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11.
12.
R. Hoelzl Christian Hoelzl Ludwig Kotz Lazlo Fabry 《Accreditation and quality assurance》1998,3(5):185-188
Inductively coupled plasma mass spectrometry (ICP-MS) and high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS)
are powerful methods of determining metallic impurities in the low- and sub-ppt level in process media such as ultra-pure
water used in semiconductor and wafer manufacturing. By using mass spectrometers for analysis, an isotope dilution analysis
(IDMS) is possible. The reproducibility of an IDMS is unmatched. For concentration levels near the instrument detection limit
a novel method is reported to find the optimal amount of isotopic spike solution. This optimal value can be derived by the
law of propagation of uncertainty combined with the Poisson statistics of the measured number of counts. Generally, an excess
of isotopic spike solution should be used to provide results of lowest possible uncertainty. The results are presented in
a diagram for easy practical use.
Received: 14 October 1997 · Accepted: 13 February 1998 相似文献
13.
The hydrogen-deuterium exchange of H-2 in 4-pyrimidone, a number of 1- and 3-alkyl-4-pyrimidones and several of their thione analogs in deuterium oxide at moderate temperatures is reported. This reaction is apparently not susceptible to acid or base catalysis. Cations of the 4-pyrimidones were found not to exchange H-2 at all in acid media. Catalytic amounts of bases do not alter the exchange rates whereas more concentrated alkali decompose the pyrimidone. However, 1,4(3,4)-dihydro-1,3-dimethyl-4-oxopyrimidinium iodide (and its 6-methyl analog) exchange H-2 quite rapidly in neutral deuterium oxide, almost instantly when triethylamine is added as a catalyst, and very slowly in dilute solutions of deuterium chloride in deuterium oxide. Mechanisms are proposed to account for these phenomena. 相似文献
14.
Summary The optimized Wittig reaction of selectively functionalized 3-acylindoles yield new, and for Diels-Alder reactions highly reactive donor- and acceptor substituted 3-vinylindoles, respectively. 相似文献
15.
Bernard A. Mikrut Krishan K. Khullar Pamela Y. P. Chan John M. Kokosa Ludwig Bauer Richard S. Egan 《Journal of heterocyclic chemistry》1974,11(5):713-718
The reaction of pyridine 1-oxide with 1-adamantanethiol in acetic anhydride produced a mixture of 2- and 3-(1-adamantanethio)pyridines, 1-aeetyl-2-(1-adamantanethio)-3-hydroxy-4-acetoxy-1,2,3,4-telrahydropyridine and the corresponding 3-acetoxyderivative. Pure substances were separated by means of column chromatography on alumina. The tetrahydropyridines were identified by means of their proton magnetic and mass spectra. 4-(1-Adamantanethio)pyridine was synthesized from 4-chloropyridinc and 1-adamantanethiol. The three isomeric (1-adamantanethio)-pyridines were, each, cleaved by concentrated hydrochloric acid to give 1-chloroadamantane and the corresponding pyridinethiol. 相似文献
16.
17.
Würthwein EU Lang G Schappele LH Mayr H 《Journal of the American Chemical Society》2002,124(15):4084-4092
A literature survey on the kinetics of hydride abstractions from CH-groups by carbocations reveals a general phenomenon: Variation of the hydride acceptor affects the rates of hydride transfer to a considerably greater extent than an equal change of the thermodynamic driving force caused by variation of the hydride donor. The origin of this relationship was investigated by quantum chemical calculations on various levels of ab initio and DFT theory for the transfer of an allylic hydrogen from 1-mono- and 1,1-disubstituted propenes (XYC=CH-CH(3)) to the 3-position of 1-mono- and 1,1-disubstituted allyl cations (XYC=CH-CH(2)(+)). The discussion is based on the results of the MP2/6-31+G(d,p)//RHF/6-31+G(d,p) calculations. Electron-releasing substituents X and Y in the hydride donors increase the exothermicity of the reaction, while electron-releasing substituents in the hydride acceptors decrease exothermicity. In line with Hammond's postulate, increasing exothermicity shifts the transition states on the reaction coordinate toward reactants, as revealed by the geometry parameters and the charge distribution in the activated complexes. Independent of the location of the transition state on the reaction coordinate, a value of 0.72 is found for Hammond-Leffler's alpha = deltaDeltaG/deltaDelta(r)G degrees when the hydride acceptor is varied, while alpha = 0.28 when the hydride donor is varied. The value of alpha thus cannot be related with the position of the transition state. Investigation of the degenerate reactions XYC=CH-CH(3) + XYC=CH-CH(2)(+) indicates that the migrating hydrogen carries a partial positive charge in the transition state and that the intrinsic barriers increase with increasing electron-releasing abilities of X and Y. Substituent variation in the donor thus influences reaction enthalpy and intrinsic barriers in the opposite sense, while substituent variation in the acceptor affects both terms in the same sense, in accord with the experimental findings. Marcus theory is employed to treat these effects quantitatively. 相似文献
18.
Isocytosine (ICH) exists in solution as two major tautomers, the keto form with N1 carrying a proton (1a) and the keto form with N3 being protonated (1b). In water, 1a and 1b exist in equilibrium with almost equal amounts of both forms present. Reactions with a series of Pd(II) and Pt(II) am(m)ine species such as (dien)Pd(II), (dien)Pt(II), and trans-(NH(3))(2)Pt(II) reveal, however, a distinct preference of these metals for the N3 site, as determined by (1)H NMR spectroscopy. Individual species have been identified by the pD dependence of the ICH resonances. pK(a) values (calculated for H(2)O) for deprotonation of the individual tautomers complexes are 6.5 and 6.4 for the N3 linkage isomers of dienPd(II) and dienPt(II), respectively, as well as 6.2 and 6.0 for the N1 linkage isomers. The dimetalated species [(dienM)(2)(IC-N1,N3)](3+) (M = Pd(II) or Pt(II)) are insensitive over a wide range of pD. The crystal structure analysis of [(dien)Pd(ICH-N3)](NO(3))(2) is reported. Ab initio calculations have been performed for tautomer compounds of composition [(NH(3))(3)Pt(ICH)](2+), cis- and trans-[(NH(3))(2)PtCl(ICH)](+), as well as trans-[(NH(3))(2)Pt(ICH)(2)](2+). Without exception, N3 linkage isomers are more stable, in agreement with experimental findings. As to the reasons for this binding preference, an NBO (natural bond orbital) analysis for [(NH(3))(3)Pt(ICH-N3)](2+)strongly suggests that intramolecular hydrogen bonding between trans-positioned NH(3) ligands and the two exocyclic groups of the ICH is of prime importance. The calculations furthermore show a marked pyramidalization of the NH(2) group of ICH in the complex once the heterocyclic ligand forms a dihedral angle <90 degrees with the Pt coordination plane. 相似文献
19.
Nusbaumer H Zakeeruddin SM Moser JE Grätzel M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(16):3756-3763
A series of new cobalt complexes [Co(LLL)(2)X(2)] were synthesized and evaluated as redox mediators for dye-sensitized nanocrystalline TiO(2) solar cells. The structure of the ligand and the nature of the counterions were found to influence the photovoltaic performance. The one-electron-transfer redox mediator [Co(dbbip)(2)](ClO(4))(2) (dbbip = 2,6-bis(1'-butylbenzimidazol-2'-yl)pyridine) performed best among the compounds investigated. Photovoltaic cells incorporating this redox mediator yielded incident photon-to-current conversion efficiencies (IPCE) of up to 80%. The overall yield of light-to-electric power conversion reached 8 % under simulated AM1.5 sunlight at 100 W m(-2) intensity and more than 4% at 1000 W m(-2). Photoelectrodes coated with a 2 microm thick nanoporous layer and a 4 microm thick light-scattering layer, sensitized with a hydrophobic ruthenium dye, gave the best results. 相似文献
20.
Ian R. Gould Jacques E. Moser Bruce Armitage Samir Farid 《Research on Chemical Intermediates》1995,21(7):793-806
The overall efficiencies of photoinduced electron transfer reactions in polar solvents are usually determined by the efficiency with which separated radical ions are formed from the initially formed geminate radical-ion pairs. These separation efficiencies are determined by the competition between retum electron transfer and separation within the geminate pairs. A method is described for determining whether variations in the quantum yields for formation of separated radical ions are due to changes in the reorganization parameters for the return electron transfer reactions, or to other factors. The use of the method is illustrated in studies of the effects of varying steric bulk and molecular size of the donors, and also in studies of the effect of using a charged sensitizer. 相似文献