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161.
Wall DB Berger SJ Finch JW Cohen SA Richardson K Chapman R Drabble D Brown J Gostick D 《Electrophoresis》2002,23(18):3193-3204
Peptide mass fingerprinting by matrix-assisted laser desorption/ionization (MALDI)-mass spectrometry (MS) is one of the standard high-throughput methods for protein identification today. Traditionally this method has been based on spotting peptide mixtures onto MALDI targets. While this method works well for more abundant proteins, low-abundance proteins mixed with high-abundance proteins tend to go undetected due to ion suppression effects, instrumental dynamic range limitations and chemical noise interference. We present an alternative approach where liquid chromatography (LC) effluent is continuously collected as linear tracks on a MALDI target. In this manner the chromatographic separation is spatially preserved on the target, which enables generation of off-line LC-MS and LC-MS/MS data by MALDI. LC-MALDI sample collection provides improved sensitivity and dynamic range, spatial resolution of peptides along the sample track, and permits peptide mass mapping of low-abundance proteins in mixtures containing high-abundance proteins. In this work, standard and ribosomal protein digests are resolved and captured using LC-MALDI sample collection and analyzed by MALDI-TOF-MS. 相似文献
162.
Reflection absorption infrared spectroscopy (RAIRS) and temperature programmed desorption (TPD) have been used to investigate the adsorption of methanol (CH(3)OH) on the highly oriented pyrolytic graphite (HOPG) surface. RAIRS shows that CH(3)OH is physisorbed at all exposures and that crystalline CH(3)OH can be formed, provided that the surface temperature and coverage are high enough. It is not possible to distinguish CH(3)OH that is closely associated with the HOPG surface from CH(3)OH adsorbed in multilayers using RAIRS. In contrast, TPD data show three peaks for the desorption of CH(3)OH. Initial adsorption leads to the observation of a peak assigned to the desorption of a monolayer. Subsequent adsorption leads to the formation of multilayers on the surface and two TPD peaks are observed which can be assigned to the desorption of multilayer CH(3)OH. The first of these shows a fractional order desorption, assigned to the presence of hydrogen bonding in the overlayer. The higher temperature multilayer desorption peak is only observed following very high exposures of CH(3)OH to the surface and can be assigned to the desorption of crystalline CH(3)OH. 相似文献
163.
Da Re RE Kuehl CJ Brown MG Rocha RC Bauer ED John KD Morris DE Shreve AP Sarrao JL 《Inorganic chemistry》2003,42(18):5551-5559
The novel charge-transfer ground state found in alpha,alpha'-diimine adducts of ytterbocene (C(5)Me(5))(2)Yb(L) [L = 2,2'-bipyridine (bpy) and 1,10-phenanthroline (phen)] in which an electron is spontaneously transferred from the f(14) metal center into the lowest unoccupied (pi*) molecular orbital (LUMO) of the diimine ligand to give an f(13)-L(*)(-) ground-state electronic configuration has been characterized by cyclic voltammetry, UV-vis-near-IR electronic absorption, and resonance Raman spectroscopies. The voltammetric data demonstrate that the diimine ligand LUMO is stabilized and the metal f orbital is destabilized by approximately 1.0 V each upon complexation for both bpy and phen adducts. The separation between the ligand-based oxidation wave (L(0/-)) and the metal-based reduction wave (Yb(3+/2+)) in the ytterbocene adducts is 0.79 V for both bpy and phen complexes. The UV-vis-near-IR absorption spectroscopic data for both the neutral adducts and the one-electron-oxidized complexes are consistent with those reported recently, but previously unreported bands in the near-IR have been recorded and assigned to ligand (pi*)-to-metal (f orbital) charge-transfer (LMCT) transitions. These optical electronic excited states are the converse of the ground-state charge-transfer process (e.g., f(13)-L(*-) <--> f(14)-L(0)). These new bands occur at approximately 5000 cm(-1) in both adducts, consistent with predictions from electrochemical data, and the spacings of the resolved vibronic bands in these transitions are consistent with the removal of an electron from the ligand pi* orbital. The unusually large intensity observed in the f --> f intraconfiguration transitions for the neutral phenanthroline adduct is discussed in terms of an intensity-borrowing mechanism involving the low-energy LMCT states. Raman vibrational data clearly reveal resonance enhancement for excitation into the low-lying pi* --> pi* ligand-localized excited states, and comparison of the vibrational energies with those reported for alkali-metal-reduced diimine ligands confirms that the ligands in the adducts are reduced radical anions. Differences in the resonance enhancement pattern for the modes in the bipyridine adduct with excitation into different pi* --> pi* levels illustrate the different nodal structures that exist in the various low-lying pi* orbitals. 相似文献
164.
Tsutsumi T Amakura Y Nakamura M Brown DJ Clark GC Sasaki K Toyoda M Maitani T 《The Analyst》2003,128(5):486-492
The chemical-activated luciferase expression (CALUX) assay is a reporter gene assay that detects dioxin-like compounds based on their ability to activate the aryl hydrocarbon receptor (AhR) and thus expression of the reporter gene. In this paper, the CALUX assay was examined for its application in the screening of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dioxin-like PCBs) in retail fish. The sample extracts were cleaned up on a sulfuric acid-silica gel column followed by an activated carbon column, and the AhR activity of the separated PCDD/F and dioxin-like PCB fractions was determined using the assay. The quantitative limit for 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) was 0.98 pg ml(-1) (0.19 pg assay(-1) in the standard curve, corresponding to 0.16 pg g(-1) of CALUX-based toxic equivalency (2,3,7,8-TCDD equivalents) in the tested sample. Recovery tests in which dioxins were added to fish samples resulted in acceptable recoveries (77-117%). The CALUX assay performed well in the analysis of dioxins in fish samples and a comparative study revealed a strong correlation between the CALUX assay and high-resolution gas chromatography-high-resolution mass spectrometry analysis for the determination of PCDD/Fs (r = 0.89) and dioxin-like PCBs (r = 0.91) in retail fish (n = 22). These data revealed that the CALUX assay would be a useful screening method for PCDD/Fs and dioxin-like PCBs in retail fish. 相似文献
165.
S. Kohn J. A. Brown R. H. Heffner C. Y. Huang T. A. Kitchens Jr. M. Leon C. E. Olsen M. E. Schillaci W. B. Gauster 《Hyperfine Interactions》1979,6(1-4):283-287
The + depolarization rate in diluteAlGd alloys containing 50 and 450 atomic ppm Gd was measured in a transverse field of 80 Oe over the temperature range 6–300 K. For both alloys, A increased dramatically above 200 K, reaching values of 0.69 and 0.93 s–1, respectively, near room temperature. The results are interpreted as providing evidence for a thermally-activated trapping mechanism.This work was supported by the U.S. Department of Energy. 相似文献
166.
R. H. Heffner J. A. Brown R. L. Hutson M. Leon D. M. Parkin M. E. Schillaci W. B. Gauster O. N. Carlson D. K. Rehbein A. T. Fiory 《Hyperfine Interactions》1979,6(1-4):237-240
We present the first results of a study of the effects of varying impurity concentration on the temperature dependence of the depolarization rate of positive muons implanted into vanadium. Data are reported for the most highly purified polycrystalline sample yet measured, and the same sample subsequently doped with about 500 ppm oxygen by weight. The data for the pure sample shows a low depolarization rate (<.15 sec–1) at all temperatures measured, showing a broad minimum centered at 35 K, followed by a sharp peak near 90 K and a rapid drop to negligible values at 200 K. The data is contrasted with previously published data [2] on less pure samples, and calls into question previous interpretations of the behavior of the + at low temperatures in impure vanadium [1] as one-phonon-assisted tunneling.This work was supported by the U. S. Department of Energy 相似文献
167.
Charles Brown Robert F. Hudson Gary A. Wartew H. Coates 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3):481-488
Abstract The reaction between finely divided white phosphorus and several alkoxide ions in the presence of tetrachloromethane and excess of alcohol has been investigated under a variety of conditions. High yields of trialkylphosphite are obtained when two equivalents of alkoxide are used. With one equivalent of alkoxide, dialkylphosphonate is formed in comparable yield. Maximum yields of triester are obtained within 1–3 h at room temperature. Prolonged treatment results in the conversion of trialkylphosphite to phosphate by reaction with tetrachloromethane. Phenolate ions are unreactive under the same experimental conditions. The mechanism of the reaction is discussed. 相似文献
168.
Anatoli Tchigvintsev Dmitri Tchigvintsev Robert Flick Ana Popovic Aiping Dong Xiaohui Xu Greg Brown Wenyun Lu Hong Wu Hong Cui Ludmila Dombrowski Jeong Chan Joo Natalia Beloglazova Jinrong Min Alexei Savchenko Amy A. Caudy Joshua D. Rabinowitz Alexey G. Murzin Alexander F. Yakunin 《Chemistry & biology》2013,20(11):1386-1398
169.
The usual method of formation of tricyclanone (1) involves thermolysis of an intimate mixture of 3-diazocamphor (3) and copper powder and is thought to involve ketocarbene (5).1 Recently this method has been supplemented2 by one which involves reaction of 3,3-dibromocamphor with diethylzinc in benzene where α-elimination to give ketocarbene (5) is mediated by 3-bromocamphor carbanion whose role is indicated by trapping as 3-bromocamphor; this material accounts for ca. 10% of product even after prolonged reaction times. 相似文献
170.
The influence of an asymmetric periodic grooved cell surface on the 2D static director configuration of a nematic liquid crystal has been investigated. The minimum in the Frank-Oseen free energy was solved numerically with the Rapini-Papoular form of the surface anchoring energy at the nematic-grating interface. Results are presented for the variation of pretilt angle in the tilted bulk director field as a function of the surface groove depth, pitch and asymmetry and the bulk parameters. The simulations demonstrate the existence of two energetically degenerate high and low pretilted bulk alignment configurations. The pretilt values in these two regimes and also for the low tilt regime with finite surface anchoring are consistent with experimental results. An effective increase in the resolution of the model is obtained by using an irregular grid to describe the surface profile. 相似文献