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51.
Optical activity, used here for the first time to gain information about the amorphous solid state, allows previously unavailable insight into the dynamic properties of polymer glasses and their effect on a chemical process. This is accomplished by dispersing in polymer glasses atropisomeric bridged binaphthyls with appended oligophenyl paddles of varying sizes and studying the racemization kinetics as a function of temperature. The racemization occurs by a simple one-dimensional twisting motion and, without effect on the intrinsic mechanism, sweeps out a variable volume of the matrix as the paddle length is increased. The racemization is limited by the polymer matrix only for probes with a minimum paddle size and only when the time scale for racemization is comparable to the time scale for segmental motion of the polymer matrix. The high barrier for this racemization is unique in probe studies of glasses and causes these overlapping time scales to occur significantly below the glass transition temperature. These measurements yield a clear quantitative view of the role of segmental dynamics on the racemization kinetics of the binaphthyls and allow the important demonstration, via the transition from first-order to stretched exponential kinetics, that heterogeneous dynamics persist deep within the glassy state. 相似文献
52.
M. W. Brandt J. E. Mulvaney H. K. Hall G. D. Green 《Journal of polymer science. Part A, Polymer chemistry》1989,27(6):1957-1965
7,8-Dicyano-7,8-diphenylquinodimethane (DCDPQ) was prepared by oxidation of the dianion of α,α′-dicyano-α,α′-diphenylxylene. 1H-NMR of a solution of the purified compound showed that the cis and trans isomers were present in a 1:1 ratio. Following further spectroscopic and electronic characterization the polymerizability of the title compound was investigated. DCDPQ did not homopolymerize at 65°C in the presence of AIBN. DCDPQ copolymerized with p-methoxystyrene and p-aminostyrene in the presence of AIBN at 65°C. Characterization of the latter two copolymers indicated that they were nearly alternating. The copolymerization between DCDPQ and p-aminostyrene proceeded in the absence of AIBN. 相似文献
53.
Abstract —Using semi-empirical analytic formulas for the transmitted and scattered ultraviolet spectral irradiance at the ground (Green, A. E. S., T. Sawada and E. P. Shettle, Photochem. Photobiol. 19 , 251–259, 1974), we calculate erythema dose rates and daily erythema doses. Results are illustrated graphically, and for the purpose of photobiological applications are given in terms of approximate analytic forms, with parameters presented in tabular form. The relative erythema data assembled by W. W. Coblentz and R. Stair (U.S. Bureau of Standards J. Res. 12 , 13–14, 1934), as fit by an analytic form, is taken as a standard spectrum in our calculations. Other forms of erythema spectra are also compared. 相似文献
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Several varieties of blue ballpoint pen inks were analyzed by high performance liquid chromatography (HPLC) and infrared spectroscopy (IR). The chromatographic data extracted at four wavelengths (254, 279, 370 and 400 nm) was analyzed individually and at a combination of these wavelengths by the soft independent modeling of class analogies (SIMCA) technique using principal components analysis (PCA) to estimate the separation between the pen samples. Linear discriminant analysis (LDA) measured the probability with which an observation could be assigned to a pen class. The best resolution was obtained by HPLC using data from all four wavelengths together, differentiating 96.4% pen pairs successfully using PCA and 97.9% pen samples by LDA. PCA separated 60.7% of the pen pairs and LDA provided a correct classification of 62.5% of the pens analyzed by IR. The results of this study indicate that HPLC coupled with chemometrics provided a better discrimination of ballpoint pen inks compared to IR. The need to develop a suitable IR method for analysing blue ballpoint pen inks has been emphasized and it is hoped that the development of such a method would indeed provide a valuable tool for the non-destructive analysis of blue ballpoint pen ink samples for forensic purposes. 相似文献
56.
Laser projection-patterned etching of GaAs in a HCl and CH3Cl atmosphere performed using a pulsed KrF-excimer laser (=248 nm, =15 ns) and deep-UV projection optics (resolution 2 m) is reported. The etching process carried out in a vacuum system having a base pressure of 10–6 mbar is shown to result from a purely thermochemical reaction. Etching takes place in two steps: (i) between the laser pulses, the etchant gas reacts with the GaAs surface-atomic layer to form chlorination products (mainly As and Ga monochlorides), (ii) local laser surface heating results in the desorption of these products allowing further reaction of the gas with the surface. The influence of the etching parameters (laser energy density, gas pressure and pulse repetition rate) on the etch rate and the morphology of the etched features was studied. Etch rates up to 0.15 nm per pulse, corresponding to the removal of 0.5 GaAs molecular layer, are achieved. The spatial resolution of the etching process is shown to be controlled by the heat spread in the semiconductor and by the nonlinear dependence of the etch rate on the surface temperature. As a result, etched features smaller or larger than the projected features of the photomask are achieved depending on the laser energy density. Etched lines having a width of 1.3 m were obtained at low fluences by the projection of 2 m wide lines onto the GaAs surface. 相似文献
57.
Ahlen S Ambrosio M Antolini R Auriemma G Baker R Baldini A Bam BB Barbarino GC Barish BC Battistoni G Bellotti R Bemporad C Bernandini P Bilokon H Bisi V Bloise C Bower C Bussino S Cafagna F Calicchio M Campana D Campana P Carboni M Cecchini S Cei F Chiarella V Cormack R Corona A Coutu S De Cataldo G Dekhissi H De Marzo C De Vincenzi M Di Credico A Diehl E Erriquez O Favuzzi C Ficenec D Forti C Fusco P Giacomelli G Giannini G Giglietto N Giubellino P Grassi M Green P Grillo A Guarino F 《Physical review letters》1994,72(5):608-612
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It is geometrically feasible to insert metal-metal-bonded M(4) tetrahedra and M(6) octahedra into the tetrahedral and octahedral holes, respectively, of the fcc C(60) lattice. The electronic structure of the hypothetical tetrahedral variants C(60)(M(4))(2), M = Rh, Co, is analyzed with approximate molecular orbital methods and band structure calculations. These compounds feature M-M and M-C(60) bonding and a variable degree of electron transfer to or from C(60). The C(60)(M(4))(2) phases should be metallic, but we have no way of predicting if they will be superconducting. A number of discrete molecular tetrahedral cluster compounds which serve as models for the solid state materials are analyzed. There is a clear indication that tetranuclear and even mononuclear Rh, Ir, and Co arene complexes should be relatively unstable. 相似文献