Chiral separation of amines by high-performance liquid chromatography after tagging with 4-(N,N-dimethylaminosulphonyl)-7-(2-chloroformylpyrrolidin-1-yl)- 2,1,3-benzoxadiazole

Chiral tagging reagents, 4-(N,N-dimethylaminosulphonyl)-7-(2-chloroformylpyrrolidin-1 -yl)-2,1,3- benzoxadiazole (R(+)-DBD-Pro-COCl and S(-)-DBD-Pro-COCl), react with mirror image enantiomers of amines to produce corresponding diastereomers in the presence of pyridine as a catalyst. The maximal excitation and emission wavelengths of the resulting diastereomers were ca. 450 nm and 560 nm, respectively. The diastereomers derived from some aliphatic amines were resolved by a reversed-phase chromatography with water-acetonitrile or normal-phase chromatography with n-hexane-ethyl acetate as the eluent. The reactivities of both enantiomers of DBD-Pro-COCl to chiral amines were almost comparable, whereas a slight difference of fluorescence intensity was observed with S(-)-DBD-Pro-COCl. When (S-)-DBD-Pro-COCl was used as the derivatization reagent, amines corresponding to S-configuration were eluted faster than R-configuration. The opposite elution order was obtained with the use of R(+)-DBD-Pro-COCl, instead of S(-)-DBD-Pro-COCl. The Rs values obtained from 1-cyclohexylethylamine (CEA) having aliphatic ring structure was larger than those of amines (1-(1-naphthyl)ethylamine (NEA) and 1-phenylethylamine (PEA)) having aromatic ring structures.     

Measurement method using coupled transmission lines for voltage transients on the distribution line

It is well known that voltage transients are caused by the operation of switchgears in a power system. The voltage transients travel along the power line as a traveling wave, and cause malfunction of electrical devices, communication systems, and the operational error of a control system. The voltage transients at the making operation of switchgear were examined to obtain the fundamental data for considering the immunity of communication systems used on a power system. However, it was difficult to observe the voltage transients using the potential transformer and the capacitance potential device because the transients were very rapid. Therefore, a measurement method using the coupled transmission line system is proposed to measure the high-speed and high-voltage transients, and the actual experimental results on the 6.9-kV power system are presented. This method enables the measurement of high-speed voltage transients in out of contact with the power system.     

Incidence of human T lymphotropic virus type I seroconversion after age 40 among Japanese residents in an area where the virus is endemic

To clarify how seroconversion after age 40 years contributes to the seroprevalence of human T lymphotropic virus type I (HTLV-I), Japanese residents were studied in an area of Kyushu in which HTLV-I is endemic. Cross-sectional data showed higher seroprevalences among subjects > or = 40 than in those < 40 years old (27.0% vs. 7.9%). The prevalence was also greater in women than men (25.5% vs. 17.6%). Six hundred subjects > or = 40 years old were tested during 1976-1993. Among 8 who seroconverted, 5 had an HTLV-seropositive spouse and 2 seroconverted after blood transfusions. The incidences per 1000 person-years of seroconversion in age groups 40-49, 50-59, and > or = 60 years were, respectively, 0.0, 0.0, and 3.3 (range, 1.38-5.13) in men and 0.0, 5.3 (range, 0.11-7.99), and 1.4 (range, 0.00-1.60) in women. The seroconversion incidence was insufficient to account for the rise of seroprevalence in those > or = 40 years old, especially among women. These results suggest that the high rate and sex discordance in HTLV-I seroprevalence after age 40 may depend mainly on the birth cohort effect for vertical or horizontal transmission.     

High levels of transforming growth factor beta 1 in patients with colorectal cancer: association with disease progression

BACKGROUND & AIMS: Contribution of transforming growth factor beta 1 (TGF-beta 1) to tumor progression has been suggested. However, little is known about the role of TGF-beta 1 in colorectal cancer. Plasma TGF-beta 1 levels and its expression were analyzed in patients with colorectal cancer. METHODS: Plasma TGF-beta 1 levels were measured in 22 patients with colorectal cancer using a TGF-beta 1 enzyme-linked immunosorbent assay. Expression of TGF-beta 1 messenger RNA and immunohistochemical distribution of the protein in colorectal cancer tissues were examined. RESULTS: Plasma TGF-beta 1 levels in patients with colorectal cancer (14.8 +/- 8.4 ng/mL) were significantly higher than in normal controls (1.9 +/- 1.4; n = 22) (P < 0.001). After curative surgical resection, plasma TGF-beta 1 levels decreased in examined patients from 11.9 +/- 6.7 to 3.8 +/- 1.2 ng/mL (P < 0.01). TGF-beta 1 messenger RNA was about 2 1/2 times more abundant in colorectal cancer tissues than in control (P < 0.01). TGF-beta 1 was detected in the cytoplasm of colorectal cancer cells immunohistochemically. Both TGF-beta 1 messenger RNA expression in colorectal adenocarcinoma tissues and its plasma levels were associated with tumor stage of Dukes' classification (P < 0.05). CONCLUSIONS: These results suggest that plasma TGF-beta 1 levels may reflect overexpression of the gene in colon cancer tissues and are associated with disease progression.     

Hall effect of a dirty type II superconductor nearH c2

The theory of the Hall effect of dirty, type II superconductors nearH _c2 by Ebisawa based on the free-electron model is extended to the case of isotropic but arbitrary energy—momentum relation. It is also shown that the detailed form of the impurity potential, i.e., the momentum dependence of its Fourier transform, which is neglected in Ebisawa's work, also contributes to the effect and its contribution is calculated. The result shows that, besides the energy dependence of the density of states and electron velocity near the Fermi energy of the host metal, the detailed nature of the impurity also has a large influence on the Hall effect. The theory is compared with experiment.On leave of absence from Research Institute of Electrical Communication, Tohoku University, Sendai, Japan.     

Fluorogenic derivatization reagents suitable for isolation and identification of cysteine-containing proteins utilizing high-performance liquid chromatography-tandem mass spectrometry

The fluorogenic derivatization reagents with a positive charge, 4-(dimethylaminoethylaminosulfonyl)-7-chloro-2,1,3-benzoxadiazole (DAABD-Cl) and 7-chloro-2,1,3-benzoxadiazole-4-sulfonylaminoethyltrimethylammonium chloride (TAABD-Cl), are proposed for use in proteomics studies. Following derivatization of protein mixtures with these reagents, a series of standard processes of isolation, digestion, and identification of the proteins were performed utilizing high-performance liquid chromatography-fluorescence detection and tandem mass spectrometry with the probability-based protein identification algorithm. Both DAABD and TAABD derivatives were detected fluorometrically at the femtomole level and showed more than 100-fold improvement in sensitivity compared to the underivatized original compounds with an electrospray ionization ion trap mass spectrometer analysis. The modification of the MASCOT database search system memorized with the fragment information of a DAABD-attached Cys residue allowed the identification of the proteolytic peptide fragments of the derivatized bovine serum albumin (BSA) with an estimated 38% sequence coverage of BSA. Utilizing DAABD-Cl as a derivatization reagent, identification of several proteins was also possible in a soluble extract of Caenorhabditis elegans (10 microg of protein). Consequently, for identification of proteins in the complex matrixes of proteins, DAABD-Cl could be a more appropriate reagent than ammonium 7-fluoro-2,1,3-benzoxadiazole-4-sulfonate as reported previously.     

Rheological interpretation of heat generation associated with fatigue of polycarbonate

Temperature change was measured of polycarbonate under monotonically increasing tensile and pulsating tensile loads. In the former case, the specimen temperature began to rise when an appreciable amount of viscoelastic strain was noticed on the stress—strain diagram. The rise, θ_v, could be formulated as a function of the viscoelastic strain, εv: In fatigue tests, the average temperature began to rise immediately after the decrease due to the thermoelastic effect. The amount of the heat generation, σ, was nearly constant for each cycle throughout the fatigue process and has a relation to the fatigue life, N_f, (α? a)·N_f = constant, where a is another adjustable constant. From a rheological aspect of dissipation energy, the equation is transformed to a relation between the viscoelastic strain and the fatigue life as εV^1/2 · N_f = constant, which is similar to the one for metals given by Manson and Coffin.⁶ The temperature rise in the fatigue was also related to the viscoelastic strain. The relation is of the same form as for static tension but less by a factor of one order.     

Comparison of the recyclability of flame-retarded plastics

Mechanical recycling of plastics from waste from electrical and electronical equipment (WEEE) is increasingly expected by regulators and demanded by original equipment manufacturers (CEMs); however, mechanical recycling is generally recognized to be the most economically costly and technically challenging method of recovering WEEE plastics. With 12% of WEEE plastics requiring the use of flame-retardants in order to ensure appropriate levels of consumer fire safety, there is a distinct need for data from comparative tests on recyclability of various flame-retarded plastics. Ten commercially available flame-retarded plastic grades commonly used in electronic equipment (eight "halogen-free" grades and two grades containing brominated flame-retardants (BFRs)) were subjected to two different recycling scenarios. A standard recycling scenario was carried out by repeatedly extruding the materials and an accelerated hydrolysis scenario was carried out to study the influence of humidity from air during use on the process. Both, virgin and recycled materials were tested for a potential formation of polybrominated dibenzodioxins/furans (PBDD/Fs), their mechanical properties were assessed and the fire safety rating was determined. Results indicate that none of the tested materials showed a potential to form the PBDD/Fs regulated by the German Chemicals Banning Ordinance. The halogen-free plastic grades showed a significant deterioration of mechanical properties after recycling, whereas those plastics containing BFRs were able to pass all test criteria, thus maintaining their original properties. With respect to the fire safety rating, none of the eight tested halogen-free plastic grades could maintain their fire safety rating after five recycling loops, whereas both BFR plastics continued to achieve their fire safety ratings. Therefore the tested BFR containing plastic materials showed superior recycling properties compared to the tested halogen-free plastic grades with respect to all investigated parameters.     

A fluorogenic reagent, 4-mercapto-7-methylthio-2,1,3-benzoxadiazole for carboxylic acids, designed by prediction of the fluorescence intensity

During the course of our studies of the development of fluorogenic reagents having a 4,7-disubstituted benzofurazan structure, we previously proposed 7-acetylamino-4-mercapto-2,1,3-benzoxadiazole (AABD-SH) as a fluorogenic reagent for carboxylic acids. Since then, progress has made it possible to estimate the fluorescence quantum yields of the 4,7-disubstituted benzofurazan compounds on the basis of the PM3 calculation of their S1-T2 energies. Subsequently, a new fluorogenic reagent, 4-mercapto-7-methylthio-2,1,3-benzoxadiazole (MTBDSH) was designed and synthesized. In the presence of condensation reagents, triphenylphosphine (TPP) and 2,2'-dipyridyl disulfide (DPDS), MTBD-SH readily reacted with n-caprylic acid within 1 min at room temperature. The derivatives of five carboxylic acids (n-caprylic acid, n-capric acid, lauric acid, myristic acid, and palmitic acid) were well-separated on a reversed-phase column and were fluorimetrically detected at 519 nm with excitation at 391 nm. The detection limits (S/N = 3) were 2.4-5.0 fmol. Thus, MTBD-SH had properties that were considered to be superior. For carboxylic acids, itwas superior not only to AABD-SH, but also to many other conventional reagents. The superiority was examined in terms of its reactivity and sensitivity and the avoidance of interfering peaks that were derived from the reagent itself or degradation products in the chromatogram.