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At least 847 records · Page 47Linked to original sources
PubMed2005

Enzymatic lipid removal from surfaces--lipid desorption by a pH-induced "electrostatic explosion".

Removal of lipidic molecules from surfaces can be accomplished using detergents containing lipases. Surface cleaning is usually performed under alkaline conditions due to increased solubility of the hydrolysis products, especially free fatty acids. This paper shows that removal of a triacylglycerol film from a surface can be dramatically enhanced in a sequential system where pH is shifted to alkaline conditions after an initial lipolytic reaction period at or below neutral pH. Data from three different biophysical techniques, attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), quartz crystal microbalance with dissipation monitoring (QCM-D), and total internal reflection fluorescence spectroscopy (TIRF) clearly show the effects of such cleaning procedure. Initially the reaction is carried out at pH below the pKa value of the fatty acids formed upon triacylglycerol hydrolysis, and the protonated fatty acids accumulate in the film. The mechanism of lipid removal, induced by increasing pH to a value above the fatty acid pKa, is explained by a burst caused by electrostatic repulsion between rapidly ionised fatty acids, i.e. by an "electrostatic explosion". Performing the initial hydrolysis at pH 6 and the subsequent rinse at pH 10, using triolein as model substrate, lipid removal from surfaces by both commercial detergent lipases and non-commercial lipases was significantly improved compared to a reaction at constant pH 10.

Adsorption↗
PubMed2005

Electrostatics of heterogeneous monolayers. Constitutive equations and mathematical models.

A new approach for modelling the electrochemistry of complex heterogeneous systems, composed of various bulk, surface and line phases, is proposed. A key step in it is the generalization of standard electrostatic boundary conditions, considered as 2D, 1D Poisson-Boltzmann equations. This viewpoint is applied to experimentally studied systems of two co-existing (e.g. liquid expanded, liquid condensed) monolayer phases. Another important feature of the given model is that, at electrochemical equilibrium, like with bulk double layers, surface double layers emerge on both sides of the contact line dividing the surface phases. A general mathematical formulation of the problem is proposed in respect of the electric potential as distributed in the complex heterogeneous system. Comments are also provided on the methods of solving the problem. The example illustrates a simplified system of two semi-infinite surface phases (monolayers) having equivalent parameters and divided by a contact line. The paper discusses the expressions obtained for the electrical potential, electrostatic energy, etc. and their dependence on the parameters of the system. Special focus is taken of the work of contact line formation.

Colloids↗
PubMed2004

Fabrication of alternating polycation and albumin multilayer coating onto stainless steel by electrostatic layer-by-layer adsorption.

Multilayer films consisting of polyethylenimine (PEI) and albumin were successfully prepared on biomedical 316L stainless steel surface via electrostatic self-assembly of the PEI and albumin. The process of electrostatic self-assembly of PEI/albumin was monitored by125I radiolabeling, electrochemical impedance spectroscopy (EIS) and atomic force microscopy (AFM). The EIS data revealed that the multilayer coating was stable in Tris-HCl (pH 7.35) buffer solution for 21 days. 125I radiolabeling experiments indicated that less than 10% albumin was eluted by PBS in 45 days. Static platelet adhesion experiments indicated that the PEI/albumin deposited on stainless steel could resist platelet adhesion effectively. Such an easy processing and shape-independent method may have good potential for surface modification of cardiovascular devices.

Adsorption↗
PubMed2006

Effect of electrostatic interactions on binding and retention of DNA oligomers to PNA liposomes assessed by FRET measurements.

A FRET-based method is used to observe the desorption of di-alkyl peptide nucleic acid amphiphiles (PNAA) from liposomes occurring on binding of complementary DNA oligomers. PNA liposomes were prepared containing fluorescein-labeled PNAA and rhodamine-labeled dipalmitoylphosphoethanolamine (DPPE). These liposomes showed efficient energy transfer from the fluorescein to rhodamine, with an average donor-to-acceptor distance of 5.91nm. In low-ionic-strength buffer (50mM Tris-HCl, pH 8.0), the FRET signal was maintained in the presence of a stoichiometric amount of 10- and 20-mers DNA complements, but the signal attenuated for 40-mer complements, indicating that DNA first binds the PNAA before the PNAA/DNA duplex desorbs from the lipid bilayer. The FRET signal was maintained in the presence of 10-, 20-, 40-, and 60-mer DNA in high ionic-strength buffer, showing that the driving force for the desorption is electrostatic repulsion between the bound DNA oligomer and the liposome surface. This conclusion is corroborated by comparison of the PNA/DNA binding energy, the energy of adsorption of the di-alkyl PNAA to the lipid bilayer, and a calculation of the DNA/lipid bilayer electrostatic repulsion using the linearized Poisson-Boltzmann equation.

Biosensing Techniques↗
PubMed2006

Electrostatic characterisation of inhaled powders: effect of contact surface and relative humidity.

Electrostatic charge accumulation on drug and excipient powders arising from interparticulate collisions or contacts between particles and other solid surfaces often leads to agglomeration and adhesion problems during the manufacture and use of dry powder inhaler (DPI) formulations. The aim of this work was to investigate the role of triboelectrification in particle interactions between micronised drug (salbutamol sulphate or ipratropium bromide monohydrate) and excipient (alpha-lactose monohydrate, 63-90 microm) during mixing in cylindrical vessels constructed from stainless steel, polypropylene and acetal under selected relative humidity (rh) conditions (0-86%). The charge was found to depend on both the nature of the powders and the mixing vessel surface. In addition, coating the vessels with drug or excipient removed the influence of the vessel material on charge generation, thus providing a technique to investigate interactions between the drug and excipient substances. A triboelectric series of all materials used, placed ipratropium at the positive end and polypropylene at the negative end. Micronised drug profoundly altered the charging properties of lactose in drug (1.46%, w/w)/lactose DPI formulations. An increase in rh in the range 0-86% produced a corresponding decrease in charge and adhesion values for each drug, lactose and DPI formulation during triboelectrification with each mixing vessel surface. The results provide increased knowledge of the role of electrostatics in DPI technology.

Administration, Inhalation↗
PubMed2004

On the origin of the electrostatic barrier for proton transport in aquaporin.

The nature of the electrostatic barrier for proton transport in aquaporins is analyzed by semimacroscopic and microscopic models. It is found that the barrier is associated with the loss of the generalized solvation energy upon moving from the bulk solvent to the center of the channel. It is clarified that our solvation concept includes the effect of the protein polar groups and ionized residues. The nature of the contributions to the solvation barrier is examined by using the linear response approximation. It is found that the residues in the NPA region contribute much less than what would be deduced from calculations that do not consider the protein reorganization. It is clarified that the contributions of different structural or electrostatic elements to the solvation barrier can be established by removing these elements and examining the corresponding effect on the barrier height. Using this definition and "mutating" the NPA residues to their non-polar analogues establishes that these residues do not provide the major contribution to the solvation barrier.

Aquaporin 1↗
PubMed2005

Charge substitution shows that repulsive electrostatic interactions impede the oligomerization of Alzheimer amyloid peptides.

The strong pH dependence of A beta oligomerization could arise from favorable intermolecular charge-charge interactions between His and carboxylate groups, or, alternatively, by mutual electrostatic repulsion of peptide molecules. To test between these two possibilities, the pH dependence of the oligomerization of A beta and three charge substitution variants with Asp, Glu and His substituted by Ala is measured. All four peptides oligomerize, as detected by thioflavin T fluorescence, turbidity, and amyloid fibril formation; therefore, specific charge-charge interactions are nonessential for oligomerization. The strong negative correlation between net charge and oligomerization indicates that electrostatic repulsion between A beta monomers impedes their association.

Alzheimer Disease↗
PubMed2005

Cooperative effect of hydrophobic and electrostatic forces on alcohol-induced alpha-helix formation of alpha1-acid glycoprotein.

Alpha1-acid glycoprotein (AGP) is a serum glycoprotein that mainly binds basic drugs. Previous reports have shown that AGP converts from a beta-sheet to an alpha-helix upon interaction with biomembranes. In the current studies, we found that alkanols, diols, and halogenols all induce this conformational change. Increased length and bulkiness of the hydrocarbon group and the presence of a halogen atom promoted this conversion, whereas the presence of a hydroxyl group inhibited it. Moreover, the effect was dependent on the hydrophobic and electrostatic properties of the alcohols. These results indicate that, in a membrane environment, hydrophobic and electrostatic factors cooperatively induce the transition of AGP from a beta-sheet to an alpha-helix.

Alcohols↗
PubMed2005

Recognition of stable protein mutants with 3D stochastic average electrostatic potentials.

As more and more proteins are applied to biochemical research there is increasing interest in studying their stability. In this study, a Markov model has been used to calculate molecular descriptors of the protein structure and these are called the average electrostatic potentials (xi(k)). These descriptors were intended to encode indirect electrostatic pair-wise interactions between amino acids located at Euclidean distance k within a given 3D protein backbone. The different xi(k) values could be calculated for the protein as a whole or for specific protein regions (orbits), which include amino acids that lie within a given range of distances from the center of charge of the protein. In this work we calculated the xi(k) values for 657 mutants of different proteins. A Linear Discriminant Analysis model correctly classified a subset of 435 out of 493 proteins according to their thermal stability - a level of predictability of 88.2%. This experiment was repeated with three additional subsets of proteins selected at random from the initial series of 657. More specifically, the model predicted 314/356 (88.2%) of mutants with higher stability than the corresponding wild-type protein and 264/301 (86.7%) of proteins with near wild-type stability. These results illustrate the possibilities for the average stochastic potentials xi(k) in the study of 3D-structure/property relationships for biochemically relevant proteins.

Markov Chains↗
PubMed2005

Inhibition of foodborne bacteria by native and modified protamine: importance of electrostatic interactions.

Protamine is a naturally occurring cationic antimicrobial peptide (CAP) that has shown some promise for control of microorganisms in food. It was hypothesized that the antibacterial effect is partially due to protamine's electrostatic affinity to the negatively charged cell envelopes of actively growing bacteria. However, nonspecific binding of the CAPs to negatively charged food particles may reduce the effect in food systems. To test the hypothesis, the antibacterial efficacies of native and reduced charge protamines (chemically modified by randomly blocking 10 to 71% of the guanido groups of the arginine residues) were compared in model and food systems. In Tryptic Soy Broth, moderate reductions of charge (<26%) resulted in either a similar or slightly improved antimicrobial efficacy, measured as the minimum inhibitory concentration (MIC) toward 21 food-related bacteria. Further reductions in positive charge led to lower antimicrobial activity. Compared to protamine, the affinity of reduced charge protamines (10 and 20%) for binding to Listeria monocytogenes cells was higher at pH 7 and 8. As perhaps would be expected, L. monocytogenes is most sensitive to modified protamines in this pH range. Protamine with reduced charge (14 and 23%) inhibited growth of L. monocytogenes in milk as well as total bacteria and coliforms in ground beef significantly (P<0.05) better than native protamine, demonstrating that the reduced charge peptides were more inhibitory in these high protein food matrices. Electrophoretic analysis of the 21 bacteria revealed a statistically significant (P<0.01) relationship with antimicrobial activity, where the most negatively charged bacteria were also the most susceptible to protamine. In conclusion, components of food matrices interfered with the antibacterial effects of the peptides, however; these undesirable interferences were reduced by altering the electrostatic properties of protamine.

Anti-Bacterial Agents↗
PubMed2005

Investigation of electrospray ionization and electrostatic focusing devices using a three-dimensional electrospray current density profiler.

A novel instrument for profiling the current density of nanoelectrospray ionization plumes in three dimensions has been developed. A hemispherically-shaped electrostatic lens at atmospheric pressure is found to be able to compress the space-charge in nano-ESI and increase the average current density in the plume to three times the nominal value. Ion transmission into a single-quadrupole mass spectrometer is found to roughly double using the electrostatic lens. Data also suggest that ion transmission into the first vacuum region for a skimmer-type mass spectrometer interface using nano-ESI may be typically 40% or better with no special focusing device used.

Journal Article↗
PubMed2004

Effect of electrostatic energy on partitioning of proteins in aqueous two-phase systems.

An attempt has been made to adopt a different approach to evaluate the effect of a protein's charge on its partitioning behaviour in PEG/salt aqueous two-phase systems (ATPS). This has been done using a computer methodology (DelPhi) that allows the calculation of the electrostatic solvation energy that charged proteins present in a particular media such as aqueous polymer-salt systems. This calculation was done for the protein in each of the phases and a correlation was investigated that related the electrostatic energy difference of the protein in each of the phases and its partition coefficient in ATPS. Such correlation resulted in a statistical model that also included the effect of molecular weight and a shape factor at each particular pH. A global correlation which included the effect of pH was also found. All the correlations were statistically evaluated and gave good results.

Chromatography, Liquid↗
PubMed2004

Effect of electrostatic, hydrodynamic, and Brownian forces on particle trajectories and sieving in normal flow filtration.

Particle deposition and fouling are critical factors governing the performance of microfiltration and ultrafiltration systems. Particle trajectories were evaluated by numerical integration of the Langevin equation, accounting for the combined effects of electrostatic repulsion, enhanced hydrodynamic drag, and Brownian diffusion. In the absence of Brownian forces, particles are unable to enter the membrane pores unless the drag associated with the filtration velocity can overcome the electrostatic repulsion. Brownian forces significantly alter this behavior, allowing some particles to enter the pore even at low filtration velocities. The average particle transmission, evaluated from the probability of having a particle enter the pore, increases with increasing filtration velocity due to the greater hydrodynamic drag force on the particle. These results provide important insights into particle behavior in membrane systems.

Journal Article↗
PubMed2004

Electrostatic free energy of interacting ionizable double layers.

The electrostatic contribution to the interaction free energy of charge-regulating materials, similar as well as dissimilar, contains electric work as well as chemical work and can be obtained from an integration over the diffuse part of the double layer together with a summation of the surface contribution to the free energy over the two surfaces. Examples for the surface contribution are given for acid, base, zwitterionic, and amphoteric (1-pK and 2-pK) materials for a diffuse double layer and for the Stern-Gouy-Chapman model, with and without ion adsorption. For charge-regulating materials, the electrostatic contribution to the interaction free energy at contact (adhesion force of curved surfaces, or particles) is always finite and can be obtained from a simple calculation.

Journal Article↗
PubMed2006

Contribution of the heme propionate groups to the electron transfer and electrostatic properties of myoglobin.

The role of the heme propionate groups in determining the electron transfer and electrostatic properties of myoglobin have been studied by thermodynamic, kinetic, and spectroscopic studies of horse heart myoglobin in which the heme propionate groups are esterified. Spectroelectrochemical analysis has established that the E(m,7) of dimethylester heme-substituted Mb (DME-Mb) (E(m,7)=100.2(2)mV vs. NHE (Normal Hydrogen Electrode) (25 degrees C) is increased approximately 40mV relative to that of the native protein with DeltaH degrees =-12.9(2) kcal/mol and DeltaS degrees =-51.0(8) cal/mol/deg (pH 7.0, mu=0.1M (phosphate)). The second order rate constant for reduction of DME-metMb by Fe(EDTA)(2-) is increased >400-fold relative to that for reduction of native metMb to a value of 1.34(2)x10(3)M(-1)s(-1) with DeltaS(double dagger)=-13(1) cal/mol/deg and DeltaH(double dagger)=9.2(3) (pH 7.0, micro=0.1M (phosphate)). Analysis of the pH dependences of the reduction potential and rate constant for reduction by Fe(EDTA)(2-) demonstrates that heme propionate esterification introduces significant changes into the electrostatic interactions in myoglobin. These changes are also manifested by differences in the pH dependences of the (1)H NMR spectra of native and DME-metMb that reveal shifts in pK(a) values for specific His residues as the result of heme propionate esterification. In sum, the current results establish that heme propionate esterification not only affects the electron transfer properties of myoglobin but also influences the titration behavior of specific His residues.

Electron Transport↗
PubMed2004

Electrostatics of ion stabilization in a ClC chloride channel homologue from Escherichia coli.

The structural determinants of electrostatics of ion stabilization within EcClC, a ClC-type chloride channel homologue from Escherichia coli, are studied using a continuum dielectric approximation. Specifically, the ion occupancy is investigated in the wild-type protein and a mutant thereof, and the contribution to the electrostatic binding free energy of local and non-local interactions is characterized at the single-residue level. This analysis shows that, in spite of the desolvation cost and the strong ion-ion repulsion, all previously reported binding sites can be occupied simultaneously. The stabilizing effect of the protein arises from hydrogen bonding as well as from longer-range favorable interactions, such as with the strictly conserved Lys131 side-chain. The latter is involved in the stabilization of the conserved GSGIP motif that delimits two of the binding sites. Interestingly, an additional low-affinity binding site, mediated by a structurally analogous motif including the side-chain of Arg340, can be identified on the extracellular side of the permeation pathway. Finally, it is shown that, in contrast to K-channels, and in analogy to the SBP/PBP sulfate/phosphate-binding proteins, the contribution of helix macrodipoles to chloride binding in EcClC is only marginal.

Amino Acid Sequence↗
PubMed2004

Electrostatic potential of nucleotide-free protein is sufficient for discrimination between adenine and guanine-specific binding sites.

Despite sharing many common features, adenine-binding and guanine-binding sites in proteins often show a clear preference for the cognate over the non-cognate ligand. We have analyzed electrostatic potential (ESP) patterns at adenine and guanine-binding sites of a large number of non-redundant proteins where each binding site was first annotated as adenine/guanine-specific or non-specific from a survey of primary literature. We show that more than 90% of ESP variance at the binding sites is accounted for by only two principal component ESP vectors, each aligned to molecular dipoles of adenine and guanine. Projected on these principal component vectors, the adenine/guanine-specific and non-specific binding sites, including adenine-containing dinucleotides, show non-overlapping distributions. Adenine or guanine specificities of the binding sites also show high correlation with the corresponding electrostatic replacement (cognate by non-cognate ligand) energies. High correlation coefficients (0.94 for 35 adenine-binding sites and 1.0 for 20 guanine-binding sites) were obtained when adenine/guanine specificities were predicted using the replacement energies. Our results demonstrate that ligand-free protein ESP is an excellent indicator for discrimination between adenine and guanine-specific binding sites and that ESP of ligand-free protein can be used as a tool to annotate known and putative purine-binding sites in proteins as adenine or guanine-specific.

Adenine↗
PubMed2004

Electrostatic interactions and the folding of the four-way DNA junction: analysis by selective methyl phosphonate substitution.

The structure and dynamics of the four-way (Holliday) junction are strongly dependent on the presence of metal ions. In this study, the importance of phosphate charge in and around the point of strand exchange has been explored by selective replacement with electrically neutral methyl phosphonate groups, guided by crystal structures of the junction in the folded, stacked X conformation. Junction conformation has been analysed by comparative gel electrophoresis and fluorescence resonance energy transfer (FRET). Three of sets of phosphate groups on the exchanging strands have been analysed; those at the point of strand exchange and those to their 3' and 5' sides. The exchanging and 3' phosphate groups form a box of negatively charged groups on the minor groove face of the junction, while the 5' phosphate groups face each other on the major groove side, with their proR oxygen atoms directed at one another. The largest effects are observed on substitution of the exchanging phosphate groups; replacement of both groups leads to the loss of the requirement for addition of metal ions to allow junction folding. When the equivalent phosphate groups on the continuous strands were substituted, a proportion of the junction folded into the alternative conformer so as to bring these phosphate groups onto the exchanging strands. These species did not interconvert, and thus this is likely to result from the alternative diasteromeric forms of the methyl phosphonate group. This shows that some of the conformational effects result from more than purely electrostatic interactions. Smaller but significant effects were observed on substitution of the flanking phosphate groups. All methyl phosphonate substitutions at these positions allowed folding to proceed at a reduced concentration of magnesium ions, with double substitutions more effective than single substitutions. Substitution of 5' phosphates resulted in a greater degree of folding at a given ionic concentration compared to the corresponding 3' phosphate substitutions. These results show that the phosphate groups at the point of strand exchange exert the largest electrostatic effect on junction folding, but a number of phosphate groups in the vicinity of the exchange region contribute to the overall effects.

DNA, Cruciform↗