Promotion by phosphorus compounds of ruthenium-catalyzed methyl formate homologation

Trivalent phosphorus compounds are promoters for methyl formate homologation to ethanol and ethyl formate catalyzed by ruthenium compounds in the presence of iodide at 220°C and 27 MPa of synthesis gas. Under these conditions the phosphines are quaternized, but decomposition of phosphonium salts occurs during the reaction. Promotion is also observed for methyltriphenyl-phosphonium bromide and triphenylphosphine sulfide, but benzyltrimethyl-ammonium bromide, triphenylarsine, and triphenylantimony are not effective. The major ruthenium species present is Ru(CO)₃I₃^- but with triphenylantimony a trimethylantimony complex, Ru(CO)₂(Sb(CH₃)₃)₂I₂, can be isolated in high yield.     

Sequence distribution of partially hydrolyzed poly(vinyl acetate)

Copolymers of vinyl acetate and vinyl alcohol were studied by differential thermal analysis. The melting points of the copolymers are not a simple function of the composition, but depend on the method of preparation of the copolymers. Partial saponification of poly(vinyl acetate) with sodium hydroxide leads to high melting, ordered copolymers, while reacetylation of poly(vinyl alcohol) leads to low melting, random copolymers. Catalytic alcoholysis of PVAc yields copolymers intermediate in melting point and order. The results are treated by assuming that equal melting points indicate similar sequence length distributions of crystallizable units.     

Microchemical characterization of paintings — A case study

Summary The fundamental importance of scientific research for the preservation and restoration of works of art is uncontestable. The methods described in this paper, such as light microscopy, microchemical tests, emission spectroscopy, chromatography, scanning electron analysis, electron microprobe analysis and infrared spectroscopy, are of special significance in this filed. Nevertheless a better understanding of the problems that arise out of new special questions of art history can be obtained only by the right interpretation of the data obtained by scientific methods.

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Mikrochemische Charakterisierung von Gemälden

Zusammenfassung Die grundlegende Bedeutung wissenschaftlicher Forschung für die Erhaltung und Restaurierung von Kunstwerken ist unbestritten. Die hier beschriebenen Methoden (Lichtmikroskopie, mikrochemische Reaktionen, Emissionsspektroskopie, Chromatographie, Rasterelektronen-Analyse und Infrarotspektroskopie) sind hierfür von zunehmender Bedeutung. Sie ermöglichen ein besseres Verständnis neuerer kunsthistorischer Probleme nur durch die richtige Interpretation der Ergebnisse wissenschaftlicher Methoden.

     

Kinetics and mechanism of the acid-catalysed decarboxylation of thecis-α- andcis-β-carbonato(3,6-dimethyl-1,8-diamino-3,6-diazaoctane)-cobalt(III) ions

Summary The acid-catalysed decarboxylation of thecis-- andcis--[CoL(CO₃)]⁺ complexes (L = 3,6-dimethyl-1,8-diamino-3,6-diazaoctane) have been studied over a range of HClO₄ concentrations and the temperatures 25, 35 and 45° at I = 1.0 mol dm^–3 (NaClO₄). The rate expression takes the form k_obs = k₀ + k₁[H⁺] where k_obs is the observed first order rate constant at constant hydrogen ion concentration. The k₀ term makes only a minor contribution to the overall reaction. Both complexes display solvent deuterium isotope effects ofca. 2.6 for the acid-catalysed decarboxylation, consistent with a rapid proton pre-equilibrium mechanism. Activation parameters have been determined and the mechanism of the reaction discussed. The magnitude of the solvent isotope effect is consistent with an A-1 type mechanism involving formation of a 5-coordinate intermediate.     

A criterion for the uniform distribution of sequences in compact metric spaces

LetX be a compact metric space, le μ be a non-negative normalized Borel measure onX and letf be a measurable bounded real-valued function defined onX such thatf is μ-almost everywhere continuous and different from zero. It is proved that a sequence (x _n ),n=1,2, … of points inX is μ-uniformly distributed if and only if for every Borel setE?X with μ(Bd(E))=0 we have \(\mathop {\lim }\limits_{N \to \infty } \frac{1}{N}\sum\limits_{n = 1}^N {f(x_n )} 1_E (x_n ) = \int\limits_E {f(x)d\mu (x)} ,\) where 1 _E denotes the characteristic function ofE andbdE the boundary ofE. Furthermore some quantitative aspects and generalizations of this theorem are discussed.     

The physical properties of linear and action-angle coordinates in classical and quantum mechanics

The quantum harmonic oscillator is described in terms of two basic sets of coordinates: linear coordinates x, p_x and angular coordinates eⁱ, P (action-angle variables). The angular coordinate eⁱ is assumed unitary, the conjugate momentum p is assumed Hermitian, and eⁱ and p are assumed to be a canonical pair. Two transformations are defined connecting the angular coordinates to the linear coordinates. It is found that x, p_x can be physical, i.e., Hermitian and canonical, only under constraints on the p eigenvalue spectrum. The conclusion is that eⁱ can be a unitary operator. A parallel analysis of the classical harmonic oscillator is done with equivalent results.     

A priori-Schranken für diskrete Lösungen monotoner Operatorgleichungen und Anwendungen

Summary Operator equationsTu=f are approximated by Galerkin's method, whereT is a monotone operator in the sense of Browder and Minty, so that existence results are available in a reflexive Banach spaceX. In a normed spaceY error estimates are established, which require a priori bounds for the discrete solutionsu _h in the norm of a suitable space . Sufficient conditions for the uniform boundedness u _{h Z} =O(1) ash0 are proved. Well-known error estimates in [3] for the special caseX=Y=Z are generalized by this. The theory is applied to quasilinear elliptic boundary value problems of order 2m in a bounded domain . The approximating subspaces are finite element spaces. Especially the caseX=W ₀ ^{m, p} (), 1<p<,Y=W ₀ ^{m. 2} (),Z=W ₀ ^{m. max (2,p)} ()W^m, () is treated. Some examples for 1<p<2 are considered. Forp2 a refined technique is introduced in the author's paper [7].

     

CHEMICALLY MODIFIED PHOTOSYNTHETIC BACTERIAL REACTION CENTERS: CIRCULAR DICHROISM, RAMAN RESONANCE, LOW TEMPERATURE ABSORPTION, FLUORESCENCE AND ODMR SPECTRA AND POLYPEPTIDE COMPOSITION OF BOROHYDRIDE TREATED REACTION CENTERS FROM Rhodobacter sphaeroides R26

Abstract— Reaction centers from Rhodobacter sphaeroides have been modified by treatment with sodium borohydride similar to the original procedure [Ditson et al., Biochim. Biophys. Acta 766 , 623 (1984)], and investigated spectroscopically and by gel electrophoresis.
(1) Low temperature (1.2 K) absorption, fluorescence, absorption- and fluorescence-detected ODMR, and microwave-induced singlet-triplet absorption difference spectra (MIA) suggest that the treatment produces a spectroscopically homogeneous preparation with one of the 'additional' bacteriochlorophylls being removed. The modification does not alter the zero field splitting parameters of the primary donor triplet (^TP870).
(2) From the circular dichroism and Raman resonance spectra in the1500–1800 cm^-1 region, the removed pigment is assigned to Bchl_M, e.g. the "extra" Bchl on the "inactive" M-branch.
(3) A strong coupling among all pigment molecules is deduced from the circular dichroism spectra, because pronounced band-shifts and/or intensity changes occur in the spectral components assigned to all pigments. This is supported by distinct differences among the MIA spectra of untreated and modified reaction centers, as well as by Raman resonance.
(4) The modification is accompanied by partial proteolytic cleavage of the M-subunit. The preparation is thus spectroscopically homogeneous, but biochemically heterogenous.