The Statistical Mechanics of Semiflexible Equilibrium Polymers

We give an overview of studies of models for semiflexible, equilibrium polymers with special emphasis on our work on both lattice and continuum models for such systems. We show, principally by Monte Carlo simulations, that, once monomers self assemble to form polymers, their semiflexibility leads to nematic phases at low temperatures. Attractive wall potentials encourage the adsorption of these equilibrium polymers on surfaces. Rapid cooling leads to the formation of glasses with entangled polymers. Shear promotes nematic ordering, but, at high shear rates, this tendency decreases since the equilibrium polymers are torn apart. A version of our model in which the polymers are directed shows the polymer analog of bosonic Mott-insulating, mass-density-wave, and supersolid phases. We give a brief comparison of our work with other studies and also explore the experimental implications of our study.     

Charge and Stability of Colloids

Summary Effect of non-electrolytes like methyl alcohol, ethyl, n-propyl, n-butyl, n-hexyl alcohols, glucose, sucrose, urea, starch and iso-electric gelatin on negatively charged selenium oxide sol has been studied by Spekker absorptiometer in presence of barium chloride as coagulating electrolyte. It has been observed that the substances studied generally stabilise the sol except ethylalcohol in all concentrations, methyl and n-propyl alcohols in high concentrations which have been found to sensitise it. It has been found that dielectric constant does not seem to explain completely the phenomenon of sensitisation and protection.

---

Zusammenfassung Mit Hilfe eines Spekker-Absorptionsmeters wurde der Einflu? von Nichtelektrolyten für Bariumchlorid als koagulierender Elektrolyt auf negativ geladenes Selenoxyd-Sol untersucht. Die angewendeten Nichtelektrolyte waren Methyl-, ?thyl-, n-Propyl-, n-Butyl- und n-Hexyl-Alkohol, Glukose, Sucrose, Harnstoff, St?rke und Gelatine (isoelektrisch). Es wurde festgestellt, da? in allen F?llen das Sol im allgemeinen stabilisiert wird au?er durch ?thyl-Alkohol bei allen Konzentrationen, Methyl- und Propyl-Alkohol bei hohen Konzentrationen. In diesen F?llen wurde das Sol sensibilisiert. Au?erdem wurde festgestellt, da? die Dielektrizit?tskonstante offensichtlich nicht vollst?ndig die Ph?nomene der Sensibilisierung und des Schutzes erkl?rt.

     

Studies in inorganic polyelectrolytes — Part II

Viscosity behaviour of several samples ofGraham's salt with varying molecular weight has been studied. Reduced viscosity (η _sp /c) versus concentration curves were found to be characteristic of polyelectrolytes. They are dependent on the molecular weight and can be reduced to straight lines by plotting the reciprocal of the reduced viscosity against the square root of concentration. The intrinsic viscosities obtained by extrapolation were found to be proportional to the square of molecular weights. The value of reduced viscosity at any particular concentration in the concentration range between 0.25% and 4.0% was linearly related to the molecular weight. Reduced viscosities were found to decrease considerably on addition of electrolytes. Reduced viscosity versus added salt concentration curves were remarkably molecular weight dependent. The p_H of the medium seemed to have no effect at all. Bivalent salts reduce the viscosity to a much greater extent than monovalent ones. By keeping the concentration of the added salt constant and varying that ofGraham's salt, curves showing hump which disappeared at higher concentration of the added salt, were obtained. In the action of electrolytes the more important factor is the valency of cation rather than the ionic strength of the medium. Most observations confirm the already well-establishedFolding-Chain Theory of polyelectrolytes developed byKatchalsky, Fuoss and others.     

Characteristics of Heterophase Graft Copolymerizations

Abstract

Persulfate-initiated graft copolymerizations of glutaraldehyde crosslinked gelatin with acrylic acid, acrylamide, vinyl acetate, and methyl methacrylate in the aqueous phase were investigated. It was observed that percentage grafting, molecular weights of the grafts, and grafting efficiencies were greatly influenced by the nature of the monomers. Hydrophilic monomers gave a higher frequency of grafting but lower molecular weights. While the frequency of grafting with hydrophobic monomers was low, the molecular weights of the grafts were comparatively high. The results are explained in terms of microdomain kinetics, similar to those encountered in emulsion or suspension polymerizations.     

On the behavior of Nd3+ in LaCl3

Various properties of Nd³⁺: LaCl₃ which are influenced strongly by the crystalline electric field (CF) have been studied in the intermediate coupling scheme. A satisfactory correlation among the diverse observed properties has been achieved with the CF of Crosswhite et al. The hitherto uncertain lattice contribution to the electric field gradient (EFG) at the nuclear site has been established quite precisely. Some interesting features in the magnetic and thermal behavior of Nd³⁺ are also predicted.     

A crystal field investigation of the properties of RCuAs2 (R=Pr, Nd, Sm, Tb, Dy, Ho, Er and Yb)

A crystal field (CF) investigation of the magnetic properties and heat capacities of RCuAs₂ (R=Pr, Nd, Sm, Tb, Dy, Ho, Er and Yb) has been carried out using the observed average magnetic susceptibilities (1.8-300 K) of the title compounds. The CF parameters proposed for the systems show a systematic variation throughout the rare-earth series. Other physical properties dependent on the CF are also computed and compared with available experimental data. The experimental heat capacity data reported for a limited range of temperature agree well with computed heat capacity for all the compounds (except SmCuAs₂ and YbCuAs₂). CF J mixing was found to be appreciable for all the samples except YbCuAs₂.     

Kinetics of Enzymatic Synthesis of Cinnamyl Butyrate by Immobilized Lipase

This work illustrates the enzymatic synthesis of cinnamyl butyrate by esterification of butyric acid and cinnamyl alcohol. Experiments were performed to study the various operating parameters such as molar ratio, enzyme concentration, temperature, and speed of agitation. Also, the suitable kinetic model for esterification reaction was predicted and the various kinetic parameters were determined. It has been observed that the experimental results agree well with the simulated results obtained by following the ping-pong bi-bi mechanism with dead-end inhibition by both the substrate acid and alcohol. The highest 90% conversion of butyric acid was observed after 12 h at the following reaction conditions: substrate molar ratio 1:2 (butyric acid/cinnamyl alcohol), temperature 50 °C, enzyme loading 2% (with respect to the weight of the substrates), and agitation speed 250 rpm. Diffusional mass transfer limitations between substrate and enzyme surface do not show significant effect on reaction kinetics. Enzyme reusability study reveals that it retains 85% of its catalytic activity after five consecutive cycles.     

Context-dependent effects of asparagine glycosylation on Pin WW folding kinetics and thermodynamics

Asparagine glycosylation is one of the most common and important post-translational modifications of proteins in eukaryotic cells. N-glycosylation occurs when a triantennary glycan precursor is transferred en bloc to a nascent polypeptide (harboring the N-X-T/S sequon) as the peptide is cotranslationally translocated into the endoplasmic reticulum (ER). In addition to facilitating binding interactions with components of the ER proteostasis network, N-glycans can also have intrinsic effects on protein folding by directly altering the folding energy landscape. Previous work from our laboratories (Hanson et al. Proc. Natl. Acad. Sci. U.S.A. 2009, 109, 3131-3136; Shental-Bechor, D.; Levy, Y. Proc. Natl. Acad. Sci. U.S.A. 2008, 105, 8256-8261) suggested that the three sugar residues closest to the protein are sufficient for accelerating protein folding and stabilizing the resulting structure in vitro; even a monosaccharide can have a dramatic effect. The highly conserved nature of these three proximal sugars in N-glycans led us to speculate that introducing an N-glycosylation site into a protein that is not normally glycosylated would stabilize the protein and increase its folding rate in a manner that does not depend on the presence of specific stabilizing protein-saccharide interactions. Here, we test this hypothesis experimentally and computationally by incorporating an N-linked GlcNAc residue at various positions within the Pin WW domain, a small β-sheet-rich protein. The results show that an increased folding rate and enhanced thermodynamic stability are not general, context-independent consequences of N-glycosylation. Comparison between computational predictions and experimental observations suggests that generic glycan-based excluded volume effects are responsible for the destabilizing effect of glycosylation at highly structured positions. However, this reasoning does not adequately explain the observed destabilizing effect of glycosylation within flexible loops. Our data are consistent with the hypothesis that specific, evolved protein-glycan contacts must also play an important role in mediating the beneficial energetic effects on protein folding that glycosylation can confer.