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41.
Hanns‐Dieter Amberger Lixin Zhang Hauke Reddmann Christos Apostolidis Olaf Walter 《无机化学与普通化学杂志》2006,632(15):2467-2470
Electronic Structures of Organometallic Compounds of f Elements. 64 Does the Zwitterionic Nature of the Triphenylphosphine Oxide Ligand Manifest itself in its Spectrochemical Properties? The triphenylphosphine oxide mono adducts of the moiety tris(η5‐cyclopentadienyl)lanthanide(III) (Ln(Cp)3; Ln = Pr ( 1 ), La ( 2 )) were synthesized and structurally characterized. The Ln–O distances of these compounds are noticeably shorter than those of the corresponding THF adducts. A crystal field (CF) analysis of the optical spectra of 1 leads to a low absolute value of the quadratic CF parameter which is comparable with those of [Pr(Cp)3(L)]? adducts with anionic bases but not with [Pr(Cp)3(MeTHF)]. Reasons for the latter finding are presented. 相似文献
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《Arabian Journal of Chemistry》2022,15(11):104272
Yinlan lipid regulatory capsule (YL) is a composite traditional Chinese medicine (TCM) new drug to alleviate hyperlipidemia, while its therapeutic mechanism in vivo was not clarified with nontargeted metabolomics investigation. An animal model was established in rats fed a high-fat diet, and their body weights, body mass index (BMI) and blood cholesterol levels were measured. Serum, liver and kidney tissue samples were also extracted for PXR-CYP3A4-ABCB1-FXR signaling pathway research using PCR and UHPLC–MS. The obtained plasma samples were analyzed by UHPLC-Q-TOF-MS metabolomic investigation, which revealed PXR-CYP3A4-related metabolites and changes induced by YL. Finally, the key metabolites were chosen as index components, and their levels in the serum, liver, small intestine and bile were used for simultaneous UHPLC–MS-MS determination. The results indicated that YL was effective in rebalancing blood TG and TC levels (compared to controls). With respect to the PXR-CYP3A4-ABCB1 pathway, as a result of YL’s effect, gene expression or activity of the two targets decreased significantly in both the liver and kidney. The same trend was observed in the serum samples mentioned above. Metabolomics screening and data revealed that 44 metabolites can be regarded as biomarkers related to hyperlipidemia, fatty acids synthesis, and body energy consumption, as well as synthesis, transportation and exertion of cholesterol. YL’s treatment focused on 26 of them, primarily bile acids, indicating that the antihyperlipidemic effect of this drug lies in its inhibitory activity of cholesterol metabolism. Subsequent analysis of those in vivo components revealed that significant increases (compared to the model group) occurred in the blood, liver, small intestine and bile in groups that received medium and high doses of YL (while the low dose was relatively unchanged). Those target components exhibit a close relationship with PXR and/or CYP3A4. The use of YL repressed PXR expression and subsequently decreased CYP3A4 activity. As a result, synthesis of related bile acids increased, while cholesterol levels decreased, consequently leading to the attenuation of hyperlipidemia. This study comprehensively investigated the antihyperlipidemia mechanism of YL based on its repression of PXR-CYP3A4 activity and related metabolite yield, establishing an accurate method for evaluating the therapeutic effect of YL. 相似文献
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《Surface and interface analysis : SIA》2006,38(5):922-930
Enargite, a copper arsenic sulfide with the formula Cu3AsS4 is of environmental concern due to its potential to release toxic arsenic species. The oxidation and dissolution of enargite are governed by the composition and chemical state of the outermost surface layer. Qualitative and quantitative analysis of the enargite surface can be initially obtained on the basis of X‐ray photoelectron spectroscopy (XPS) binding energy and intensity data. However, a more precise determination of the chemical state of the principal elements of enargite (copper, arsenic and sulfur) in the altered surface layer and in the bulk of the mineral requires a combined analysis based on XPS photoelectron lines and the corresponding X‐ray excited Auger lines. On the basis of results obtained on natural and synthetic enargite samples and on standards of sulfides and oxides, the Auger parameter α′ of different compounds was calculated and the Wagner chemical state plots were drawn for arsenic, copper and sulfur. Arsenic in enargite is found to be in a chemical environment similar to that of arsenides or elemental arsenic, whereas copper in enargite is in a chemical state that corresponds to copper sulfide, Cu2S, for all samples irrespective of surface treatment (natural or freshly cleaved). Only sulfur changed from a chemical state similar to that of copper or iron sulfide in freshly cleaved samples to another state in natural enargite in the as‐received state. Thus, it is the sulfur atom at the surface of enargite that is most susceptible to changes in the enargite surface state and composition. A more detailed interpretation of this behavior, based on differences in the initial and final state effects, is proposed here. The concept of Auger parameter and chemical state plot, used here for the first time for investigating enargite, has proved to be a method to unambiguously assign the chemical state of the principal elements copper, arsenic and sulfur in these minerals. Copyright © 2006 John Wiley & Sons, Ltd. 相似文献
46.
Benedetti M Tamasi G Cini R Natile G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(24):6122-6132
The use of a sterically hindered diamine ligand (Me(4)DACH) has allowed for the first time, the isolation and characterization, both in the solid state (X-ray crystallography) and in solution (circular dichroism), of pure DeltaHT rotamers of [Pt(Me(4)dach)(5'-GMP)(2)] (compounds 1 and 2 for R,R and S,S configurations of the Me(4)DACH ligand, respectively). Comparison of the CD spectra obtained for each rotamer, which differ only in the chirality of the Me(4)DACH ligand (R,R or S,S) or in the chirality of the HT conformation (Delta or Lambda), allowed us to conclude that, in the 200-350 nm range, the contributions to the overall CD spectrum that stem from diamine chirality and diamine-induced chirality of platinum d--d transitions or from sugar chirality are negligible relative to the exciton chiral coupling that occurs for pi-pi* transitions of the cis guanines. Accurate molecular structures of 1.10 D(2)O and 2.14 D(2)O (conventional crystallographic agreement indexes R(1) convergent to 2.07 % and 2.18 %, respectively) revealed that the crystallized rotamers have a DeltaHT conformation that is in agreement with all previously reported X-ray structures of [Pt(diamine)(nucleos(t)ide)(2)] complexes. This conformation allows the 5'-phosphate to be located in proximity to the Me(4)DACH ligand so that (P)O...HC(N) hydrogen-bond interactions exists in both complexes. For both structures, the canting of the guanine planes on the coordination plane is right-handed (R; canting angle (Phi) of 80.9 degrees and 73.2 degrees, respectively); this indicates that the canting direction is driven by the HT conformation chirality (Delta for both compounds) and not by the chirality of the carrier ligand (different for the two compounds). Density functional theory analysis of the conformational space as a function of Phi indicated a good agreement between the computed and experimental structures. The increase in energy for Phi values below 65 degrees and 55 degrees (for 1 and 2, respectively) is mainly due to the short intramolecular contacts between C(8)H and the cis N-Me groups on the same side of the platinum coordination plane. 相似文献
47.
Li—Ni—La—O系复合氧化物催化剂上甲烷氧化偶联的研究 总被引:2,自引:0,他引:2
考察了Li-Ni-La-O系催化剂的组成、结构及反应条件对甲烷氧化偶联反应活性的影响。在780℃、CH4:O2:N2=2:1:7、空速15000h^-1时,C2烃收率可达25.8%。XRD、IR、XPS及SEM等的结构分析表明,在LiLa1-xNixO2催化剂中,当0.1≤x≤0.9时,该催化剂由LiNiO2和La2Ni1-yLiyO4-λ两相组成,x<0.3时出现了LiLaO2相,La2Ni1- 相似文献
48.
Four lanthanide coordination polymers with benzophenone‐4,4′‐dicarboxylic acid (H2bpndc) and 1,10‐phenanthroline (phen), [Ln2(bpndc)3(phen)] (Ln=La (1), Pr (2) and Tb (3)), [Yb(bpndc)15(phen)].05H2O (4) were obtained through solvothermal synthesis. The crystallographic data show that 1, 2, and 3 are isostructural, the Ln(III) ions in 1, 2 and 3 are all eight‐ and ten‐coordinated, respectively, and thus the Ln(III) ions are connected by bpndc ligands, resulting in an interpenetrating 3D structure. While in 4, the Yb(III) ions are eight‐coordinated and connected by bpndc ligands into a 3D structure with 1D rhombic channels, which result from the effect of lanthanide contraction from La(III) to Yb(III) ions, and the bpndc ligands in 1, 2, 3, and 4 display three types of coordination modes. 相似文献
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50.
Immo Weber Frank W. Heinemann Panagiotis Bakatselos Ulrich Zenneck 《Helvetica chimica acta》2007,90(4):834-845
A pressure‐controlled procedure for the SN1 reaction of rac‐1‐[(dimethylamino)methyl]‐2‐(tributylstannyl)ferrocene ( 1 ) to rac‐1‐(phthalimidomethyl)‐2‐(tributylstannyl)ferrocene ( 2 ) was developed. Pd0‐Catalyzed Stille coupling of 2 with iodobenzene afforded rac‐1‐phenyl‐2‐(N‐phthalimidomethyl)ferrocene ( 5 ) in 74% yield; after trace enrichment by crystallization of the combined mother liquors, one single crystal of each, 5 , catalysis intermediate trans‐iodo(σ‐phenyl)bis(triphenylarsino)palladium(II) ( 7 ), trans‐diiodobis(triphenylarsino)palladium(II) ( 8 ), and rac‐2,2′‐bis(phthalimidomethyl)‐1,1′‐biferrocene ( 9 ) could be isolated by crystal sorting under a microscope and characterized by X‐ray crystal structure analysis. Furthermore, 5 was deprotected to amine ( 11 ), which does even survive the Birch reduction to rac‐1‐(aminomethyl)‐2‐(cyclohexa‐2,5‐dienyl)ferrocene ( 12 ). 相似文献