Neutral Hexacoordinate Phosphorus(V) Compounds Containing Tridentate Dianionic Ligands Obtained from Salicylideneamines, 2,2′-Azodiphenol and a Thio(Diphenol)

Abstract

Neutral hexacoordinate phosphorus(V) compounds of a number of univalent bidentate ligands are known.^l,2 The silylated forms of tridentate, dianionic Schiff base ligands: N-(2-hydroxyphenyl)salicylideneamine H₂L^I, N-(4-tert-butyl-2-hydroxyphenyl)-salicylideneamine H₂L^II, N-(2-hydroxy-4-nitrophenyl)salicylidene-amine H₂L^III, and 2,2′-azodiphenol H₂L^IV gave, with halogeno- and (trifluoromethyl)halogenophosphoranes, neutral hexa-coordinate derivatives with bis-chelate structures. The ligands form bicyclic five- and six-membered chelate rings in a meridional conformation, with two P-O bonds and one N→P donor bond. Hexacoordinate structures were evidenced by high-field ³¹P NMR chemical shifts (-136 to -148 ppm), characteristic J _PF coupling patterns and was further substantiated by crystal structures of Cl₃L^II (A) and F₃PL^II (B).     

A Yeast Chemical Genetic Screen Identifies Inhibitors of Human Telomerase

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Highlights? Growth arrest induced by human telomerase in yeast is chemically reversible ? Readout is sensitive to telomerase catalytic activity and telomere recruitment ? Three cell-permeable compounds also inhibit purified human telomerase ? Yeast can be successfully used to screen for human telomerase inhibitors     

Future of the Particle Replication in Nonwetting Templates (PRINT) Technology

Particle replication in nonwetting templates (PRINT) is a continuous, roll‐to‐roll, high‐resolution molding technology which allows the design and synthesis of precisely defined micro‐ and nanoparticles. This technology adapts the lithographic techniques from the microelectronics industry and marries these with the roll‐to‐roll processes from the photographic film industry to enable researchers to have unprecedented control over particle size, shape, chemical composition, cargo, modulus, and surface properties. In addition, PRINT is a GMP‐compliant (GMP=good manufacturing practice) platform amenable for particle fabrication on a large scale. Herein, we describe some of our most recent work involving the PRINT technology for application in the biomedical and material sciences.     

Patterning Surfaces for Controlled Platelet Adhesion and Detection of Dysfunctional Platelets

Platelets play a fundamental role in thrombus formation and in the pathogenesis of arterial thrombosis. Patterning surfaces for controlled platelet adhesion paves the way for adhesion and activation mechanisms in platelets and detection of platelet functional defects. Here, a new and simple method based on controlled polymerization of 2‐methacryloyloxyethyl phosphorylcholine (MPC) on the surface of styrene‐block‐(ethylene‐co‐butylene)‐block‐styrene (SEBS) is shown. The competition between polymerization and degradation enables platelet adhesion on SEBS to be switched on and off. The adhesive sites of the platelets can be down to single cell level, and the dysfunctional platelets can be quantitatively detected.

     

Determination of avilamycin as dichloroisoeverninic acid in poultry and porcine muscles by isotope dilution liquid chromatography–tandem mass spectrometry

Avilamycin residue in food is regulated as its marker residue dichloroisoeverninic acid (DIA). An isotope dilution liquid chromatography–tandem mass spectrometry method is established for the accurate determination of DIA in animal muscles without any pre-extraction and preconcentration prior to alkaline hydrolysis. Optimization of the sample cleanup procedures such as liquid–liquid extraction and solid phase extraction was performed by fine-tuning several critical parameters to reduce the matrix effects. Quantification of DIA in edible muscle was accomplished by using matrix-matched calibration with dichloroisoeverninic acid-d₆ as internal standard. The method was validated with DIA and avilamycin-fortified poultry and porcine muscles at three different levels (25, 50, and 100 μg/kg). Conversion of avilamycin to DIA by alkaline hydrolysis was ≥92 %. The recoveries of DIA in both muscles at three fortification levels ranged from 94 to 106 % and RSDs were ≤11 % in all cases. The estimated limit of detection values in poultry and porcine muscles were 2.7 and 0.7 μg/kg, respectively. The estimated limit of quantitation values in poultry and porcine muscles were 8.3 and 2.4 μg/kg, respectively. This method is suitable for routine monitoring of avilamycin residue in food safety surveillance programs.     

Performance evaluation of polycyclic aromatic hydrocarbons analysis in sediment from proficiency testing with metrological reference values

This paper describes a metrological approach to evaluate the measurement capability of laboratories participating in two proficiency testing (PT) programmes involving the analysis of five polycyclic aromatic hydrocarbons (PAHs) in sediment samples. Reference values of PAHs in the programmes for performance assessment were obtained from an accurate isotope dilution gas chromatography mass spectrometry (ID-GCMS) method which was thoroughly validated and verified. Isotope dilution mass spectrometry (IDMS) technique usually has a well-defined measurement uncertainty budget and a traceability link to an International System of Units. Provision of the metrological reference values in PT enables the establishment of a technical platform to assess the actual competence of the participating laboratories in sediment PAHs analysis. Results of the PT programmes showed that about 80 % of the laboratories employed gas chromatography in their analyses and the remaining used liquid chromatography. Irrespective of the techniques being used, however, the majority of the participating laboratories were observed to underestimate values in which the mean values of the five reported PAHs were less than those of the ID-GCMS-derived reference values by 13–20 %. Only 41–44 % of the participating laboratories were able to achieve satisfactory z-scores. The present study revealed that the reinforcement of the capability for accurate measurement of PAHs in sediment samples in laboratories worldwide should be addressed.     

Synthesis of Benzo[a]Phenanthro[9,10-e]-Cyclooctene

A phenanthrene-fused cyclooctatetraene, namely benzo[a]phenanthro[9,10-e]cyclooctene has been synthesized by employing the “Reich-Paquette” procedure.     

Message passing interface and multithreading hybrid for parallel molecular docking of large databases on petascale high performance computing machines

A mixed parallel scheme that combines message passing interface (MPI) and multithreading was implemented in the AutoDock Vina molecular docking program. The resulting program, named VinaLC, was tested on the petascale high performance computing (HPC) machines at Lawrence Livermore National Laboratory. To exploit the typical cluster‐type supercomputers, thousands of docking calculations were dispatched by the master process to run simultaneously on thousands of slave processes, where each docking calculation takes one slave process on one node, and within the node each docking calculation runs via multithreading on multiple CPU cores and shared memory. Input and output of the program and the data handling within the program were carefully designed to deal with large databases and ultimately achieve HPC on a large number of CPU cores. Parallel performance analysis of the VinaLC program shows that the code scales up to more than 15K CPUs with a very low overhead cost of 3.94%. One million flexible compound docking calculations took only 1.4 h to finish on about 15K CPUs. The docking accuracy of VinaLC has been validated against the DUD data set by the re‐docking of X‐ray ligands and an enrichment study, 64.4% of the top scoring poses have RMSD values under 2.0 Å. The program has been demonstrated to have good enrichment performance on 70% of the targets in the DUD data set. An analysis of the enrichment factors calculated at various percentages of the screening database indicates VinaLC has very good early recovery of actives. © 2013 Wiley Periodicals, Inc.     

Interaction of Metal–Dipeptide Complex with Ninhydrin in the Absence and Presence of Conventional CTAB Surfactant

The present work is aimed at studying the interaction between copper-glycyltyrosine [(Cu(II)-Gly-Tyr)]⁺ and ninhydrin in water and in micelles formed by cetyltrimethylammonium bromide (CTAB) using spectrophometric measurements at 80°C and pH 5.0. The order of reaction remains the same in the two systems, that is, first- and fractional-order kinetics with respect to [Cu(II)-Gly-Tyr]⁺ and [ninhydrin], respectively, in the excess of ninhydrin over [Cu(II)-Gly-Tyr]⁺. It was observed that the product formed is same in both the media. The reaction is catalyzed by CTAB, and the maximum rate enhancement is about three fold. Quantitative kinetic analysis of k_ψ–[CTAB] data was explained in terms of pseudo-phase of the micelles (assuming the association/incorporation of both the reactants at the micellar surface).