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11.
Mitamura K Setaka M Shimada K Honma S Namiki M Koh E Mizokami A 《Biomedical chromatography : BMC》2005,19(10):796-801
A promising liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) for analysis of the sulfates of 5alpha-androgen, androsterone and epiandrosterone (A-S and EpiA-S) in human serum was developed. The method was used to assess one of the markers of 5alpha-reductase activity of males including patients with prostate cancer (PC). After deproteinization with acetonitrile, the androgen sulfates and the internal standard, [7,7,16,16-2H4]dehydroepiandrosterone-S, were extracted from human serum using a solid-phase extraction cartridge and washed with hexane. The extract was reconstituted and applied to the LC/ESI-MS system operated in the selected ion monitoring mode. The method was validated over the range 0.02-5 microg/mL (A-S) and 0.005-1.5 microg/mL (EpiA-S) using 10 microL of human serum. The method was a concise procedure without chemical or enzymatic hydrolysis of the conjugates, purification by high-performance liquid chromatography and/or derivatization, and proved to be satisfactory in its reproducibility and accuracy. The levels of these androgen sulfates tended to decrease during aging, and the A-S levels in the sera obtained from both healthy males and patients with PC were correlated with their EpiA-S levels. 相似文献
12.
A practical LC-MS method for determination of (24R)-24,25-dihydroxyvitamin D(3) [24,25(OH)(2)D(3)] in human plasma has been developed using derivatization with a Cookson-type reagent, 4-[4-(6-methoxy-2-benzoxazolyl)phenyl]-1,2,4-triazoline-3,5-dione (MBOTAD). The derivatization with MBOTAD significantly improved the ionization efficiency of the analyte with a detection limit of 18 fmol [equivalent to 7.5 pg of 24,25(OH)(2)D(3)] per injection. The method employed protein precipitation with acetonitrile, purification with OASIS HLB cartridge and silica gel column, derivatization with MBOTAD and atmospheric pressure chemical ionization MS detection. The mass spectrometer was operated in the positive-ion mode of mass chromatography and [26,26,26,27,27,27-(2)H(6)]-24,25(OH)(2)D(3) was used as an internal standard. The intra- and inter-assay coefficients of variation were below 3.4 and 2.5%, respectively, and the analytical recovery of 24,25(OH)(2)D(3) was quantitative. Assay linearity was obtained in the range of 0.05-1.2 ng per tube and the limit of quantitation was 0.23 ng/mL for a 0.3 mL plasma aliquot. The developed method was applied to plasma samples obtained from volunteers and gave satisfactory results. 相似文献
13.
T. Takahagi I. Shimada M. Fukuhara K. Morita A. Ishitani 《Journal of polymer science. Part A, Polymer chemistry》1986,24(11):3101-3107
In the carbon fiber production process from polyacrylonitrile (PAN), PAN precursor is heated first in air to secure stabilization in the succeeding carbonization process at higher temperature. The mechanism of the stabilization reaction and chemical structure of the stabilized PAN have been examined by x-ray photoelectron spectroscopy and elemental analysis. The stabilized PAN was determined to have a ladderlike structure consisting of 40% acridone ring, 30% naphtyridine ring, 20% hydronaphtyridine ring, and others. This structure well explains the stability of the polymer in the succeeding carbonization process on carbon fiber production with conjugated π-electron systems over the whole polymer chain and intermolecular hydrogen bonds. A comonomer addition to the precursor was found to accelerate the dehydrogenation reaction in the stabilization process. 相似文献
14.
Chetiyanukornkul T Toriba A Kizu R Kimura K Hayakawa K 《Biomedical chromatography : BMC》2004,18(9):655-661
A simple liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS) method for the determination of nicotine and cotinine in human hair was established. In the procedure, a hair sample (10 mg) was washed with dichloromethane and digested in 2.5 M sodium hydroxide. The digest was extracted with dichloromethane and then 25 mM hydrochloric acid in methanol was added to the extract, to prevent loss of analytes. The solution was evaporated and redissolved in the mobile phase, methanol/10 mM ammonium acetate (30/70, v/v). A 20 microL aliquot of redissolved solution was subjected to analysis. Nicotine and cotinine in human hair were quantified by using deuterated analytes as internal standards. The quantification limits were 8 microg/L for nicotine and 0.9 microg/L for cotinine. The proposed method was applied to measure the concentrations of nicotine and cotinine in hair of smokers and non-smokers to evaluate their self-reported smoking and exposure to environmental tobacco smoke. In both cases, the method provided good selectivity, accuracy and precision. 相似文献
15.
I. Shimada T. Takahagi M. Fukuhara K. Morita A. Ishitani 《Journal of polymer science. Part A, Polymer chemistry》1986,24(8):1989-1995
The stabilized fibers prepared by heating PAN and a PAN copolymer in air and under reduced pressure have been examined by FT-IR spectroscopy in order to determine their chemical structures. Three kinds of reactions, cyclization, dehydrogenation, and oxygen uptake are found to occur almost simultaneously in the stabilization process in air by digital difference spectrum method. The effect of the comonomer is confirmed to accelate the dehydrogenation reaction and also the formation of acridone ring in the thermal stabilization in air by kinetic study. 相似文献
16.
A new sensitive method is described for the determination of 17-ketosteroid sulphates, particularly dehydroepiandrosterone sulphate, in human serum by high-performance liquid chromatography with electrochemical detection. The 17-ketosteroid sulphates in serum were extracted with acetonitrile and derivatized with p- nitrophenylhydrazine in trichloroacetic acid--benzene solution. The p- nitrophenylhydrazones were separated by high-performance liquid chromatography on a mu Bondapak C18 column using methanol--0.5% ammonium dihydrogen phosphate (8:3) as a mobile phase. The proposed method proved to be applicable to the quantitation of 17-ketosteroid sulphates with satisfactory sensitivity and reliability, providing a quantitation limit of 80 ng/ml and coefficient of variation of 4%. A good correlation was observed between the values obtained by the present method and radioimmunoassay for dehydroepiandrosterone sulphate in serum. 相似文献
17.
The effect of diazepam (DZP) on melatonin synthesis in rat pineal gland was investigated in vivo. Subcutaneous injection of DZP (3 mg/kg) 1 h before the start of darkness significantly suppressed nocturnal elevations of pineal N-acetylserotonin (NAS) and melatonin contents in rats, and caused a 2-h delay in reaching the maximum melatonin level in the dark phase. DZP treatment also markedly suppressed the dark-induced increase of pineal N-acetyltransferase activity, which catalyzes the rate-limiting step in melatonin synthesis, but had no effect on hydroxyindole-O-methyltransferase activity, which catalyzes the final step of melatonin formation. Pineal norepinephrine and dopamine contents, in contrast, were not altered by DZP injection. The distribution rate of DZP to the brain reached the highest level 30 min after a single injection, while that to the pineal gland was observed 5 h later (i.e., 4 h after the start of darkness). It is clear that the inhibitory effect of DZP on melatonin synthesis in rat pineal gland appears concomitantly with the increase in the distribution volume of DZP into this gland. These results suggest that the inhibitory effect of DZP on melatonin synthesis results from the drug's direct action on the rat pineal gland. 相似文献
18.
Shigeru Shimada Osamu Yamazaki Yohichi Suzuki 《Journal of organometallic chemistry》2004,689(19):3012-3023
Hypervalent organobismuth compounds, 6-tert-butyl-5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismocines, with 13 different substituents on the bismuth atom including halogens, alkyl, alkenyl, alkynyl, aryl, or phenylthio groups have been synthesized. A key compound, 12-chloro-6-tert-butyl-5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismocine, which is a precursor for other azabismocines, has been synthesized by two different procedures; one is based on Akiba’s method using 2-bromobenzylbromide as one of the starting materials and the other is a newly developed one using a cheaper starting material, 2-chlorobenzyl chloride. The structures of 12 new bismuth compounds were determined by X-ray diffraction. The eight-membered tetrahydroazabismocine ring has proved to be highly flexible and the hypervalent Bi-N bond distances vary ranging from 2.568(3) to 2.896(5) Å, depending on the electronic nature of the substituents on the bismuth atom. The Bi-N bond distances have good linear relationship against Hammett’s σm constants. 相似文献
19.
1. Introduction As an effective utilization of methane, the methane dehydro-aromatization was focused in the last decade [1-28]. Over the Mo/HZSM-5 bi- functional catalyst at high reaction temperature, methane can be converted into light aromatics (ben- zene and naphthalene) and hydrogen. Mo active species can activate the C—H bond of methane; and HZSM-5 supplies the acid sites for the oligomeriza- tion and cyclization of hydrocarbons to form aromat- ics, and suppresses the deeper condens… 相似文献
20.