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61.
Arsenic glutathione (As–GSH) complexes have been suggested as possible metabolites in arsenic (As) metabolism. Extensive research has been performed on the toxicological and apoptotic effects of As, while few reports exist on its metabolism at the cellular level due to the analytical challenges. In this study, an efficient extraction method for arsenicals from cell lines was developed. Evaluation of extraction tools; vortex, ultrasonic bath and ultrasonic probe and solvents; water, chemicals (methanol and trifluoroacetic acid), and enzymes (pepsin, trypsin and protease) was performed. GSH effect on the stability of As–GSH complexes was studied. Arsenic metabolites in dimethylarsino glutathione (DMA(GS)) incubated multiple myeloma cell lines were identified following extraction. Intracellular GSH concentrations of myeloma cell lines were imitated in the extraction media and its corresponding effect on the stability and distribution of As metabolites was studied. An enhancement in both extraction recoveries and time efficiency with the use of the ultrasonic probe was observed. Higher stabilities for the As species in water, pepsin and trypsin were obtained. The presence of 0.5 mM GSH in the extraction media (PBS, pH 7.4) could not stabilize the As–GSH complexes compared to the 5 mM GSH, where high stabilization of the complexes was observed over a 5 day storage study. Finally, the speciation analysis of the DMA(GS) culture incubated cell lines in the presence or absence of GSH revealed the important role GSH plays in the preservation of DMA(GS) identity. Hence, caution is required during the extraction of arsenicals especially the As–GSH complexes, since their identification is highly dependent on GSH concentration. 相似文献
62.
Guo J Baker GA Hillesheim PC Dai S Shaw RW Mahurin SM 《Physical chemistry chemical physics : PCCP》2011,13(27):12395-12398
In this work, we provide new experimental evidence for chain length-dependent self-aggregation in room temperature ionic liquids (RTILs) using fluorescence correlation spectroscopy (FCS). In studying a homologous series of N-alkyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl) imide, [C(n)MPy][Tf(2)N] RTILs of varying alkyl chain length (n = 3, 4, 6, 8, and 10), biphasic rhodamine 6G solute diffusion dynamics were observed; both the fast and slow diffusion coefficients decreased with increasing alkyl chain length, with the relative contribution from slower diffusion increasing for longer-chain [C(n)MPy][Tf(2)N]. We propose that the biphasic diffusion dynamics originate from self-aggregation of the nonpolar alkyl chains in the cationic [C(n)MPy](+). 相似文献
63.
Two atom insertions into the silacyclopropane and silacyclopropene rings: mechanistic considerations
Dietmar Seyferth Steven C. Vick Mark L. Shannon Thomas F.O. Lim Don P. Duncan 《Journal of organometallic chemistry》1977,135(2):C37-C44
Novel two atom insertion reactions into the SiC2 rings of hexamethylsilirane and 1,1-dimethyl-2,3-bis(trimethylsilyl)-1-silirene involving the C bonds of styrene and α-methylstyrene, 1,3-butadiene and its 2-methyl and 2,3-dimethyl derivatives, and, in the presence of ultraviolet radiation, of aliphatic aldehydes and ketones, are reported. A radical mechanism is suggested tobe operative in these reactions. Also described are novel palladium-catalyzed reactions of the silirene with terminal and internal acetylenes. 相似文献
64.
Crecelius AC Cornett DS Caprioli RM Williams B Dawant BM Bodenheimer B 《Journal of the American Society for Mass Spectrometry》2005,16(7):1093-1099
We have developed a method to visualize matrix-assisted laser desorption ionization imaging mass spectrometry (MALDI IMS) data aligned with optically determinable tissue structures in three dimensions. Details of the methodology are exemplified using the 3-D reconstruction of myelin basic protein (MBP) in the corpus callosum of a mouse brain. In this procedure, optical images obtained from serial coronal sections are first aligned to each other to reconstruct a surface of the corpus callosum from segmented contours of the aligned images. The MALDI IMS data are then coregistered to the optical images and superimposed into the surface to create the final 3-D visualization. Correlating proteomic data with anatomical structures provides a more comprehensive understanding of healthy and pathological brain functions, and holds promise to be utilized in more complex anatomical arrangements. 相似文献
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El Saghir A. Kennedy C. Shannon S. 《IEEE transactions on plasma science. IEEE Nuclear and Plasma Sciences Society》2010,38(2):156-162
69.
Problem-based learning (PBL) and science, technology, engineering, and mathematics (STEM) are two acronyms widely visible in education literature today. However, few studies have explored these in connection with one another, specifically with regard to teacher preparation. This study investigated how 47 prospective elementary teachers developed PBL units and how they integrated STEM and other disciplines into those units. It also addressed the affordances and constraints of integrated STEM as perceived by the prospective elementary teachers. Data sources in this multimethod study included PBL units and interviews. Findings revealed that all of the units integrated at least two of the STEM disciplines, as well as literacy, in a variety of ways. The prospective teachers articulated perceived benefits of integrated STEM, such as: making connections across content areas, preparing students for the real world, teaching students that failure is not a bad thing, and providing future opportunities. They also addressed perceived barriers of integrated STEM, such as: having limited experience with the content, diminishing the effect of individual content areas, and needing better curriculum alignment. Overall, this study provides evidence that PBL can be a pedagogical approach to integrate STEM. Implications for teachers, teacher educators, and curriculum specialists are discussed. 相似文献
70.
Teeters-Kennedy SM Rodriguez KR Rogers TM Zomchek KA Williams SM Sudnitsyn A Carter L Cherezov V Caffrey M Coe JV 《The journal of physical chemistry. B》2006,110(43):21719-21727
The flow of polarized light through a metal film with an array of microchannels is controlled by the phase of an optically active, phospholipid nanocoating, even though the coating does not cover the open area of the microchannels. The molecular details of the assembly (DPPC phospholipid monolayer/bilayer on a hexadecanethiol monolayer on a copper- or nickel-coated microarray) were determined using the infrared, surface-plasmon-mediated, extraordinary transmission of the metal microarrays. Infrared absorption spectra with greatly enhanced absorptions by comparison to literature were recorded and used as a diagnostic for the phase, composition, and molecular geometry of these nanocoatings. This approach presents new tools for nanoscale construction in constricted microspaces, which may ultimately be useful with individual microchannels. 相似文献