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61.
The influence of various aliphatic diols on the temperature of maximum density (TMD) of water has been investigated. 1,2-Propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 2,5-hexanediol were found to yield positive structural contributions to the solute-induced shift in the TMD, i.e., they are structure makers. Contrariwise, data from the literature indicate that 1,2-ethanediol is a structure breaker. Relationships between the structure making/breaking tendencies of the solutes and the relative positions of the two hydroxyl groups are discussed. 相似文献
62.
Dynamical phases of the Hindmarsh-Rose neuronal model: studies of the transition from bursting to spiking chaos 总被引:1,自引:0,他引:1
The dynamical phases of the Hindmarsh-Rose neuronal model are analyzed in detail by varying the external current I. For increasing current values, the model exhibits a peculiar cascade of nonchaotic and chaotic period-adding bifurcations leading the system from the silent regime to a chaotic state dominated by bursting events. At higher I-values, this phase is substituted by a regime of continuous chaotic spiking and finally via an inverse period doubling cascade the system returns to silence. The analysis is focused on the transition between the two chaotic phases displayed by the model: one dominated by spiking dynamics and the other by bursts. At the transition an abrupt shrinking of the attractor size associated with a sharp peak in the maximal Lyapunov exponent is observable. However, the transition appears to be continuous and smoothed out over a finite current interval, where bursts and spikes coexist. The beginning of the transition (from the bursting side) is signaled from a structural modification in the interspike interval return map. This change in the map shape is associated with the disappearance of the family of solutions responsible for the onset of the bursting chaos. The successive passage from bursting to spiking chaos is associated with a progressive pruning of unstable long-lasting bursts. 相似文献
63.
64.
A capillary electrophoresis method with UV detection was developed for the determination of 8-hydroxy-2'-deoxyguanosine (8-OHdG) in untreated urine samples. The calibration graph for 8-OHdG in urine is linear in the concentration range 10-500 mg/l. and the detection limit is 5 mg/l (17 microM). 8-OHdG was determined in urine from oncological patients treated by radiation therapy. Its concentrations relative to creatinine were found to be in the range 10-47 microg 8-OHdG/l mg creatinine (4-19 micromol 8-OHdG/mmol creatinine). The overall time of the analysis of a urine sample was less than 15 min. 相似文献
65.
Summary AssumeE is a real topological vector space,F is a real Banach space,K is a discrete subgroup ofF andC is a symmetric, convex and compact subset ofF such thatK (6C) = {0}. If a functionh:E F is continuous at at least one point andh(x + y) – h(x) – h(y) K + C for allx, y E, then there exists a continuous linear functiona:E F such thath(x) – a(x) K + C for everyx E. 相似文献
66.
Ab initio geometry optimizations were performed on gaseous protonated glycine using the second-order Møller–Plesset perturbation theory with the 6-31G*, 6-31G**, 6-31+G**, and 6-311+G** basis sets. Eight energy minima and 12 saddle points in the low-energy region of the electronic potential energy surface were characterized. The global minimum was an amino N-protonated conformer containing an ionic H bond between the (SINGLE BOND)NH3+ and O(DOUBLE BOND)C(DIAGONAL BOND)(DIAGONAL BOND) groups. The lowest energy O-protonated conformer was stabilized by a conjugative attraction between the nitrogen lone-pair electrons and the positively charged planar fragment (SINGLE BOND)C(OH)2+. Relative electronic energies of the nine N- and 11 O-protonated species fall in the ranges of 0–10 and 30–40 kcal mol−1. At room temperature the equilibrium distribution contained the most stable N-protonated conformer almost exclusively. Additional subjects for investigation include the effects of basis set and electron correlation on the predicted structures, nonbonded interactions that influence the relative stability of protonated conformers, conformational interconversions based on intrinsic reaction coordinate calculations, and kinetic pathways for protonation and associated changes in Gibbs free energy. The work provides geometric, energetic, and thermodynamic data pertinent to the study of gas-phase ion chemistry of amino acids and peptides. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 1862–1876, 1998 相似文献
67.
Goodchild I Collier L Millar SL Prokes I Lord JC Butts CP Bowers J Webster JR Heenan RK 《Journal of colloid and interface science》2007,307(2):455-468
The surface, phase and aggregation behaviour of mixtures of 1-alkyl-3-methylimidazolium halide, [C(n)mim]X, where n is the alkyl chain length, with water has been explored using a variety of methods. Critical micelle concentrations (cmc) and micelle structures have been determined for aqueous [C(n)mim]Br solutions for n=2, 4, 6, 8, and 10. Small-angle neutron scattering (SANS) measurements reveal that for the n=8 and 10 systems, at concentrations just above the cmc, small near-spherical aggregates exist, which, after initial growth, possess core radii (aggregation numbers) at intermediate concentrations of 10.5+/-0.5 Angstrom (22+/-2) and 13.2+/-0.5 Angstrom (40+/-3), respectively, for n=8 and n=10. Towards higher concentrations, the aggregates appear to grow, with the aggregates in the [C(10)mim]Br system becoming increasingly elongated (prolate) with increasing concentration. No evident aggregates are formed in the systems with n=2 and 4. In the n=6 system, it appears that oblate aggregates with radius approximately 9 Angstrom form at the cmc and that the radius increases with increasing concentration. For longer alkyl chain lengths, at high concentrations lyotropic mesophases form in some systems. The mesophase region for the [C(8)mim]Cl system has been explored across the composition range using X-ray diffraction and (2)H NMR spectroscopy. Both techniques suggest that a major hexagonal phase with lattice parameter of 29.5+/-0.5 Angstrom coexists with a minor lamellar phase (23.5+/-0.3 Angstrom) or possibly a second hexagonal phase (27.1+/-0.4 Angstrom). The area per adsorbed molecule at the surface of [C(8)mim]Br solutions has been measured as a function of concentration using neutron reflectometry. A minimum in the area per molecule behaviour is coincident with a minimum identified in the surface tension isotherm occurring close to the cmc. The data suggest depletion of [C(8)mim]Br from the surface region occurs at concentrations immediately above the cmc. 相似文献
68.
Dr. Silvia Bracco Dr. Mario Beretta Dr. Alice Cattaneo Prof. Angiolina Comotti Prof. Andrea Falqui Dr. Ke Zhao Prof. Charles Rogers Prof. Piero Sozzani 《Angewandte Chemie (International ed. in English)》2015,54(16):4773-4777
New mesoporous covalent frameworks, based on hybrid fluorinated organosilicas, were prepared to realize a periodic architecture of fast molecular rotors containing dynamic dipoles in their structure. The mobile elements, designed on the basis of fluorinated p‐divinylbenzene moieties, were integrated into the robust covalent structure through siloxane bonds, and showed not only the rapid dynamics of the aromatic rings (ca. 108 Hz at 325 K), as detected by solid‐state NMR spectroscopy, but also a dielectric response typical of a fast dipole reorientation under the stimuli of an applied electric field. Furthermore, the mesochannels are open and accessible to diffusing in gas molecules, and rotor mobility could be individually regulated by I2 vapors. The iodine enters the channels of the periodic structure and reacts with the pivotal double bonds of the divinyl‐fluoro‐phenylene rotors, affecting their motion and the dielectric properties. 相似文献
69.
An efficient Heck coupling of 2-hydroxy-3-iodo-naphthoquinone with a series of electron-deficient alkenes in aqueous solution has been accomplished. The method is characterized by simple conditions and facile work-up to isolate the products in good to excellent yields. The products contain the motif present in several naphthoquinone pigments but with enhanced polarity. 相似文献