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91.
Lauceri R Fasciglione GF D'Urso A Marini S Purrello R Coletta M 《Journal of the American Chemical Society》2008,130(32):10476-10477
Kinetics of the porphyrin aggregation leading to a chiral memory system shows a remarkable "catalytic" effect of the noncovalent templates explaining their self-replication ability. 相似文献
92.
Rinaldo M. Colombo Helge Holden 《Zeitschrift für Angewandte Mathematik und Physik (ZAMP)》2016,67(5):131
In this paper we study isentropic flow in a curved pipe. We focus on the consequences of the geometry of the pipe on the dynamics of the flow. More precisely, we present the solution of the general Cauchy problem for isentropic fluid flow in an arbitrarily curved, piecewise smooth pipe. We consider initial data in the subsonic regime, with small total variation about a stationary solution. The proof relies on the front-tracking method and is based on [1]. 相似文献
93.
94.
Baya M Houghton J Daran JC Poli R Male L Albinati A Gutman M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(19):5347-5359
Complexes [MoCp(#)(PMe(3))(2)H(3)] (Cp(#)=1,2,4-C(5)H(2)tBu(3), 2 a; C(5)HiPr(4), 2 b) have been synthesized from the corresponding compounds [MoCp(#)Cl(4)] (1 a, 1 b) and fully characterized, including by X-ray crystallography and by a neutron diffraction study for 2 a. Protonation of 2 a led to complex [Mo(1,2,4-C(5)H(2)tBu(3))(PMe(3))(2)H(4)](+) (3 a) in THF and to [Mo(1,2,4-C(5)H(2)tBu(3))(PMe(3))(2)(MeCN)H(2)](+) (4 a) in MeCN. Complex 4 b analogously derives from protonation of 2 b in MeCN, whereas the tetrahydride complex 3 b is unstable. One-electron oxidation of 2 a and 2 b by [FeCp(2)]PF(6) produces the EPR-active 17-electron complexes 2 a(+) and 2 b(+). The former is thermally more stable than the latter and could be crystallographically characterized as the PF(6) (-) salt by X-ray diffraction, providing evidence for the presence of a stretched dihydrogen ligand (H...H=1.36(6) angstroms). Controlled thermal decomposition of 2 a(+) yielded the product of H(2) elimination, the 15-electron monohydride complex [Mo(1,2,4-C(5)H(2)tBu(3))(PMe(3))(2)H]PF(6) (5 a), which was characterized by X-ray crystallography and by EPR spectroscopy at liquid He temperature. The compound establishes an equilibrium with the solvent adduct in THF. An electrochemical study by cyclic voltammetry provides further evidence for a rapid H(2) elimination process from the 17-electron complexes. In contrast to the previously investigated [MoCp*(dppe)H(3)](+) system (dppe=1,2-bis(diphenylphosphino)ethane; Cp*=pentamethylcyclopentadienyl), the decomposition of 2 a(+) by H(2) substitution with a solvent molecule appears to follow a dissociative pathway in MeCN. 相似文献
95.
Svistunenko DA Reeder BJ Wankasi MM Silaghi-Dumitrescu RL Cooper CE Rinaldo S Cutruzzolà F Wilson MT 《Dalton transactions (Cambridge, England : 2003)》2007,(8):840-850
Myoglobin (Mb) from gastropod mollusc Aplysia limacina shows only 20% sequence homology to the 'prototype' sperm whale Mb but exhibits a typical Mb fold and can reversibly bind oxygen. An intriguing feature of aplysia Mb is that it lacks the distal histidine and displays a ligand stabilisation based on an arginine. Here we report the reaction of aplysia metMb with hydrogen peroxide studied by optical and electron paramagnetic resonance (EPR) spectroscopies. Two electron oxidation of the protein by H2O2 results in formation of two intermediates typical for this class of reactions, the oxoferryl haem state and a globin-bound free radical. An unusual characteristic of the aplysia Mb reaction is formation, prior to haem oxidation, of an optically distinct compound with an EPR spectrum typical of the low spin Fe3+ haem state. This compound is interpreted as the complex between H2O2 and the ferric haem state (Compound), formed prior to cleavage of the dioxygen bond. We conclude that H2O2 is singly deprotonated in Compound which can thus be notated as [Fe3+--OOH]. A new low spin ferric haem state has been observed over the period of Compound decay, and hypotheses have been formulated as to its identity and role. The location of the protein bound radical observed in aplysia Mb is discussed in light of the fact that the protein does not have any tyrosine residues, the most common site of free radical formation in the haem protein/peroxide systems. All intermediates of the reaction are kinetically characterised. 相似文献
96.
The solutions of the dfferential equation Lnx + a0(t)x = 0, where Ln is a disconjugate operator and a0 is of one sign, are studied according to their behavior as t → ∞. We prove equivalence theorems between solutions of this equation and its adjoint in terms of property A and property B. These theorems generalize the results known for n = 3 and for odd order binomial equations. Some applications are given too. 相似文献
97.
Barbara DeSantis AnnaLaura Iamiceli RinaldoMarini Bettolo LuisaMaria Migneco Rita Scarpelli Giorgio Cerichelli Giancarlo Fabrizi Doriano Lamba 《Helvetica chimica acta》1998,81(12):2375-2387
The factors responsible for the diastereoselective formation of the 6-endo-hydroxybicyclo[2.2.2]octan-2-one by acid-catalyzed intramolecular aldol reaction of 3-oxocyclohexaneacetaldehydes have been investigated. This study, carried out on (1SR,4RS,6RS)-6-hydroxybicyclo[2.2.2]octan-2-one 1a , (1SR,4RS,6SR)-6-hydroxybicyclo[2.2.2]octan-2-one 1b , and 3,3-(ethylenedioxy)cyclohexaneacetaldehyde 2a , allowed to demonstrate the absence of intramolecular H-bonding in 1a as a stabilizing factor, and to ascertain the presence of unfavorable steric interactions in 1b . 相似文献
98.
Rinaldo M. Colombo 《PAMM》2003,3(1):20-23
The terms phase transitions have been used since some years in the trafic modeling literarure to label a set of recurrent phenomena experimentally observed. This talk aims at the presentation of a system of p.d.e.s that models these phenomena, within the framework provided by phase transitions in systems of hyperbolic conservation laws. 相似文献
99.
Austin Nevin Daniela Comelli Iacopo Osticioli Lucia Toniolo Gianluca Valentini Rinaldo Cubeddu 《Analytical and bioanalytical chemistry》2009,395(7):2139-2149
The assessment of the influence of natural and artificial ageing on the spectrofluorescence of triterpenoid varnishes dammar
and mastic is the focus of this work. Both Fourier transform infrared (FTIR) microscopy using attenuated total reflectance
and Raman spectroscopy have been employed for complementary molecular analysis of samples. Synchronous fluorescence spectroscopy,
excitation emission spectroscopy, and statistical analysis of data have been used to monitor changes in the optical properties
of varnish samples. Assessment of naturally and artificially aged samples using excitation emission spectroscopy suggests
that extensive exposure to visible light does not lead to easily appreciable differences in the fluorescence of mastic and
dammar; cluster analysis has been used to assess changes, which occur with artificial ageing under visible light, indicating
that differences in the fluorescence spectra of aged triterpenoids may be insufficient for their discrimination. The results
highlight significant differences between the initial fluorescence of films of dammar and mastic and the fluorescence, which
develops with ageing and oxidation, and specific markers, which change with ageing in FTIR and Raman spectra, have been identified. 相似文献
100.
Baya M Maresca O Poli R Coppel Y Maseras F Lledós A Belkova NV Dub PA Epstein LM Shubina ES 《Inorganic chemistry》2006,45(25):10248-10262
The isomerization of complex [Cp*Fe(dppe)(eta2-H2)]+, generated in situ by low-temperature protonation of Cp*Fe(dppe)H with either HBF4 or CF3COOH, to the dihydride tautomer trans-[Cp*Fe(dppe)(H)2]+ is irreversible and follows first-order kinetics in the -10 to +15 degrees C range with Delta H double dagger = 21.6 +/- 0.8 kcal mol(-1) and DeltaS double dagger = 5 +/- 3 eu. The isomerization rate constant is essentially independent of the nature and quantity of a strong acid. Density functional theory (DFT) calculations on various models, including the complete system at both the quantum mechanics/molecular mechanics (QM/MM) and full QM levels, probe the relative importance of steric and electronic effects for the relative stability of the nonclassical and classical isomers and identify two likely isomerization mechanisms: a "direct" pathway involving simultaneous H-H bond breaking and cis-trans isomerization and a "via Cp" pathway involving agostic C5Me5H intermediates. Both pathways are characterized by activation energies in close correspondence with the experimental value (21.3 and 22.2 kcal mol(-1), respectively). Further kinetic studies were carried out for the Cp*Fe(dppe)H + CF3COOD and Cp*Fe(dppe)D + CF3COOD systems at 273 K. The [Cp*Fe(dppe)(eta2-HD)]+ complex establishes a very rapid isotope redistribution equilibrium with the eta2-H2 and eta2-D2 analogues. The equilibrium constant value (K = 3.3 +/- 0.3) indicates a significant equilibrium isotope effect. Simulation of the rate data provides access to the individual isomerization rate constants kHH, kHD, and kDD for the three isotopomers, yielding kinetic isotope effects: kHH/kHD = 1.24 +/- 0.01 and kHD/kDD = 1.58 +/- 0.01 (and, consequently, kHH/kDD = 1.96 +/- 0.02). The analysis of the DFT-calculated frequencies, using the [Cp*Fe(dhpe)H2]+ model system, for the [Cp*Fe(dhpe)(eta2-XY)]+ isotopomers as well as transition states for the "direct" (TSdir) and "via Cp" (TSrot) pathways (X = H, D) allowed the computation of the expected isotope effects. A comparison with the experiment strongly suggests that the mechanism occurs via the "direct" pathway for the present system, although the small difference in the calculated energy barriers suggests that the "via Cp" pathway may be preferred in other cases. 相似文献