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Experimental dipole moments of a number of the title compounds are given and theoretical dipole moments have been calculated by vector addition for all possible conformations. The graphical method has been used to correlate experimental and calculated dipole moments. The more probable conformation in solution of the title compounds and especially of the imide group is proposed. 相似文献
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M. J. Tornaritis A. G. Coutsolelos 《Journal of polymer science. Part A, Polymer chemistry》1992,30(13):2791-2795
Polyene polymers [natural rubber (cis-polyisoprene), trans-polyisoprene, and cis-polybutadiene] were transformed to the corresponding polyepoxides which are a polyalcohol and soap precursor. The catalysts used were chloro- or acetato-manganese(III) tetraphenylporphyrin [MnIII(TPP)Cl or MnIII(TPP)OAc] in association with two different oxygen donors, sodium hypochloride and iodosylbenzene (Por, unspecified porphyrinato ligand; TPP, 5,10,15,20-tetraphenylporphyrinato ligand). This transformation in either biphasic system, H2O(aqua)-CH2Cl2 or PhIO(solid)-CH2Cl2, was monitored by 1H-NMR and IR spectroscopy. In both cases the transformation to the polyepoxide was completed within a few hours. © 1992 John Wiley & Sons, Inc. 相似文献
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A New Approach for the Photosynthetic Antenna–Reaction Center Complex with a Model Organized Around an s‐Triazine Linker 下载免费PDF全文
Susanne Kuhri Dr. Georgios Charalambidis Prof. Panagiotis A. Angaridis Prof. Theodore Lazarides Dr. Georgia Pagona Dr. Nikos Tagmatarchis Prof. Dr. Athanassios G. Coutsolelos Prof. Dr. Dirk M. Guldi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(7):2049-2057
Two new artificial mimics of the photosynthetic antenna‐reaction center complex have been designed and synthesized (BDP‐H2P‐C60 and BDP‐ZnP‐C60). The resulting electron‐donor/acceptor conjugates contain a porphyrin (either in its free‐base form (H2P) or as Zn‐metalated complex (ZnP)), a boron dipyrrin (BDP), and a fulleropyrrolidine possessing, as substituent of the pyrrolidine nitrogen, an ethylene glycol chain terminating in an amino group C60‐X‐NH2 (X=spacer). In both cases, the three different components were connected by s‐triazine through stepwise substitution reactions of cyanuric chloride. In addition to the facile synthesis, the star‐type arrangement of the three photo‐ and redox‐active components around the central s‐triazine unit permits direct interaction between one another, in contrast to reported examples in which the three components are arranged in a linear fashion. The energy‐ and electron‐transfer properties of the resulting electron‐donor/acceptor conjugates were investigated by using UV/Vis absorption and emission spectroscopy, cyclic voltammetry, and femtosecond transient absorption spectroscopy. Comparison of the absorption spectra and cyclic voltammograms of BDP‐H2P‐C60 and BDP‐ZnP‐C60 with those of BDP‐H2P, BDP‐ZnP and BDP‐C60, which were used as references, showed that the spectroscopic and electrochemical properties of the individual constituents are basically retained, although some appreciable shifts in terms of absorption indicate some interactions in the ground state. Fluorescence lifetime measurements and transient absorption experiments helped to elucidate the antenna function of BDP, which upon selective excitation undergoes a rapid and efficient energy transfer from BDP to H2P or ZnP. This is then followed by an electron transfer to C60, yielding the formation of the singlet charge‐separated states, namely BDP‐H2P .+‐ C60 .? and BDP‐ZnP .+‐ C60 . ?. As such, the sequence of energy transfer and electron transfer in the present models mimics the events of natural photosynthesis. 相似文献
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Summary A method of calculating the separated flow of a viscous fluid is proposed, which allows to split up properly the boundary condition problem from the viscous phenomena. The theory is developed for the flow past a plate and yields wakes of finite extension having an underpressure which depends directly on the amount of vorticity diffusion and dissipation occurring in the fluid. Application of the method to real flows shows good agreement between the calculated and the measured velocity distributions in front of the plate and in the wake.
Résumé Une méthode de calcul de l'écoulement décollé d'un fluide visqueux est proposée qui permet de séparer clairement le problème aux limites des phénomènes visqueux. La théorie est développée pour l'écoulement autour d'une plaque et donne des sillages de longueur finie ayant une dépression de culot directement dépendante de l'intensité de la diffusion et dissipation de la vorticité se produisant dans le fluide. L'application de la méthode à des écoulements réels montre une bonne concordance entre les répartitions de vitesse calculées et mesurées sur le devant de la plaque et dans le sillage.相似文献
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MA Freitas CL Hendrickson AG Marshall 《Rapid communications in mass spectrometry : RCM》1999,13(15):1639-1642
We present a novel approach for the determination of activation energy for the unimolecular dissociation of a large (>50 atoms) ion, based on measurement of the unimolecular dissociation rate constant as a function of continuous-wave CO(2) laser intensity. Following a short ( approximately 1 s) induction period, CO(2) laser irradiation produces an essentially blackbody internal energy distribution, whose 'temperature' varies inversely with laser intensity. The only currently available method for measuring such activation energies is blackbody infrared radiative dissociation (BIRD). Compared with BIRD, FRAGMENT: (a) eliminates the need to heat the surrounding ion trap and vacuum chamber to each of several temperatures (each requiring hours for temperature equilibration); (b) offers a three-fold wider range of effective blackbody temperature; and (c) extends the range of applications to include initially cold ions (e.g., gas-phase H/D exchange). Our FRAGMENT-determined activation energy for dissociation of protonated bradykinin, 1.2 +/- 0.1 eV, agrees within experimental error to the value, 1.3 +/- 0.1 eV, previously reported by Williams et al. from BIRD experiments. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
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Ioannis D. Kostas Athanassios G. Coutsolelos Georgios Charalambidis 《Tetrahedron letters》2007,48(38):6688-6691
For the first time, a palladium complex with a porphyrin ligand is used as a catalyst precursor for cross-coupling reactions. The synthesis of a palladium complex with a phosphine-free and water-soluble potassium carboxylate salt of a porphyrin, and its evaluation in the Suzuki-Miyaura reaction of phenylboronic acid with aryl bromides (from electron-rich to electron-poor), in neat water, under aerobic conditions is described. Catalysis is performed at 100 °C for 4 h, using K2CO3 as base, and a substrate to catalyst molar ratio of 1000:1, leading to yields of coupling products in the range of 80-100%. The catalyst can be recycled and reused, but unfortunately, with a loss in activity. 相似文献
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