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1.
Group theoretic methods are presented for the transformations of integrals and the evaluation of matrix elements encountered in multiconfigurational self-consistent field (MCSCF) and configuration interaction (CI) calculations. The method has the advantages of needing only to deal with a symmetry unique set of atomic orbitals (AO) integrals and transformation from unique atomic integrals to unique molecular integrals rather than with all of them. Hamiltonian matrix element is expressed by a linear combination of product terms of many-center unique integrals and geometric factors. The group symmetry localized orbitals as atomic and molecular orbitals are a key feature of this algorithm. The method provides an alternative to traditional method that requires a table of coupling coefficients for products of the irreducible representations of the molecular point group. Geometric factors effectively eliminate these coupling coefficients. The saving of time and space in integral computations and transformations is analyzed. © 1994 by John Wiley & Sons, Inc. 相似文献
2.
Peng Chen Xiaojun Luo Guanqi Dai Yuchuan Jiang Yue Luo Shuang Peng Hao Wang Penghui Xie Chen Qu Wenyu Lin Jian Hong Xue Ning Aimin Li 《Experimental & molecular medicine》2020,52(7):1062
Dexmedetomidine (DEX) is an anesthetic that is widely used in the clinic, and it has been reported to exhibit paradoxical effects in the progression of multiple solid tumors. In this study, we sought to explore the mechanism by which DEX regulates hepatocellular carcinoma (HCC) progression underlying liver fibrosis. We determined the effects of DEX on tumor progression in an orthotopic HCC mouse model of fibrotic liver. A coculture system and a subcutaneous xenograft model involving coimplantation of mouse hepatoma cells (H22) and primary activated hepatic stellate cells (aHSCs) were used to study the effects of DEX on HCC progression. We found that in the preclinical mouse model of liver fibrosis, DEX treatment significantly shortened median survival time and promoted tumor growth, intrahepatic metastasis and pulmonary metastasis. The DEX receptor (ADRA2A) was mainly expressed in aHSCs but was barely detected in HCC cells. DEX dramatically reinforced HCC malignant behaviors in the presence of aHSCs in both the coculture system and the coimplantation mouse model, but DEX alone exerted no significant effects on the malignancy of HCC. Mechanistically, DEX induced IL-6 secretion from aHSCs and promoted HCC progression via STAT3 activation. Our findings provide evidence that the clinical application of DEX may cause undesirable side effects in HCC patients with liver fibrosis.Subject terms: Cancer microenvironment, Cell growth 相似文献
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Inchul Shin Ian Davis Karinel Nieves-Merced Yifan Wang Stanton McHardy Aimin Liu 《Chemical science》2021,12(11):3984
SfmD is a heme-dependent enzyme in the biosynthetic pathway of saframycin A. Here, we present a 1.78 Å resolution de novo crystal structure of SfmD, which unveils a novel heme cofactor attached to the protein with an unusual HxnHxxxC motif (n ∼ 38). This heme cofactor is unique in two respects. It contains a single thioether bond in a cysteine–vinyl link with Cys317, and the ferric heme has two axial protein ligands, i.e., His274 and His313. We demonstrated that SfmD heme is catalytically active and can utilize dioxygen and ascorbate for a single-oxygen insertion into 3-methyl-l-tyrosine. Catalytic assays using ascorbate derivatives revealed the functional groups of ascorbate essential to its function as a cosubstrate. Abolishing the thioether linkage through mutation of Cys317 resulted in catalytically inactive SfmD variants. EPR and optical data revealed that the heme center undergoes a substantial conformational change with one axial histidine ligand dissociating from the iron ion in response to substrate 3-methyl-l-tyrosine binding or chemical reduction by a reducing agent, such as the cosubstrate ascorbate. The labile axial ligand was identified as His274 through redox-linked structural determinations. Together, identifying an unusual heme cofactor with a previously unknown heme-binding motif for a monooxygenase activity and the structural similarity of SfmD to the members of the heme-based tryptophan dioxygenase superfamily will broaden understanding of heme chemistry.The de novo crystal structure of SfmD reveals a novel c-type heme cofactor for promoting a monooxygenation reaction in the biosynthetic pathway of saframycin A. 相似文献
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A strain ofRhodococcus equi SHB-121 forming 3-cyanopyridine hydratase was screened from nitrile-polluted soil. The optimum conditions for the formation
of 3-cyanopyridine hydratase by the strain SHB-121 have been studied. Under the optimum conditions, the specific activity
of the enzyme reached 5.32 U/mg of dry cell, 95 times higher than that cultured in screening medium. In addition, the activity
of coexistent amidase was very low.
3-Cyanopyridine hydratase was purified from methylacrylamide-induced cells ofRh. equi SHB-121 by procedures including ultrasonic oscillation, ammonium sulfate precipitation, and column chromatographies on DEAE-cellulose
DE52, hydroxyapatite, and Sephadex G-25. The overall purification was 31-fold. The molecular weight of the enzyme was about
30 kDA by SDS-PAGE. The pI value was 4.1. The transition temperature and pH were 7.0°C and 6.0, respectively, resulting from
the differential spectra.
The optimum pH and temperature for the enzyme reaction were 8.0 and 30°C. The enzyme activity was strongly inhibited by Ag+, Hg2+, Cu2+, and NH4
+, whereas it was enhanced by Fe3+ slightly. The enzyme catalyzed the hydration of 3-cyanopyridine to nicotinamide, and itsKm value was 0.1 mol/L. Uncompetitive inhibitor sodium cyanide has a K, value of 5 mmol/L. 相似文献
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Guodong Feng Yanfu Huan Yanbo Cao Shuhua Wang Xinghua Wang Jie Jiang Aimin Yu Qinhan Jin Hongmei Yu 《Microchemical Journal》2004,76(1-2):17
An unique miniature simultaneous microwave plasma torch (MPT) atomic emission spectrometer employing linear UV intensified charge-coupled device (ICCD) array detector has been developed and studied preliminarily. The detection limits and precisions of the spectrometer for Ag, Al, Ba, Ca, Cr, Cu, Fe, Mg, Mn, Sr and V by using different CCD exposure times have been determined. An analysis of a practical sample has been carried out. The preliminary results demonstrate that such simultaneous spectrometer has advantages of saving sample and time, especially suitable for use as detector for chromatography and in combination with flow injection systems. Taking analytical figures of merit and portability into accounts, the miniature simultaneous MPT system will have extended application areas and greater competition potential as compared with commercialized scanning MPT spectrometers. 相似文献
9.
Wang X Zhang J Song A Lebrilla CB Lam KS 《Journal of the American Chemical Society》2004,126(18):5740-5749
In the "one-bead one-compound" (OBOC) combinatorial library method, each compound bead displays only one compound entity. Hundreds of thousands to millions of compound beads can be synthesized rapidly and screened simultaneously. Positive compound beads are then isolated for structural analysis. To fully exploit the power of OBOC combinatorial small molecule libraries, a robust and high throughput encoding method is needed to decode the positive compound beads. In this paper, we report on the development of a novel encoding strategy that combines the concepts of ladder-synthesis and chemical encoding on bilayer beads. In these encoded libraries, small molecule compounds are displayed on the bead surface, and cleavable coding tags consisting of a series of truncated molecules reside in the bead interior. Such a library can be easily constructed using the biphasic approach (J. Am. Chem. Soc.2002, 124, 7678) to topologically segregate the functionalities of the beads during library synthesis. The ladder members and coding tags are then released for MALDI-TOF-MS analysis. To simplify the interpretation of the mass spectra, we purposely add bromine into the cleavable linker so that the cleavage products generate a characteristic isotope fingerprint. The chemical structure of library compounds can be determined by analyzing the mass differences between adjacent peaks on the mass spectra. This encoding strategy also provides valuable information on the quality of the testing compound on the surface of the bead. To validate this methodology, a model OBOC small molecule library with 12,288 members was synthesized on TentaGel beads and screened against streptavidin. The chemical structures of the compound on each positive bead were unambiguously identified. 相似文献
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