Mixing Schemes for Aqueous Dimethyl Sulfoxide: Support by X-ray Diffraction Data

Aqueous dimethyl sulfoxide (DMSO) was studied by X-ray diffraction at room temperature. The results indicated that there are three distinct composition regions. In the DMSO-rich region, DMSO molecules retain the same molecular arrangement as in the pure state, while H₂O does not show any structural feature. These findings are in the complete agreement with the suggestion by our earlier thermodynamic study on aqueous DMSO.⁽¹⁾ In the H₂O-rich region, there is an indication that DMSO molecules exist as small clusters bound mainly by S=O dipole attraction. Hence, hydrophobic CH₃ groups point outward from such a cluster and DMSO acts in effect as a hydrophobic solute. This is also consistent with the findings of our earlier thermodynamic study. In the intermediate region, a gradual change in the radial distribution function with composition was observed.     

Honda’s thermobalance

Kotaro Honda (2/23/1870–2/12/1954) graduated from the Department of Physics, Tokyo Imperial University in 1897. Between 1907 and 1911, he stayed in Europe, and spent the majority of his time at Göttingen University to study physical metallurgy under Professor Gustav Tammann. In 1911, he returned to Japan and was nominated professor of physics at Tohoku Imperial University, Sendai. An university-affiliated institute for research on iron and steel was established on a permanent basis in 1919, and the institute developed to the Research Institute for Iron, Steel, and Other Metals (RIISOM, KINKEN in Japanese) in 1922. Professor Honda served as the Director of the Institute until 1933. The RIISOM was reorganized as a national collaborative research institute named Institute for Materials Research in 2001. Professor Honda and his colleagues achieved distinguished research works of physical metallurgy, in which thermoanalytical techniques such as differential thermal analysis (DTA), thermodilatometry and thermomagnetometry were utilized effectively. Professor Honda also played an important role in the field of thermogravimetry (TG) by means of the first development of the thermobalance. In the present paper, Honda’s original thermobalance, various modifications carried out by his school, the commercialized Honda’s thermobalance and other related matters are briefly summarized.     

Calculating a minimal sphere containing a polytope defined by a system of linear inequalities

We will propose an algorithm for calculating a minimal sphere containing a polytope defined by a system of linear inequalities in low dimensional Euclidean space. This algorithm is a straightforward application of the algorithm for maximizing a convex quadratic function over a polytope. It will be shown that this algorithm successfully generates a minimal sphere when the dimensions of the underlying space is up to five.International Digital Communication Inc.     

Dynamic molecular movements and aggregation structures of lipids in a liquid state

This paper discusses the molecular conformations and the liquid structures of triacylglycerols (TGs) and fatty acids in their melts. Three models for liquid state ordering have been proposed for TG melts to date: the smectic liquid crystal model, the nematic liquid crystal model, and the discotic model. To completely resolve the liquid structure of TGs, further research is required. However, some information on the molecular level has been obtained for fatty acids that are relatively simple compounds. The combination of various spectroscopic and thermodynamic measurements revealed that the hydrogen-bonded dimers of fatty acids are units of intermolecular and intramolecular movements in the liquids and in non-polar solvents. The dimers that construct the clusters resemble the smectic liquid crystal and determine the physicochemical properties of the liquid of the fatty acid. Cholesterol stabilizes the clusters, while ethanol destroys them. Self-diffusion and neutron diffraction measurements revealed that two kinds of fatty acids exist in their binary liquid mixture exist as the homodimers composed of same species.     

Phase transition in the mixed state of Bi2Sr2CaCu2Oy observed by local and macroscopic magnetometry

In Bi₂Sr₂CaCu₂O_y under magnetic fields along the c-axis, both the local and the macroscopic magnetization show clear steps indicating the first order phase transition (FOPT) in the vortex lattice (VL). Local measurements have revealed that the FOPT occurs from the center of the sample owing to the field inhomogeneity originated from the geometrical effect. The heights of the steps are strongly suppressed in local measurements by the demagnetization effect. With decreasing temperature, the irreversibility in the magnetization just below the step begins to increase and is smoothly connected to the second peak at low temperatures.     

Effect of penetrant-induced isothermal glass transition on sorption,dilation, and diffusion behavior of polybenzylmethacrylate/CO2

The effect of a penetrant-induced isothermal glass transition on sorption, dilation, and diffusion behavior was studied in a single experimental run for CO₂ in cast polybenzylmethacrylate films. The dual-mode type sorption isotherms below the glass transition temperature of the polymer changed to linear ones above a certain concentration. Meanwhile, partial molar volume of CO₂ determined from the dilation of the films above the concentration gave a value very close to the one reported for rubbery polymers, and diffusion coefficients became less concentration-dependent. The results were conformable to the concept of unrelaxed volume in glassy polymers. © 1996 John Wiley & Sons, Inc.     

Potassium enolates of N,N‐dialkylamides as initiators of anionic polymerization

Stable potassium enolates of N,N‐diethylacetamide [α‐potassio‐N,N‐diethylacetamide ( 1 )], N,N‐diethylpropionamide [α‐potassio‐N,N‐diethylpropionamide ( 2 )], and N,N‐diethylisobutyramide [α‐potassio‐N,N‐diethylisobutyramide ( 3 )] were prepared by the proton abstraction of the corresponding N,N‐diethylamides with diphenylmethylpotassium (Ph₂CHK) or potassium naphthalenide in THF. The relative nucleophilicity of 1 – 3 was estimated to be in the order of 1 < 3 < 2 from the results of the alkylation reaction with methyl iodide. N,N‐diethylacetamide transferred its α‐proton to 2 quantitatively in THF at 0 °C, whereas no reaction occurred between N,N‐diethylisobutyramide and 2 ; this indicated the relative basicity to be 1 < 2 ～ 3 . Anionic polymerizations of N,N‐diethylacrylamide (DEA) and methyl methacrylate were quantitatively initiated with 2 in THF at ?78 °C, whereas the initiation efficiencies of 2 for styrene and 2‐vinylpyridine were about 2 and 67%, respectively. The initiation of DEA with 1 – 3 at ?78 or 0 °C in THF gave poly (DEA)s having broad molecular weight distributions (MWDs; M_w/M_n = 2) and ill‐controlled molecular weights. In contrast, poly(DEA)s of narrow MWDs (M_w/M_n < 1.2) and predicted M_n's were obtained with 2 in the presence of diethylzinc (Et₂Zn) at ?78 °C, whereas the initiations with 1 /Et₂Zn and 3 /Et₂Zn at ?78 °C resulted in poor control of the molecular weights. At the higher temperature of 0 °C, all the binary initiator systems ( 1 – 3 /Et₂Zn) induced controlled polymerizations of DEA in terms of the conversion, molecular weight, and MWD. The poly(DEA)s produced with 1 – 3 /Et₂Zn at 0 °C showed mr‐rich configurations (mr = 76–89%), as observed for the poly(DEA) generated with Ph₂CHK/Et₂Zn. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1260–1271, 2007     

Thermoelectric properties of Bi-Sb semiconducting alloys prepared by quenching and annealing

Bi_100−xSb_x (x=8-17) alloys were prepared by direct melting of constituent elements, which was followed by quenching and annealing. The synthesis of high-homogeneity alloys was confirmed by X-ray diffraction, differential thermal analyses and electron microprobe analysis. The semiconducting and thermoelectric properties of the samples were investigated by measuring Hall coefficient, electrical resistivity and Seebeck coefficient in the temperature range from 20 to 300 K for both the as-quenched and annealing samples. The properties change gradually with the Sb concentration x, which is attributed to the variation of the energy gap. The Hall mobility was enhanced by annealing, which leads to a small electrical resistivity and a large Seebeck coefficient. Consequently, large values of about 8.5 mW/mK² for the power factor were obtained in the annealed alloys of x=8,12, and 14.