Improvement in superconductivity of TlBa2CaCu2Oy system by introduction of oxygen loss

The T_c and oxygen content of TlBa₂CaCu₂O_y have been investigated by quenching experiments, in which the heat-treated samples were dropped into liquid nitrogen. The oxygen loss, v, of TlBa₂CaCu₂O_{yo − v} was determined by thermogravimetry in a nitrogen atmosphere using an oxygen-annealed specimen of TlBa₂CaCu₂O_yo and also by measurements of the weight differences before and after quenching. T_c increased from 80 K of the oxygen-annealed specimen up to about 110 K with increasing oxygen loss up to v = 0.035 by annealing at 500°C in a nitrogen atmosphere. Judging from the high T_c above 110 K achieved by a small oxygen loss about v = 0.035, the as-sintered oxygen-annealed TlBa₂CaCu₂O_yo specimen was in the over-doping state and probably has an oxygen vacancy of 7 − y_o0.     

Go-and-Back method: effective estimation of the hidden motion of proteins from single-molecule time series

We present an effective method for estimating the motion of proteins from the motion of attached probe particles in single-molecule experiments. The framework naturally incorporates Langevin dynamics to compute the most probable trajectory of the protein. By using a perturbation expansion technique, we achieve computational costs more than 3 orders of magnitude smaller than the conventional gradient descent method without loss of simplicity in the computation algorithm. We present illustrative applications of the method using simple models of single-molecule experiments and confirm that the proposed method yields reasonable and stable estimates of the hidden motion in a highly efficient manner.     

Biodegradable polymers based on renewable resources. VII. Novel random and alternating copolycarbonates from 1,4:3,6‐dianhydrohexitols and aliphatic diols

Novel copolycarbonates containing 1,4:3,6‐dianhydro‐D ‐glucitol or 1,4:3,6‐dianhydro‐D ‐mannitol units, with various methylene chain lengths, were synthesized by bulk and solution polycondensations, of several combinations of carbonate‐modified sugar derivatives and aliphatic diols. Bulk polycondensations of 1,4:3,6‐dianhydro‐2,5‐bis‐O‐(phenoxycarbonyl)‐D ‐glucitol or 1,4:3,6‐dianhydro‐2,5‐bis‐O‐(phenoxycarbonyl)‐D ‐mannitol with four α,ω‐alkanediols having methylene chain lengths of 4, 6, 8, and 10, respectively, at 180 °C afforded the corresponding copolycarbonates with number‐average molecular weight (M_n) values up to 19.₂ × 10³. ¹³C NMR analysis disclosed that these polymers had scrambled structures in which the sugar carbonate and aliphatic carbonate moieties were nearly randomly distributed along a polymer chain. However, solution polycondensations between 1,4:3,6‐dianhydro‐2,5‐bis‐O‐(p‐nitrophenoxycarbonyl)‐D ‐glucitol or 1,4:3,6‐dianhydro‐2,5‐bis‐O‐(p‐nitrophenoxycarbonyl)‐D ‐mannitol, and the α,ω‐alkanediols in sulfolane or dimethyl sulfoxide at 60 °C gave well‐defined copolycarbonates having regular structures consisting of alternating sugar carbonate and aliphatic carbonate moieties with M_n values up to 33.₈ × 10³. Differential scanning calorimetry demonstrated that all the copolycarbonates were amorphous with glass‐transition temperatures ranging from 1 to 65 °C, which decreased with increasing lengths of the methylene chain of the aliphatic diols. Additionally, all the copolycarbonates were stable up to 310–330 °C as estimated by thermogravimetric analysis. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2312–2321, 2003     

Oxidation behavior of NiAl alloy at low temperatures

Oxidation behavior of NiAl alloy at low temperatures was studied. A NiAl plate was oxidized by exposure to ambient atmosphere at room temperature, heated at 473 K in air, and heated at 773 K in air. The oxide formed on the NiAl surface was investigated by angle‐resolved X‐ray photoelectron spectroscopy (AR‐XPS). Chemical composition and atomic concentration in the oxide layer were analyzed with factor analysis of XPS spectra. Exposure of the NiAl plate to the ambient atmosphere resulted in the formation of an Al₂O₃ layer along with a small amount of NiO. Oxidation of the NiAl plate at 473 K in air formed a film of double‐layered oxide; the top layer consisted of NiAl₂O₄ and a small amount of NiO, and the second layer was Al₂O₃. Successive oxidation at 773 K only changed the oxide‐layer thickness without changing the structure. Formation of oxide observed in the present study corresponds to the thermodynamic prediction for the oxidation behavior of NiAl at 1373 K. Copyright © 2007 John Wiley & Sons, Ltd.     

Estimation of the thickness or composition of a covering layer on a solid by XPS or AES

A method is proposed for semi-quantitative determination of the thickness or composition of a covering layer on a solid by XPS or by micro-AES using neither a series of standard samples nor argon-ion etching. In the case of XPS, the thickness or relative composition of the covering layer is calculated by means of the intensity ratio between one element and another in a specimen and using physical parameters such as inelastic mean free paths of electrons and photoionization cross-sections.In the case of AES, the physical parameters for the quantification can be eliminated by using the ratio of the relative intensity for two elements in the sample to that in a suitable, comparable reference.     

A novel cyclization reaction of oxidodiazoalkanes: formation of pyrazoles and pyridazines

The thermal decomposition of dialkali metal salts of β- and γ-hydroxyketone tosyl-hydrazones in refluxing DME produced pyrazoles and pyridazines, respectively.     

Selective cleavage of ethers by sodium iodide-acyl chloride

Cyclic and acyclic ethers are regioselectively cleaved at less substituted α-carbon-oxygen bond in the absence of Lewis acid by the reagent system of sodium iodide and acyl chlorides.     

ESCA Investigation of the surface of mixed precipitates

Quantitative ESCA has been used for studying the surface of mixed precipitates. When the precipitation is complete and homogeneous, as with titanium and zirconium hydroxides, almost complete correlation is found between the atomic ratio of the elements in the precipitate and that estimated by the Hirokawa-Ebel method, but not for incomplete mixed precipitation, as with copper and silver hydroxides. When precipitated copper and silver are reduced to the metals with iron or zinc, the surface is enriched in copper.     

Complete stereochemistry of neamphamide A and absolute configuration of the beta-methoxytyrosine residue in papuamide B

The absolute stereochemistry of the three unresolved structural components in neamphamide A (1) was determined to be (R)-beta-methoxy-L-tyrosine, (2R,3R,4S)-4-amino-7-guanidino-2,3-dihydroxyheptanoic acid, and (2R,3R,4R)-3-hydroxy-2,4,6-trimethylheptanoic acid. Stereochemical assignments were made by chemical degradation of 1, derivatization of the resulting products, and then spectroscopic and chromatographic comparison of the derivatives with synthetically prepared standards. Using the same analytical protocol developed for 1, the beta-methoxytyrosine residue in papuamide B (2) was found to be (R)-beta-methoxy-D-tyrosine. This represents a rare example of divergent stereochemistry in an unusual amino acid residue that is present in two closely related classes of peptides.