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91.
Rao PV Bhaduri S Jiang J Hong D Holm RH 《Journal of the American Chemical Society》2005,127(6):1933-1945
The construction of a synthetic analogue of the A-cluster of carbon monoxide dehydrogenase/acetylcoenzyme synthase, the site of acetylcoenzyme A formation, requires as a final step the formation of an unsupported [Fe(4)S(4)]-(mu(2)-SR)-Ni(II) bridge to a preformed cluster. Our previous results (Rao, P. V.; Bhaduri, S.; Jiang, J.; Holm, R. H. Inorg. Chem. 2004, 43, 5833) and the work of others have addressed synthesis of dinuclear complexes relevant to the A-cluster. This investigation concentrates on reactions pertinent to bridge formation by examining systems containing dinuclear and mononuclear Ni(II) complexes and the 3:1 site-differentiated clusters [Fe(4)S(4)(LS(3))L'](2-) (L' = TfO(-) (14), SEt (15)). The system 14/[{Ni(L(O)-S(2)N(2))}M(SCH(2)CH(2)PPh(2))](+) results in cleavage of the dinuclear complex and formation of [{Ni(L(O)-S(2)N(2))}Fe(4)S(4)(LS(3))]- (18), in which the Ni(II) complex binds at the unique cluster site with formation of a Ni(mu(2)-SR)(2)Fe bridge rhomb. Cluster 18 and the related species [{Ni(phma)}Fe(4)S(4)(LS(3))](3)- (19) are obtainable by direct reaction of the corresponding cis-planar Ni(II)-S(2)N(2) complexes with 14. The mononuclear complexes [M(pdmt)(SEt)]- (M = Ni(II), Pd(II)) with 14 in acetonitrile or Me(2)SO solution react by thiolate transfer to give 15 and [M(2)(pdmt)(2)]. However, in dichloromethane the Ni(II) reaction product is interpreted as [{Ni(pdmt)(mu(2)-SEt)}Fe(4)S(4)(LS(3))](2-) (20). Reaction of Et(3)NH(+) and 15 affords the double cubane [{Fe(4)S(4)(LS(3))}(2)(mu(2)-SEt)](3-) (21). Cluster 18 contains two mutually supportive Fe-(mu(2)-SR)-Ni(II) bridges, 19 exhibits one strong and one weaker bridge, 20 has one unsupported bridge (inferred from the (1)H NMR spectrum), and 21 has one unsupported Fe-(mu(2)-SR)-Fe bridge. Bridges in 18, 19, and 21 were established by X-ray structures. This work demonstrates that a bridge of the type found in the enzyme A-clusters is achievable by synthesis and implies that more stable, unsupported single thiolate bridges may require reinforcement by an additional covalent linkage between the Fe(4)S(4) and nickel-containing components. (LS(3) = 1,3,5-tris((4,6-dimethyl-3-mercaptophenyl)thio)-2,4,6-tris(p-tolylthio)benzene(3-); L(O)-S(2)N(2) = N,N'-diethyl-3,7-diazanonane-1,9-dithiolate(2-); pdmt = pyridine-2,6-methanedithiolate(2-); phma = N,N'-1,2-phenylenebis(2-acetylthio)acetamidate(4-); TfO = triflate.). 相似文献
92.
L. F. Brum Malta Marta Eloisa Medeiros 《Journal of Thermal Analysis and Calorimetry》2005,81(1):149-152
Summary This work reports the room-temperature stabilization of the Bi4V2-xFexIIO11-1.5x γ ‘ phase, a promising ionic conductive material that finds application in solid oxide fuel cell and oxygen sensor devices. The Fe(II) cation proved to be a better stabilizer than Fe(III), which was previously used, since a lower substitution degree of V5+ is needed for the former. Powder X-ray diffraction, Fourier-transform infrared spectroscopy and differential scanning calorimetry were used in these experiments. 相似文献
93.
Thermal decomposition of strontium titanyl oxalate tetrahydrate and calcium titanyl oxalate hexahydrate have been studied employing TG, DTA, gas and chemical analysis. The decompositions proceed through three major steps: dehydration, decomposition of the oxalate to a carbonate and the decomposition of the carbonate to yield the final products, the metatitanates. The intermediates of the oxalate decomposition are found to be Sr2Ti2O4+x(CO3)2-x(CO2)x and Ca2Ti2O4(CO3)2, respectively. The entrapment of carbon dioxide in the former and the presence of non-equivalent carbonate groups in the latter are substantiated by their i.r. spectra. The penultimate solid residues are poorly crystalline Sr2Ti2O5CO3 and amorphous Ca2Ti2O5CO3. Decompositions of these carbonates are accompanied by growth in particle size of the products, SrTiO3 and CaTiO3, respectively. 相似文献
94.
Hans König 《Analytical and bioanalytical chemistry》1973,266(2):119-124
The separation of a mixture of 22 bactericides has been achieved by gas chromatography on columns with silicone rubber W-982 as stationary phase with temperatures between 100° and 300°C. The unchanged compounds as well as their silylation products have been used. The latter are more conveniently used especially for the quantitative determination. To be able to calculate the retention indices after Kovats gas chromatography has been performed isothermally at 180°C for the more volatile compounds and at 250°C for all other bactericides.The retention indices obtained under these conditions are tabulated together with the limits of detection. 相似文献
95.
Y. X. Xia J. I. Friese D. A. Moore P. P. Bachelor L. Rao 《Journal of Radioanalytical and Nuclear Chemistry》2007,274(1):79-86
The complexation of plutonium(IV) with sulfate at variable temperatures has been investigated by solvent extraction method.
A NaBrO3 solution was used as holding oxidant to maintain the plutonium(IV) oxidation state throughout the experiments. The distribution
ratio of Pu(IV) between the organic and aqueous phases was found to decrease as the concentrations of sulfate were increased.
Stability constants of the 1:1 and 1:2 Pu(IV)-HSO4
− complexes, dominant in the aqueous phase, were calculated from the effect of [HSO4
−] on the distribution ratio. The enthalpy and entropy of complexation were calculated from the stability constants at different
temperatures using the Van’t Hoff equation. 相似文献
96.
(2S)- and (2R)-2-Amino-4-bromobutanoic acid were prepared starting from N-Boc-glutamic acid α tert-butyl ester. The double tert-butyl protection was necessary to prevent a partial racemisation during Barton’s radical decarboxylation used to transform the γ-carboxylic group into a bromide. This bromide reacted with different nitrogen, oxygen and sulphur nucleophiles to give nonnatural amino acids characterised by basic or heterocyclic side chains. The title compound was also used to prepare a conformationally constrained peptidomimetic. 相似文献
97.
In this paper, by capturing the atomic information and reflecting the behaviour governed by the nonlinear potential function,
an analytical molecular mechanics approach is proposed. A constitutive relation for single-walled carbon nanotubes (SWCNT’s)
is established to describe the nonlinear stress-strain curve of SWCNT’s and to predict both the elastic properties and breaking
strain of SWCNT’s during tensile deformation. An analysis based on the virtual internal bond (VIB) model proposed by P. Zhang
et al. is also presented for comparison. The results indicate that the proposed molecular mechanics approach is indeed an
acceptable analytical method for analyzing the mechanical behavior of SWCNT’s.
The project supported by the National Natural Science Foundation of China (10121202, 90305015 and 10328203), the Key Grant
Project of Chinese Ministry of Education (0306) and the Research Grants Council of the Hong Kong Special Administrative Region,
China (HKU 7195/04E). 相似文献
98.
Comprehensive study on novel Linear-Dispersion Division Multiple-Access(LDDMA) for multi-user uplink Multiple-Input Multiple-Output(MIMO)systems is proposed.In the new multiplexing scheme,each user’s information symbol is dispersed by a User-Specific Matrix(USM)both in space and time domain and linearly combined at base-station side.And a simple random search algorithm,based on capacity maximization criteria,is developed to generate a bank of USMs.Simulation results are presented to demonstrate the advantages of LDDMA.When the Bit Error Rate(BER) reaches 10^–3,the performance gains are 3dB and 5dB,compared with Time-Division Linear Dispersion Codes(TD-LDC)and BLAST,respectively. 相似文献
99.
A sparse-matrix factorization is developed for the discrete sine transform (DST). This factorization has a recursive structure and leads directly to an efficient algorithm for implementing the DST, a feature most desirable and very similar ot that of the DCT. This algorithm requires fewer arithmetic operations compared to that for the discrete cosine transform (DCT). 相似文献
100.
Boris Kapilevich Yosef Pinhasi Ruth Arusi Michael Anisimov Danny Hardon Boris Litvak Yan Wool 《Journal of Infrared, Millimeter and Terahertz Waves》2010,31(11):1370-1381
A single-pixel imaging remote sensor operating at 330 GHz is described. It is based on a frequency modulated continuous wave
(FMCW) and aimed at detection of concealed objects for ranges up to 40 m. The system consists of 2 horn-lens antennas integrated
with a homodyne transceiver. The synthesized linear FMCW signal at X-band is multiplied by a factor of 32 to generate the
transmitted signal. An intermediate frequency (IF) signal obtained in the output port of the 2-nd harmonic mixer is employed
for image processing. Distance measurements were made by performing data acquisition unit based on LabView interface and resulting
in a range resolution about 1 cm. Examples of 2D and 3D images reconstructed with this sensor are presented. 相似文献