Stabilization of unusual structures in peptides using alpha,beta-dehydrophenylalanine: Crystal and solution structures of Boc-Pro-Delta Phe-Val-Delta Phe-Ala-OMe and Boc-Pro-Delta Phe-Gly-Delta Phe-Ala-OMe

The structures of two dehydropentapeptides, Boc-Pro-Delta Phe-Val-Delta Phe-Ala-OMe (I) and Boc-Pro-Delta Phe-Gly-Delta Phe-Ala-OMe (II) (Boc: t-butoxycarbonyl), have been determined by nuclear magnentic resonance (NMR), circular dichroism (CD), and X-ray, crystallographic studies. The peptide I assumes a S-shaped flat beta-bend structure, characterized by two partially overlapping type II beta-bends and absence of a second 1 <- 4 (N4-H center dot center dot center dot O1') intramolecular hydrogen bond. This is in contrast to the generally observed 3(10)-helical conformation in peptides with Delta Phe at alternate positions. This report describes the novel conformation assumed by peptide I and compares it with that of the conserved tip of the V3 loop of the HIV-1 envelope glycoprotein gp120 (sequence, G:P319 to F:P324, PDB code IACY). The tip of the V3 loop also assumes a S-shaped conformation with Arg:P322, making an intramolecular side-chain-backbone interaction with the carbonyl oxygen of Gly:P319. Interestingly, in peptide I, C(gamma)HVal(3) makes a similar side-chain-backbone C-H center dot center dot center dot O hydrogen bond with the carbonyl oxygen of the Boc group. The observed overall similarity indicates the possible use of the peptide as a viral antagonist or synthetic antigen. Peptide 11 adopts a unique turn followed by a 3(10)-helix. Both peptides I and II are classical examples of stabilization of unusual structures in oligopeptides.

Unconventional mechanism of stabilization of a tetragonal phase in the perovskite ferroelectric (PbTiO3)(1-x)(BiFeO3)(x)

Temperature-dependent x-ray powder-diffraction study of the tetragonal compositions of PbTiO3-BiFeO3 series has revealed that, unlike for all the known ferroelectric perovskites, the compositions exhibiting giant tetragonality is stabilized from the cubic phase via a complex transition pathway which involve (i) formation of minor monoclinic phase with a large pseudotetragonality along with an intermediate tetragonal phase (major) with a small tetragonality, (ii) gradual vanishing of the intermediate tetragonal phase and concomitant increase in the monoclinic regions, and finally (iii) gradual transformation of the monoclinic phase to the tetragonal phase with giant tetragonality.The system seems to adopt such a complex transition pathway to create amicrostructure with very large number of domains and interfaces for stress relief, which would not have been possible in case of a direct cubic-tetragonal transition.

Synergistic use of thermogravimetric and electrochemical techniques for thermodynamic study of TiOx (1.67 <= x <= 2.0) at 1573 K

A thermodynamic study of the Ti-O system at 1573 K has been conducted using a combination of thermogravimetric and emf techniques. The results indicate that the variation of oxygen potential with the nonstoichiometric parameter delta in stability domain of TiO2-delta with rutile structure can be represented by the relation, Delta mu o(2) = -6RT In delta - 711970(+/-1600) J/mol. The corresponding relation between non-stoichiometric parameter delta and partial pressure of oxygen across the whole stability range of TiO2-delta at 1573 K is delta proportional to P-O2(-1/6). It is therefore evident that the oxygen deficient behavior of nonstoichiometric TiO2-delta is dominated by the presence of doubly charged oxygen vacancies and free electrons. The high-precision measurements enabled the resolution of oxygen potential steps corresponding to the different Magneli phases (Ti-n O2n-1) up to n = 15. Beyond this value of n, the oxygen potential steps were too small to be resolved. Based on composition of the Magneli phase in equilibrium with TiO2-delta, the maximum value of n is estimated to be 28. The chemical potential of titanium was derived as a function of composition using the Gibbs-Duhem relation. Gibbs energies of formation of the Magneli phases were derived from the chemical potentials of oxygen and titanium. The values of -2441.8(+/-5.8) kJ/mol for Ti4O7 and -1775.4(+/-4.3) kJ/mol for Ti3O5 Obtained in this study refine values of -2436.2(+/-26.1) kJ/mol and-1771.3(+/-6.9) kJ/mol, respectively, given in the JANAF thermochemical tables.

Nature of nitrogen adsorbed on transition metal surfaces as revealed by electron spectroscopy and cognate techniques

The nature of the chemisorbed states of nitrogen on various transition metal surfaces is discussed comprehensively on the basis of the results of electron spectroscopic investigations augmented by those from other techniques such as LEED and thermal desorption. A brief discussion of the photoemission spectra of free N2, a comparison of adsorbed N2 and CO as well as of physisorption of N2 on metal surfaces is also presented. We discuss the chemisorption of N2 on the surfaces of certain metals (e.g. Ni, Fe, Ru and W) in some detail, paying considerable attention to the effect of electropositive and electronegative surface modifiers. Features of the various chemisorbed states (one or more weakly chemisorbed gamma-states, strongly chemisorbed alpha-states with bond orders between 1 and 2. and dissociative chemisorbed beta-states) on different surfaces are described and relations between them indicated. While the gamma-state could be a precursor of the alpha-state, the alpha-state could be the precursor of the beta-state and this kind of information is of direct relevance to ammonia synthesis. The nature of adsorption of N2 on the surfaces of some metals (e.g. Cr, Co) deserves further study and such investigations might as well suggest alternative catalysts for ammonia synthesis.

Visualization of enantiomers and determination of homo- and hetero-nuclear residual dipolar and scalar couplings: The natural abundant C-13 edited J/D-resolved NMR techniques

The simple two dimensional C-13-satellite J/D-resolved experiments have been proposed for the visualization of enantiomers, extraction of homo- and hetero-nuclear residual dipolar couplings and also H-1 chemical shift differences between the enantiomers in the anisotropic medium. The significant advantages of the techniques are in the determination of scalar couplings of bigger organic molecules. The scalar couplings specific to a second abundant spin such as F-19 can be selectively extracted from the severely overlapped spectrum. The methodologies are demonstrated on a chiral molecule aligned in the chiral liquid crystal medium and two different organic molecules in the isotropic solutions. (C) 2010 Elsevier B.V. All rights reserved.

Nature inspired optimization techniques for the design optimization of laminated composite structures using failure criteria

The design optimization of laminated composites using naturally inspired optimization techniques such as vector evaluated particle swarm optimization (VEPSO) and genetic algorithms (GA) are used in this paper. The design optimization of minimum weight of the laminated composite is evaluated using different failure criteria. The failure criteria considered are maximum stress (MS), Tsai-Wu (TW) and failure mechanism based (FMB) failure criteria. Minimum weight of the laminates are obtained for different failure criteria using VEPSO and GA for different combinations of loading. From the study it is evident that VEPSO and GA predict almost the same minimum weight of the laminate for the given loading. Comparison of minimum weight of the laminates by different failure criteria differ for some loading combinations. The comparison shows that FMBFC provide better results for all combinations of loading. (C) 2010 Elsevier Ltd. All rights reserved.

An investigation of well-characterized small gold clusters by photoelectron spectroscopy, tunneling spectroscopy, and cognate techniques

After microscopic characterization of the size distributions of gold clusters, deposited on carbon substrates by vacuum evaporation or by soft landing, Au(4f') binding energy of the clusters has been measured as a function of the mean cluster size. Similar measurements have been carried out on Au clusters prepared from sols by chemical means and high-nuclearity cluster compounds. In general, small clusters with a mean diameter of $2 nm show significantly larger binding energies than the bulk metal value, due to the onset of nonmetallicity. Nonmetallicity manifests itself in terms of a tunneling conductance gap only in clusters of diameter ;5 1 nm containing 40 atoms or fewer.

Investigation of the (PEG)xLiCl system using conductivity, DSC and NMR techniques

Electrolytes based on polyethylene glycol (PEG, mol.wt.8000) and LiCl of compositions, (PEG)(x)LiCl, x=4, 6, 8, 10, 12, 40, 60, where x is the O/Li ratio, were prepared by solution casting from methanol solutions. FTIR studies indicate that the ether oxygens of the polymer chain participate in Li+ ion conduction. The presence of a salt-polymer complex that melts around 190 degrees C was evidenced by DSC measurements for the electrolytes with compositions x<12. The highest conductivity was obtained at the composition x=10 which was attributed to the presence of a mostly amorphous compound. NMR measurements indicated two regions of motional narrowing, one attributable to the glass transition and another to translational diffusion.

Stabilization of α-nickel hydoxide in the presence of organic additives: chemical route to bulk synthesis

Organic molecules such as glucose or lactose mediate the synthesis and stabilize alpha-nickel hydroxide in a simple precipitation reaction, while, in the absence of these additives, beta-nickel hydroxide is formed. The additives are not incorporated in the product phase.

Understanding changes in the Himalayan cryosphere using remote sensing techniques

In the Himalayas, a large area is covered by glaciers and seasonal snow and changes in its extent can influence availability of water in the Himalayan Rivers. In this paper, changes in glacial extent, glacial mass balance and seasonal snow cover are discussed. Glacial retreat was estimated for 1868 glaciers in 11 basins distributed in the Indian Himalaya since 1962. The investigation has shown an overall reduction in glacier area from 6332 to 5329km2 from 1962 to 2001/2 - an overall deglaciation of 16%. Snow line at the end of ablation season on the Chhota Shigri glacier observed using field and satellite methods suggests a change in altitude from 4900 to 5200m from the late 1970s to present. Seasonal snow cover was monitored in the 28 river sub-basins using normalized difference snow index (NDSI) technique in Central and Western Himalaya. The investigation has shown that in the early part of winter, i.e. from October to December, a large amount of snow retreat was observed. For many basins located in lower altitude and in the south of the Pir Panjal range, snow ablation was observed throughout the winter season. In addition, average stream runoff of the Baspa basin for the month of December increased by 75%. This combination of glacial retreat, negative mass balance, early melting of seasonal snow cover and winter-time increase in stream runoff might suggest an influence of global warming on the Himalayan cryosphere.

Reduced Order Suboptimal Control Design for a Class of Nonlinear Distributed Parameter Systems Using POD and /spl thetas/-D Techniques

A new computational tool is presented in this paper for suboptimal control design of a class of nonlinear distributed parameter systems. First proper orthogonal decomposition based problem-oriented basis functions are designed, which are then used in a Galerkin projection to come up with a low-order lumped parameter approximation. Next, a suboptimal controller is designed using the emerging /spl thetas/-D technique for lumped parameter systems. This time domain sub-optimal control solution is then mapped back to the distributed domain using the same basis functions, which essentially leads to a closed form solution for the controller in a state feedback form. Numerical results for a real-life nonlinear temperature control problem indicate that the proposed method holds promise as a good suboptimal control design technique for distributed parameter systems.

Joining of dissimilar metals: issues and modelling techniques

Joining of dissimilar metals involves a number of scientific issues, the modelling of which offers unique challenges. This review discusses the complexities in different joining processes and dissimilar combinations, and the corresponding computational techniques that have the potential to address the same. Future directions in modelling at both macroscopic and microscopic scales are also suggested.