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Solution Properties (solution + property)
Selected AbstractsRAFT Synthesis and Solution Properties of pH-Responsive Styrenic-Based AB Diblock Copolymers of 4-Vinylbenzyltrimethylphosphonium Chloride with N,N -DimethylbenzylvinylamineMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 21 2007Andrew B. Lowe Abstract The RAFT synthesis and solution properties of AB block copolymers of 4-vinylbenzyltrimethylphosphonium chloride (TMP) and N,N -dimethylbenzylvinylamine (DMBVA) is described. The pH-dependent self-assembly properties of the AB diblock copolymers were examined using of 1H NMR, DLS, and fluorescence spectroscopy. The size of the polymeric aggregates depends on the block copolymer composition/molecular mass. The self assembly is completely reversible, as predicted from the tunable hydrophilicity/hydrophobicity of the DMBVA residues. The AB diblock copolymers can be effectively locked in the self-assembled state using a straightforward core crosslinking reaction between the tertiary amine residues of DMBVA and difunctional 1,4-bis(bromomethyl)benzene. [source] Influence of Grafting on the Solution Properties and the Dissociation Behavior of Ionic/Nonionic Grafted CopolymersMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 6 2007Jens Weber Abstract A new synthetic approach towards grafted terpolymers based on a poly[(methyl vinyl ether)- alt -(maleic anhydride)] backbone and poly(ethylene glycol) monomethyl ether (MPEG) side chains is presented. Resulting comb polymers with controllable grafting degree still have highly reactive anhydride moieties along the polymer backbone, as proved by IR spectroscopy. Grafting degree depends on the anhydride hydroxide stoichiometric ratio. It is not influenced by the molecular weight of MPEG. An increase in the grafting degree leads to a contraction of the polymer in the solution. Evaluation of potentiometric titration data gave a deeper insight into the dissociation process. The copolymers showed a two-step dissociation behavior. No significant influence of the grafting degree on the acidic strength was observed, whilst there is a strong effect of the grafting degree on the free energy change upon neutralization ,Gel. Grafting leads to a higher change in free energy ,Gel,1 for the first step but to lower ,Gel,2 required for the second step. [source] Porous Capsules {(M)M5}12FeIII30 (M=MoVI, WVI): Sphere Surface Supramolecular Chemistry with 20 Ammonium Ions, Related Solution Properties, and Tuning of Magnetic Exchange Interactions,ANGEWANDTE CHEMIE, Issue 3 2010Maria Todea Dr. Eine Vielfalt von Wasserstoffbrücken-Bindungsoptionen auf einer hochfunktionalisierten Kapseloberfläche mit 20 kronenetherartigen Poren ermöglicht die Fixierung/Erkennung von 20 Ammoniumionen (siehe Bild; W grün, Fe orange, O rot, N blau, H hellgrau), die in Lösung zum Teil abgegeben werden, und zwar unter Bildung entsprechender Gleichgewichte. [source] ChemInform Abstract: Porous Capsules {(M)M5}12FeIII30 (M: MoVI, WVI): Sphere Surface Supramolecular Chemistry with 20 Ammonium Ions, Related Solution Properties, and Tuning of Magnetic Exchange Interactions.CHEMINFORM, Issue 15 2010Achim Mueller Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Rationalizing the Solution Properties of Zwitterions by Means of Computational ChemistryCHEMISTRY & BIODIVERSITY, Issue 11 2005Richard This short review describes our computational studies of carnitine, acetylcarnitines, and betaines over the past two decades. Interspersed among the three computational studies , a molecular mechanics study of the conformer population of carnitine and acetylcarnitine, an AM1 study of the energetics of hydrolysis of acetylcarnitine, and an HF 6-31G* study of the solvation energies and structures of a homologous series of betaines , are brief overviews of our research in designing and testing new therapeutic agents for non-insulin dependent diabetes and for protection against sexually transmitted diseases. The three studies also show how computational chemistry has evolved during this time to enable an evaluation of the structure and energetics of zwitterions in aqueous solution. [source] Synthesis, characterization, and solution properties of some new organotellurium compounds based on di(cyclohexylmethyl)tellurideHETEROATOM CHEMISTRY, Issue 1 2007Ali Z. Al-Rubaie A new series of organotellurium(IV) compounds based on di(cyclohexylmethyl)telluride (1) (i.e., (C6H11CH2)2TeX2 and (C6H11CH2)2Te(R)X) was prepared by the reaction of compound 1 with halogens, N-bromosuccinimide, and alkyl halides. Phenylation of (C6H11CH2)2TeX2 with sodium tetraphenylborate gave di(cyclohexylmethyl)phenyltelluronium tetraphenylborate in good yield. Conductivity measurements in dimethylsulfoxide (DMSO) showed a considerable ionic character of these compounds and they behave as 1:1 electrolytes. 1H NMR studies in CDCl3 solution indicated that telluronium salts employed in this study are unstable toward reductive elimination. Reaction of di(cyclohexylmethyl)telluride, (C6H11CH2)2Te(CH3)I, and (C6H11CH2)2Te(PhCH2)Br with HgX2 (X = Cl or Br) afforded 1:1 complexes. All compounds were characterized by elemental analyses and spectroscopic data. © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:93,99, 2007; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20240 [source] A corrected XFEM approximation without problems in blending elementsINTERNATIONAL JOURNAL FOR NUMERICAL METHODS IN ENGINEERING, Issue 5 2008Thomas-Peter Fries Abstract The extended finite element method (XFEM) enables local enrichments of approximation spaces. Standard finite elements are used in the major part of the domain and enriched elements are employed where special solution properties such as discontinuities and singularities shall be captured. In elements that blend the enriched areas with the rest of the domain problems arise in general. These blending elements often require a special treatment in order to avoid a decrease in the overall convergence rate. A modification of the XFEM approximation is proposed in this work. The enrichment functions are modified such that they are zero in the standard elements, unchanged in the elements with all their nodes being enriched, and varying continuously in the blending elements. All nodes in the blending elements are enriched. The modified enrichment function can be reproduced exactly everywhere in the domain and no problems arise in the blending elements. The corrected XFEM is applied to problems in linear elasticity and optimal convergence rates are achieved. Copyright © 2007 John Wiley & Sons, Ltd. [source] New sets of solubility parameters of linear and crosslinked aromatic polyamidesJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2010Stefano Fiori Abstract As generally accepted, also in the case of polyamides linear and crosslinked polymeric materials are believed to be characterized by the same solution properties and, consequently, by the same solubility parameters. However, despite their great practical importance, a thorough study aimed to determine the best solvent media able to dissolve linear aromatic polyamides has not been performed yet or, at least, has not been published. In this study, we report on our study on the solubility parameters of linear and crosslinked aromatic polyamides. We demonstrate that the assumption of considering these two classes as having the same solubility properties can lead to dramatically erroneous results. Two new different sets for linear and crosslinked aromatic polyamides are proposed. Namely, linear poly(p -phenylene terephthalamide) is characterized by ,p, ,d, and ,H equal to 8.6, 18.4, and 11.3, respectively; by contrast, the corresponding values of the crosslinked aromatic polyamides taken into consideration are: 11.5, 16.8, and 10.2. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] The influence of electrospinning parameters on the structural morphology and diameter of electrospun nanofibersJOURNAL OF APPLIED POLYMER SCIENCE, Issue 5 2010Valencia Jacobs Abstract Electrospinning is a simple method of producing nanofibers by introducing electric field into the polymer solutions. We report an experimental investigation on the influence of processing parameters and solution properties on the structural morphology and average fiber diameter of electrospun poly ethylene oxide (PEO) polymer solution. Experimental trials have been conducted to investigate the effect of solution parameters, such as concentration, molecular weight, addition of polyelectrolyte in PEO solution, solvent effect, as well as governing parameter, such as applied voltage. The concentration of the aqueous PEO solution has shown noteworthy influence on the fiber diameter and structural morphology of electrospun nanofibers. At lower concentrations of PEO polymer solution, the fibers showed irregular morphology with large variations in fiber diameter, whereas at higher concentrations, the nanofibers with regular morphology and on average uniform fiber diameter were obtained. We find that the addition of polyelectrolytes, such as sodium salt of Poly acrylic acid (PAA) and Poly allylamine hydrochloride (PAH), increases the conductivity of PEO solutions and thereby decreases the bead formation in electrospun nanofibers. The increase in applied voltage has been found to affect the structural morphology of nanofiber while the addition of ethanol in PEO solution diminishes the bead defects. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] Characterization and solution properties of a partially hydrolyzed graft copolymer of polyacrylamide and dextranJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2008S. Krishnamoorthi Abstract Graft copolymers of dextran (Dx) and polyacrylamide (PAM) were synthesized through the grafting of PAM chains onto a Dx backbone with a ceric-ion-induced solution polymerization technique. By the variation of the amount of the initiator (ceric ammonium nitrate), four different grades of graft copolymers were synthesized. The partial alkaline hydrolysis of Dx- g -PAM was carried out in an alkaline medium. Three grades of partially hydrolyzed products were synthesized through the variation of the amount of alkali. These hydrolyzed graft copolymers were characterized with elemental analysis, infrared spectroscopy, neutralization equivalent measurements, a rheological technique, scanning electron microscopy, thermal analysis, viscometry, and X-ray diffraction. The flocculation efficiency and viscosifying characteristics of the graft copolymers were enhanced upon their alkaline hydrolysis. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008. [source] ANTHOCYANIN INTERACTIONS WITH DNA: INTERCALATION, TOPOISOMERASE I INHIBITION AND OXIDATIVE REACTIONSJOURNAL OF FOOD BIOCHEMISTRY, Issue 5 2008MICHAEL R. WEBB ABSTRACT Anthocyanins and their aglycone anthocyanidins are pigmented flavonoids found in significant amounts in many commonly consumed foods. They exhibit a complex chemistry in aqueous solution, which makes it difficult to study their chemistry under physiologic conditions. Here we used a gel electrophoresis assay employing supercoiled DNA plasmid to examine the ability of these compounds (1) to intercalate DNA; (2) to inhibit human topoisomerase I through both inhibition of plasmid relaxation activity (catalytic inhibition) and stabilization of the cleavable DNA,topoisomerase complex (poisoning); and (3) to inhibit or enhance oxidative single-strand DNA nicking. We found no evidence of DNA intercalation by anthocyan(id)ins in the physiologic pH range for any of the compounds used in this study , cyanidin chloride, cyanidin 3- O -glucoside, cyanidin 3,5- O -diglucoside, malvidin 3- O -glucoside and luteolinidin chloride. The anthocyanins inhibited topoisomerase relaxation activity only at high concentrations (>50 µM), and we could find no evidence of topoisomerase I cleavable complex stabilization by these compounds. However, we observed that all of the anthocyan(id)ins used in this study were capable of inducing significant oxidative DNA strand cleavage (nicking) in the presence of 1 mM dithiothreitol, while the free radical scavenger, dimethyl sulfoxide (DMSO), at concentrations typically used in similar studies, completely inhibited DNA nicking. Finally, we proposed a mechanism to explain the anthocyan(id)in-induced oxidative DNA cleavage observed under our experimental conditions. PRACTICAL APPLICATIONS This study provided improved understanding of the mechanisms by which anthocyan(id)ins interact with DNA. By characterizing the chemistry and solution properties of these important dietary components, we obtained improved information on how the anthocyan(id)ins might function in living systems. [source] Self-association of cromolyn sodium in aqueous solution characterized by nuclear magnetic resonance spectroscopyJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 5 2004Xuan Ding Abstract The major objective of this study was to investigate and characterize the solution properties of cromolyn sodium (in D2O or D2O/H2O phosphate buffer at pH 7.5) using nuclear magnetic resonance (NMR) spectroscopy. The self-association of cromolyn molecules was examined primarily via one-dimensional 1H and 13C, and two-dimensional homonuclear NOESY NMR. Significant spectral shifts were observed for a majority of cromolyn 1H and 13C resonances, and are attributed to inter-molecular ring-stacking association accompanied by intra-molecular conformational changes. The critical self-association concentration was determined to be 10 mg/mL at pH 7.5 and 25°C by measuring the chemical shift of a specific cromolyn 1H resonance. The observed magnitude and sign changes of NOESY correlations indicate the formation of cromolyn aggregates with restricted molecular mobility. Mesomorphic liquid crystal formation is suggested by uniformly pronounced line broadening in concentrated cromolyn solutions; the transition concentration was approximately 60 mg/mL at 25°C, which is consistent with literature findings based on other techniques. A stronger tendency toward association was observed at lower temperature but aggregation appeared to be independent of pH. Lastly, it was concluded that self-association of cromolyn is promoted by the presence of monovalent cations as a result of reduced electrostatic repulsive forces. © 2004 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 93:1351,1358, 2004 [source] Solution, thermal and optical properties of novel poly(pyridinium salt)s derived from conjugated pyridine diamines,JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 20 2010Alexi K. Nedeltchev Abstract Several novel poly(pyridinium salt)s with heterocyclic pyridine moieties in their backbones with tosylate and triflimide counterions were prepared by either ring-transmutation polymerization reaction of phenylated-bis(pyrylium tosylate) with isomeric pyridine diamines of 4-phenyl-2,6-bis(4-aminophenyl)pyridine in dimethyl sulfoxide (DMSO) for 48 h at 130,140 °C or by metathesis reaction of the respective tosylate polymers with lithium triflimide in DMSO at about 60 °C. Their chemical structures were characterized by FTIR, 1H, 13C NMR spectroscopy, and elemental analysis. Their number-average molecular weights (Mn) were in the range of 8,000,51,000 and their polydispersities in the range of 1.18,2.13 as determined by gel permeation chromatography. They had excellent thermal stabilities of 340,458 °C and high glass transition temperatures >200 °C. As they showed good solubilities in common organic solvents, their solution properties were also characterized for their lyotropic liquid-crystalline properties with polarizing optical microscopy (POM) studies. Their photoluminescent properties were examined by using a spectrofluorometer in both solution and solid states. Their quantum yields were rather low, which were in the range of 1.3,2.0%. Additionally, hand-drawn fibers from the melts were examined to determine their morphologies with a number of microscopic techniques including POM, scanning electron microscopy, and transmission electron microscopy. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 [source] Preparation of polybenzoxazole fibers via electrospinning and postspun thermal cyclization of polyhydroxyamideJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 24 2008Steve Lien-Chung Hsu Abstract Polybenzoxazole (PBO) fibers with a submicron diameter were successfully prepared by electrospinning its precursor, polyhydroxyamide (PHA), solutions to obtain the PHA fibers first, followed by appropriate thermal treatments for cyclization reaction. BisAPAF-IC PHA with two different molecular weights (MWs) were synthesized from a low temperature polymerization of 2,2,-bis(3-amino-4-hydroxyphenyl) hexafluoropropane (BisAPAF) and isophthaloyl chloride (IC). Using dimethylacetamide (DMAc) and tetrahydrofuran (THF), solvent effects on the electrospinnability of PHA solutions were investigated. For balancing the solution properties, it was found that DMAc/THF mixture with a weight ratio of 1/9 was the best cosolvent to prepare smooth PHA fibers; uniform PHA fibers with a diameter of 325,720 nm were obtained by using 20 wt % PHA/(DMAc/THF) solutions. For a fixed PHA concentration, solutions with a lower MW of PHA yielded thinner electrospun fibers under the same electrospinning condition. After obtaining the electrospun BisAPAF-IC PHA fibers, subsequent thermal cyclization up to 350 °C produced the corresponding thermally stable BisAPAF-IC PBO fibers with a diameter of 305,645 nm. The structure of the precursor fibers and the fully cyclized fibers were characterized by FTIR. For the cyclized BisAPAF-IC PBO fibers, thermogravimetric analysis showed a 5% weight loss temperature at 523 °C in nitrogen atmosphere. The interconnected fiber structure in the BisAPAF-IC PBO fiber mats was irrelevant to the curing process, but resulted from the jet merging during the whipping process as revealed by the high speed camera images. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8159,8169, 2008 [source] Hybrid linear dendritic macromolecules: From synthesis to applicationsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 16 2008Ivan Gitsov Abstract Linear-dendritic copolymers are intriguing macromolecules, which offer challenge and fascination as purely synthetic objects at the crossroad of organic and polymer chemistry and as promising materials for diverse advanced applications. This review traces their discovery and highlights the synthetic strategies used for their construction. The ambivalent character of the linear-dendritic architecture opens numerous avenues towards emerging and potential applications. Specific solution properties enable the construction of nanometer-sized nanoreactors for reactions in environmentally friendly media, and the creation of "nanosponges" for selective passive binding of fluorescent pH-indicators for environmental or biomonitoring. Another structure,property relationship is used for noncovalent and site-specific modification of glycoproteins, which leads to the formation of "semiartificial" enzymes with enhanced and broadened catalytic activity. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5295,5314, 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] Roles of rhenium diimine complexes as metal-ion probes and photosensitizers in functional polyurethanesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 11 2003Ching Sum Hui Abstract Polyurethanes incorporated with rhenium diimine complexes were synthesized. The polymers exhibited interesting morphologies and solution properties. Results from gel permeation chromatography suggested the formation of polymer aggregates in solutions. The polymers could act as probes for metal ions. The addition of metal ions to polymer solutions led to significant changes in the electronic absorption properties of the polymer solutions. This was attributed to the interactions between the polyether moieties and metal ions. The metal complexes could also act as efficient photosensitizers. After doping with charge-transport viologens, the photoconductivity of the polymers was greatly enhanced. The experimental quantum efficiency was simulated with Onsager's theory. The thermalization distances and the primary yields were typically 12,14 Å and 10,3, respectively. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1708,1715, 2003 [source] Synthesis and solution properties of a new pH-responsive polymer containing amino propanesulfonic acid residuesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 1 2003Sk. Asrof Ali Abstract The reaction of diallyl amine with 1,3-propane sultone led to the synthesis of the zwitterionic monomer 3-(N,N -diallylammonio)propanesulfonate. The sulfobetaine was cyclopolymerized in water in the presence of sodium chloride with t -butylhydroperoxide as an initiator to afford a polysulfobetaine (PSB) in very good yield. PSB, upon treatment with sodium hydroxide, was converted into an anionic polyelectrolyte (APE). Although APE was readily soluble in salt-free water, PSB needed the presence of low-molecular-weight salts (e.g., NaCl, KI, etc., in the range of 0.135,1.04 N) for its dissolution. The solution properties of PSB and APE were investigated with potentiometric and viscometric techniques. The basicity constant of the amine was apparent and followed the modified Henderson,Hasselbalch equation; as the degree of protonation (,) of the whole macromolecule increases, the protonation of the amine nitrogens becomes increasingly more difficult. The composition and phase diagram of the aqueous two-phase systems of APE/PSB and poly(ethylene glycol) were also explored. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 172,184, 2003 [source] RAFT Synthesis and Solution Properties of pH-Responsive Styrenic-Based AB Diblock Copolymers of 4-Vinylbenzyltrimethylphosphonium Chloride with N,N -DimethylbenzylvinylamineMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 21 2007Andrew B. Lowe Abstract The RAFT synthesis and solution properties of AB block copolymers of 4-vinylbenzyltrimethylphosphonium chloride (TMP) and N,N -dimethylbenzylvinylamine (DMBVA) is described. The pH-dependent self-assembly properties of the AB diblock copolymers were examined using of 1H NMR, DLS, and fluorescence spectroscopy. The size of the polymeric aggregates depends on the block copolymer composition/molecular mass. The self assembly is completely reversible, as predicted from the tunable hydrophilicity/hydrophobicity of the DMBVA residues. The AB diblock copolymers can be effectively locked in the self-assembled state using a straightforward core crosslinking reaction between the tertiary amine residues of DMBVA and difunctional 1,4-bis(bromomethyl)benzene. [source] Ultrafine Electrospun Polyamide-6 Fibers: Effects of Solvent System and Emitting Electrode Polarity on Morphology and Average Fiber DiameterMACROMOLECULAR MATERIALS & ENGINEERING, Issue 9 2005Pitt Supaphol Abstract Summary: In the present contribution, polyamide-6 (PA-6) solutions were prepared in various pure and mixed-solvent systems and later electrospun with the polarity of the emitting electrode being either positive or negative. The PA-6 concentration in the as-prepared solutions was fixed at 32% w/v. Some of the solution properties, i.e., shear viscosity, surface tension, and conductivity, were measured. Irrespective of the polarity of the emitting electrode, only the electrospinning of PA-6 solution in formic acid (85 wt.-% aqueous solution) produced uniform electrospun fibers, while solutions of PA-6 in m -cresol or sulfuric acid (either 20 or 40 wt.-% aqueous solution) did not. In the mixed-solvent systems, formic acid (85 wt.-% aqueous solution) was blended with m -cresol, sulfuric acid (either 20 or 40 wt.-% aqueous solution), acetic acid, or ethanol in the compositional range of 10,40 vol.-% (based on the amount of the minor solvent). Generally, the average fiber diameter increased with increasing amount of the minor solvent or liquid. Interestingly, the diameters of the fibers obtained under the negative electrode polarity were larger than those obtained under the positive one. Optical images of electrospun fibers from solutions of polyamide-6 in a mixed solvent of 85 wt.-% formic acid and 20 vol.-% m -cresol under positive (left) and negative (right) electrode polarity. [source] Switching the Solubility of PMMA Bearing Attached Cyclodextrin-Moieties by Supramolecular Interactions with Ionic LiquidsMACROMOLECULAR RAPID COMMUNICATIONS, Issue 11 2009Sadik Amajjahe Abstract Methacrylate-modified , -cyclodextrin (, -CD) and methyl methacrylate (MMA) have been radically copolymerized to obtain hydrophobic CD copolymers. The water-insoluble copolymers are able to form highly stable inclusion complexes with anions of ionic liquids. Surprisingly, the inclusion of the anions in the CD cavity results in a significant change of thermal and solution properties. Furthermore, it can be shown that the structure of the ionic liquid anions influences the coil structure of the copolymers. The obtained results could be proven by means of microcalorimetry, differential scanning calorimetry, and dynamic light scattering. [source] Determination of molar mass and solution properties of cationic hydroxyethyl cellulose derivatives by multi-angle laser light scattering with simultaneous refractive index detectionPOLYMER INTERNATIONAL, Issue 10 2009Wei Gao Abstract BACKGROUND: A complete understanding of the molar mass and solution properties of raw materials in bio/pharmaceutical products under bio-application and natural conditions ensures process control, product performance and quality. Biopolymers including polymeric cationic hydroxyethyl cellulose derivatives (e.g. Polyquaterium-10 or Polymer JR) have long been used in health care formulations including shampoos, lotions, eye drops and contact lens multi-purpose solutions. Previously reported molar masses and conformation of Polymer JR were based on size exclusion chromatography-related techniques, which required highly concentrated buffered salt solutions and organic solvent modifiers to prevent undesirable interactions, and did not represent the isotonic conditions in products and applications. RESULTS: This paper describes the characterization of Polymer JR in saline using a new approach that combines micro-batch mode multi-angle laser light scattering with simultaneous refractive index measurements (MB-MALLS-RI). Mass-average molar mass, z -average radius of gyration and second virial coefficient values in phosphate buffer saline (PBS) were obtained and are discussed in detail. CONCLUSION: The molar mass and solution properties of Polymer JR in PBS, with the same pH and ionic strength as most health care solution products, can be characterized using the MB-MALLS-RI technique. The approach is practical and can be widely used for the analysis of other cationic biopolymers. Copyright © 2009 Society of Chemical Industry [source] Oxygen infusions (hemoglobin-vesicles and albumin-hemes) based on nano-molecular sciences,POLYMERS FOR ADVANCED TECHNOLOGIES, Issue 2-3 2005Professor Eishun Tsuchida Abstract Since the discovery of a red-colored saline solution of a heme derivative that reversibly binds and releases oxygen (1983), significant efforts have been made to realize an oxygen infusion as a red cell substitute based on the sciences of both molecular assembling phenomena and macromolecular metal complexes. The authors have specified that hemoglobin (Hb)-vesicles (HbV) and recombinant human serum albumin-hemes (rHSA-heme) would be the best systems that meet the clinical requirements. (A) Hb is rigorously purified from outdated, donated red cells via pasteurization and ultrafiltration, to completely remove blood type antigen and pathogen. The HbV encapsulates thus purified concentrated Hb solution with a phospholipid bimolecular membrane (diameter, 250,nm,), and its solution properties can be adjusted comparable with blood. Surface modification of HbV with a water-soluble polymer ensures stable dispersion state and storage over a year at 20°C. In vivo tests have clarified the efficacy for extreme hemodilution and resuscitation from hemorrhagic shock, and safety in terms of biodistribution, metabolism in reticuloendothelial system (RES), clinical chemistry, blood coagulation, etc. The HbV does not induce vasoconstriction thus maintains blood flow and tissue oxygenation. (B) rHSA is now manufactured in Japan as a plasma-expander. The rHSA can incorporate eight heme derivatives (axial base substituted hemes) as oxygen binding sites, and the resulting rHSA-heme is a totally synthetic O2 -carrier. Hb binds endothelium-derived relaxation factor, NO, and induces vasoconstriction. The rHSA-heme binds NO as Hb does, however, it does not induce vasoconstriction due to its low pI (4.8) and the resulting low permeability across the vascular wall (1/100 of Hb). A 5%-albumin solution possesses a physiologic oncotic pressure. Therefore, to increase the O2 -transporting capacity, albumin dimer is effective. Albumin dimer can incorporate totally 16 hemes with a regulated oncotic pressure. The rHSA-heme is effective not only as a red cell substitute but also for oxygen therapeutics (e.g. oxygenation for tumor). Significant efforts have been made to produce HbV and rHSA-heme with a facility of Good Manufacturing Practice (GMP) standard, and to start preclinical and finally clinical trials. Copyright © 2005 John Wiley & Sons, Ltd. [source] New scope for synthesis of divinyl ether and maleic anhydride copolymer with narrow molecular mass distribution,POLYMERS FOR ADVANCED TECHNOLOGIES, Issue 10-12 2002I. F. Volkova Abstract The alternating copolymer of divinyl ether and maleic anhydride (DIVEMA) possesses diverse biological activity and uses for production of drug delivery systems. DIVEMA's biological effects are determined by molecular mass, therefore it is necessary to have information about copolymer molecular mass and its distribution. A direct method for gel permeation chromatography analysis of DIVEMA molecular mass characteristics in aqua solution without any preliminary modification was developed. The effect of a number of factors (the concentration of monomers and their ratios, the concentration of initiator, the nature of the solvents) on DIVEMA's solution properties and molecular mass distribution was studied by gel permeation chromatography and viscometry. The approach to synthesis of DIVEMA with narrow molecular mass distribution was designed. The substantial influence of water on DIVEMA molecular mass characteristics was determined. The proposal was made that water may play a part in the formation of charge-transfer complexes playing a significant role in copolymerization. Copyright © 2003 John Wiley & Sons, Ltd. [source] Hydrophobically modified polyelectrolytes II: synthesis and characterization of poly(acrylic acid-co-alkyl acrylate)POLYMERS FOR ADVANCED TECHNOLOGIES, Issue 11-12 2001Dong-qing Zhuang Abstract A series of hydrophobically modified poly(acrylic acid)(RH -PAA) were synthesized by solution copolymerization of acrylic acid with a small amount of alkyl acrylate (alkyl chain with a length of 8, 12, 14, 16, 18) and their solution properties were also systematically studied. It was found that the random distribution of alkyl acrylate along the polymeric backbone imparts these new materials pronounced associating ability in aqueous solution and the associating abilities vary with the chain length of the hydrophobic groups. In dilute solution, intramolecular association is observed from the intrinsic viscosity and the dependence of the intrinsic viscosity on chain length and ionic strength is also discussed. In semiconcentration solution, the modified polymers exhibit viscosities of several orders of magnitude higher than the unmodified poly(sodium acrylate) due to the strong intermolecular hydrophobic association. And the viscosifying effects become more significant with the increasing length of the alkyl chain. The copolymer solutions are highly pseudoplastic. Evidences for the hydrophobically associating interaction between hydrocarbon groups are provided by the dependence of the Brookfield viscosity on concentration, temperature, shear rate, ionic strength and pH. Copyright © 2001 John Wiley & Sons, Ltd. [source] Dynamic adjustment cost models with forward-looking behaviourTHE ECONOMETRICS JOURNAL, Issue 1 2006Luca Fanelli Summary, In this paper we propose a new approach for dynamic decision problems where forward-looking agents choose a set of non-stationary variables subject to quadratic adjustment costs. It is assumed that expectations are computed by a cointegrated Vector Equilibrium Correction Model (VEqCM). The role of feedbacks from the decision to the explanatory variables on solution properties and modelling approach is discussed. We show that once the system of interrelated Euler equations stemming from the agent's optimization problem is embedded within the VEqCM, a switching algorithm based on Generalized Least Squares can be used to estimate and test the model. A labour demand model for two Danish manufacturing industries is investigated empirically. [source] An experimental charge density of HEPESACTA CRYSTALLOGRAPHICA SECTION B, Issue 4 2010We report the experimental charge density of HEPES [4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid], which is a common buffering agent. The structure was refined using the Hansen,Coppens formalism. The ability of the HEPES molecule to form stable intermolecular interactions and intermolecular hydrogen bonds in the crystal structure is discussed in terms of its buffering properties. The protonation mode observed in the crystal structure is different from that expected in solution, suggesting that additional factors must be taken into consideration in order to explain the solution properties of the compound. As ordered HEPES molecules are found in the active sites of proteins in several protein crystal structures, our results will allow for quantitative analysis of the electrostatic potential of the interacting surfaces of those proteins. [source] Effects of excluded volume and polydispersity on solution properties of lentinan in 0.1 M NaOH solution,BIOPOLYMERS, Issue 4 2005Xufeng Zhang Abstract Seven lentinan fractions of various weight-average molecular weights (Mw), ranging from 1.45 × 105 to 1.13 × 106 g mol,1 were investigated by static light scattering and viscometry in 0.1M NaOH solution at 25°C. The intrinsic viscosity [,] , Mw and radius of gyration ,s2, , Mw relationships for lentinan in 0.1M NaOH solution were found to be represented by [,] = 5.1 × 10,3M cm3 g,1 and ,s2, = 2.3 × 10,1M nm, respectively. Focusing on the effects of the Mw polydispersity with the Schulz,Zimm distribution function, the data of Mw, ,s2,, and [,] was analyzed on the basis of the Yoshizaki,Nitta,Yamakawa theory for the unperturbed helical wormlike chain combined with the quasi-two-parameter (QTP) theory for excluded-volume effects. The persistence length, molecular weight per unit contour length, and the excluded-volume strength were determined roughly to be 6.2 nm, 980 nm,1, and 0.1, respectively. Compared with the theoretical value calculated by the Monte Carlo model, the persistence length is longer than that of the single (1 , 3)-,- D -glucan chain. The results revealed that lentinan exists as single-stranded flexible chains in 0.1M NaOH solution with a certain degree of expansion due to the electrostatic repulsion from the interaction between the OH, anions and lentinan molecules. © 2005 Wiley Periodicals, Inc. Biopolymers 78: 187,196, 2005 [source] Chain stiffness of heteropolysaccharide from Aeromonas gum in dilute solution by dynamic light scatteringBIOPOLYMERS, Issue 6 2002Xiaojuan Xu Abstract Dynamic light scattering measurements have been made on 15 fractions of aeromonas (A) gum, an extracellular heteropolysaccharide produced by the strain Aeromonas nichidenii, with dimethylsulfoxide containing 0.2M lithium chloride as the solvent at 25°C. Data for the translational diffusion coefficient D covering a molecular weight range from 4.5 × 105 to 2.1 × 106 and ratios of the z -average radius of gyration ,s2,z1/2 to the hydrodynamic radius RH (calculated with previous ,s2,z data) suggest that the polymer behaves like a semiflexible chain in this solvent similar to the stiffness of cellulose derivatives. Thus the D data are analyzed on the basis of the Yamakawa,Fujii theory for the translational friction coefficient of a wormlike cylinder by coarse-graining the heteropolysaccharide molecule. Excluded-volume effects are taken into account in the quasi-two-parameter scheme, as was done previously for ,s2,z and [,] (the intrinsic viscosity) of A gum in the same solvent. The molecular weight dependence of RH is found to be explained by the perturbed wormlike chain with a persistence length of 10 nm, a linear mass density of 1350 nm,1, an excluded-volume strength parameter of 1.3 nm, and a chain diameter of 2.8 nm. These parameters are in substantial agreement with those estimated previously from ,s2,z and [,] data, demonstrating that the solution properties (D, ,s2,z, and [,]) of the heteropolysaccharide are almost quantitatively described by the current theories for wormlike chains in the molecular weight range studied. © 2002 Wiley Periodicals, Inc. Biopolymers 65: 387,394, 2002 [source] Probing protein colloidal behavior in membrane-based separation processes using spectrofluorometric Rayleigh scattering dataBIOTECHNOLOGY PROGRESS, Issue 3 2010Rand Elshereef Abstract One of the primary problems in membrane-based protein separation is membrane fouling. In this study we explored the feasibility of employing Rayleigh light scattering data from fluorescence studies combined with chemometric techniques to determine whether a correlation could be established with membrane fouling phenomena. Membrane flux was measured in a dead-end UF filtration system and the effect of protein solution properties on the flux decline was systematically investigated. A variety of proteins were used as a test case in this study. In parallel, the colloidal behavior of the protein solutions was assessed by employing multiwavelength Rayleigh scattering measurements. To assess the usefulness of Rayleigh scattering measurements for probing the colloidal behavior of proteins, a protein solution of ,-lactoglobulin was used as a base-case scenario. The colloidal behavior of different ,-lactoglobulin solutions was inferred based on published data for this protein, under identical solution conditions, where techniques other than Rayleigh scattering had been used. Using this approach, good agreement was observed between scattering data and the colloidal behavior of this protein. To test the hypothesis that a high degree of aggregation will lead to increased membrane fouling, filtration data was used to find whether the Rayleigh scattering intensity correlated with permeate flux changes. It was found that for protein solutions which were stable and did not aggregate, fouling was reduced and these solutions exhibited reduced Rayleigh scattering. When the aggregation behavior of the solution was favored, significant flux declines occurred and were highly correlated with increased Rayleigh scattering. © 2010 American Institute of Chemical Engineers Biotechnol. Prog., 2010 [source] | ||||||||||||||||