Double-layer effects on simple electrode reactions II. The effects of specifically adsorbed anions and ion-pairing on the reduction of Eu3+ and Cr3+

The kinetics of the reduction of Eu³⁺ and Cr³⁺ at mercury electrodes have been studied in various mixed perchlorate electrolytes containing iodide, bromide, and p-toluene-sulfonate as adsorbing anions. Specific adsorption data were obtained by means of the constant ionic strength approach due to Hurwitz and Parsons. The rate enhancements observed in the presence of the first two (monatomic) anions were in good agreement with the predictions of the simple Frumkin model only when the experimental, rather than calculated diffuse-layer capacitances were employed in the data analysis. It was demonstrated that the effects of ion-pairing and ligand-bridging of the reactants with the adsorbing anions were negligible under the experimental conditions chosen. From experiments with these systems and also with weakly adsorbing chloride electrolytes it was concluded that ion-pairing did not enhance the electrochemical reactivity of either Eu³⁺ or Cr³⁺. The value of the analyses described in separating various contributions to the catalytic effects of adsorbing anions is emphasized.     

Low temperature absorption spectra of TcO 4 − and ReO 4 − in KClO4

The low temperature spectra of TcO ₄ ^– and ReO ₄ ^– both show two band systems with pronounced vibrational structures. The bands are identified as¹ A ₁¹ T ₂ transitions. No other bands are observed with certainty. It seems likely that the KClO₄ crystals contain KReO₄ crystallites. They are therefore not pure mixed crystals. It is concluded that the virtual orbital (2e) used in the construction of the low lying states resembles an atomic nd orbital more and more when going from n=3, Mn to n=5, Re.

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Zusammenfassung Die Tieftemperaturspektren von TcO ₄ ^– und ReO ₄ ^– zeigen beide zwei Bandensysteme mit ausgeprägten Schwingungsstrukturen. Die Banden werden als ¹ A ₁¹ T ₂-Übergänge identifiziert. Keine anderen Banden werden mit Sicherheit beobachtet. Es scheint wahrscheinlich, daß die KClO₄-Kristalle KReO₄-Kristallite enthalten und deswegen keine reinen Mischkristalle sind. Es wird geschlossen, daß das virtuelle Orbital (2e), welches zur Konstruktion der tiefliegenden Zustände gebraucht wird, in der Reihe n=3, Mn bis n=5, Re immer weitgehender einem nd-Atomorbital ähnelt.

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Nachwuchsstipendiat, Schweizerischer Nationalfonds.     

Mechanism and scope of salen bifunctional catalysts in asymmetric aldehyde and α-ketoester alkylation

Metal complexes of C₂-symmetric Lewis acid/Lewis base salen ligands provide bifunctional activation resulting in rapid rates in the enantioselective addition of diethylzinc to aldehydes (up to 92% ee). Further experiments probed the reactivity of the individual Lewis acid and Lewis base components of the catalyst and established that both moieties are essential for asymmetric catalysis. These catalysts are also effective in the asymmetric addition of diethylzinc to α-ketoesters. This finding is significant because α-ketoesters alone serve as their own ligands to accelerate racemic 1,2-carbonyl addition of Et₂Zn and racemic carbonyl reduction. The latter proceeds via a metalloene pathway, and often accounts for the predominant product. Singular Lewis acid catalysts do not accelerate enantioselective 1,2-addition over these two competing paths. The bifunctional amino salen catalysts, however, rapidly provide enantioenriched 1,2-addition products in excellent yield, complete chemoselectivity, and good enantioselectivity (up to 88% ee). A library of the bifunctional amino salens was synthesized and evaluated in this reaction. The utility of the α-ketoester method has been demonstrated in the synthesis of an opiate antagonist.     

Carbohydrate analysis prepares to enter the "Omics" era

In this issue, Houseman and Mrksich describe a carbohydrate array preparation method that can be used to analyze protein-carbohydrate interactions and to characterize the substrate specificity of a carbohydrate-modifying enzyme. Carbohydrate chips were prepared by a novel procedure that allows the covalent attachment of carbohydrate-diene conjugates to a specially engineered monolayer surface. The surface presents a precisely controllable ratio of reactive benzoquinone and inert ethylene glycol groups. Nonspecific adsorption of proteins to the surface is extremely low, and the surface is compatible with popular detection techniques. The immobilization technique was demonstrated to be compatible with recently developed automated solid phase carbohydrate synthesis methods, paving the way for the development of highly complex carbohydrate arrays.     

Electron-capture negative ionization calibrants for magnetic sector mass spectrometers

Fomblin [poly(perfluoropropylene oxide)], PFK (perfluorokerosene) and FC-43 (perfluorotributylamine) are investigated as mass calibrants in electron-capture negative ionization mass spectrometry on a magnetic sector hybrod mass spectrometer. This work provides exact negative ion mass tables of these three calibrants obtained using high-resolution peak matching of representative ions of the calibrants against ions of known mass. The suitability of these calibrants for full data system control in the negative ionization mode is demonstrated for the techniques of high-resolution scanning, selected ion recording and calibration of the quadrupole sector of a hybrid instrument.     

Quantification of fg-pg amounts by electron capture negative ion mass spectrometry — Parameter optimisation and practical advices

Electron capture negative ion mass spectrometry (ECNI-MS) is a very suitable and popular technique for the identification and quantification of fg-pg amounts of compounds with a sufficiently high electron affinity. Many users of the ECNI mode have faced a lot of frustrating problems due to instrument contamination and wrong recommendations concerning instrument optimisation. This article summarises 14 years of experience with ECNI-MS using a large number of different instruments. Recommendations are given concerning optimisation procedures of important parameters such as ion source pressure and temperature as well as electron energy. An ion pressure optimisation method is proposed using a gas chromatograph. ECNI-MS is very sensitive against trace amounts of contaminants in the mass spectrometer and requires very clean components in the reagent gas line. Recommendations are given concerning suitable parts. Different other contamination sources are also discussed. The construction of a simple and clean gas inlet system is presented. Furthermore, contamination-free cleaning methods for the ion source are suggested. A test method based on the detection of hexachlorobenzene in the full scan mode (m/z 34–300) is proposed. It allows to evaluate both the background level in the mass spectrometer and the overall system performance. Clean instruments should show a signal-to-noise ratio of the total ion current GC signal of at least 20:1 without applying any mass signal area reject threshold. A linearity test procedure is also suggested. It shows that the linear range of a clean and optimised instrument is at least 3 orders of magnitude in the ECNI mode.     

EVIDENCE FOR THE PHOTOPROTECTIVE EFFECTS OF VITAMIN E

Abstract— The antioxidant vitamin E (α-tocopherol) may protect both animal and plant cell membranes from light-induced damage. The various biochemical and biophysical modes of protection are considered. An examination is made of the evidence that vitamin E plays an important prophylactic role against a number of serious light-induced diseases and conditions of the eye (cataractogenesis and retinal photodeterioration) and skin (erythrocyte photohem-olysis, photoerythema, photoaging and photocarcinogenesis) that are mediated by photooxidative damage to cell membranes.     

Divergence Criterion for a Class of Random Series Related to the Partial Sums of I.I.D. Random Variables

Journal of Theoretical Probability - Let $$ \{X, X_{n};~n \ge 1 \}$$ be a sequence of independent and identically distributed Banach space valued random variables. This paper is devoted to...     

Neue Näherungsgleichung zur einheitlichen Berechnung von Wärmeübertragern

Zusammenfassung Es wird eine für alle Stromführungen einheitliche Näherungsgleichung mit drei oder vier anpaßbaren Parametern zur Berechnung des Korrekturfaktors für die mittlere logarithmische Temperaturdifferenz angegeben. Die anpaßbaren Parameter wurden für etwa 50 verschiedene Stromführungen durch Ausgleichsrechnung bestimmt. Die Genauigkeit der Gleichung ist für die Berechnung im praktisch wichtigen Bereich mehr als ausreichend.

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New approximate equation for uniform heat exchanger design

An approximate equation with three or four empirical parameters for the uniform calculation of the LMTD-correction factor of all heat exchanger configurations is proposed. The empirical parameters have been determined for about 50 different flow configurations using least squares estimation. The accuracy of the equation is more than sufficient for practical design purposes.

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Formelzeichen A Übertragungsfläche - a, b, c, d Parameter der Näherungsgleichung - Wärmekapazitätsstrom - F Korrekturfaktor für die logarithmische mittlere Temperaturdifferenz - k Wärmedurchgangskoeffizient - m, n Zahl der Durchgänge oder Einzelapparate - NTU Anzahl der Übertragungseinheiten (number of transfer units); NTU_i=kA/ _i - P dimensionslose Temperaturänderung - R Wärmekapazitätsstromverhältnis;R ₁=₁/₂;R ₂=₂/₁ - relativer Fehler - Mittelwert von NTU₁ und NTU₂ Indizes 1, 2 Stoffstrom 1, 2 - G Gegenstrom - s Schätzwert Herrn Prof. Dr.-Ing. E.h. K. Stephan zum 65. Geburtstag gewidmet.     

A note on pseudocompactifications

There exists a countable spaceV _ω such that:

1. V _ω has a single non-isolated point,
2. V _ω has no pseudocompactificationX witht(X)=ω.