Photocyclisation of 3-alkoxy-6-chloro-2-(3-methylthiophen-2-yl)-4H-chromen-4-ones

Photocyclisation of 3-alkoxy-6-chloro-2-(3-methylthiophen-2-yl)-4H-chromen-4-ones in methanol with pyrex filtered UV-light lead to the formation of tetracyclic compounds through intramolecular γ-hydrogen abstraction. The methyl group on the thiophenyl ring does not interfere in the photocyclisation although it does effect the product formation.     

In silico characterization of alkaline proteases from different species of Aspergillus

A total of 49 protein sequences of alkaline proteases retrieved from GenBank representing different species of Aspergillus have been characterized for various physiochemical properties, homology search, multiple sequence alignment, motif, and super family search and phylogenetic tree construction. The sequence level homology was obtained among different groups of alkaline protease enzymes, viz alkaline serine protease, oryzin, calpain-like protease, serine protease, subtilisin-like alkaline proteases. Multiple sequence alignment of alkaline protease protein sequence of different Aspergillus species revealed a stretch of conserved region for amino acid residues from 69 to 110 and 130–204. The phylogenetic tree constructed indicated several Aspergillus species-specific clusters for alkaline proteases namely Aspergillus fumigatus, Aspergillus niger, Aspergillus oryzae, Aspergillus clavatus. The distributions of ten commonly observed motifs were analyzed among these proteases. Motif 1 with a signature amino acid sequence of 50 amino acids, i.e., ASFSNYGKVVDIFAPGQDILSCWIGSTTATNTISGTSMATPHIVGLSCYL, was uniformly observed in proteases protein sequences indicating its involvement with the structure and enzymatic function. Motif analysis of acidic proteases of Aspergillus and bacterial alkaline proteases has revealed different signature amino acid sequences. The superfamily search for these proteases revealed the presence of subtilases, serine-carboxyl proteinase, calpain large subunit, and thermolysin-like superfamilies with 45 representing the subtilases superfamily.     

Demonstration of a 100 Hz repetition rate gain-saturated diode-pumped table-top soft x-ray laser

We demonstrate the operation of a gain-saturated table-top soft x-ray laser at 100?Hz repetition rate. The laser generates an average power of 0.15?mW at λ=18.9 nm, the highest laser power reported to date from a sub-20-nm wavelength compact source. Picosecond laser pulses of 1.5?μJ energy were produced at λ=18.9 nm by amplification in a Mo plasma created by tailoring the temporal intensity profile of single pump pulses with 1?J energy produced by a diode-pumped chirped pulse amplification Yb:YAG laser. Lasing was also obtained in the 13.9?nm line of Ni-like Ag. These results increase by an order of magnitude the repetition rate of plasma-based soft x-ray lasers opening the path to milliwatt average power table-top lasers at sub-20?nm wavelengths.     

Metal ions as cofactors for aggregation of therapeutic peptide salmon calcitonin

The effects of multivalent metal ions (Cu(2+)/Zn(2+)/Al(3+)) on the aggregation of salmon calcitonin (sCT)--a therapeutic peptide used worldwide in the treatment of osteoporosis and Paget's disease--have been studied in vitro using NMR (both solution state and solid state), TEM, ThT-fluorescence, and FT-IR spectroscopy. Overall, the various results indicated that the metal-ions-induced conformational transitions in the peptide--mostly toward the β-sheet--facilitate the aggregation of sCT in solution. First, the solution NMR has been used to check the interaction between the peptide and the metal ions. Following this, the formation and characterization of calcitonin aggregates has been performed using TEM, solid state NMR, and FT-IR spectroscopy. The TEM and ThT-fluorescence results revealed that the sCT peptide incubated with Cu(2+) and Zn(2+) metal ions (in aqueous environment) forms globular aggregates, while that with Al(3+) ions forms fibrils. The solid state NMR and FT-IR studies revealed the presence of a substantial amount of β-sheet content in sCT aggregates (formed in the presence of these metal ions) compared to the monomeric sCT, indicating that the metal binding is concomitant with conformational changes. The present study becomes crucial while prescribing this drug peptide under physio-pathological conditions associated with an abnormal accumulation of metal ions (Cu(2+)/Zn(2+)/Al(3+)) in the body (i.e., abnormal metal ion homeostasis).     

Characterization of amino acid‐derived betaines by electrospray ionization tandem mass spectrometry

Betaines belong to the naturally occurring osmoprotectants or compatible solutes present in a variety of plants, animals and microorganisms. In recent years, metabolomic techniques have been emerging as a fundamental tool for biologists because the constellation of these molecules and their relative proportions provide with information about the actual biochemical condition of a biological system. Therefore, identification and characterization of biologically important betaines are crucial, especially for metabolomic studies. Most of the natural betaines are derived from amino acids and related homologues. Although, theoretically, all the amino acids can be converted to corresponding betaines by simple methylation of the amine group, only a few of the amino acid‐derived betaines were fully characterized in the literature. Here, we report a combined electrospray ionization tandem and high‐resolution mass spectrometry study of all the betaines derived from amino acids, including the isomeric betaines. The decomposition pathway of protonated, sodiated and potassiated molecule ions that enable unambiguous characterization of the betaines including the isomeric betaines and overlapping ionic species of different betaines is distinctive. Copyright © 2012 John Wiley & Sons, Ltd.     

Binomial and factorial congruences for Fq[t]

We present several elementary theorems, observations and questions related to the theme of congruences satisfied by binomial coefficients and factorials modulo primes (or prime powers) in the setting of polynomial ring over a finite field. When we look at the factorial of n or the binomial coefficient ‘n choose m’ in this setting, though the values are in a function field, n and m can be usual integers, polynomials or mixed. Thus there are several interesting analogs of the well-known theorems of Lucas, Wilson etc. with quite different proofs and new phenomena.     

A Helson-Lowdenslager-deBranges Theorem in

This paper presents a generalization of the invariant subspace theorem of Helson and Lowdenslager along the lines of de Branges' generalization of Beurling's theorem.

     

Kinetics and Mechanism of Ruthenium(III) Catalyzed Oxidation of Dimethyl Sulfoxide by N-Chlorosuccinimde in Aqueous Alkaline Medium

The ruthenium(III) catalyzed oxidation of dimethyl sulfoxide by N-chlorosuccinimide (NCS) in aqueous alkaline medium is found to occur via substrate-catalyst complex formation followed by the interaction of active species of NCS viz., HOCl and the complex in a slow step to yield the products with regeneration of the catalyst. One of the products, succinimide, retards the rate of reaction. The reaction is first order in [NCS] and [Ru(III)], lower than first order in [DMSO] and of inverse fractional order in [OH^-]. A suitable mechanism is proposed and the reaction constants of individual steps involved in the mechanism have been evaluated. This revised version was published online in June 2006 with corrections to the Cover Date.