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991.
Roberto Fernández de la Pradilla 《Tetrahedron》2006,62(11):2684-2692
(E,E) and (Z,E) γ-alkoxy dienyl sulfones undergo nucleophilic epoxidation with remarkable regio- and stereoselectivity to render syn oxiranes in a process mainly controlled by the alkoxy stereocenter. Upon epoxidation γ-hydroxy dienyl sulfoxides provide sulfinyl and sulfonyl oxiranes along with bis-epoxides formed through a Payne rearrangement that can be prevented by silylation of the OH group. Interestingly, the presence of a γ-silyloxy group can invert the stereochemical trend of the molecule affording mainly an anti epoxidation process. 相似文献
992.
LONG-RANGE TRIPLET-SINGLET ENERGY TRANSFER FROM ENZYME GENERATED TRIPLET ACETONE TO XANTHENE DYES 总被引:1,自引:0,他引:1
Enzyme-generated and protected acetone transfers its energy to xanthene dyes by a nontrivial process. The relative populations of the S1 state are indicative of the operation of a heavy atom effect, being 1:15:100 for fluorescein, eosine and Rose Bengal. On the other hand Stern-Volmer constants and k ET 0 values are similar for the three dyes and are remarkably higher than for collisional processes.
It is tentatively suggested that at least for eosine and Rose Bengal, a triplet-triplet cxciton transfer may occur to populate an upper triplet state of the dye followed by heavy-atom enhanced intersystem crossing to the S1 state. 相似文献
It is tentatively suggested that at least for eosine and Rose Bengal, a triplet-triplet cxciton transfer may occur to populate an upper triplet state of the dye followed by heavy-atom enhanced intersystem crossing to the S
993.
Adams LA Aggarwal VK Bonnert RV Bressel B Cox RJ Shepherd J de Vicente J Walter M Whittingham WG Winn CL 《The Journal of organic chemistry》2003,68(24):9433-9440
A simple and high-yielding method for the preparation of cyclopropane amino acids is described. The novel method involves the one-pot cyclopropanation of readily available dehydroamino acids using aryl and unsaturated diazo compounds generated in situ from the corresponding tosylhydrazone salts. It was found that thermal 1,3-dipolar cycloaddition followed by nitrogen extrusion gave the cyclopropane amino acid derivatives with good E selectivity, while reactions in the presence of meso-tetraphenylporphyrin iron chloride gave predominantly the corresponding Z isomers. The synthetic utility of this process was demonstrated in the synthesis of (+/-)-(Z)-2,3-methanophenylalanine [(+/-)-(Z)-1], the anti-Parkinson (+/-)-(E)-2,3-methano-m-tyrosine [(+/-)-(E)-2], and the natural product (+/-)-coronamic acid [(+/-)-3]. 相似文献
994.
Luiza N.H. Arakaki Maria G. da Fonseca Edson C. da Silva Filho Ana Paula de M. Alves Kaline S. de Sousa Andr Leonardo P. Silva 《Thermochimica Acta》2006,450(1-2):12-15
The reaction of ethylene sulfide with 3-aminopropyltrimethoxysilane gave a new silylating agent, which was anchored onto a silica surface via the sol–gel procedure. This surface displayed a chelating moiety containing nitrogen and two sulfur basic centers potentially capable of extracting cations from aqueous solutions. The process of metal extraction was followed by a batch method, and fitted to a modified Langmuir equation. The maximum adsorption capacities found were: 2.06 ± 0.01, 3.72 ± 0.02, and 5.14 ± 0.02 mmol g−1 for Pb(II), Cd(II), and Hg(II), respectively. The enthalpies of bending are: −1.16 ± 0.04, −3.60 ± 0.10, and −8.94 ± 0.03 kJ mol−1 for Cd(II), Pb(II), and Hg(II), respectively. The Gibbs free energies of binding agree with the spontaneity of the proposed reactions between cations and basic centers. 相似文献
995.
Ramo Marceli Fernandes Gelson Manzoni de Oliveira Ernesto Schulz Lang Ezequiel M. Vzquez‐Lpez 《无机化学与普通化学杂志》2004,630(15):2687-2691
The reaction of tellurium(IV) tetrahalides with hydrochloric and hydrobromic acid leads to the formation of (H3O)2[TeX6], which reacts subsequently with (2‐Br‐C5NH5)+X‐ to afford (2‐Br‐C5NH5)2[TeCl6] ( 1 ) and (2‐Br‐C5NH5)2[TeBr6] ( 2 ). The structure of the complex salts were analysed by X‐ray diffractometry affording the centrosymmetric space groups P21/n (monoclinic, 1 ) and P1¯ (triclinic, 2 ). Interionic hydrogen bondings hold their lattices in bidimensional supramolecular arrays not yet described in the literature. The lone electron pair of the AX6E‐system of the hexahalotellurates [TeX6]2‐ (X = Cl, Br) seems to be fully delocalized since only small octahedral deviations were observed for the anionic species. The structures of the title compounds were refined with the Te atoms occupying sites with full point symmetry, approximately m3¯m. In both cases the Te atoms enclose centers of inversion and the octahedrally dynamic structures are enforced and stabilized along the supramolecular lattices by the crystal field of the 2‐Br‐pyridinium cations. 相似文献
996.
An electrochemically stable monolayer of tris(2,2'-bipyridyl)ruthenium(II) was obtained for the first time. It was based on the electrostatic attachment of Ru(bpy)(3)(2+) to the benzene sulfonic acid monolayer film, which was covalently bound onto glassy carbon electrode by the electrochemical reduction of diazobenzene sulfonic acid. The surface-confined Ru(bpy)(3)(2+) underwent reversible surface process, and reacted with the coreactant, tripropylamine, to produce electrochemiluminescence. In view of the stability of the electrode, the results strongly suggested that light was emitted from the surface-confined Ru(bpy)(3)(2+), not from the detached Ru(bpy)(3)(2+). The Ru(bpy)(3)(2+) modified electrode was used to the determination of tripropylamine. It showed good linearity in the concentration range from 5 muM to 1 mM with a detection limit of 1 muM (S/N=4). The good stability of the Ru(bpy)(3)(2+) modified electrode also showed that the benzene sulfonic acid monolayer film prepared can be served as an excellent support to construct multilayers. 相似文献
997.
J.W. Hofstraat M. Engelsma R.J. van de Nesse U.A.Th. Brinkman C. Gooijer N.H. Velthorst 《Analytica chimica acta》1987
The effluent from a narrow-bore liquid chromatographic (l.c.) separation can be immobilized on thin-layer chromatographic (t.l.c.) plates with little loss of resolution. The deposited compounds are then available for further inspection. For off-line detection, direct fluorescence emission, fluorescence excitation emission spectra, and fluorescence line-narrowing spectroscopy are investigated with tetracene and benz[k] fluoranthene as model compounds. Detection based on direct emission measurements and on measurements for which complete spectra are obtained for the separated compounds, is suitable for identification and determination. Detection limits are of the same order of magnitude as those for on-line detection in narrow-bore l.c. The fluorescence spectra of immobilized compounds can be obtained with a conventional fluorescence spectrometer equipped with a solid-sample accessory. No other special apparatus is needed. The immobilized chromatogram is also suitable for techniques incompatible with flow systems, e.g., fluorescence line-narrowing spectroscopy, which yields fluorescence spectra via laser excitation of low-temperature solid samples. Very selective narrow-line fluorescence spectra were obtained for tetracene deposited on t.l.c. plates in amounts down to the low picogram level. 相似文献
998.
Montserrat Ferrer Anna Juli Roser Reina Oriol Rossell Miquel Seco Dominique de Montauzon 《Journal of organometallic chemistry》1998,560(1-2)
Treatment of [(ClAu)2(diphosphine)] {diphosphine=bis(diphenylphosphino)methane (dppm), bis(diphenylphosphino)isopropane (dppip), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp)} with two equivalents of the anion [Fe2(μ-CO)(CO)6(μ-PPh2)]− in the presence of TlBF4 gives the new heterometallic diclusters [{Fe2(μ-CO)(CO)6(μ-PPh2)Au}2(diphosphine)] that have been isolated and characterized. Their 31P-NMR spectra show different patterns as a function of the diphosphine ligand. The electrochemical behavior of these compounds has been investigated and compared with that of the mono- [Fe2(μ-CO)(CO)6(μ-PPh2)(μ-AuPPh3)] and tricluster [{Fe2(μ-CO)(CO)6(μ-PPh2)Au}3(triphos)] derivatives. 相似文献
999.
Background
The completion of several genome-sequencing projects has increased our need to assign functions to newly identified genes. The presence of a specific protein domain has been used as the determinant for suggesting a function for these new genes. In the case of proteins that are predicted to interact with mRNA, most RNAs bound by these proteins are still unknown. In yeast, several protocols for the identification of protein-protein interactions in high-throughput analyses have been developed during the last years leading to an increased understanding of cellular proteomics. If any of these protocols or similar approaches shall be used for the identification of mRNA-protein complexes, the integrity of mRNA is a critical factor. 相似文献1000.
A method for the simultaneous spectrophotometric determination of the divalent ions of iron, cobalt, nickel and copper based on the formation of their complexes with 1,5-bis(di-2-pyridylmethylene) thiocarbonohydrazide (DPTH) is proposed. The resolution of quaternary mixtures of these metallic ions was accomplished by several chemometric approaches. A comparative study of the results obtained for simultaneous determinations in mixture by using principal component regression (PCR) and partial least-squares regression (PLS-1 and PLS-2) for absorbance, first-derivative and second-derivative data is presented. In general, the best recovery values are obtained by the PLS-2 method for absorbance data. This procedure allows the simultaneous determination of the cited ions in alloys and biological materials Good reliability of the determination was proved. 相似文献