were observed to shift to lower temperature than that for PNIPA homopolymers. This work investigates their micellar characteristics in the aqueous phase by fluorescence spectroscopy, transmission electron microscopy (TEM), and dynamic light scattering (DLS). The block copolymers formed micelles in the aqueous phase with critical micelle concentrations (CMCs) in the range of 0.29,2.74 mg L,1, depending on polymer compositions, which dramatically affect micelle shape. Drug entrapment efficiency and drug loading content of micelles depend on block polymer compositions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] The totally miscible in ternary hydrogen-bonded polymer blend of poly(vinyl phenol)/phenoxy/phenolicJOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2009Shiao-Wei KuoArticle first published online: 28 MAY 200 Abstract The individual binary polymer blends of phenolic/phenoxy, phenolic/poly(vinyl phenol) (PVPh), and phenoxy/PVPh have specific interaction through intermolecular hydrogen bonding of hydroxyl,hydroxyl group to form homogeneous miscible phase. In addition, the miscibility and hydrogen bonding behaviors of ternary hydrogen bond blends of phenolic/phenoxy/PVPh were investigated by using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy, and optical microscopy. According to the DSC analysis, every composition of the ternary blend shows single glass transition temperature (Tg), indicating that this ternary hydrogen-bonded blend is totally miscible. The interassociation equilibrium constant between each binary blend was calculated from the appropriate model compounds. The interassociation equilibrium constant (KA) of each individually binary blend is higher than any self-association equilibrium constant (KB), resulting in the hydroxyl group tending to form interassociation hydrogen bond. Photographs of optical microscopy show this ternary blend possess lower critical solution temperature (LCST) phase diagram. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source] Grafting of poly(N -isopropylacrylamide) onto nylon and polystyrene surfaces by atmospheric plasma treatment followed with free radical graft copolymerizationJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2007Xiaoling Wang Abstract Stimuli-responsive polymer materials (SRPs) have potential uses in drug delivery, tissue engineering, bioreactors, and cell-surface adhesion control. Temperature-responsive surfaces were fabricated by grafting poly(N -isopropylacrylamide) (PNIPAM) onto nylon and polystyrene surfaces via a new procedure, i.e., He atmospheric plasma treatment followed by free radical graft copolymerization. The atmospheric plasma exhibits the activation capability to initiate graft copolymerization. The procedure is suitable for integration into a continuous manufacturing process. To reduce homopolymerization and enhance graft yield, Mohr's salt was added. The graft of PNIPAM was confirmed by Fourier transform infrared spectroscopy and atomic force microscopy. Dramatic water contact angle increase was found for PNIPAM-grafted polymers at about 32°C, indicating the temperature sensitivity of the grafted surface, i.e., the change of surface from hydrophilic to hydrophobic when temperature increases above the lower critical solution temperature (LCST). The addition of Mohr's salt enhances the grafting reaction and the magnitude of temperature sensitivity. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3614,3621, 2007 [source] Flow characteristics of thermo-responsive microspheres in microchannel during the phase transitionAICHE JOURNAL, Issue 6 2009Ming-Yu Zhou Abstract To probe into the flow and aggregation behaviors of thermo-responsive microspheres in microchannel during the phase transition, the flow characteristics of monodisperse poly(n -isopropylacrylamide) (PNIPAM) microspheres in microchannel with local heating are investigated systematically. When the fluid temperature in the microchannel increases across the lower critical solution temperature (LCST), the PNIPAM microspheres finish the phase transition within 10 s and are easily get aggregated during the phase transition. The diameter ratio of microsphere to microchannel, number of microspheres, initial distance between microspheres, and flow direction of fluid in microchannel, are key parameters affecting the flow and aggregation behaviors of the microspheres in microchannel during the phase transition. If a proper combination of these parameters is designed, the microspheres can aggregate together during the phase transition and stop automatically at a desired position in the microchannel by local heating, which is what the targeting drug delivery system expected. © 2009 American Institute of Chemical Engineers AIChE J, 2009 [source] Thermoresponsive transport through porous membranes with grafted PNIPAM gatesAICHE JOURNAL, Issue 4 2003Liang-Yin Chu Both thermoresponsive flat membranes and core-shell microcapsule membranes, with a porous membrane substrate and grafted poly(N-isopropylacrylamide) (PNIPAM) gates, were successfully prepared using a plasma-graft pore-filling polymerization method. PNIPAM was proven to be grafted homogeneously onto the porous membrane substrates, in the direction of both the membrane thickness and surface. Regardless of the solute molecular size, temperature had an opposite effect on diffusion coefficients of the solute across the PNIPAM-grafted membranes with low graft yields as opposed to those with high graft yields. The PE-g-PNIPAM membranes change from positive thermo-response to negative thermoresponse types with increasing pore-filling ratios at around 30%. Phenomenological models were developed for predicting the diffusion coefficient of the solute across PNIPAM-grafted membranes at temperatures, both above and below the lower critical solution temperature (LCST). Predicted diffusional coefficients of solutes across both the PNIPAM-grafted flat and PNIPAM-grafted microcapsule membranes fit the experimental values. To obtain an ideal result for the diffusional thermoresponsive controlled release through PNIPAM-grafted membranes, the substrates strong enough to prevent any conformation changes are more suitable for preparing thermoresponsive membranes than weak ones. [source] Water-soluble, thermoresponsive, hyperbranched copolymers based on PEG-methacrylates: Synthesis, characterization, and LCST behaviorJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 13 2010Mario Luzon Abstract A series of water-soluble thermoresponsive hyperbranched copoly(oligoethylene glycol)s were synthesized by copolymerization of di(ethylene glycol) methacrylate (DEG-MA) and oligo(ethylene glycol) methacrylate (OEG-MA, Mw = 475 g/mol), with ethylene glycol dimethacrylate (EGD-MA) used as the crosslinker, via reversible addition fragmentation chain transfer polymerization. Polymers were characterized by size exclusion chromatography and nuclear magnetic resonance analyses. According to the monomer composition, that is, the ratio of OEG-MA: DEG-MA: EGD-MA, the lower critical solution temperature (LCST) could be tuned from 25 °C to 90 °C. The thermoresponsive properties of these hyperbranched copolymers were studied carefully and compared with their linear analogs. It was found that molecular architecture influences thermoresponsive behavior, with a decrease of around 5,10 °C in the LCST of the hyperbranched polymers compared with the LCST of linear chains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2783,2792, 2010 [source] Water-soluble triply-responsive homopolymers of N,N -dimethylaminoethyl methacrylate with a terminal azobenzene moietyJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 12 2010Xinde Tang Abstract Novel water-soluble triply-responsive homopolymers of N,N -dimethylaminoethyl methacrylate (DMAEMA) containing an azobenzene moiety as the terminal group were synthesized by atom transfer radical polymerization (ATRP) technique. The ATRP process of DMAEMA was initiated by an azobenzene derivative substituted with a 2-bromoisobutyryl group (Azo-Br) in the presence of CuCl/Me6TREN in 1,4-dioxane as a catalyst system. The molecular weights and their polydispersities of the resulting homopolymers (Azo-PDMAEMA) were characterized by gel permeation chromatography (GPC). The homopolymers are soluble in aqueous solution and exhibit a lower critical solution temperature (LCST) that alternated reversibly in response to Ph and photoisomerization of the terminal azobenzene moiety. It was found that the LCST increased as pH decreased in the range of testing. Under UV light irradiation, the trans -to- cis photoisomerization of the azobenzene moiety resulted in a higher LCST, whereas it recovered under visible light irradiation. This kind of polymers should be particularly interesting for a variety of potential applications in some promising areas, such as drug controlled-releasing carriers and intelligent materials because of the multistimuli responsive property. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2564,2570, 2010 [source] Synthesis and characterization of synthetic polymer colloids colloidally stabilized by cationized starch oligomersJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 7 2009Marianne Gaborieau Abstract A method is developed for anchoring enzymatically degraded cationized starch as electrosteric stabilizers onto synthetic latices, using cerium(IV) to create free-radical grafting sites on the starch. Direct anchoring of debranched starch onto a poly(methyl methacrylate) seed latex yields a latex stabilized by well-defined oligosaccharides. Using ,-amylase to randomly cleave starch to form (1,4)-,-glucans, and a comonomer, N -isopropyl acrylamide (NIPAM), whose corresponding polymer exhibits a lower critical solution temperature (LCST), creates a means to synthesize block (or graft) oligomers of oligosaccharide and synthetic polymer, which are water soluble at room temperature. Above 30 °C, they become amphiphilic and form self-emulsifying nanoparticles (sometimes termed "frozen micelles") from which a synthetic latex is grown after addition of methyl methacrylate, the collapsed NIPAM-containing entities functioning as a type of in situ seed. This synthesis of stable synthetic latex particles is shown to have a high grafting efficiency. The starch fragments were characterized by 1H solution-state NMR before grafting, and 13C solid-state cross-polarization magic-angle spinning (CP-MAS) NMR was used to characterize the starch oligomers actually grafted on the final latex. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1836,1852, 2009 [source] Preparation of novel acrylamide-based thermoresponsive polymer analogues and their application as thermoresponsive chromatographic matricesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 16 2008Yoshikatsu Akiyama Abstract New thermoresponsive polymers based on poly(N -(N, -alkylcarbamido)propyl methacrylamide) analogues were designed with increased hydrophobic content to facilitate temperature-dependent chromatographic separations of peptides and proteins from aqueous mobile phases. These polymer solution exhibited a lower critical solution temperature (LCST) when the alkyl group is methyl, ethyl, isopropyl, propyl, butyl, and isobutyl. However, larger alkyl groups such as hexyl and phenyl were not soluble in aqueous solutions at any temperature. Phase transition temperatures were lower for larger alkyl groups and increased with decreasing polymer molecular weight and concentration in solution. LCST dependence on polymer molecular weight and concentration is more significant compared with well-studied poly(N -isopropylacrylamide) (PIPAAm). Partition coefficient (log P) values for N -(N, -butylcarbamide)propylmethacrylamide and N -(N, -isobutylcarbamide)propyl methacrylamide (iBuCPMA) monomers are larger than that for IPAAm monomer, suggesting higher hydrophobicity than IPAAm. Chromatographic evaluation of poly(N -(N, -isobutylcarbamide)propyl methacrylamide) (PiBuCPMA) grafted silica particles in aqueous separations revealed larger k, values for peptides, insulin, insulin chain B, and angiotensin I than PIPAAm-grafted silica beads. In particular, k, values for insulin obtained from PiBuCPMA-grafted silica separations were much larger than those from PIPAAm-grafted surface separations, indicating that PiBuCPMA should be more hydrophobic than PIPAAm. These results support the introduction of alkylcarbamido groups to efficiently increase thermoresponsive polymer hydrophobicity of poly(N -alkylacrylamides) and poly(N -alkylmethacrylamides). Consequently, poly(N -(N, -alkylcarbamido)propyl methacrylamide) analogues such as PiBuCPMA and poly(N -(N, -alkylcarbamido)alkylmehacrylamide) are new thermoresponsive polymers with appropriate hydrophobic partitioning properties for protein and peptide separations in aqueous media, depending on selection of their alkyl groups. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5471,5482, 2008 [source] Novel temperature- and pH-responsive graft copolymers composed of poly(L -glutamic acid) and poly(N -isopropylacrylamide)JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 12 2008Chaoliang He Abstract A series of novel temperature- and pH-responsive graft copolymers, poly(L -glutamic acid)- g -poly(N -isopropylacrylamide), were synthesized by coupling amino-semitelechelic poly(N -isopropylacrylamide) with N -hydroxysuccinimide-activated poly(L -glutamic acid). The graft copolymers and their precursors were characterized, by ESI-FTICR Mass Spectrum, intrinsic viscosity measurements and proton nuclear magnetic resonance (1H NMR). The phase-transition and aggregation behaviors of the graft copolymers in aqueous solutions were investigated by the turbidity measurements and dynamic laser scattering. The solution behavior of the copolymers showed dependence on both temperature and pH. The cloud point (CP) of the copolymer solution at pH 5.0,7.4 was slightly higher than that of the solution of the PNIPAM homopolymer because of the hydrophilic nature of the poly(glutamic acid) (PGA) backbone. The CP markedly decreased when the pH was lowered from 5 to 4.2, caused by the decrease in hydrophilicity of the PGA backbone. At a temperature above the lower critical solution temperature of the PNIPAM chain, the copolymers formed amphiphilic core-shell aggregates at pH 4.5,7.4 and the particle size was reduced with decreasing pH. In contrast, larger hydrophobic aggregates were formed at pH 4.2. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4140,4150, 2008 [source] Facile preparation of core-crosslinked micelles from azide-containing thermoresponsive double hydrophilic diblock copolymer via click chemistryJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 3 2008Xiaoze Jiang Abstract Double hydrophilic diblock copolymer, poly(N,N -dimethylacrylamide)- b -poly(N -isopropylacrylamide- co -3-azidopropylacrylamide) (PDMA- b -P(NIPAM- co -AzPAM), containing azide moieties in one of the blocks was synthesized via consecutive reversible addition-fragmentation chain transfer polymerization. The obtained diblock copolymer molecularly dissolves in aqueous solution at room temperature, and can further supramolecularly self-assemble into core-shell nanoparticles consisting of thermoresponsive P(NIPAM- co -AzPAM) cores and water-soluble PDMA coronas above the lower critical solution temperature of P(NIPAM- co -AzPAM) block. As the micelle cores contain reactive azide residues, core crosslinking can be facilely achieved upon addition of difunctional propargyl ether via click chemistry. In an alternate approach in which the PDMA- b -P(NIPAM- co -AzPAM) diblock copolymer was dissolved in a common organic solvent (DMF), the core-crosslinked (CCL) micelles can be fabricated via "click" crosslinking upon addition of propargyl ether and subsequent dialysis against water. CCL micelles prepared by the latter approach typically possess larger sizes and broader size distributions, compared with that obtained by the former one. In both cases, the obtained (CCL) micelles possess thermoresponsive cores, and the swelling/shrinking of which can be finely tuned with temperature, rendering them as excellent candidates as intelligent drug nanocarriers. Because of the high efficiency and quite mild conditions of click reactions, we expect that this strategy can be generalized for the structural fixation of other self-assembled nanostructures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 860,871, 2008 [source] Synthesis and supramolecular self-assembly of thermosensitive amphiphilic star copolymers based on a hyperbranched polyether coreJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 2 2008Haiyan Hong Abstract A novel amphiphilic thermosensitive star copolymer with a hydrophobic hyperbranched poly (3-ethyl-3-(hydroxymethyl)oxetane) (HBPO) core and many hydrophilic poly(2-(dimethylamino) ethyl methacrylate) (PDMAEMA) arms was synthesized and used as the precursor for the aqueous solution self-assembly. All the copolymers directly aggregated into core,shell unimolecular micelles (around 10 nm) and size-controllable large multimolecular micelles (around 100 nm) in water at room temperature, according to pyrene probe fluorescence spectrometry and 1H NMR, TEM, and DLS measurements. The star copolymers also underwent sharp, thermosensitive phase transitions at a lower critical solution temperature (LCST), which were proved to be originated from the secondary aggregation of the large micelles driven by increasing hydrophobic interaction due to the dehydration of PDMAEMA shells on heating. A quantitative variable temperature NMR analysis method was designed by using potassium hydrogen phthalate as an external standard and displayed great potential to evaluate the LCST transition at the molecular level. The drug loading and temperature-dependent release properties of HBPO- star -PDMAEMA micelles were also investigated by using indomethacin as a model drug. The indomethacin-loaded micelles displayed a rapid drug release at a temperature around LCST. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 668,681, 2008 [source] A doubly responsive AB diblock copolymer: RAFT synthesis and aqueous solution properties of poly (N -isopropylacrylamide- block -4-vinylbenzoic acid)JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 24 2007Andrew B. Lowe Abstract We describe herein the synthesis and self-assembly characteristics of a doubly responsive AB diblock copolymer comprised of N -isopropylacrylamide (NIPAM) and 4-vinylbenzoic acid (VBZ). The AB diblock copolymer was prepared via reversible addition-fragmentation chain transfer (RAFT) radical polymerization in DMF employing a trithiocarbonate-based RAFT agent. PolyNIPAM was employed as the macroRAFT agent. The NIPAM homopolymerization was shown to possess all the characteristics of a controlled process, and the blocking with VBZ was judged, by size exclusion chromatography, to be essentially quantitative. The NIPAM-VBZ block copolymer was subsequently demonstrated to be able to form normal and inverse micelles in the same aqueous solution by taking advantage of the stimuli responsive characteristics of both building blocks. Specifically, and as judged by NMR spectroscopy and dynamic light scattering, raising the temperature to 40 °C (above the lower critical solution temperature of the NIPAM block), while at pH 12 results in supramolecular self-assembly to yield nanosized species that are composed of a hydrophobic NIPAM core stabilized by a hydrophilic VBZ corona. Conversely, lowering the solution pH to 2.0 at ambient temperature results in the formation of aggregates in which the VBZ block is now hydrophobic and in the core, stabilized by the hydrophilic NIPAM block. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5864,5871, 2007 [source] New environmentally responsive fluorescent N -isopropylacrylamide copolymer and its application to DNA sensingJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 19 2006Chang-Chung Yang Abstract We report two novel multifunctional copolymers consisting of a temperature-responsive poly(N -isopropylacrylamide) (PNIPAA) segment and a fluorescent fluorene-containing acrylic polymer segment with pH responsiveness and/or DNA-sensing ability. The functional acrylic monomer with a fluorene dimer side group substituted with amino units was synthesized first. Then, it was copolymerized with N -isopropylacrylamide to result in a new water-soluble, fluorescent PNIPAA copolymer (P1). The fluorescent properties of P1 under neutral and acidic conditions did not change with the temperature. However, significant variation was observed under basic conditions. The protonation of the amino moiety at a low pH improved the solubility and prevented aggregation for fluorescence quenching, but not under the basic conditions. Although aggregation of the fluorene units was significant at room temperature under basic conditions, the aggregation was resolved at a temperature above the lower critical solution temperature. These findings indicated the pH- and temperature-responsive characteristics of P1. Moreover, after the amino groups were quaternized, the obtained polymer could be used as a biosensor because the fluorescence intensity was quenched with the addition of DNA. This study demonstrates that multifunctional materials with pH- and temperature-sensing characteristics and biological molecules could be realized by the incorporation of a functional fluorene-containing moiety with PNIPAA. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5495,5504, 2006 [source] Synthesis and characterization of core,shell-type polymeric micelles from diblock copolymers via reversible addition,fragmentation chain transferJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 10 2006Ping Zhang Abstract A method was developed to enable the formation of nanoparticles by reversible addition,fragmentation chain transfer polymerization. The thermoresponsive behavior of polymeric micelles was modified by means of micellar inner cores and an outer shell. Polymeric micelles comprising AB block copolymers of poly(N -isopropylacrylamide) (PIPAAm) and poly(2-hydroxyethylacrylate) (PHEA) or polystyrene (PSt) were prepared. PIPAAm- b -PHEA and PIPAAm- b -PSt block copolymers formed a core,shell micellar structure after the dialysis of the block copolymer solutions in organic solvents against water at 20 °C. Upon heating above the lower critical solution temperature (LCST), PIPAAm- b -PHEA micelles exhibited an abrupt increase in polarity and an abrupt decrease in rigidity sensed by pyrene. In contrast, PIPAAm- b -PSt micelles maintained constant values with lower polarity and higher rigidity than those of PIPAAm- b -PHEA micelles over the temperature range of 20,40 °C. Structural deformations produced by the change in the outer polymer shell with temperature cycles through the LCST were proposed for the PHEA core, which possessed a lower glass-transition temperature (ca. 20 °C) than the LCST of the PIPAAm outer shell (ca. 32.5 °C), whereas the PSt core with a much higher glass-transition temperature (ca. 100 °C) retained its structure. The nature of the hydrophobic segments composing the micelle inner core offered an important control point for thermoresponsive drug release and the drug activity of the thermoresponsive polymeric micelles. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3312,3320, 2006 [source] Synthesis of poly[N -isopropylacrylamide- g -poly(ethylene glycol)] with a reactive group at the poly(ethylene glycol) end and its thermosensitive self-assembling characterJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 4 2006Michihiro Iijima Abstract Poly[N -isopropylacrylamide- g -poly(ethylene glycol)]s with a reactive group at the poly(ethylene glycol) (PEG) end were synthesized by the radical copolymerization of N -isopropylacrylamide with a PEG macromonomer having an acetal group at one end and a methacryloyl group at the other chain end. The temperature dependence of the aqueous solutions of the obtained graft copolymers was estimated by light scattering measurements. The intensity of the light scattering from aqueous polymer solutions increased with increasing temperature. In particular, at temperatures above 40°C, the intensity abruptly increased, indicating a phase separation of the graft copolymer due to the lower critical solution temperature (LCST) of the poly(N -isopropylacrylamide) segment. No turbidity was observed even above the LCST, and this suggested a nanoscale self-assembling structure of the graft copolymer. The dynamic light scattering measurements confirmed that the size of the aggregate was in the range of several tens of nanometers. The acetal group at the end of the PEG graft chain was easily converted to the aldehyde group by an acid treatment, which was analyzed by 1H NMR. Such a temperature-induced nanosphere possessing reactive PEG tethered chains on the surface is promising for new nanobased biomedical materials. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1457,1469, 2006 [source] Morphology and temperature responsiveness,swelling relationship of poly(N -isopropylamide,chitosan) copolymers and their application to drug releaseJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 12 2004Chia-Fen Lee Abstract Poly [N -isopropylacrylamide (NIPAAm),chitosan] crosslinked copolymer particles were synthesized by soapless emulsion copolymerization of NIPAAm and chitosan. An anionic initiator [ammonium persulfate (APS)] and a cationic initiator [2,2,-azobis(2-methylpropionamidine)dihydrochloride (AIBA)] were used to initiate the reaction of copolymerization. The chitosan,NIPAAm copolymer synthesized by using APS as the initiator showed a homogeneous morphology and exhibited the characteristic of a lower critical solution temperature (LCST). The copolymer synthesized by using AIBA as an initiator showed a core,shell morphology, and the characteristic of LCST was insignificant. The LCST of the chitosan,NIPAAm copolymer depended on the morphology of the copolymer particles. In addition, the chitosan,NIPAAm copolymer particles were processed to form copolymer disks. Then, the effect of various variables such as the chitosan/NIPAAm weight ratio, the concentration of crosslinking agent, and the pH values on the swelling ratio of chitosan,NIPAAm copolymer disks were investigated. Furthermore, caffeine was used as the model drug to study the characteristics of drug loading of the chitosan,NIPAAm copolymer disks. Variables such as the chitosan/NIPAAm weight ratio and the concentration of the crosslinking agent significantly influenced the behavior of caffeine loading. Two factors (pore size and swelling ratio) affected the behavior of caffeine release from the chitosan,NIPAAm copolymer disks. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3029,3037, 2004 [source] Preparation of macroporous poly(N -isopropylacrylamide) hydrogel with improved temperature sensitivityJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 15 2003J.-T. Zhang Macroporous poly(N -isopropylacrylamide) (PNIPA) hydrogels with improved temperature sensitivity were prepared in aqueous glucose solutions. Compared with the conventional PNIPA hydrogel prepared in water, the gels thus prepared showed significantly faster response as the temperature increased above the lower critical solution temperature. The improved properties were due to the macroporous structure, that was formed during gel preparation caused by the phase separation in glucose solutions. [source] Synthesis and Structure/Property Relationships of Regioselective 2- O -, 3- O - and 6- O -Ethyl CellulosesMACROMOLECULAR BIOSCIENCE, Issue 6 2010Hiroshi Kamitakahara Abstract Regioselectively ethylated celluloses, 2- O - (1), 3- O - (2), and 6- O -ethyl- (3) celluloses were synthesized via ring-opening polymerization of glucopyranose orthopivalate derivatives. The number-average degrees of polymerization (DPns) of compounds 1 and 2 were calculated to be 10.6 and 49.4, respectively. Three kinds of compound 3 with different DPns were prepared: DPns,=,12.9 (3-1), 60.3 (3-2), and 36.1 (3-3). The 2- O -, 3- O -, and 6- O -ethylcelluloses were soluble in water, confirmed by NMR analysis. Furthermore, the 3- O - (2), and 6- O -ethyl- (3-2) celluloses showed thermo-responsive aggregation behavior and had a lower critical solution temperature (LCST) at about 40,°C and 70,°C, respectively, based on the results from turbidity tests and DSC measurements. The 6- O -ethyl-cellulose (3-3) with DPn,=,36.1 and DPw,=,54.6 showed gelation behavior over approx 70,°C, whereas the 6- O -ethyl-celluloses 3-1 and 3-2 with lower and higher molecular weight, such as DPns 12.9 and 60.3, did not show gelation behavior at this temperature. It was revealed that the position of ethyl group affected the phase transition temperature. According to our experiments, the 3- O -ethyl and 6- O -ethyl groups along the cellulose chains caused the thermo-responsive property of their aqueous solutions. The appropriate DP of the regioselective 6- O -ethyl-cellulose existed for gelation of the aqueous solution. [source] Novel Biodegradable and Thermosensitive Dex-AI/PNIPAAm HydrogelMACROMOLECULAR BIOSCIENCE, Issue 2 2003Xian-Zheng Zhang Abstract The dextran-allyl isocyanate/poly(N -isopropylacrylamide) (Dex-AI/PNIPAAm) hydrogel was designed and prepared by copolymerization of the modified dextran with N -isopropylacrylamide (NIPAAm). This novel Dex-AI/PNIPAAm hydrogel is biodegradable and intelligent due to its biodegradable dextran linkage and thermosensitive PNIPAAm moiety. With an increase in dextran content, it exhibits the increased lower critical solution temperature (LCST) and decreased porous microstructure. Also, the thermosensitivity of this hydrogel is also controllable and adjustable depending on the different compositions. SEM micrographs of the Dex-AI/PNIPAAm hydrogels. [source] Thermal Sensitivity of tert -Butyloxycarbonylmethyl-Modified Polyquats in Condensed Phase and Solubility Properties of Copolymers with N -IsopropylacrylamideMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 15 2010Nina Gonsior Abstract The synthesis of the easily decomposable ionic monomer 2- tert -butoxy- N -[2-(methacryloyl-oxy)ethyl]- N,N -dimethyl-2-oxoethanammonium chloride (3) via thermally induced syn-elimination of a tert -butyl ester group was realized simply by mixing N,N -dimethylaminoethyl methacrylate (1) and tert -butyl chloroacetate (2) at ambient temperature without solvent. The obtained salt was polymerized via free radical polymerization. The decomposition and foaming via iso -butene formation takes place by heating up to about 160,°C. IR, DSC, TGA, and GC/MS measurements were performed to follow this pyrolysis reaction. Furthermore, the copolymerization of 3 with N -isopropylacrylamid (NiPAAm, 5) was carried out with different monomer ratios. Molar mass distributions were measured using an asymmetrical flow field-flow fractionation (aFFFF) system. The obtained copolymers 6,10 exhibit lower critical solution temperature (LCST) behaviour in water with cloud points at different temperatures depending on the monomer ratio. [source] Response Characteristics of Thermoresponsive Polymers Using Nanomechanical Cantilever SensorsMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 16 2009Calvin Bradley Abstract We investigated coatings of thermally responsive thin polymer films prepared on nanomechanical cantilever sensor (NCS): (i) a PNIPAM brush, and (ii) an interlinked ppDEA polymer. Upon heating from 22 to 50,°C in water, a minimum in the differential deflection between 31.9,±,1.7,°C (PNIPAM) and 47.7,±,1.9,°C (ppDEA) was measured. The minimum in differential deflection can be associated with the lower critical solution temperature (LCST) of the films. Below the LCST the NCS deflection corresponds to a bending toward the thermally responsive polymer film side, associated to dehydration. At higher temperature, the deflection was reversed, i.e., away from the polymer coating. This response is mainly attributed to a bimaterial effect between the collapsed polymer and the NCS material. The LCST of the PNIPAM brush layer and the ppDEA film were close to that reported for the bulk polymers. [source] | ||||||||||||||||||||||||||||