Thermal and magnetic studies of mixed ligand complexes of chromium(III) containing dithiocarbamate and acetylacetone/oxine/glycine moieties

Chromium(III) complexes of the type Cr(A)(A′)2, Cr(A)2(A′) and Cr(A)3 have been prepared (whereA is either piperidyldithiocarbamate or morpholyldithiocarbamate andA′ is glycine or oxine or acetylacetone moiety). The mixed ligand complexes have been charac terized by elemental analyses, magnetic susceptibility measurements and thermal studies. The complexes show magnetic moment in the range of 3.5–4.3 B.M. which corresponds to three unpaired electrons. TG studies have also been carried out, in order to study the mode of decomposition of the complexes and to evaluate various kinetic parameters.     

Chelation controlled regiospecific O-substitution of myo-inositol orthoesters: convenient access to orthogonally protected myo-inositol derivatives

A general method for the completely regioselective protection of the three secondary hydroxyl groups of orthoester derivatives of myo-inositol, utilizing the subtle differences in reactivity exhibited by its alkali metal alkoxides due to differences in their ability to form chelates, is described. This method provides convenient access to orthogonally protected myo-inositol derivatives. A comparison of the methylation of racemic 4-O-trityl-myo-inositol 1,3,5-orthoformate in the presence of sodium or lithium ions showed that stabilization of the C4-alkoxide by chelation with lithium overrides steric hindrance offered by the C6-axial substituent in deciding the regioselectivity during the nucleophilic O-substitution.     

Composition and in vitro cytotoxic activities of essential oil of Hedychium spicatum from different geographical regions of western Himalaya by principal components analysis

The rhizome of Hedychium spicatum has been widely used in traditional medicines. The present study deals with the evaluation of the cytotoxic potential of rhizome essential oils from four different regions of the Western Himalaya (India) along with comparative correlation analysis to characterise the bioactive cytotoxic component. The essential oils were coded as MHS-1, MHS-2, MHS-3 and MHS-4, and characterised using GC-FID and GC–MS. The main volatile compounds identified were 1,8-cineol, eudesmol, cubenol, spathulenol and α-cadinol. In vitro cytotoxic activities were assessed against human cancer cell lines such as, the lung (A549), colon (DLD-1, SW 620), breast (MCF-7, MDA-MB-231), head and neck (FaDu), and cervix (HeLa). MHS-4 is significantly active in comparison to other samples against all cancer cell lines. Sample MHS-4 has major proportion of monoterpene alcohol mainly 1,8-cineol. Principal components analysis was performed for the experimental results and all four samples were clustered according to their percentage inhibition at different doses.     

Targeted mass spectrometric strategy for global mapping of ubiquitination on proteins

Post-translational modifications of proteins including phosphorylation, glycosylation, acetylation and ubiquitination facilitate the regulation of many cellular processes and intracellular signaling events. Ubiquitination plays a key role in the functional regulation and degradation of many classes of proteins, and the study of ubiquitination and poly-ubiquitination has emerged as one of the most active areas in proteomic research. A variety of mass spectrometric methods have been described for the identification of ubiquitination sites, the study of poly-ubiquitin topology and the identification of ubiquitin substrates. The most popular workflow for both ubiquitination site mapping and poly-ubiquitination chain topology characterization is to take advantage of the Gly-Gly signature on the substrate's lysine residue observed after tryptic digestion. Although a number of protocols have been described for the mapping of ubiquitination sites, one major challenge is that ubiquitination is typically heterogeneous, and several lysine residues may be ubiquitinated within a protein. When multiple ubiquitination sites are present, multiple analyses are often required to cover all of the potential modification sites which in turn can necessitate the usage of larger quantities of material. In addition, the level of ubiquitination on endogenous and recombinant proteins may be of low intensity, adding further analytical challenges in the identification of this modification. The use of the multiple reaction monitoring (MRM)-initiated detection and sequencing workflow (MIDAS) for the identification of phosphorylation sites has previously been described. Here, we explore the use of an MRM workflow for ubiquitination site mapping on the substrate protein, receptor interacting protein (RIP).     

Synthesis and structural characterization of glucopyranosylamide films on gold

Self-assembled monolayers (SAMs) of glucose derivatives on gold have been prepared from alpha- and beta-glucopyranosylamide derivatives. The glucosyl conjugates were synthesized stereoselectively via the in situ generation of glucosyl isoxazolines followed by treatment with thiopyridyl esters. The resulting film structures were characterized by atomic force microscopy, reflection Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The experimental data indicated that alpha- or beta-linked glucopyranosylamide derivatives with free hydroxyl groups attach to gold via the thiol linker. Both derivatives form monolayer films with high packing densities--comparable to those typically observed for alkanethiol monolayers on gold. Acetate analogues of these conjugates do not form SAMs on gold; they form multilayered films under identical deposition conditions.     

Highly Efficient Non‐Palladium‐Catalyzed Controlled Synthesis and X‐ray Analysis of Functionalized 1,2‐Diaryl‐, 1,2,3‐Triaryl‐, and 1,2,3,4‐Tetraarylbenzenes

A general, two‐step, highly efficient synthesis of 1,2‐diaryl‐, 1,2,3‐triaryl‐, and 1,2,3,4‐tetraarylbenzenes from simple stitching of α‐oxo‐ketene‐S,S‐acetals and active methylene compounds via a lactone intermediate is described. This procedure offers easy access to highly functionalized arylated benzenes that contain sterically demanding groups in good to excellent yields. The novelty of the procedure lies in the construction of aromatic compounds with the desired conformational flexibility along the molecular axis in a transition‐metal‐free environment through easily accessible precursors. Crystal analysis of these arylated benzene scaffolds showed that the peripheral aryl rings are arranged in a propeller‐like fashion with respect to the central benzene ring. Examination of the crystal packing in the structure of a 1,2,3,4‐tetraarylbenzene revealed an N???π interaction between molecules related by a two‐fold screw axis running in the direction of the a axis. Interestingly, the repeating array of N???π interactions around the axis of this 1,2,3,4‐tetraarylbenzene forces the molecules into a helical pattern.     

Synthesis and Biological Evaluation of 5′-O-Fatty Acyl Ester Derivatives of 3′-Fluoro-2′,3′-dideoxythymidine as Potential Anti-HIV Microbicides

A number of 5′-O-fatty acyl derivatives of 3′-fluoro-2′,3′-dideoxythymidine (FLT, 1) were synthesized. These conjugates were evaluated for their potential as topical microbicides with anti-HIV activity against cell-free (X4 and R5), cell-associated, and multidrug-resistant viruses. Compared to FLT and 3′-azido-2′,3′-dideoxythymidine (AZT), 5′-O-(12-azidododecanoyl) (5), 5′-O-myristoyl (6), and 5′-O-(12-thioethyldodecanoyl) (8) derivatives of FLT were found to be more active against both cell-free viruses (lymphocytotropic and monocytotropic strains) with EC₅₀ values of 0.4 μM, 1.1 μM, and <0.2 μM, respectively, as well as cell-associated virus with EC₅₀ values of 12.6, 6.4, and 2.3 μM, respectively. Conjugates 5, 6, and 8 exhibited >4 and >30 times better antiviral index than FLT and AZT, respectively. Conjugates 5 and 8 were significantly more potent than FLT against many multidrug-resistant strains. A comparison of the anti-HIV activity with the corresponding non-hydrolyzable ether conjugates suggested that ester hydrolysis to FLT and fatty acids is critical to enable anti-HIV activity. Cellular uptake studies were conducted using fluorescent derivatives of FLT attached with 5(6)-carboxyfluorescein through either β-alanine (23) or 12-aminododecanoic acid (24) spacers. The lipophilic fluorescent analog with a long chain (24) showed more than 12 times higher cellular uptake profile than the fluorescent analog with a short chain (23). These studies further confirmed that the attachment of fatty acids improved the cellular uptake of nucleoside conjugates. In addition, 5, 6, and 8 were the least cytotoxic and did not alter vaginal cell and sperm viability compared to the positive control, a commercial topical spermicide (N-9), which significantly decreased sperm and vaginal cell viability inducing the generation of proinflammatory cytokines.     

Designs of all-optical buffer and OR gate using SOA-MZI

In the paper a novel scheme for an all-optical buffer and OR logic gates based on Mach–Zehnder interferometer structure is discussed. The operations of the scheme with 10 Gb/s return to zero pseudorandom bit streams simulated correctly with extinction ratio 19.21 and 17.61 dB where Q-factor 25.94 and 11.22 for buffer and OR gate respectively. With the help of numerical analyses, it can be seen that the extinction ratio of the OR operation is degraded and the output pattern effect is decreased by 0.9 dB compared to optical buffer schemes under the same condition. Furthermore, the carrier recovery time of a semiconductor optical amplifier is no longer a crucial parameter to restrict the operation speed of this scheme. The scheme is also potentially capable of multi input OR operation at higher speed.     

Magneto-thermo-elastic waves in an infinite perfectly conducting elastic solid with energy dissipation

The generalized thermo-elasticity theory, i.e., Green and Naghdi （G-N） Ⅲ theory, with energy dissipation （TEWED） is employed in the study of time-harmonic plane wave propagation in an unbounded, perfectly electrically conducting elastic medium subject to primary uniform magnetic field. A more general dispersion equation with com- plex coefficients is obtained for coupled magneto-thermo-elastic wave solved in complex domain by using the Leguerre＇s method. It reveals that the coupled magneto-thermoelastic wave corresponds to modified dilatational and thermal wave propagation with finite speeds modified by finite thermal wave speeds, thermo-elastic coupling, thermal diffusivity, and the external magnetic field. Numerical results for a copper-like material are presented.