The effects of charge density and concentration on the composition of polyelectrolyte complexes

Polyelectrolyte complex formation involving carboxymethylcellulose and quaternized poly(vinylpyridine) as the polyions has been studied using viscosity and u.v. spectroscopic methods. The influence of charge density and molecular weight of two polycations on the composition of the complex has been investigated at two different concentrations. The charge density of the polycation is found to have different influences on the composition at different concentrations. The molecular weight of the polycation and the location of the ionic site on the polycation do not show any effect on the composition. A drastic increase in the viscosity of the polyion mixture containing quaternized poly(2-vinylpyridine) in the non-stoichiometric ratio shows evidence for the existence of the soluble polyelectrolyte complex. The results are analysed on the basis of the relative extension of the polyelectrolyte chains.

The variants of the protein toxins abrin and ricin A useful guide to understanding the processing events in the toxin transport

Kinetic data on inhibition of protein synthesis in thymocyte by three abrins and ricin have been obtained. The intrinsic efficiencies of A chains of four toxins to inactivate ribosomes, as analyzed by k1-versus-concentration plots were abrin II, III > ricin > abrin I. The lag times were 90, 66, 75 and 105 min at a 0.0744 nM concentration of each of abrin I, II, III and ricin, respectively. To account for the observed differences in the dose-dependent lag time, functional and structural variables of toxins such as binding efficiency of B chains to receptors and low-pH-induced structural alterations have been analyzed. The association constants obtained by stopped flow studies showed that abrin-I (4.13 × 105 M−1 s−1) association with putative receptor (4-methylumbelliferyl-α-D-galactoside) is nearly two times more often than abrin III (2.6 × 105 M−1 s−1) at 20°C. Equillibrium binding constants of abrin I and II to thymocyte at 37°C were 2.26 × 107 M−1 and 2.8 × 107 M−1 respectively. pH-induced structural alterations as studied by a parallel enhancement in 8-anilino-L-naphthalene sulfonate fluorescence revealed a high degree of qualitative similarity. These results taken with a nearly identical concentration-independent lag time (minimum lag of 41–42 min) indicated that the binding efficiencies and internalization efficiencies of these toxins are the same and that the observed difference in the dose-dependent lag time is causally related to the proposed processing event. The rates of reduction of inter-subunit disulfide bond, an obligatory step in the intoxication process, have been measured and compared under a variety of conditions. Intersubunit disulfide reduction of abrin I is fourfold faster than that of abrin II at pH 7.2. The rate of disulfide reduction in abrin I could be decreased 1 I-fold by adding lactose, compared to that without lactose. The observed differences in the efficiencies of A chains, the dose-dependent lag period, the modulating effect of lactose on the rates of disulfide reduction and similarity in binding properties make the variants a valuable tool to probe the processing events in toxin transport in detail.

Study of interdiffusion and growth of topologically closed packed phases in the Co-Nb system

Interdiffusion study of the Co-Nb system is conducted to determine the diffusion parameters in different phases. The integrated diffusion coefficients at different temperatures are calculated for the Nb2Co7 phase, which has very narrow composition range. The interdiffusion coefficients at different compositions in the NbCo2 Laves phase are determined. The interdiffusion coefficient in this phase decreases with increasing Nb content to the stoichiometric composition. Further, the average interdiffusion coefficient in the N6Co7-mu phase is determined. The activation energies for diffusion in different phases are calculated, providing valuable information regarding the diffusion mechanism. In addition, an experiment using Kirkendall markers is conducted to calculate the relative mobilities of the species.

Combustion synthesis of oxide materials for nuclear waste immobilization

Oxide materials like perovskite, zirconolite, hollandite, pyrochlore, NASICON and sphene which are used for nuclear waste immobilization have been prepared by a solution combustion process. The process involves the combustion of stoichiometric amount of corresponding metal nitrates and carbohydrazide/tetraformyl trisazine/diformyl hydrazide at 450 degrees C. The combustion products have been characterized using powder X-ray diffraction, infrared spectroscopy, and Si-29 MAS-NMR. The fine particle nature of the combustion derived powders has been studied using density, particle size, BET surface area measurements and scanning electron microscopy. Sintering of combustion derived powder yields 85-95% dense ceramics in the temperature range 1000 degrees-1300 degrees C.

High Yield Room Temperature Synthesis And Spectral Studies Of Tri(Amino)Silanes: (R2n)3SIH

Tri(amino)silanes were prepared by the condensation of trichlorosilane with secondary amines in 1:6 molar ratio. Reactions of trichlorosilane with pyrrolidine, piperidine, hexamethyleneimine, morpholine, N-methylpiperazine and diethylamine afford the tri(amino)silanes in nearly quantitative yields. Their physical and spectroscopic properties are discussed. All these compounds are highly sensitive to moisture and hydrolyse to silica and the respective amine with the evolution of hydrogen. The compounds have been characterised by IR, 1H NMR, [1H]29Si NMR spectroscopic methods and CHN elemental analysis.

Multiscale Modeling Approach to Acoustic Emission during Plastic Deformation

We address the long-standing problem of the origin of acoustic emission commonly observed during plastic deformation. We propose a framework to deal with the widely separated time scales of collective dislocation dynamics and elastic degrees of freedom to explain the nature of acoustic emission observed during the Portevin-Le Chatelier effect. The Ananthakrishna model is used as it explains most generic features of the phenomenon. Our results show that while acoustic emission bursts correlated with stress drops are well separated for the type C serrations, these bursts merge to form nearly continuous acoustic signals with overriding bursts for the propagating type A bands.

Metathesis of carbon dioxide and phenyl isocyanate catalysed by group(IV) metal alkoxides: An experimental and computational study

The insertion reactions of zirconium(IV) n-butoxide and titanium(IV) n-butoxide with a heterocumulene like carbodiimide, carbon dioxide or phenyl isocyanate are compared. Both give an intermediate which carries out metathesis at elevated temperatures by inserting a second heterocumulene in a head-to-head fashion. The intermediate metallacycle extrudes a new heterocumulene, different from the two that have inserted leading to metathesis. As the reaction is reversible, catalytic metathesis is feasible. In stoichiometric reactions heterocumulene insertion, metathesis and metathesis cum insertion products are observed. However, catalytic amounts of the metal alkoxide primarily led to metathesis products. It is shown that zirconium alkoxides promote catalytic metathesis (isocyanates, carbon dioxide) more efficiently than the corresponding titanium alkoxide. The difference in the metathetic activity of these alkoxides has been explained by a computational study using model complexes Ti(OMe)(4) (1bTi) and Zr(OMe)(4) (1bZr). The computation was carried out at the B3LYP/LANL2DZ level of theory.

Dynamic structure factors of a dense mixture

We compute the dynamic structure factors of a dense binary liquid mixture. These describe dynamics on molecular length scales, where structural relaxation is important. We find that the presence of a few large particles in a dense fluid of small particles slows down the dynamics considerably. We also observe a deep narrowing of the spectrum for a disordered mixture composed of a nearly equal packing of the two species. In contrast, a few small particles diffuse easily in the background of a dense fluid of large particles. We expect our results to describe neutron scattering from a dense mixture.

Ultrafast underdamped solvation: Agreement between computer simulation and various theories of solvation dynamics

A theoretical analysis of the three currently popular microscopic theories of solvation dynamics, namely, the dynamic mean spherical approximation (DMSA), the molecular hydrodynamic theory (MHT), and the memory function theory (MFT) is carried out. It is shown that in the underdamped limit of momentum relaxation, all three theories lead to nearly identical results when the translational motions of both the solute ion and the solvent molecules are neglected. In this limit, the theoretical prediction is in almost perfect agreement with the computer simulation results of solvation dynamics in the model Stockmayer liquid. However, the situation changes significantly in the presence of the translational motion of the solvent molecules. In this case, DMSA breaks down but the other two theories correctly predict the acceleration of solvation in agreement with the simulation results. We find that the translational motion of a light solute ion can play an important role in its own solvation. None of the existing theories describe this aspect. A generalization of the extended hydrodynamic theory is presented which, for the first time, includes the contribution of solute motion towards its own solvation dynamics. The extended theory gives excellent agreement with the simulations where solute motion is allowed. It is further shown that in the absence of translation, the memory function theory of Fried and Mukamel can be recovered from the hydrodynamic equations if the wave vector dependent dissipative kernel in the hydrodynamic description is replaced by its long wavelength value. We suggest a convenient memory kernel which is superior to the limiting forms used in earlier descriptions. We also present an alternate, quite general, statistical mechanical expression for the time dependent solvation energy of an ion. This expression has remarkable similarity with that for the translational dielectric friction on a moving ion.

Fe-Cr/Al2O3 metal-ceramic composites: Nature and size of the metal particles formed during hydrogen reduction

Fe-Cr/Al2O3 metal-ceramic composites prepared by hydrogen reduction at different temperatures and for different periods have been investigated by a combined use of Mossbauer spectroscopy, x-ray diffraction, transmission electron microscopy, and energy-dispersive x-ray spectroscopy in order to obtain information on the nature of the metallic species formed. Total reduction of Fe3+ does not occur by increasing the reduction time at 1320 K from 1 to 30 h, and the amount of superparamagnetic metallic species is essentially constant (about 10%). Temperatures higher than 1470 K are needed to achieve nearly total reduction of substitutional Fe3+. Interestingly, iron favors the reduction of chromium. The composition of the Fe-Cr particles is strongly dependent on their size, the Cr content being higher in particles smaller than 10 nm.

High pressure study of Fe3O4 through the verwey transition

The thermopower (TEP) and electrical resistance of stoichiometric Fe3O4 crystals have been measured up to pressures of 6 GPa over the temperature range of 80-160 K. The resistance decreases markedly with increasing pressure below the Verwey transition temperature TV and TV decreases linearly with increasing pressure. The magnitude of the TEP as well as the discontinuity at TV decrease with increasing pressure. The thermopower of Fe3O4 shows an interesting upswing at low temperatures (lt;100 K) which is affected significantly by pressure.

Crystal structure of Salmonella typhimurium 2-methylcitrate synthase: Insights on domain movement and substrate specificity

2-Methylcitric acid (2-MCA) cycle is one of the well studied pathways for the utilization of propionate as a source of carbon and energy in bacteria such as Salmonella typhimurium and Escherichia coli. 2-Methylcitrate synthase (2-MCS) catalyzes the conversion of oxaloacetate and propionyl-CoA to 2-methylcitrate and CoA in the second step of 2-MCA cycle. Here, we report the X-ray crystal structure of S. typhimurium 2-MCS (StPrpC) at 2.4 A resolution and its functional characterization. StPrpC was found to utilize propionyl-CoA more efficiently than acetyl-CoA or butyryl-CoA. The polypeptide fold and the catalytic residues of StPrpC are conserved in citrate synthases (CSs) suggesting similarities in their functional mechanisms. In the triclinic P1 cell, StPrpC molecules were organized as decamers composed of five identical dimer units. In solution, StPrpC was in a dimeric form at low concentrations and was converted to larger oligomers at higher concentrations. CSs are usually dimeric proteins. In Gram-negative bacteria, a hexameric form, believed to be important for regulation of activity by NADH, is also observed. Structural comparisons with hexameric E. coil CS suggested that the key residues involved in NADH binding are not conserved in StPrpC. Structural comparison with the ligand free and bound states of CSs showed that StPrpC is in a nearly closed conformation despite the absence of bound ligands. It was found that the Tyr197 and Leu324 of StPrpC are structurally equivalent to the ligand binding residues His and Val, respectively, of CSs. These substitutions might determine the specificities for acyl-CoAs of these enzymes. (C) 2010 Elsevier Inc. All rights reserved.

Structural Behavior of Story-High Cement-Stabilized Rammed-Earth Walls under Compression

A rammed-earth wall is a monolithic construction made by compacting processed soil in progressive layers in a rigid formwork. There is a growing interest in using this low-embodied-carbon building material in buildings. The paper investigates the strength and structural behavior of story-high cement-stabilized rammed-earth (CSRE) walls, reviews literature on the strength of CSRE, and discusses results of the compressive strength of CSRE prisms, wallettes, and story-high walls. The strength of the story-high wall was compared with the strength of wallettes and prisms. There is a nearly 30% reduction in strength as the height-to-thickness ratio increases from about 5 to 20. The ultimate compressive strength of CSRE walls predicted using the tangent modulus theory is in close agreement with the experimental values. The shear failures noticed in the story-high walls resemble the shear failures of short-height prism and wallette specimens. The paper ends with a discussion of structural design and characteristic compressive strength of CSRE walls. DOI: 10.1061/(ASCE)MT.1943-5533.0000155. (C) 2011 American Society of Civil Engineers.

Synthesis, x-ray structure and redox properties of [Ru2(?-O) (?-O2CMe)2(Me2NCH2CH2NH2)2(PPh3)2](ClO4)2

The title complex has been prepared from a reaction of [Ru2O(O22CMe)2 (MeCN)4(PPH3)2](ClO4)2 with N,N-dimethyl-1,2-diaminoethane (dmen) in MeOH. The crystal structure of [Ru2O(O2CMe)2(dmen)2(PPh3)2](ClO4)2.MeOH shows the presence of a [Ru2(mu-O)(mu-O2CMe)2]2+ core. The terminal ligands on each metal are a PPh3 and a bidentate chelating dmen. The Ru-Ru distance and Ru-O-Ru angle in the core are 3.271(2) angstrom and 120.9(4)-degrees. The more electron-donating site of the dmen ligand is bonded at the terminal sites trans to the mu-oxo ligand. The complex displays a visible absorption band at 566 nm (epsilon, 6960 M-1 cm-1) in MeCN and undergoes a nearly reversible one-electron oxidation at 1.02 V and an irreversible reduction at -0.52 V (vs SCE) in MeCN-0.1 M [NBu4n](ClO4).

Structural and electrical properties of radio frequency magnetron sputtered tantalum oxide films: Influence of post-deposition annealing

The as-deposited and annealed radio frequency reactive magnetron sputtered tantalum oxide (Ta2O5) films were characterized by studying the chemical binding configuration, structural and electrical properties. X-ray photoelectron spectroscopy and X-ray diffraction analysis of the films elucidate that the film annealed at 673 K was stoichiometric with orthorhombic beta-phase Ta2O5. The dielectric constant values of the tantalum oxide capacitors with the sandwich structure of Al/Ta2O5/Si were in the range from 14 to 26 depending on the post-deposition annealing temperature. The leakage current density was < 20 nA cm(-2) at the gate bias voltage of 0.04 MV/cm for the annealed films. The electrical conduction mechanism observed in the films was Poole-Frenkel. (C) 2010 Elsevier Ltd. All rights reserved.