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31.
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
32.
We have carried out a systematic study of N(2)O dissociation on a TiO(2) (110) surface by means of plane-wave pseudopotential density-functional theory calculations. We have made use of both static and dynamic calculations in order to elucidate N(2)O decomposition mechanisms. We find that dissociation is not favorable on the stoichiometric surface. On the other hand, the presence of oxygen bridging vacancies make the N(2)O decomposition possible. The role of the defective surface is to provide electrons to the adsorbed molecule. We find two channels for decomposition, depending on whether the molecule is adsorbed with the O or the N end of the molecule on a vacancy. The first case is energetically downhill and proceeds spontaneously, leading to N(2) ejection from the surface and vacancy oxidation. The second case relies on the formation of an intermediate bridging configuration of the adsorbed molecule and is hindered by a small energy barrier. In this case, molecule breaking produces N(2) in the gas phase and leaves oxygen adatoms on the surface. We relate our results to recent experimental findings. 相似文献
33.
Brown SP Pérez-Torralba M Sanz D Claramunt RM Emsley L 《Journal of the American Chemical Society》2002,124(7):1152-1153
A new method for detecting hydrogen bonds in the solid state is presented. Using two-dimensional NMR correlation experiments, it is shown that a hydrogen-bond mediated J coupling can be observed in a powder under magic-angle spinning conditions, even though the J coupling is 2 orders of magnitude smaller than the dominant anisotropic interactions encountered in solid-state NMR. Specifically, the observation of a pair of peaks in a two-dimensional 15N-15N solid-state INADEQUATE experiment due to two nitrogens that have no covalent connectivity is attributed to the presence of a J coupling across a linking hydrogen bond. 相似文献
34.
M. A. Sanz N. Granizo M. Gradzielski M. M. Rodrigo M. Valiente 《Colloid and polymer science》2005,283(6):646-652
We have made a comparative study between the micellar regions of the octyl -d-glucoside (OG)–tetraethylene glycol monododecyl ether and the OG–poly(ethylene glycol) 20,000 systems by means of surface tension and viscosimetric measurements. The incorporation of the tetraethylene glycol monododecyl ether nonionic surfactant in the OG micelles decreases the critical micelle concentration, whereas the presence of polymer increases it. The nonionic surfactant mixture exhibits nonideal mixing behaviour. The data fit to Rubinghs treatment with a value of –5.1, which implies a modest attraction between both surfactants. The surfactant–poly(ethylene glycol) 20,000 system does not form mixed micelles. The incorporation of polymer increases the critical micelle concentration of the surfactant. The viscosity for the surfactant–polymer system is higher than that for the pure polymer, demonstrating a surfactant-induced structuring. 相似文献
35.
The melting temperature of ice I(h) for several commonly used models of water (SPC, SPC/E,TIP3P,TIP4P, TIP4P/Ew, and TIP5P) is obtained from computer simulations at p = 1 bar. Since the melting temperature of ice I(h) for the TIP4P model is now known [E. Sanz, C. Vega, J. L. F. Abascal, and L. G. MacDowell, Phys. Rev. Lett. 92, 255701 (2004)], it is possible to use the Gibbs-Duhem methodology [D. Kofke, J. Chem. Phys. 98, 4149 (1993)] to evaluate the melting temperature of ice I(h) for other potential models of water. We have found that the melting temperatures of ice I(h) for SPC, SPC/E, TIP3P, TIP4P, TIP4P/Ew, and TIP5P models are T = 190 K, 215 K, 146 K, 232 K, 245 K, and 274 K, respectively. The relative stability of ice I(h) with respect to ice II for these models has also been considered. It turns out that for SPC, SPC/E, TIP3P, and TIP5P the stable phase at the normal melting point is ice II (so that ice I(h) is not a thermodynamically stable phase for these models). For TIP4P and TIP4P/Ew, ice I(h) is the stable solid phase at the standard melting point. The location of the negative charge along the H-O-H bisector appears as a critical factor in the determination of the relative stability between the I(h) and II ice forms. The methodology proposed in this paper can be used to investigate the effect upon a coexistence line due to a change in the potential parameters. 相似文献
36.
37.
P. Cabildo R.M. Claramunt D. Sanz M.C. Foces-Foces F. Hernandez Cano J. Catalan J. Elguero 《Tetrahedron》1985,41(2):473-478
Crystal structures of 1-(1-adamantyl)pyrazole, 1a, and 1-(1-adamantyl-3-ol)-4-nitropyrazole, 2a, have been solved by X-ray analysis. The space groups and cell parameters are P21, a, 7.4021(3), b, 10.7529(5),c, 6.9651(2)Å, β, 90.206(3)° for 1a with Z = 2 and P2/n, a, 31.1172(14), b, 6.8506(1), c, 12.0313(3)Å, β 94.873(3)° for 2a with Z = 8. Refinements were carried out down to R values of 0.043 (Rw, = 0.046) and 0.079 (Rw = 0.061) for the 951 (2σ(I)) and 2461 (3σ(I)) observed reflections respectively. The conformation about the bond between the heterocycle and the carbocycle is discussed on theoretical grounds INDO calculations): the adamantane behaves as a free rotor. The stcricinteractions of the adamantyl residue with the methyl substituents in 2- and 5-position of pyrazole are apparent in the C-13 chemical shifts. 相似文献
38.
1H NMR spectra corresponding to H2 adsorption on high-surface Rh/CeO2 catalysts (S(BET) approximately 55 m2/g) are formed by two lines, attributed to hydrogen adsorbed on ceria (resonance line A) and rhodium-metal particles (upfield-shifted line B). The evolution of 1H NMR spectra as a function of temperature, time, and type of reduction (static or dynamic) allows the study of the progressive establishment of the strong metal-support interaction (SMSI) in Rh/CeO2 catalysts. As the reduction progresses, the mean adsorption heat and the amount of hydrogen adsorbed on the metal, deduced from volumetry, NMR, and calorimetry techniques, decrease considerably. As a consequence of the decrease in metal activity, the amount of hydrogen transferred to the support CeO2 is also reduced (spill-over processes). Outgassing of samples at 773 K eliminates hydrogen species retained at the metal-support surface, and oxidation treatments at 473 and 673 K eliminate the electronic effect and physical blocking of metal particles. The oxidation at 673 K recuperates the total adsorption capacity of metal particles. On the basis of these treatments, the contribution of different processes to the SMSI effect is analyzed. Electronic perturbation of rhodium particles is higher when reductions are performed in dynamic conditions; however, the importance of physical blocking of metal particles increases in static reductions. High reducibility of ceria strengthens electronic effects in Rh/CeO2 compared to those observed in Rh/TiO2 catalysts. 相似文献
39.
Maria-Agustina Rossi Veronica Martinez Philip Hinchliffe Maria F. Mojica Valerie Castillo Diego M. Moreno Ryan Smith Brad Spellberg George L. Drusano Claudia Banchio Robert A. Bonomo James Spencer Alejandro J. Vila Graciela Mahler 《Chemical science》2021,12(8):2898
Infections caused by multidrug resistant (MDR) bacteria are a major public health threat. Carbapenems are among the most potent antimicrobial agents that are commercially available to treat MDR bacteria. Bacterial production of carbapenem-hydrolysing metallo-β-lactamases (MBLs) challenges their safety and efficacy, with subclass B1 MBLs hydrolysing almost all β-lactam antibiotics. MBL inhibitors would fulfil an urgent clinical need by prolonging the lifetime of these life-saving drugs. Here we report the synthesis and activity of a series of 2-mercaptomethyl-thiazolidines (MMTZs), designed to replicate MBL interactions with reaction intermediates or hydrolysis products. MMTZs are potent competitive inhibitors of B1 MBLs in vitro (e.g., Ki = 0.44 μM vs. NDM-1). Crystal structures of MMTZ complexes reveal similar binding patterns to the most clinically important B1 MBLs (NDM-1, VIM-2 and IMP-1), contrasting with previously studied thiol-based MBL inhibitors, such as bisthiazolidines (BTZs) or captopril stereoisomers, which exhibit lower, more variable potencies and multiple binding modes. MMTZ binding involves thiol coordination to the Zn(ii) site and extensive hydrophobic interactions, burying the inhibitor more deeply within the active site than d/l-captopril. Unexpectedly, MMTZ binding features a thioether–π interaction with a conserved active-site aromatic residue, consistent with their equipotent inhibition and similar binding to multiple MBLs. MMTZs penetrate multiple Enterobacterales, inhibit NDM-1 in situ, and restore carbapenem potency against clinical isolates expressing B1 MBLs. Based on their inhibitory profile and lack of eukaryotic cell toxicity, MMTZs represent a promising scaffold for MBL inhibitor development. These results also suggest sulphur–π interactions can be exploited for general ligand design in medicinal chemistry.Metallo-β-lactamases (MBLs) are major culprits of resistance to carbapenems in bacteria. A series of thiazolidines are potent MBL inhibitors, restoring the activity of carbapenems. Metal binding and sulphur–π interactions are key to inhibition. 相似文献
40.