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81.
Matrix effects on the multi-collector inductively coupled plasma mass spectrometric analysis of high-precision cadmium and zinc isotope ratios 总被引:2,自引:0,他引:2
Alyssa E. Shiel Jane Barling Kristin J. Orians Dominique Weis 《Analytica chimica acta》2009,633(1):29-83
Resin-derived contaminants added to samples during column chemistry are shown to cause matrix effects that lead to inaccuracy in multi-collector inductively coupled plasma mass spectrometry measurement of small natural variations in Cd and Zn isotopic compositions. These matrix effects were evaluated by comparing pure Cd and Zn standards and standards doped with bulk column blank from the anion exchange chromatography procedure. Doped standards exhibit signal enhancements (Cd, Ag, Zn and Cu), instrumental mass bias changes and inaccurate isotopic compositions relative to undoped standards, all of which are attributed to the combined presence of resin-derived organics and inorganics. The matrix effect associated with the inorganic component of the column blanks was evaluated separately by doping standards with metals at the trace levels detected in the column blanks. Mass bias effects introduced by the inorganic column blank matrix are smaller than for the bulk column blank matrix but can still lead to significant changes in ion signal intensity, instrumental mass bias and isotopic ratios. Chemical treatment with refluxed HNO3 or HClO4/HNO3 removes resin-derived organic components resulting in matrix effects similar in magnitude to those associated with the inorganic component of the column blank.Mass bias correction using combined external normalization-SSB does not correct for these matrix effects because the instrumental mass biases experienced by Cd and Zn are decoupled from those of Ag and Cu, respectively. Our results demonstrate that ion exchange chromatography and associated resin-derived contaminants can be a source of error in MC-ICP-MS measurement of heavy stable element isotopic compositions. 相似文献
82.
Mirka‐Kristin Verhoefen Karsten Neumann Ingrid Weber Clemens Glaubitz Josef Wachtveitl 《Photochemistry and photobiology》2009,85(2):540-546
Femtosecond time‐resolved spectroscopy in the visible and IR range was utilized to study the primary reaction dynamics of the proteorhodopsin (PR) D97N mutant in comparison with wild type PR at different pH values. The analysis of the data obtained in the mid‐IR closely resembles the results for wild type PR. The observation of the first ground state intermediate K is initially obscured by a complex reaction scheme of vibrational relaxation and heating effects, but its spectral signature clearly emerges at long delay times. In the visible range, a biexponential decay of the excited state within 30 ps and the formation of the K photoproduct is observed. The decay time constants derived for the D97N mutant in D2O are slightly larger than in H2O due to H/D exchange. This kinetic isotope effect is even less pronounced than for wild type PR at pH 6. These results support the current notion of a pH dependent hydrogen bonding network in the retinal binding pocket of PR and a weaker interaction between the retinal Schiff base and the counter ion complex compared to bacteriorhodopsin. 相似文献
83.
Matkovich KM Thorne LM Wolf MO Pace TC Bohne C Patrick BO 《Inorganic chemistry》2006,45(12):4610-4618
A series of Ru(II) complexes, tcc-RuX2(POC4Pyr-P,O)2 (X = Cl (3), Br (4), I (5)), containing the hemilabile phosphine pyrenyl ether ligand 4-{2-(diphenylphosphino)phenoxy}butylpyrene (POC4Pyr (1)) are reported. The synthesis and spectroscopic properties of both the ligand, POC4pyr (1), and ligand oxide, P(=O)OC4pyr 2, and the solid-state structure of 1 are reported. Complexes 3-5 react rapidly with CO to give complexes ttt-RuX2(CO)2(POC4pyr-P)2 (X = Cl (6), Br (7), I (8)). No pyrene excimer emission is detected from 3-5; however, different intensities of excimer emission are observed for 6-8. The intensity of excimer emission decreases through the series, with 6 showing the most intense response. The emission is solely due to intramolecular pyrene excimers at low concentrations (< or =10(-4) M). Comparison of the UV-vis and steady-state fluorescence spectra shows overlap between the low energy d-d absorption of 7 and 8 with excimer emission (480 nm), suggesting nonradiative energy transfer may be occurring. Once excess CO is removed, complexes 6-8 isomerize to cis-dicarbonyl complexes cct-RuX2(CO)2(POC4Pyr-P)2 (X = Cl (9), Br (10), I (11)). The intensity of excimer emission from 9-11 increases with respect to the excimer emission observed for 6-8, with 9 showing a significant increase in excimer intensity. 相似文献
84.
Lockery SR Hulme SE Roberts WM Robinson KJ Laromaine A Lindsay TH Whitesides GM Weeks JC 《Lab on a chip》2012,12(12):2211-2220
This paper describes the fabrication and use of a microfluidic device for performing whole-animal chemical screens using non-invasive electrophysiological readouts of neuromuscular function in the nematode worm, C. elegans. The device consists of an array of microchannels to which electrodes are attached to form recording modules capable of detecting the electrical activity of the pharynx, a heart-like neuromuscular organ involved in feeding. The array is coupled to a tree-like arrangement of distribution channels that automatically delivers one nematode to each recording module. The same channels are then used to perfuse the recording modules with test solutions while recording the electropharyngeogram (EPG) from each worm with sufficient sensitivity to detect each pharyngeal contraction. The device accurately reported the acute effects of known anthelmintics (anti-nematode drugs) and also correctly distinguished a specific drug-resistant mutant strain of C. elegans from wild type. The approach described here is readily adaptable to parasitic species for the identification of novel anthelmintics. It is also applicable in toxicology and drug discovery programs for human metabolic and degenerative diseases for which C. elegans is used as a model. 相似文献
85.
Wunschel DS Melville AM Ehrhardt CJ Colburn HA Victry KD Antolick KC Wahl JH Wahl KL 《The Analyst》2012,137(9):2077-2085
The investigation of crimes involving chemical or biological agents is infrequent, but presents unique analytical challenges. The protein toxin ricin is encountered more frequently than other agents and is found in the seeds of Ricinus communis, commonly known as the castor plant. Typically, the toxin is extracted from castor seeds utilizing a variety of different recipes that result in varying purity of the toxin. Moreover, these various purification steps can also leave or differentially remove a variety of exogenous and endogenous residual components with the toxin that may indicate the type and number of purification steps involved. We have applied three gas chromatography-mass spectrometry (GC-MS) based analytical methods to measure the variation in seed carbohydrates and castor oil ricinoleic acid, as well as the presence of solvents used for purification. These methods were applied to the same samples prepared using four previously identified toxin preparation methods, starting from four varieties of castor seeds. The individual data sets for seed carbohydrate profiles, ricinoleic acid, or acetone amount each provided information capable of differentiating different types of toxin preparations across seed types. However, the integration of the data sets using multivariate factor analysis provided a clear distinction of all samples based on the preparation method, independent of the seed source. In particular, the abundance of mannose, arabinose, fucose, ricinoleic acid, and acetone were shown to be important differentiating factors. These complementary tools provide a more confident determination of the method of toxin preparation than would be possible using a single analytical method. 相似文献
86.
Jerri HA Adolfsen KJ McCullough LR Velegol D Velegol SB 《Langmuir : the ACS journal of surfaces and colloids》2012,28(4):2262-2268
Moringa oleifera (Moringa) seeds contain a natural cationic protein (MOCP) that can be used as an antimicrobial flocculant for water clarification. Currently, the main barrier to using Moringa seeds for producing potable water is that the seeds release other water-soluble proteins and organic matter, which increase the concentration of dissolved organic matter (DOM) in the water. The presence of this DOM supports the regrowth of pathogens in treated water, preventing its storage and later use. A new strategy has been established for retaining the MOCP protein and its ability to clarify and disinfect water while removing the excess organic matter. The MOCP is first adsorbed and immobilized onto sand granules, followed by a rinsing step wherein the excess organic matter is removed, thereby preventing later growth of bacteria in the purified water. Our hypotheses are that the protein remains adsorbed onto the sand after the functionalization treatment, and that the ability of the antimicrobial functionalized sand (f-sand) to clarify turbidity and kill bacteria, as MOCP does in bulk solution, is maintained. The data support these hypotheses, indicating that the f-sand removes silica microspheres and pathogens from water, renders adhered Escherichia coli bacteria nonviable, and reduces turbidity of a kaolin suspension. The antimicrobial properties of f-sand were assessed using fluorescent (live-dead) staining of bacteria on the surface of the f-sand. The DOM that can contribute to bacterial regrowth was shown to be significantly reduced in solution, by measuring biochemical oxygen demand (BOD). Overall, these results open the possibility that immobilization of the MOCP protein onto sand can provide a simple, locally sustainable process for producing storable drinking water. 相似文献
87.
Butterworth K Chiang CT Cunningham B Freindorf M Furlani TR DeLeon RL Garvey JF 《The journal of physical chemistry. A》2012,116(8):1877-1883
Reactions occurring within gas phase fluorobenenze-ammonia heterocluster cations (FC(6)H(5)-(NH(3))(n=1-4)) have been studied through the use of a triple quadrupole mass spectrometer as well as employing density functional theory (DFT). Collision induced dissociation (CID) experiments were conducted in which mass selected cluster ions are accelerated into a cell containing argon gas and the resulting products then subsequently mass analyzed. Two dominate reaction channels are observed. The first is simple evaporative loss of neutral ammonia from the cluster ion. The second involves a substitution reaction occurring within the cluster ion to form the aniline cation, C(6)H(5)NH(2)(+), where the reactivity was found to vary as a function of cluster size. DFT calculations have been performed to both help analyze the structure and the reactivity of these cluster ions. Pronounced differences in activation energies were found that provide an explanation for the observed variation of reactivity as a function of cluster size. An ad hoc model based upon the Arrhenius equation was developed to fit both the experimental collision energy dependence of the reaction and the observed lowering of the reaction barrier to aniline formation as a function of cluster size. 相似文献
88.
Schneider N Hindle S Lange G Klein R Albrecht J Briem H Beyer K Claußen H Gastreich M Lemmen C Rarey M 《Journal of computer-aided molecular design》2012,26(6):701-723
The HYDE scoring function consistently describes hydrogen bonding, the hydrophobic effect and desolvation. It relies on HYdration and DEsolvation terms which are calibrated using octanol/water partition coefficients of small molecules. We do not use affinity data for calibration, therefore HYDE is generally applicable to all protein targets. HYDE reflects the Gibbs free energy of binding while only considering the essential interactions of protein-ligand complexes. The greatest benefit of HYDE is that it yields a very intuitive atom-based score, which can be mapped onto the ligand and protein atoms. This allows the direct visualization of the score and consequently facilitates analysis of protein-ligand complexes during the lead optimization process. In this study, we validated our new scoring function by applying it in large-scale docking experiments. We could successfully predict the correct binding mode in 93% of complexes in redocking calculations on the Astex diverse set, while our performance in virtual screening experiments using the DUD dataset showed significant enrichment values with a mean AUC of 0.77 across all protein targets with little or no structural defects. As part of these studies, we also carried out a very detailed analysis of the data that revealed interesting pitfalls, which we highlight here and which should be addressed in future benchmark datasets. 相似文献
89.
This report demonstrates that the mechanical stability of focal adhesions exhibits a biphasic and sensitive pH dependence. These studies used isolated focal adhesions, which retain many of the properties of the intracellular structures, including protein composition and force-dependent reinforcement by cytosolic proteins. The focal adhesion structures are least stable to applied force at a pH of 6.4, and significantly more stable at slightly higher and lower pH values. This trend is consistent with previous work that characterized the pH dependence of cell migration and may therefore be relevant to controlling the invasiveness of metastatic cancer cells. This approach is significant because it allows biochemical studies of large protein complexes previously studied only in cell culture, and therefore offers new opportunities for performing mechanistic studies of a range of factors that contribute to focal adhesion stability. 相似文献
90.
Emily C. Corcoran William Forest Robert Horton David G. Kelly Kristine Mattson Curtis McDonld Kathy S. Nielsen Kristin Topping Ron D. Weir Andre Yonkeu 《Journal of Radioanalytical and Nuclear Chemistry》2012,291(1):251-256
Commercial radio-opaque combat (CRC) fabrics, for incorporation into personal protective equipment used by first responders
and armed forces, are marketed as having the ability to provide a level of protection against specific types of radiation.
For a CRC material, a standard combat uniform and a multi-layered chemical, biological, radiological, nuclear (CBRN) protective
material, the present work examines chemical composition and radiation protection against gamma-rays and neutron fluxes. Significant
reduction in gamma-ray transmittance occurs only for the CRC fabric (46–514 keV) with gamma-ray attenuation coefficients of
3.10 to <0.10 cm2 g−1. Reduction in neutron transmittance, for all three fabrics, could not be assessed with certainty as the measured transmittance
was obscured by large statistical uncertainties. 相似文献