Deoxycholate induced tetramer of αA-crystallin and sites of phosphorylation: fluorescence correlation spectroscopy and femtosecond solvation dynamics

Structure and dynamics of acrylodan labeled αA-crystallin tetramer formed in the presence of a bile salt (sodium deoxycholate, NaDC) has been studied using fluorescence correlation spectroscopy (FCS) and femtosecond up-conversion techniques. Using FCS it is shown that, the diffusion constant (D(t)) of the αA-crystallin oligomer (mass ~800 kDa) increases from ~35 μm(2) s(-1) to ~68 μm(2) s(-1). This corresponds to a decrease in hydrodynamic radius (r(h)) from ~6.9 nm to ~3.3 nm. This corresponds to about 10-fold decrease in molecular mass to ~80 kDa and suggests formation of a tetramer (since mass of αA-crystallin monomer is ~20 kDa). The steady state emission maximum and average solvation time (<τ(s)>) of acrylodan labeled at cysteine 131 position of αA-crystallin is markedly affected on addition of NaDC, while the tryptophan (trp-9) becomes more exposed. This suggests that NaDC binds near the cys-131 and makes the terminal region of αA-crystallin exposed. This may explain the enhanced auto-phosphorylation activity of αA-crystallin near the terminus of the 173 amino acid protein (e.g., at the threonine 13, serine 45, or serine 169 and 172) and suggests that phosphorylation at ser-122 (close to cys-131) is relatively less important.     

Synthesis of the Upstream Terminal Disaccharide of the O-Antigenic Polysaccharide of Vibrio cholerae O37

The terminal disaccharide of the O-antigenic polysaccharide of Vibrio cholerae O37, 4-O-methyl-α-D-QuiNAc-(1→4)-α-d-QuiNAc, was synthesized as methyl glycoside involving glycosylation between glycosyl donor ethyl 2-azido-3-O-benzyl-2,6-dideoxy-4-O-methyl-6-iodo-1-thio-α-d-glucopyranoside and glycosyl acceptor methyl 2-azido-3-O-benzyl-2,6-dideoxy-6-iodo-α-d-glucopyranoside. Dehalogenation, global deprotection, and reduction of the azide to amine were effected in one step by catalytic hydrogenation. It was followed by selective N-acetylation to give the desired deprotected disaccharide.     

Biomass‐derived Nitrogen and Phosphorus Co‐doped Hierarchical Micro/mesoporous Carbon Materials for High‐performance Non‐enzymatic H2O2 Sensing

Nitrogen and phosphorus co‐doped hierarchical micro/mesoporous carbon (N,P‐MMC) was prepared by simple thermal treatment of freeze‐dried okra in the absence of any other additives. The 0.96 wt % of N and 1.47 wt % of P were simultaneously introduced into the graphitic framework of N,P‐MMC, which also possesses hierarchical porous structure with mesopores centered at 3.6 nm and micropores centered at 0.79 nm. Most importantly, N,P‐MMC carbon exhibits excellent catalytic activity for electrocatalytic reduction of H₂O₂, resulting in a new strategy to construct non‐enzymatic H₂O₂ sensor. The N,P‐MMC‐based H₂O₂ sensor displays two linear detection range about 0.1 mM–10 mM (R²=0.9993) and 20 mM–200 mM (R²=0.9989), respectively. The detection limit is estimated to be 6.8 μM at a signal‐to‐noise ratio of 3. These findings provide insights into synthesizing functional heteroatoms doped porous carbon materials for biosensing applications.     

New synthesis of 4-phenyl coumarins: dalbergin and nordalbergin

A successful route to the synthesis of 4-phenylcoumarins in good yield has been developed. Vanillin on Dakin reaction yielded O-methoxyhydroquinone which on subsequent condensation with ethyl benzoyl acetate furnished dalbergin (overall yield, 65%). The latter on demethylation afforded nordalbergin (overall yield, 62%). This procedure is applicable to the synthesis of other 4-phenylcoumarins.     

Biomimetic Cyclization of Enamide-Containing Polyenes as a New Route to Azapolycycles

Enamide 4 was studied for its effectiveness as a polyene precursor in biomimetic cyclizations. While most conventional Lewis acids were poor cyclization promoters, FeCl(3).6H(2)O initiated the conversion of 4 into tricycles 6 and 7 in excellent yield. The two isomeric products result from the cyclization of intermediate aldehyde 5 by either a chair or boat B-ring transition state. These results suggest that enamides may be incorporated into polyene precursors for the construction of larger azapolycycles such as azasteroids.     

Kinetics of densification of powder compacts during the initial stage of sintering with constant rates of heating. A thermal analysis approach. Part I. Theoretical considerations

Densification of powder compacts during sintering (initial stage) under constant heating rate has been studied and methods of analysing the densification kinetic data have been suggested. p]Green compacts can broadly be envisaged to consists of two phases, viz. porosity and solid material. Annihilation of the pores causes densification of the compacts during sintering. So, the kinetics of the initial stage of densification may very well be represented by a densification parameter (α),where

Here, v_s and v_p,respectively, denote the pore volumes of the sintered and the green compact. Continuous and in situ recording of the linear shrinkage (ΔL) of the compacts during the sintering may be done with a dilatometer and using this value of ΔL,the value of α at any temperature (T) may be calculated.These kinetic data (α vs. T)may then be subjected to analysis using the well-known methods of thermal analysis, and the so-called “derived activation energy (E)” of densification may be evaluated therefrom. The exact form of g(α)—governing rate equation—is ascertained by a trial-and-error method.These methods were used to analyse the densification kinetic data of haematite, copper and silver powders (with particles of irregular shapes and sizes). The results of such analyses will appear on other parts of this paper.     

Patterning of neural stem cells on poly(lactic-co-glycolic acid) film modified by hydrophobin

Patterning of neural stem cells (NSCs) is of great importance for its potential applications in the therapy of nerve injuries. Due to the critical requirements and the great difficulty in NSCs cultivation, developing new methods for NSCs patterning is very challenging and has progressed slowly in recent years. In this study, we reported a new method for patterning NSCs on a hydrophobin II (HFBI) modified poly(lactic-co-glycolic acid) (PLGA) film by using microcontact printing (μCP) technique. HFBI modification converted the PLGA surface from hydrophobic to hydrophilic, which should facilitate the absorption of serum on it. Serum was transferred onto the modified PLGA film by microcontact printing (μCP) to promote NSCs adhesion on the PLGA surface. Since the serum-coated PLGA surface promoted NSCs adhesion and the serum-free PLGA surface inhibited NSCs adhesion, micro-patterns of NSCs were obtained by directly culturing NSCs on the PLGA surface patterned with serum. This method allows the precise control of NSCs adhesion on the PLGA film without using the conventional cell-repellent species, which is anticipated to make great contribution in the fields of therapy of nerve injuries.     

Determination of molybdenum and tungsten at trace levels in rocks and minerals by solvent extraction and X-ray fluorescence spectrometry

Separation by solvent extraction followed by X-ray fluorescence spectrometry has been used for determination of molybdenum and tungsten in rocks and minerals. Samples are decomposed either by heating with a mixture of hydrofluoric acid and perchloric acid or by fusion with potassium pyrosulphate, followed by extraction of molybdenum and tungsten with N-benzoylphenylhydroxylamine in toluene from 4-5M sulphuric acid medium. The extract is collected on a mass of cellulose powder, which is dried in vacuum, mixed thoroughly and pressed into a disc for XRF measurements. The method is free from all matrix effects and needs no mathematical corrections for interelement effects. The method is suitable for determination of molybdenum and tungsten in geological materials down to ppm levels, with reasonable precision and accuracy.