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31.
T.A. Ford 《Journal of Molecular Spectroscopy》1975,58(2):185-193
The infrared (from 4000 to 100 cm?1) and Raman spectra of CH2I2 and CD2I2 have been recorded in the liquid and gaseous phases. Assignments have been made for all observed bands and, in the case of CH2I2, compared with those previously reported. Some bands appearing in the CD2I2 spectrum have been attributed to the presence of CHDI2. The wavenumbers of the fundamental bands of CHDI2 have been calculated from those of CH2I2 and CD2I2 using Brodersen and Langseth's rule, and compared with those observed in the CD2I2 spectrum. 相似文献
32.
Zolleis KR Ford CJ Kardynal B Ritchie DA Linfield EH Rose PD Jones GA 《Physical review letters》2002,89(14):146803
The tunneling current between an electron gas with a periodic potential in two dimensions and a plain two-dimensional electron system (2DES) has been studied. The strength of the periodic potential, the subband energy of the plain 2DES, and an applied in-plane magnetic field were varied, mapping the Fourier transform of the periodic wave function. Periodic peaks were observed and explained by translations in the reciprocal lattice. When the potential was strongly modulated to form an array of antidots, commensurability peaks were seen in lateral transport, but, as expected, not in tunneling. 相似文献
33.
Guldi DM Rahman GM Qin S Tchoul M Ford WT Marcaccio M Paolucci D Paolucci F Campidelli S Prato M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(8):2152-2161
Dispersible single-walled carbon nanotubes grafted with poly(4-vinylpyridine), SWNT-PVP, were tested in coordination assays with zinc tetraphenylporphyrin (ZnP). Kinetic and spectroscopic evidence corroborates the successful formation of a SWNT-PVPZnP nanohybrid. Within this SWNT-PVPZnP nanohybrid, static electron-transfer quenching (2.0+/-0.1) x 10(9) s(-1) converts the photoexcited-ZnP chromophore into a radical-ion-pair state with a microsecond lifetime, namely one-electron oxidized-ZnP and reduced-SWNT. 相似文献
34.
This investigation is concerned with modeling the evaporation, or decay, of n-nonane molecular clusters. We use a unique cluster decay model that was first developed to estimate the decay time scale of argon clusters using molecular-dynamics simulations. In this study we seek to enhance the model so that it represents a more complex cluster decay dynamic, suitable for n-nonane clusters. Experimental measurements of nucleation rates of n-nonane droplets have been used to deduce the rate at which a molecule escapes from the cluster. Typically for an n-nonane cluster containing 40 molecules, at an experimental temperature of 225 K, the empirical decay time, which is the inverse of the decay rate, is estimated to be 50 ns. For this time scale, the direct observation of n-nonane cluster decay from a molecular-dynamics trajectory is not feasible, since decay events are so rare. However, the cluster decay model uses a combination of molecular dynamics and stochastic dynamics in order to resolve the problem associated with long decay time scales. The model is based on a Langevin treatment that views cluster decay as single-particle escape from a confining potential of mean force. It is used to predict kinetic decay times of n-nonane clusters. We discover this result differs significantly from a classically derived decay time scale determined from a continuum thermodynamic treatment of the population balance equations of clusters. However, the dynamically generated results obtained from the kinetic decay model compare more favorably than the classical results with the empirical decay times that are deduced from experimental measurements of n-nonane clusters. 相似文献
35.
Ford WE Yasuda A Wessels JM 《Langmuir : the ACS journal of surfaces and colloids》2008,24(7):3479-3485
Coprecipitation of urea-melt modified carbon nanotubes and calcium carbonate from an aqueous solution by two methods yielded microcrystalline composite particles. Powders obtained by colloidal crystallization from a supersaturated solution that were isolated and dried soon after precipitation were a mixture of raspberry-shaped and rhombohedral particles. These were shown by infrared and X-ray diffraction analyses to be mainly calcite. Particles that were kept wet for 1 day or longer before being isolated were typically entirely rhombohedral with edge lengths in the range of 5-30 microm. Scanning electron microscopy investigations revealed that the nanotubes were adsorbed on the particle surface and also incorporated into the interior matrix. Removal of the calcium carbonate component by treating the particles with acid yielded nanotube shells whose size and shape reflected those of the original particles. 相似文献
36.
A series of nitrosyl tris(5,10,15-aryl)corrolate complexes of iron(III) Fe(Ar3C)(NO) with different substituents on the aryl groups have been prepared, and certain spectroscopic and reaction properties were compared. The cyclic voltammetric analysis of the various Fe(Ar3C)(NO) complexes demonstrated that both the one-electron oxidation and one-electron reduction potentials respond in systematic and nearly identical trends relative to the electron-donor properties of the substituents. A similar pattern was seen in the nitrosyl stretching frequency, nu(NO), which modestly decreased with the stronger donor substituents. Flash photolysis of Fe(Ar3C)(NO) solutions in toluene leads to NO dissociation followed by rapid [NO]-dependent decay of the transients formed (presumably Fe(Ar3C)) to regenerate the original spectra. As was seen in an earlier flash photolysis study of Fe(TNPC)(NO) (TNPC3- = 5,10,15-tris(4-nitro-phenyl)corrolate; Joseph, C.; Ford, P. C. J. Am. Chem. Soc. 2005, 127, 6737-6743), the second-order rate constants, k(NO), are all much faster ((1-9) x 10(8) M(-1) s(-1) at 298 K) than those for analogous iron(III) complexes of porphyrins. However, on a more microscopic level there is no obvious pattern in these rates with respect to the donor properties of the aryl ring substituents. The high reactivity of the ferric triarylcorrolates with NO data is interpreted in terms of the strongly electron-donating character of the Ar3C3- ligand and the quartet electronic configuration of the Fe(Ar3C) intermediate. 相似文献
37.
Density functional calculations at the B3LYP/6-311+G(2d,p)//pBP/DN level predict all cationic adducts combining guanine, at either its N2, O6, N7, or C8 positions, with phenylnitrenium ion, at either its N, 2, or 4 positions, to be lower in energy than the separated reactants. This relative stability of all adducts is preserved after addition of aqueous solvation free energies computed at the SM2 level, although some leveling of the adduct relative energies one to another is predicted. Cations having the lowest relative energies in solution correspond structurally to those adducts most commonly found when guanine reacts with larger, biologically relevant nitrenium ions in vitro and in vivo. One of these, the N-C8 adduct, is stabilized both by a rearomatized phenyl ring and by the operation of an anomeric effect not found in any of the others. On the basis of energetic analysis, direct conversion of an N-N7 cation to an N-C8 cation according to a previously proposed mechanism is unlikely; however, an alternative rearrangement converting a 2-N7 cation to an N-C8 cation via the intermediacy of a five-membered ring may be operative in nitrenium ions with aromatic frameworks better able than phenyl to stabilize endocyclic cationic charge. 相似文献
38.
39.
Grape stilbenes are a well-known family of plant polyphenolics that have been confirmed to have many biological activities in relation to health benefits. In the present study, we investigated the effect of methyl jasmonate (MeJA) elicitor at four different concentrations (25, 50, 100 and 200 μM) in combination or not with high-level light irradiation (10,000 LUX) on a cell line obtained from the pulp of Vitis vinifera cv. Shahani. Our results showed that the stilbene synthesis pathway is inhibited by high-light conditions. A concentration of 50 μM MeJA was optimum for efficient production and high accumulation of total phenolics and total flavonoids as well as total stilbenoids. Furthermore, we showed that there is a significant negative correlation between the production of these metabolites and cell growth. These data provide valuable information for the future scale-up of cell cultures for the production of these very high value compounds in bioreactor system. 相似文献
40.
Graham E. O'Mahony Kevin S. Eccles Robin E. Morrison Alan Ford Simon E. Lawrence Anita R. Maguire 《Tetrahedron》2013
Steric and electronic effects in the copper-catalysed asymmetric oxidation of aryl benzyl, aryl alkyl and alkyl benzyl sulfides have been investigated. The presence of an aryl group directly attached to the sulfur is essential to afford sulfoxides with high enantioselectivities, with up to 97% ee for 2-naphthyl benzyl sulfoxide, the highest enantioselectivity achieved to date for copper-catalysed asymmetric sulfoxidation. In contrast, the benzyl substituent can be replaced by sterically comparable groups with no effect on enantioselectivity. Copper-mediated oxidation of substituted aryl benzyl sulfides display modest steric and electronic effects resulting in comparable or lower enantioselectivities to those obtained with the unsubstituted benzyl phenyl sulfide. 相似文献