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PubMed1997

Theoretical study of the electrostatic and steric effects on the spectroscopic characteristics of the metal-ligand unit of heme proteins. 3. Vibrational properties of Fe(III)CN-.

The vibronic theory of chemical activation and quantum chemical calculations are applied to calculate the stretching vibrational frequency of cyanide, coordinated by the complex of ferric porphyrin with imidazole. The results show that the frequency of the stretching vibration of the cyanide strongly depends on its coordination geometry and is hardly affected by the electrostatic perturbations of reasonable magnitude. The comparison of these results with the experimental data on the cyanide complexes of different heme proteins and their models allows to elucidate the cyanide coordination geometry. The combined infrared and resonance Raman scattering experimental investigation of the cyanide and carbonyl complexes with the same heme protein is proposed to distinguish between the steric and electrostatic contributions to the heme-protein interaction.

Chemical Phenomena↗
PubMed1989

Electrostatic complementarity in molecular associations.

In this paper, I attempt to summarize the main qualitative features of electrostatic complementarity and similarity, important determinants of molecular recognition. The two aspects, Coulombic and hydrophobic matching, can be formulated in terms of molecular electrostatic potentials and fields. The Coulombic aspect is equivalent to the requirement to produce a potential pattern in the host cavity that is opposite in sign to that emerging from a guest. Hydrophobic complementarity is best described by the similis simili gaudet principle. This means that field patterns near the interacting molecular surfaces must be of similar magnitude. The above rules, which may find useful application in molecular graphics, were studied for different cases of enzyme-ligand interactions in trypsin. A further example, a noncovalent structural model of the catalytic diad in Streptomyces Griseus protease A, supports the observation that the same molecular entities form similar associations even in different environments, as is the case in the complex of small species in a crystal and amino acid residues with structural water molecules in a protein.

Binding Sites↗
PubMed1998

Effect of charge interactions on the carboxylate vibrational stretching frequency in c-type cytochromes investigated by continuum electrostatic calculations and FTIR spectroscopy.

The FTIR spectra of the asymmetric carboxylate absorption region of three c-type cytochromes--namely horse heart, yeast and bonito cytochromes c--as well as continuum electrostatic calculations performed on their respective protein matrices, show that these combined methods can target specific protein regions and yield pertinent protein charge information that correlates with the observed spectral data. Deconvolution of the IR carboxylate stretch frequency region (1525-1675 cm-1) in the three cytochromes yield different v(oco)a distributions. In the case of the bonito cytochrome c carboxylates, two v(oco)a populations are clearly distinguishable in the deconvoluted spectra--which is not the case for the more complex v(oco)a deconvolutions of the other two cytochromes. The frequency distributions of the calculated potentials are consistent with the experimental observations and we conclude that the IR carboxylate absorption in proteins can be modified by the electrostatic environment.

Animals↗
PubMed1998

A spectroscopic and molecular dynamics study of native and of a mutant of Xenopus laevis Cu,Zn superoxide dismutase: mechanistic consequences of replacing four charged amino acids on the 'electrostatic' loop.

Neutralisation by site-directed mutagenesis of four charged and highly conserved residues of the electrostatic loop of Cu,Zn superoxide dismutase from Xenopus laevis, involved in the electrostatic attraction of the substrate: Lys120-->Leu, Asp130-->Gln, Glu131-->Gln and Lys134-->Thr, gives rise to a mutant enzyme which displays an affinity for monovalent inhibitor anions, such as N3-, higher than that of the wild type. Analysis of 300 ps of molecular dynamics simulation carried out on the wild type and on the Xenopus laevis Cu,Zn superoxide dismutase mutant indicates that the two proteins display a distinct dynamical behaviour. In particular the root mean square deviation from the starting structure, the number of residues in random coil conformations, the number of residues in unfavourable regions of the Ramachandran plot indicate that the mutant displays a rigidity higher than the native enzyme. This is also evidenced by the loss of dynamical cross correlations in the simulation of the mutant, which on the other hand are present in the wild type. Moreover the mutant protein shows a different organisation of the backbone-to-backbone hydrogen bonds network that generates a rigid structure leading to an increase of the active site accessibility when compared to the native enzyme. It is suggested that the rigid state in which the mutant is confined, accompanied by the increase of the solvent accessible surface of the active site may explain the difference in reactivity toward the inhibitor anion.

Amino Acid Sequence↗
PubMed1999

Optimized atomic radii for protein continuum electrostatics solvation forces.

Recently, we presented a Green's function approach for the calculation of analytic continuum electrostatic solvation forces based on numerical solutions of the finite-difference Poisson-Botzmann (FDPB) equation [Im et al., Comp. Phys. Comm. 111 (1998) 59]. In this treatment the analytic forces were explicitly defined as the first derivative of the FDPB continuum electrostatic free energy with respect to the coordinates of the solute atoms. A smooth intermediate region for the solute-solvent dielectric boundary needed to be introduced to avoid abrupt discontinuous variations in the solvation free energy and forces as a function of the atomic positions. In the present paper we extend the set of optimized radii, which was previously parametrized from molecular dynamics free energy simulations of the 20 standard amino acids with explicit solvent molecules [Nina et al., J. Phys. Chem. 101 (1997) 5239], to yield accurate solvation free energy by taking the influence of the smoothed dielectric region into account.

Journal Article↗
PubMed2003

Electrostatic interactions observed when imaging proteins with the atomic force microscope.

The atomic force microscope (AFM) is now an established and valuable tool for the study of biological macromolecules in aqueous environments. In this paper we form a patterned boundary via the microcontact printing of individually isolated proteins, covalently attached to a solid support. We use this boundary to investigate electrostatic interactions that can occur between an AFM tip and a protein surface during imaging in solution. The observed height variations of the protein film are found to be a combination of not only structural considerations and thickness of the protein film, but also the repulsive contribution from electrostatic interactions between the AFM tip and the sample. These variations in measured heights of the protein surface can be described by Derjaguin, Landau, Verway, Overbeek (DLVO) theory. Our experimental results show that height measurements can be manipulated either negatively or positively by adjusting the pH and concentration of the electrolyte buffer that is utilised.

Algorithms↗
PubMed2000

Initial resolution measurements of an improved magnetic-electrostatic detector objective lens for LVSEM

In this paper we present some initial resolution measurements of an improved magnetic-electrostatic detector objective lens for a low-voltage scanning electron microscope. The electron optical design of the lens was already proposed by the authors [G. Knell, E. Plies, Nucl. Instr. & Meth. A 427 (1999) 99]. The magnetic circuit of this lens has a radially arranged pole-piece gap. Thus, the specimen is immersed in a strong magnetic field of 106 mT (working distance: 1 mm, primary electron energy: 200 eV). The electrostatic field strength of our optimized lens variant amounts to a moderate value of 100 V/mm for a working distance of 1 mm. At a final beam energy of 1 keV a resolution of 3 nm, at 260 eV a resolution of 5 nm was obtained.

Journal Article↗
PubMed1996

Electrostatic attraction: the driving force for the presynaptic vesicle-cell membrane fusion.

In this theoretical conception, it is suggested that the driving force for presynaptic vesicle-cell membrane fusion during action potential that results with the neurotransmitter release is the electrostatic attraction of the differently charged outer lipid layer of the presynaptic vesicle membrane and the inner lipid layer of the cell membrane. All other previously described processes that take place during presynaptic vesicle-cell membrane fusion could serve to modulate the basic electrostatic process presented here.

Animals↗
PubMed2003

Electrostatic charge on spacer devices and salbutamol response in young children.

Electrostatic charge on plastic spacer devices may affect the efficacy of inhaled drugs, but its consequences have never been evaluated in asthmatic children with airflow limitation. At the end of a positive metacholine challenge, 64 children (51.3+/-12.9 months, 32 boys, specific airway resistance (SRaw) 257.1+/-56.7% and forced expiratory volume in 1s (FEV(1)) 64.2+/-17.9% of the predicted value) inhaled one puff of hydrofluoroalkane-134a (HFA-134a) salbutamol (Ventoline((R))), and 15min later two other puffs (total dose of 300 microgram), delivered through either a new static Babyhaler((R)) (n=21), a detergent-coated, reduced static, Babyhaler((R)) (n=20), or a metal NES-Spacer((R)) (n=23) equipped with facemask. SRaw and FEV(1) were measured after each treatment and compared between groups by a Kruskal-Wallis test. The first 100 microgram salbutamol induced a 151.7+/-43.9% decrease in SRaw and a 19.9+/-10.6% increase in FEV(1). Additional 200 microgram salbutamol allowed a supplementary decrease of 35.1+/-25.7% in SRaw and increase of 12.1+/-11.8% in FEV(1), without significant difference between the spacer devices. Electrostatic charge on spacer devices does not affect bronchodilation with HFA-134a salbutamol in metacholine-challenged pre-school children. This could be in part explained by the use of supramaximal doses of salbutamol.

Administration, Inhalation↗
PubMed1999

Surface modification and electrostatic charge of polystyrene particles.

Particle surface modification by poloxamer adsorption can significantly alter the electrostatic charge, adhesion behaviour and consequently handling properties of a material. The charge reduction on polystyrene spheres achieved by this modification technique is dependent on the concentration, molecular weight and conformation of poloxamer at the particle surface. Adsorption isotherms of poloxamers on polystyrene particles follow a Langmuir profile and there is an apparent correlation between the extent of adsorption and ability of poloxamer to reduce electrostatic charge. Surface analysis techniques, X-ray photoelectron spectroscopy and Time of Flight Secondary Ion Mass Spectrometry have generated data on the thickness of the adsorbed poloxamer layer and provided evidence to suggest that the polypropylene oxide component of the poloxamer adsorbs to the polystyrene surface and there is a polyethylene oxide rich outer surface which may influence the charge alteration.

Adsorption↗
PubMed1997

Synaptotagmin-syntaxin interaction: the C2 domain as a Ca2+-dependent electrostatic switch.

Synaptotagmin I is a synaptic vesicle protein that is thought to act as a Ca2+ sensor in neurotransmitter release. The first C2 domain of synaptotagmin I (C2A domain) contains a bipartite Ca2+-binding motif and interacts in a Ca2+-dependent manner with syntaxin, a central component of the membrane fusion complex. Analysis by nuclear magnetic resonance spectroscopy and site-directed mutagenesis shows that this interaction is mediated by the cooperative action of basic residues surrounding the Ca2+-binding sites of the C2A domain and is driven by a change in the electrostatic potential of the C2A domain induced by Ca2+ binding. A model is proposed whereby synaptotagmin acts as an electrostatic switch in Ca2+-triggered synaptic vesicle exocytosis, promoting a structural rearrangement in the fusion machinery that is effected by its interaction with syntaxin.

Amino Acid Sequence↗
PubMed2001

Near-infrared induced membrane surface electrostatic potential, fluorescent measurements.

The change of the electrostatic surface potential induced by near-infrared radiation was monitored by the fluorescence probe technique. Fluorescence intensity of 1-anilinonaphtalene-8-sulfate (ANS) was studied in the pH range 4.8-9.5 before and after exposition to NIR (700-2000 nm). The intensity of fluorescence changed (decreased after exposition on radiation) only at pH 7.4. The effect is due to decreasing concentration of ANS in liposome membrane after irradiation. The modified distribution of ANS in liposome membrane upon irradiation is attributed to the dehydration of membrane surface. Dehydratation diminishes the electrostatic surface potential about 36+/-15 mV.

Journal Article↗
PubMed1991

Effect of calcium ions on cell surface electrostatics of Bacteroides gingivalis and other oral bacteria.

Surface electrostatics of Bacteroides gingivalis and other oral bacteria were examined. A polarization circuit was employed using platinum electrodes exposed in each bacterial suspension and the number of bacteria adsorbed to the anode and cathode were then estimated. In all bacteria (B. gingivalis, Streptococcus sobrinus, S. mutans, S. salivarius, S. sanguis and Actinomyces viscosus), the number of cells adsorbed to the anode were much greater than the number of cells adsorbed to the cathode. Treating these bacteria with calcium ions tended to decrease the ratio of the number of cells adsorbed to the anode to the number of cells adsorbed to the cathode in all bacteria examined. Moreover, in the case of B. gingivalis, the number of cells adsorbed to the anode and cathode was in an inverse relationship to the number counted before calcium ion treatment. These findings indicate that the cell surfaces of oral bacteria are generally negatively charged but only the cell surface electrostatics of B. gingivalis was dramatically affected by calcium ion treatment. Thus, divalent metal bridges such as calcium bridges contribute to the adherence of the periodontopathic bacterium, B. gingivalis rather than to that of other oral bacteria including cariogenic bacteria.

Actinomyces↗
PubMed1998

Electrostatic effects in macromolecules: fundamental concepts and practical modeling.

The past few years have seen an exponential growth in the calculations of electrostatic energies of macromolecules and an increased recognition of the crucial role of electrostatic effects. This review considers the current state of the field. Focus is placed on calculations of pKas, redox potentials and binding energies in macromolecules and clarification of the fact that the value of the dielectric 'constant' of a protein depends on its definition and that small dielectric constants should not be used in describing charge-charge interactions by current continuum models.

Enzymes↗
PubMed1995

Electrostatic analysis of TEM1 beta-lactamase: effect of substrate binding, steep potential gradients and consequences of site-directed mutations.

BACKGROUND: Escherichia coli TEM1 is a penicillinase and belongs to class A beta-lactamases. Its naturally occurring mutants are responsible for bacterial resistance to beta-lactamin-based antibiotics. X-ray structure determinations show that all class A beta-lactamases are similar, but, despite the numerous kinetic investigations, the reaction mechanism of these enzymes is still debated. We address the questions of what the molecular contexts during the acylation and deacylation steps are and how they contribute to the efficiency of these penicillinases. RESULTS: Electrostatic analysis of the 1.8 A resolution refined X-ray structure of the wild-type enzyme, and of its modelled Michaelis and acyl-enzyme complexes, showed that substrate binding induces an upward shift in the pKa of the unprotonated Lys73 by 6.4 pH units. The amine group of Lys73 can then abstract the Ser70 hydroxyl group proton and promote acylation. In the acyl-enzyme complex, the deacylating water is situated between the carboxylate group of Glu166, within the enzyme, and the estercarbonyl carbon of the acyl-enzyme complex, in an electrostatic potential gradient amounting to 30 kTe-1 A-1. Other residues, not directly involved in catalysis, also contribute to the formation of this gradient. The deacylation rate is related to the magnitude of the gradient. The kinetic behavior of site-directed mutants that affect the protonation state of residue 73 cannot be explained on the basis of the wild-type enzyme mechanism. CONCLUSIONS: In the wild-type enzyme, the very high rates of acylation and deacylation of class A beta-lactamases arise from an optimal chemical setup in which the acylation reaction seems triggered by substrate binding that changes the general base property of Lys73. In site-directed mutants where Lys73 is protonated, acylation may proceed through activation of a water molecule by Glu166, and Lys73 contributes as a proton shuffle partner in this pathway.

Acylation↗
PubMed1997

Electrostatic interaction of myristoylated proteins with membranes: simple physics, complicated biology.

Cell membrane association by several important peripheral proteins, such as Src, MARCKS, HIV-1 Gag, and K-Ras, requires nonspecific electrostatic interactions between a cluster of basic residues on the protein and acidic phospholipids in the plasma membrane. A simple theoretical model based on the nonlinear Poisson-Boltzmann equation describes well the experimentally measured electrostatic association between such proteins and the cell membrane.

Amino Acid Sequence↗
PubMed2002

Electrostatic control of the membrane targeting of C2 domains.

Many proteins involved in signal transduction and vesicle trafficking contain C2 domains whose membrane association is often regulated by calcium. Here, finite-difference Poisson-Boltzmann calculations are used to describe the electrostatic interactions between C2 domains of known structure and phospholipid membranes. The results explain how calcium binding can drive the association of some C2 domains to negatively charged membranes and others to neutral, zwitterionic membranes. Nonspecific electrostatic interactions are shown to be a general feature of many C2 domains of known structure, including the calcium-independent C2 domain of the PTEN tumor suppressor.

Animals↗
PubMed2004

Infrared intensity in dielectric media by an electrostatic model.

A change in an infrared intensity in dielectric media is treated by an electrostatic model. The basic model is originally formalized for a dipolar liquid. The model is satisfactorily applied to the infrared intensity of the C-H stretching of chloroform, which changes 22 times large in the liquid state at -43 degrees C as in the gaseous state. A change in the infrared intensity in lithium ammonium tartrate, where a ferroelectric phase transition takes place, is analyzed on the basis of a local polarization above T(c) or a spontaneous polarization below T(c), deducing important quantities on a phase transition. A difference in the infrared intensity of the C-Br stretching of 1,10-dibromodecane between the urea clathrate and the crystalline state is analyzed by evaluating electric fields due to bond moments and oscillating dipoles. These analyses confirm the mechanism of the change in the absolute infrared intensity, which originates from an electrostatic interaction with an electric field applied to a molecule or a functional group closely related to a normal mode.

Carbon↗