The effect of the amphiprotic nature of human hair keratin on the adsorption of high charge density cationic polyelectrolytes

Adsorption of the cationic polymers poly(methacrylamidopropyltrimethyl ammonium chloride) (PMAPTAC) and poly(1,1-dimethylpiperidinium-3,5-diallylmethylene chloride) (PDMPDAMC) on human hair was studied by measurements of the amount of polymer adsorbed and by the streaming potential method. Results reflect the amphoteric nature of the keratin surface and show that the excess of anionic sites at pH values above 4 is the main driving force for the adsorption of cationic polyelectrolytes. Lowering the pH below 4 or addition of neutral salt (KCl) reduces the amount of adsorbed polymer. It was shown that the adsorption of cationic polymer in the concentration range 0.01 to 0.1 % and at neutral pH reverses the overall character of the surface from anionic to cationic. Keratin fibers modified in this manner do not exhibit amphoteric character and bear excess positive charge in the pH range 2–9.5. The value of the amount of the polymer adsorbed at saturation concentration (2 mg/g) as well as the lack of molecular weight effect in the range (5 · 10⁴ – 10⁶) on the amount of polymer adsorbed suggest that polymer chains adopt a rather extended conformation on the fiber surface. Some data concerning the formation of a complex between adsorbed cationic polymer and anionic detergents or polyelectrolytes are also presented.     

Control of the EOF in CE using polyelectrolytes of different charge densities

The control of the EOF direction and magnitude remains one of the more challenging issues for the optimization of separations in CE. In this work, we investigated the possibility to use variously charged polyanions for a fine-tuning of the EOF using polyelectrolyte multilayers. For that purpose, polyanions of poly(acrylamide-co-2-acrylamido-2-methyl-1-propanesulfonate) (PAMAMPS) with different chemical charge rates varying between 3 and 100% were used. These copolymers are statistic hydrophilic copolymers of acrylamide (AM) and 2-acrylamido-2-methyl-1-propanesulfonate (AMPS). The study of the influence of the chemical charge rate (AMPS molar proportion in the copolymer) on the electroosmotic mobility (mu(eo)) of a capillary modified by a polyelectrolyte bilayer (polycation/PAMAMPS) revealed that the fine-tuning of the EOF was possible, at least for cathodic or slightly anodic EOF (micro(eo) from -5 x 10(-5) to +35 x 10(-5) cm(2)V(-1)s(-1)). Electroosmotic mobility values were compared with the free-draining electrophoretic mobilities of the PAMAMPS constituting the last layer of the capillary coating. The stability of the EOF is discussed in detail on the basis of successive determinations of electroosmotic mobility and migration times. The application to the separation of a model peptide mixture demonstrated the interest (and the simplicity) of this approach for optimizing resolution and analysis time. Experimental resolutions were compared to the theoretical ones that we would obtain on a fused-silica capillary having the same EOF as the coated capillary.     

Theoretical study on the structure and property relationship of the cationic conjugated polyelectrolytes

A theoretical study using density functional theory was performed to understand the structure/property relationship of the cationic conjugated polyelectrolytes, poly[9,9-bis-(6′-N,N,N-trimethylammonium) hexyl] fluorene-alt-4,7-(2,1,3-benzothiadiazole)] (PFBT-X, where X = Br). The torsion angle between the fluorene and benzothiadiazole units in the PFBT monomer was found to substantially affect the structural and electronic properties of the cationic PFBT monomer. The changes of geometrical parameter, HOMO and LUMO energy levels, and band gap, as well as the absorption maximum are discussed in terms of the torsion in the PFBT monomer structure. For comparison, its neutral analogue, the monomer of poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) was also studied. The length of conjugation backbone was also examined.     

Effect of charge balance vacancies on the ultraviolet photocatalytic activity of Fe3+-doped anatase

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Effect of introduced charge in cellulose gels on surface interactions and the adsorption of highly charged cationic polyelectrolytes

The interaction between cellulose surfaces in aqueous solution has been measured using colloidal probe microscopy. Cellulose thin films with varying charge through carboxyl group substitution were used in this study with the surface forces fit to DLVO theory. It was found that the surface potential increased, as expected, with increasing carboxyl substitution. Furthermore, for a given degree of substitution, the surface potential increased as a function of increasing pH. At low pH, the surface forces interaction were attractive and could be fit to the non-retarded Hamaker equation using a constant of 3 x 10(-21) J. At pH greater than 5, the force interactions were monotonically repulsive, regardless of the ionic strength of the solution for all charge densities of the cellulose thin films. The adsorption of polyDADMAC to these charged cellulose films was also investigated using the quartz crystal microbalance. It was found that for the low charge film, a low surface excess of PDADMAC was sensed and that the adsorbed conformation was essentially flat. However for the higher charged cellulose film, a spontaneous de-swelling was observed resulting in no possibility of quantitatively determining the sensed mass using QCM.     

Behaviour of cationic polyelectrolytes upon binding of electrolytes: effects of polycation structure, counterions and nature of the solvent

 The effects of polycation structure, counterions and the nature of the solvent on the interaction between low-molecular-weight salts with some cationic polyelectrolytes in water and methanol were investigated. The polyelectrolytes used in this study were cationic polymers with quaternary nitrogen atoms in the backbone with or without a nonpolar side chain (polymer type PCA₅H₁, PCA₅D₁ and PCA₅) or tertiary amine nitrogen atoms in the main chain (polymer type PEGA). LiCl, NaCl, KCl, NaBr, NaI and Na₂SO₄ were used as low-molecular-weight salts. The interaction between polycations and salts was followed by viscometric and conductometric measurements. The study of the interaction of monovalent counterions with cationic polyelectrolytes emphasized an increase in the interaction with the decrease in the radius of the hydrated counterion, both for strong polycations and for weak polycations, suggesting that counterion binding is nonspecific. In the case of SO²⁻ ₄ anions, the Λ_m−c ^1/2 curve passes through a minimum at c _p values between 1 × 10⁻³ and 3 × 10⁻³ unit mol/l; this phenomenon can be explained by the maximum counterion interaction owing to the capacity of the polyvalent counterion to bind two charged groups by intra- or interchain bridges. The investigation of the influence of the polycation structure on the counterion binding indicated an increase in charged group–counterion interactions with a decrease in the nonpolar chain length and an increase in the quaternary ammonium salt group content (charge density) in the chain. The polyelectrolyte with tertiary amine groups in the chain, PEGA, showed, on one hand, a cation adsorption order as K⁺>Na⁺>Li⁺ and, on the other hand, a stronger association between ions and PEGA chains in methanol than in water owing to the poorer solvating effect of methanol on the cations. Received: 20 February 2001 Accepted: 29 June 2001     

Electronic structure of some adenosine receptor antagonists: I. Equilibrium geometries,charge density distributions,and substituent effects

Ab initio molecular orbital calculations were implemented to investigate the variation of the electronic structure of a series of different xanthine derivatives. MP2(full)/6‐31G calculations have been carried out and used to investigate the geometric features of the studied compounds. Alkyl xanthines studied in the present work are highly polarized with the σ and π frameworks polarized in opposite directions. This polarization is sensitive to substitution. The trend observed for the variation of dipole moment with substitution is interesting. Thus, electron‐withdrawing substituents lower the magnitude of the dipole moment, which reaches its smallest value in the case of ? CF₃ substituent. The ? NO₂ group not only reduces the dipole moment but it also inverts its direction as well. The effect of the basis set on these geometric features has been investigated through implementation of polarization function in MP2(full)/6‐31G/6‐311G** calculations, where it was found that inclusion of the polarization function led to a noticeable redistribution of the charge density. Thus, charge density that was originally accumulated on the atomic centers is redistributed into the bonding regions and this is the reason for the smaller net charges and the larger bond orders predicted at the 6‐311G** level. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

Lubrication properties of bottle-brush polyelectrolytes: an AFM study on the effect of side chain and charge density

The effect of side chain to charge ratio on the frictional properties of adsorbed layers formed by bottle-brush polyelectrolytes with poly(ethylene oxide) side chains has been investigated. The brush polyelectrolytes were preadsorbed from 0.1 mM NaNO(3) solutions onto mica and silica surfaces; the interfacial friction was then measured in polyelectrolyte-free solutions via AFM (with the silica surface acting as the colloidal probe). It was concluded that the decisive factor for achieving favorable lubrication properties is the concentration of nonadsorbing poly(ethylene oxide) side chains in the interfacial region. However, contrary to what may be expected, the results showed that an ideal brush layer structure with the adsorbed polymers adopting comb-like conformation is not necessary for achieving a low coefficient of friction in the asymmetric mica-silica system. In fact, the lowest coefficient of friction (<0.01) under applied pressures as high as 30 MPa was observed for a system with a side chain to charge ratio of 9:1, incapable of forming brush-like layers.     

Qualitative degradation of the pesticide coumaphos in solution,controlled aerosol,and solid phases on quaternary ammonium fluoride polymer brushes

With the growing demand for measurements of organophosphate (OP) pesticide use in agriculture along with the potential threat of OP‐based chemical warfare agents, there is a need for new devices or surfaces that can quickly degrade OPs into less toxic substances in a variety of environments. Using surface‐initiated atom transfer radical polymerization and post‐polymerization synthesis, we prepared a series of quaternary ammonium fluoride‐based polymer brushes designed to absorb and degrade OPs. Specifically, a polymer brush was formed using 2‐dimethylamino‐ethyl methacrylate (DMAEMA) as monomer, which, following post‐polymerization quaternization of the tertiary amine with alkylating agents and fluoride ion exchange, afforded the OP‐reactive polymer surfaces. Poly(DMAEMA) brushes were grown to thicknesses of ~100 nm on silicon wafers and glass slides and characterized by ellipsometry, atomic force microscopy, and Raman spectroscopy. Quaternization and subsequent ion exchange of the brushes were characterized by Raman spectroscopy and X‐ray photoelectron spectroscopy, respectively. The interaction of the brushes with OPs was evaluated using the OP‐based pesticide coumaphos, through the presence of the highly fluorescent degradation product chlorferon; analyzed qualitatively via fluorescence microscopy; and confirmed via nuclear magnetic resonance and mass spectrometry. We found that the fluoride form of the brush reliably degraded coumaphos deposited via controlled solution‐based applications and aerosol applications (electrohydrodynamic jetting) and from microcontact printing of the dried solid directly onto the brush. No degradation was seen for coumaphos deposited on poly(DMAEMA) or the iodide form of the quaternized brush. Copyright © 2016 John Wiley & Sons, Ltd.     

Effects of charge density and hydrophobicity of ionene polymer on cell binding and viability

The binding of cationic ionenes onto budding protoplast was investigated and the results were associated with the cell viability. There are critical numbers of carbon atoms to induce effective cell disruption and cell binding. The longer the alkyl chain of the ionene, the lower the concentration at which cell disruption occurs. The ionenes with increased charge density undergo effective binding, while almost 2 orders of magnitude higher concentration are required for effective cell disruption. These results were associated with the cooperativity of the binding process, which induces local stress and solubilization of the lipid membrane. Received: 26 October 1999 Accepted: 23 March 2000     

The influence of polymer structure on the electrical and mechanical properties of some synthetic films

Various physico-chemical properties of films prepared from PP/PE blends are investigated and compared with those of homopolymers. Crystallographic structure and morphology of films are correlated with the properties studied. Special emphasis is made toward investigation of dependences between the structure and the properties: electrical, mechanical as well as water sorption.     

Spectrophotometric determination of cationic and anionic surfactants with anionic dyes in the presence of nonionic surfactants,part I: A general aspect

The behavior of color development of anionic azo dyes, methyl orange and its analogues, was examined in aqueous media by changing the microenvironment of the dyes. The addition of alcohols, organic onium ions, anionic surfactants and nonionic surfactants brought about a decrease of the band at wavelengths near 480 nm and an increase of the band at wavelengths near 420 nm. Such a shift toward the shorter wavelengths in spectra was attributed to the change of the micro-environment around the dyes from a polar field to a less polar field; that is, the shift is caused by the change of the contribution of the following resonance forms, On the basis of the color change phenomena, the spectrophotometric methods for the determination of organic onium ions and anionic surfactants were proposed.     

The effects of polyelectrolytes on the inhibition and aggregation of calcium oxalate crystallization

The influence of polyelectrolytes with different architecture on spontaneous batch crystallization of calcium oxalate was investigated. A series of acidic acrylate block copolymers were been made, by radical polymerization, with defined molecular weight and structure. Radical polymerization of acrylic acid (AA) was carried out in the presence of α‐thiopolyethylene glycol monomethylether as a chain transfer agent to produce poly(ethylene glycolblockacrylic acid) copolymers. Poly(ethylene glycol) (PEG) block length in the copolymers was controlled by using three different molecular weight chain transfer agents (M_n = 350, 750 and 2000 g/mol). The presence of copolymers inhibited the crystal growth of calcium oxalate possibly through adsorption onto the active growth sites for crystal growth due to the charge and hydrophilic effects. Copyright © 2006 John Wiley & Sons, Ltd.     

Electrical conductivity of some cationic polysaccharides. I. Effects of polyelectrolyte concentration,charge density,substituent at the ionic group,and solvent polarity

Electrolytic conductivity behavior of some cationic polysaccharides in water, methanol, and the mixtures water/methanol is presented. The polyelectrolytes investigated contain quaternary ammonium salt groups, N‐alkyl‐N,N‐dimethyl‐2‐hydroxypropyleneammonium chloride, attached to a dextran backbone. This study considers the influences of polymer concentration (1 × 10^?6 < C < 1 × 10^?2 monomol L^?1) and the charge density (ξ = 0.48–3.17) modified either by changing charge distance (b) or dielectric constant of the solvent (ε) on polyion–counterion interaction in salt‐free solutions. Above the critical value, ξ_c = 1, the variation of the equivalent conductivity (Λ) as a function of concentration is typical for a polyelectrolyte behavior. The conductometric data in water were analyzed in terms of the Manning's counterion condensation theory. The presence of longer alkyl chains at quaternary N atoms was found to have a negligible influence on the Λ values. The results show that the decrease of the medium polarity results in the decrease of the number of free ions and, consequently, of the equivalent conductivity values. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3584–3590, 2005     

Effect of layer charge density on orientation and aggregation of a cationic laser dye incorporated in the interlayer space of montmorillonites

Effect of layer charge density of clay on the orientation and aggregation state of a laser dye, oxazine 4, in dye/clay complexes was investigated using a series of layer-charge-controlled montmorillonites as host materials. By the combination of polarized UV-vis spectroscopy and powder X-ray diffraction methods, it was revealed that the higher layer charge caused the formation of higher-order H-aggregates with the molecular axis nearly perpendicular to the silicate layer, and that the basal spacing was mostly governed by the degree of dye aggregation.     

Consequences of the nanoporosity of cellulosic fibers on their streaming potential and their interactions with cationic polyelectrolytes

Electrokinetic tests, based on the streaming potential method, were used to elucidate interactions between cationic polyelectrolytes and cellulosic fibers and to reveal aspects of fibers’ nanoporosity. The fibrillated and nanoporous nature of bleached kraft fibers gave rise to time-dependent changes in streaming potential, following treatment of the wetted fibers with poly-diallyldimethylammonium chloride. Electrokinetic test results were consistent with an expected longer time required for higher-mass polyelectrolytes to diffuse into pore spaces, compared to lower-mass polyelectrolytes. Further evidence of the relative inability of polyelectrolyte molecules to diffuse into the pores of cellulose was obtained by switching back and forth between high and low ionic strength conditions during repeated measurement of streaming potential, after the fibers had been treated with a moderate amount of cationic polymer. By changing the concentration of sodium sulfate it was possible to switch the sign of streaming potential repeatedly from positive to negative and back again. Such results imply that a continuous path for liquid flow exists either in a fibrillar layer or within the cell walls. The same concepts also helped to explain the dosages of high-charge cationic polymer needed to achieve maximum dewatering rates, as well as the results of retention experiments using positively and negatively charged microcrystalline cellulose particles.     

The effect of some phenyltin compounds on the thermotropic phase behaviour and the structure of model membranes

The effects of diphenyltin dichloride (DPhT), triphenyltin chloride (TPhT) and tetraphenyltin (TTPhT) on the thermotropic phase behaviour of phosphatidylcholine bilayers were studied. All the phenyltin compounds investigated affected phase transitions differently. TTPhT broadened the main phase transition but it left the transition temperatures and enthalpy unchanged. TPhT reduced the transition temperatures and the enthalpies while DPhT showed a dual effect on the pretransition and the main transition. At low concentrations DPhT reduced the temperatures of the transitions slightly and at higher concentrations it increased them. Based on differential scanning calorimetry (DSC) and also ¹H NMR and ³¹P NMR measurements, it is suggested that DPhT induces interdigitated gel phase formation and TPhT induces hexagonal phase formation. TTPhT seems to affect the structure only a little. The toxic activity of DPhT and TPhT seems to be connected with their ability to induce changes in the membrane structure. Copyright © 2000 John Wiley & Sons, Ltd.     

Electronic structure and band gaps in cationic heterocyclic oligomers. Multidimensional analysis of the interplay of heteroatoms, substituents, molecular length, and charge on redox and transparency characteristics

Oxidative doping of extended pi-conjugated polymers and oligomers produces dramatic changes in optical and electrical properties, arising from polaron and soliton-derived midgap states. Despite the great importance of such changes for materials properties, far less is known about the cationic polaron states than about the neutral, semiconducting or insulating, undoped materials. The systematic, multifactor computational analysis of oligoheterocycles such as oligothiophenes, oligofurans, and oligopyrroles presented here affords qualitative and quantitative understanding of the interplay among skeletal substitution pattern, electronic structure, and the effective band gap reduction on p-doping. A simple linear relation is derived for predicting p-doped oligomer and polymer effective band gaps based on those of the neutral oligomers; this relationship confirms the effectiveness of a "fixed band" approximation and explains the counterintuitive increase of the effective band gap on p-doping of many small band gap oligomers. The present analysis also suggests new candidates for transparent conductive polymers and predicts limiting behavior of ionization potential, electron affinity, and other properties for various polyheterocyclic systems. The results yield insight into materials constraints in electrochromic polymers as well as on p- and n-type conductors and semiconductors.     

氢氧化铝镁钠米颗粒的零电荷点及电荷密度研究

探讨了电位滴定(PT)法测定的零电荷点的物理意义, 认为是零净电荷点(ZPNC)。并对零净电荷点pH(pHZPNC), 零可变电荷点pH(pHZPVC), 永久电荷密度(σP), 可变电荷密度(σV)和净电荷密度(σT)之间的关系进行了理论分析。用PT法测定了氢氧化铝镁纳米颗粒的pHZPNC和σP, 探讨了电解质浓度和pH对各电化学性质的影响规律。另外, 还考察了CO3^2^-对PT法测定结果的影响。