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41.
Manojkumar TK Suh SB Oh KS Cho SJ Cui C Zhang X Kim KS 《The Journal of organic chemistry》2005,70(7):2651-2659
[reaction: see text] We present an ab initio study of the acid-promoted hydrolysis reaction mechanism of N-formylaziridine in comparison with formamide. Since the rate of amide hydrolysis reactions depends on the formation of the tetrahedral intermediate, we focused our attention mainly on the reactant complex, the tetrahedral intermediate, and the transition state connecting these two stationary points. Geometries were optimized using the density functional theory, and the energetics were refined using ab initio theory including electron correlation. Solvent effects were investigated by using polarizable continuum method calculations. The proton-transfer reaction between the O-protonated and N-protonated amides was investigated. In acidic media, despite that the N-protonated species is more stable than the O-protonated one, it is predicted that both N-protonated and O-protonated pathways compete in the hydrolysis reaction of N-formylaziridine. 相似文献
42.
Hohyun Kim Moon Sun Jang Jung-Ae Lee Dongjin Pyo Hye-Ran Yoon Hee Joo Lee Kyung Ryul Lee 《Chromatographia》2004,60(5-6):335-339
A sensitive and selective method for the determination of sofalcone in human plasma was established by use of protein precipitation and liquid chromatography-tandem mass spectrometry. Plasma samples were transferred into 96-well plate using an automated sample handling system and spiked with 10 L of 2 g mL–1 internal standard solution (d3-sofalcone). 0.5 mL of acetonitrile was added to the 96-well plate and the plasma samples were then vortexed for 30 sec. After centrifugation, the supernatant was transferred into another 96-well plate and completely evaporated at 40 °C under a stream of nitrogen. The dry residue was reconstituted with mobile phase. All sample transfer and protein precipitation was automated through the application of both the PerkinElmer MultiPROBE II HT and TOMTEC Quadra 96 workstation. The limit of quantitation of sofalcone was 2 ng mL–1 using a sample volume of 0.2 mL for the analysis. The reproducibility of the method was evaluated by analyzing five samples at nine quality control (QC) levels over the nominal concentration range from 2 ng mL–1 to 1000 ng mL–1. Validation of the method showed that the assay has good precision and accuracy. Sofalcone and internal standard produced a protonated precursor ion ([M+H]+) at m/z 451 and 454, and both gave a corresponding product ion at m/z 315. The high sample throughput of the method has been successfully applied to a pharmacokinetic study of sofalcone in human plasma. 相似文献
43.
In the hydrolysis reaction of dichlorosilanes having an intramolecular coordinating atom, dcisiloxane-1,3-diols, [(OH){o-(CH3)2NCH2-C6H4}RSi]2O(R=CH2CH (1), C6H5 (2), o-(CH3)2NCH2C6H4 (3), Me (4)), were obtained in high yields. The results of the crystal structure analyses of meso-2, rac-2a, rac-2b and 3 are reported. They showed strong intramolecular hydrogen bondings between the hydroxy group and the nitrogen atom. We have also found that the diastereomeric isomerization of meso-2 to rac-2 in CDCl3 solvent containing moisture occurred to result in the 55:45 equilibrium mixtures of the isomers and vice versa. 相似文献
44.
Jung HW La SJ Kim JY Heo SK Kim JY Wang S Kim KK Lee KM Cho HR Lee HW Kwon B Kim BS Kwon BS 《Experimental & molecular medicine》2003,35(6):501-508
Herpes virus entry mediator (HVEM) is a newly discovered member of the tumor necrosis factor receptor (TNFR) superfamily that has a role in herpes simplex virus entry, in T cell activation and in tumor immunity. We generated mAb against HVEM and detected soluble HVEM (SHVEM) in the sera of patients with various autoimmune diseases. HVEM was constitutively expressed on CD4(+) and CD8(+) T cells, CD19(+) B cells, CD14(+) monocytes, neutrophils and dendritic cells. In three-way MLR, mAb 122 and 139 were agonists and mAb 108 had blocking activity. An ELISA was developed to detect sHVEM in patient sera. sHVEM levels were elevated in sera of patients with allergic asthma, atopic dermatitis and rheumatoid arthritis. The mAbs discussed here may be useful for studies of the role of HVEM in immune responses. Detection of soluble HVEM might have diagnostic and prognostic value in certain immunological disorders. 相似文献
45.
Earlier study showed that glucocorticoid induced tumor necrosis factor receptor (GITR), a new TNFR family, activated murine macrophages to express inducible nitric oxide synthase (iNOS) and to generate nitric oxide (NO). A possible involvement of pro-inflammatory cytokines on NO production by GITR was investigated in vitro systems and signaling molecules contributing to sGITR-induced iNOS production are determined in Raw 264.7 cells, a murine macrophage cell line. The result showed that the synergy was afforded by the combination of GITR with IFN-g in a dose-dependent manner but IFN-gamma alone was not able to induce NOS. No effects were observed with TNF-alpha, IL-1beta, or IL-6 co-treated with GITR. To determine signaling molecules contributing to sGITR-induced iNOS production, a specific inhibitor for signal pathway proteins tested showed that PDTC (NF-kappaB) and genistein (tyrosine kinase) inhibited NOS induction significantly, while sodium orthovanadate (tyrosine phosphatase) potentiated NOS expression. These results suggest that activations of NF-kappaB were involved in induction of iNOS by GITR and IFN-gamma priming caused earlier and stronger NF-kappaB activation. 相似文献
46.
Determination of Glimepiride in Human Plasma by LC-MS-MS and Comparison of Sample Preparation Methods for Glimepiride 总被引:1,自引:0,他引:1
Hohyun Kim Kyu Young Chang Chang Hun Park Moon Sun Jang Jung-Ae Lee Hee Joo Lee Kyung Ryul Lee 《Chromatographia》2004,60(1-2):93-98
A sensitive and selective method for quantitation of glimepiride in human plasma was established using liquid chromatography-electrospray ionization tandem mass spectrometry. Three different methods for the sample preparation of glimepiride and an internal standard were investigated (liquid-liquid extraction, solid-phase extraction and protein precipitation). Glipizide was used as an internal standard. Compounds were separated on a C18 column with 80% acetonitrile and 20% deionized water (adjusted to pH 3.5 with acetic acid), as mobile phase at a flow rate of 200 L min–1. By use of multiple reaction monitoring mode in MS-MS with liquid-liquid extraction and solid-phase extraction, glimepiride and glipizide were detected without severe interference from the human plasma matrix. Glimepiride produced a protonated precursor ion ([M+H]+) at m/z 491 and a corresponding product ion at m/z 352, and the internal standard produced a protonated precursor ion ([M+H]+) at m/z 446 and a corresponding product ion at m/z 321. The limit of quantitation was 0.1 ng mL–1, 0.5 ng mL–1 and 1.0 ng mL–1 when using liquid-liquid extraction, solid-phase extraction and protein precipitation, respectively. The validation, reproducibility, stability, and recovery of the different sample preparation methods were comparable and all the methods gave reliable results. The method has been successfully applied to pharmacokinetic study of glimepiride in human plasma. 相似文献
47.
Heekyoung Choi Sojeong Heo Seonae Lee Ka Young Kim Jong Hyeon Lim Sung Ho Jung Shim Sung Lee Hiroyuki Miyake Jin Yong Lee Jong Hwa Jung 《Chemical science》2020,11(3):721
We report kinetically controlled chiral supramolecular polymerization based on ligand–metal complex with a 3 : 2 (L : Ag+) stoichiometry accompanying a helical inversion in water. A new family of bipyridine-based ligands (d-L1, l-L1, d-L2, and d-L3) possessing hydrazine and d- or l-alanine moieties at the alkyl chain groups has been designed and synthesized. Interestingly, upon addition of AgNO3 (0.5–1.3 equiv.) to the d-L1 solution, it generated the aggregate I composed of the d-L1AgNO3 complex (d-L1 : Ag+ = 1 : 1) as the kinetic product with a spherical structure. Then, aggregate I (nanoparticle) was transformed into the aggregate II (supramolecular polymer) based on the (d-L1)3Ag2(NO3)2 complex as the thermodynamic product with a fiber structure, which led to the helical inversion from the left-handed (M-type) to the right-handed (P-type) helicity accompanying CD amplification. In contrast, the spherical aggregate I (nanoparticle) composed of the d-L1AgNO3 complex with the left-handed (M-type) helicity formed in the presence of 2.0 equiv. of AgNO3 and was not additionally changed, which indicated that it was the thermodynamic product. The chiral supramolecular polymer based on (d-L1)3Ag2(NO3)2 was produced via a nucleation–elongation mechanism with a cooperative pathway. In thermodynamic study, the standard ΔG° and ΔHe values for the aggregates I and II were calculated using the van''t Hoff plot. The enhanced ΔG° value of the aggregate II compared to that of the formation of aggregate I confirms that aggregate II was thermodynamically more stable. In the kinetic study, the influence of concentration of AgNO3 confirmed the initial formation of the aggregate I (nanoparticle), which then evolved to the aggregate II (supramolecular polymer). Thus, the concentration of the (d-L1)3Ag2(NO3)2 complex in the initial state plays a critical role in generating aggregate II (supramolecular polymer). In particular, NO3− acts as a critical linker and accelerator in the transformation from the aggregate I to the aggregate II. This is the first example of a system for a kinetically controlled chiral supramolecular polymer that is formed via multiple steps with coordination structural change.The nanoparticles were transformed into the supramolecular polymer as the thermodynamic product, involving a helical inversion from left-handed to right-handed helicity. 相似文献
48.
Eupatilin (5,7-dihydroxy-3',4',6-trimethoxy flavone) is an active ingredient of an ethanol extract of Artemisia asiatica (DA-9601) that is used in the treatment of gastritis. In vitro and in vivo metabolism of eupatilin in the rats has been studied by LC-electrospray mass spectrometry. Rat liver microsomal incubation of eupatilin in the presence of NADPH and UDPGA resulted in the formation of four metabolites (M1-M4). M1, M2, M3 and M4 were tentatively identified as 3'- or 4'-O-demethyl-eupatilin glucuronide, eupatilin glucuronide, 6-O-demethyleupatilin and 3'- or 4'-O-demethyl-eupatilin, respectively. Those metabolites from in vitro study were also characterized in bile, plasma or urine samples after an intravenous administration of eupatilin to rats. In rat bile, plasma and urine samples, eupatilin glucuronide (M2) was a major metabolite, whereas M3, M4 and M4 glucuronide (M1) were the minor metabolites. 相似文献
49.
Determination of rimantadine in pharmaceutical preparations by capillary zone electrophoresis with indirect detection or after derivatization 总被引:2,自引:0,他引:2
Summary Rimantadine is synthetic analog of amantadine; both are antiviral agents used for prophylaxis and treatment of influenza A.
A capillary zone electrophoretic (CZE) procedure for the determination of rimantadine has been developed. As the direct determination
of rimantadine is poorly sensitive because the compound is almost transparent in the UV/Vis range, several indirect methods
were studied. Two were found to be the particularly useful: (a) indirect detection using 5 mM 4-methylbenzylamine in 1:4 methanol-water
as absorbing background electrolyte, with detection at 210 nm, and (b) derivatization of rimantadine with 1,2-naphthoquinone-4-sulfonic
acid in alkaline medium and subsequent determination of the derivative by CZE (40 mM tetraborate, pH 9.2, detection at 280
nm). Uncoated capillary tubing, 44 cm length ×75 μM i.d., was used for both determinations. The detection limits were 0.1
and 2 ppm for methods a and b, respectively. The methods were used to determine rimantadine in pharmaceutical products and
for dissolution testing of Flumadin? tablets. 相似文献
50.