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91.
Inelastic scattering induces dephasing in mesoscopic systems. An analysis of previous models to simulate inelastic scattering
in such systems is presented and a relatively new model based on wave attenuation is introduced. The problem of Aharonov-Bohm
(AB) oscillations in conductance of a mesoscopic ring is studied. We show that the conductance is symmetric under flux reversal
and the visibility of AB oscillations decays to zero as a function of the incoherence parameter, signaling dephasing. Further
the wave attenuation model is applied to a fundamental problem in quantum mechanics, that of the conditional (reflection/transmission)
times spent in a given region of space by a quantum particle before scattering off from that region. 相似文献
92.
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94.
Mulder P Mozenson O Lin S Bernardes CE Minas da Piedade ME Santos AF Ribeiro da Silva MA Dilabio GA Korth HG Ingold KU 《The journal of physical chemistry. A》2006,110(32):9949-9958
There are conflicting reports on the origin of the effect of Y substituents on the S-H bond dissociation enthalpies (BDEs) in 4-Y-substituted thiophenols, 4-YC(6)H(4)S-H. The differences in S-H BDEs, [4-YC(6)H(4)S-H] - [C(6)H(5)S-H], are known as the total (de)stabilization enthalpies, TSEs, where TSE = RSE - MSE, i.e., the radical (de)stabilization enthalpy minus the molecule (de)stabilization enthalpy. The effects of 4-Y substituents on the S-H BDEs in thiophenols and on the S-C BDEs in phenyl thioethers are expected to be almost identical. Some S-C TSEs were therefore derived from the rates of homolyses of a few 4-Y-substituted phenyl benzyl sulfides, 4-YC(6)H(4)S-CH(2)C(6)H(5), in the hydrogen donor solvent 9,10-dihydroanthracene. These TSEs were found to be -3.6 +/- 0.5 (Y = NH(2)), -1.8 +/- 0.5 (CH(3)O), 0 (H), and 0.7 +/- 0.5 (CN) kcal mol(-1). The MSEs of 4-YC(6)H(4)SCH(2)C(6)H(5) have also been derived from the results of combustion calorimetry, Calvet-drop calorimetry, and computational chemistry (B3LYP/6-311+G(d,p)). The MSEs of these thioethers were -0.6 +/- 1.1 (NH(2)), -0.4 +/- 1.1 (CH(3)O), 0 (H), -0.3 +/- 1.3 (CN), and -0.8 +/- 1.5 (COCH(3)) kcal mol(-1). Although all the enthalpic data are rather small, it is concluded that the TSEs in 4-YC(6)H(4)SH are largely governed by the RSEs, a somewhat surprising conclusion in view of the experimental fact that the unpaired electron in C(6)H(5)S(*) is mainly localized on the S. The TSEs, RSEs, and MSEs have also been computed for a much larger series of 4-YC(6)H(4)SH and 4-YC(6)H(4)SCH(3) compounds by using a B3P86 methology and have further confirmed that the S-H/S-CH(3) TSEs are dominated by the RSEs. Good linear correlations were obtained for TSE = rho(+)sigma(p)(+)(Y), with rho(+) (kcal mol(-1)) = 3.5 (S-H) and 3.9 (S-CH(3)). It is also concluded that the SH substituent is a rather strong electron donor with a sigma(p)(+)(SH) of -0.60, and that the literature value of -0.03 is in error. In addition, the SH rotational barriers in 4-YC(6)H(4)SH have been computed and it has been found that for strong electron donating (ED) Ys, such as NH(2), the lowest energy conformer has the S-H bond oriented perpendicular to the aromatic ring plane. In this orientation the SH becomes an electron withdrawing (EW) group. Thus, although the OH group in phenols is always in-plane and ED irrespective of the nature of the 4-Y substituent, in thiophenols the SH switches from being an ED group with EW and weak ED 4-Ys, to being an EW group for strong ED 4-Ys. 相似文献
95.
Bernardes JS Norrman J Piculell L Loh W 《The journal of physical chemistry. B》2006,110(46):23433-23442
The phase behavior of ternary mixtures containing an alkyltrimethylammonium polyacrylate complex salt, water, and a nonpolar "oil" (n-decanol, p-xylene or cyclohexane) is investigated. The complex salts were prepared with short or long polyacrylates (30 or 6000 repeating units) and with hexadecyltrimethylammonium or dodecyltrimethylammonium surfactant ions. Phase diagrams and structures were determined by visual inspection and small-angle X-ray scattering analyses. Systems containing decanol display a predominance of lamellar phases, while hexagonal phases prevail in systems containing p-xylene or cyclohexane. The difference is interpreted as a result of the different locations of the oils within the surfactant aggregates. Decanol is incorporated at the aggregate interface, leading to a decrease in its curvature, which favors the appearance of lamellar structures. p-Xylene and cyclohexane, on the other hand, are mostly incorporated in the interior of the cylindrical aggregate, as reflected by its swelling as the oil content increases. The comparison of these results with those reported for similar systems with monovalent (bromide) counterions indicates a much more limited swelling of the lamellar phases with polymeric counterions by water. This limited swelling behavior is predominantly ascribed to bridging due to the polyions. 相似文献
96.
Nilson C. Bernardes Jr. 《Journal of Mathematical Analysis and Applications》2006,319(2):651-659
Given a metrizable compact topological n-manifold X with boundary and a finite positive Borel measure μ on X, we prove that for the typical continuous function , it is true that for every point x in a full μ-measure subset of X the limit set ω(f,x) is a Cantor set of Hausdorff dimension zero, f maps ω(f,x) homeomorphically onto itself, each point of ω(f,x) has a dense orbit in ω(f,x) and f is non-sensitive at each point of ω(f,x); moreover, the function x→ω(f,x) is continuous μ-almost everywhere. 相似文献
97.
Franco D.R. Amado Marco A.S. Rodrigues Daniel A. Bertuol Andra M. Bernardes Jane Z. Ferreira Carlos A. Ferreira 《Journal of membrane science》2009,330(1-2):227-232
In this study, different membranes were prepared using conventional polymer (high impact polystyrene) and polyaniline to evaluate their use in electrodialysis. Two different preparation modes were tested: chemical mixture with subsequent solvent evaporation; and mechanical mixture with subsequent pressing under heating. The purpose was to understand the effect of production methods on membrane microstructure and ionic transport. Membranes were characterized by swelling study, Fourier transformed infrared spectroscopic, scanning electron microscopy, thermogravimetric analysis and dynamic mechanical analysis. Ionic transport through the membranes was evaluated using a three-compartment cell. The results of the produced membranes were compared with those of the commercial Nafion 450 membrane. 相似文献
98.
The immune system may be seen as a complex system, characterized using tools developed in the study of such systems, for example, surface roughness and its associated Hurst exponent. We analyze densitometric (Panama blot) profiles of immune reactivity, to classify individuals into groups with similar roughness statistics. We focus on a population of individuals living in a region in which malaria endemic, as well as a control group from a disease-free region. Our analysis groups individuals according to the presence, or absence, of malaria symptoms and number of malaria manifestations. Applied to the Panama blot data, our method proves more effective at discriminating between groups than principal-components analysis or super-paramagnetic clustering. Our findings provide evidence that some phenomena observed in the immune system can be only understood from a global point of view. We observe similar tendencies between experimental immune profiles and those of artificial profiles, obtained from an immune network model. The statistical entropy of the experimental profiles is found to exhibit variations similar to those observed in the Hurst exponent. 相似文献
99.
Maria J. Matos Claudio D. Navo Tuuli Hakala Xhenti Ferhati Ana Guerreiro David Hartmann Barbara Bernardim Kadi L. Saar Ismael Compan Francisco Corzana Tuomas P. J. Knowles Gonzalo Jimnez‐Oss Gonalo J. L. Bernardes 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(20):6712-6716
Quaternized vinyl‐ and alkynyl‐pyridine reagents were shown to react in an ultrafast and selective manner with several cysteine‐tagged proteins at near‐stoichiometric quantities. We have demonstrated that this method can effectively create a homogenous antibody–drug conjugate that features a precise drug‐to‐antibody ratio of 2, which was stable in human plasma and retained its specificity towards Her2+ cells. Finally, the developed warhead introduces a +1 charge to the overall net charge of the protein, which enabled us to show that the electrophoretic mobility of the protein may be tuned through the simple attachment of a quaternized vinyl pyridinium reagent at the cysteine residues. We anticipate the generalized use of quaternized vinyl‐ and alkynyl‐pyridine reagents not only for bioconjugation, but also as warheads for covalent inhibition and as tools to profile cysteine reactivity. 相似文献
100.
Nilson C. Bernardes Jr. 《Proceedings of the American Mathematical Society》2002,130(7):1983-1992
Let be a metric space. A function is said to be non-sensitive at a point if for every 0$"> there is a 0$"> such that for any choice of points , , , we have that for every . Let be the set of all homeomorphisms from onto endowed with the topology of uniform convergence. The main goal of the present paper is to prove that for certain spaces , ``most' functions in are non-sensitive at ``most' points of .