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141.
Molecular electroactive monolayers have been produced from vinylferrocene (VFC) via light-assisted surface anchoring to H-terminated n- and p-Si(1 0 0) wafers prepared via wet chemistry, in a controlled atmosphere. The resulting Si-C bound hybrids have been characterized by means of XPS and AFM. Their performance as semiconductor functionalized electrodes and their surface composition have been followed by combining electrochemical and XPS measurements on the same samples, before and after use in an electrochemical cell. White-light photoactivated anchoring at short (1 h) exposure times has resulted in a mild route, with a very limited impact on the initial quality of the silicon substrate. In fact, the functionalized Si surface results negligibly oxidized, and the C/Fe atomic ratio is close to the value expected for the pure molecular species. The VFC/Si hybrids can be described as (η5-C5H5)Fe2+(η5-C5H4)-CH2-CH2-Si species, on the basis of XPS results. Electrochemical methods have been applied in order to investigate the role played by a robust, covalent Si-C anchoring mode towards substrate-molecule electronic communication, a crucial issue for a perspective development of molecular electronics devices. The response found from cyclic voltammograms for p-Si(1 0 0) functionalized electrodes, run in the dark and under illumination, has shown that the electron transfer is not limited by the number of charge carriers, confirming the occurrence of electron transfer via the Si valence band. The hybrids have shown a noticeable electrochemical stability and reversibility under cyclic voltammetry (cv), and the trend in peak current intensity vs. the scan rate was linear. The molecule-Si bond is preserved even after thousands of voltammetric cycles, although the surface coverage, evaluated from cv and XPS, decreases in the same sequence. An increasingly larger surface concentration of Fe3+ at the expenses of Fe2+ redox centers has been found at increasing number of cv’s, experimentally associated with the growth of silicon oxide. Surface SiO groups from deprotonated silanol termination, induced by the electrochemical treatments, are proposed as the associated counterions for the Fe3+ species. They could be responsible for the observed decrease in the electron transfer rate constant with electrode ageing.  相似文献   
142.
    
The diversity of products in the reaction of diethyl azodicarboxylate (DEAD)/diisopropyl azodicarboxylate (DIAD) and activated acetylenes with PIII compounds bearing oxygen or nitrogen substituents is discussed. New findings that are useful in understanding the nature of intermediates involved in the Mitsunobu reaction are highlighted. X-ray structures of two new compounds (2-t-Bu-4-MeC6H3O)P (μ-N-t-Bu)2P+[(NH-t-Bu)N[(CO2]-i-Pr)(HNCO2-i-Pr)]](Cl-)(2-t-Bu-4-MeC6H3OH)(23)and [CH2(6-t-Bu-4-Me-C6H2O)2P(O)C(CO2Me)C-(CO2Me)CClNC(O)Cl] (33) are also reported. The structure of23 is close to one of the intermediates proposed in the Mitsunobu reaction.  相似文献   
143.
A nonlinear (in the cubic approximation) relaxation equation of state is derived for a rod containing cracks partially filled with an incompressible viscous liquid. The nonlinear effects of the self-action and interaction of low-and high-frequency longitudinal elastic waves propagating in such a rod are studied for the cases of identical and size-varied cracks. Linear and nonlinear acoustic parameters characterizing the self-action and interaction of elastic waves in a cracked rod are determined.  相似文献   
144.
The dynamics of the photoinduced differential absorption and excited-state bleaching spectra of single-walled carbon nanotubes suspended in a micellar solution were studied in the spectral range from 40 to 1000 nm within a time interval from 70 fs to 150 ps under excitation by 50-fs pulses with photon energies 2 and 4 eV. The bleaching and absorption bands were observed in the spectra; the positions of the bleaching peaks were independent of the photon energy of the exciting femtosecond pulse in the range 2–4 eV. It was established that, for delay times shorter than 1 ps, the shape of the differential spectrum of excited nanotubes coincided with the shape of the second derivative of the absorption spectrum of unexcited nanotubes in the frequency range of exciting pulse above 18000 cm?1 (the range of absorption bands of metallic nanotubes). In the frequency range below 16000 cm?1 (the range of absorption peaks of semiconducting nanotubes), the bleaching peaks in the differential spectrum of excited nanotubes undergo a high-frequency shift of 200–300 cm?1 with respect to the second-derivative spectrum of unexcited nanotubes. The excited-state relaxation rate constants were measured. They are well approximated by the exponential dependences and depend on the probe-pulse wavelength. An assumption was made about the nature of the observed spectra of excited nanotubes and about the excitation relaxation.  相似文献   
145.
By using a novel free-flying, rotating, optical bench aboard the International Space Station (ISS) as the basis for a measurement of differential acceleration between two gravitating bodies, in principle the Newtonian inverse-square law and the constant of gravitation, G, can be determined at the parts in 106 level.  相似文献   
146.
Equivalent acoustic source characterization of duct-borne fluid machinery noise is often undertaken by interpolating the results of two-microphone pressure measurements with different external acoustic loads over a linear one-port source model. If the source is time-invariant, the one-port source characteristics can be determined by using only two external loads. This is well known as the two-load method. An extension of the two-load method for time-variant sources is also available and known as the multiple-load method. In these methods the source is treated as a ‘black-box’. This paper addresses the problem of one-port source characterization when the linear operations inherent in the ‘black-box’ are known explicitly. The equations governing the explicit one-port source models are derived and the source characteristics are shown to be measurable using only few acoustic loads. It is not the purpose of this paper to discuss the application of these models to any specific fluid machinery; however, of particular interest are the explicit source models that require only two loads. Numerical results are presented to show some features of such time-invariant and time-variant explicit one-port source models.  相似文献   
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