RESUMO
Cellular membranes contain various lipids including glycolipids (GLs). The hydrophilic head groups of GLs extend from the membrane into the aqueous environment outside the cell where they act as recognition sites for specific interactions. The first steps of interaction of virions with cells often include contacts with GLs. To clarify the details of such contacts, we have used the total internal reflection fluorescence microscopy to explore the interaction of individual unlabelled virus-like particles (or, more specifically, norovirus protein capsids), which are firmly bound to a lipid bilayer, and fluorescent vesicles containing glycosphingolipids (these lipids form a subclass of GLs). The corresponding binding kinetics were earlier found to be kinetically limited, while the detachment kinetics were logarithmic over a wide range of time. Here, the detachment rate is observed to dramatically decrease with increasing concentration of glycosphingolipids from 1% to 8%. This effect has been analytically explained by using a generic model describing the statistics of bonds in the contact area between a virion and a lipid membrane. Among other factors, the model takes the formation of GL domains into account. Our analysis indicates that in the system under consideration, such domains, if present, have a characteristic size smaller than the contact area between the vesicle and the virus-like particle.
Assuntos
Glicoesfingolipídeos/metabolismo , Bicamadas Lipídicas/metabolismo , Norovirus/fisiologia , Vírion/metabolismo , Proteínas do Capsídeo/metabolismo , Membrana Celular/metabolismo , Cinética , Microscopia de FluorescênciaRESUMO
Glycosphingolipids are involved in the first steps of virus-cell interaction, where they mediate specific recognition of the host cell membrane. We have employed total-internal-reflection fluorescence microscopy to explore the interaction kinetics between individual unlabeled noroviruslike particles, which are attached to a glycosphingolipid-containing lipid bilayer, and fluorescent vesicles containing different types and concentrations of glycosphingolipids. Under association equilibrium, the vesicle-binding rate is found to be kinetically limited, yielding information on the corresponding activation energy. The dissociation kinetics are logarithmic over a wide range of time. The latter is explained by the vesicle-size-related distribution of the dissociation activation energy. The biological, pharmaceutical, and diagnostic relevance of the study is briefly discussed.
Assuntos
Glicoesfingolipídeos/metabolismo , Bicamadas Lipídicas/metabolismo , Vírion/metabolismo , Cinética , Microscopia de Fluorescência , Fatores de TempoRESUMO
Single lipid vesicles adsorbed on SiO(2) were manipulated using an atomic force microscope (AFM) operated in contact mode. For large force setpoints, single vesicles were either pushed sideways or ruptured by the tip, depending on the tip type (sharp or blunt) used, while for small force setpoints the vesicles were imaged by the tip. To extend the interpretation of and to guide the experiment, we have developed a generic model of the vesicle-tip-substrate system and performed Monte Carlo simulations, addressing the influence of force setpoint and tip speed and shape on the type of imaging or manipulation observed. Specifically, we have explored AFM-image height and width variations versus force setpoint, typical AFM images for small and large force setpoints, tip-induced vesicle strain versus force setpoint, typical vesicle shapes during pushing for different tip speeds, and the details of vesicle rupture induced by the tip.
Assuntos
Simulação por Computador , Lipídeos/química , Microscopia de Força Atômica/métodos , Método de Monte Carlo , Adsorção , Tamanho da Partícula , Dióxido de Silício/química , Propriedades de SuperfícieRESUMO
One of the main approaches employed to reach fast chromatographic separation is based on using columns containing up to 1000 capillaries with the diameter size down to 10-100 microm. The efficiency of such columns depends on the dispersion of the capillary radius and on the way of the liquid-film loading. We present general equations describing these effects. Specifically, we show theoretically and experimentally that the separation efficiency can be improved by using the loading methods specially designed in order to take into account correlation between the film thickness and capillary radius.
Assuntos
Cromatografia Gasosa/instrumentação , Cromatografia Gasosa/métodos , Modelos TeóricosRESUMO
Scrutinizing the Monte Carlo algorithm, used by D.-Y. Hua and Y.-Q. Ma [Phys. Rev. E 66, 066103 (2002)] in order to simulate the effect of defect sites on bistable kinetics of CO oxidation on single-crystal surfaces, we show that in their study (i) the rules for describing CO adsorption, desorption, and surface diffusion contradict the detailed balance principle and (ii) the ratio of the rates of CO diffusion and reaction between adsorbed CO and O species is opposite compared to that observed in reality.
RESUMO
In fuel cells, electrochemical reactions are often assumed to occur on metal catalyst particles contacting simultaneously the ion-conducting electrolyte and gas phase. Our kinetic Monte Carlo simulations demonstrate that in this case the deviations from the Tafel law in the dependence of the reaction rate on the electrode potential may be related to diffusion of one of the adsorbed reactants along catalyst particles.
RESUMO
In my numeration, the criticism of my simulations of kinetic oscillations in NO reduction by H2 on Pt(100) [V. P. Zhdanov, Phys. Rev. E 59, 6292 (1999)] by Kuzovkov, Kortlüke, and von Niessen [preceding paper, Phys. Rev. 63, 023101 (2001)] contains 19 comments. I show that four comments are irrelevant. The other 15 comments are wrong, because they either contradict the basic principles of the theory of phase transitions, Monte Carlo simulations, and catalytic chemistry or ignore numerous experimental data on adsorbate-induced restructuring of the Pt(100) surface.
RESUMO
We present two-dimensional Monte Carlo simulations of enzymatic cellular reaction occurring via the Michaelis-Menten scheme in the case of attractive interactions between the reaction products. The model employed predicts phase separation in the cell provided that the reaction is relatively fast. The shape of the corresponding patterns varies from a few separate islands to a large patch located in the center of the cell. The fluctuations of the reaction rate during such regimes are found to be much higher than those predicted by the Poissonian distribution.
Assuntos
Células/enzimologia , Enzimas/química , Algoritmos , Biofísica/métodos , Cinética , Modelos Biológicos , Fatores de TempoRESUMO
Recent experimental investigations of the kinetics of vesicle adsorption in solution on SiO2 demonstrate a thermally activated transition from adsorbed intact vesicles to a supported lipid bilayer. Our Monte Carlo simulations clarify the mechanism of this process. The model employed is an extension of the model used earlier to describe vesicle adsorption at room temperature. Specifically, it includes limitations of the adsorption rate by vesicle diffusion in the solution, and adsorption- and lipid-membrane-induced rupture of arriving and already adsorbed vesicles. Vesicles and lipid molecules, formed after rupture of vesicles, are considered immobile. With these ingredients, the model is able to quantitatively reproduce the temperature-dependent adsorption kinetics, including a higher critical surface concentration of intact vesicles for lower temperatures, and the apparent activation energy for the vesicle-to-bilayer transition E(a) approximately 5 kcal/mol.
Assuntos
Materiais Biocompatíveis , Bicamadas Lipídicas/química , Adsorção , Algoritmos , Simulação por Computador , Difusão , Cinética , Lipossomos , Substâncias Macromoleculares , Modelos Estatísticos , Método de Monte Carlo , Fosfatidilcolinas , Temperatura , Fatores de TempoRESUMO
We present Monte Carlo simulations of the reaction kinetics corresponding to two coupled catalytic oscillators in the case when oscillations result from the interplay between the reaction steps and adsorbate-induced surface restructuring. The model used is aimed to mimic oscillations on a single nm catalyst particle with two kinds of facets or on two catalyst particles on a support. Specifically, we treat the NO reduction by H(2) on a composite catalyst containing two catalytically active Pt(100) parts connected by an inactive link. The catalyst is represented by a rectangular fragment of a square lattice. The left- and right-hand parts of the lattice mimic Pt(100). With an appropriate choice of the model parameters, these sublattices play a role of catalytic oscillators. The central catalytically inactive sublattice is considered to be able only to adsorb NO reversibly and can be viewed as a Pt(111) facet or a support. The interplay of the reactions running on the catalytically active areas occurs via NO diffusion over the boundaries between the sublattices. Using this model, we show that the coupling of the catalytically active sublattices may synchronize nearly harmonic oscillations observed on these sublattices and also may result in the appearance of aperiodic partly synchronized oscillations. The spatio-temporal patterns corresponding to these regimes are nontrivial. In particular, the model predicts that, due to phase separation, the reaction may be accompanied by the formation of narrow NO-covered zones on the left and right sublattices near the boundaries between these sublattices and the central sublattice. Such patterns cannot be obtained by using the conventional mean-field reaction-diffusion equations based on the mass-action law. The experimental opportunities to observe the predicted phenomena are briefly discussed. (c) 2001 American Institute of Physics.
RESUMO
Hypoxia plays an important role in pathogenesis of infectious diseases. Therefore, its correction is an essential factor in pathogenetic antibacterial treatment. Hyperbaric oxygenation (HBO) as a leading method in current antihypoxic therapy was studied in combined medication for typhoid, diphtheria, meningococcal infection, viral hepatitis. HBO sessions were given to 331 patients, 363 controls did not receive HBO. Utilization of HBO provided much better saturation of blood with oxygen, eliminated metabolic disorders, warranted favorable course and outcomes of the diseases.
Assuntos
Doenças Transmissíveis/terapia , Oxigenoterapia Hiperbárica , Doença Aguda , Adulto , Terapia Combinada , Difteria/terapia , Hepatite A/terapia , Humanos , Masculino , Infecções Meningocócicas/terapia , Pessoa de Meia-Idade , Febre Tifoide/terapiaRESUMO
We derive general equations describing the diffusion-limited kinetics of irreversible adsorption of biomolecules on nanoparticles, fabricated on a flat surface, in the case of no hydrodynamic flow in the solution. Under such conditions, the gradients in the concentration of biomolecules occur near the surface, while in more remote regions the gradients may or may not be significant depending on the surface concentration and size of nanoparticles and the bulk concentration of biomolecules. The equations obtained make it possible to understand the conditions of realization of various regimes of adsorption.
Assuntos
Nanopartículas/química , Proteínas/química , Adsorção , Difusão , Cinética , Tamanho da Partícula , Propriedades de SuperfícieAssuntos
Doenças Transmissíveis/reabilitação , Militares , Afeganistão , Hepatite A/reabilitação , Humanos , Recidiva , TurcomenistãoRESUMO
The authors present a generic model of CH4 oxidation on Pt with the emphasis on the role of surface-oxide formation. The latter process is treated in terms of the theory of first-order phase transitions. The corresponding Monte Carlo simulations indicate that the surface-oxide formation may result in stepwise features in the reaction kinetics. Specifically, with increasing CH4 pressure and/or decreasing O2 pressure, the model predicts a sharp transition from a low-reactive state with the surface completely covered by oxide to a high-reactive state with the surface covered by chemisorbed oxygen. In the former case, the reaction is first order in CH4 and zero order in O2. In the latter case, both reaction orders are positive. All these findings help in interpreting available experiments.
RESUMO
Using quartz crystal microbalance with dissipation and ellipsometry, we show that during adsorption of fibrinogen on evaporated tantalum films the saturation uptake increases with increasing root-mean-square roughness (from 2.0 to 32.9 nm) beyond the accompanying increase in surface area. This increase is attributed to a change in the geometrical arrangement of the fibrinogen molecules on the surface. For comparison, the adsorption of a nearly globular protein, bovine serum albumin, was studied as well. In this case, the adsorption was less influenced by the roughness. Simple Monte Carlo simulations taking into account surface roughness and the anisotropic shape of fibrinogen reproduce the experimentally observed trend.
Assuntos
Fibrinogênio/química , Quartzo/química , Soroalbumina Bovina/química , Tantálio/química , Adsorção , Animais , Bovinos , Propriedades de SuperfícieRESUMO
We extend our earlier Monte Carlo simulations of isothermal kinetic oscillations in the NO-H(2)/Pt(100) system [V. P. Zhdanov, Phys. Rev. E 59, 6292 (1999)]. The analysis, based on a lattice-gas model describing surface restructuring in terms of the statistical theory of first-order phase transitions, is primarily focused on adsorbate-diffusion-mediated synchronization of oscillations. The conventional condition for synchronization, (D tau)(1/2)>L (D is the diffusion coefficient, tau the oscillation period, and L the lattice size), is proved to considerably underestimate the role of surface diffusion. Due to the formation of mesoscopic islands, well developed oscillations are found to be possible in the cases when the left part of this condition is much lower than the right part.