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排序方式: 共有107条查询结果,搜索用时 31 毫秒
91.
Juan M. López-Alcalá M. C. Puerta F. González-Vílchez 《Transition Metal Chemistry》1985,10(7):247-248
Summary Two new dinitrogen complexes of CrIII with EDTA and CDTA have been prepared from reaction of [Cr(Y-H)H2O] (Y = EDTA, CDTA) with sodium azide in aqueous solution. Both complexes exhibit characteristic bands at 2070 cm–1 in the i.r. spectra corresponding to (N2). The 10 Dq and B parameters were calculated from the u.v. visible spectra. 相似文献
92.
Schlosser G Pocsfalvi G Malorni A Puerta A de Frutos M Vékey K 《Rapid communications in mass spectrometry : RCM》2003,17(24):2741-2747
Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) was used to detect an immune complex formed between beta-lactoglobulin and polyclonal anti-beta-lactoglobulin antibody in the gas phase. The most important experimental parameters to detect such a specific antibody-antigen complex by MALDI were the use of solutions at near-neutral pH and of sinapinic acid matrix prepared by the dried-droplet method. Under such conditions, predominantly one but also two molecules of antigen protein were complexed by the antibody. Specific formation of the antibody-antigen complex was confirmed by performing competitive reactions. Addition of antibody to a 1:1 mixture of beta-lactoglobulin and one control protein resulted not only in the appearance of the expected antibody-antigen complex, but also in a strong decrease in the free beta-lactoglobulin signal, while the abundance of the control protein was not influenced. 相似文献
93.
The wide use of the ligand 3-hydroxy-2-methyl-4-pyrone (maltol) in bioinorganic chemistry has prompted an effort to further exploit this ligand class by achieving an efficient, one-step synthesis of the chelator 3-hydroxy-2-methyl-4-thiopyrone (thiomaltol). Complexes of thiomaltol with nickel(II) and iron(III) have been prepared and studied by using UV-visible spectroscopy and electrochemical methods. In addition, both complexes as well as the free thiomaltol ligand have been structurally characterized by using single-crystal X-ray diffraction methods. The ligand is found to exert a strong trans influence on the structure of the complexes in the solid state with the nickel(II) and iron(III) complexes demonstrating a cis and fac geometry, respectively. The compounds described here should significantly expand the scope and utility of O,S-donor ligands derived from maltol and related precursors. 相似文献
94.
Heinz F. Falk Bodo Hattendorf K. Krengel-Rothensee Nataly Wieberneit Sarah L. Dannen 《Fresenius' Journal of Analytical Chemistry》1998,362(5):468-472
An approach for the determination of trace element concentrations in high purity metals, using an inductively coupled plasma
mass spectrometer (ICP-MS) with a laser-ablation system for direct solid sample introduction after calibration with nebulized
liquid standards was made. Due to the inherent differences in the rate of sample introduction with laser-ablation and pneumatic
nebulization, a matrix element must be used as an internal standard. This is problematical for elements that have no isotope
with a relative abundance of less than 0.1 %, since the ion signals would be too high for direct measurement, and reduction
of the ablation rate would compromise the sensitivity for trace elements. Due to the high stability of ICP-unit and mass filter
of the instrument used, it was found that the tail of a mass-peak of the matrix element could be used as an internal standard.
Therefore, a position at –0.5 amu from the matrix-isotope (e.g. 62.5Cu in copper samples) was used for internal standardization. The standard deviation of this signal in a period of 2.5 h was
3.6% RSD with no notable drift when the laser ablation was used for sample introduction. The calibration of the matrix-element
by nebulizing liquid standards showed that the ion signal measured on the peak-tail is directly proportional to the element
concentration in the ICP. This indicates that the peak shape is not only stable, but also independent of the peak height.
The advantages of this method lie in the easy preparation of calibration standards for quantitative measurements with a laser-ablation
system and access to homogeneous standards for materials, that are difficult to homogenize in the solid state. The calibration
of the traces is performed relatively to a fixed concentration of the matrix element. Calibrations were carried out for trace
concentrations in high purity copper and good recoveries were obtained for high-purity reference standards.
Received: 23 February 1998 / Revised: 20 July 1998 / Accepted: 25 July 1998 相似文献
95.
Jiménez-Tenorio M Puerta MC Salcedo I Valerga P Costa SI Gomes PT Mereiter K 《Chemical communications (Cambridge, England)》2003,(10):1168-1169
The pseudotetrahedral, formally 5-coordinate complex [Ni(eta 3-CH2C(CH3)CH2)(SbPh3)3][BAr'4] (Ar' = 3,5-C6H3(CF3)2) as well as the 4-coordinate derivative [Ni(eta 3-CH2C(CH3)CH2)(AsPh3)2][BAr'4] act as extremely efficient catalysts for the oligomerization of styrene. 相似文献
96.
The tetrahedral zinc complex [(Tp(Me,Ph))ZnOH] (Tp(Me,Ph) = hydrotris(5,3-methylphenylpyrazolyl)borate) was combined with acetohydroxamic acid, 3-mercapto-2-butanone, N-(methyl)mercaptoacetamide, beta-mercaptoethanol, 3-mercapto-2-propanol, and 3-mercapto-2-butanol to generate the complexes [(Tp(Me,Ph))Zn(ZBG)] (ZBG = zinc-binding group). These complexes were prepared to determine the mode of binding for three different types of thiol-derived matrix metalloproteinase (MMP) inhibitors. The solid-state structures of all six metal complexes were determined by X-ray crystallography. The structures reveal that while beta-mercaptoketones and beta-mercaptoamides bind the zinc ion in a bidentate fashion, the three beta-mercaptoalcohol compounds only demonstrate monodentate coordination via the sulfur atom. Prior to this work, no experimental data were available for the binding conformation of these types of inhibitors to the zinc active site of MMPs. The results of these model studies reveal different binding modes for these ZBGs and are useful for explaining the results of inhibition assays and in second-generation drug design. This work demonstrates the utility of model complexes as a tool for revealing drug-metalloprotein interactions. 相似文献
97.
Bustelo E Carbó JJ Lledós A Mereiter K Puerta MC Valerga P 《Journal of the American Chemical Society》2003,125(11):3311-3321
The reaction of the chloro-complex [CpRuCl(PEt(3))(2)] with acetylene gas in methanol gave the pi-alkyne complex [CpRu(eta(2)-HCtbd1;CH)(PEt(3))(2)][BPh(4)] (1), which has been structurally characterized by X-ray analysis. The alkyne complex undergoes spontaneous isomerization even at low temperature, yielding the metastable alkynyl-hydride complex [CpRu(H)(Ctbd1;CH)(PEt(3))(2)][BPh(4)] (2), as the result of the oxidative addition of the alkyne C-H bond. This compound has also been structurally characterized despite it tautomerizes spontaneously into the stable primary vinylidene [CpRu(=C=CH(2))(PEt(3))(2)][BPh(4)] (3). This species has been alternatively prepared by a two-step deprotonation/protonation synthesis from the pi-alkyne complex. Moreover, the reaction of the initial chloro-complex with monosubstituted alkynes HCtbd1;CR (R = SiMe(3), Ph, COOMe, (t)Bu) has been studied without detection of pi-alkyne intermediates. Instead of this, alkynyl-hydride complexes were obtained in good yields. They also rearrange to the corresponding substituted vinylidenes. In the case of R = SiMe(3), the isomerization takes place followed by desilylation, yielding the primary vinylidene complex. X-ray crystal structures of the vinylidene complexes [CpRu(=C=CH(2))(PEt(3))(2)][BPh(4)] (3) and [CpRu(=C=CHCOOMe)(PEt(3))(2)][BPh(4)] (10) have also been determined. Both, full ab initio and quantum mechanics/molecular mechanics (QM/MM) calculations were carried out, respectively, on the model system [CpRu(C(2)H(2))(PH(3))(2)](+) (A) and the real complex [CpRu(C(2)H(2))(PEt(3))(2)](+) (B) to analyze the steric and electronic influence of ligands on the structures and relative energies of the three C(2)H(2) isomers. QM/MM calculations have been employed to evaluate the role of the steric effects of real ligands, whereas full ab initio energy calculations on the optimized QM/MM model have allowed recovering the electronic effects of ligands. Additional pure quantum mechanics calculations on [CpRu(C(2)H(2))(PH(3))(2)](+) (C) and [CpRu(C(2)H(2))(PMe(3))(2)](+) (D) model systems have been performed to analyze in more detail the effects of different ligands. Calculations have shown that the steric effects induced by the presence of bulky substituents in phosphine ligand are responsible for experimentally observed alkyne distortion and for relative destabilization of the alkyne isomer. Moreover, increasing the phosphine basicity and sigma donor capabilities of ligands causes a relative stabilization of an alkynyl-hydride isomer. The combination of both steric and electronic effects, makes alkyne and alkynyl-hydride isomers to be close in energy, leading to the isolation of both complexes. 相似文献
98.
Nina A. Nedolya Nataly I. Schlyakhtina Lyudmila V. Klyba Igor A. Ushakov Sergei V. Fedorov Lambert Brandsma 《Tetrahedron letters》2002,43(52):9679-9681
Reaction of lithiated methoxyallene, 1-ethoxyethoxyallene, 1-(methylthio)propyne and 2-butyne with methoxymethyl isothiocyanate, MeOCH2N=C=S followed by methylation affords the imidothioates H2C=C=C(R)C(SMe)=NCH2OMe [R=Me, OMe, OCH(Me)OEt, SMe]. Rearrangement to the fully conjugated systems H2C=CH---C(R)=C(SMe)---N=CHOMe and subsequent electrocyclisation of these compounds leads to the 5-substituted 6-(methylthio)-2-methoxy-2,3-dihydropyridines with good to excellent yields. In the presence of acidic catalysts or by heating at elevated temperatures these dihydropyridines eliminate methanol to afford 3-substituted 2-(methylthio)pyridines. The aroma compound 2-(methylthio)-3-pyridinol was obtained by acid-catalysed treatment of 3-(1-ethoxyethoxy)-2-(methylthio)pyridine. 相似文献
99.
Manoj Trivedi Daya Shankar Pandey M.Carmen Puerta 《Journal of organometallic chemistry》2004,689(4):879-882
The reactions of [RuH(CO)Cl(PPh3)3] with N,N′-bis(salicylidine)-hydrazine (H2bsh) and N,N′-bis(salicylidine)-p-phenylene diammine (H2bsp) in presence of KOH in methanol led in the formation of neutral mononuclear complexes with the formulations [RuH(CO)(PPh3)2(L)] (LHbsh or Hbsp). These present the first examples where the ligands H2bsh or H2bsp provide only two of its available donor sites for interaction with the metal centre. The complexes have been characterized by elemental analyses, FAB-MS, IR, 1H, 13C, 31P NMR and electronic spectral studies. Molecular structure of the representative complex [RuH(CO)(PPh3)2(Hbsh)] have been determined by single crystal X-ray analysis. 相似文献
100.
Dana Hayoun‐Neeman Nataly Korover Sharon Etzion Rivka Ofir Rachel G. Lichtenstein Smadar Cohen 《先进技术聚合物》2019,30(10):2493-2505
Engineering human cardiac tissue is a promising solution for myocardial repair of injured hearts and for drug screening. Herein, we examined the capability of chemically defined alginate scaffolds to promote cardiac tissue regeneration from human embryonic stem cell‐derived cardiomyocytes (hESC‐CMs) in serum‐free, chemically defined medium. The cells were single seeded or coseeded with human dermal fibroblasts (HFs) in macroporous scaffolds made from pristine alginate or alginate modified with arginine‐glycine‐aspartate (RGD) peptide and heparin‐binding peptide (HBP). Our results show that the addition of fibroblasts to the 3‐D culture is indispensable for the formation of functional cardiac tissues and that the presence of RGD/HBP attached to the alginate matrix further improves its functionality. The engineered tissue displayed the typical fiber morphology with massive striation. An increase in contraction amplitude and calcium transients with time, together with a decrease in excitation threshold, indicated advancement toward tissue maturation. Our results thus point to the importance of co‐cultivating fibroblasts with hESCs‐CMs in chemically defined peptide‐functionalized alginate scaffolds and culture medium for regenerating functional cardiac tissue in vitro. 相似文献