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21.
Vladimir L. Kolesnichenko Victor B. Rybakov Leonid A. Aslanov Sergei V. Volkov 《Journal of Cluster Science》1997,8(1):27-45
Thioselenohalide complexes Mo2(μ-S2)2Cl6(SeCl2)2 (I), Mo2(μ-S2)2Br6(SeBr2)2 (II), and W2(μ-S2)2Br6(SeBr2)2 (III) were synthesized by the reactions of corresponding metal halides or carbonyls or molybdenum metal with excesses of S2 X 2+Se2 X 2 mixtures. The complex W2(μ-S2)2Cl6(SeCl2)2 (IV) was obtained by an exchange reaction between (III) and excess of Se2Cl2. Coordination of the neutral SeX 2 ligands to thiohalidesM 2(μ-S2)2 X 6 results in higher thermal stability, and suggests the possibility to synthesize SeX 2 complexes of the unstable parent tungsten thiohalides. An unusual oxidative addition reaction of (I) was detected: {fx27-1} Both (I) and (IV) were characterized by X-ray crystal structure analysis. They are isostructural and form discrete molecules. Bridging S 2 2? ligands are coordinated perpendicularly to the metal-metal bond;d(M?M)=2.8066 Å and 2.793 Å for I and IV, respectively. Nonequivalence of chlorine atoms which are bound to the metal atom, relate to nonequivalence of halogen atoms in the complexesM 2(μ?S2)2 X 8 2? . Chlorine atomstrans to SeCl2 ligands form short bonds with the metal; the corresponding35Cl NQR frequency is increased. The selenium dichloride ligand is ambidentate. The selenium atom binds as a donor to the metal and as an acceptor to two chlorine atoms which are also bound covalently to the same metal atom. 相似文献
22.
Aránzazu Espina Enrique Jaimez Sergei A. Khainakov Camino Trobajo José R. García Julio Rodríguez 《Journal of inclusion phenomena and macrocyclic chemistry》1998,30(4):333-352
The intercalation of some amines (aniline, benzylamine, cyclohexylamine,piperidine, pyridine, pyrazine and piperazine) into -titaniumphosphate, Ti(HPO4)2×H2O,has been investigated by the batch method and/or by exposing the host to thevapour of the amines. The changes in the interlayer distance of the solidduring the intercalation process was followed by X-ray powder diffraction.The new intercalates were characterised by chemical and thermal analysis.Materials with a monolaminar and/or bilaminar arrangement of amine moleculesin the phosphate interlayer region are obtained depending on the nature ofthe amine. Due to steric hindrance, saturated phases are not obtained forall amines studied. The thermal decomposition of the intercalates (nitrogenatmosphere), takes place in three stages: dehydration, removal of amines andcondensation of the hydrogenphosphate to pyrophosphate groups. 相似文献
23.
Werner Fuss Wolfram E Schmid Sergei A Trushin Paul S Billone William J Leigh 《Chemphyschem》2007,8(4):592-598
Photochemical pericyclic reactions are believed to proceed via a so-called pericyclic minimum on the lowest excited potential surface (S(1)), which is common to both the forward and backward reactions. Such a common intermediate has never been directly detected. The photointerconversion of 1,3-butadiene and cyclobutene is the prevailing prototype for such reactions, yet only diene ring closure proceeds with the stereospecificity that the Woodward-Hoffmann rules predict. This contrast seems to exclude a common intermediate. Using ultrafast spectroscopy, we show that the excited states of two cyclobutene/diene isomeric pairs are linked by not one, but by two common minima, p* and ct*. Starting from the diene side (cyclohepta-1,3-diene and cycloocta-1,3-diene), electrocyclic ring closure passes via the pericyclic minimum p*, whereas ct* is mainly responsible for cis-trans isomerization. Starting from the corresponding cyclobutenes (bicyclo[3.2.0]heptene-6 and bicyclo[4.2.0]octene-7), the forbidden isomer is formed from ct*. The path branches at the first (S(2)/S(1)) conical intersection towards p* and ct*. The fact that the energetically unfavorable ct* path can compete is ascribed to a dynamic effect: the momentum in C=C twist direction, acquired--such as in other olefins--in the Franck-Condon region of the cyclobutenes. 相似文献
24.
Alexandra E. BotchkarevaFabiana Fini Sergei EreminJosep V. Mercader Angel MontoyaStefano Girotti 《Analytica chimica acta》2002,453(1):43-52
A heterogeneous chemiluminescent (CL) flow immunoassay for DDT was optimized comparing different types of immunoaffinity supports: beads, nylon coils and membranes (membranes HyBondN+). In order to characterize solid immunoaffinity supports two basic immunoassay formats were performed, using (1) enzyme-labeled secondary and (2) enzyme-labeled specific monoclonal antibodies (MAbs). In both formats, hapten DDT5 conjugated to ovalbumin immobilized on solid supports according to the appropriate immobilization procedure, enzyme label (horseradish peroxidase, HRP) and luminescent detection (luminol/H2O2/p-iodophenol) were used. The lowest limit of detection (LOD), 1 nM p,p-DDT, was obtained with a membrane-based flow immunoassay with HRP-labeled specific antibody. Beads and packed tubing were discarded as appropriate supports because of the difficulties encountered for reproducible packing and the occurrence of light scatterring (beads), which seriously compromised the performance and reproducibility of the flow immunoassay. 相似文献
25.
The solvation and transport of the hydrated excess proton is studied using the Car-Parrinello molecular-dynamics (CPMD) simulation method. The simulations were performed using BLYP and HCTH gradient-corrected exchange-correlation energy functionals. The fictitious electronic mass was chosen to be small enough so that the underlying water structural and dynamical properties were converged with respect to this important CPMD simulation parameter. An unphysical overstructuring of liquid water in the CPMD simulations using the BLYP functional resulted in the formation of long-lived hydrogen-bonding structures involving the excess proton and a particular (special) water oxygen. The excess proton was observed to be attracted to the special oxygen through the entire length of the BLYP CPMD simulations. Consequently, the excess proton diffusion was limited by the mobility of the special oxygen in the slowly diffusing water network and, in turn, the excess proton self-diffusion coefficient was found to be significantly below the experimental value. On the other hand, the structural properties of liquid water in the HCTH CPMD simulation were seen to be in better agreement with experiment, although the water and excess proton diffusions were still well below the experimental value. 相似文献
26.
Han G Li J Chen G Ling L Li S Khorobrykh AA Zharmukhamedov SK Klimov VV Kuang T 《Journal of photochemistry and photobiology. B, Biology》2005,81(2):114-120
The efficiency of a trinuclear and two binuclear manganese complexes in reconstituting electron transport and O(2) evolution activity in Mn-depleted Photosystem II preparations is analyzed. The trinuclear Mn-complex is more efficient than two binuclear Mn-complexes in restoring oxygen evolution, but it is less effective as an electron donor than binuclear Mn-complexes. It is inferred from our results that recovery of electron transport and O(2) evolution with polynuclear Mn-complexes is affected with different factors. Moreover, the trinuclear Mn-complex is extremely sensitive to the addition of CaCl(2). It is suggested that there is an interaction between Ca(2+) and carboxyl within the trinuclear Mn-complex during photoactivation and this interaction benefits the ligation of Mn atom to the apo-WOC and form an active WOC. Binuclear Mn(III)Mn(III) complex shows slightly higher efficiency than binuclear Mn(III)Mn(IV) complex in restoration of O(2) evolution activity. The efficiency of three Mn-complexes in the reconstitution of WOC is in an order: trinuclear Mn(3)(III)>binuclear Mn(III)Mn(III)>binuclear Mn(III)Mn(IV). 相似文献
27.
Cianetti S Négrerie M Vos MH Martin JL Kruglik SG 《Journal of the American Chemical Society》2004,126(43):13932-13933
Cytochrome c (cyt c) is an electron-transfer heme protein that also binds nitric oxide (NO). In resting cyt c, two endogenous ligands of the heme iron are histidine-18 (His) and methionine-80 (Met) side chains, and NO binding requires the cleavage of one of the axial bonds. Previous femtosecond transient absorption studies suggested the photolysis of either Fe-His or Fe-Met bonds. We aimed at unequivocally identifying the internal side chain that is photodissociated in ferrous cyt c and at monitoring heme structural dynamics, by means of time-resolved resonance Raman (TR3) spectroscopy with approximately 0.6 ps time resolution. The Fe-His stretching mode at 216 cm-1 has been observed in photoproduct TR3 spectra for the first time for a c-type heme. The same transient mode was observed for a model ferrous cyt c N-fragment (residues 1-56) ligated with two His in the resting state. Our TR3 data reveal that upon ferrous cyt c photoexcitation, (i) distal Met side chain is instantly released, producing a five-coordinated domed heme structure, (ii) proximal His side chain, coupled to the heme, exhibits distortion due to strain exerted by the protein, and (iii) alteration in heme-cysteine coupling takes place along with the relaxation of the protein-induced deformations of the heme macrocycle. 相似文献
28.
A convenient method has been developed to synthesize diaryl arylphosphonates from triaryl phosphites, triethyl phosphite, and aromatic halides. The new method relies on the triethyl phosphite assisted nickel catalyzed Arbuzov reaction and can be applied to synthesize certain diaryl alkylphosphonates without catalysts. 相似文献
29.
Express detection of nonylphenol in water samples by fluorescence polarization immunoassay 总被引:6,自引:0,他引:6
Yakovleva JN Lobanova AY Shutaleva EA Kourkina MA Mart'ianov AA Zherdev AV Dzantiev BB Eremin SA 《Analytical and bioanalytical chemistry》2004,378(3):634-641
The development of express method for detection of endocrine-disrupting chemicals (EDC) such as alkylphenols is required for ecological monitoring. Several attempts have been made to produce antibodies against 4-nonylphenol (NP) in recent years. This work describes the production of new antibodies against NP and also summarizes the characterization of antibodies obtained earlier. Three approaches used to produce alkylphenol-specific antibodies are compared; these are based on: 1. omega-(4-hydroxyphenyl)nonanoic or omega-(4-hydroxyphenyl)heptanoic acid NP derivatives designed to mimic the linear NP isomer; 2. 4-aminophenol, which potentially mimics various substituted phenolic compounds with different side-chain structures at position 4 of the benzene ring; and 3. a mixture of branched NP isomers, conjugated to the carrier protein via a benzene ring by the Mannich reaction, and expected to be the closest mimic of NP structure by preserving its natural alkyl moiety.Fluorescence polarization immunoassays based on different combinations of antibody and labeled antigen for screening detection of NP were developed and structural aspects of assay sensitivity and specificity were investigated. The assays based on the antisera raised against omega-(4-hydroxyphenyl)nonanoic acid and NP conjugate via Mannich reaction are capable of express detection of NP with detection limit of 7 microg mL(-1 )and assay dynamic range of 18-300 microg mL(-1). 相似文献
30.
Aleksandr V. Prichodko Evgenii V. Shatkovski Sergei G. Yastrebov 《International Journal of Infrared and Millimeter Waves》1994,15(3):579-584
Photostimulated changes in thin carbon films deposited onto fused silica substrates by reactive magnetron sputtering and irradiated by the light of the first (1060nm) and the second (530nm) harmonics of a QW-switched Nd3+ AVG laser were investigated. The changes are supposed to be connected with the reordering of chemical bounds. 相似文献