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461.
Goldsmith RH DeLeon O Wilson TM Finkelstein-Shapiro D Ratner MA Wasielewski MR 《The journal of physical chemistry. A》2008,112(19):4410-4414
The temperature dependence of intramolecular charge separation in a series of donor-bridge-acceptor molecules having phenothiazine (PTZ) donors, 2,7-oligofluorene FL(n) (n = 1-4) bridges, and perylene-3,4:9,10-bis(dicarboximide) (PDI) acceptors was studied. Photoexcitation of PDI to its lowest excited singlet state results in oxidation of PTZ via the FL(n) bridge. In toluene, the temperature dependence of the charge separation rate constants for PTZ-FL(n)-PDI, (n = 1-4) is relatively weak and is successfully described by the semiclassical Marcus equation. The activation energies for charge separation suggest that bridge charge carrier injection is not the rate limiting step. The difficulty of using temperature and length dependence to differentiate hopping and superexchange is discussed, with difficulties in the latter topic explored via an extension of a kinetic model proposed by Bixon and Jortner. 相似文献
462.
Pavone M Cimino P Crescenzi O Sillanpää A Barone V 《The journal of physical chemistry. B》2007,111(30):8928-8939
The role of stereoelectronic, environmental, and short-time dynamic effects in tuning the hyperfine and gyromagnetic tensors of a prototypical nitroxide spin probe has been investigated by an integrated computational approach based on extended Lagrangian molecular dynamics and discrete-continuum solvent models. Trajectories were generated in two protic solvents as well as in the gas phase for reference; structural analysis of the dynamics, and comparison with optimized solute-solvent clusters, allowed for the identification of the prevailing solute-solvent hydrogen-bonding patterns and helped to define the strategy for the computation of magnetic parameters. This was performed in a separate step, on a large number of frames, by a high-level DFT approach coupling the PBE0 hybrid functional with a tailored basis set and with proper account of specific and bulk solvent effects. Remarkable changes in solvation networks are found on going from aqueous to methanol solution, thus providing a rationalization of indirect experimentally available evidence. The computed magnetic parameters are in satisfactory agreement with the available measured values and allow for an unbiased evaluation of the role of different effects in tuning the overall EPR observables. Apart from their intrinsic interest, our results pave the route toward the development of tunable detection protocols based on specific spectroscopic signatures. 相似文献
463.
The Cl‐atom‐initiated oxidation of two esters, ethyl formate [HC(O)OCH2CH3] and ethyl acetate [CH3C(O)OCH2CH3], has been studied at pressures close to 1 atm as a function of temperature (249–325 K) and O2 partial pressure (50–700 Torr), using an environmental chamber technique. In both cases, Cl‐atom attack at the CH2 group is most important, leading in part to the formation of radicals of the type RC(O)OCH(O?)CH3 [R = H, CH3]. The atmospheric fate of these radicals involves competition between reaction with O2 to produce an anhydride compound, RC(O)OC(O)CH3, and the so‐called α‐ester rearrangement that produces an organic acid, RC(O)OH, and an acetyl radical, CH3C(O). For both species studied, the α‐ester rearrangement is found to dominate in air at 1 atm and 298 K. Barriers to the rearrangement of 7.7 ± 1.5 and 8.4 ± 1.5 kcal/mole are estimated for CH3C(O)OCH(O?)CH3 and HC(O)OCH(O?)CH3, respectively, leading to increased occurrence of the O2 reaction at reduced temperature. The data are combined with those obtained from similar studies of other simple esters to provide a correlation between the rate of occurrence of the α‐ester rearrangement and the structure of the reacting radical. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 397–413, 2010 相似文献
464.
The photoemission properties of fluorescent chromophores have a widespread application in many fields ranging from chemical-physics and biology to organic light emitting devices. These systems usually display high fluorescence conversion efficiency, which makes them suitable for transient/gain experiments also in liquid solutions, thin films and eventually in protein environments.Pump and probe methods have been widely employed for wavelength-resolved spectroscopy in the subpicosecond time scale. In our group, we have recently assembled a new experimental setup for pump and probe spectroscopy: preliminary tests on the Rhodamine B dye in ethanol have been performed in order to optimize the setup. The dynamic response of photoinduced changes of the chromophore dispersed into a suitable solvent has been studied with a subpicosecond time resolution.The optically prepared initial state of the Rhodamine B in ethanol solution appears to evolve on a timescale of few picoseconds into a successive state, which could be attributed to an intramolecular charge transfer state. 相似文献
465.
A simple and highly selective electrochemical method was developed for the single or simultaneous determination of paracetamol (N-acetyl-p-aminophenol, acetaminophen) and caffeine (3,7-dihydro-1,3,7-trimethyl-1H-purine-2,6-dione) in aqueous media (acetate buffer, pH 4.5) on a boron-doped diamond (BDD) electrode using square wave voltammetry (SWV) or differential pulse voltammetry (DPV). Using DPV with the cathodically pre-treated BDD electrode, a separation of about 550 mV between the peak oxidation potentials of paracetamol and caffeine present in binary mixtures was obtained. The calibration curves for the simultaneous determination of paracetamol and caffeine showed an excellent linear response, ranging from 5.0 × 10−7 mol L−1 to 8.3 × 10−5 mol L−1 for both compounds. The detection limits for the simultaneous determination of paracetamol and caffeine were 4.9 × 10−7 mol L−1 and 3.5 × 10−8 mol L−1, respectively. The proposed method was successfully applied in the simultaneous determination of paracetamol and caffeine in several pharmaceutical formulations (tablets), with results similar to those obtained using a high-performance liquid chromatography method (at 95% confidence level). 相似文献
466.
Determination of the chemical oxygen demand (COD) using a copper electrode: a clean alternative method 总被引:1,自引:0,他引:1
Claudineia R. Silva Cleone D. C. Conceição Viviane G. Bonifácio Orlando Fatibello Filho Marcos F. S. Teixeira 《Journal of Solid State Electrochemistry》2009,13(5):665-669
A clean alternative method for the determination of chemical oxygen demand (COD) was developed using a copper electrode as
an electrocatalytic sensor. The measuring principle is based on oxidation current of organic compounds in the wastewater.
The effects of important experimental conditions, such as electrolytic solution concentration and potential scan rate, on
analytical performance have been investigated. Analytical linear range of 53.0–2,801.4 mg l−1 COD with detection limit of 20.3 mg l−1 COD was achieved. The procedure was successfully applied to the COD determination in wastewater from soft industries. The
results obtained using the proposed method were in good agreement with those obtained using the conventional (i.e., dichromate)
COD method. In this fashion, the COD value of a sample can be determined in a simple, rapid, accurate manner, and the end
products do not contain toxic metals. 相似文献
467.
Liana Alvares Rodrigues Tiago Moreira Bastos Campos Manoel Orlando Alvarez-Mendes Aparecido dos reis Coutinho Kumiko Koibuchi Sakane Gilmar Patrocínio Thim 《Journal of Sol-Gel Science and Technology》2012,63(2):202-210
Carbon xerogel (CX) was used for phenol adsorption from aqueous solution. CX was synthesized by sol?Cgel polycondensation of resorcinol with formaldehyde using sodium carbonate (Na2CO3) as catalyst. Then, it was dried by convective drying technique and pyrolyzed under inert atmosphere. Phenol adsorption kinetics was very fast, what was attributed to the presence of open pore structure. The kinetic studies showed that the adsorption process could be fitted to a pseudo-second-order model and the particle diffusion process is the rate-limiting step of the adsorption. The phenol removal was maximum and unaffected by pH changes when the initial pH of the phenol solution was in the range of 3?C8. The optimum adsorbent dose obtained for phenol adsorption onto CX was 0.075?g/50?cm3 solution. The Langmuir model described the adsorption process better than the Freundlich isotherm model and the monolayer adsorption capacity is 32?mg?g?1. Among the desorbing solutions used in this study, the most efficient desorbent was EtOH (100?%) which released about 87?% of phenol bound with the CX. 相似文献
468.
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470.
A flow-injection turbidimetric procedure exploiting merging zones is proposed for determining homatropine methylbromide (HMB) in pharmaceutical preparations. The determination is based on the precipitation reaction of homatropine methylbromide with silicotungstic acid in acidic medium to form a precipitate, which was measured at 410 nm. The analytical curve was linear in the HMB concentration range from 8.1 × 10−5 to 2.2 × 10−4 mol l−1, with a detection limit of 5.0 × 10−6 mol l−1. The recoveries ranged from 96 to 103%, the sampling frequency was 70 determinations per hour and relative standard deviations were less than 1.5% (n = 10). The results obtained for commercial formulations using the FIA procedure were in good agreement with those obtained by using a comparative method. 相似文献