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PubMed1985

Steric control in the polymerization of 1,2-anhydro-3,4,6-tri-O-benzyl-beta-D-mannopyranose.

Polymerization of 1,2-anhydro-3,4,6-tri-O-benzyl-beta-D-mannopyranose under acid catalysis has led to a series of polymers varying in anomeric configuration from approximately 90% alpha to 70% beta. Optical rotations follow 13C-n.m.r. estimates of anomeric composition linearly over this range. Low-temperature polymerization with trifluoromethanesulfonic anhydride as initiator favors mainly cis-opening of the anhydro ring, presumably through the intermediary of a macroester. These results are compared with related glycosylation and polymerization reactions on 1,2-anhydro sugar derivatives, and some mechanistic conclusions are proposed.

Glycosides↗
PubMed2002

Stabilization of polymerized vesicular systems: an application of the dynamic molecular shape concept.

A series of glycolipid surfactants derived from Tris(hydroxymethyl)acrylamidomethane (THAM) and bearing hydrocarbon or perfluorocarbon tails and an acryloyl group attached to their polar head was prepared to explore the aqueous behavior of the supramolecular systems they form. The dispersion of surfactants was achieved in water under ultrasonication conditions. Hydrocarbon compounds give heterogeneous vesicular assemblies. In the case of perfluorocarbon derivatives homogeneous vesicles were obtained. However after 1-day storage, all these systems fuse. To stabilize these vesicles, polymerization by ultra violet (UV) irradiation was carried out. During this reaction, a precipitation in water was observed for the hydrocarbon surfactants, whereas fluorocarbon structures provide stable vesicles without any alteration of their size. According to these results, the polymerization process was achieved, in the case of hydrocarbon glycolipid, in the presence of different cosurfactants bearing a single hydrocarbon tail or a polyhydroxylated head and a cholesterol terminus. In such conditions, homogeneous stable vesicles were prepared. Moreover, the THAM derived telomers bearing a cholesterol terminus were able to stabilize and reduce the size of vesicles formed with synthetic glycolipid surfactants. The drug encapsulation ability of these systems was investigated by measurement of the release kinetics of a fluorescent dye, carboxyfluorescein (CF), before and after polymerization.

Calorimetry, Differential Scanning↗
PubMed2003

Histidine 454 plays an important role in polymerization of human glutamate dehydrogenase.

Although previous chemical modification studies have suggested several residues to be involved in the maintenance of the quaternary structure of glutamate dehydrogenase (GDH), there are conflicting views for the polymerization process and no clear evidence has been reported yet. In the present study, cassette mutagenesis at seven putative positions (Lys333, Lys337, Lys344, Lys346, Ser445, Gly446, and His454) was performed using a synthetic human GDH gene to examine the polymerization process. Of the mutations at the seven different sites, only the mutagenesis at His454 results in depolymerization of the hexameric GDH into active trimers as determined by HPLC gel filtration analysis and native gradient polyacrylamide gel electrophoresis. The mutagenesis at His454 has no effects on expression or stability of the protein. The K(M) values for NADH and 2-oxoglutarate were 1.5-fold and 2.5-fold greater, respectively, for the mutant GDH than for wild-type GDH, indicating that substitution at position 454 had appreciable effects on the affinity of the enzyme for both NADH and 2-oxoglutarate. The V(max) values were similar for wild-type and mutant GDH. The k(cat)/K(M) value of the mutant GDH was reduced up to 2.8-fold. The decreased efficiency of the mutant, therefore, results from the increase in K(M) values for NADH and 2-oxoglutarate. The results with cassette mutagenesis and HPLC gel filtration analysis suggest that His454 is involved in the polymerization process of human GDH.

Biopolymers↗
PubMed2004

Lignin dehydrogenative polymerization mechanism: a poplar cell wall peroxidase directly oxidizes polymer lignin and produces in vitro dehydrogenative polymer rich in beta-O-4 linkage.

An investigation was performed to determine whether lignin dehydrogenative polymerization proceeds via radical mediation or direct oxidation by peroxidases. It was found that coniferyl alcohol radical transferred quickly to sinapyl alcohol. The transfer to syringaresinol was slower, however, the transfer to polymeric lignols occurred very slightly. This result suggests that the radical mediator theory does not sufficiently explain the mechanism for dehydrogenative polymerization of lignin. A cationic cell wall peroxidase (CWPO-C) from poplar (Populus alba L.) callus showed a strong substrate preference for sinapyl alcohol and the sinapyl alcohol dimer, syringaresinol. Moreover, CWPO-C was capable of oxidizing high-molecular-weight sinapyl alcohol polymers and ferrocytochrome c. Therefore, the CWPO-C characteristics are important to produce polymer lignin. The results suggest that CWPO-C may be a peroxidase isoenzyme responsible for the lignification of plant cell walls.

Alcohols↗
PubMed1996

Probing phosphatidylinositolphosphates and adenosinenucleotides on talin nucleated actin polymerization.

We have investigated the binding of PI, PIP and PIP2 to talin and the effect of phosphoinositides and adenosinenucleotides on talin-induced actin polymerization. At physiological salt concentrations, talin coprecipitates with liposomes when containing phosphoinositides but not when containing PI. The nucleating effect of talin as reflected by a twofold increase of fluorescence during the polymerization of actin labelled with NBD is not inhibited by phosphoinositides. The polymerization of ADP-actin versus ATP-actin was investigated in the presence and absence of talin by NBD fluorescence. ADP-actin nucleation induced by talin is comparably efficient as with ATP-actin. These experimental findings in summary have implications when evaluating the role of talin during cell activation.

Actins↗
PubMed1996

Effects of synaptic vesicles on actin polymerization.

We have analyzed the effects of synaptic vesicles on actin polymerization by using a time-resolved spectrofluorometric assay. We have found that synaptic vesicles have complex effects on the kinetics of actin polymerization, which vary depending on whether the synaptic vesicle-specific phosphoprotein synapsin I is absent or present on their membrane. Synapsin I bound either to synaptic vesicles or to pure phospholipid vesicles exhibits phosphorylation-dependent actin-nucleating activity. Synaptic vesicles depleted of endogenous synapsin I decrease the rate and the final extent of actin polymerization, an effect which is not observed with pure phospholipid vesicles. Thus, the state of association of synapsin I with synaptic vesicles, which is modulated by its state of phosphorylation, may affect actin assembly and the physico-chemical characteristics of the synaptic vesicle microenvironment.

Actins↗
PubMed2001

Comparison of monomeric and polymeric amino acid based surfactants for chiral separations.

To better understand chiral recognition with polymeric amino acid based surfactants, the chromatographic performance of 18 monomeric and polymeric surfactants were compared for chiral analytes with various charge states and hydrophobicities. In this study, four amino acids (glycine, L-alanine, L-valine, and L-leucine) were chosen, and all possible combinations of the chiral single amino acid and dipeptide surfactants were synthesized. The results indicate that polymeric surfactants usually provide better chiral resolution for enantiomers of lorazepam, temazepam, 1,1'-bi-2-naphthol, and propranolol as compared to monomeric surfactants. In contrast, monomers perform better for chiral recognition of the 1,1'-bi-2-naphthyl-2,2'-diyl hydrogenphosphate enantiomers.

Amino Acids↗
PubMed1990

Polymeric dimethylaminopyridinium reagents for derivatization of weak nucleophiles in high-performance liquid chromatography-ultraviolet/fluorescence detection.

This paper introduces a novel polymeric dimethylaminopyridinium 9-fluorenyl-methoxycarbonyl reagent for off-line derivatizations of weak nucleophiles in high-performance liquid chromatography. The method of synthesis and characterization of the polymeric reagent via loading determinations is presented and discussed. Derivatization conditions (solvent, time, and temperature) for primary and secondary alcohols were optimized. As one application, off-line derivatizations of 2-chloro-1-propanol, a potential carcinogen in foodstuffs, were carried out with this polymeric reagent with single-blind and standard addition techniques. A specific sample treatment procedure was also developed. The accuracy and precision of the method were determined and data were statistically evaluated.

1-Propanol↗
PubMed1987

Reversed-phase high-performance liquid chromatographic separation of phenolic derivatives of benzo[a]pyrene, benz[a]anthracene, and chrysene with monomeric and polymeric C18 columns.

The separation of monohydroxylated derivatives (phenols) of benzo[a]pyrene, benz[a]anthracene, and chrysene was studied by reversed-phase high-performance liquid chromatography using a monomeric Zorbax ODS column and a polymeric Vydac C18 column. The Vydac C18 column resolved the phenols of each hydrocarbon with a wide range of retention times than the Zorbax ODS column. Four K-region phenols of benzo[a]pyrene are either not separated or marginally separated on both monomeric and polymeric columns. Other K-region and non-K-region phenols of all three hydrocarbons can be separated by using the monomeric and polymeric columns in combination.

Animals↗
PubMed2002

Kinetic study of the polymerization of alpha-amino acid N-carboxyanhydrides in aqueous solution using capillary electrophoresis.

N-Carboxyanhydrides of amino acids (NCAs) are very reactive monomers able to polymerize into oligopeptides. They are assumed to be prebiotic precursors of the first polypeptides. Few reports have been published on the study of NCA polymerization in aqueous solution. In this work, a kinetic study focused on the hydrolysis of NCA and its coupling with amino acids and homopeptides (up to tripeptide) was carried out, taking L-valine derivatives as model compounds. For that purpose, capillary electrophoresis appeared to be an effective and reliable technique for the measurement of the kinetic constants. The electrophoretic separation conditions, the procedure for stopping NCA reactivity, as well as the conditions of reaction are discussed in detail. We report the variation of the kinetic constant of the coupling reaction of the NCA of valine with an oligovaline as a function of its degree of polymerization. Finally, a temperature study also allowed us to estimate the activation energies associated with the NCA of valine hydrolysis and its coupling reaction with valine.

Amino Acids↗
PubMed2000

Studies of retention and stability of a horizontally polymerized bonded phase for reversed-phase liquid chromatography.

We have studied the novel horizontally polymerized mixed trichloropropyl-trichlorooctadecyl silane bonded phase described by Wirth. These materials can be reproducibly prepared and give very high bonded phase density (>7.5 micromol m(-2)). They show significantly improved alkaline stability and chromatographic selectivity towards PAHs similar to conventional monomeric phases. Study of retention by the Linear Solvation Energy Relationship approach as well as measurement of dead volume and retention of methanol indicate that less mobile phase is sorbed by a horizontally polymerized phase than by conventional phases. Silanophilic interaction of amines are decidedly weaker on a silica modified by horizontal polymerization compared to a conventionally modified phase. In addition, this work provides additional support for the "partition-like" retention mechanism of bonded phase RPLC.

Chromatography, Liquid↗
PubMed2003

Synthesis and aqueous solution properties of polyelectrolyte-grafted silica particles prepared by surface-initiated atom transfer radical polymerization.

A range of polyelectrolyte-grafted silica particles have been prepared by grafting suitable initiators onto near-monodisperse, 304-nm-diameter silica particles using siloxane chemistry, followed by surface-initiated atom transfer radical polymerization (ATRP) of four ionic vinyl monomers, namely sodium 4-styrenesulfonate (SStNa), sodium 4-vinylbenzoate (NaVBA), 2-(dimethylamino)ethyl methacrylate (DAM), and 2-(diethylamino)ethyl methacrylate (DEA) in protic media. The resulting polyelectrolyte-grafted silica particles were characterized using dynamic light scattering (DLS), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), helium pycnometry, and diffuse reflectance infrared Fourier transfer spectroscopy (DRIFTS). The TGA results indicated that the polyelectrolyte contents of the silica particles could be varied from 0.6% to 6.0% in weight. SEM studies revealed several surface morphologies for the grafted polyelectrolytes and XPS analysis of the particle surface also provided good evidence for surface grafting. Combined aqueous electrophoresis and DLS studies confirmed that these polyelectrolyte-grafted silica particles had pH-dependent colloid stabilities, as expected. Cationic polyelectrolyte-grafted silica particles were colloidally stable at low or neutral pH, but became aggregated at high pH. Conversely, anionic polyelectrolyte-coated silica particles became unstable at low pH. It was found that the rate of surface-initiated ATRP was substantially slower than the analogous solution polymerization. Finally, there was some evidence to suggest that, at least in some cases, a significant fraction of polymer chains became detached from the silica particles during polymerization.

Journal Article↗
PubMed2003

X-ray photoelectron spectroscopic studies of hydrophilic surfaces modified via admicellar polymerization.

Admicellar polymerization with styrene monomer was used to coat the surface of two porous solids: titanium dioxide and alumina. X-ray photoelectron spectroscopy (XPS) measurements clearly indicate that after admicellar polymerization, organic material and surfactant are present on the surface of the solids. Water washes, performed immediately after admicellar polymerization, were successful in removing approximately 30% of the organic material, presumably mostly surfactant. The water wash was followed by Soxhlet extraction with toluene, with no measurable removal of organic material according to ignition loss measurements of the solid, gel permeation chromatography of the extracting solvent and also UV/VIS spectroscopy of the extracting solvent. However, there was a 5-15% drop in organic material after Soxhlet extraction according to XPS measurements. This difference is attributed to the difference in sampling; XPS samples only the exterior surface area while these bulk measurements sample both the interior and exterior surface area. This study details the ability of different washing steps to remove materials from the porous substrates used in this study.

Journal Article↗
PubMed1997

Effects of polymerization on the hypertensive action of diaspirin cross-linked hemoglobin in rats.

It is believed that the hypertensive effect of diaspirin crosslinked hemoglobin, a viable blood substitute, can be resolved by polymerization, which reduces the diffusion of this derivative into the interstitial space between nitric oxide-producing endothelium and the target vascular smooth muscle. We studied the systemic and renal responses to infusion of three cell-free human hemoglobins in anesthetized isovolemic rats: unmodified (HbA0), crosslinked (alpha-DBBF), and polymerized crosslinked (poly alpha-DBBF). HbA0 produced a significant increase in mean arterial blood pressure (MAP) throughout the 60-minute infusion. alpha-DBBF, on the other hand, produced a more marked and prolonged increase in MAP over 120 minutes. Only a moderate increase in MAP was observed in rats after a 30-minute infusion with poly alpha-DBBF. The extent of renal insufficiency produced by these proteins, as determined by the glomerular filtration rate, was in the following order: HbA0 > poly alpha-DBBF > alpha-DBBF. Infusion of poly alpha-DBBF, under hypovolemic but not isovolemic conditions in rats, produced an increase in heart rate, cardiac output, and stroke volume and a decrease in total peripheral resistance after 60 minutes. Chemical polymerization to increase the size of alpha-DBBF does not appear to improve its hemodynamic properties in rats, especially under partial exchange transfusion, a more clinically relevant indication for a hemoglobin-based blood substitute.

Analysis of Variance↗
PubMed2002

Acid Denaturation of alpha1-antitrypsin: characterization of a novel mechanism of serpin polymerization.

The native serpin architecture is extremely sensitive to mutation and environmental factors. These factors induce the formation of a partially folded species that results in the production of inactive loop-sheet polymers. The deposition of these aggregates in tissue, results in diseases such as liver cirrhosis, thrombosis, angioedema and dementia. In this study, we characterize the kinetics and conformational changes of alpha(1)-antitrypsin polymerization at pH 4 using tryptophan fluorescence, circular dichroism, turbidity changes and thioflavin T binding. These biophysical techniques have demonstrated that polymerization begins with a reversible conformational change that results in partial loss of secondary structure and distortion at the top of beta-sheet A. This is followed by two bimolecular processes. First, protodimers are formed, which can be dissociated by changing the pH back to 8. Then, an irreversible conformational change occurs, resulting in the stabilization of the dimers with a concomitant increase in beta-sheet structure, allowing for subsequent polymer extension. Electron microscopy analysis of the polymers, coupled with the far-UV CD and thioflavin T properties of the pH 4 polymers suggest they do not form via the classical loop-beta-sheet A linkage. However, they more closely resemble those formed by the pathological variant M(malton). Taken together, these data describe a novel kinetic mechanism of serine proteinase inhibitor polymerization.

Acids↗
PubMed1995

Mechanical properties of a light-polymerizing provisional restorative material with and without reinforcement fibers.

Interim restorations are vulnerable to inadvertent fracture during mastication. Autopolymerizing acrylic resins have traditionally been selected for fabrication of provisional restorations. Triad light-polymerizing tooth-colored acrylic resin was recently introduced as an alternative material for this procedure. This material does not contain methyl methacrylate monomer and permits an increased working time. Heavy occlusal forces may initiate cracks within these restorations, and propagation of these cracks may ultimately lead to failure. Various forms of reinforcement fibers are available and are marketed for strengthening dental resins used for provisional restorations. Investigators have demonstrated that the mechanical properties of acrylic resins may be improved with the incorporation of reinforcing fibers, but a published evaluation of fiber-reinforced light-polymerizing provisional restorative materials is lacking. This investigation recorded and compared two mechanical properties of one light-polymerizing provisional restorative material with and without incorporation of vertically and horizontally oriented woven, matted, polyethylene fibers. No significant difference in modulus of rupture was recorded between groups with and without fibers. The mean flexural elastic modulus of the group with the horizontally oriented fibers was significantly greater than the mean flexural elastic modulus of the specimens without incorporated fibers.

Acrylic Resins↗
PubMed1999

Effects of occlusal loading and thermocycling on the marginal gaps of light-polymerized and autopolymerized resin provisional crowns.

STATEMENT OF PROBLEM: Resin crowns appear to be increasingly at risk for increases in marginal gap size as a result of thermocycling and occlusal loading. PURPOSE: This in vitro study compared the effects of occlusal loading and thermocycling on the margins of provisional crowns made from a conventional autopolymerized provisional acrylic resin (Jet) to those made from a light-polymerized resin (Unifast LC). METHODS AND MATERIAL: Crowns made from the 2 materials were thermocycled and loaded on custom dies to simulate 6 to 8 weeks of oral function. Gap sizes were measured before and after thermocycling and occlusal loading. RESULTS: Provisional crowns made from light-polymerized resin exhibited smaller changes in marginal gap size than did those made from conventional autopolymerized resin. CONCLUSIONS: The improved characteristics of the light-polymerized material may prove useful for provisional crowns that must remain for long periods in the oral environment.

Acrylic Resins↗
PubMed1999

Color stability of heat-polymerized and autopolymerized soft denture liners.

STATEMENT OF PROBLEM: The physical and mechanical properties of soft denture liners are influenced by a number of factors. Aging is one factor that has an effect on the characteristics of polymers. The resistance of denture liners to aging can potentially influence the color stability of these liners. PURPOSE: This study attempted to determine the color stability of soft liners by subjecting them to an in vitro accelerated aging test. MATERIAL AND METHODS: Two autopolymerizing and 3 heat polymerizing commercially available soft denture lining materials were tested. Seven sample disks were made of each material according to manufacturers' instructions. Color measurements were recorded before and after the accelerated aging process. Color changes (DeltaE) were calculated by measuring tristimulus values at several wavelengths in the visual spectrum with the use of Commission International de l'Eclairge Lab (CIE-LAB) uniform color scale. RESULTS: Kruskall-Wallis variance analysis and Mann-Whitney U-Wilcoxon rank sum W tests were performed for statistical comparison of the DeltaE values. Ufigel P and Simpa liner materials showed significantly greater color changes than the other tested materials. There were no significant differences in color change among Ufigel L-Molloplast B, Ufigel L-Flexor, and Molloplast B-Flexor liner materials. However, a significant difference in color change was found between Ufigel P and Simpa liners. CONCLUSION: Heat-polymerized soft liners were more color stable than autopolymerized soft liners. No significant differences were found among heat polymerized materials; however, significant differences in color change were found between the 2 autopolymerized liners.

Analysis of Variance↗