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71.
A mathematical framework for translational Brownian motion on hypersurfaces is presented, using an imbedding of the surface and Ito diffusions in the ambient space. This includes a survey of Ito calculus and differential geometry. Computational methods for time correlation functions relevant to spin relaxation studies on curved interfaces are given, and explicit calculations of time correlation functions and order parameters for a Rippled surface are presented. 相似文献
72.
The present paper gives an account of different aspects of the tracer diffusion of Cs+ ions in alkali metal bromides. We have measured the diffusion coefficients, D, of cesium ions in 1% agar gel medium at 25 ∘C using a zone-diffusion technique over a concentration range of 5 × 10−5 to 0.1 mol,dm−3. The values of the diffusion coefficients were found to deviate from theory, which are explained on the basis of different
types of interactions occurring in the ion-gel-water system. The study is also focused on the effect of alkali metal bromides
on the obstruction effect and activation energy for the tracer-diffusion of cesium ions in agar gel medium. It is observed
that both parameters, extent of obstruction, ∝, and activation energy, E, decrease with increasing charge density of the cation of the supporting electrolyte. The influence of these trends is explained
on the basis of competitive hydration between the ions and agar molecules, and the relative distortion in the water structure
that is brought about by these different ions and agar molecules. 相似文献
73.
J. Eisenlauer 《Colloid and polymer science》1984,262(11):906-910
Different results from recent communications on the hydrodynamic characterization of ultrasonicated silica (®Aerosil) hydrosols led to a critical reappraisal of the data.It can be concluded that the degree of dispersion achievable in pyrogenic (Aerosil) hydrosols by ultrasonication is highly sensitive to the detailed parameters of the dispersion process. Characterization in terms ofabsolute numbers of a limiting particle morphology, corresponding to minima of aggregate size, porosity and number of primary particles in the aggregate is not possible.The most straightforward approach for hydrodynamic characterization seems to be a combination of sedimentation and diffusion data.Other approaches using a combination of sedimentation and viscosity data underestimate the particle dimensions. Moreover, they are quite arbitrary since the final result depends upon the proper choice between several equations for fitting the viscosity concentration dependence; the most rigorous approach seems to be an extended Einstein equation which has recently been adapted to particle aggregates. 相似文献
74.
P. V. Katsikopoulos C. D. Papaspyrides 《Journal of polymer science. Part A, Polymer chemistry》1994,32(3):451-456
Loss of diamine and distinct transition phenomena from the solid to the melt state restrain solid-state polymerization (SSP) of nylon salts from industrial application. To depress these phenomena temperatures well below the melting point of the starting material are employed, resulting however in low reaction rates. The need to use catalysts arises and accordingly in this study hexamethylenediammonium adipate (HMA) particles were polymerized containing a strictly controlled amount of uniformly distributed catalyst. The catalysts included boric, sulphuric, and phosphoric acids with boric acid being the most effective in accelerating the reaction while eliminating the tendency to agglomeration. In general, catalyst concentration up to a critical value plays a considerable role in the overall behavior. Furthermore, in agreement with non catalytic processes, the reaction temperature remains an influential parameter. © 1994 John Wiley & Sons, Inc. 相似文献
75.
As a model for a binary alloy undergoing an unmixing phase transition, we consider a square lattice where each site can be either taken by an A atom, a B atom, or a vacancy (V), and there exists a repulsive interaction between AB nearest neighbor pairs. Starting from a random initial configuration, unmixing proceeds via random jumps of A atoms or B atoms to nearest neighbor vacant sites. In the absence of any interaction, these jumps occur at jump rates
A and
B, respectively. For a small concentration of vacancies (c
v=0.04) the dynamics of the structure factorS(k,t) and its first two momentsk
1(t),k
2
2
(t) is studied during the early stages of phase separation, for several choices of concentrationc
B of B atoms. Forc
B=0.18 also the time evolution of the cluster size distribution is studied. Apart from very early times, the mean cluster sizel(t) as well as the moments of the structure function depend on timet and the ratio of the jump rates (=
B/
A) only via a scaled timet/(). Qualitatively, the behavior is very similar to the direct exchange model containing no vacancies. Consequences for phase separation of real alloys are briefly discussed. 相似文献
76.
Craig C. Martens 《Journal of statistical physics》1992,68(1-2):207-237
We describe our work on qualitative methods for visualizing the quantum eigenstates of systems with nonlinear classical dynamics. For two-degree-of-freedom systems, our approach is based on the use of generalized coherent states, and allows systems with nonoscillator kinematics to be investigated. The general approach is illustrated with two examples involving vibration-rotation interaction in polyatomic molecules. We apply the coherent states of the Lie groupH
4SU(2) to define quantum surfaces of section for a model involving centrifugal coupling of a harmonic bend with molecular rotation, andSU(2)SU(2) coherent states to study two harmonic normal modes coupled to overall molecular rotation through coriolis interaction. In both systems, quantum states are visualized on the rotational surface of section and compared with the corresponding classical phase space structure. Striking classical-quantum correspondence is observed. We then describe recent results on the quantum states of (N 3)-dimensional systems of coupled nonlinear oscillators, which reveal a quantum delocalization that is reminiscent of classical Arnold diffusion. 相似文献
77.
Ivanauskas F. Kaunietis I. Laurinavičius V. Razumienė J. Šimkus R. 《Journal of mathematical chemistry》2005,38(3):355-366
The plate-gap model of porous enzyme doped electrode has been proposed and analyzed. It was suggested that reaction diffusion conditions in pores of bulk electrode resemble particular conditions in thin gap between parallel conducting plates. The model is based on the diffusion equations containing a nonlinear term related to the Michaelis–Menten kinetic of the enzymatic reaction inside gap. Steady state current was calculated for the wide range of given parameters and substrate concentrations. All dependences of current on substrate concentration were approximated by hyperbolas in order to obtain “apparent” parameters (maximal currents and apparent Michaelis constants) of modelled biosensors. Simple approximate relationships between given and apparent parameters were derived. The applicability of theoretical plate-gap model was tested for the case of carbon paste electrodes which were doped with PQQ – dependent glucose dehydrogenase. It was found, that soluble glucose dehydrogenase based biosensors exhibit characteristic features of the theoretical plate-gap biosensors. 相似文献
78.
A dual-electrode approach for highly selective detection of glucose based on diffusion layer theory: experiments and simulation 总被引:1,自引:0,他引:1
A dual-electrode configuration for the highly selective detection of glucose in the diffusion layer of the substrate electrode is presented. In this approach, a glassy carbon electrode (GCE, substrate) modified with a conductive layer of glucose oxidase/Nafion/graphite (GNG) was used to create an interference-free region in its diffusion layer by electrochemical depletion of interfering electroactive species. A Pt microelectrode (tip, 5 microm in radius) was located in the diffusion layer of the GNG-modified GCE (GNG-G) with the help of scanning electrochemical microscopy. Consequently, the tip of the electrode could sense glucose selectively by detecting the amount of hydrogen peroxide (H2O2) formed from the oxidization of glucose on the glucose oxidase layer. The influences of parameters, including tip-substrate distance, substrate potential, and electrolyzing time, on the interference-removing efficiency of this dual-electrode approach have been investigated systematically. When the electrolyzing time was 30 s, the tip-substrate distance was 1.8 a (9.0 microm) (where a is the radius of the tip electrode), the potentials of the tip and substrate electrodes were 0.7 V and 0.4 V, respectively, and a mixture of ascorbic acid (0.3 mM), uric acid (0.3 mM), and 4-acetaminophen (0.3 mM) had no influence on the glucose detection. In addition, the current-time responses of the tip electrode at different tip-substrate distances in a solution containing interfering species were numerically simulated. The results from the simulation are in good agreement with the experimental data. This research provides a concept of detection in the diffusion layer of a substrate electrode, as an interference-free region, for developing novel microelectrochemical devices. 相似文献
79.
Homogeneity and structure of organically modified polysiloxane networks prepared by sol-gel co-condensation, as well as location and nature of water molecules and silanol groups were studied by 1D and 2D solid-state NMR. 1H–29Si and 1H–1H interatomic distances were estimated from variable contact-time CP/MAS experiments, 1H NMR chemical shifts and off-resonance WISE NMR. A structure model of these networks is proposed and discussed. The fraction of proton-inaccessible units Q4 in the networks decreases with increasing amounts of dimethylsiloxane (D) and methylsiloxane (T) units. In contrast to systems prepared by co-condensation of tetraethoxysilane (TEOS) with dimethyl(diethoxy)silane (DMDEOS), proton-inaccessible units form essential fraction in networks prepared by co-condensation of TEOS with methyl(triethoxy)silane (MTEOS). The proton-accessible part of the networks with high O/Si ratios is nano-heterogeneous phase, which is composed of water containing Q
i
particles separated by copolymer domains. The overall homogeneity and uniformity of binding sites around silanol groups increases by co-condensation TEOS with DMDEOS or MTEOS, while the amount of physisorbed water as well as the hydrogen bond strength decreases, as compared with neat silica gel prepared by polycondensation of TEOS. 相似文献
80.
Veronika Valkov Hana úranov Nenad L. Vukovic Milena Vukic Maciej Kluz Miroslava Ka
niov 《Molecules (Basel, Switzerland)》2022,27(10)
The possibilities of the practical utilization of essential oils (EOs) from various plant species in the food industry have attracted the attention of the scientific community. Following our previous studies, the antifungal activities of three further commercial EOs, Melaleuca armillaris subsp. armillaris (rosalina; REO), Melaleuca quinquenervia (niaouli; NEO), and Abies alba (fir; FEO), were evaluated in the present research in respect to their chemical profiles, over four different concentrations, 62.5 μL/L, 125 μL/L, 250 μL/L, and 500 μL/L. The findings revealed that the major compounds of REO, NEO, and FEO were linalool (47.5%), 1,8-cineole (40.8%), and α-pinene (25.2%), respectively. In vitro antifungal determinations showed that the inhibition zones of a Penicillium spp. mycelial growth ranged from no inhibitory effectiveness (00.00 ± 00.00 mm) to 16.00 ± 1.00 mm, indicating a very strong antifungal activity which was detected against P. citrinum after the highest REO concentration exposure. Furthermore, the in situ antifungal efficacy of all EOs investigated was shown to be dose-dependent. In this sense, we have found that the highest concentration (500 µL/L) of REO, NEO, and FEO significantly reduced (p < 0.05) the growth of all Penicillium strains inoculated on the bread, carrot, and potato models. These results indicate that the investigated EOs may be promising innovative agents in order to extend the shelf life of different types of food products, such as bread, carrot and potato. 相似文献