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1.
The flow of KCl solutions through thin quartz capillaries coated with an adsorbed layer of a cationic polyelectrolyte (CPE), poly(dimethyldiallylammonium chloride) (molecular mass M = 500000), is studied. It is found that the adsorption layer is soft and its thickness depends on shear stress generated by the liquid flow through the capillary. The hydrodynamic thickness of the CPE adsorption layer is 80–90 nm at low flow rates of a solution, and it decreases to values comparable with the experimental error at high flow rates. The dried adsorption layer appears to be hydrophobic (the advancing contact angle is about 80°); in these capillaries, the flow rate of a KCl solution is increased that can be interpreted as a solution slip on the surface of CPE adsorption layer. The long-term contact of the dried CPE adsorption layer with KCl solution, probably, results in the swelling of the adsorption layer, which is accompanied by a decrease in the contact angle and ζ potential of the adsorption layer surface as calculated from the streaming potential of the same solution.  相似文献   

2.
The formation and properties of adsorption layers of poly(dimethyldiallylammonium chloride) with different molecular masses on the surface of fused quartz are studied by the capillary electrokinetics method. It is shown that the value of ζ potential depends on the flow rate of liquid determined by the pressure drop. Such behavior can be explained by the deformation of the adsorption layer. At low rates of liquid flow, constant values of adsorption and time needed to achieve these values decrease for the samples of lower molecular masses, which is probably related to the more closely packed structure and, hence, to the lower deformability of the adsorption layers, as well as to the shortest times during which conformational rearrangements proceed in the layer. The time of conformational changes in the adsorption layer significantly exceeds the time of adsorption. The adsorption of cationic polyelectrolyte is irreversible. It is found that the compaction of adsorption layers increases with time; the rate of compaction of layers of a low-molecular-mass polyelectrolyte is higher and the layers of a high-molecular-mass polyelectrolyte retain the residual deformability even for six days. The measurements of the filtration of polyelectrolyte solutions through thin quartz capillaries allow the thickness of adsorption layers and their deformation under pressure to be estimated.  相似文献   

3.
This paper demonstrates the use of polyelectrolytes to modify and manipulate the adsorption of ionic surfactants onto the hydrophilic surface of silica. We have demonstrated that the cationic polyelectrolyte poly(dimethyl diallylammonium chloride), poly-dmdaac, modifies the adsorption of cationic and anionic surfactants to the hydrophilic surface of silica. A thin robust polymer layer is adsorbed from a dilute polymer/surfactant solution. The resulting surface layer is cationic and changes the relative affinity of the cationic surfactant hexadecyl trimethylammonium bromide, C16TAB, and the anionic surfactant sodium dodecyl sulfate, SDS, to adsorb. The adsorption of C16TAB is dramatically reduced. In contrast, strong adsorption of SDS was observed, in situations where SDS would normally have a low affinity for the surface of silica. We have further shown that subsequent adsorption of the anionic polyelectrolyte sodium poly(styrene sulfonate), Na-PSS, onto the poly-dmdaac coated surface results in a change back to an anionic surface and a further change in the relative affinities of the cationic and anionic surfactants for the surface. The relative amounts of C16TAB and SDS adsorption depend on the coverage of the polyelectrolyte, and these preliminary measurements show that this can be manipulated.  相似文献   

4.
Polyampholites are synthesized by the alkylation of poly-4-vinylpyridine with ω-bromocarboxylic acids, and their interaction with the negatively charged bilayer lipid vesicles (liposomes) is studied. In the above polymers, quaternized pyridine units are zwitterion (betaine) groups, in which cationic and anionic groups are linked by the -(CH2) n -bridges. Via the methods of fluorescence, laser scattering, and DSC, the length of the ethylene spacer in the betaine group is shown to control the ability of the polymer to interact with anionic liposomes and induce structural rearrangements in the liposomal membrane. At n = 1, polybetaine is not linked to anionic liposomes. At n = 2, polybetaine is sorbed on the membrane, but it causes no dramatic structural rearrangements in the bilayer. At n = 3, the adsorption of polybetaine triggers the lateral segregation of lipids in the outer membrane layer. At n = 5, adsorption of polymer is accompanied by the lateral segregation and flip-flop of lipid molecules; as a result, all anionic membrane lipids are involved in the microphase separation. This evidence is of evident interest for the controlled design of polymers and related complexes and conjugates for biomedical applications.  相似文献   

5.
Formation of complexes obtained by the adsorption of a cationic polymer, poly(N-ethyl-4-vinylpyridium bromide), with a degree of polymerization of 600 on the surface of 50-nm bilayer vesicles (liposomes) formed from neutral phosphatidyl choline, anionic diphosphatidyl glycerol (cardiolipin), and a surfactant with one alkyl radical, such as electroneutral n-hexadecylphosphocholine, palmitic acid, or heptanoic acid, is studied. The incorporation of these surfactants into the liposomal membrane stimulates the appearance of oxidized forms of lipids in it. The incorporation of n-hexadecylphosphocholine into the membrane of n-hexadecylphosphocholine and palmitic acid with the alkyl radical, whose length is comparable with the length of alkyl radicals in a lipid molecule, has no effect on the permeability of the membrane. However, these liposomes lose integrity upon the adsorption of polycation; as a result, complexation becomes irreversible. Electroneutral and anionic surfactants with long hydrocarbon chains may accumulate in a cellular membrane owing to the oxidative degradation of unsaturated radicals in lipid molecules. This finding may be used in the design of polymeric therapeutic means specifically interacting with damaged cells.  相似文献   

6.
In order to elucidate the mechanisms of flocculation by polymer mixtures, the effect of adsorption of non-ionic poly(ethylene oxide) — PEO, two samples of strongly (SNF FO 4800) and medium charged (SNF FO 4350) cationic and two samples of medium (SNF AN 935) and weakly charged (SNF AN 905) anionic polyelectrolytes (PE) as well as their binary mixtures on the electrokinetic potential of bentonite and kaolin particles has been studied. It is shown that in the presence of PEO-anionic/cationic polymer mixture, the electrokinetic potential of particles is determined by the adsorption of the polyelectrolyte; neither cationic nor anionic segments can be displaced by the non-ionic polymer. In mixtures of cationic and anionic polyelectrolytes, the ζ-potential of particles is determined by the adsorbed amount of anionic polymer independently of the charge density of PE and way of addition of the mixture components to the suspension, i.e. (1) first adding the cationic polymer, then the anionic one, or (2) first adding the anionic polymer then the cationic one, or (3) adding an increasing amount of pre-prepared 1: 1 mixture. The highest absolute ζ-potential values are observed for pH 7.5 when the surface of bentonite or kaolin particles is “purely” negatively charged and the anionic PE layer is most extended because of few contacts to the surface. With decreasing the pH, the (negative) ζ-potential of particles decreases due to appearance of a small amount of positive charges on the surface that bond an increasing amount of negative segments and results in shrinking of the adsorbed layer of the anionic PE. It is shown also that the electrokinetic potential of particles in anionic and cationic PE mixtures at all studied pH (4, 5, and 7.5) depends on the spatial distribution of negatively charged segments near the surface. The regularities observed are explained by formation of long loops and tails of anionic segments on the surface because of the small number of contacts to the surface; the cationic polyelectrolyte forms on the surface a thin layer with a big number of contacts and which is hidden behind the more extended anionic polymer layer.  相似文献   

7.
Polyelectrolyte multilayer adsorption on mica was studied by the streaming potential method in the parallel-plate channel setup. The technique was calibrated by performing model measurements of streaming potential by using monodisperse latex particles. Two types of polyelectrolytes were used in our studies: poly(allylamine) hydrochloride (PAH), of a cationic type, and poly(sodium 4-styrenesulfonate) (PSS) of an anionic type, both having molecular weight of 70,000. The bulk characteristics of polymers were determined by measuring the specific density, diffusion coefficient for various ionic strengths, and zeta potential. These measurements as well as molecular dynamic simulations of chain shape and configurations suggested that the molecules assume an extended, wormlike shape in the bulk. Accordingly, the diffusion coefficient was interpreted in terms of a simple hydrodynamic model pertinent to flexible rods. These data allowed a proper interpretation of polyelectrolyte multilayer adsorption from NaCl solutions of various concentrations or from 10(-3) M Tris buffer. After completing a bilayer, periodic variations in the apparent zeta potential between positive and negative values were observed for multilayers terminated by PAH and PSS, respectively. These limiting zeta potential values correlated quite well with the zeta potential of the polymers in the bulk. The stability of polyelectrolyte films against prolonged washing (reaching 26 h) also was determined using the streaming potential method. It was demonstrated that the PSS layer was considerably more resistant to washing, compared to the PAH layer. It was concluded that the experimental data were consistent with the model postulating particle-like adsorption of polyelectrolytes with little chain interpenetration. It also was concluded that due to high sensitivity, the electrokinetic method applied can be effectively used for quantitative studies of polyelectrolyte adsorption, desorption, and reconformation.  相似文献   

8.
Layer-by-layer deposition of anionic and cationic polyelectrolytes readily converts polymeric ultrafiltration membranes into materials capable of nanofiltration. ATR-FTIR spectra confirm that layer-by-layer deposition occurs on the ultrafiltration substrates, and adsorption of as few as 2.5 bilayers of poly(styrenesulfonate) (PSS)/protonated poly(allylamine) (PAH) or 3.5 bilayers of PSS/poly(diallyldimethylammonium chloride) (PDADMAC) reduces the molecular weight cutoff of polyethersulfone ultrafiltration supports from 50 kDa to <500 Da. Deposition of multilayer polyelectrolyte films on 300 and 500 kDa membranes also decreases molecular weight cutoffs, but solute rejections are significantly lower when using these supports, suggesting that the polyelectrolyte films do not completely cover large (0.2-0.4 microm in diameter) pores. On the 50 kDa substrates, PSS/PDADMAC films containing 3.5 bilayers exhibit a 95% rejection of SO(4)(2-) and a chloride/sulfate selectivity of 27, whereas 4.5-bilayer PSS/PAH coatings show a glucose/raffinose selectivity of 100. Pure water flux for [PSS/PAH](3)PSS-coated membranes at 4.8 bar is 1.6 m(3)/(m(2)day), which is more than 2-fold higher than that through a commercial 500 Da membrane.  相似文献   

9.
The capillary electrokinetics method (measurement of streaming potential and current in a capillary with a radius of 5–7 μm made of fused quartz) is employed to study the structure formation at interfaces between quartz and solutions containing a cationic polyelectrolyte (poly(diallyldimethylammonium chloride) with molecular mass M = 100000−200000) and an anionic surfactant (sodium dodecyl sulfate). The kinetics of surface layer formation is studied upon the layer-by-layer adsorption of the components and the adsorption of their complexes at the same component ratios. It is established that the formation time and the electrokinetic potentials of the surface layers are almost independent of the procedure of their formation. In the case of the layer-by-layer adsorption, the first layers of the polyelectrolyte appear to be virtually undeformed, thus indicating that molecules with a planar conformation prevail in the adsorption layer. Surfactant adsorption enhances the deformation (layer loosening), which decreases with time (layer aging). Layers formed from the complexes have a denser (less deformable) structure. Variations in the electrokinetic potentials of the layers during the long-term pumping of a background electrolyte solution through a capillary witnesses the prevailing desorption of the anionic surfactant, with the desorption being noticeably more pronounced for the layers resultant from the adsorption of the complexes.  相似文献   

10.
S. Barany 《Colloid Journal》2002,64(5):533-537
The interaction between the anionic and cationic polyelectrolytes of various molecular masses and charges and the ionic surfactants in aqueous and salt solutions is studied by viscometry, conductometry, light scattering, and electrophoresis. Oppositely charged molecules of surfactant and polymer form strong complexes due to the forces of electrostatic attraction that is manifested in a significant decrease in the viscosity and light transmission, as well as in the relative reduction in solution conductivity. As the surfactant/polyelectrolyte ratio increases, the forming complexes precipitated and then dissolved again. In the case of strongly charged polyelectrolytes, the partial dissolution of precipitates was observed preceding the wide region of destabilization. In this region, the value of surfactant/polyelectrolyte charge ratio reaches 3–4. The interaction between the cationic surfactants and anionic polyelectrolyte increases with the lengthening of alkyl radical, thus indicating the presence of cooperative interactions between the surfactant molecules bonded to polymer and the important role of relevant hydrophobic interactions. As a result, the interaction between the high-molecular-weight anionic polyelectrolytes and anionic surfactants containing aromatic core takes place in some cases.  相似文献   

11.
Polyelectrolyte monolayers on solid substrates are studied with optical reflectivity and the quartz crystal microbalance (QCM). In particular, we investigate the adsorption of anionic poly(styrene sulfonate) (PSS) on amino-functionalized silica as well as cationic poly(allylamine hydrochloride) (PAH) and poly-L-lysine (PLL) on bare silica. By comparing the dry and wet masses measured on identical substrates with these two techniques, we obtain information on the layer thickness and water content of these layers. Monolayers typically feature an adsorbed dry mass of about 0.1-2 mg/m(2), a layer thickness of 0.5-2 nm, and a water content of 20-50%. One finds that the layer thickness increases with increasing concentrations of monovalent salts and polyelectrolytes.  相似文献   

12.
In this study, highly permeable ion-selective membranes are prepared via immobilization of polyelectrolyte multilayer networks within the inner pore structure of a microporous (pore size = 0.2 microm) support. Electrostatic layer-by-layer assembly is achieved through alternate adsorption of cationic and anionic polyelectrolytes under convective flow conditions. To initiate pore assembly, the first layer consists of covalently bound charged polypeptides (poly(L-glutamic acid) (PLGA) or poly(L-lysine) (PLL)) establishing a charged support for subsequent adsorption. Nonstoichiometric immobilization of charged multilayers within a confined pore geometry leads to an enhanced volume density of ionizable groups in the membrane phase. This overall increase in the effective charge density allows for Donnan exclusion of ionic species (especially divalent co-ions) using microporous materials characterized by permeability values that exceed conventional membrane processes. Multilayer assemblies are fabricated using both PLGA/PLL and synthetic polyelectrolytes (poly(styrenesulfonate)/poly(allylamine)) in an attempt to compare the level of adsorption and separation properties of the resulting materials. The role of salt concentration in the carrier solvent on overall polyelectrolyte adsorption was examined to determine its effect on both solute (Cl-, SO4(2-), As(V)) and water transport. Constriction of the pore size induced by multilayer propagation was monitored through permeability measurements and dextran rejection studies at each stage of the deposition process.  相似文献   

13.
Polyelectrolytes offer a widespread potential for the defined modification of planar inorganic or polymer surfaces. Essential parameters for the regular adsorption of subsequent polymer layers by electrostatic interactions are the charge of polyelectrolyte and of the outermost surface region, the surface of the substrate, and the molar mass of the polyelectrolyte. To study such effects in mono- and multilayers we used poly(diallyldimethylammonium chloride (PD) with a molar mass from 5000 to 400000 g/mol as a strong polycation and poly(ethyleneimine) (PEI) with 75000 g/mol as a weak polycation and poly(sodium styrenesulfonate) (PSS) from 70000 to 1Mio g/mol in the diluted and semi-diluted region. The characterization of the layers was performed by streaming potential, in-situ SPR and UV-Vis spectroscopy. Thereby the layer built up at the solid/liquid-interface could be followed and quantified at the molecular level. SPR revealed that the thicknesses of the multilayer depends strongly on pK values of the polyelectrolyte (strong or weak) and the molar masses. We observed a linear growth if both polyelectrolytes are strong and an exponential growth if one polyelectrolyte is weak. The thickness increased with higher molar masses of the polyelectrolytes. The process was followed in-situ in short time steps.  相似文献   

14.
The adsorption behavior of a low charge density cationic polyelectrolyte to cellulosic fibers has been studied. Cationic dextran served as a model polyelectrolyte, as it can be prepared over a range in molecular mass and charge density. The adsorption behavior of the cationic dextran was measured in electrolyte-free conditions using polyelectrolyte titration techniques. By fluorescent labeling the cationic dextran, the extent to which adsorption occurs inside the porous structure was further determined by fluorescent confocal laser scanning microscopy. Cationic dextran having a sufficiently low charge density adsorbed into the pores, although the extent the cationic dextran adsorbed was governed by the molecular mass. The adsorption behavior of the cationic dextran was also studied in various electrolyte concentrations. The adsorbed mass monotonically decreased with increasing electrolyte, as the electrostatic interaction with the substrate was more effectively screened. This behavior also suggests that the interactions between adsorbed polyelectrolyte chains, i.e. lateral correlation effects, are negligible for low charge density polyelectrolytes. Finally, the effect of having a preadsorbed layer of cationic dextran on the adsorption behavior was determined in electrolyte-free conditions using fluorescent double staining techniques. The preadsorbed cationic dextran had almost no effect on the adsorption of low molecular mass fractions. Low molecular mass fractions directly adsorbed into the pore structure, as opposed to adsorbing to a free surface and diffusing into the pores. It was also shown that cationic dextran can be selectively adsorbed to different locations, such that the surface of a porous substrate can be treated uniquely from the bulk.  相似文献   

15.
The adsorption of cationic polyelectrolytes on colloidal silica-particles is investigated. The polyelectrolytes poly(diallyl-dimethyl-ammoniumchloride) PDADMAC of different molar mass have been used. The adsorbed amount is influenced by the ionic strength and pH of the suspension and the molar mass of the macromolecule. The adsorption determines the zetapotential of the covered particles. The electrostatic interaction between the particles as well as the structure of the adsorbed polyelectrolytes play an important role in the stabilization and flocculation behaviour of the polyelectrolyte covered suspensions.  相似文献   

16.
The adsorption behavior of highly charged cationic polyelectrolytes onto porous substrates is electrostatic in nature and has been shown to be highly dependent on the polyelectrolyte properties. Copolymers of acrylamide (AM) and diallyldimethylammonium chloride (DADMAC) were synthesized to have a range of macromolecular properties (i.e., charge density and molecular mass). Traditional titration methods have been complemented by fluorescence labeling techniques that were developed to directly observe the extent that fluorescently labeled poly(AM- co-DADMAC) adsorbs into the pore structure of a cellulosic substrate. Although contributing to the electrostatic driving force, the charge density acts to limit adsorption to the outermost surface under electrolyte-free conditions. However, adsorption into the pores can occur if both the molecular mass and charge density of poly(AM- co-DADMAC) are sufficiently low. Adsorption initially increases as the electrolyte concentration is increased. However, the electrostatic persistence length of poly(AM- co-DADMAC) restricts the polyelectrolyte from entering the pores. Therefore, changes in the adsorption behavior at moderate electrolyte concentrations have been attributed to swelling of the polyelectrolyte layer at the fiber exterior. The adsorption behavior changes again at high electrolyte concentrations such that poly(AM- co-DADMAC) could adsorb into the pore structure. This occurred when the electrolyte concentration was sufficient to screen the electrostatic persistence length of poly(AM- co-DADMAC), provided that the entropic driving force for adsorption still existed. It is suggested that adsorption into the pore structure is a kinetic process that is governed by localized electrostatic interactions between poly(AM- co-DADMAC) and the charges located within the pores.  相似文献   

17.
A novel in-situ streaming-potential optical reflectometry apparatus (SPOR) was constructed and utilized to probe the molecular architecture of aqueous adsorbates on a negatively charged silica surface. By combining optical reflectometry and electrokinetic streaming potentials, we measure simultaneously the adsorption density, gamma, and zeta potential, zeta, in a rectangular flow cell constructed with one transparent wall. Both dynamic and equilibrium measurements are possible, allowing the study of sorption kinetics and reversibility. Using SPOR, we investigate the adsorption of a classic nonionic surfactant (pentaethylene glycol monododecyl ether, C12E5), a simple cationic surfactant (hexadecyl trimethylammonium bromide, CTAB) of opposite charge to that of the substrate surface, and two cationic polyelectrolytes (poly(2-(dimethylamino)ethyl methacrylate), PDAEMA; (poly(propyl methacrylate) trimethylammonium chloride, MAPTAC). For the polyethylene oxide nonionic surfactant, bilayer adsorption is established above the critical micelle concentration (cmc) both from the adsorption amounts and from the interpretation of the observed zeta potentials. Near adsorption saturation, CTAB also forms bilayer structures on silica. Here, however, we observe a strong charge reversal of the surface. The SPOR data, along with Gouy-Chapman theory, permit assessment of the net ionization fraction of the CTAB bilayer at 10% so that most of the adsorbed CTAB molecules are counterion complexed. The adsorption of both C12E5 and CTAB is reversible. The adsorption of the cationic polymers, however, is completely irreversible to a solvent wash. As with CTAB, both PDAEMA and MAPTAC demonstrate strong charge reversal. For the polyelectrolyte molecules, however, the adsorbed layer is thin and flat. Here also, a Gouy-Chapman analysis shows that less than 20% of the adsorbed layer is ionized. Furthermore, the amount of charge reversal is inversely proportional to the Debye length in agreement with available theory. SPOR provides a new tool for elucidating aqueous adsorbate molecular structure at solid surfaces.  相似文献   

18.
A new water-soluble polyelectrolyte—the copolymer of sodium 2-acrylamido-2-methylpropanesulfonate and monoethanolamine vinyl ether—has been synthesized by free-radical copolymerization. The concentration behavior of the reduced viscosity of copolymer solutions that is typical for polyelectrolytes has been revealed. The reactivity ratios of the monomers have been measured. These values indicate a lower reactivity of monoethanolamine vinyl ether than that of sodium 2-acrylamido-2-methylpropanesulfonate. The complexation of this copolymer with poly(acrylic acid) and poly(N,N-dimethyl-N,N-diallylammonium chloride) has been studied. It has been found that the copolymer demonstrates the polyampholytic behavior and is able to form interpolymer complexes both with polycations and polyanions. It has been established that the polycomplex of the copolymer with polyacrylic acid has the unfolded structure due to the presence of sulfonate groups uninvolved in complexation, while the complex of the copolymer with poly(N,N-dimethyl-N,N-diallylammonium chloride) is compact owing to enhancement of hydrophobic interactions, and the sizes of its species are of the order of 80 nm.  相似文献   

19.
Ethanol/water pervaporation through ultrathin polyelectrolyte multilayer membranes is described. The membranes were prepared by the layer-by-layer technique, i.e. by alternating sequential adsorption of cationic and anionic polyelectrolytes on a porous support. The separation capability was optimized by variation of the chemical structure of the polyelectrolytes, by variation of pH and ionic strength of the polyelectrolyte solutions used for membrane preparation and by annealing of the polyelectrolyte membranes. It was found that the separation is mainly affected by the charge density of the polyelectrolytes which is controlled by the chemical structure and the degree of ionisation of the polar groups. Selectivity for water was highest, if polyelectrolytes of high charge density such as polyethyleneimine (PEI), polyvinylamine (PVA) and polyvinylsulfate (PVS) were used and if the pH of the polyelectrolyte solutions was equal to the mean of the pKa values of the corresponding cationic and anionic polyelectrolyte. Best results were obtained for PVA/PVS and PEI/PVS membranes which are characterized in detail with regard to their separation behavior.  相似文献   

20.
The process of reduction of divalent copper ions with tert-butylamine borane in dilute aqueous solutions of poly(N-vinylpyrrolidone) is investigated. The influence of polymer molecular mass on properties of the resultant Cu2O sols is studied. It is shown that Cu2O nanoparticles with an average diameter of 6–8 nm independent of polymer molecular mass and a relatively narrow size distribution of particles are formed in the systems under study. The contour length of macromolecules and the hydrodynamic diameter of a poly(N-vinylpyrrolidone) macromolecular coil are compared with the diameter of Cu2O particles. Poly(N-vinylpyrrolidone) with M ≥ 1 × 104 can be used to produce Cu2O nanoparticles. Poly(N-vinylpyrrolidone) with M > 4 × 104 should be used for the formation of long-living Cu2O sols.  相似文献   

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