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91.
Monomeric Chini‐Type Triplatinum Clusters Featuring Dianionic and Radical‐Anionic π*‐Systems 下载免费PDF全文
Brandon R. Barnett Prof. Arnold L. Rheingold Prof. Joshua S. Figueroa 《Angewandte Chemie (International ed. in English)》2016,55(32):9253-9258
Owing to their unique topologies and abilities to self‐assemble into a variety of extended and aggregated structures, the binary platinum carbonyl clusters [Pt3(CO)6]n2? (“Chini clusters”) continue to draw significant interest. Herein, we report the isolation and structural characterization of the trinuclear electron‐transfer series [Pt3(μ‐CO)3(CNArDipp2)3]n? (n=0, 1, 2), which represents a unique set of monomeric Pt3 clusters supported by π‐acidic ligands. Spectroscopic, computational, and synthetic investigations demonstrate that the highest‐occupied molecular orbitals of the mono‐ and dianionic clusters consist of a combined π*‐framework of the CO and CNArDipp2 ligands, with negligible Pt character. Accordingly, this study provides precedent for an ensemble of carbonyl and isocyanide ligands to function in a redox non‐innocent manner. 相似文献
92.
Oleamide is an interesting compound, which shows various pharmacological activities including the inhibitory effect of gap junction formation. Recently, the studies of the gap junction have been some of the hot topics in biology and its inhibitors have become more useful tools [Cravatt, B. F.; Garcia, O. P.; Siuzdak, G.; Gilula, N. B.; Henriksen, S. J.; Boger, D. L.; Lerner, R. A. Science1995, 268, 1506-1509; Cravatt, B. F.; Lerner, R. A.; Boger, D. L. J. Am. Chem. Soc.1996, 118, 580-590; Guan, X; Cravatt, B. F.; Ehring, G. R.; Hall, J. E.; Boger, D. L.; Lerner, R. A.; Gilula, N. B. J. Cell Biol.1997, 139, 1785-1792; Boger, D. L.; Patterson, J. E.; Guan, X.; Cravatt, B. F.; Lerner, R. A.; Gilula, N. B. Proc. Natl. Acad. Sci. U.S.A.1998, 95, 4810-4815; Ito, A.; Morita, N.; Miura, D.; Koma, Y.; Kataoka, T. R.; Yamasaki, H.; Kitamura, Y.; Kita, Y.; Nojima, H. Carcinogenesis2004, 25, 2015-2022]. However, many reports suggest that the functionalizations of oleamide to retain its biological activity were difficult [Boger, D. L.; Patterson, J. E.; Guan, X.; Cravatt, B. F.; Lerner, R. A.; Gilula, N. B. Proc. Natl. Acad. Sci. U.S.A.1998, 95, 4810-4815; Ito, A.; Morita, N.; Miura, D.; Koma, Y.; Kataoka, T. R.; Yamasaki, H.; Kitamura, Y.; Kita, Y.; Nojima, H. Carcinogenesis2004, 25, 2015-2022]. The synthesis of the functionalized oleamide derivatives, whose biological activity is not blocked, has become attractive in both the biological and chemical fields.Herein, by linking the fluorophore to the oleamide by alkyl chains, we synthesized the fluorescently tagged oleamide whose biological feature is similar to that of oleamide. Moreover, we also synthesized other bioactive derivatives tagged by other groups such as the sugars and biotin via alkyl chain linkers. 相似文献
93.
Photochromic symmetrical diarylethene derivatives 1a-6a bearing different long alkyl chains at 2-position of thiophene rings have been synthesized and their structures have been determined by single-crystal X-ray diffraction analysis. The effect of alkyl chain length on their optoelectronic properties, such as photochromism in solution as well as in the crystalline phase and electrochemical performance was investigated in detail. These diarylethenes have showed good photochromic behavior both in solution and in the single crystalline phase. Introduction of the long alkyl chains at 2-position of bis(5-formyl-3-thienyl)perfluorocyclopentene increased the absorption coefficients of both open- and closed-ring isomers and induced bathochromic shifts of the maximal wavelength absorption of the closed-ring isomers. The long alkyl chains can also decrease the cyclization/cycloreversion quantum yields and the oxidation potentials. The cyclic voltammetry indicated that the band gap of these diarylethene derivatives was significantly affected by the alkyl chain length. 相似文献
94.
Diethylzinc-mediated radical addition to CN bonds was investigated in the presence of phenylorganotellurium compounds as radical precursors. As group transfer agents, secondary alkyl phenyl tellurides were shown to be about twice as reactive as the corresponding alkyl iodides towards ethyl radical. Their use was proven to be advantageous regarding both chemoselectivity and yield. The replacement of diethylzinc by dimethylzinc, offers no advantage in these reactions. 相似文献
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Surface diffusion in reversed-phase liquid chromatography (RPLC) using silica gels bonded with C1 and C18 alkyl ligands of different densities was studied from the viewpoints of two extrathermodynamic relationships, i.e., enthalpy-entropy compensation (EEC) and linear free energy relationship (LFER). First, according to the four methods proposed by Krug et al., the values of surface diffusion coefficient (Ds) were analyzed to confirm that an actual EEC resulting from substantial physico-chemical effects takes place for surface diffusion. Then, it was also demonstrated that a LFER is observed between surface diffusion and the retention equilibrium. The establishment of EEC and LFER suggests a mechanistic similarity of molecular migration by surface diffusion, irrespective of the alkyl chain length and the densities of C1 and C18 ligands. Finally, a thermodynamic model for the LFER based on the real EEC was used to estimate Ds values under various RPLC conditions. The Ds values can be estimated with a mean square deviation of about 25–30%. The agreement between the Ds values estimated and those experimentally measured suggests that the total mass flux by surface diffusion consists of the two contributions due to C1 and C18 ligands and that the contribution of each ligand is proportional to the ligand density. 相似文献
99.
Morvan J Saluden M Agasse V Barbot F Cardinael P Bouillon JP Decock G 《Analytical and bioanalytical chemistry》2006,384(6):1409-1415
Bachus et al. [1] recently described a new derivatisation method using 2-furoyl chloride for the characterisation of mixtures of polyethoxylated
alcohols and their corresponding sulfates. This paper deals with the control of the derivatisation steps; hydrolysis and extraction
conditions were optimised. The method is extended to the characterisation of alkyl sulfosuccinates, alkyl sulfoacetates and
alkyl phosphates and to the analysis of residual polyethoxylated alcohols in surfactants. Extraction of non-ionic compounds
using solid-phase extraction cartridges was performed before derivatisation. Residual amounts of alcohol were determined in
five commercial anionic surfactants. Moreover, direct derivatisation without preliminary SPE in the same anionic surfactants
proved to be efficient for dry samples. 相似文献
100.
Georgiy B. Shul’pin Camilla C. Golfeto Lidia S. Shul’pina 《Tetrahedron letters》2005,46(27):4563-4567
The H2O2-FeCl3-bipy system in acetonitrile efficiently oxidises alkanes predominantly to alkyl hydroperoxides. Turnover numbers attain 400 after 1 h at 60 °C. It has been assumed that bipy facilitates proton abstraction from a H2O2 molecule coordinated to the iron ion (these reactions are stages in the catalytic cycle generating hydroxyl radicals from the hydrogen peroxide). Hydroxyl radicals then attack alkane molecules finally yielding the alkyl hydroperoxide. 相似文献