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991.
Aqua dissociation nature of cesium hydroxide 总被引:1,自引:0,他引:1
To understand the mechanism of aqueous base dissociation chemistry, the ionic dissociation of cesium-hydroxide in water clusters is examined using density functional theory and ab initio calculations. In this study, we report hydrated structures, stabilities, thermodynamic quantities, dissociation energies, infrared spectra, and electronic properties of CsOH(H(2)O)(n=0-4). With the addition of water molecules, the Cs-OH bond lengthened significantly from 2.46 A for n=1 to 3.08 A for n=4, which causes redshift in Cs-O stretching frequency. It is found that three water molecules are needed for the dissociation of Cs-OH, in contrast to the case of strong acid dissociation which requires at least four water molecules. However, the dissociation for n=3 could be considered as incomplete because a very weak CS em leader OH stretch mode is still present, while that for n=4 is complete since the Cs em leader OH mode no longer exists. This study can be related with hydration chemistry of cations and anions, and extended into the intra- and intercharge-transfer phenomena. 相似文献
992.
Shaginian A Patel M Li MH Flickinger ST Kim C Cerrina F Belshaw PJ 《Journal of the American Chemical Society》2004,126(51):16704-16705
We describe the development of photolabile protecting groups based on the 3,4,5-trimethoxyphenacyl group (TMP). Orthogonal safety-catches were created by introducing an acid-activatible dimethyl ketal (AA-TMP) and an oxidatively activatible 1,3-dithiane (OA-TMP) into the photolabile TMP group. We demonstrate the application of these protecting groups in light-directed synthesis of small molecule microarrays with diversity elements radially attached to a hydroxyproline scaffold. 相似文献
993.
All four stereoisomers of 2-alkyl-3,4-iminobutanoic acid, a novel class of beta-amino acids bearing a chemically versatile aziridine ring, were synthesized starting with aspartic acid. The synthetic strategy involves the introduction of an alkyl group at the beta-position of fully protected optically active aspartic acid followed by the construction of an aziridine ring making use of the alpha-carboxylate and alpha-amino groups. The alpha-carboxylate was reduced to the corresponding alcohol, which was then subjected to cyclization to form an aziridine ring with the N-protected amino group. Removal of the protection groups yielded the target compounds. 相似文献
994.
Characterization of amiodarone metabolites and impurities using liquid chromatography/atmospheric pressure chemical ionization mass spectrometry 总被引:1,自引:0,他引:1
Myung SW Chang YJ Min HK Kim DH Kim M Kang TK Yoo EA Sohn YT Yim YH 《Rapid communications in mass spectrometry : RCM》2000,14(21):2046-2054
Using the high performance liquid chromatography/atmospheric pressure chemical ionization tandem mass spectrometry (HPLC/APCI-MS/MS) technique, together with established trends from the literature, the structures of metabolites and impurities of amiodarone, an anti-arrhythmic drug, have been assigned. By comparing analyses of products of incubation with rat liver microsomes with controls in which glucose 6-phosphate dehydrogenase was omitted, metabolites could be distinguished from impurities. Structures for the two proposed metabolites and four impurities are proposed. 相似文献
995.
A tandem free radical cyclization-rearrangement sequence was designed and executed to produce tricyclo[4.3.2.0(1,5)]undecane 7 from cyclopentene 6A in a single operation. The total synthesis of suberosenone was accomplished from 7. 相似文献
996.
[reaction: see text]. Unified and highly convergent total syntheses of (+)-macrosphelides A and B are described. Key features of the syntheses include (1) concise synthesis of the optically active delta-hydroxy-gamma-keto alpha,beta-unsaturated acid fragment via the direct addition of a trans-vinylogous ester anion equivalent to the readily available Weinreb amide and (2) facile construction of the 16-membered macrolide core of the macrosphelide series via an intramolecular nitrile-oxide cycloaddition (INOC). 相似文献
997.
The goal of the present study is to test the hypothesis that LPA induces proliferation of astrocytes in hippocampus in vivo via phosphorylation of ERK 1/2. We first characterized the expression of GFAP, a special marker fiber protein of astrocytes,
in brain slices after direct injection of LPA into hippocampus by immunohistochemistry, and found that LPA induced a remarkable
proliferation of astrocytes. Then double-lablled immunofluorescence was used to detect GFAP and phosphorylation ERK 1/2 (p-ERK
1/2), LPA induced an immediate (10 min) and transient (<30 min) phosphorylation of ERK 1/2, and sequence sustained activation
of ERK 1/2 was observed, which last for at least 3 weeks after injection of LPA. Reactions are inhibited by U0126, a specific
pharmacological mitogen-activated protein kinase (MEK) inhibitor. Laser confocal scanning was used to study spatial relationship
of p-ERK and astrocytes. Amazingly, the early (<7 days) phosphorylation of ERK 1/2 is not expressed in astrocytes but in area
where neurons and/or in other cell type(s) occupied, expression of p-ERK 1/2 in astrocytes is not detected until 14 days after
LPA injection and lasts for at least 3 weeks. Taken together, these data suggest that LPA play an important role in proliferation
of astrocytes through phosphorylation of ERK 1/2 in hippocampus. It provides further proof for the functions of LPA in CNS
injury, and may contribute to clinical therapy for relative diseases. 相似文献
998.
A high-performance capillary electrophoretic (CE) method with electrochemical detection (ED) has been developed for determination of the pharmacologically active flavonoids in Ginkgo biloba L. and phytopharmaceuticals containing its extract. Epicatechin, catechin, rutin, apigenin, luteolin, and quercetin are important flavonoids in this plant. Operated in a wall-jet configuration, a 300 micro m diameter carbon-disk electrode was used as working electrode with good response to the six analytes at +1000 mV (relative to the SCE). Under the optimum conditions, the analytes were separated within 22 min in a borax buffer (pH 9.0). Excellent linearity was obtained over two orders of magnitude and detection limits (S/N=3) ranged from 1.4 x 10(-7) to 5.0 x 10(-7) g mL(-1) for all six analytes. The method was successfully used for assay of Ginkgo biloba L. and its phytopharmaceuticals after a relatively simple extraction procedure; the results obtained were satisfactory. 相似文献
999.
The aftermath of the interplay between the endoplasmic reticulum stress response and redox signaling
Kashi Raj Bhattarai Thoufiqul Alam Riaz Hyung-Ryong Kim Han-Jung Chae 《Experimental & molecular medicine》2021,53(2):151
The endoplasmic reticulum (ER) is an essential organelle of eukaryotic cells. Its main functions include protein synthesis, proper protein folding, protein modification, and the transportation of synthesized proteins. Any perturbations in ER function, such as increased demand for protein folding or the accumulation of unfolded or misfolded proteins in the ER lumen, lead to a stress response called the unfolded protein response (UPR). The primary aim of the UPR is to restore cellular homeostasis; however, it triggers apoptotic signaling during prolonged stress. The core mechanisms of the ER stress response, the failure to respond to cellular stress, and the final fate of the cell are not yet clear. Here, we discuss cellular fate during ER stress, cross talk between the ER and mitochondria and its significance, and conditions that can trigger ER stress response failure. We also describe how the redox environment affects the ER stress response, and vice versa, and the aftermath of the ER stress response, integrating a discussion on redox imbalance-induced ER stress response failure progressing to cell death and dynamic pathophysiological changes.Subject terms: Mechanisms of disease, Cell biology 相似文献
1000.
Photoactivation of pheophorbide a induces a mitochondrial-mediated apoptosis in Jurkat leukaemia cells 总被引:5,自引:0,他引:5
Lee WY Lim DS Ko SH Park YJ Ryu KS Ahn MY Kim YR Lee DW Cho CW 《Journal of photochemistry and photobiology. B, Biology》2004,75(3):119-126
The mechanism of cell death by pheophorbide a (Pba) which has been established to be a potential photosensitizer was examined in experimental photodynamic therapy (PDT) on Jurkat cells, a human lymphoid tumor cell line. In 30-60 min after irradiation, Pba treated cells exhibited apoptotic features including membrane blebbing and DNA fragmentation. Pba/PDT caused a rapid release of cytochrome c from mitochondria into the cytosol. Sequentially, activation of caspase-3 and the cleavage of poly ADP-ribose polymerase (PARP) were followed. Meanwhile, no evidence of activation of caspase-8 was indicated in the cells. In experiments with caspase inhibitors, it was found that caspase-3 alone was sufficient initiator for the Pba-induced apoptosis of the cells. Pba specific emission spectra were confirmed in the mitochondrial fraction and the light irradiation caused a rapid change in its membrane potential. Thus, mitochondria were entailed as the crucial targets for Pba as well as a responsible component for the cytochrome c release to initiate apoptotic pathways. Taken together, it was concluded that the mode of Jurkat cell death by Pba/PDT is an apoptosis, which is initiated by mitochondrial cytochrome c release and caspase-3-pathways. 相似文献