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91.
The formal treatment of the diffusion-controlled growth of n binary compounds with narrow homogeneity range during the reaction of a sphere of reactant A immersed in reactant B is presented and discussed. Both constituents are assumed to be mobile. The reaction products are assumed to grow simultaneously as uniform and compact concentric layers with ideal contact at the interfaces as well as at the external surface of the sphere. The kinetic equations follow from the coupling between chemical reactions and partitioning of the diffusion flux at phase boundaries. The results for the formation of two and three compounds are presented. The influence of the initial radius of the sphere, of the relative magnitude of the kinetic constants, and of the volume variation is discussed in detail. 相似文献
92.
We tell the tale of the first writing of a partial transpose, without guaranteeing historical authenticity.
Dedicated to Prof. Asher Peres, Haifa, on the occasion of his 70th birthday. 相似文献
93.
Schreiner E Nicolini C Ludolph B Ravindra R Otte N Kohlmeyer A Rousseau R Winter R Marx D 《Physical review letters》2004,92(14):148101
The temperature-dependent behavior of a solvated oligopeptide, GVG(VPGVG), is investigated. Spectroscopic measurements, thermodynamic measurements, and molecular dynamics simulations find that this elastinlike octapeptide behaves as a two-state system that undergoes an "inverse temperature" folding transition and reentrant unfolding close to the boiling point of water. A molecular picture of these processes is presented, emphasizing changes in the dynamics of hydrogen bonding at the protein/water interface and peptide backbone librational entropy. 相似文献
94.
Busacca CA Grossbach D Campbell SJ Dong Y Eriksson MC Harris RE Jones PJ Kim JY Lorenz JC McKellop KB O'Brien EM Qiu F Simpson RD Smith L So RC Spinelli EM Vitous J Zavattaro C 《The Journal of organic chemistry》2004,69(16):5187-5195
The Boehringer-Ingelheim phosphinoimidazoline (BIPI) ligands were applied to the formation of chiral quaternary centers in the asymmetric Heck reaction. Several different substrates were examined in detail, using more than 70 members of this new ligand class. Hammett relationships were determined through systematic variation of the ligand electronics. All substrates showed essentially the same Hammett behavior, where enantioselectivity increased as the ligands were made more electron-deficient. Ligand optimization has led to catalysts which give the highest enantioselectivities reported to date for these difficult systems. 相似文献
95.
The oxidation chemistry of 17beta-estradiol (1) is of central relevance to the nongenomic effects of estrogens and offers valuable prospects in the search for novel steroidal scaffolds of academic and industrial interest. Herein, we report the results of a detailed investigation into the nature of the oligomer products formed by phenolic oxidation of 1. Of the oxidants tested, the peroxidase/H2O2 system proved to be the most effective in inducing conversion of 1 to a complex mixture of oligomer species. Repeated chromatographic fractionation followed by extensive 2D NMR and mass spectrometric analysis allowed identification of a series of phenolic coupling products comprising, besides the C2-symmetric dimers 2 and 3, a 2,4' dimer (4), two O-linked dimers (5, 6), and the novel trimers 7-9. All 4-linked biphenyl-type oligomers, i.e., 3 and 7-9, occurred as couples of atropoisomers, reflecting steric hindrance at biphenyl linkages. For all atropoisomers, absolute configuration was established by the exciton chirality method and the interconversion energy was determined by dynamic NMR. These results provide the first systematic inventory of oxidative coupling products of 1 and lay the foundation for future studies aimed to develop novel estrogen derivatives based on oligomeric scaffolds. 相似文献
96.
Dionigi C Nozar P Di Domenico D Calestani G 《Journal of colloid and interface science》2004,275(2):445-449
In this paper we propose a simple model for the formation of monodisperse polymer colloids, which provides a convenient set of synthetic parameters for given bead diameters. We provide experimental data in support of this model. 相似文献
97.
Mimmi MC Gullotti M Santagostini L Battaini G Monzani E Pagliarin R Zoppellaro G Casella L 《Dalton transactions (Cambridge, England : 2003)》2004,(14):2192-2201
The dinuclear and trinuclear Cu(II) complexes of an octadentate ligand derived from (S)-1,1'-binaphthyl-2,2'-diamine have been prepared and characterized by UV/Vis, CD, EPR and NMR spectroscopy. The ligand contains two tridentate aminobis(benzimidazole) donor arms connected to a central bidentate diaminobinaphthyl linker, which hosts the chiral unit. In the dinuclear Cu complex the ligation occurs essentially within the tridentate arms of the ligand. The two Cu centers are EPR nonequivalent and noninteracting. The EPR data suggests that one of the Cu ions additionally interacts with one of the tertiary aminonaphthyl donors. In the trinuclear complex the two aminonaphthyl donors bind the third Cu ion. The EPR spectrum of this complex shows the signal for a mononuclear Cu(II) center bound to a tridentate arm, while the remaining two Cu(II) centers are coupled through hydroxo groups. The CD spectrum shows that in the free ligand a severe reduction of the dihedral angle between the naphthyl groups from the strain free range occurs. This conformation is stabilized by ring stacking interactions with the benzimidazole groups. On complex formation this interaction is removed because the benzimidazole groups are involved in metal binding. In the dinuclear Cu complex the conformation of the binaphthyl chromophore probably approaches the strain free range, while in the trinuclear Cu complex a marked flattening of the dihedral angle between the two naphthyl rings occurs. Both complexes are active catalysts in the oxidation of L-/D-Dopa derivatives to quinones. High enantioselectivity is observed in the oxidation of L-/D-Dopa methyl ester catalyzed by the dinuclear Cu complex, which exhibits strong preference for the d enantiomer. The enantioselectivity is largely lost for the trinuclear Cu complex. 相似文献
98.
We study the entanglement properties of the output state of a universal cloning machine. We analyse in particular bipartite and tripartite entanglement of the clones, and discuss the classical limit of infinitely many output copies. 相似文献
99.
The study of the transport mechanisms connected to solid-liquid interactions is fundamental in the determination of the extension of the pollution of a site and in the evaluation of the best remediation process to be applied. The sorption of hydrophobic ionizable organic contaminants from the groundwaters is supervised not only by the physico-chemical properties of soil and pollutants, but also by the groundwaters pH, which deeply influences their solubility in the aqueous media, and consequently their transport mechanisms in the aquifer. In this work an experimental study of the sorption of phenol and 2-nitrophenol on two soils, different in particle-size distribution, CEC and organic carbon content, was realized. The sorption potential of the soils was evaluated by means of a physical, mineralogical and chemical characterization. The experimental data coming from some batch tests, performed at pH values equal to 4, 7 and 10 were fitted by means of linear, Freundlich and Langmuir isotherms models. The soil-contaminants interaction mechanisms that influence the isotherms shapes were then analyzed and discussed, and a comparison between the theoretical and experimental values of the partitioning coefficient KD was performed. 相似文献
100.
Cossu S Cimenti C Peluso P Paulon A De Lucchi O 《Angewandte Chemie (International ed. in English)》2001,40(21):4086-4089