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51.
52.
Ortiz W Krueger BP Kleiman VD Krause JL Roitberg AE 《The journal of physical chemistry. B》2005,109(23):11512-11519
We present a theoretical investigation of energy transfer in the phenylene ethynelene dendrimer known as the nanostar. Data from extensive molecular dynamics simulations are used to model the dynamical effects caused by torsional motion of the phenyl groups. We compare rate constants for energy transfer between the two-ring chromophore and the three-ring chromophore obtained via the F?rster model, the ideal dipole approximation (IDA), and the transition density cube (TDC) method, which has as its limit an exact representation of the Coulombic coupling. We find that the rate constants obtained with the TDC are extremely sensitive to the phenyl group rotation, whereas the constants computed with the F?rster model and the IDA are not. The implications of these results for the interpretation of recent pump-probe experiments on the nanostar are discussed in detail. Finally, we predict the temperature dependence of the rate constant for energy transfer. 相似文献
53.
We propose an alternative new material (2,4,5-trifluoroimidazole impregnated Nafion) for use as a high-temperature, water-free membrane for proton-exchange membrane fuel cells. This material has been tested computationally using molecular dynamics and quantum mechanics techniques, leading to an estimated conductivity of approximately 0.06 S/cm at 177 degrees C. This material overcomes the weakness of the imidazole-impregnated membranes, i.e., the poisoning of the Pt electrode. We find that 2,4,5-trifluoroimidazole binds weakly to platinum surfaces, so poisoning is not expected. 相似文献
54.
Amendola V Mangano C Pallavicini P 《Dalton transactions (Cambridge, England : 2003)》2004,(18):2850-2854
Three-component systems made of a tetradentate bis-amino bis-quinoline ligand, a transition metal cation (Ni2+ or Cu2+) and a fluorescent indicator (Coumarin 343) have been studied in a water-dioxane (1 : 4 v/v) mixture, through potentiometric, pH-spectrophotometric and pH-fluorimetric titrations. For the Cu2+ containing systems, an "on-off-on" variation of fluorescence intensity vs. pH has been observed, whereas in the presence of Ni2+ a simple "on-off" profile of the fluorescence intensity vs. pH was obtained. These ternary systems thus behave as window-shaped or conventional pH-indicators, depending whether Cu2+ or Ni2+ is used as the cation. 相似文献
55.
Fernandez YD Gramatges AP Amendola V Foti F Mangano C Pallavicini P Patroni S 《Chemical communications (Cambridge, England)》2004,(14):1650-1651
A new approach based on self-assembly inside micelles has been individuated to prepare a system behaving as a water-operating selective fluorescent sensor for Cu2+ and Ni2+. 相似文献
56.
Busico V Van Axel Castelli V Aprea P Cipullo R Segre A Talarico G Vacatello M 《Journal of the American Chemical Society》2003,125(18):5451-5460
The 150 MHz (13)C NMR microstructural analysis of polypropylene samples produced with two representative "oscillating" metallocene catalysts of largely different steric hindrance, namely [(2-(3,5-di-tert-butyl-4-methoxyphenyl)indenyl)(2)ZrP](+) and [(2-phenylindenyl)(2)ZrP](+) (P = polymeryl), and the implications on the origin of the stereocontrol are presented and discussed in detail. The original mechanistic proposal of an "oscillation" between a rac-like (isotactic-selective) and a meso-like (nonstereoselective) conformation cannot explain the observed polymer configuration. The isotactic-stereoblock nature of the polymers obtained with the former catalyst proves unambiguously that the active cation "oscillates" between the two enantiomorphous rac-like conformations at an average frequency that, even at high propene concentration, is only slightly lower than that of monomer insertion. The less-hindered [(2-phenylindenyl)(2)ZrP](+) gives instead a largely stereoirregular polypropylene, which is the logical consequence of a faster ligand rotation; however, depending on the use conditions (in particular, on the nature of the cocatalyst and the polarity of the solvent), the polymerization products may also contain appreciable amounts of a fairly isotactic fraction. The peculiar microstructure of this fraction, with isotactic blocks of the same relative configuration spanned by very short atactic ones, rules out the possibility that the latter are due to an active species in meso-like conformation and points rather to a conformationally "locked" rac-like species with restricted ring mobility. The hypothesis of a stereorigidity induced by the proximity to a counteranion, which would play the role of the interannular bridge in the rac-bis(indenyl) ansa-metallocenes, was tested by computer modeling on a [rac-(2-phenylindenyl)(2)ZrMe(C(3)H(6))][B(C(6)F(5))(4)] ion couple and found viable. 相似文献
57.
58.
Valeria Angeli Simona Biagi Silvia Ghimenti Massimo Onor Alessandro D'Ulivo Emilia Bramanti 《Spectrochimica Acta Part B: Atomic Spectroscopy》2011,66(11-12):799-804
Monomethylmercury and ethylmercury were determined on line using flow injection-chemical vapor generation atomic fluorescence spectrometry without neither requiring a pre-treatment with chemical oxidants, nor UV/MW additional post column interface, nor organic solvents, nor complexing agents, such as cysteine. Inorganic mercury, monomethylmercury and ethylmercury were detected by atomic fluorescence spectrometry in an Ar/H2 miniaturized flame after sodium borohydride reduction to Hg0, monomethylmercury hydride and ethylmercury hydride, respectively. The effect of mercury complexing agent such as cysteine, ethylendiaminotetracetic acid and HCl with respect to water and Ar/H2 microflame was investigated.The behavior of inorganic mercury, monomethylmercury and ethylmercury and their cysteine-complexes was also studied by continuous flow-chemical vapor generation atomic fluorescence spectrometry in order to characterize the reduction reaction with tetrahydroborate. When complexed with cysteine, inorganic mercury, monomethylmercury and ethylmercury cannot be separately quantified varying tetrahydroborate concentration due to a lack of selectivity, and their speciation requires a pre-separation stage (e.g. a chromatographic separation). If not complexed with cysteine, monomethylmercury and ethylmercury cannot be separated, as well, but their sum can be quantified separately with respect to inorganic mercury choosing a suitable concentration of tetrahydroborate (e.g. 10? 5 mol L? 1), thus allowing the organic/inorganic mercury speciation.The detection limits of the flow injection-chemical vapor generation atomic fluorescence spectrometry method were about 45 nmol L? 1 (as mercury) for all the species considered, a relative standard deviation ranging between 1.8 and 2.9% and a linear dynamic range between 0.1 and 5 μmol L? 1 were obtained. Recoveries of monomethylmercury and ethylmercury with respect to inorganic mercury were never less than 91%. Flow injection-chemical vapor generation atomic fluorescence spectrometry method was validated by analyzing the TORT-1 certificate reference material, which contains only monomethylmercury, and obtaining 83 ± 5% of monomethylmercury recovered, respectively. This method was also applied to the determination of monomethylmercury in saliva samples. 相似文献
59.
Siraye E. Debebe Desta A. Gedefaw Wendimagegn Mammo Teketel Yohannes Francesca Tinti Alberto Zanelli Valeria Fattori Nadia Camaioni 《Journal of polymer science. Part A, Polymer chemistry》2011,49(12):2693-2699
The synthesis and characterization of a novel polythiophene substituted with a 2′‐pentyloxy‐5′‐(1″′‐oxooctyl) phenyl group (PPOPT) is reported. The bulk transport properties of thin films of PPOPT are investigated by admittance spectroscopy. The dramatic effect of the phenyl side chain on the mobility of positive carriers in films of PPOPT is described. The photophysics of PPOPT in both solution and thin film is also investigated and correlated to substituent‐driven intrachain and interchain arrangements. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
60.
Valerio Annovazzi-Lodi Giuseppe Aromataris Mauro Benedetti Michael Hamacher Sabina Merlo Valeria Vercesi 《Optical and Quantum Electronics》2010,42(3):143-156
In this paper, we numerically evaluate private data transmission using a three-laser scheme, consisting of a pair of twin
semiconductor lasers, driven to chaos by delayed optical feedback in a short cavity, and optically injected by a third chaotic
laser which forces them to synchronize. This laser is selected with different internal parameters with respect to the twin
pair, so that the emissions of the synchronized, matched lasers, are highly correlated, whereas their correlation with the
driver is low. The digital message modulates the emission of the transmitter, as in a standard Chaos Modulation scheme. Message
recovery is then obtained by subtracting, from the transmitted chaos-masked message, the chaos, locally generated by the synchronized
receiver laser. Simulations have been performed with the Lang-Kobayashi model, and, in view of application to private transmission,
we have investigated the effect of the parameter mismatch, between transmitter and receiver, on message recovery. A preliminary
experimental evaluation has been also performed using specially designed InP integrated modules. 相似文献