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61.
Baseski HM Watson CJ Cellar NA Shackman JG Kennedy RT 《Journal of mass spectrometry : JMS》2005,40(2):146-153
In vivo microdialysis sampling was coupled to capillary liquid chromatography (LC)/electrospray ionization quadrupole ion trap mass spectrometry (MS) to monitor [Met]enkephalin and [Leu]enkephalin in the striatum of anesthetized and freely-moving rats. The LC system utilized a high-pressure pump to load 2.5 microl samples and desalt the 25 microm i.d. by 2 cm long column in 12 min. Samples were eluted with a separate pump at approximately 100 nl min(-1). A rapid gradient effectively separated the endogenous neuropeptides in 4 min. A comparison was made for operating the mass spectrometer in the MS2 and MS3 modes for detection of the peptides. In standard solutions, the detection limits were similar at 1-2 pM (2-4 amol injected); however, the reproducibility was improved with MS3 as the relative standard deviation was <5% compared with 20% for MS2 for 60 pM samples. For dialysate solutions, reconstructed ion chromatograms and tandem mass spectra had much higher signal-to-noise ratios in the MS3 mode, resulting in more confident detection at in vivo concentrations. The method was successfully used to monitor the peptides under basal conditions and with stimulation of peptide secretion by infusion of elevated K+ concentration. 相似文献
62.
The synthesis and thermal bromination of octahydropentalene was studied. The reaction afforded 1a,3a,4b,6b-tetrabromo-1,2,3,4,5,6-hexahydropentalene (14) with remarkable regio- and stereospecificity. The structure of the product was determined by 1H and 13C NMR data and single X-ray structural analysis. The treatment of octahydropentalene with tenfold bromine gave the octabromopentalene derivative. The formation mechanism of the products is discussed. 相似文献
63.
Sequencing and four-state minisatellite variant repeat mapping of the D1S7 locus (MS1) by fluorescence detection 总被引:1,自引:0,他引:1
Minisatellite variant repeat mapping by polymerase chain reaction (MVR-PCR) reveals an enormous degree of variation in the human minisatellite regions. The original approach involved the use of 32P-labelled probes to detect the MVR-PCR products generated. To date, the loci mapped include D1S8, D7S21 and D16S309. However, the most polymorphic locus, D1S7 (MS1), which has been used in forensic analysis, has presented technical difficulties, initially due to its short 9 bp repeats that are much shorter than any conventional primer sequences. This was overcome by using the method of "wrapping around" primers employing inosine at the redundancy position. The difficulty of cloning highly repetitive DNA was overcome by utilising specialised competent SURE cells. We report the cloning and sequencing of selected short MS1 alleles to determine the variety of repeat types. This survey revealed nine types, four of which represented greater than 80% of the sequenced repeats. The reported MVR-PCR system maps the MS1 locus for these four common repeat types by fluorescence detection. 相似文献
64.
E. R. Dixon R. J. Laughlin C. J. Watson D. J. Hatch 《Rapid communications in mass spectrometry : RCM》2010,24(5):519-528
Nitrogenous materials can be transferred out of the topsoil, either vertically to a greater depth, or in lateral pathways to surface waters, and they may also become transformed, with the potential of generating environmentally active agents. We measured the production of NO and N2O in two contrasting subsoils (70 to 90 cm): one poorly drained and the other freely drained and compared this with the topsoil (0 to 20 cm) of the corresponding soils. The soils were incubated aerobically in jars with subtreatments of either synthetic cattle urine or deionised water and sampled at intervals up to 34 days. 15N‐NO was used to determine the processes responsible for NO and N2O production. The headspace was analysed for the concentrations of N2O, NO and CO2 and 15N enrichment of N2O. The soil samples were extracted and analysed for NO, NO and NH, and the 15N enrichment of the extracts was measured after conversion into N2O and N2. The study demonstrated the potential for NO, N2O and NO to be generated from subsoils in laboratory incubations. Differences in these N dynamics occurred due to subsoil drainage class. In the freely drained subsoil the rates of NO and NO production were higher than those observed for the corresponding topsoil, with mean maximum production rates of 3.5 µg NO‐N g−1 dry soil on day 16 and 0.12 µg NO‐N g−1 dry soil on day 31. The calculated total losses of N2O‐N as percentages of the applied synthetic urine N were 0.37% (freely drained subsoil), 0.24% (poorly drained subsoil), 0.43% (freely drained topsoil) and 2.09% (poorly drained topsoil). The calculated total losses of NO‐N as percentages of the applied synthetic urine N were 1.53% (freely drained subsoil), 0.02% (poorly drained subsoil), 0.25% (freely drained topsoil) and 0.08% (poorly drained topsoil). Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
65.
R. J. Goodwin L. MacIntyre D. G. Watson S. P. Scullion A. R. Pitt 《Rapid communications in mass spectrometry : RCM》2010,24(11):1682-1686
Matrix application continues to be a critical step in sample preparation for matrix‐assisted laser desorption/ionization (MALDI) mass spectrometry imaging (MSI). Imaging of small molecules such as drugs and metabolites is particularly problematic because the commonly used washing steps to remove salts are usually omitted as they may also remove the analyte, and analyte spreading is more likely with conventional wet matrix application methods. We have developed a method which uses the application of matrix as a dry, finely divided powder, here referred to as dry matrix application, for the imaging of drug compounds. This appears to offer a complementary method to wet matrix application for the MALDI‐MSI of small molecules, with the alternative matrix application techniques producing different ion profiles, and allows the visualization of compounds not observed using wet matrix application methods. We demonstrate its value in imaging clozapine from rat kidney and 4‐bromophenyl‐1,4‐diazabicyclo(3.2.2)nonane‐4‐carboxylic acid from rat brain. In addition, exposure of the dry matrix coated sample to a saturated moist atmosphere appears to enhance the visualization of a different set of molecules. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
66.
Dr. Matthew A. Watson Dr. Scott L. Cockroft 《Angewandte Chemie (International ed. in English)》2016,55(4):1345-1349
Biological molecular machines operate far from equilibrium by coupling chemical potential to repeated cycles of dissipative nanomechanical motion. This principle has been exploited in supramolecular systems that exhibit true machine behavior in solution and on surfaces. However, designed membrane‐spanning assemblies developed to date have been limited to simple switches or stochastic shuttles, and true machine behavior has remained elusive. Herein, we present a transmembrane nanoactuator that turns over chemical fuel to drive autonomous reciprocating (back‐and‐forth) nanomechanical motion. Ratcheted reciprocating motion of a DNA/PEG copolymer threaded through a single α‐hemolysin pore was induced by a combination of DNA strand displacement processes and enzyme‐catalyzed reactions. Ion‐current recordings revealed saw‐tooth patterns, indicating that the assemblies operated in autonomous, asymmetric cycles of conformational change at rates of up to one cycle per minute. 相似文献
67.
Dr. Luis M. Mori‐Quiroz Kirk W. Shimkin Dr. Sina Rezazadeh Ryan A. Kozlowski Prof. Dr. Donald A. Watson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(44):15654-15658
The oxidative copper‐catalyzed cross‐coupling of functionalized alkyl boronic esters with primary amides is reported. Through the identification of appropriate diketimine ligands, conditions for efficient coupling of both primary and secondary alkyl boronic esters with diverse primary amides, including acetamide, have been developed. 相似文献
68.
The asymmetric rearrangement of allylic trichloroacetimidates catalyzed by palladium(II) complexes of the COP family is a powerful method for the preparation of enantioenriched chiral allylic amines from prochiral allylic alcohols. A detailed kinetic analysis of this reaction was performed to elucidate the rate- and enantiodetermining step of this important reaction. The results of these studies support a cyclization-induced rearrangement mechanism and prompted DFT studies (B3LYP/LACVP**+) of C-N bond formation, believed to be the enantiodetermining step of this catalytic cycle. On the basis of these calculations, a model for enantioinduction was developed, in which the planar chirality of the catalyst controls the enantioselectivity. These studies should allow the rational design of more enantioselective catalysts. 相似文献
69.
Ozerov OV Watson LA Pink M Caulton KG 《Journal of the American Chemical Society》2007,129(18):6003-6016
Operationally unsaturated (i.e., 16/18-electron) (PNPR)Re(H)4, where PNPR is N(SiMe2CH2PR2)2, is reactive at 22 degrees C with cyclic olefins. The first observed products are generally (PNPR)Re(H)2(cycloalkylidene), with hydrogenated olefin as the product of hydrogen abstraction from the tetrahydride. The tetrahydride complex with R = tBu generally fails to react (too bulky), that with R = cyclohexyl suffers a (controllable) tendency to abstraction of 3H from one ring, forming an eta3-cyclohexenyl compound, and that with R = iPr generally gives the richest bimolecular reactivity. The cyclic monoolefins studied show distinct reactivity, C6 giving first the carbene and then coordinated cyclohexadiene, C5 giving carbene, then diene, and then eta5-C5H5, C8 giving carbene and then eta2-cyclooctyne, and C12 giving an eta3-allyl. Norbornene gives a pi-complex of the norbornene in thermal equilibrium with its carbene isomer; at 90 degrees C, hydrocarbon ligand Calpha-Cbeta bond cleavage occurs to give, for the first time, a carbyne complex from an internal olefin. Two compounds synthesized here have the formal composition "(PNPR)Re + olefin", and each of these is capable of dehydrogenating the methyl group of a variety of alkanes at 110 degrees C to form (PNP)ReH triple bond (CR). 相似文献
70.
Saracoglu N Talaz O Azizoglu A Watson WH Balci M 《The Journal of organic chemistry》2005,70(14):5403-5408
[reaction: see text] endo- and exo-2,3,4,7-tetrahydro-1H-1,4-methanobenzocycloheptene-7-carboxylic acid ethyl esters have been synthesized, and their Diels-Alder cycloaddition reactions with maleic anhydride, dimethyl acetylenedicarboxylate and singlet oxygen have been investigated. The X-ray analysis of four adducts indicated the pyramidalization of the central double bond. Density functional theory calculations on the isolated products and model compounds showed excellent agreement between the experimental and theoretical determined butterfly angles. Furthermore, it has been shown that a cyclopropyl group fused to [2.2.2] system decreases significantly the degree of the pyramidalization which is attributed to the steric interactions between the cyclopropyl group and ethano bridge of the norbornene systems. Due to the instability of the bicyclic endoperoxides, their X-ray analysis could not be carried out. DFT calculations on model compounds showed increased bending in the case of the product obtained by the addition of singlet oxygen to endo-2,3,4,7-tetrahydro-1H-1,4-methanobenzocycloheptene-7-carboxylic acid ethyl ester. 相似文献