Modulation of Self-healing of Polyion Complex Hydrogel by Ion-specific Effects

We have prepared polyion complex (PIC) hydrogel consisting of poly(3-(methacryloylami no) propyl-trimethylamonium chloride) and poly(sodium p-styrenesulfonate) polyelectrolytes via a two-step polymerization procedure and have investigated specific ion effects on the selfhealing of the PIC hydrogel. Our study demonstrates that the mechanical properties of the PIC hydrogel are strongly dependent on the type of the ions doped in the hydrogel. The ion-specific effects can be used to modulate the self-healing efficiency of the PIC hydrogel. As the doped anions change from kosmotrops to chaotropes, the self-healing efficiency of the PIC hydrogel increases. A more chaotropic anion has a stronger ability to break the ionic bonds formed within the hydrogel, leading to a higher efficiency during the healing.     

Aggregation-induced emission of an aminated silole: A fluorescence probe for monitoring layer-by-layer self-assembling processes of polyelectrolytes

A new fluorescence technique for monitoring layer-by-layer self-assembling processes of polycations and polyanions is developed in this work. The fluorescent probe is a fluorogenic dye named 1,1-bis[p-(diethylaminomethyl)phenyl]-2,3,4,5-tetraphenylsilole (A₂HPS). Whereas fluorescence of a “normal” fluorophore is often quenched by aggregate formation, the protonated salt of A₂HPS, i.e., [H₂A₂HPS]²⁺, emits strong light in the suspensions of its nanoaggregates and in the solid films of its blends with poly(diallyldimethylammonium chloride) (PDDAC), thanks to its novel aggregation-induced emission (AIE) characteristics. When ([H₂A₂HPS]²⁺+PDDAC) cations and poly(styrenesulfonate) (PSS) anions were used to fabricate thin films via layer-by-layer deposition processes on quartz and glass substrates, the emission intensity of [H₂A₂HPS]²⁺ showed linear relationship with the number of ([H₂A₂HPS]²⁺+PDDAC)/PSS bilayers, due to the uniform co-deposition of [H₂A₂HPS]²⁺ cations into the PDDAC/PSS bilayers. This proves that the AIE fluorophore is an excellent probe for monitoring the layer-by-layer self-assembling processes of the polyelectrolytes on various substrates.     

Polyelectrolyte multilayers as stationary phases for open tubular ion chromatography

Polyelectrolyte multilayers deposited on the wall of fused silica capillaries were used as stationary phases in open tubular ion chromatography. The multilayers were formed by flushing the capillaries with solutions of polyanions and polycations such as polydiallyldimethylammonium chloride and dextran sulphate. Columns with several bi-layers were constructed and used in low pressure non-suppressed open tubular ion chromatography of common inorganic anions (F⁻, Cl⁻, NO₃⁻) and cations (Li⁺, Na⁺, NH₄⁺, K⁺, Cs⁺) with contactless conductometric detection. Using sodium benzoate and tartaric acid eluents the separations were typically achieved in less than 35 min with separation efficiencies between 2000 and 9000 theoretical plates. A bi-functional column was prepared that contains both anionic and cationic functional groups and was used for simultaneous separation of anions and cations.     

Embedding copper nanoparticle-anchored conductive nano-blocks in polyelectrolyte

Conductive carbon nanotubes （CNTs） or alternatively polyaniline （PANI） nano-blocks was introduced into aqueous solutions of polyvinyl alcohol （PVA） and copper （II） salt, to assist the reduction of copper （II） ions and the anchoring of the resulting copper nanoparticles onto the conductive blocks. The mixture solutions of nano-blocks, copper （lI） salts and PVA were spin-coated onto the cathode surface, forming swollen cathode films （SCFs）. The copper （II） ions in the film assembled onto the surfaces of the conductive blocks and were then reduced under an appropriate voltage. It is important that the copper nanoparticles grew only on the surfaces of the conductive blocks. PVA which acted as the matrix of the composites played a role in stabilizing the resulting copper nanoparticles. Morphologies of these polymeric composite films were studied by various characterization methods. Moreover, the mechanism of migration of copper （II） ions, the formation of these polymeric composites, and the overall procedure were investigated in detail.     

Fabrication of microelectrodes using flow layer-by-layer self assembly of gold nanoparticles

Microelectrodes to be used in microfluidic devices were prepared from the layer-by-layer flow deposition of gold nanoparticles. Pre-designed microfluidic channels were used as templates for the flow driven deposition of the nanoparticles in sequence with poly (diallyldimethyl amonium chloride) (PDADMAC). The electrical resistivity of the gold nanoparticle assembly was found to be strongly dependant on the concentration of sodium citrate used in the gold nanoparticle synthesis. As the electrical properties of the film changed from insulating to conducting when decreasing the citrate concentration, a 4 point probe setup was used to measure the resistivity of the film. Near bulk conductivity (5.42 × 10⁻⁶ Ω cm) was achieved with only 10 layers of film. The thickness and morphology of the flow-printed multilayer microelectrode was characterized using atomic force microscopy (AFM) and a field emission scanning electron microscope (FE-SEM). To demonstrate its usefulness, the microelectrode assembly was then tested toward the detection of KCl in solution, having a concentration ranging from 1 to 20 mM using AC current detection in a simple setup. Good linearity and stability of the electrode confirmed that this method could be very convenient for the fabrication of microelectrodes for lab-on-chip applications.     

Enzyme-catalyzed modification of PES surfaces: reduction in adsorption of BSA, dextrin and tannin

The effect of pH on the build-up of polyelectrolyte multilayers, PEMs, composed by poly-L-lysine and heparin onto two different substrates, silica and gold, has been studied by means of ellipsometry and quartz crystal microbalance with dissipation, QCM-D. Ellipsometry results indicate that the dry mass grows exponentially with the number of layers, and that this amount is larger as the pH values are raised. From QCM-D data the viscoelastic properties of the multilayered structure have been obtained. These data reflect that PEMs become more viscoelastic as the pH values are increased for silica substrates, while for gold the highest viscoelastic behavior is obtained at neutral pH and the elastic behavior becomes dominant as the pH is further increased or decreased. By combining these two surface techniques it has been also possible to determine the solvent content in the multilayers and reach a deeper understanding of the internal structure.     

Hydration of calcium sulfate hemihydrate (CaSO4· H2O) into gypsum (CaSO4·2H2O). The influence of the sodium poly(acrylate)/surface interaction and molecular weight

The retarding influence of sodium poly(acrylate) (PANa) on the hydration of calcium sulfate hemihydrate (CaSO₄· H₂O) was investigated. This study reports the influence of sodium poly(acrylate) on hemihydrate dissolution, on homogenous and heterogeneous gypsum (CaSO₄·2H₂O) nucleation as well as on gypsum growth. It is shown that adsorption of PANa does not hinder the dissolution of hemihydrate in the present experimental conditions. The specific interaction of PANa with gypsum can explain the oriented growth of gypsum crystal. The gypsum growth is slowed down but cannot be blocked by the adsorption of PANa. On the other hand, PANa can block the heterogeneous and homogenous gypsum nucleation. As soon as a critical surface density of PANa onto the hemihydrate surface is reached, the heterogeneous gypsum nucleation is prevented and hemihydrate hydration is indefinitely blocked. The interaction between PANa and the hemihydrate surface is of prime importance to control hydration. Also, the influence of the molecular weight of PANa on homogenous nucleation has been investigated. The precipitation of calcium polyacrylate can explain the differences between the two molecular weights used (2100 and 20 000). This work leads to the conclusion that heterogeneous nucleation is the key process that controls hydration of a system in which hemihydrate dissolution, gypsum nucleation and growth are all occurring at the same time in a continuous manner.     

Controlled synthesis of stable poly(vinyl formamide-co-vinyl amine)/silica hybrid particles by interfacial post-cross-linking reactions

 The chemical synthesis and the physicochemical properties of stable poly(vinyl formamide-co-vinyl amine)/silica hybrid particles are presented. Copolymers of poly(vinyl formamide) (PVFA) and poly(vinyl amine) (PVAm) and their protonated forms were adsorbed onto silica from aqueous solutions. The influences of the pH strength and the ion concentration of the aqueous solution as well as the copolymer composition (degree of hydrolyzation of PVFA), and the molecular mass on the adsorption process were investigated by electrokinetic measurements, potentiometric titration, and quantitative elemental analyses. Silica surface-charge neutralization is achieved at a pH strength above 10 for highly hydrolyzed (95%) PVFA polymers. Decreasing the amino content in the PVAm chain shifts successively both the point of zero charge and the isoelectric point to lower pH values. PVFA-co-PVAm layers onto silica are adsorbed weakly. To fix these layers irreversibly, cross-linking reactions with (4,4′-diisocyanate)diphenyl methane were carried out on the surface of solid PVFA-co-PVAm/silica hybrid particles suspended in acetone. The cross-linking reaction, which is connected with the conversion of amino groups, is also a tool to control the surface charge of the PVFA-co-PVAm/silica hybrids. X-ray photoelectron spectroscopy and solid-state ¹³C cross-polarization magic-angle spinning NMR spectroscopy were used to obtain information on the number of and the structure of the functionalized polyelectrolyte layers on silica. The success of cross-linking was also shown by the results of these spectroscopic methods. Received: 28 June 1999 /Accepted: 27 August 1999     

Polyelectrolyte complex capsules as a material for enzyme immobilization

The polyelectrolyte complex (PEC) membrane formed by cellulose sulfate and poly(dimethyldiallylammonium chloride) was used to encapsulate lactate dehydrogenase. The exclusion limit of the membrane was found to be low enough to secure irreversible entrapping of the enzyme. The obtained capsules were checked for their functionality in a stirred-batch reactor by following the kinetics of NADH oxidation. The data were fitted with an isotropic kinetic model including competitive product-inhibition phenomenon. The results of mathematical modeling demonstrated that the anisotropic system, like PEC capsules, could be satisfactorily described by the isotropic model.     

Polyelectrolyte brushes

We survey recent progress made in the field of polyelectrolyte brushes. These systems consist of long polyelectrolyte chains that are grafted densely to planar or curved surfaces. The main feature of all polyelectrolyte brushes is the strong confinement of the counterions within the brush layer. The high osmotic pressure which is thus built up explains the unusual features of these systems. Here we focus on the most recent experimental developments which are rationalized on the basis of existing theoretical predictions and opens new challenging problems. In particular, we shall discuss briefly the experimental systems used for comparing theory and experiment lately. Moreover, we review various aspects related to the experimental analysis of polyelectrolyte brushes. As a final point, we survey trends in recent applications which demonstrate that polyelectrolyte brushes have an excellent prospect for future nanotechnology.