Excess molar heat capacities of ((<Emphasis Type="Italic">R</Emphasis>)-(+)-α-pinene+(<Emphasis Type="Italic">S</Emphasis>)-(-)- α-pinene) at temperatures between 293.15-308.15 K

Summary {\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}} \viewkind4\uc1\pard\f0\fs20 New explanations are given for two types of irregular thermogravimetric (TG) data. A TG relationship between mass and temperature is derived on the basis of migration behavior of bubbles generated in bulk of sample system, and superposed on that derived on the basis of kinetics of the 4\super th\nosupersub order event, which is superposed on the experimental TG data obtained from three reference papers. This suggests that these TG data are reflecting migration of bubbles. A dependence of TG behavior on heating rate, which is contrary to usual that, is shown and is explained in terms of event-rate determination by boiling. \par }     

Specific gel electrophoresis method detects two isoforms of human intestinal alkaline phosphatase

We have demonstrated that the 6.0% polyacrylamide disc gel electrophoresis (PAGE) method in the presence of 1% Triton X-100 clearly separated both normal molecular mass intestinal alkaline phosphatase (NIAP) and bone alkaline phosphatase (BAP) in serum regardless of the ABO blood group and the secretor status of the subjects. From the results under the usual 7.5% PAGE condition, overlapping mobilities of NIAP and BAP were found in particular in nonsecretor subjects after a high-fat meal. Under the above conditions, the apparent BAP percentage three hours after a meal was higher in nonsecretors than in subjects under fasting conditions, because NIAP activity in serum rose sharply following a high-fat meal. In contrast, under our 6.0% PAGE method, the NIAP and BAP were clearly separated from each other regardless of whether the subjects were fasting or had ingested a high-fat meal. In addition, an elevated level of the circulating NIAP can be another marker for patients with liver cirrhosis. Considering all these factors, the 6.0% PAGE method proposed by us is not only a useful method for the separation of intestinal alkaline phosphatase (IAP) isoforms, but can also be useful for the analysis of other usual AP isozymes.     

Smart cleavage reactions: the synthesis of benzimidazoles and benzothiazoles from polymer-bound esters

The preparation of an array of benzimidazoles and benzothiazoles from polymer-bound esters is described. Polymer-bound esters were treated with 2-aminothiophenols or 1,2-phenylenediamines in the presence of a Lewis acid to afford the corresponding benzothiazole or benzimidazole cleavage products. The reaction of 2-aminophenols with the polymer-bound esters failed to give the desired benzoxazole products using this procedure.     

A passive sampler-GC/ECD method for analyzing 18 volatile organohalogen compounds in indoor and outdoor air and its application to a survey on indoor pollution in Shizuoka, Japan

A simple and reliable method was developed for analysis of 18 volatile organohalogen compounds (VOHCs) both indoors and outdoors, consisting of VOHC collection by a passive sampler, extraction with toluene by mechanical shaking, and automatic separation analysis by capillary gas-chromatography with electron capture detector (GC/ECD). The passive sampler is a porous polytetrafluoroethylene (PTFE) tube (30.30+/-0.37 mm net collection length, 5.0 mm inside diameter, 0.990 g weight) uniformly packed with activated charcoal (194.4+/-3.8 mg). The procedure was applied to a field survey on indoor and outdoor VOHC pollution in Shizuoka, Japan. Ten VOHCs, including trichloroethylene, tetrachloroethylene, chloroform, carbon tetrachloride, and p-dichlorobenzene, were detected from indoor and outdoor air samples. The ratios of maximum to minimum VOHC concentrations, both outdoors and indoors, were large. The indoor and outdoor concentrations of 1,1-dichloroethylene, dichloromethane, 1,1,1-trichloroethylene, carbon tetrachloride and trichloroethylene were found to be similar. Indoor concentrations of trihalomethanes, p-dichlorobenzene and tetrachloroethylene were higher than those of outdoors.     

Relaxed excited states and anomalous hyperfine structure of muonium centers in KBr

We report on the luminescence induced by positive muons implanted (with 4 MeV) into KBr crystal, which evidences a long-lived (lifetime=13.3 s excited state produced by muon radiolysis. The temperature dependence of the luminescence yield has a strong correlation with the amplitude of an anomalous muonium center: both are observed only below 50 K. This correlation strongly suggests that the muonium center is perturbed by the muon-induced excitons to cause the anomalous hyperfine structure. Moreover, the luminescence energy and decay time indicate that the observed luminescence is not associated with the intrinsic or impurity-related self-trapped excitons, but with a relaxed excited state specific to the muon(ium)-KBr system.     

Preparation of immunoaffinity mini-columns for the analysis of platelet activating factor (PAF) in biological samples.

Using an antibody to BN 52719, an analogue of platelet activating factor (PAF), immunoaffinity mini-columns for the separation of PAF from biological samples were prepared. Rabbits were immunized with BN 52719 and immunoglobulin G (IgG) from the antiserum was coupled with Sepharose 4B. The resulting suspension of the IgG-coated Sepharose 4B in 25 mM phosphate buffer (pH 6.9) was poured into a plastic mini-column (bed volume 2.0 x 0.8 cm). Stepwise elution of the column with methanol revealed that lyso-PAF is eluted with 20-30% methanol in water whereas PAF is eluted with 50-80% methanol. For the determination of PAF in biological samples, it is recommended that lipids are extracted from the samples and the extract, reconstituted in 20% methanol, is loaded on the column. The column is then washed with 50% methanol followed by elution of PAF with 80% methanol. A small amount of [3H]PAF is added to the samples for measurement of the recoveries of PAF during the procedures of extraction and elution. The PAF is then quantified by radioimmunoassay or bioassay. Employing the immunoaffinity mini-column and radioimmunoassay, the contents of PAF in macrophages and conditioned medium after stimulation with calcium ionophore A23187, or tumor promoters such as TPA and thapsigargin, were measured.     

Ab initio potential energy surfaces of the ion-molecule reaction: C2H2 + O+

High level ab initio calculations using complete active space self-consistent field and multi reference single and double excitation configuration interaction methods with cc-pVDZ (correlation consistent polarized valence double zeta) and cc-pVTZ (triple zeta) basis sets have been performed to elucidate the reaction mechanism of the ion-molecule reaction, C2H2(1Sigmag+) + O+(4S), for which collision experiment has been performed by Chiu et al. [J. Chem. Phys. 109, 5300 (1998)]. The minor low-energy process leading to the weak spin-forbidden product C2H2+ (2Piu) + O(1D) has been studied previously and will not be discussed here. The major pathways to form charge-transfer (CT) products, C2H2+ (2Piu) + O(3P) (CT1) and C2H2+ (4A2) + O(3P) (CT2), and the covalently bound intermediates are investigated. The approach of the oxygen atom cation to acetylene goes over an energy barrier TS1 of 29 kcal/mol (relative to the reactant) and adiabatically leads the CT2 product or a weakly bound intermediate Int1 between CT2 products. This transition state TS1 is caused by the avoided crossing between the reactant and CT2 electronic states. As the C-O distance becomes shorter beyond the above intermediate, the C1 reaction pathway is energetically more favorable than the Cs pathway and goes over the second transition state TS2 of a relative energy of 39 kcal/mol. Although this TS connects diabatically to the covalent intermediate Int2, there are many states that interact adiabatically with this diabatic state and these lead to the other charge-transfer product CT1 via either of several nonadiabatic transitions. These findings are consistent with the experiment, in which charge transfer and chemical reaction products are detected above 35 and 39 kcal/mol collision energies, respectively.     

Highly sensitive automatic analysis of polycyclic aromatic hydrocarbons in indoor and outdoor air

A method for the quantitation of polycyclic aromatic hydrocarbons (PAHs) in indoor and outdoor air by high-performance liquid chromatography (HPLC) with a spectrofluorometric detection and programmed excitation and emission wavelength pairs is proposed. The mobile phase is a linear gradient of methanol-water. The relative standard deviations (n = 5) are in the range 0.38-1.7% at concentration levels of 0.69-11.40 ng ml(-1). The determination limits (S N = 10 ) are 0.5-15.9 pg. The proposed method was successfully applied to quantitate 12 PAHs in gas phase and particulates in indoor and outdoor air. The recoveries of PAHs from gas phase and particulates were 95.7-117.5 and 94.8-112.4%, respectively. This highly sensitive automatic HPLC analysis for PAHs both in gas phase and particulates can be applied to indoor and outdoor survey.