Outer-sphere effects on reduction potentials of copper sites in proteins: the curious case of high potential type 2 C112D/M121E Pseudomonas aeruginosa azurin

Redox and spectroscopic (electronic absorption, multifrequency electron paramagnetic resonance (EPR), and X-ray absorption) properties together with X-ray crystal structures are reported for the type 2 Cu(II) C112D/M121E variant of Pseudomonas aeruginosa azurin. The results suggest that Cu(II) is constrained from interaction with the proximal glutamate; this structural frustration implies a "rack" mechanism for the 290 mV (vs NHE) reduction potential measured at neutral pH. At high pH (～9), hydrogen bonding in the outer coordination sphere is perturbed to allow axial glutamate ligation to Cu(II), with a decrease in potential to 119 mV. These results highlight the role played by outer-sphere interactions, and the structural constraints they impose, in determining the redox behavior of transition metal protein cofactors.     

Isotopic composition of Australian leads I. Preparation of tetramethyl lead samples

Summary Routine preparation of pure tetramethyl lead from minerals containing more than 1% of lead has been carried out on a small scale by a method involving reactions not hitherto used in this type of work. The method is simple to operate, involves the use of a minimum of reagents, and has been applied successfully to all types of lead mineral so far encountered. PbCl₂ is prepared by an HCl leach followed by precipitation from ethanol. It is then treated, in ether solution, with LiCH₃ in the presence of excess CH₃I, and the product is purified by vacuum distillation. Some further observations are made on a previously reported side-product of the preparation which leads to a wrong value of the lead isotope abundances.

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Zusammenfassung Die routinemäßige Herstellung kleiner Mengen von reinem Tetramethylblei aus Mineralien, die mehr als 1% Blei enthalten, wurde mit einer bisher für diesen Zweck noch nicht benützten Methode durchgeführt. Sie ist einfach, benötigt nur wenige Reagenzien und konnte mit vollem Erfolg bei allen in Frage kommenden Bleimineralien angewandt werden. Durch Auflösung des Minerals mit Salzsäure wird Bleichlorid erhalten und mit Äthanol ausgefällt. Das Salz reagiert mit überschüssigem Methyljodid in ätherischer Lösung und wird mittels Vakuumdestillation gereinigt. Außerdem wurden weitere Beobachtungen ein Nebenprodukt betreffend gemacht (über das früher berichtet wurde), das zu einem falschen Wert bei der Angabe der Bleiisotopüberschüsse führt.

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Résumé On a réalisé la préparation en série de plomb tétraméthyle pur à partir de minerais contenant plus de 1% de plomb, sur une petite échelle, suivant une méthode utilisant des réactions inutilisées jusqu'ici dans ce genre de travail. La méthode est simple à réaliser, ne nécessite l'emploi que d'un minimum de réactifs, et a été appliquée avec de bons résultats à tous les types de minerais de plomb rencontrés jusqu'ici. On prépare PbCl₂ par un lessivage à l'acide chlorhydrique suivi d'une précipitation à partir de l'éthanol. On le traite alors, en solution dans l'éther, par LiCH₃ en présence d'un excès de CH₃I et l'on purifie le produit par distillation dans le vide. On a fait quelques autres observations sur un sous-produit de la préparation signalé auparavant, qui conduit à une valeur fausse des abondances isotopiques du plomb.

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Publication No. 202.     

Ueber das Atomgewicht des Baryums

Ohne Zusammenfassung     

Ueber activirte Metalle (Metallpaare) und die Verwendung des activirten Aluminiums zur Reduction in neutraler Lösung

Analytical and Bioanalytical Chemistry -     

Hyperfine interactions,including Bhf[FrFe], studied in the decay chain of225Ra by alpha and gamma anisotropy measurements

A low temperature nuclear orientation experiment has been performed on the 14.8d²²⁵Ra activity. Gamma anistotropy [²²¹Fr (4.8m) and²¹³Bi (45.6m)] and alpha anisotropy [²²⁵Ac (10.0d),²²¹Fr,²¹⁷At (32.3ms) and²⁰⁹Po (4.2μs)] measurements has been carried out and values for the hyperfine field of²²⁵Ac and²²¹Fr in iron and the magnetic moment of²¹³Bi are reported.     

Exact Misclassification Probabilities for Plug-In Normal Quadratic Discriminant Functions: II. The Heterogeneous Case

We consider the problem of discriminating between two independent multivariate normal populations, N_p(μ₁, Σ₁) and N_p(μ₂, Σ₂), having distinct mean vectors μ₁ and μ₂ and distinct covariance matrices Σ₁ and Σ₂. The parameters μ₁, μ₂, Σ₁, and Σ₂ are unknown and are estimated by means of independent random training samples from each population. We derive a stochastic representation for the exact distribution of the “plug-in” quadratic discriminant function for classifying a new observation between the two populations. The stochastic representation involves only the classical standard normal, chi-square, and F distributions and is easily implemented for simulation purposes. Using Monte Carlo simulation of the stochastic representation we provide applications to the estimation of misclassification probabilities for the well-known iris data studied by Fisher (Ann. Eugen.7 (1936), 179–188); a data set on corporate financial ratios provided by Johnson and Wichern (Applied Multivariate Statistical Analysis, 4th ed., Prentice–Hall, Englewood Cliffs, NJ, 1998); and a data set analyzed by Reaven and Miller (Diabetologia16 (1979), 17–24) in a classification of diabetic status.