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81.
Azzaroni O Mir M Alvarez M Tiefenauer L Knoll W 《Langmuir : the ACS journal of surfaces and colloids》2008,24(6):2878-2883
In the present work, we describe the properties of a bifunctional redox-labeled bioconjugate at electrode surfaces mediating the electron transfer across the electrode-electrolyte interface. We show that the assembly of ferrocene-labeled streptavidin on biotinylated electrodes results in a reproducible unidirectional current flow in the presence of electron donors in solution. Such rectifying films were built up by spontaneous binding of tetrameric streptavidin molecules to biotin centers immobilized on the electrode surface. Due to the high affinity of biotin to streptavidin, such bifunctional films completely bind any biotinylated compounds. The charge transport between donors in solution and the Au electrode is mediated by the ferrocene moieties, allowing us to develop a molecular rectifier. Our experimental results suggest that such redox-labeled proteins with a high binding capacity constitute a promising alternative to organic compounds used in molecular electronics. 相似文献
82.
Louis R. Pignotti Natcharee Kongprakaiwoot William W. Brennessel Jonas Baltrusaitis Rudy L. Luck Eugenijus Urnezius 《Journal of organometallic chemistry》2008,693(20):3263-3272
Reactions of 1,4-difluoro-2,5-dimethoxybenzene with LDA (1:2) at low temperatures generated organodilithio intermediates; quenching the reaction mixtures with chlorophosphines ClPR2 produced 1,4-bis(phosphino)-2,5-difluoro-3,6-dimethoxybenzenes 1a (R = Ph) and 1b (R = iPr). Demethylation of 1a–b was accomplished by BBr3, yielding bis(phosphino)hydroquinones 2a–b. Treating 2a–b with excess hydrogen peroxide produced bis(phosphinyl)hydroquinones 3a–b. The binucleating properties of 2a were established by the formation of a bimetallic nickel complex upon reaction with Ph2Ni(PMe3)2. Electrochemical activity of hydroquinones 2a–b and 3a–b was examined by cyclic voltammetry. In addition, compounds 2a, 3a and 3b were obtained in crystalline form and characterized by single-crystal X-ray diffraction. The influence of the fluorine substituents on the composition of the frontier orbitals of 2a and 3a was examined by computational methods. 相似文献
83.
Louis Marchildon 《Foundations of Physics》2004,34(1):59-73
In a recently proposed interpretation of quantum mechanics, U. Mohrhoff advocates original and thought-provoking views on space and time, the definition of macroscopic objects, and the meaning of probability statements. The interpretation also addresses a number of questions about factual events and the nature of reality. The purpose of this note is to examine several issues raised by Mohrhoff's interpretation, and to assess whether it helps providing solutions to the long-standing problems of quantum mechanics. 相似文献
84.
AbstractIn strongly alkaline media ([OH?]?≥?0.12 M), nicotinamide (nica) forms a complex with square-planar Ag(OH)4? [nica]?≥?0.05 M. The complex decomposes in seconds to nicotinamide N-oxide. The correlation of maximum absorbance of the complex with concentrations of nicotinamide and hydroxide requires that the complex is either the five-coordinate Ag(OH)4(H-1nica)2? or the six-coordinate Ag(OH)5(nica)2?. Comparison with the reactions of Ag(OH)4? with nicotinate ion (nic?) and acetamide under similar conditions indicates that nicotinamide coordinates with Ag(OH)4? by the amido group rather than the nitrogen on the pyridine ring or the amido oxygen. Kinetics of the Ag(III)-nica redox reaction are consistent with direct reaction between nicotinamide and uncoordinated Ag(OH4)?. Oxidation takes place at the pyridine ring, yielding nicotinamide N-oxide. Silver(III) is reduced to monovalent silver. 相似文献
85.
Louis P. Lee Daniel J. Cole Mike C. Payne Chris‐Kriton Skylaris 《Journal of computational chemistry》2013,34(6):429-444
First principles electronic structure calculations are typically performed in terms of molecular orbitals (or bands), providing a straightforward theoretical avenue for approximations of increasing sophistication, but do not usually provide any qualitative chemical information about the system. We can derive such information via post‐processing using natural bond orbital (NBO) analysis, which produces a chemical picture of bonding in terms of localized Lewis‐type bond and lone pair orbitals that we can use to understand molecular structure and interactions. We present NBO analysis of large‐scale calculations with the ONETEP linear‐scaling density functional theory package, which we have interfaced with the NBO 5 analysis program. In ONETEP calculations involving thousands of atoms, one is typically interested in particular regions of a nanosystem whilst accounting for long‐range electronic effects from the entire system. We show that by transforming the Non‐orthogonal Generalized Wannier Functions of ONETEP to natural atomic orbitals, NBO analysis can be performed within a localized region in such a way that ensures the results are identical to an analysis on the full system. We demonstrate the capabilities of this approach by performing illustrative studies of large proteins—namely, investigating changes in charge transfer between the heme group of myoglobin and its ligands with increasing system size and between a protein and its explicit solvent, estimating the contribution of electronic delocalization to the stabilization of hydrogen bonds in the binding pocket of a drug‐receptor complex, and observing, in situ, the n → π* hyperconjugative interactions between carbonyl groups that stabilize protein backbones. © 2012 Wiley Periodicals, Inc. 相似文献
86.
Huang W Todaro L Yap GP Beer R Francesconi LC Polenova T 《Journal of the American Chemical Society》2004,126(37):11564-11573
Vanadium environments in Keggin oxopolytungstates were characterized by (51)V solid-state MAS NMR spectroscopy. (C(4)H(9))(4)N(+)-, K(+)-, Cs(+)-, as well as mixed Na(+)/Cs(+)- salts of the mono-, di-, and trivanadium substituted oxotungstates, [VW(11)O(40)](4-), [V(2)W(10)O(40)](5-), and [V(3)W(9)O(40)](6-), have been prepared as microcrystalline and crystalline solids. Solid-state NMR spectra report on the local environment of the vanadium site in these Keggin ions via their anisotropic quadrupolar and chemical-shielding interactions. These (51)V fine structure constants in the solid state are determined by the number of vanadium atoms present in the oxoanion core. Surprisingly, the quadrupolar anisotropy tensors do not depend to any significant extent on the nature of the countercations. On the other hand, the chemical-shielding anisotropy tensors, as well as the isotropic chemical shifts, display large variations as a function of the cationic environment. This information can be used as a probe of the local cationic environment in the vanadium-substituted Keggin solids. 相似文献
87.
Bianconi PA Joray SJ Aldrich BL Sumranjit J Duffy DJ Long DP Lazorcik JL Raboin L Kearns JK Smulligan SL Babyak JM 《Journal of the American Chemical Society》2004,126(10):3191-3202
The synthesis of poly(hydridocarbyne), one of a class of carbon-based random network polymers and a structural isomer of polyacetlyene, is reported. The network backbone of this polymer is primarily composed of tetrahedrally hybridized carbon atoms, each bearing one hydride substituent and linked via three carbon-carbon single bonds into a three-dimensional random network of fused rings. This atomic-level carbon network backbone confers unusual properties on the polymer, including facile thermal decomposition to form diamond or diamond-like carbon high-quality films at atmospheric pressure, by direct deposition or by chemical vapor deposition (CVD), without the use of hydrogen or any other reagent. 相似文献
88.
Harrak Y Blaszykowski C Bernard M Cariou K Mainetti E Mouriès V Dhimane AL Fensterbank L Malacria M 《Journal of the American Chemical Society》2004,126(28):8656-8657
5-En-1-yn-3-ol substrates bearing a free hydroxyl group or an acyl group are highly versatile partners for PtCl2-catalyzed cycloisomerizations. Electrophilic activation of the alkyne moiety triggers at wish a hydride or an O-acyl migration yielding at the end to regioisomeric keto derivatives. The efficient preparation of Sabina ketone, an important monoterpene precursor, has been worked out. 相似文献
89.
Hussain F Bassil BS Kortz U Kholdeeva OA Timofeeva MN de Oliveira P Keita B Nadjo L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(17):4733-4742
The dititanium-containing 19-tungstodiarsenate(III) [Ti(2)(OH)(2)As(2)W(19)O(67)(H(2)O)](8-) (1) has been synthesized and characterized by IR, TGA, elemental analysis, electrochemistry, and catalytic studies. Single-crystal X-ray analysis was carried out on Cs(8)[Ti(2)(OH)(2)As(2)W(19)O(67)(H(2)O)].2CsCl.12H(2)O (Cs-1), which crystallizes in the monoclinic system, space group P2(1)/m, with a=12.7764(19), b=19.425(3), c=18.149(3) A, beta=110.234(3) degrees, and Z=2. Polyanion 1 comprises two (B-alpha-As(III)W(9)O(33)) Keggin moieties linked through an octahedral {WO(5)(H(2)O)} fragment and two unprecedented square-pyramidal {TiO(4)(OH)} groups, leading to a sandwich-type structure with nominal C(2v) symmetry. Synthesis of 1 was accomplished by reaction of TiOSO(4) and K(14)[As(2)W(19)O(67)(H(2)O)] in a 2:1 molar ratio in aqueous, acidic medium (pH 2). Polyanion 1 could also be isolated as a tetra-n-butyl ammonium (TBA) salt, {(n-C(4)H(9))(4)N}(5)H(3)[Ti(2)(OH)(2)As(2)W(19)O(67)(H(2)O)] (TBA-1). TBA-1 was studied by cyclic voltammetry in acetonitrile (MeCN) solutions containing 0.1 M LiClO(4) and compared with the results obtained with Cs-1 in aqueous media. In MeCN, the Ti(IV) and W(VI) waves could not be separated distinctly. An important adsorption phenomenon on the glassy carbon working electrode was encountered both in cyclic voltammetry and in controlled potential electrolysis and was confirmed by Electrochemical Quartz Crystal Microbalance (EQCM) studies on a carbon film. TBA-1, dissolved in MeCN, reacts with H(2)O(2) to give peroxo complexes stable enough for characterization by UV-visible spectroscopy, cyclic voltammetry, and EQCM. TBA-1 shows high catalytic activity (TOF=11.3 h(-1)) in cyclohexene oxidation with aqueous H(2)O(2) producing products typical of a heterolytic oxidation mechanism. The stability of TBA-1 under turnover conditions was confirmed by using IR, UV-visible spectroscopy as well as cyclic voltammetry. 相似文献
90.
Water-soluble carbosilane dendrimers protect phosphorothioate oligonucleotides from binding to serum proteins 总被引:3,自引:0,他引:3
Chonco L Bermejo-Martín JF Ortega P Shcharbin D Pedziwiatr E Klajnert B de la Mata FJ Eritja R Gómez R Bryszewska M Muñoz-Fernandez MA 《Organic & biomolecular chemistry》2007,5(12):1886-1893
Treatment of dendriplexes formed between water-soluble carbosilane dendrimers and phosphorothioate oligodeoxynucleotides (ODN) with the anionic detergent sodium dodecyl sulfate disrupted the complexes indicating that the nature of the union in such dendriplexes is merely electrostatic. However, dendriplexes were not dissociated by serum proteins like bovine or human serum albumins, as assessed by gel electrophoresis and fluorescence experiments. This would imply a dendrimer-mediated protective effect able to prevent ODN interactions with serum proteins and additionally could translate into a reduction of the ODN doses needed to achieve the biological effects. The employment of carbosilane dendrimers as carriers may solve the problem of ODN kidnapping by plasmatic proteins as a key drawback for therapeutics involving ODNs. As examples, transfection processes on normal primary peripheral blood cells and diagnosis of HIV infection in the presence of serum have been assayed. 相似文献