Electrostatic Influence Research Articles

A theoretical study of glucose mutarotation in aqueous solution

In this work the mechanism of glucose mutarotation is investigated in aqueous solution considering the most likely pathways proposed from experimental work. Two mechanisms are studied. The first involves an intramolecular proton transfer as proposed by textbooks of organic chemistry, and the second uses one solvent water molecule to assist proton transfer. Both mechanisms are studied in the gas phase and in aqueous solution with the help of a polarizable continuum model, which is adopted to introduce the electrostatic nonspecific influence of bulk solvent. The structures are fully characterized through the calculation of the corresponding vibrational frequencies. The rate coefficients for each mechanism are calculated following transition-state theory in both the gas phase and in aqueous solution. Values computed for the water-assisted pathway in the continuum solvent agree best with the experimental results.

Electrostatic Influence of PsaC Protein Binding to the PsaA/PsaB Heterodimer in Photosystem I

The absence of the PsaC subunit in the photosystem I (PSI) complex (native PSI complex) by mutagenesis or chemical manipulation yields a PSI core (P700-FX core) that also lacks subunits PsaD and PsaE and the two iron-sulfur clusters FA and FB, which constitute an integral part of PsaC. In this P700-FX core, the redox potentials (Em) of the two quinones A1A/B and the iron-sulfur cluster FX as well as the corresponding protonation patterns are investigated by evaluating the electrostatic energies from the solution of the linearized Poisson-Boltzmann equation. The B-side specific Asp-B558 changes its protonation state significantly upon isolating the P700-FX core, being mainly protonated in the native PSI complex but ionized in the P700-FX core. In the P700-FX core, Em(A1A/B) remains practically unchanged, whereas Em(FX) is upshifted by 42mV. With these calculated Em values, the electron transfer rate from A1 to FX in the P700-FX core is estimated to be slightly faster on the A1A side than that of the wild type, which is consistent with kinetic measurements.

Modal and Stability Analysis of a Micro-Beam Structure Actuated by Electrostatic Force

For the design of a vibrating micro-beam structure, modal and stability analyses of the structure actuated by electrostatic force is performed in the present study. Static deflection of the micro-beam caused by the electrostatic force is first obtained by solving the nonlinear equilibrium equation and the modal and stability characteristics are calculated at the static equilibrium position. It is found that the amplitude and the frequency of the applied electrostatic voltage influence the stability of the structure significantly. A design specification of a vibrating micro-beam structure can be effectively determined from the modal and the stability analysis results.

Induced conformational changes upon Cd 2+ binding at photosynthetic reaction centers

Cd(2+) binding at the bacterial photosynthetic reaction center (bRC) from Rhodobacter sphaeroides is known to inhibit proton transfer (PT) from bulk solvent to the secondary quinone Q(B). To elucidate this mechanism, we calculated the pK(a) for residues along the water channels connecting Q(B) with the stromal side based on the crystal structures of WT-bRC and Cd(2+)-bound bRC. Upon Cd(2+) binding, we observed the release of two protons from His-H126/128 at the Cd(2+) binding site and significant pK(a) shifts for residues along the PT pathways. Remarkably, Asp-L213 near Q(B), which is proposed to play a significant role in PT, resulted in a decrease in pK(a) upon Cd(2+) binding. The direct electrostatic influence of the Cd(2+)-positive charge on these pK(a) shifts was small. Instead, conformational changes of amino acid side chains induced electrostatically by Cd(2+) binding were the main mechanism for these pK(a) shifts. The long-range electrostatic influence over approximately 12 A between Cd(2+) and Asp-L213 is likely to originate from a set of Cd(2+)-induced successive reorientations of side chains (Asp-H124, His-H126, His-H128, Asp-H170, Glu-H173, Asp-M17, and Asp-L210), which propagate along the PT pathways as a "domino" effect.

Quantum microscopic vs. classical macroscopic calculations on the phenomenon of electrostatic influence

In order to compare microscopic and macroscopic approaches to the phenomenon of electrostatic influence, we have studied the atomic charges of an electric conductor, obtained either from macroscopic classical electrostatics, or microscopic quantum ab initio calculations. A torus was chosen as conducting material, built from valence monoelectronic atoms and influenced by an external point charge. The classical electric charges are obtained by integrating the macroscopic density over “atomic" sectors. This density is determined from a numerical integration of linearized electrostatic equations. The quantum charges are defined from Natural Orbitals in MP2/6-31G* calculations on clusters of different sizes. The overall agreement is good, with reasonable discrepancies due (i) to the continuity of the macroscopic model, which ignores the oscillations on atomic distances; and (ii) to the linearity constraint in the macroscopic equations.

Cysteine-scanning Mutagenesis of Serotonin Transporter Intracellular Loop 2 Suggests an α-Helical Conformation

Like other proteins involved in neurotransmitter transport, serotonin transporter (SERT) activity is regulated by multiple intracellular signal transduction pathways. The second intracellular loop (IL2) of SERT contains consensus sequences for cGMP-dependent protein kinase and protein kinase C. A 24-residue region of SERT including IL2, from Ile-270 through Ser-293, was analyzed by cysteine-scanning mutagenesis and chemical modification. 2-(Aminoethyl)methanethiosulfonate hydrobromide (MTSEA) failed to inhibit serotonin transport or binding of the cocaine analog 2beta-carbomethoxy-3beta-(4-[125I]iodophenyl)tropane (beta-CIT) in intact cells expressing these mutants, but it inactivated beta-CIT binding in membrane preparations. From the pattern of sensitivity, IL2 appears to extend from Trp-271 through Ile-290, a significantly longer region than that initially predicted by hydropathy analysis. Six mutants reacted with MTSEA much faster than the others, and the pattern of the more reactive mutations suggested that IL2 is in an alpha-helical conformation. Some of the mutants had significantly elevated transport rates, suggesting a possible mechanism for the regulation of SERT activity.

A CMOS integrated capacitive fingerprint sensor with 32-bit RISC microcontroller

The SOC implementation of a capacitive fingerprint sensor, which embeds the 32-bit microcontroller for performing an identification algorithm, is described for user authentication on small, thin, and portable equipment. The SOC is composed of a 160/spl times/192 pixel array with a sensor detection circuit and the embedded 32-bit RISC microcontroller. The proposed sensor detection circuit increases the voltage difference between a ridge and valley about 180% more than conventional detection circuit does and minimizes any electrostatic discharge influence by applying an effective isolation structure. The test chip was fabricated on a 0.35-/spl mu/m standard CMOS 1-poly 4-metal process.

Electrostatic influence of active-site waters on the nucleophilic aromatic substitution catalyzed by 4-chlorobenzoyl-CoA dehalogenase

The 4-chlorobenzoyl-CoA dehalogenase catalyzes the hydrolytic dechlorination of 4-chlorobenzoyl-CoA via a two-step mechanism, namely nucleophilic aromatic substitution and ester hydrolysis. The mutation of an active-site Histidine residue has been shown to reduce the catalytic activity in both the substitution and subsequent hydrolysis steps. In this communication, we report a quantum mechanical/molecular mechanical simulation of the potential of mean force for the substitution step, which confirms the increased barrier height in the H90Q mutant and provides evidence on the electrostatic influence of two active-site waters on the rate-limiting barrier.

Theoretical Studies on the Intramolecular Hydrogen Bond and Tautomerism of 8-Mercaptoquinoline in the Gaseous Phase and in Solution Using Modern DFT Methods

A theoretical quantum chemical study of the intramolecular hydrogen bonding interactions in 8-mercaptoquinoline has been carried out. Special attention has been paid to the rotation of S-H bond and intramolecular proton-transfer reactions. Therewith, the B3LYP/6-311++G(d,p), B3LYP/6-31+G(2d,2p), MPW1K/6-311++G(d,p), MPW1K/6-31+G(2d,2p), BH&HLYP/6-311++G(d,p), and G96LYP/6-311++G(d,p) methods have been used. By means of the Onsager and PCM reaction field methods, the effects of solvent on hydrogen-bond energies, conformational equilibria, rotational barriers, and tautomerism in aqueous solution have been studied. These simulations were done at the MPW1K/6-311++G(d,p) and B3LYP/6-311++G(d,p) levels. Natural-bond orbital analysis has been performed to study the intramolecular hydrogen bond (IHB) in the gaseous phase and in aqueous medium. The stability of forms under consideration in solution does not coincide with that in the gaseous phase, underlining a great importance of the electrostatic influence of solvent. Double-proton transfer in the prototropic tautomerization of 8-mercaptoquinoline, one water molecule complex in the gaseous phase and in solution, has been systematically studied. The double-proton transfer occurs concertedly and synchronously. The water-assisted tautomerization is kinetically less, but thermodynamically more favorable, compared to that of the single-proton transfer. As in the case with single-proton transfer, for water-assisted reaction, the tautomerization energies and barrier heights decrease with the increase in dielectric constant, which implies faster and more complete tautomerization of 8-mercaptoquinoline in a polar solvent.

A comparison of the electronic structure and NO adsorption on the (0 0 1)-V 2O 5 surfaces and (0 0 1)-V 2O 5 surfaces with Mo defects—DFT cluster studies

DFT calculations were performed for models of the (0 0 1) surfaces of non-reduced and reduced vanadia, represented by V 12O 30 and V 12O 29 clusters, as well as for models of (0 0 1) V 2O 5 surfaces with Mo defects, represented by V 11MoO 30 and V 11MoO 29 clusters. The clusters were embedded in a set of point charges in order to consider electrostatic bulk influence. Surface reduction was modeled by the removal of vanadyl/molybdenyl oxygen. Analysis of the electronic structure in all the clusters was conducted in terms of the Mulliken population analysis, Mayer bond-orders, atomic Fukui function values, and molecular electrostatic potential (MEP) distribution. The results show that substituting a V atom with Mo leads to a reduction of the adjacent metal atom, practically without changing the electronic properties of the oxygen atoms. Furthermore, the NO adsorption on the reduced surfaces of V 2O 5 and V 2O 5 with Mo defects has been studied. In all cases, adsorption is exothermic; the energetic stabilization is the largest for the V 11MoO 29 from which the molybdenyl atom was removed. However, the calculated adsorption energies are similar, within ca. 3 kcal/mol (12 kJ/mol). Thus, the effect of the molybdenum presence for energetic stabilization of adsorbed NO is not very distinct.

Like‐Charge Attraction: A Combined Electrostatic–Hydrodynamic Approach

This article discusses the like‐charge attraction of colloidal spheres close to a charged plate and compares results produced by an electrostatic and a hydrodynamic model with experimental data. Hydrodynamic coupling is shown to be the dominating effect, while the electrostatic influence may often be neglected. Some observations, however, can be explained only by means of a combined electrostatic–hydrodynamic model, which is derived in this work. The combined model is able to predict not only the attractive force between particles of similar charge close to a charged plate but also the change to a purely repulsive force once the sphere‐plate distance is further reduced. This prediction matches qualitatively results of experiments reported in the literature.

Influence of electrostatic interaction on fibrinogen adsorption on gold studied by imaging ellipsometry combined with electrochemical methods

Imaging ellipsometry was combined with electrochemical methods for studying electrostatic interactions of protein and solid surfaces. The potential of zero charge for gold-coated silicon wafer/solution interfaces wad determined by AC impedance method. The potential of the gold-coated silicon wafer was controlled at the potential of zero charge, and the adsorption of fibrinogen on the potential-controlled and non-controlled surfaces was measured in real time at the same time by imaging ellipsometry. The effect of electrostatic interaction was studied by comparing the difference between the potential of controlled adsorption and the potential of noncontrolled adsorption. It was shown that the rate of fibrinogen adsorption on the potentiostatic surface was faster than that on the nonpotentiostatic surface. The electrostatic influence on fibrinogen adsorption on the gold-coated silicon wafer was weak, so the hydrophobic interaction should be the major affinity.

Interactions of peptides with metallic cations. I. Complexes glycylglycine–M + (M=Li, Na)

In view of better understanding interactions of aminoacids and peptides with metallic cations, in the isolated state and in water, the model system glycylglycine–M + (M=Li, Na) has been studied theoretically. The computations have been performed with the help of the density functional theory (DFT) and the B3LYP functional. The extended basis set was the standard 6-31++G**. In solution we used a recent model of continuum with a multicentric multipole expansion of the charge distribution. Our study shows that low energy complexes with lithium and sodium are rather similar. In the isolated state, the most stable form corresponds to a bidentate complex in which the cation interacts with two oxygen atoms, one from the terminal COOH and one from the amidic carbonyl. In solution, the coordination of the cation in the most stable form is 3, the nitrogen of the end amino group being the third ligand. The energy range between the lowest energy structure and the highest energy one, in both cases, is slightly reduced under the electrostatic influence of the solvent.

Drosophila Alcohol Dehydrogenase: Acetate–Enzyme Interactions and Novel Insights into the Effects of Electrostatics on Catalysis

Drosophila alcohol dehydrogenase (DADH) is an NAD+-dependent enzyme that catalyzes the oxidation of alcohols to aldehydes/ketones and that is also able to further oxidize aldehydes to their corresponding carboxylic acids. The structure of the ternary enzyme-NADH-acetate complex of the slow alleloform of Drosophila melanogaster ADH (DmADH-S) was solved at 1.6 A resolution by X-ray crystallography. The coenzyme stereochemistry of the aldehyde dismutation reaction showed that the obtained enzyme-NADH-acetate complex reflects a productive ternary complex although no enzymatic reaction occurs. The stereochemistry of the acetate binding in the bifurcated substrate-binding site, along with previous stereochemical studies of aldehyde reduction and alcohol oxidation shows that the methyl group of the aldehyde in the reduction reaction binds to the R1 and in the oxidation reaction to the R2 sub-site. NMR studies along with previous kinetic studies show that the formed acetaldehyde intermediate in the oxidation of ethanol to acetate leaves the substrate site prior to the reduced coenzyme, and then binds to the newly formed enzyme-NAD+ complex. Here, we compare the three-dimensional structure of D.melanogaster ADH-S and a previous theoretically built model, evaluate the differences with the crystal structures of five Drosophila lebanonensis ADHs in numerous complexed forms that explain the substrate specificity as well as subtle kinetic differences between these two enzymes based on their crystal structures. We also re-examine the electrostatic influence of charged residues on the surface of the protein on the catalytic efficiency of the enzyme.

Electrostatic influence on rotational mobilities of sol-gel-encapsulated solutes by NMR and EPR spectroscopies.

The rotational mobilities of small solute molecules encapsulated in tetramethyl orthosilicate (TMOS) sol-gels have been investigated by EPR spectroscopy of encapsulated nitroxide probes and by high-resolution NMR spectroscopic measurements of transferred NOE's (trNOE's), of T(1)'s, and of T(1)'s in the rotating frame (T(1)rho). The two spectroscopic methods are sensitive to motions on different time scales and hence, are nicely complementary. Suites of neutral, positively, and negatively charged nitroxide probes (EPR) and of simple diamagnetic small molecules (NMR) were selected to disclose influences of electrostatic interactions with the sol-gel walls and to probe the presence of multiple populations of molecules in distinct regions of the sol-gel pores. For neutral and negatively charged solute probes, both techniques disclose a single population with a significantly increased average rotational correlation time, which we interpret at least in part as resulting from exchange between free-volume and transiently immobilized surface populations. The electrostatic attraction between cationic probes and the negatively charged sol-gel walls causes the positively charged probes to be more effectively immobilized and/or causes a greater percentage of probes to undergo this transient immobilization. The EPR spectra directly disclose a population of cationic probes which are immobilized on the X-band EPR time scale: tau(c) greater than or approximately equal 10(-7) s. However, NMR measurements of trNOE's and of T(1)rho demonstrate that this population does exchange with the free-volume probes on the slower time scale of NMR. This approach is equally applicable to the study of solutes within other types of confined spaces, as well.

Paracoccus pantotrophus pseudoazurin is an electron donor to cytochrome c peroxidase.

The gene for pseudoazurin was isolated from Paracoccus pantotrophus LMD 52.44 and expressed in a heterologous system with a yield of 54.3 mg of pure protein per liter of culture. The gene and protein were shown to be identical to those from P. pantotrophus LMD 82.5. The extinction coefficient of the protein was re-evaluated and was found to be 3.00 mM(-1) cm(-1) at 590 nm. It was confirmed that the oxidized protein is in a weak monomer/dimer equilibrium that is ionic-strength-dependent. The pseudoazurin was shown to be a highly active electron donor to cytochrome c peroxidase, and activity showed an ionic strength dependence consistent with an electrostatic interaction. The pseudoazurin has a very large dipole moment, the vector of which is positioned at the putative electron-transfer site, His81, and is conserved in this position across a wide range of blue copper proteins. Binding of the peroxidase to pseudoazurin causes perturbation of a set of NMR resonances associated with residues on the His81 face, including a ring of lysine residues. These lysines are associated with acidic residues just back from the rim, the resonances of which are also affected by binding to the peroxidase. We propose that these acidic residues moderate the electrostatic influence of the lysines and so ensure that specific charge interactions do not form across the interface with the peroxidase.

A new method for charge trapping measurement during electron beam irradiation: application to glass containing alkali ions and single-crystalline quartz

The aim of this work is to study the electron irradiation behaviour of an insulating material surface using a scanning electron microscope (SEM). The charging phenomena caused in two kinds of insulating materials (quartz and glass) by continuous electron irradiation have been observed. The discharging phenomena following switching off of irradiation have also been studied. The trapped charge density is determined by using the so-called electrostatic influence method based on the measurement, during and after the irradiation, of the influence and leakage currents using an arrangement adapted to the SEM. The experimental results reveal that the behaviour under irradiation of glass is entirely different from that of quartz. The trapped charges are found to be different, and the dependence of charging on the primary beam energy is discussed.The charging and discharging time constants have been determined accurately, and their evolution versus the mean electron penetration depth is qualitatively explained. Moreover, the role of secondary electron emission in the regulation mechanism of charging is underlined.

Effect of Ionic Strength on the Binding of α-Chymotrypsin to Nanoparticle Receptors

Negatively charged carboxylate-functionalized mixed monolayer protected clusters (MMPCs) effectively bind and inhibit alpha-chymotrypsin based on complementary electrostatic surface recognition. We demonstrate that this binding can be disrupted by varying the ionic strength of the medium. Enzyme activity in the presence of MMPCs increases from 5% to 97% of native activity as salt concentration is increased from 0 to 1.5 M. Variation of ionic strengths after complete binding over 13 h results only in a modest restoration of enzymatic activity (< 35%). The conformation of chymotrypsin was characterized using circular dichroism and fluorescence spectroscopy, correlating structure with enzymatic activity. This work provides a useful insight of the electrostatic influence on protein--MMPC interactions and can be applied toward MMPC-based controlled release of proteins in vivo.

Dynamics Studies of a Malachite Green−RNA Complex Revealing the Origin of the Red-Shift and Energetic Contributions of Stacking Interactions

RNA plays a central role in many biological processes and is therefore an important target for drug development. In recent years an increasing wealth of structural and functional information about RNA−ligand complexes has been obtained using in vitro selected RNAs (aptamers). However, all those studies focused on structure and changes of the nucleic acid and mostly considered the ligand as a rigid target. Experimental characterization of the dynamics of a malachite green (MAG)−RNA aptamer complex revealed surprisingly asymmetric changes in the 13C chemical shift of the ligand methyl groups, which indicate that the dye undergoes changes in its conformation and charge distribution upon binding, in addition to the red-shift in its maximum absorption frequency. Earlier computational work explored the electrostatic influence of the highly charged RNA backbone and surrounding counterions for these asymmetrical changes in 13C chemical shift. The work presented here examines the dynamical nature of the MAG molecule inside the RNA ligand-binding site using molecular dynamics with explicit solvent to explore the intermolecular and dynamic influences on the red-shift and to calculate the binding affinity. An induced fit behavior, similar to that caused by the electrostatic field alone, is observed. The binding strength of a series of malachite green derivatives correlates with the structural flatness of the ligand. These findings are important for the rational design of RNA ligands and for understanding the properties of RNA−ligand complexes.

Electrostatic influence on ion transport through the alphaHL channel.

The current-voltage relationship of a single Staphylococcus aureus alpha-hemolysin (alphaHL) channel is nonlinear, rectifying, and depends on the bulk pH and the ionic strength. The data are described qualitatively by a simple one-dimensional Nernst-Planck analysis in which the fixed charges inside and near the pore's entrances affect the transport of ions through the channel. The distances of these fixed charges from one of the channel's entrances are obtained from the channel's crystal structure. The model demonstrates that rectification of monovalent ion flow through the alphaHL channel can be related to the asymmetry in the location of the ionizable amino acid side chains.