A. K. Berkovich

Dipole potential as a driving force for the membrane insertion of polyacrylic acid in slightly acidic milieu

In this work, we report on the interaction of polyacrylic acid with phosphatidylcholine bilayers and monolayers in slightly acidic medium. We found that adsorption of polyacrylic acid on liposomes composed of egg lecithin at pH 4.2 results in the formation of small pores permeable for low molecular weight solutes. However, the pores were impermeable for trypsin indicating that no solubilization of liposomes occurred. The pores were permeable for both positively charged trypsin substrate N-benzoyl-l-arginine ethyl ester and negatively charged pH-indicator pyranine. Two lines of evidence were obtained confirming the involvement of the membrane dipole potential in the insertion of polyacrylic acid into lipid bilayer. (i) Addition of phloretin, a molecule which is known to decrease dipole potential of lipid bilayer, reduced the rate of a polyacrylic acid induced leakage of pyranine from liposomes. (ii) Direct measurements of air/lipid monolayer/water interface surface potential using Kelvin probe showed that adsorption of polyacrylic acid at pH 4.2 induced a decrease in both boundary and dipole potential by 37 and 62mV for ester lipid dioleoylphosphatidylcholine (DOPC). Replacement of DOPC by ether lipid 1,2-di-O-oleyl-sn-glycero-3-phosphocholine (DiOOPC) which is known to form monolayers and bilayers with only minor dipole component of membrane potential showed that addition of PAA produced similar response in the boundary potential (by 50mV) but negligible response in dipole potential of monolayer. These observations agree with our assumption that dipole potential is an important driving force for the insertion of polyacids into biological membranes.

Interaction of polyanions with electroneutral liposomes in a slightly acidic medium

In this study, the interaction between poly(styrene sulfonic acid), polyacrylic acid, poly(meth-acrylic acid), poly(L-glutamic acid), poly(vinyl sulfate), and ternary copolymer of styrene with maleic anhydride and methacrylic acid (3: 2: 1), as well as DNA with lipid vesicles composed of zwitterion (electroneutral) lipid phosphatidylcholine, has been investigated. The methods of centrifuge ultrafiltration and dynamic light scattering reveal that, at pH 4.2, all polyacids under study are effectively adsorbed on the phospholipid membrane. The polymer-membrane complex is stabilized by hydrogen bonds and hydrophobic interactions in addition to electrostatic bonds. Even though, to a greater or lesser extent, all polyacids are capable of undergoing adsorption on the membrane in a slightly acidic medium, their effect on the membrane permeability is substantially different and is correlated with the ability of a polymer to form multiple interactions with phospholipid molecules. Poly(acrylic acid), poly(methacrylic acid), poly(styrene sulfonic acid), and the ternary copolymer of styrene with maleic anhydride and methacrylic acid can produce the membrane pores that are permeable to low-molecular-mass compounds. At the same time, poly(L-glutamic acid), poly(vinyl sulfate), and DNA exert no effect on the membrane permeability, although they are sorbed on the membrane surface.

Rheological properties of polyacrylonitrile solutions containing highly dispersed carbon nanotubes

Rheological properties of dispersions of carbon nanotubes in dimethylsulfoxide solutions of polyacrylonitrile are studied at different concentrations of the components. The viscosity values of all the studied dispersions are substantially dependent on shear rate. For a number of systems, the energies of activation of viscous flow are determined. The relationship of viscosity and the energy of activation of flow to the compositions and possible structural features of dispersions is discussed. The concentration regime where a thermally reversible mixed network exists with crosslinks formed by physical contacts of the polymer with nano-tubes is characterized.

Cellulose–co-polyacrylonitrile blends: Properties of combined solutions in N-metylmorpholine-N-oxide and the formation and thermolysis of composite fibers

Combined solutions of cellulose and an acrylonitrile-based copolymer in N-methylmorpholine-N-oxide have been prepared for the first time, new composite fibers have been formed, and the properties of the solutions and fibers under standard conditions and during thermal treatment have been studied. On the basis of studying the phase state and morphological peculiarities of combined cellulose solutions with polyacrylonitrile additives, it has been shown that the completed solutions make emulsions in the entire range of investigated concentrations. The rheological behavior of combined solutions changes with temperature. With the use of IR spectroscopy methods, it has been found that the addition of polyacrylonitrile to cellulose results in the association of nitrile groups with hydroxyl groups of cellulose, which favors the cyclization of CN groups during heating and the appearance of polyconjugated bonds in polyacrylonitrile chains. Thermal transformations of cellulose and polyacrylonitrile in the course of mixed-fiber carbonization have been studied via DSC and TGA. It has been shown that polyacrylonitrile inhibits the dehydration processes in cellulose and reduces the intensity of the peak due to the first stage of the structural rearrangement, i.e., acts as a “catalyst” of pyrolysis.

Composite fibers based on cellulose and polyacrylonitrile copolymers

Composite fibers were obtained from highly concentrated solutions of cellulose and polyacrylonitrile (PAN) copolymers in N-methylmorpholine-N-oxide (MMO). The processes of co-dissolving cellulose and PAN in MMO and the rheological properties of the resulting composite solutions were examined. It was shown that introduction of PAN into the cellulose matrix affects the structurization processes. Specifically, an increase of the PAN content in the cellulose matrix affects the thermal behavior and mechanical properties of the composite fibers.

Enhanced adhesion strength of polymer fiber/epoxy matrix in terphase as a result of their modification by detonation nanodiamond soot

The presented study is dedicated to evaluation of the effect of two types of detonation nanodiamond soot particles differing in surface charge polarity on the adhesion strength of the interphase between highly oriented poly(vinyl alcohol) fibers and epoxy matrix. Two major strategies for such modification are considered: 1—only one of the constituent components (either matrix or fiber) is being impregnated with nanodiamond soot; 2—both components of the composite system are being modified with nanodiamond soot. The second approach is further complicated by the fact that fiber and epoxy matrix can either be modified by the same type of nanodiamond soot (i.e. fiber and matrix both contain particles of equal surface polarity) or the modification is being carried out by using different types of nanodiamond soot for impregnating the fiber and the matrix (which results in these components containing disperse particles of the same morphology but opposite surface charge polarity). In the presented study both approaches are addressed.

Structural and Morphological Features of Carbon—Silicon-Carbide Fibers Based on Cellulose and Triethoxyvinylsilane

Carbon—silicon-carbide fibers were produced from cellulose and triethoxyvinylsilane and spun using the solid-phase NMMO-process. Scanning and transmission electron microscopy studies, energydispersive x-ray spectrometry, and x-ray structure analysis of composite carbon fibers established and identified the structure and morphology of carbon fibers that varied from an isotropic shell to regularly organized lamellae of graphite-like layers of the fiber core. Distributions of chemical elements were plotted. The nano-sized dimensions of silicon-carbide regions in the carbon fibers were determined.

Carbon—Silicon-Carbide Fibers Prepared from Solid Solutions of Cellulose in N-Methylmorpholine-N-Oxide with Added Tetraethoxysilane

Composite fibers were prepared by solid-state dissolution of cellulose in N-methylmorpholine-N-oxide with added tetraethoxysilane (TEOS). It was shown that adding TEOS to the cellulose matrix increased up to 16% the fiber carbon residue during heat treatment. Bonds formed between Si and C during their high-temperature treatment according to IR spectra of the composite cellulose fibers. The thermal behavior of the fibers was studied using TGA and TMA. The fiber morphology and the structure of the Si-containing additive particles were examined using SEM and TEM. The mechanical properties of carbon fibers prepared from cellulose-hydrate and composite fibers were compared.

Composites based on acrylic polymers and carbon nanotubes as precursors of carbon materials

The effect of carbon nanotubes on the properties of composite fibers and films based on polyacrylonitrile is analyzed. It is shown that the introduction of carbon nanotubes makes it possible to improve the mechanical characteristics of the composite material. Data on the effect of carbon nanotubes on chemical reactions occurring during the thermal stabilization and carbonization of these materials are cited.