Melanie Bradley

Interaction between lysozyme and colloidal poly(NIPAM-co-acrylic acid) microgels

The interaction between lysozyme and colloidal poly(NIPAM-co-acrylic acid) microgels is investigated in aqueous solutions at neutral pH. Lysozyme binding isotherms, obtained within the ionic strength range 10-220 mM, indicate that the maximum uptake at 10 mM is 2.4 g lysozyme per gram dry gel, and that the uptake capacity decreases with increasing ionic strength to approximately 0 at 220 mM. Swelling isotherms, obtained from photon correlation spectroscopy measurements, show that the binding is accompanied by a substantial deswelling of the microgels. The microgel suspension is stable up to a protein-to-polymer charge ratio in the microgels of about 0.6, largely independent of ionic strength, whereas flocculation/sedimentation occurs at higher charge ratios. The charge ratio 0.6 corresponds to a zeta-potential of about -6 mV, as obtained from measurements of electrophoretic mobility. Binding and swelling isotherms are analyzed in detail and compared with predictions of theoretical model calculations. The influence of protein-protein attraction is highlighted, as well as the interplay between electrostatic interactions and network elasticity.

Poly(vinylpyridine) Core/Poly(N-isopropylacrylamide) Shell Microgel Particles : Their Characterization and the Uptake and Release of an Anionic Surfactant

The use of microgel particles for controlled uptake and release of active species has great potential. The compatibility of microgel particles with their environment and the functionality of the particles can be achieved by modification of the core microgel through the addition of a shell. In this work, core-shell microgel particles, with a pH-responsive core (polyvinylpyridine) and a temperature-responsive shell (poly-N-isopropylacrylamide), have been prepared and characterized. The uptake and release of an anionic surfactant from the microgels has been investigated as a function of solution pH and temperature. The results indicate that electrostatic attraction between the anionic surfactant and the cationically charged core of the microgel particles is the dominant mechanism for absorption of the surfactant into the core-shell microgel particles.

Cluster formation of Janus polymer microgels

Spherical particles whose surfaces are divided into two distinct chemical regions are termed Janus particles. The anisotropic architecture of Janus particles allows their directed assembly into multiple-particle structures. Here, a heteroaggregation technique between positively charged poly(2-vinylpyridine) microgel particles and much larger, negatively charged poly(2-vinylpyridine-co-styrene) latex particles was used to mask one face of the microgel particles. On the exposed face, atom transfer radical polymerisation was used to graft poly(N-isopropylacrylamide). The resultant pH- and temperature-responsive Janus microgels were isolated through dissolution of the latex particles, and characterised by transmission and scanning electron microscopy. The Janus microgel particles form spherical clusters in solution. The clusters can be formed reversibly by changing the solution temperature, or irreversibly through the addition of an electrolyte. The ability to control the flocculation of particles into small defined clusters may lead to advances in separation processes, optical sensing, and their use as delivery vehicles.

Symmetric and asymmetric adsorption of pH-responsive gold nanoparticles onto microgel particles and dispersion characterisation.

The interaction between carboxylic acid-stabilised gold nanoparticles (AuNP) and pH-responsive microgels is shown. The microgel particles are a copolymer of N-[3-(dimethylamino)propyl]methacrylamide (DMAPMA) and N-isopropylacrylamide (NIPAM). The microgel properties are presented by their hydrodynamic diameter and electrophoretic mobility in response to pH. These microgel particles are pH-responsive under neutral conditions decreasing in diameter beyond pH 7. The dispersion characteristics of AuNP adsorbed onto the microgel network are shown with respect to adsorbed amount and the pH-responsive properties of the AuNP. This data is presented between pH 3 and 6 where the microgel properties remain constant. Asymmetric adsorption of AuNP onto poly(DMAPMA-co-NIPAM) microgels is achieved by adsorption of nanoparticles, from the aqueous phase, onto microgel-stabilised oil-in-water emulsions. These asymmetrically modified microgels display very different dispersion behaviour, in response to pH, due to their dipolar nature.

The Uptake and Release of Cationic Surfactant from polyampholyte Microgel Particles in Dispersion and as an Adsorbed Monolayer

The use of novel polyampholyte microgel particles for the controlled absorption and release of a cationic surfactant has been investigated. The addition of cetylpyridinium chloride (CPC) to aqueous dispersions of poly(2-diethylamino)ethyl methacrylate-co-methacrylic acid (DEAEM-co-MAAc) microgel particles has been studied with respect to CPC concentration and solution pH. CPC was found to absorb into the polyampholyte microgel particles, resulting in reduced hydrodynamic diameter and electrophoretic mobility, when added to microgel dispersion at pH 11. Strong desorption could be induced by switching the pH from 11 to 3, with most of the desorption occurring in the region of the isoelectric pH of the particles. The properties of surface-adsorbed monolayers of polyampholyte microgel particles were also investigated, both in the presence and absence of CPC. The substrate surface charge was found to influence the swelling profile of the adsorbed microgel monolayers. The interaction of CPC surfactant with monolayers of adsorbed microgel particles shows strong correlations with the interaction of CPC surfactant with microgel particles in dispersion.

Photo-responsive properties of poly(NIPAM-co-AAc) microgel particles with absorbed, hydrophobically modified organic salts

The absorption of two hydrophobically modified organic salts (HMOSs), containing azobenzene units, into poly(N-isopropylacrylamide-co-acrylic acid) microgel particles has been studied at pH 8 and 20 °C. These dispersions were then irradiated with UV light (wavelength 365 nm) for 10 min to observe the effect on the microgel particle properties, such as the adsorbed amount of the HMOS, the particle size, and the electrophoretic mobility. We show that irradiation of these dispersions with UV light can lead to induced, partial desorption of the HMOS molecules, with concomitant changes in the size and electrophoretic mobility of the microgel particles. This is due to a conformational switch (trans-form to cis-form) in the HMOS molecules, which reduces the strength of the hydrophobic interaction between the HMOS molecules and the isopropyl moieties within the microgel network. Moreover, the original absorbed amounts, size, and electrophoretic mobility values can be largely restored after storage in the dark for extended periods.

Controlling Gold Nanoparticle Stability with Triggerable Microgels

The interaction of a photodegradable surfactant (PS, 4-hexylphenylazosulfonate, C(6)PAS) with microgels (MGs) of poly(2-vinyl pyridine) (MGA) in the protonated state (pH 3) has been investigated. Electrophoretic mobility measurements confirm that negatively charged PS interacts with positively charged MGA to form mixed PS-MG complexes. This was sensed by a decrease in the effective PS-MGA charge and a switch in sign of electrophoretic mobility, from positive to negative, with increasing PS concentration. After the addition of extra positive microgels (MGB), the system undergoes coflocculation. Incident UV irradiation was used to photolyze the anionic PS, effectively eliminating the headgroups, thereby lowering the electrostatic interactions between PS and MGA microgel networks. Consequently, a reversal of MGA charge occurred, leading to electrostatic repulsions and causing the MGs to reswell and redisperse, with both MGA and MGB now being positively charged and hence stabilized against coflocculation. Extending this approach, negatively charged gold nanoparticles (AuMES) have been incorporated into the PS-MGA complexes. Atomic absorption spectroscopy (AAS) showed that 100% of the AuMES particles were recovered after coflocculation of (PS-MGA)-AuMES complexes with MGB. Furthermore, approximately 75% of the AuMES could be redispersed after UV irradiation to restabilize the dispersion. This system provides an interesting method for phase separation and gold nanoparticle recovery for reuse and recycling.

Chemistry at the polymer–particle interface for the design of innovative materials

The chemical modification of preformed polymer particles, in particular stimulus-responsive microgel particles, is paving the way for innovative technology. A summary is provided of the chemical reactions that are commonly used at the polymer particle interface to add functionality to polymer particles or enable their development into new materials. The advantages of being able to perform further chemistry on polymer particles will be discussed in terms of materials engineering, where microgel particles have been used as building blocks in the formation of hydrogels. Then the functionalities that have been added to individual polymer particles will be discussed in terms of application, particularly biomedical application.

Effect of chain length on the interaction between modified organic salts containing hydrocarbon chains and poly(N-isopropylacrylamide-co-acrylic acid) microgel particles.

A series of four hydrophobically modified, diphenylazo-based organic salts have been prepared and characterized. To achieve this a C(x) (x = 4, 6, 8, or 10) hydrocarbon chain was inserted between the diphenylazo moiety and the quaternary ammonium headgroup of the salt. The absorption of each of the four modified organic salts into anionic microgel particles of poly(N-isopropylacrylamide-co-acrylic acid) has been studied at pH 8. In addition, the hydrodynamic diameters and electrophoretic mobilities of the microgel particles have been studied as a function of the organic salt concentration, also at pH 8. In addition to the electrostatic attraction between the quaternary ammonium head groups of the organic salts and the anionic groups within the microgel particles, hydrophobic association between the chains of the organic salts within the microgel particles plays a role, with this effect increasing strongly from x=4 to 10. Desorption of the x=4 and 6 organic salts occurs readily on changing, in situ, the pH from 8 to 2.5 (and thereby eliminating the electrostatic interaction) but is only partially achieved for the x=8 and 10 organic salts. Indeed, for the x=10 organic salt, only about 80% of the organic salt is desorbed upon dilution of the microgel particles into a large excess of water.

Biocompatible, Polyampholyte Microgel Particles

Biocompatible, polyampholyte microgel particles have been prepared by the acid hydrolysis of t-butyl groups within (2-diethylamino)ethyl methacrylate-co-t-butyl methacrylate microgel particles to give (2-diethylamino)ethyl methacrylate-co-methacrylic acid microgel particles. The hydrodynamic diameter and electrophoretic mobility of both the pre-hydrolyzed and post-hydrolyzed microgel particles have been investigated as a function of pH for three microgel dispersions differing in their monomer compositions. The swelling properties and isoelectric point pH are shown to depend on the monomer composition.