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排序方式: 共有397条查询结果,搜索用时 46 毫秒
81.
Jinghui Wang Danny X. Liu Marcello Canova R. Gregory Downing Lei R. Cao Anne C. Co 《Journal of Radioanalytical and Nuclear Chemistry》2014,301(1):277-284
Measuring the distribution of lithium in high capacity lithium-ion battery (LIB) electrodes is essential to understanding the coulombic losses during the lithiation/delithiation processes that occur while charging and discharging the cell. In this research, two half-cell prototypes were fabricated by electrochemically lithiating Sn foil anodes in 1M LiBF4 in a 1:1 (wt:wt) ethylene carbonate and dimethyl carbonate solutions at a constant potential of 0.50 and 0.67 V (vs. Li/Li+). The neutron depth profiling (NDP) technique was employed to study the Li distributions in the anodes. Li concentration profiles were resolved for the samples lithiated under different conditions for LIB studies. In addition, this paper demonstrated an in situ NDP measurement of an electrochemical cell with a thin window design, which reveals the dynamics of lithium distribution within the Sn anode. 相似文献
82.
Clive S. Penkett Rupert O. Sims Simon Berritt Stephen P. Rushton Peter B. Hitchcock 《Tetrahedron》2006,62(40):9403-9409
Whilst seeking to improve the yield of a Heck-style arylation/fragmentation reaction using a silyloxy substituted meta photocycloadduct, an alternative reaction pathway was discovered that led to the formation of the unique oxidatively cyclised compound 8. This tricyclic ether is believed to form as the result of the meta photocycloadduct structure fragmenting to give a π-allyl palladium species and then subsequently being displaced by a neighbouring hydroxyl group. An attempt to develop an enantioselective version of this reaction via the desymmetrisation of a meso π-allyl palladium intermediate was made using the meta photocycloadduct derived from anisole and Z-but-2-ene-1,4-diol, however no enantioenrichment of the products could be detected. 相似文献
83.
Kubista J Spanel P Dryahina K Workman C Smith D 《Rapid communications in mass spectrometry : RCM》2006,20(4):563-567
The value of the gas chromatography (GC) and selected ion flow tube mass spectrometry (SIFT-MS) combination for the analysis of trace gases is demonstrated by the quantification of acetone in air samples using the three precursor ions available to SIFT-MS, viz. H3O+, NO+ and O2+, and by the separation of the isomers 1-propanol and 2-propanol, and their analysis using H3O+ precursor ions. It is shown that the GC/SIFT-MS combination allows for accurate trace gas quantification obviating the regular, time-consuming calibrations that are usually required for the more commonly used detectors of GC systems, and the positive identification of isomers in mixtures that is often challenging using SIFT-MS alone. Thus, the GC/SIFT-MS combination paves the way to more confident analyses of complex mixtures such as exhaled breath. 相似文献
84.
Zhu D Wang Y Pang Y Liu A Guo J Bouwman CA West CE van Breemen RB 《Rapid communications in mass spectrometry : RCM》2006,20(16):2427-2432
Among more than 50 provitamin carotenoids, beta-carotene is the most metabolically active source of retinol. Despite diets rich in fruits and vegetables containing beta-carotene, vitamin A deficiency is the leading cause of blindness and childhood mortality in developing countries. In addition, the uncertainty of beta-carotene bioconversion into vitamin A suggests that new data are needed to update the nutritional guidelines in developed countries. Previously, we reported the development of a carotene/retinol plateau isotopic enrichment method (CarRet PIE) for the determination of beta-carotene bioavailability and bioconversion into retinol, which utilizes positive ion atmospheric pressure chemical ionization (APCI) liquid chromatography/mass spectrometry (LC/MS). While seeking to validate the CarRet PIE using a mass balance approach requiring fecal measurements of beta-carotene and retinol, interference was encountered that required substantial modifications of the LC/MS assay. Here we report a new LC/MS assay that is based on the detection of molecular anions of beta-carotene using negative ion APCI with a reversed-phase C30 column for HPLC separation. Sample preparation required saponification to eliminate interfering triglycerides. The limit of detection (LOD) of beta-carotene was 0.25 pmol calculated on the basis of an injection of 20 microL of 0.0125 microM beta-carotene, and the limit of quantitation (LOQ) was 1.0 pmol based on the injection of 20 microL of 0.050 microM beta-carotene. The linear range was 1.1 to 2179 pmol on-column. The wide linear range and low LOD and LOQ of this assay facilitated the sensitive and selective quantitative analysis of beta-carotene in both serum and fecal samples in support of an on-going clinical investigation of beta-carotene bioavailability and bioconversion into vitamin A. 相似文献
85.
Dufour DG Drummond JR McElroy CT Midwinter C Bernath PF Walker KA Nowlan C 《The journal of physical chemistry. A》2006,110(45):12414-12418
Laboratory measurements of NO(2) absorption were obtained in the visible (400-700 nm) and mid-infrared (3.4 mum) regions simultaneously using SCISAT-1's ACE-FTS (atmospheric chemistry experiment-Fourier transform spectrometer) and MAESTRO (measurement of aerosol extinction in the stratosphere and troposphere retrieved by occultation) spectrometers. An intercomparison of these measurements was used to verify the consistency between the HITRAN 2004 3.4-mum band strengths and the strengths of three different visible cross section data sets. These measurements should be of interest to the remote-sensing community, since NO(2) measurements obtained by infrared-range instruments are often compared to those obtained by visible-range instruments without accurate knowledge of the consistency between the visible and infrared absorption coefficients. Two significant results were obtained in this study: (1) A 0.5% agreement was found between the HITRAN 2004 line strengths and the Vandaele et al. (Vandaele, A. C.; Hermans, C.; Fally, S.; Carleer, M.; Colin, R.; Mérienne, M.-F.; Jenouvrier, A.; Coquart, B. J. Geophys. Res. 2002, 107 (D18), 4348) temperature-corrected cross sections, and (2) the mean pressure-broadened half-width of NO(2) by NO in the 3.4-mum band was measured as being 0.096 +/- 0.001 cm(-1) atm(-1). The latter finding is thought to be unreported by the literature. 相似文献
86.
A family of bis-terdentate iridium(III) complexes is reported which contain a cyclometalated, N/\C[wedge]N-coordinating 1,3-di(2-pyridyl)benzene derivative. This coordination mode is favored by blocking competitive cyclometalation at the C4 and C6 positions of the ligand. Thus, 1,3-di(2-pyridyl)-4,6-dimethylbenzene (dpyxH) reacts with IrCl3 x 3H2O to generate a dichlorobridged dimer [Ir(dpyx-N,C,N)Cl(mu-Cl)]2, 1. This dimer is cleaved by DMSO to give [Ir(dpyx)(DMSO)Cl2], the X-ray crystal structure of which is reported here, confirming the N/\C/\N coordination mode of dpyx. The dimer 1 can also be cleaved by a variety of other ligands to generate novel classes of mononuclear complexes. These include charge-neutral bis-terdentate complexes of the form [Ir(N/\C/\N)(C/\N/\C)] and [Ir(N/\C/\N)(C/\N/\O)], by reaction of 1 with C/\N/\C-coordinating ligands (e.g., 2,6-diphenylpyridine and derivatives) and C/\N/\O-coordinating ligands (based on 6-phenylpicolinate), respectively. Treatment of 1 with terpyridines leads to dicationic complexes of the type [Ir(N/\C/\N)(N/\N/\N)]2+, while 2-phenylpyridine gives [Ir(dpyx-N/\C/\N)(ppy-C,N)Cl]. All of the charge-neutral complexes are luminescent in fluid solution at room temperature. Assignment of the emission to charge-transfer excited states with significant MLCT character is supported by DFT calculations. In the [Ir(N/\C/\N)(C/\N/\C)] class, fluorination of the C/\N/\C ligand at the phenyl 2' and 4' positions leads to a blue-shift in the emission and to an increase in the quantum yield (lambda(max) = 547 nm, phi = 0.41 in degassed CH(3)CN at 295 K) compared to the nonfluorinated parent complex (lambda(max) = 585 nm, phi = 0.21), as well as to a stabilization of the compound with respect to photodissociation through cleavage of mutually trans Ir-C bonds. [Ir(dpyx-N/\C/\N)(ppy-C,N)Cl] is an exceptionally bright emitter: phi = 0.76, lambda(max) = 508 nm, in CH(3)CN at 295 K. In contrast, the [Ir(N/\C/\N)(C/\N/\O)] complexes are much less emissive, shown to be due to fast nonradiative decay of the excited state, probably involving reversible Ir-O bond cleavage. The [Ir(N/\C/\N)(N/\N/\N)]2+ complexes are very feeble emitters even at 77 K, probably due to the almost exclusively interligand charge-transfer nature of the lowest-energy excited state in these complexes. 相似文献
87.
L. R. Cao J. R. Hattrick-Simpers R. Bindel B. E. Tomlin R. Zeisler R. Paul L. A. Bendersky R. G. Downing 《Journal of Radioanalytical and Nuclear Chemistry》2010,283(1):63-68
Cold neutron prompt gamma activation analysis (PGAA) was used to determine the mass of hydrogen in Mg hydride thin films with
varying hydrogenation times. The results suggest that hydrogenation of the Mg thin films remains unsaturated even after 48 h
of treatment, contrary to the indications of inferential hydrogen measurement methods. To demonstrate PGAA as an effective
combinatorial methodology for hydride thin films, a continuously varying composition gradient of thin MgyTi(1−y) hydride film with y ranging from 0.65 to 0.94 was prepared and analyzed by both PGAA and instrumental neutron activation
analysis (INAA). The variation in the molar ratio of Mg, Ti, and H was obtained for nine 5 mm wide segments of the film. 相似文献
88.
A new tandem catalysis strategy that transforms alkyne derivatives to (E)-enol-equivalents followed by stereoselective anti-selective aldol coupling or syn-selective [3,3]-rearrangement transformations is reported. The mechanism is thought to proceed through an interchanging series of Lewis acid and Brønsted acid catalyzed reactions via the intermediacy of a ketiminum ion species. 相似文献
89.
S. M. Çetiner K. Ünlü R. G. Downing 《Journal of Radioanalytical and Nuclear Chemistry》2007,271(2):275-281
Neutron depth profiling (NDP) is a nondestructive, near-surface technique, which utilizes a thermal/cold neutron beam to determine
the concentration of specific light elements versus the depth in materials. The depth distribution is obtained by measuring
the energy loss spectrum of protons, alphas, or recoil atoms in the substrate materials. For conventional NDP, the depth resolution
is highly dependent on the limited ability of the detectors and associated electronics. A novel technique, the time-of-flight
(TOF) method that is based on a completely different energy-measurement mechanism, can greatly improve the depth resolution
for the accurate measurement of the dopant depth profile in especially shallow junction devices. Such a set of TOF NDP facility
is being constructed at the 1 MW Breazeale Nuclear Reactor at Penn State University, Radiation Science and Engineering Center.
In the TOF-NDP, a timing start signal is obtained from electrons emitted simultaneously with a neutron-induced recoil particle
leaving the surface of the sample. The same particle generates the subsequent stop signal, whereby the residual energy of
the particle is much more precisely determined from the particle flight time than currently obtained by the use of surface
barrier detectors. In this paper, the Penn State conventional NDP measurement results will be presented and TOF-NDP facility
will be described. 相似文献
90.
(+)-Puraquinonic acid (1a) was synthesized, using a route based on ring-closing metathesis and radical cyclization, the chirality of the quaternary carbon being controlled by a temporary adjacent asymmetric center. 相似文献