Structural characterization of folded and extended conformations in peptides containing gamma amino acids with proteinogenic side chains: crystal structures of gamma(n), (alpha gamma)(n) and gamma gamma delta gamma sequences

The crystal structures of nine peptides containing gamma(4)Val and gamma(4)Leu are described. The short sequences Boc-gamma(4)(R)Val](2)-OMe 1, Boc-gamma(4)(R)Val](3)-NHMe 2 and Boc-gamma(4)(S)Val-gamma(4)(R)Val-OMe 3 adopt extended apolar, sheet like structures. The tetrapeptide Boc-gamma(4)(R)Val](4)-OMe 4 adopts an extended conformation, in contrast to the folded C-14 helical structure determined previously for Boc-gamma(4)(R)Leu](4)-OMe. The hybrid alpha gamma sequence Boc-Ala-gamma(4)(R)Leu](2)-OMe 5 adopts an S-shaped structure devoid of intramolecular hydrogen bonds, with both alpha residues adopting local helical conformations. In sharp contrast, the tetrapeptides Boc-Aib-gamma(4)(S)Leu](2)-OMe 6 and Boc-Leu-gamma(4)(R)Leu](2)-OMe 7 adopt folded structures stabilized by two successive C-12 hydrogen bonds. gamma(4)Val residues have also been incorporated into the strand segments of a crystalline octapeptide, Boc-Leu-gamma(4)(R)Val-Val-(D)Pro-Gly-Leu-gamma(4)(R)Val-Val-OMe 8. The gamma gamma delta gamma tetrapeptide containing gamma(4)Val and delta(5)Leu residues adopts an extended sheet like structure. The hydrogen bonding pattern at gamma residues corresponds to an apolar sheet, while a polar sheet is observed at the lone delta residue. The transition between folded and extended structures at gamma residues involves a change of the torsion angle from the gauche to the trans conformation about the C-beta-C-alpha bond.

Effective Degradation of Aqueous Nitrobenzene Using the SrFeO3-delta Photocatalyst under UV Illumination and Its Kinetics and Mechanistic Studies

In this article, the SrFeO3-delta photocatalyst was synthesized by a solution combustion method and applied for the photocatalytic degradation of aqueous nitrobenzene in the presence and absence of H2O2. The SrFeO3-delta photocatalyst was characterized by XRD, FT-IR, FE-SEM, TEM, TG-DTG, XPS, and UV visible spectroscopy. The band gap energy of SrFeO3-delta was found to be 3.75 eV which lies in the UV region. The XPS results indicate that the oxidation state of Sr and Fe in SrFeO3-delta was 2+ and 3+, respectively, and the surface atomic ratio of Sr and Fe is 0.995. The photocatalytic activity reveals that the degradation of nitrobenzene over the SrFeO3-delta catalyst itself (UV/SFO) is superior compared to SrFeO3-delta in the presence of H2O2 (UV/SFO/H2O2) with a degradation efficiency of 99-96%. The degradation of nitrobenzene obeys first-order kinetics in both UV/SFO and UV/SFO/H2O2 processes. The decrease in degradation efficiency with UV/SFO/H2O2 was attributed due to the formation of strontium carbonate on the photocatalyst surface.

Peptide delta-Turn: Literature Survey and Recent Progress

Among the various types of a-peptide folding motifs, delta-turn, which requires a central cis-amide disposition, has been one of the least extensively investigated. In particular, this main-chain reversal topology has been studied in-depth neither in linear/cyclic peptides nor in proteins. This Minireview article assembles and critically analyzes relevant data from a literature survey on the d-turn conformation in those compounds. Unpublished results from recent conformational energy calculations and a preliminary solution-state analysis on a small model peptide, currently ongoing in our laboratories, are also briefly outlined.

Relationship between entropy and diffusion: A statistical mechanical derivation of Rosenfeld expression for a rugged energy landscape

Diffusion-a measure of dynamics, and entropy-a measure of disorder in the system are found to be intimately correlated in many systems, and the correlation is often strongly non-linear. We explore the origin of this complex dependence by studying diffusion of a point Brownian particle on a model potential energy surface characterized by ruggedness. If we assume that the ruggedness has a Gaussian distribution, then for this model, one can obtain the excess entropy exactly for any dimension. By using the expression for the mean first passage time, we present a statistical mechanical derivation of the well-known and well-tested scaling relation proposed by Rosenfeld between diffusion and excess entropy. In anticipation that Rosenfeld diffusion-entropy scaling (RDES) relation may continue to be valid in higher dimensions (where the mean first passage time approach is not available), we carry out an effective medium approximation (EMA) based analysis of the effective transition rate and hence of the effective diffusion coefficient. We show that the EMA expression can be used to derive the RDES scaling relation for any dimension higher than unity. However, RDES is shown to break down in the presence of spatial correlation among the energy landscape values. (C) 2015 AIP Publishing LLC.

Synthesis and Photoluminescence Properties of Eu3+ activated Ce0.5Al0.5O2-delta Nanophosphors for WLEDs Application

A series of Eu3+ activated Ce0.5Al0.5O2-delta nanophosphors have been synthesized by the nitrate - citrate gel combustion method. All the compounds crystallized in the cubic fluorite CeO2 structure with space group Fm-3m (No. 225). FESEM revealed the flakes-like morphology. The average particle size was estimated from TEM studies and found to be in the range 15-25 nm. The values were in good agreement with the Scherer's method. In photoluminescence (PL) spectra, the D-5(0) -> F-7(2) (612 nm) transition dominates than other transitions which indicates that the Eu3+ ions occupy a site without inversion center. CIE chromaticity diagram confirmed that these nanophosphors can be useful in the fabrication of red component in white light emitting diodes (WLEDs).

Potency and pharmacokinetics of broad spectrum and isoform-specific p110 gamma and delta inhibitors in cancers

Emerging data on cancer suggesting that target-based therapy is promising strategy in cancer treatment. PI3K-AKT pathway is extensively studied in many cancers; several inhibitors target this pathway in different levels. Recent finding on this pathway uncovered the therapeutic applications of PI3K-specific inhibitors; PI3K, AKT, and mTORC broad spectrum inhibitors. Noticeably, class I PI3K isoforms, p110 and p110 catalytic subunits have rational therapeutic application than other isoforms. Therefore, three classes of inhibitors: isoform-specific, dual-specific and broad spectrum were selected for molecular docking and dynamics. First, p110 structure was modelled; active site was analyzed. Then, molecular docking of each class of inhibitors were studied; the docked complexes were further used in 1.2ns molecular dynamics simulation to report the potency of each class of inhibitor. Remarkably, both the studies retained the similar kind of protein ligand interactions. GDC-0941, XL-147 (broad spectrum); TG100-115 (dual-specific); and AS-252424, PIK-294 (isoform-specific) were found to be potential inhibitors of p110 and p110, respectively. In addition to that pharmacokinetic properties are within recommended ranges. Finally, molecular phylogeny revealed that p110 and p110 are evolutionarily divergent; they probably need separate strategies for drug development.

Influence of the upwelling events on the delta C-13 and delta O-18 of the benthic bivalve shells of the South Western Continental Margin of India

In this study, the influence of the spatial and temporal variability of upwelling intensity and the associated biological productivity observed during different phases of summer monsoon along the southwestern continental margin of India (SWCMI) on the delta C-13 and delta O-18 of the inorganic biogenic carbonate shells was investigated. Multispecies benthic bivalve shells (1-5 mm) separated from ten surface sediment samples of SWCMI (off 12 degrees N, 10 degrees N and 9 degrees N) collected during the onset (OSM) and peak (PSM) phase of the summer monsoon of 2009 were analysed for delta C-13 and delta O-18. Sea surface temperature along the study region indicates prominent upwelling in PSM than in OSM. A comparison of analytical and predicted values for delta O-18 in the bivalve shells confirmed their in situ origin during both the sampling periods. During PSM, the delta C-13 values in the benthic bivalve shells were more depleted in C-13 than during OSM which recorded lower values of delta C-13 in dissolved inorganic carbon of bottom waters expected in the study region in PSM due to the upwelled waters, high surface productivity and the associated high degradation of the organic matter in the subsurface and bottom waters. However, this depletion of delta C-13 was not observed in benthic bivalve shells obtained from 10 degrees N, since it is influenced by high export fluxes of carbon from the Cochin estuary since early monsoon months.