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Solution Temperature (solution + temperature)
Kinds of 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] Kinetic studies on the influence of temperature and growth rate history on crystal growthCRYSTAL RESEARCH AND TECHNOLOGY, Issue 12 2008P. M. Martins Abstract Crystallization experiments of sucrose were performed in a batch crystallizer to study the effect of temperature and growth rate history on the crystal growth kinetics. In one of the growth methods adopted, the isothermal volumetric growth rate (RV) is determined as a function of supersaturation (S) at 35, 40 and 45 ºC. In the other, crystals are allowed to grow at constant supersaturation by automatically controlling the solution temperature as the solute concentration decreased. Using the latter method RV is calculated as the solution is cooled. The obtained results are interpreted using empirical, engineering and fundamental perspectives of crystal growth. Firstly, the overall activation energy (EA) is determined from the empirical growth constants obtained in the isothermal method. The concept of falsified kinetics, widely used in chemical reaction engineering, is then extended to the crystal growth of sucrose in order to estimate the true activation energy (ET) from the diffusion-affected constant, EA. The differences found in the isothermal and constant supersaturation methods are explained from the viewpoint of the spiral nucleation mechanism, taking into account different crystal surface properties caused by the growth rate history in each method. Finally, the crystal growth curve obtained in the batch crystallizer at 40 ºC is compared with the one obtained in a fluidized bed crystallizer at the same temperature. Apparently divergent results are explained by the effects of crystal size, hydrodynamic conditions and growth rate history on the crystallization kinetics of sucrose. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [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] Determination of ,, solution temperature in Re-rich Ni-base superalloy by small-angle neutron scatteringJOURNAL OF APPLIED CRYSTALLOGRAPHY, Issue 5 2001Pavel Strunz A harmful segregation of heavy elements (e.g. W, Mo, Re) during solidification of Ni-base superalloys can only be eliminated by using a homogenizing heat treatment, which needs to be carried out in the single-phase (,) field above the ,, solvus temperature but below the solidus temperature. Small-angle neutron scattering (SANS) was employed for in situ observation of the dissolution of precipitates in an Re-rich superalloy. The temperature dependence of the relative volume fraction and the size distribution of smaller ,, precipitates, and the specific surface of large inhomogeneities as well as some other parameters were determined from the two-dimensional scattering curves measured for as-cast and heat-treated samples. Overlap of the incipient melting region with the region where a certain amount of precipitates remained undissolved was observed, thus complicating a determination of the temperature at which all ,, precipitates are already dissolved. Nevertheless, conclusions about the temperature at which the precipitates dissolve and about the temperature at which the incipient melting starts could be formulated. The total scattering probability is suggested as the measure of the overall homogeneity of the distribution of elements in the sample. The temperature dependence of this parameter indicates the optimum solution procedure. [source] Facile method to manipulate the molecular weight and practical mass production of chitosan by mechanical shearing and concurrent ultrafiltration treatmentJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2010Min Lang Tsai Abstract The objective of this study was to propose a facile method to manipulate the molecular weight and practical mass production of chitosan by mechanical shearing and concurrent ultrafiltration (UF) treatment. The proposed method was based on the degradation rate and rate constant of various process variables, such as: solution temperature, reaction time, concentration of chitosan solution, with or without concurrent removal of degraded fragments during mechanical shearing. The result obtained was that the degradation rate constant was 1.8,6.0 times higher for those using UF to remove smaller degraded molecules concurrently during treatment, than that without UF treatment. The degradation rate constant increased with increasing solution temperature; however, the solution temperature should not exceed than 50°C to prevent the undesired color changes of the resulting product. A method combining mechanical shearing/UF treatment at 50°C and ultrasonic radiation or microfluidization/UF treatment at 30°C is proposed here for a facile method to manipulate the molecular weight of the resultant chitosan with an energy saving, efficient and practical mass production. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [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] Perfluorosulfonic acid,Tetraethoxysilane/polyacrylonitrile (PFSA-TEOS/PAN) hollow fiber composite membranes prepared for pervaporation dehydration of ethyl acetate,water solutionsJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2008Hai-Kuan Yuan Abstract Preparation of organic-inorganic composite membranes and their pervaporation (PV) permeation and separation characteristics for the aqueous solution of ethyl acetate were described. Polyacrylonitrile (PAN) hollow fiber ultrafiltration membrane as support membrane, the mixtures of perfluorosulfonic acid (PFSA) and tetraethoxysilane (TEOS) by the sol-gel reaction as the coating solution, the PFSA-TEOS/PAN hollow fiber composite membranes by the different annealing conditions were prepared. The swelling of PFSA in ethyl acetate aqueous solutions was inhibited with addition of TEOS. The PFSA-TEOS/PAN composite membranes containing up to 30 wt % TEOS in coating solution exhibited high selectivity towards water, then the selectivity decreased and permeation flux increased with increasing the TEOS concentration more than 30 wt %. When the PFSA-TEOS/PAN composite membranes were annealed, the separation factor increased with increasing annealing temperature and time. Higher annealing temperature and longer annealing time promoted the crosslinking reaction between PFSA and TEOS in PFSA-TEOS/PAN composite membranes, leading to the enhanced selectivity towards water. For the PFSA/PAN and PFSA-TEOS/PAN composite membrane with 5 and 30 wt % TEOS annealed at 90°C for 12 h, their PV performance of aqueous solution 98 wt % ethyl acetate were as follows: the separation factors were 30.8, 254 and 496, while their permeation flux were 1430, 513 and 205 g/m2 h at 40°C, respectively. In addition, the PV performance of PFSA-TEOS/PAN composite membranes was investigated at different feed solution temperature and concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Phase behavior on the binary and ternary mixtures of poly(isooctyl acrylate) + supercritical fluid solvents + isooctyl acrylate and CO2 + isooctyl acrylate systemJOURNAL OF APPLIED POLYMER SCIENCE, Issue 2 2008Hun-Soo Byun Abstract Experimental cloud-point data to the temperature of 180 °C and the pressure up to 2000 bar are presented for ternary mixtures of poly(isooctyl acrylate) + supercritical fluid solvents + isooctyl acrylate systems. Cloud-point pressures of poly(isooctyl acrylate) + CO2 + isooctyl acrylate system is measured in the temperature range of 60,180°C and to pressures as high as 2000 bar with isooctyl acrylate concentration of 0,44.5 wt. This system changes the pressure,temperature slope of the phase behavior curves from upper critical solution temperature (UCST) region to lower critical solution temperature (LCST) region as the isooctyl acrylate concentration increases. Poly(isooctyl acrylate) does dissolve in pure CO2 to the temperature of 180°C and the pressure of 2000 bar. The phase behavior for poly(isooctyl acrylate) + CO2 + 9.5, 14.8, 30.6, and 41.9 wt % dimethyl ether (DME) mixture show the curve changes from UCST to LCST as the DME concentration increases. Also, the cloud-point curves are measured for the binary mixtures of poly(isooctyl acrylate) in supercritical propane, propylene, butane, and 1-butene. High pressure phase behaviors are measured for the CO2 + isooctyl acrylate system at 40, 60, 80, 100, and 120°C and pressure up to 200 bar. This system exhibits type-I phase behavior with a continuous mixture-critical curve. The experimental results for the CO2 + isooctyl acrylate system are modeled using the Peng-Robinson equation of state. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008 [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] A modified cellulose adsorbent for the removal of nickel(II) from aqueous solutionsJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 11 2006David W O'Connell Abstract A series of adsorption studies was carried out on a glycidyl methacrylate- modified cellulose material functionalised with imidazole (Cellulose- g -GMA-Imidazole) to assess its capacity in the removal of Ni(II) ions from aqueous solution. The study sought to establish the effect of a number of parameters on the removal of Ni(II) from solution by the Cellulose- g -GMA-Imidazole. In particular, the influence of initial metal concentration, contact time, solution temperature and pH were assessed. The studies indicated a Ni(II) uptake on the Cellulose- g -GMA-Imidazole sorbent of approximately 48 mg g,1 of nickel from aqueous solution. The adsorption process fitted the Langmuir model of adsorption and the binding process was mildly endothermic. The kinetics of the adsorption process indicated that nickel uptake occurred within 400 min and that pseudo-second order kinetics best describe the overall adsorption process. Nickel(II) adsorption, recovery and re-adsorption studies indicated that at highly acidic pH values the adsorbent material becomes unstable, but in the range pH 3,6, the adsorbent is stable and shows limited but significant Ni(II) recovery and re-adsorption capability. Copyright © 2006 Society of Chemical Industry [source] APPLICATION OF RESPONSE SURFACE METHODOLOGY FOR THE OSMOTIC DEHYDRATION OF CARROTSJOURNAL OF FOOD PROCESS ENGINEERING, Issue 6 2006BAHADUR SINGH ABSTRACT Osmotic dehydrations of carrot cubes in sodium chloride salt solutions at different solution concentrations, temperatures and process durations were analyzed for water loss and solute gain. The osmotically pretreated carrot cubes were further dehydrated in a cabinet dryer at 65C and were then rehydrated in water at ambient temperature for 8,10 h and analyzed for rehydration ratio, color and overall acceptability of the rehydrated product. The process was optimized for maximum water loss, rehydration ratio and overall acceptability of rehydrated product, and for minimum solute gain and shrinkage of rehydrated product by response surface methodology. The optimum conditions of various process parameters were 11% salt concentration, 30C osmotic solution temperature and process duration of 120 min. [source] Effect of molecular weight of poly(N -isopropyl acrylamide) temperature-sensitive flocculants on dewateringAICHE JOURNAL, Issue 8 2009Haihong Li Abstract The influence of molecular weight (MW) and dose of Poly(N-isopropyl acrylamide) (PNIPAM) (temperature-sensitive flocculant) on sedimentation rate, sediment density, and supernatant clarity of silica suspensions was investigated. The addition of PNIPAM resulted in rapid sedimentation (T > critical solution temperature, CST) and low sediment moisture (T < CST). Higher MW polymers resulted in more effective flocculation and sediment consolidation. At 10 ppm, PNIPAM (3.6 million Da) produced 20 m/h settling rate and 48 vol % solids sediment density, whereas 0.23 million Da polymer produced 0.1 m/h settling rate. PNIPAM produces effective flocculation and consolidation by cycling the interparticle interactions between repulsion and attraction as temperature is cycled around the CST. The change in temperature produces a hydrophilic/hydrophobic transition of the polymer, influencing adsorption onto the surface and the inter-particle forces. Conventional polyacrylamide flocculants (not influenced by temperature), cannot be used to produce both rapid sedimentation and dense sediments. © 2009 American Institute of Chemical Engineers AIChE J, 2009 [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] Crystal growth rate dispersion modeling using morphological population balanceAICHE JOURNAL, Issue 9 2008Cai Y. Ma Abstract Crystal growth in solution is a surface-controlled process. The variation of growth rates of different crystal faces is considered to be due to the molecular arrangement in the crystal unit cell as well as the crystal surface structures of different faces. As a result, for some crystals, the growth rate for a specific facet is not only a function of supersaturation, but also dependent on some other factors such as its size and the lattice spread angle. This phenomenon of growth rate dispersion (GRD) or fluctuation has been described in literature to have attributed to the formation of some interesting and sophisticated crystal structures observed in experimental studies. In this article, GRD is introduced to a recently proposed morphological population balance model to simulate the dynamic evolution of crystal size distribution in each face direction for the crystallization of potash alum, a chemical that has been reported to show GRD phenomenon and sophisticated crystal structures. The GRD is modeled as a function of the effective relative supersaturation, which is directly related to crystal size, lattice spread angle, relative supersaturation, and solution temperature. The predicted results clearly demonstrated the significant effect of GRD on the shape evolution of the crystals. © 2008 American Institute of Chemical Engineers AIChE J, 2008 [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] | ||||||||||||||||||||||||||||||||||