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991.
992.
High-resolution electron energy loss spectroscopy (HREELS), temperature-programmed desorption (TPD), and density functional theory (DFT) calculations were used to study the adsorption and reaction of 1-epoxy-3-butene (EpB) on Pt(111). These investigations were conducted to help elucidate mechanisms for improving olefin hydrogenation selectivity in reactions of unsaturated oxygenates. EpB dosed to Pt(111) at 91 K adsorbs molecularly on the surface through the vinyl group with apparent rehybridization to a di-sigma-bound state. By 233 K, however, EpB undergoes epoxide ring opening to form an aldehyde intermediate, which further decomposes upon heating to yield gas phase products CO, H2, and propylene. Comparison of the HREELS and TPD data to experiments performed with 2-butenal (crotonaldehyde) shows that EpB and 2-butenal decompose through related pathways. However, the EpB-derived aldehyde intermediate clearly has a unique structure, features of which have been elucidated by DFT calculations. In conjunction with previous surface science studies of EpB chemistry, these results can help explain selectivity trends for reactions of EpB on Pt catalysts and bimetallic PtAg catalysts, with indications that the enhanced olefin hydrogenation selectivity of PtAg catalysts likely originates from a bifunctional effect. 相似文献
993.
Elegbede AI Banerjee J Hanson AJ Tobwala S Ganguli B Wang R Lu X Srivastava DK Mallik S 《Journal of the American Chemical Society》2008,130(32):10633-10642
Matrix metalloproteinases (MMPs) constitute a class of extracellular-matrix-degrading enzymes overexpressed in many cancers and contribute to the metastatic ability of the cancer cells. We have recently demonstrated that liposomal contents can be released when triggered by the enzyme MMP-9. Herein, we report the results of our mechanistic studies of the MMP-9-triggered release of liposomal contents. We synthesized peptides containing the cleavage site for MMP-9 and conjugated them with fatty acids to prepare the corresponding lipopeptides. By employing circular dichroism (CD) spectroscopy, we demonstrated that the lipopeptides, when incorporated into liposomes, are demixed in the lipid bilayers and generate triple-helical structures. MMP-9 cleaves the triple-helical peptides, leading to the release of the liposomal contents. Other MMPs, which cannot hydrolyze triple-helical peptides, fail to release the contents from the liposomes. We also observed that the rate and extent of release of the liposomal contents depend on the mismatch between the acyl chains of the synthesized lipopeptide and phospholipid components of the liposomes. CD spectroscopic studies imply that the observed differences in the release reflect the ability of the liposomal membrane to anneal the defects following the enzymatic cleavage of the liposome-incorporated lipopeptides. 相似文献
994.
Bazzicalupi C Bencini A Bianchi A Faggi E Giorgi C Santarelli S Valtancoli B 《Journal of the American Chemical Society》2008,130(8):2440-2441
995.
The thiomethylene‐linked U*[s]U(*) dimers 9 – 14 were synthesized by substitution of the 6‐[(mesyloxy)methyl]uridine 6 by the thiolate derived from the uridine‐5′‐thioacetates 7 and 8 followed by O‐deprotection. Similarly, the thiomethylene‐linked A*[s]A(*) dimers 9 – 14 were obtained from the 8‐(bromomethyl)adenosine 15 and the adenosine‐5′‐thioacetates 16 and 17 . The concentration dependence of both H? N(3) of the U*[s]U(*) dimers 9 – 14 evidences the formation of linear and cyclic duplexes, and of linear higher associates, C(8 or 6)CH2OH and/or C(5′/II)OH groups favouring the formation of cyclic duplexes. The concentration dependence of the chemical shift for both H2N? C(6) of the A*[s]A(*) dimers 18 – 23 evidences the formation of mainly linear associates. The heteroassociation of U*[s]U(*) to A*[s]A(*) dimers is stronger than the homoassociation of U*[s]U(*) dimers, as evidenced by diluting equimolar mixtures of 11 / 20 and 13 / 22 . A 1 : 1 stoichiometry of the heteroassociation is evidenced by a Job's plot for 11 / 20 , and by mole ratio plots for 9 / 18, 10 / 19, 12 / 21, 13 / 22 , and 14 / 23 . 相似文献
996.
Nicolas Bogliotti Anne Ritter Séverine Hebbe Andrea Vasella 《Helvetica chimica acta》2008,91(11):2181-2202
The A*[s]U(*) dinucleosides 1 and 2 form thermoreversible gels in organic solvents. The basis of the gelation is the formation of linear aggregates by base pairing following desolvation of the nucleobases. This is evidenced by the absence of gel formation by the C(6)‐deaminated analogue 3 of 1 , the correlation of gelation with the anti‐conformation, as preferred for 1 , and the temperature‐, concentration‐, and time‐dependent CD spectra. The gels were also characterized by the minimum gelation concentration, the gel–sol transition (melting) temperature, and rheological properties. 相似文献
997.
Listorti A Accorsi G Rio Y Armaroli N Moudam O Gégout A Delavaux-Nicot B Holler M Nierengarten JF 《Inorganic chemistry》2008,47(14):6254-6261
Heteroleptic copper(I) complexes CuPOP-F and CuFc-F have been prepared from a fullerene-substituted phenanthroline ligand and bis[2-(diphenylphosphino)phenyl] ether (POP) and 1,1'-bis(diphenylphosphino)ferrocene (dppFc), respectively. Electrochemical studies indicate that some ground-state electronic interaction between the fullerene subunit and the metal-complexed moiety are present in both CuPOP-F and CuFc-F. Their photophysical properties have been investigated by steady state and time-resolved UV-vis-NIR luminescence spectroscopy and nanosecond laser flash photolysis in a CH2Cl2 solution and compared to those of the corresponding model copper(I) complexes CuPOP and CuFc and of the fullerene model compound F. Selective excitation of the methanofullerene moiety in CuPOP-F results in regular deactivation of the lowest singlet and triplet states, indicating no intercomponent interactions. Conversely, excitation of the copper(I)-complexed unit (405 nm, 40% selectivity) shows that the strongly luminescent triplet metal-to-ligand charge-transfer ((3)MLCT) excited state located at 2.40 eV is quenched by the carbon sphere with a rate constant of 1.6 x 10(8) s(-1). Details on the mechanism of photodynamic processes in CuPOP-F via transient absorption are hampered by the rather unfavorable partition of light excitation between the two chromophores. By determination of the yield of formation of the lowest fullerene triplet level through sensitized singlet oxygen luminescence in the NIR region, it is shown that the final sink of photoinduced processes is always the fullerene triplet. This can be populated via a two-step charge-separation charge-recombination process and a less favored (3)MLCT --> (3)C60 triplet-triplet energy-transfer pathway. In CuFc-F, both of the photoexcited copper(I)-complexed and fullerene moieties are quenched by the presence of the ferrocene unit, most likely via ultrafast energy transfer. 相似文献
998.
A bimetallic coordination polymer, infinity (2)[{LNi (II)Co (II)}(dca) 2], has been constructed from heterobinuclear [Ni (II)Co (II)] nodes and dicyanamido spacers [L (2-) is the dianion of the Schiff base resulting from the 2:1 condensation of 3-methoxysalicyladehyde with 1,3-propanediamine; L (2-) = N, N'-propylenebis(3-methoxysalycilideneiminato)]. The intranode Co (II)-Ni (II) interaction was found to be ferromagnetic because of the orthogonality of the magnetic orbitals. Below 12 K, the onset of the canted ferromagnetic ordering is observed. 相似文献
999.
Aragoni MC Arca M Bencini A Biagini S Blake AJ Caltagirone C Demartin F De Filippo G Devillanova FA Garau A Gloe K Isaia F Lippolis V Valtancoli B Wenzel M 《Inorganic chemistry》2008,47(18):8391-8404
Two new mixed aza-thia crowns 5-aza-2,8-dithia[9]-(2,9)-1,10-phenanthrolinophane (L(4)) and 2,8-diaza-5-thia[9]-(2,9)-1,10-phenanthrolinophane (L(7)) have been synthesized and characterized. The coordination behavior of L(4) and L(7) toward the metal ions Cu(II), Zn(II), Pb(II), Cd(II), Hg(II), and Ag(I) was studied in aqueous solution by potentiometric methods, in CD3CN/D2O 4:1 (v/v) by (1)H NMR titrations and in the solid state. The data obtained were compared with those available for the coordination behavior toward the same metal ions of structurally analogous mixed donor macrocyclic ligands L(1)-L(3), L(5), L(6): all these contain a phenanthroline subunit but have only S/O/N(aromatic) donor groups in the remaining portion of the ring and are, therefore, less water-soluble than L(4) and L(7). The complexes [Cd(NO3)2(L(5))], [Pb(L(7))](ClO4)2 x 1/2MeCN, [Pb(L(4))](ClO4)2 x MeCN, and [Cu(L(7))](ClO4)2 x 3/2MeNO2 were characterized by X-ray crystallography. The efficacy of L(1)-L(7) in competitive liquid-liquid metal ion extraction of Cu(II), Zn(II), Cd(II), Pb(II), Ag(I), and Hg(II) was assessed. In the absence of Hg(II), a clear extraction selectivity for Ag(I) was observed in all systems investigated. 相似文献
1000.
Hypersilyl(trimethylsilyl)aminodichlorophosphine, (hyp)N(SiMe3)PCl2, was treated with GaCl3, which resulted in the formation of an interesting novel bicycle, composed of a four-membered SiNP2 ring and a five-membered P2Ga2Cl ring. In the presence of Me3SiN3, the same reaction provided access to a cyclo-2-phospha-4-sila-1,3-diazenium tetrachlorogallate. The free chloro-cyclo-phosphasiladiazane was obtained by the addition of nucleophilic bases. 相似文献