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1.
Herold S Kalinga S Matsui T Watanabe Y 《Journal of the American Chemical Society》2004,126(22):6945-6955
Hemoproteins are known to react with the strong nitrating and oxidizing agent peroxynitrite according to different mechanisms. In this article, we show that the iron(iii) forms of the sperm whale myoglobin (sw Mb) mutants H64A, H64D, H64L, F43W/H64L, and H64Y/H93G catalyze the isomerization of peroxynitrite to nitrate. The two most efficient catalysts are H64A (k(cat) = (5.8 +/- 0.1) x 10(6) M(-1) s(-1), at pH 7.5 and 20 degrees C) and H64D metMb (k(cat) = (4.8 +/- 0.1) x 10(6) M(-1) s(-1), at pH 7.5 and 20 degrees C). The pH dependence of the values of k(cat) shows that HOONO is the species which reacts with the heme. In the presence of physiologically relevant concentrations of CO(2) (1.2 mM), the decay of peroxynitrite is accelerated by these metMb mutants via the concurring reaction of HOONO with their iron(iii) centers. Studies in the presence of free added tyrosine show that the metMb mutants prevent peroxynitrite-mediated nitration. The efficiency of the different sw metMb mutants correlates with the value of k(cat). Finally, we show that sw WT-metMb is nitrated to a larger extent than horse heart metMb, a result that suggests that the additional Tyr151 is a site of preferential nitration. Again, the extent of nitration of the tyrosine residues of the metMb mutants correlates with the values of k(cat). 相似文献
2.
The microwave acid digestion method was applied to the decomposition of rock samples and optimum conditions were investigated. Samples of 10–100 mg were decomposed by changing the amount and composition of acid, heating time and number of reheating steps and then the concentrations of Si, Fe, Mn, Na, K and Mg in these samples were measured. The concentrations agreed with reported values when 10 mg of sample were decomposed by heating for 60 s with 0.3 ml of concentrated HNO3 and 0.1 ml of concentrated HF. Similarly, 100 mg of sample were also decomposed successfully by heating for 45–110 s with 0.3–1.0 ml of concentrated HNO3 and 0.4–0.7 ml of concentrated HF. It is concluded that the microwave acid digestion method decomposes rock samples with a very short heating time and with small amount of reagents compared with methods using conventional sealed PTFE vessels, which require several hours for the heating step and several millilitres of reagents. 相似文献
3.
Mitsuru Ueda Toshitaka Koyama Motokazu Mano Masahiko Yazawa 《Journal of polymer science. Part A, Polymer chemistry》1989,27(3):751-762
Ethyl α-hydroxymethylacrylate (EHMA) was synthesized and homopolymerized in bulk and in solution. The poly(EHMA) is readily soluble in alcohol, acetone, tetrahydrofuran, and methylene chloride at room temperature. Intramolecular lactone formation occurred when poly(EHMA) was heated to 180–230°C. The kinetics of EHMA homopolymerization was investigated in ethyl acetate, using α,α′-azobisisobutylonitrile as an initiator. The rate of polymerization Rp was expressed by Rp = k[AIBN]0.50[EHMA]1.4 and the overall activation energy was calculated as 71.9 kJ/mol. Kinetic constants for EHMA polymerization were obtained as follows: kp/k = 0.17L0.9mol?0.9s?0.5; 2fkd = 1.5 × 10?5 s?1. The relative reactivity ratios of EHMA(M2) copolymerization with styrene (r1 = 0.472, r2 = 0.564) in ethyl acetate were obtained. Applying the Q-e scheme led to Q = 0.84 and e = 0.35 for EHMA. 相似文献
4.
An air-segmented continuous-flow method has been developed for the determination of molybdenum at ultra trace levels using
the catalytic effect of molybdate during the oxidation of L-ascorbic acid by hydrogen peroxide. Incorporation of an on-line
ion exchange column improved the tolerance limit for various ions. The detection limits with and without the column were 64 pmol L−1 and 17 pmol L−1, and the reproducibilities at 10 nmol L−1 were 2.1% and 0.2%, respectively. The proposed method was applied to the determination of molybdenum in seawater and lake
water as well as in rock and sediment samples. This method has the highest sensitivity among the available literature to our
knowledge, and is also convenient for routine analysis of molybdenum in various natural samples.
Author for correspondence. E-mail: masahito.sugiyama@ sojin0206.mbox.media.kyoto-u.ac.jp
Received October 23, 2002; accepted January 28, 2003
Published online May 19, 2003 相似文献
5.
Hideaki Iizuka Shoko Watanabe Mayuko Koshikawa Yurie Matsumoto Yuki Aoyama Hideaki Ichiba Toshitaka Nabeshima Takeshi Fukushima 《Analytical and bioanalytical chemistry》2013,405(25):8137-8141
It has been reported that repeated phencyclidine (PCP) treatment induces schizophrenia-like behavior in mice. l-Tryptophan (Trp) concentrations in brain tissues of control (n?=?8) and PCP-treated mice (10 mg/kg/day, s.c., 14 days, n?=?10) were determined using high-performance liquid chromatography (HPLC) with fluorescence detection. The HPLC method involved pre-column fluorescence derivatization with (R)-(?)-4-(N,N-dimethylaminosulfonyl)-7-(3-isothiocyanatopyrrolidin-1-yl)-2,1,3-benzoxadiazole (DBD-PyNCS). Eight different parts of the brain, namely, the frontal cortex, nucleus accumbens, striatum, hippocampus, amygdala, thalamus, hypothalamus, and cerebellum, of both groups were investigated. A significant decrease in the l-Trp concentration in the nucleus accumbens (p?=?0.024) and hippocampus (p?=?0.027) was observed in PCP-treated mice, suggesting that alteration of the l-Trp metabolism might occur in these brain parts. 相似文献
6.
This review describes impulse response techniques with a curve-fitting method to measure thermodynamic properties, such as binary diffusion coefficient, retention factor, and partial molar volume, under supercritical conditions. Theoretical background, parameter sensitivity, sources of experimental error, noise elimination technique, and the correction of apparent binary diffusion coefficients due to column coiling are discussed based on recent studies, together with data sources and predictive correlations for binary diffusion coefficients. 相似文献
7.
The theoretical basis of a Gaussian-like approximate solution was applied to a chromatographic impulse response technique with curve fitting for measuring binary diffusion coefficients and retention factors using a polymer-coated capillary column. The formulae were derived for evaluating both the accuracy of the approximate solution and the sensitivity of the parameters. The validity of the solution also was confirmed experimentally for pulse injection of phenol in acetone into supercritical carbon dioxide flowing at 313.15 K and 11.6-28.6 MPa. Potential sources for experimental errors of the method are discussed. 相似文献
8.
Toshitaka Gamo 《Trends in analytical chemistry : TRAC》2011,30(8):1308-1319
The Sea of Japan, a semi-closed marginal sea (greatest depth ∼3700 m) in the northwestern-most Pacific Ocean, has an independent, deep convection system, which is driven by the formation and the sinking of cool, saline surface water towards the bottom in severe winters. Continuous measurement of dissolved oxygen using highly precise versions of the Winkler titration method has revealed 8-10% decreases in the bottom concentration of oxygen (O2) over the past 30 years. The temporal decrease in O2 means an imbalance between the supply of O2 from the surface and the in situ consumption of O2 in decomposing organic matter, suggesting that the change in the deep convection pattern of the Sea of Japan is probably caused by global climate change to reduce winter cooling of surface seawater. 相似文献
9.
10.
Cotton cellulose subjected to a dilute aqueous formic acid solution, at acid concentrations up to 1% (w/w), under hydrothermal conditions in a semi-batch reactor was converted into glucose and oligomers with lower degrees of polymerizations (DP). After heating at 250 °C for 60 min in 0.1% (w/w) aqueous formic acid solution, yields of glucose and total sugar with DP = 1 to 9 were 36.6 and 83.8% (100 × gC/gC of initial cotton sample), respectively, and 5-hydroxymethylfurfural was almost as low as 1%. The yields of glucose and oligomers were significantly improved by adding the acid. The reaction was represented by first-order reaction kinetics with regard to (1 ?C x) where x is the conversion based on the total sugar or glucose yield. At 250 °C, the differences in the rate constants (k ? k water) were proportional to the square root of formic acid concentration. 相似文献