Search results for "Potential"

Characterization and Investigation of NLO Properties of some Selected Electrodeposited Polythiophenes

2009

In this work we study the electronic properties of ClO− doped polythiophenes and discuss the nonlinear optical properties of these organic 4 compounds galvanostatically electrodeposited on ITO glasses. The investigation on the electronic properties (band gap, flat band potential) was performed by means of a non-destructive optical technique, photocurrent spectroscopy (PCS). The investigation on the nonlinear optical response was carried out by means of second and third harmonic generation (SHG and THG) measurements. In particular, the effect of the oxidation state of the polymeric films was studied by comparing the NLO response of oxidized and reduced polythiophenes. Reduced poly- meric films …

Measurement of higher cumulants of net-charge multiplicity distributions in Au+Au collisions at √sNN = 7.7-200 GeV

2016

We report the measurement of cumulants (Cn,n = 1,...,4) of the net-charge distributions measured within pseudorapidity (|η| < 0.35) in Au + Au collisions at √sNN = 7.7–200 GeV with the PHENIX experiment at the Relativistic Heavy Ion Collider. The ratios of cumulants (e.g., C1/C2, C3/C1) of the net-charge distributions, which can be related to volume independent susceptibility ratios, are studied as a function of centrality and energy. These quantities are important to understand the quantum-chromodynamics phase diagram and possible existence of a critical end point. The measured values are very well described by expectation from negative binomial distributions. We do not observe any nonmono…

Increased Gamma Connectivity in the Human Prefrontal Cortex during theBereitschaftspotential

2017

The Bereitschaftspotential (BP) is a slow negative cortical potential preceding voluntary movement. Since movement preparation is dependent upon the synchronous activity of a variety of neurons, BP may develop through the exchange of information among motor-related neurons. However, the relationship between BP and information flow is not yet well-known. In the present study, we aimed to investigate how the connectivity in the prefrontal cortex (PFC) changes during the occurrence of BP. Electrocorticography (ECoG) was recorded in five patients with epilepsy. The subjects performed self-paced hand grasping. We compared the intraregional connectivity between PFC and non-PFC regions using parti…

Electrochemical and Spectroelectrochemical Properties of Free-Base Pyridyl- and N -Alkyl-4-Pyridylporphyrins in Nonaqueous Media

2015

International audience; Twelve structurally related pyridyl and meso-N-methylpyridylporphyrin derivatives are investigated electrochemically in different nonaqueous media. The UV/Vis spectrum of each newly investigated porphyrin was measured before and after electro-reduction and, based on this data, the site of electron transfer is proposed. An interaction occurs between the meso-pyridyl or meso-N-alkyl-4-pyridyl substituents and the porphyrin p-ring system, the magnitude of which depends upon the number of linked pyridyl or N-alkyl-4-pyridyl groups in the compound, the solvent, the supporting electrolyte, and/or other anions added to the solution.

Preorganization and reorganization as related factors in enzyme catalysis: the chorismate mutase case.

2003

In this paper a deeper insight into the chorismate-to prephenate-rearrangement, catalyzed by Bacillus subtilis chorismate mutase, is provided by means of a combination of statistical quantum mechanics/molecular mechanics simulation methods and hybrid potential energy surface exploration techniques. The main aim of this work is to present an estimation of the preorganization and reorganization terms of the enzyme catalytic rate enhancement. To analyze the first of these, we have studied different conformational equilibria of chorismate in aqueous solution and in the enzyme active site. Our conclusion is that chorismate mutase preferentially binds the reactive conformer of the substrate--that…

Seeking the Source of Catalytic Efficiency of Lindane Dehydrochlorinase, LinA.

2020

Herein we present the results of an in-depth simulation study of LinA and its two variants. In our analysis, we combined the exploration of protein conformational dynamics with and without bound substrates (hexachlorocyclohexane (HCH) isomers) performed using molecular dynamics simulation followed by the extraction of the most frequently visited conformations and their characteristics with a detailed description of the interactions taking place in the active site between the respective HCH molecule and the first shell residues by using symmetry-adapted perturbation theory (SAPT) calculations. A detailed investigation of the conformational space of LinA substates has been accompanied by desc…

A Multisite Molecular Mechanism for Baeyer-Villiger Oxidations on Solid Catalysts Using Environmentally Friendly H2O2 as Oxidant

2005

The molecular mechanism of the Baeyer-Villiger oxidation of cyclohexanone with hydrogen peroxide catalyzed by the Sn-beta zeolite has been investigated by combining molecular mechanics, quantum-chemical calculations, spectroscopic, and kinetic techniques. A theoretical study of the location of Sn in zeolite beta was performed by using atomistic force-field techniques to simulate the local environment of the active site. An interatomic potential for Sn/Si zeolites, which allows the simulation of zeolites containing Sn in a tetrahedral environment, has been developed by fitting it to the experimental properties of quartz and SnO 2 (rutile). The tin active site has been modeled by means of a S…

2002

Previous observations have suggested a role for nitric oxide in the activity of the globus pallidus, but this functional involvement has not yet been tested in vivo. The extracellular activity of single units of the globus pallidus was recorded, and neuronal nitric oxide synthase was inhibited by systemically administering 7-nitro-indazole to a group of anaesthetised rats. Forty-five per cent of cells responded with a decrease in the firing rate. In another group of rats, the microiontophoretic administration of 3-morpholino-sydnonimin-hydrocloride (a nitric oxide donor) induced an increase in neuronal firing rate (24/28 cells), whereas the administration of Nω-nitro-L-arginine methyl ester…

Gravity-Driven Infiltration and Subsidence Phenomena in Posidonia oceanica Residues

2019

A simplified infiltration model for highly permeable porous media was introduced, assuming the matric potential gradient as negligible compared to the gravitational gradient. This model enabled us to determine the delay time, i.e., the time that the water front takes (from the beginning of rainfall) to reach the bottom of the highly permeable layer. Posidonia oceanica (Linnaeus) Delile residues were used as a porous media, in order to study the infiltration process that provides salt leaching under natural rainfall when these residues are arranged in a storage area, before reusing. By using a laboratory rainfall simulator, delay times were measured to verify the applicability of the aforeme…

Computational Modeling of Biological Systems: The LDH Story

2010

Lactate dehydrogenases, LDH, catalyzed reaction has been used in this chapter as a conductor wire to present the evolution and difficulties on computing methods to model chemical reactions in enzymes, since the early calculations based at semiempirical level carried out in gas phase to the recent sophisticated simulations based on hybrid Quantum Mechanical/Molecular Mechanics Dynamics (QM/MM MD) schemes. LDH catalyzes the reversible transformation of pyruvate into lactate. The chemical step consists in a hydride and a proton transfer from the cofactor (NADH) and a protonated histidine (His195), respectively. This fact has generated a lot of controversy about the timing of both transfers in …