Search results for "kinetics"
showing 10 items of 2224 documents
Unusual crystallization kinetics in a hard sphere colloid-polymer mixture.
2008
We investigated the crystallization kinetics of a hard sphere colloid-polymer mixture at conditions where about 95% of solid coexists with about 5% of fluid. From time resolved Bragg and small angle light scattering, we find that the crystallite size increases with a power law of exponent alpha approximately 1/3 during both the conversion and the coarsening stage. This observation points to a single conserved order parameter for both stages and cannot be explained if the mixture is regarded as an effective one-component system. We alternatively suggest that--based on local geometric demixing--the polymer density takes the role of the conserved order parameter.
Crystal structure of the bifunctional soybean Bowman-Birk inhibitor at 0.28-nm resolution. Structural peculiarities in a folded protein conformation.
1996
The Bowman-Birk inhibitor from soybean is a small protein that contains a binary arrangement of trypsin-reactive and chymotrypsin-reactive subdomains. In this report, the crystal structure of this anticarcinogenic protein has been determined to 0.28-nm resolution by molecular replacement from crystals grown at neutral pH. The crystal structure differs from a previously determined NMR structure [Werner, M. H. & Wemmer, D. E. (1992) Biochemistry 31, 999-1010] in the relative orientation of the two enzyme-insertion loops, in some details of the main chain trace, in the presence of favourable contacts in the trypsin-insertion loop, and in the orientation of several amino acid side chains. The p…
Dominance of Chain Entanglement over Transient Sticking on Chain Dynamics in Hydrogen-Bonded Supramolecular Polymer Networks in the Melt
2018
The chain dynamics in supramolecular polymer networks is determined by the interplay of the kinetics of transient interchain association and relaxation of the network chains themselves. This interplay can be addressed by studying model supramolecular polymer networks in which the number of associative side groups and the molar mass of the covalently jointed backbone polymers are both varied systematically. To realize this idea, we use precursor chains with three different molar masses, which comes along with different extents of entanglement in the melt state. For each molar mass, the precursor polymers are functionalized with three different relative contents of associative side groups, gi…
Probe diffusion in homogeneous diblock copolymers
1998
Forced Rayleigh scattering was used to investigate the diffusion of a photoreactive dye molecule in two homogeneous poly(styrene-b-isoprene) (SI) diblock copolymers with overall molecular weights of approximately 2000. Although diffusion rates were intermediate to TTI transport in homopolymer polystyrene (PS) and polyisoprene (PI), system dynamics appear to be largely dictated in each case by the PI block. The size of the polymer jumping unit, on the other hand, is evaluated from a free-volume analysis of the data, and is found to be governed predominantly by the PS component of the copolymer. The mechanism for tracer diffusion in low-molecular-weight block copolymers appears analogous to t…
Reactions Occurring during the Melt Mixing of Nylon 6 and Oxazoline−Cyclophosphazene Units
2009
Specific reactions of amino and carboxyl end groups of Nylon 6 with the reactive oxazoline groups belonging to a cyclophosphazene compound (referred as CP20XA) were carried out at 240 °C for different times, under inert atmosphere. Ny6 polymers terminated with one specific reactive chain end (-COOH or NH2) were reacted with different amounts of CP20XA to study the kinetic order of the reactions. All Ny6-CP20XA reacted products soluble in trifluoroethanol (TFE) were well characterized by MALDI-TOF MS, FT-IR and ( 1H and 13C) NMR techniques. The MALDI-TOF results show that the oxazoline rings react with the carboxyl chain ends of Ny6 following second-order kinetics. The reactions with amino c…
Proton-dependent kinetics of citrate uptake in growing cells ofLactococcus lactissubsp.lactisbv.diacetylactis
1995
The kinetic analysis of citrate uptake in growing cells of Lactococcus lactis subsp. lactis biovar. diacetylactis identified a proton-dependent transport and suggested the divalent anionic species as the form of citrate transported across cell membranes. The reaction followed Michaelis-Menten kinetics for a two-substrate reaction. The limiting steps were the formation of the ternary complex and the rate of transport. Temperature modified the activity of the permease, increasing the uptake rate.
Phase Separation of Colloid Polymer Mixtures Under Confinement
2013
Colloid polymer mixtures exhibit vapor-liquid like and liquid-solid like phase transitions in bulk suspensions, and are well-suited model systems to explore confinement effects on these phase transitions. Static aspects of these phenomena are studied by large-scale Monte Carlo simulations, including novel “ensemble switch” methods to estimate excess free energies due to confining walls. The kinetics of phase separation is investigated by a Molecular Dynamics method, where hydrodynamic effects due to the solvent are included via the multiparticle collision dynamics method.
Structure and phase transitions of a liquid crystalline polymer
1981
The structures, textures as well as thermodynamic properties of a side chain polymer exhibiting a liquid crystalline phase in addition to a partially crystalline state and the isotropic fluid state were investigated. Furthermore the kinetics of phase transitions between these states were analyzed. It was found that the properties of this polymer are intermediate between that of low molecular weight liquid crystals and common polymers. In particular it was observed that the relation between the liquid crystalline texture and the structure is different from that of low molecular weight liquid crystals and that the properties of the crystalline and liquid crystalline state depend strongly on t…
Reaction kinetics in dense two-dimensional polymer solutions : an excimer probe study
1994
We report measurements of the time dependent reaction rate of excimer formation in two-dimensional solutions of a polymerized amphiphile with partially pyrene-labelled chains in monolayers at the air-water-interface. We find a time dependent reaction rate for excimer formation obeying a power law r(t) ∞ t -β . The exponent β has a value of 0.22±0.12. This value is consistent with β=1/4, as has been predicted for bimolecular diffusion-controlled reactions in two-dimensional polymer melts by de Gennes. The measurements demonstrate the usefulness of the excimer technique to explore polymer dynamics
Crystallization of polymer melts under fast cooling. II. High-purity iPP
1992
SYNOPSIS Samples of a high-purity isotactic polypropylene (iPP) were quenched from the melt so as to monitor cooling history. A continuous variation of morphology and crystal structure was obtained with cooling rate. This is discussed in relation to sample thermal history evidencing that cooling history relevant to quenched samples is in the neighborhood of 90°C. In particular the samples are essentially mesomorphic when at this temperature cooling rates larger than 80°C/s were adopted, while below a few tens of °C/s only a monocline form is obtained. Densities of quenched samples were compared with predictions of an isokinetic extrapolation of Avrami model of polymer crystallization kinet…