A sequential formula for electronic coupling in long range bridge-assisted electron transfer: Formulation of theory and application to alkanethiol monolayers

A recursion relation is formulated for the Green's function for calculating the effective electron coupling in bridge-assisted electronic transfer systems, within the framework of the tight-binding Hamiltonian. The recursion expression relates the Green's function of a chain bridge to that of the bridge that is one unit less. It is applicable regardless of the number of orbitals per unit. This method is applied to the system of a ferrocenylcarboxy-terminated alkanethiol on the Au(111) surface. At larger numbers of bridge units, the effective coupling strength shows an exponential decay as the number of methylene(–CH2–) units increases. This sequential formalism shows numerical stability even for a very long chain bridge and, since it uses only small matrices, requires much less computer time for the calculation. Identical bridge units are not a requirement, and so the method can be applied to more complicated systems

Linear response in theory of electron transfer reactions as an alternative to the molecular harmonic oscillator model

The effect of solvent fluctuations on the rate of electron transfer reactions is considered using linear response theory and a second-order cumulant expansion. An expression is obtained for the rate constant in terms of the dielectric response function of the solvent. It is shown thereby that this expression, which is usually derived using a molecular harmonic oscillator ("spin-boson") model, is valid not only for approximately harmonic systems such as solids but also for strongly molecularly anharmonic systems such as polar solvents. The derivation is a relatively simple alternative to one based on quantum field theoretic techniques. The effect of system inhomogeneity due to the presence of the solute molecule is also now included. An expression is given generalizing to frequency space and quantum mechanically the analogue of an electrostatic result relating the reorganization free energy to the free energy difference of two hypothetical systems [J. Chem. Phys. 39, 1734 (1963)]. The latter expression has been useful in adapting specific electrostatic models in the literature to electron transfer problems, and the present extension can be expected to have a similar utility

On the Theory of Electron Transfer Reactions: Superexchange Coupling and Polar Solvation Dynamics

A recursion relation is formulated for the Green's function for calculating the effective electron coupling in bridge-assisted electron transfer systems, within the framework of the tight-binding Hamiltonian. The non-perturbative recursion expression relates the Green’s function of a chain bridge to that of a bridge which is one unit less. The method is used to calculate the electronic coupling between a gold electrode and each of the molecules. (η⁵-C₅H₅)Fe(η⁵-C₅H₄)CO₂(CH₂)ₙSH and (η⁵-C₅H₅)Fe(η⁵-C₅H₄)(CH₂)ₙSH (n = 3 to 50). At larger numbers of bridge units, the effective coupling strength shows an exponential decay as the number of methylene units increases. This sequential formalism shows numerical stability even for a very long chain bridge and. since it uses only small matrices, requires much less computer time for the calculation. Identical bridge units are not a requirement, and so the method can be applied to more complicated systems, such as proteins. Most of the calculated coupling strengths, if converted to rate constants according to a nonadiabatic expression, agree well with the experimental results. The time-dependent dynamic Stokes shift function, which describes the solvent response to a sudden change in the charge distribution of a solute molecule, is expressed in terms of experimentally measured dielectric dispersion data of the solvent, using a simple dielectric continuum model. The result is applied to photoexcited coumarin 343 in water, and encouraging agreement with the experimental data is obtained. A simple formula is also derived which includes the effect of a pump pulse of finite duration. Such an effect is negligible when the frequency of a pump pulse is close to the maximum in the absorption spectrum, but a deviation from the standard formula can be expected for the pump pulse tuned to a far wing of the absorption band of the chromophore. To calculate further the time-dependent fluorescence spectral lineshapes, a method is described for incorporating the vibronic transitions of a solute molecule. The intramolecular vibrational relaxation is assumed to be much faster than the observation delay time. Calculations are made for coumarin 153 in acetonitrile. The results are again in encouraging agreement with experimental spectra. Results are also given for the dynamic Stokes shift in methanol.</p

Dynamic Stokes shift in solution: Effect of finite pump pulse duration

The time-evolution of the fluorescence spectrum of a dissolved chromophore excited by an ultrafast pump pulse is considered. The average value of the energy difference of the solute in its excited and ground states is used to describe the relaxation of the maximum of the transient fluorescence spectrum to its equilibrium value (dynamic Stokes shift, DSS). A simple formula for the normalized DSS is obtained which generalizes an earlier standard classical expression and includes the effect of a pump pulse of finite duration. As an example, dielectric dispersion data are used for a dipolar solute in water to estimate the quantum correction to the standard DSS expression. The correction is negligible when the frequency of the pump pulse is close to the maximum in the absorption spectrum, but a deviation from the standard formula can be expected for the pump pulse tuned to a far wing of the absorption band of the chromophore. An expression is given for this deviation

Future change in extreme precipitation in East Asian spring and Mei-yu seasons in two high-resolution AGCMs

Precipitation in the spring and Mei-yu seasons, the main planting and growing period in East Asia, is crucial to water resource management. Changes in spring and Mei-yu extreme precipitation under global warming are evaluated based on two sets of high-resolution simulations with various warming pattern of sea surface temperature (SST'spa). In the spring season, extreme precipitation exhibits larger enhancements over the northern flank of the present-day prevailing rainy region and a tendency of increased occurrence and enhanced intensity in the probability distribution. These changes imply a northward extension of future spring rainband. Although the mean precipitation shows minor change, enhanced precipitation intensity, less total rainfall occurrence, and prolonged consecutive dry days suggest a more challenging water resource management in the warmer climate. The projected enhancement in precipitation intensity is robust compared with the internal variability related to initial conditions (σˆint) and the uncertainty caused by SST'spa (σˆΔSST). In the Mei-yu season, extreme precipitation strengthens and becomes more frequent over the present-day prevailing rainband region. The thermodynamic component of moisture flux predominantly contributes to the changes in the spring season. In the Mei-yu season, both the thermodynamic and dynamic components of moisture flux enhance the moisture transport and intensify the extreme precipitation from southern China to northeast Asia. Compared with spring season, projecting future Mei-yu precipitation is more challenging because of its higher uncertainty associated with 1) the σˆint and σˆΔSST embedded in the projections and 2) the model characteristics of present-day climatology that determines the spatial distribution of precipitation enhancement.publishedVersio

SUMOylation of the MAGUK protein CASK regulates dendritic spinogenesis

Membrane-associated guanylate kinase (MAGUK) proteins interact with several synaptogenesis-triggering adhesion molecules. However, direct evidence for the involvement of MAGUK proteins in synapse formation is lacking. In this study, we investigate the function of calcium/calmodulin-dependent serine protein kinase (CASK), a MAGUK protein, in dendritic spine formation by RNA interference. Knockdown of CASK in cultured hippocampal neurons reduces spine density and shrinks dendritic spines. Our analysis of the time course of RNA interference and CASK overexpression experiments further suggests that CASK stabilizes or maintains spine morphology. Experiments using only the CASK PDZ domain or a mutant lacking the protein 4.1–binding site indicate an involvement of CASK in linking transmembrane adhesion molecules and the actin cytoskeleton. We also find that CASK is SUMOylated. Conjugation of small ubiquitin-like modifier 1 (SUMO1) to CASK reduces the interaction between CASK and protein 4.1. Overexpression of a CASK–SUMO1 fusion construct, which mimicks CASK SUMOylation, impairs spine formation. Our study suggests that CASK contributes to spinogenesis and that this is controlled by SUMOylation

Elevated plasma level of visfatin/pre-b cell colony-enhancing factor in male oral squamous cell carcinoma patients

Objectives: Visfatin, also known as nicotiamide phosphoribosyltransferase or pre-B cell colony enhancing factor, is a pro-inflammatory cytokine whose serum level is increased in various cancers. In this study, we investigated whether plasma visfatin levels were altered in patients with oral squamous cell carcinoma (OSCC). The relation ship between plasma visfatin levels and the pretreatment hematologic profile was also explored. Study Design: Plasma visfatin concentrations were measured through ELISA in OSCC patients and control sub- D esign: Plasma visfatin concentrations were measured through ELISA in OSCC patients and control sub- esign: Plasma visfatin concentrations were measured through ELISA in OSCC patients and control sub jects. A total of 51 patients with OSCC and 57 age- and body mass index (BMI)-matched control subjects were studied. All study subjects were male. Results: Plasma visfatin was found to be elevated in patients with OSCC (7.0 ± 4.5 vs. 4.8 ± 1.9 ng/ml, p = 0.002). Multiple logistic regression analysis revealed visfatin as an independent association factor for OSCC, even after full adjustment of known biomarkers. Visfatin level was significantly correlated with white blood cell (WBC) count, neutrophil count, and hematocrit (all p < 0.05). In addition, WBC count, neutrophil count, and visfatin gradually increased with stage progression, and hematocrit gradually decreased with stage progression (all p < 0.05). Conclusion: Increased plasma visfatin levels were associated with OSCC, independent of risk factors, and were cor related with inflammatory biomarkers. These data suggest that visfatin may act through inflammatory reactions to play an important role in the pathogenesis of OSC