Configuration-dependent diffusion can shift the kinetic transition state and barrier height of protein folding

We show that diffusion can play an important role in protein-folding kinetics. We explicitly calculate the diffusion coefficient of protein folding in a lattice model. We found that diffusion typically is configuration- or reaction coordinate-dependent. The diffusion coefficient is found to be decreasing with respect to the progression of folding toward the native state, which is caused by the collapse to a compact state constraining the configurational space for exploration. The configuration- or position-dependent diffusion coefficient has a significant contribution to the kinetics in addition to the thermodynamic free-energy barrier. It effectively changes (increases in this case) the kinetic barrier height as well as the position of the corresponding transition state and therefore modifies the folding kinetic rates as well as the kinetic routes. The resulting folding time, by considering both kinetic diffusion and the thermodynamic folding free-energy profile, thus is slower than the estimation from the thermodynamic free-energy barrier with constant diffusion but is consistent with the results from kinetic simulations. The configuration- or coordinate-dependent diffusion is especially important with respect to fast folding, when there is a small or no free-energy barrier and kinetics is controlled by diffusion. Including the configurational dependence will challenge the transition state theory of protein folding. The classical transition state theory will have to be modified to be consistent. The more detailed folding mechanistic studies involving phi value analysis based on the classical transition state theory also will have to be modified quantitatively.

Spatial dynamics of a population with stage-dependent diffusion

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Coordinate and time-dependent diffusion dynamics in protein folding

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Configuration-Dependent Diffusion Dynamics of Downhill and Two-State Protein Folding

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Stability analysis of Crank-Nicolson and Euler schemes for time-dependent diffusion equations

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Antineoplasic Drug Methotrexate Redox Mechanism Using a Glassy Carbon Electrode

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

The Origin of Nonmonotonic Complex Behavior and the Effects of Nonnative Interactions on the Diffusive Properties of Protein Folding

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Fractal concepts in relation to soil water diffusivity

Fractal geometry would appear to offer promise for new insight on water transport in unsaturated soils, This study was conducted to evaluate possible fractal influence on soil water diffusivity, and/or the relationships from which it arises, for several different soils, Fractal manifestations, consisting of a time-dependent diffusion coefficient and anomalous diffusion arising out of fractional Brownian motion, along with the notion of space-filling curves were gleaned from the literature, It was found necessary to replace the classical Boltzmann variable and its time t(1/2) factor with the basic fractal power function and its t(n) factor, For distinctly unsaturated soil water content theta, exponent n was found to be less than 1/2, but it approached 1/2 as theta approached its sated value, This function n = n(theta), in giving rise to a time-dependent, anomalous soil water diffusivity D, was identified with the Hurst exponent H of fractal geometry, Also, n approaching 1/2 at high water content is a behavior that makes it possible to associate factal space filling with soil that approaches water saturation, Finally, based on the fractally interpreted n = n(theta), the coalescence of both D and 8 data is greatly improved when compared with the coalescence provided by the classical Boltzmann variable.

Mineralogy of the clay fraction of alfisols in two slope curvatures: IV - spatial correlation with physical properties

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

GPS receivers for georeferencing of spatial variability of soil attributes

A caracterização da variabilidade espacial dos atributos do solo é indispensável para subsidiar práticas agrícolas de maneira sustentável. A utilização da geoestatística para caracterizar a variabilidade espacial desses atributos, como a resistência mecânica do solo à penetração (RP) e a umidade gravimétrica do solo (UG), é, hoje, prática usual na agricultura de precisão. O resultado da análise geoestatística é dependente da densidade amostral e de outros fatores, como o método de georreferencimento utilizado. Desta forma, o presente trabalho teve como objetivo comparar dois métodos de georreferenciamento para a caracterização da variabilidade espacial da RP e da UG, bem como a correlação espacial dessas variáveis. Foi implantada uma malha amostral de 60 pontos, espaçados em 20 m. Para as medições da RP, utilizou-se de penetrógrafo eletrônico e, para a determinação da UG, utilizou-se de trado holandês (profundidade de 0,0-0,1 m). As amostras foram georreferenciadas, utilizando-se do método de Posicionamento por Ponto Simples (PPS), com de (retirar) receptor GPS de navegação, e Posicionamento Relativo Semicinemático, com receptor GPS geodésico L1. Os resultados indicaram que o georreferenciamento realizado pelo PPS não interferiu na caracterização da variabilidade espacial da RP e da UG, assim como na estrutura espacial da relação dos atributos.

Soil CO2 emission of sugarcane fields as affected by topography

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Soil sampling intensity and spatial distribution pattern of soils attributes and corn yield in no-tillage system

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Chaotic diffusion caused by close encounters with several massive asteroids The (4) Vesta case

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Species composition and spatial distribution of a stream fish assemblage in the east coast of Brazil: comparison of two field study methodologies

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

The sugarcane borer Diatraea saccharalis (Fabr.) (Lep., Crambidae) and its parasitoids: a synchrony approach to spatial and temporal dynamics

A data set on Diatraea saccharalis and its parasitoids, Cotesia flavipes and tachinid flies, was analysed at five spatial scales-sugarcane mill, region, intermediary, farm and zone-to determine the role of spatial scale in synchrony patterns, and on temporal population variability. To analyse synchrony patterns, only the three highest spatial scales were considered, but for temporal population variability, all spatial scales were adopted. The synchrony-distance relationship revealed complex spatial structures depending on both species and spatial scale. Temporal population variability [SD log(x+1)] levels were highest at the smallest spatial scales although, in the majority of the cases, temporal variability was inversely dependent on sample size. All the species studied, with a few exceptions, presented spatial synchrony independent of spatial scale. The tachinid flies exhibited stronger synchrony dynamics than D. saccharalis and C. flavipes in all spatial scales with the latter displaying the weakest synchrony levels, except when mill spatial scales were compared. In some cases spatial synchrony may at first decay and then increase with distance, but the presence of such patterns can change depending on the spatial scale adopted.