Effect of cationic polyacrylamides on the interactions between cellulose fibers.

The interaction between cellulose fibers in the presence of cationic polyacrylamide (CPAM) was analyzed by rheology as a function of polyelectrolyte concentration, charge density, and molecular weight. CPAM was found to strongly influence the yield stress of cellulose suspensions; low doses of CPAM increased the yield stress, but at higher concentrations the yield stress declined. The charge density of the CPAM was the most significant factor in how yield stress responded to CPAM concentration; this effect was able to be normalized to a master curve by considering only the charged fraction of the polymer. The molecular weight of CPAM samples had some effect at high concentrations, but for lower CPAM doses the yield stress was independent of molecular weight over the range studied. The data suggest that CPAM modifies the interaction between cellulose surfaces via several mechanisms, with electrostatic interactions in the form of charge neutralization and charged patch formation dominating; polymer bridging and steric repulsion also influence the overall balance of forces between interacting cellulose fibers.

Complexity in nanoparticle assembly and function obtained by direct-grafted peptides.

We synthesize peptide-functionalized nanoparticles by growing the peptide directly from the nanoparticles in a grafting-from process. We demonstrate the procedure by grafting a short, pH and oxidation responsive peptide sequence from 300 nm silica nanoparticles. The peptide allows destabilization of the particles in response to pH by neutralization of electrostatic charge, while manipulation of oxidizing conditions in the system offers the ability to select for irreversible, covalent bonding between the particles. In one system, we show the assembly of an asymmetrically functionalized set of particles, which may have applications in the formation of binary particle networks. The method of preparing peptide-coated particles should greatly simplify existing processes used to create peptide-functionalized nanoparticles.

Peptides grafted from solids for the control of interfacial properties.

We have used solid-phase peptide synthesis to graft a peptide monolayer from a solid in order to modify the interfacial properties. We grafted a 15-residue peptide, EKEKEKEKEKEKEGG, containing a zwitterionic sequence of alternating lysine and glutamic acid residues from the surface of an aminosilanized silicon wafer by placing the silicon wafer within a commercial microwave peptide synthesizer. Such synthesizers are routinely used to make peptides on porous beads, but the peptides are subsequently cleaved and used independently of the solid support; our aim is to utilize the covalently bound peptide to control the surface properties without the need for cleavage and reattachment. We confirmed the presence of this peptide layer on the surface by X-ray photoelectron spectroscopy and ellipsometry. Atomic force microscopy was then used to study the forces between the peptide-modified surface and a borosilicate glass sphere as a function of the solution pH. The adsorbed peptide makes the silicon wafer pH responsive: at high pH the glass particle is repelled from the wafer, and at low pH it is attracted. Previous studies with synthetic polymers have shown that the "grafting from" method allows a much higher film density than "grafting to". We propose that the application of grafting from strategies to peptide layers may offer three additional benefits: (1) the film density can be controlled independently of the primary sequence of the peptide, (2) the sequence constraints for spontaneous adsorption are removed, and (3) the procedure is fast and efficient, which may lead to lower costs and the ability for high-throughput surface biofunctionalization. Moreover, peptide layers offer increased sequence diversity, control, and functionality compared to conventional polymer brushes.

Surface chemistry and rheology of polysulfobetaine-coated silica.

We have measured the viscosity of suspensions of colloidal silica particles (d = 300 nm) and the properties of silica surfaces in solutions of a polymer consisting of zwitterionic monomer groups, poly(sulfobetaine methacrylate), polySBMA. This polymer has potential use in modifying surface properties because the polymer is net uncharged and therefore does not generate double-layer forces. The solubility of the polymer can be controlled and varies from poor to good by the addition of sodium chloride salt. Ellipsometry was used to demonstrate that polySBMA adsorbs to silica and exhibits an increase in surface excess at lower salt concentration, which is consistent with a smaller area per molecule at low salt concentration. Neutron reflectivity measurements show that the adsorbed polymer has a thickness of about 3.7 nm and is highly hydrated. The polymer can be used to exercise considerable control over suspension rheology. When silica particles are not completely covered in polymer, the suspension produces a highly viscous gel. Atomic force microscopy was used to show this is caused by bridging of polymer between the particles. At higher surface coverage, the polymer can produce either a high or very low viscosity slurry depending on the sodium chloride concentration. At high salt concentration, the suspension is stable, and the viscosity is lower. This is probably because the entrainment of many small ions renders the polymer film highly hydrophilic, producing repulsive surface forces and lubricating the flow of particles. At low salt concentrations, the polymer is barely soluble and more densely adsorbed. This produces less stable and more viscous solutions, which we attribute to attractive interactions between the adsorbed polymer layers.