Electrophilic aromatic substituted luciferins as bioluminescent probes for glutathione S-transferase assays

New highly sensitive latent bioluminescent luciferin substrates were designed and synthesized for monitoring mammalian glutathione S-transferase (GST) and Schistosoma japonicum enzyme activities.     

Quasi-static deformation and final fracture behaviour of aluminium alloy 5083: influence of cryomilling

The commercial aluminium alloy 5083 was processed via cryomilling to produce nanocrystalline (NC) powders with an average grain size of ～25–50?nm. The powders were subsequently degassed at 723 K (450°C), pre-heated and immediately quasi-isostatic (QI)-forged to produce a thermally stable bulk ultrafine grain (UFG) material having average grain size values ranging from 190 to 350?nm, depending on the processing conditions used. In this paper, the tensile properties and fracture behaviour of the bulk UFG material are presented and compared with the tensile properties of its conventionally processed counterpart. The specific influence of preheat temperature on strength and ductility of the alloy is briefly discussed. Three different pre-heat temperatures of 523, 623 and 723?K (250, 350 and 450°C) were chosen and used with the primary objective of controlling grain growth during forging. The influence of preheat temperature on tensile deformation and final fracture behaviour is highlighted. The macroscopic fracture modes of the bulk nanostructured material (BNM) prepared following three pre-heat temperatures are investigated. The microscopic mechanisms controlling tensile deformation and final fracture behaviour are discussed with regards to the intrinsic microstructural effects in the UFG alloy, nature of loading, and the kinetics and mechanisms of deformation.     

The size Ramsey number of short subdivisions of bounded degree graphs

For graphs G and F, write if any coloring of the edges of G with colors yields a monochromatic copy of the graph F. Suppose is obtained from a graph S with s vertices and maximum degree d by subdividing its edges h times (that is, by replacing the edges of S by paths of length h + 1). We prove that there exists a graph G with no more than edges for which holds, provided that . We also extend this result to the case in which Q is a graph with maximum degree d on q vertices with the property that every pair of vertices of degree greater than 2 are distance at least h + 1 apart. This complements work of Pak regarding the size Ramsey number of “long subdivisions” of bounded degree graphs.     

Energy transfer dynamics in Re(I)-based polynuclear assemblies: a quantitative application of Förster theory

The synthesis, structure, and photophysical properties of a new family of tetranuclear FeRe 3 chromophore-quencher complexes having the general form [Fe(pyacac) 3(Re(bpy')(CO) 3) 3](OTf) 3 (where pyacac = 3-(4-pyridyl)-acetylacetonate and bpy' is 4,4',5,5'-tetramethyl-2,2'-bipyridine (tmb, 1), 2,2'-bipyridine (bpy, 2), and 4,4'-diethylester-2,2'-bipyridine (deeb, 3)) are reported. Time-resolved emission data acquired in room-temperature CH 2Cl 2 solutions exhibited single exponential decay kinetics with observed lifetimes of 450 +/- 30 ps, 755 +/- 40 ps, and 2.5 +/- 0.1 ns for complexes 1, 2, and 3, respectively. The emission in each case is assigned to the decay of the Re (I)-based (3)MLCT excited state; the lifetimes are all significantly less than the corresponding AlRe 3 analogues (2250 +/- 100 ns, 560 +/- 30 ns, and 235 +/- 20 ns for 4, 5, and 6, respectively), which were also prepared and characterized. Electron transfer is found to be thermodynamically unfavorable for all three Re (I)-containing systems: this fact coupled with the absence of optical signatures for the expected charge-separated photoproducts in the time-resolved differential absorption spectra and favorable spectral overlap between the donor emission and the acceptor absorption profiles implicates dipolar energy transfer from the Re (I)-based excited state to the high-spin Fe (III) core as the dominant quenching pathway in these compounds. Details obtained from the X-ray structural data of complex 2 allowed for a quantitative application of Forster energy transfer theory by systematically calculating the separation and spatial orientation of the donor and acceptor transition moment dipoles. Deviations between the calculated and observed rate constants for energy transfer were less that a factor of 3 for all three complexes. This uncommonly high degree of precision testifies to both the appropriateness of the Forster model as applied to these systems, as well as the accuracy that can be achieved in quantifying energy transfer rates if relative dipole orientations can be accounted for explicitly.     

Effects of catalyst introduction methods using PAMAM dendrimers on selective electroless nickel deposition on polyelectrolyte multilayers

We studied the effects of catalyst introduction methods using poly(amidoamine) (PAMAM) dendrimers on the nickel patterning of polyelectrolyte multilayer (PEM)-coated substrates. Three different approaches to palladium catalyst introduction using microcontact printing as the patterning technique were utilized and compared. The catalyst introduction methods are (1) direct catalyst stamping, (2) directed assembly using PAMAM dendrimer stamping, and (3) catalyst encapsulation and reduction to nanoparticles within PAMAM dendrimers before stamping. After patterning, the sample surfaces were placed in an electroless bath where nickel was selectively plated onto the patterns. The patterned surfaces were characterized using optical microscopy, atomic force microscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The metal plating rates on different homogeneous surfaces that simulate the patterned surfaces were measured using a quartz crystal microbalance. In addition, the effect of PEM film thickness (i.e., number of bilayers) on the selectivity of nickel patterning was investigated.     

Chemical fingerprint analysis and quantitative determination of steroidal compounds from Dioscorea villosa,Dioscorea species and dietary supplements using UHPLC‐ELSD

Ultra high‐performance liquid chromatography (UHPLC) with evaporative light scattering detection was used for the quantification of steroidal saponins and diosgenin from the rhizomes or tubers of various Dioscorea species and dietary supplements that were purported to contain Dioscorea. The analysis was performed on an Acquity UPLC? system with an UPLC? BEH Shield RP₁₈ column using a gradient elution with water and acetonitrile. Owing to their low UV absorption, the steroidal saponins were observed by evaporative light scattering detection. The 12 compounds could be separated within 15 min using the developed UHPLC method with detection limits of 5–12 µg/mL with 2 μL injection volume. The analytical method was validated for linearity, repeatability, accuracy, limits of detection and limits of quantification. The relative standard deviations for intra‐ and inter‐day experiments were <3.1%, and the recovery efficiency was 97–101%. The total content of standard compounds was found to be in the ranges 0.01–14.5% and 0.9–28.6 mg daily intake for dry plant materials and solid commercial preparations, respectively. UHPLC–mass spectrometry with a quadrupole mass analyzer and ESI source was used only for confirmation of the identity of the various saponins. The developed method is simple, rapid and especially suitable for quality control analysis of commercial products. Copyright © 2013 John Wiley & Sons, Ltd.