The optimal amount of isotopic spike solution for ultratrace analysis by isotope dilution mass spectrometry

 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     

Deuterium exchange of 4-pyrimidones and 4-pyrimidthiones

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.     

Wittig-Olefinierung zu neuen donor- und akzeptor-substituierten 3-Vinylindolen: Optimierte Syntheseverfahren

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.

     

(1-Adamantanethio)pyridines and tetrahydropyridines from the reaction of 1-adamantanethiol with pyridine I-oxide in acetic anhydride

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.     

Regressions and monotone chains II: The poset of integer intervals

A regressive function (also called a regression or contractive mapping) on a partial order P is a function mapping P to itself such that (x)x. A monotone k-chain for is a k-chain on which is order-preserving; i.e., a chain x ₁<...ksuch that (x ₁)...(x_k). Let P _nbe the poset of integer intervals {i, i+1, ..., m} contained in {1, 2, ..., n}, ordered by inclusion. Let f(k) be the least value of n such that every regression on P _nhas a monotone k+1-chain, let t(x,j) be defined by t(x, 0)=1 and t(x,j)=x ^t(x,j–1). Then f(k) exists for all k (originally proved by D. White), and t(2,k) < f(K) <t( + _k, k) , where _k 0 as k. Alternatively, the largest k such that every regression on P _nis guaranteed to have a monotone k-chain lies between lg^*(n) and lg^*(n)–2, inclusive, where lg^*(n) is the number of appliations of logarithm base 2 required to reduce n to a negative number. Analogous results hold for choice functions, which are regressions in which every element is mapped to a minimal element.     

Rate-equilibrium relationships in hydride transfer reactions: the role of intrinsic barriers

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.     

Complex formation of isocytosine tautomers with PdII and PtII

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.     

Carbon-13 spectra of some tetrahydropyridines. The structure of the tetrahydropyridines from 3,5-lutidine 1-oxide and mercaptans in acetic anhydride

The reaction of 3,5-lutidine 1-oxide ( 1 ) with t-butyl mereaptan in acetic anhydride, with or without triethylamine, was reinvestigated. There was obtained 2-t-butylthio-3,.5-lutidine as the major product, a small quantity of 3-(t-bulylthio)methyl-5-picoline, 1-acetyl-2,3-diacetoxy-3,5-dirnethyl-6-t-butylthio-1,2,3,6-tetrahydropyridine (which represents a structure revision) and l-acetyl-2,6-dihydroxy-3-t-butylthio-3,5-dimethyl-1,2,3,6-tetrahydropyridine. A similar reaction of 1 with 1-adamantyl mercaptan furnished 2-(l-adamantylthio)-3,5-lutidine and 1-acetyl-2,3-diacetoxy-3,5-dimethyl-6-(1-adamantylthio)-1,2,3,6-tetrahydropyridine. The structures of these new tetrahydropyridines were established primarily by carbon-13 nmr spectra.     

Thiazolo-N-hydroxyuracils

The partial Lossen degradation of the hydroxamic acid group at C-4 or C-5 of sodium 4,5-thiazoledicarbohydroxamate (IIIb) and its 2-methyl analog (IIIe) initiated a multicoursed reaction which furnished a mixture of thiazolo[4,5-d]- and thiazolo[5,4-d]-N-hydroxyuracils. The isomer distribution was sensitive to the solvent systems in which these reactions were carried out. The structure of the isomers so obtained was established by chemical and spectral methods.     

GLOBAL ANALYSIS OF FLUORESCENCE DECAY: APPLICATIONS TO SOME UNUSUAL EXPERIMENTAL AND THEORETICAL STUDIES

The methodology for the simultaneous analysis of fluorescence decay curves is shown to create the possibility for some new types of fluorescence decay experiments. These new experiments include the use of the T-format in anisotropy experiments without the need to match the timing characteristics of photomultiplier tubes. Decay surfaces obtained at multiple timing calibrations can be analyzed simultaneously to resolve widely differing decay rates. Methodologies are described for the discrimination of associative from nonassociative behavior for multiexponential anisotropy decay. A systems theory approach to the analysis of excited state reactions is described.