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21.
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
22.
Vincenzo Santagada Ferdinando FiorinoElisa Perissutti Beatrice SeverinoSara Terracciano Giuseppe CirinoGiuseppe Caliendo 《Tetrahedron letters》2003,44(6):1145-1148
A novel and convenient microwave-assisted dimerization of an active peptide compound using the DKPs as scaffold is described. The key reaction giving rise to the diketopiperazine scaffold is the intermolecular coupling. No epimerization was detected in the reactions used. Conventional and microwave heating of the reactions are compared. Synthesis by microwave irradiation gave the desired compounds in higher yields and in shorter reaction times than those obtained by conventional heating. 相似文献
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24.
Giuseppe Coppola Andrea Irace Giovanni Breglio Mario Iodice Luigi Zeni Antonello Cutolo Pasqualina M. Sarro 《Optics and Lasers in Engineering》2003,39(3):317-332
In this paper we describe two different kind of optoelectronic devices both based on a three terminals active device and exploit the plasma dispersion effect to achieve the desired working. The first device exploits this effect in order to obtain an optical modulation. The second device is an optoelectronic router based on the mode-mixing principle together with the injection-induced optical phase shift. Both devices are integrated into a Silicon on Silicon optical channel waveguide which can be realized using a standard bipolar process. The possibility of using standard, well-known technology presents several advantages with respect to III–V Optoelectronics. The active three terminal device used is a Bipolar Mode Field Effect Transistor (BMFET). Numerical simulation results are presented on both devices. 相似文献
25.
The paper deals with the riskiness analysis for a large portfolio of life annuities. By means of the limiting distribution of the present value of the portfolio, in the first part of the paper a model for evaluating the investment and the projection risks is presented. In the second part, with regard to the investment risk's effects, the insolvency risk is measured considering the cumulative probability distribution function of the discounted average cost per policy. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
26.
R. Pizzoferrato L. Lagonigro T. Ziller A. Di Carlo R. Paolesse F. Mandoj A. Ricci C. Lo Sterzo 《Chemical physics》2004,300(1-3):217-225
We study the infrared emission at 1.54 μm of an organolanthanide complex, Er(III)-tetraphenylporphyrin [Er(TPP)acac], both as a result of direct optical excitation and via energy transfer from host π-conjugate polymers of type poly(arylene–ethynylene) [PAE]. In the first case, the emission of the neat complex is characterized in inert transparent materials and a value of the quantum yield at 1.54 μm φIR=4×10−4 is measured. Then, fluorescence resonance transfer is investigated in blends of Er(TPP)acac with PAEs by monitoring the quenching of the polymer fluorescence along with the enhancement of both the visible emission of the ligand and the near-infrared band of Er3+. These different procedures allow a detailed analysis of the transfer efficiency within a specific implementation of the Förster model for polymeric donors. The experimental values of the critical radius R0, ranging from 1.3 to 2.5 nm for the different blends, are in good agreement with theory for a wide interval of the physical and spectroscopic parameters. This suggests that other mechanisms for excitation transfer do not play a significant role in these materials. 相似文献
27.
Rendiconti del Circolo Matematico di Palermo Series 1 - 相似文献
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Alberto Plaza Sonia Piacente Angela Perrone Arafa Hamed Cosimo Pizza Giuseppe Bifulco 《Tetrahedron》2004,60(52):12201-12209
Stemmosides C and D, two novel pregnane glycosides characterized by an unusual C-17 side chain were isolated from the pericarps of Solenostemma argel. In addition, stemmoside D displays an uncommon 14β proton configuration, apparently being the first pregnane isolated from plants known to have a 15 keto, cis CD ring junction. Their structures have been established by ESIMS and NMR experiments. The relative configuration of the molecules was determined using a strategy based on the simulation of 1H, 13C, and J coupling NMR parameters. DFT calculations of 1H and 13C chemical shifts, and of the 1H homonuclear spin–spin coupling constants were performed with the mPW1PW91 functional using the 6-31G(d,p) basis set on the fully optimized geometries of all the possible stereoisomers. 相似文献
30.