Thomas Hellweg

Influence of charge density on the swelling of colloidal poly(N-isopropylacrylamide-co-acrylic acid) microgels

Abstract The volume phase transition of colloidal poly(N-isopropylacrylamide-co-acrylic acid) microgels depends in a complex way on the effective charge density within the polymer network. A series of monodisperse PNIPAM/AAc microgels with different content of acrylic acid were synthesized by surfactant-free emulsion polymerization employing sonication instead of a conventional stirring technique. Subsequently, the colloids were characterized by dynamic light scattering and electron microscopy. Potentiometric titrations provided the amount of carboxyl groups incorporated into the copolymer. The effective charge density was systematically controlled by the content of acrylic acid monomers, the pH value of the suspension, and the salt concentration. The hydrodynamic dimensions of the microgels have been measured by dynamic light scattering. The swelling/deswelling behavior is determined by the delicate balance between hydrophobic attraction of NIPAM and the repulsive electrostatic interactions of the carboxylate group of the acrylic acid moieties. Compared to their macroscopic counterparts the charged microgel particles show a significantly different swelling/deswelling behavior. This manifests in the occurrence of a two-step volume phase-transition process with increasing acrylic acid content. Hydrogen bonding has to be considered to understand this two step volume phase transition uniquely observed for colloidal microgels. Another interesting phenomenon presented here is the reversible formation of well-defined aggregates at low pH and under high salt conditions.

Structural changes in PNIPAM microgel particles as seen by SANS, DLS, and EM techniques

Abstract Thermo-sensitive poly(N-isopropylacrylamide) (PNIPAM) microgels with different cross-linker density have been investigated by complementary scattering methods and high-resolution imaging techniques. The swelling behavior of the colloidal particles as probed by dynamic light scattering (DLS), is discussed together with information on local structure and dynamics of the particles as obtained from small angle neutron scattering (SANS). Below the volume phase transition the static structure factor reveals liquid-like contributions. This is similar to macroscopic gels, but for low q the scattering behavior is different because of the influence of the particle form factor P(q). Beyond the phase transition temperature, Tc, the system becomes completely phase separated and interfacial scattering dominates the measured SANS profiles (I( q )∝ q −4 ). Slight deviations from the ideal Porod behavior can be interpreted in terms of surface roughness of the collapsed particles. This corresponds to structures visible on AFM micrographs.

Temperature, pH, and ionic strength induced changes of the swelling behavior of PNIPAM-poly(allylacetic acid) copolymer microgels

The volume phase transition of colloidal microgels made of N-isopropylacrylamide (NIPAM) is well-studied and it is known that the transition temperature can be influenced by copolymerization. A series of poly( N-isopropylacrylamide- co-allylacetic acid) copolymers with different contents of allylacetic acid (AAA) was synthesized by means of a simple radical polymerization approach. The thermoresponsive behavior of these particles was studied using dynamic light scattering (DLS). Further characterization was done by employing transmission electron microscopy (TEM) and zeta potential measurements. TEM observations reveal the approximately spherical shape and low polydispersity of the copolymer particles. In addition, the measured zeta potentials provide information about the relative surface charge. Since these copolymers are much more sensitive to external stimuli such as pH and ionic strength than their pure PNIPAM counterparts, the volume phase transition was investigated at two different pH values and various salt concentrations. At pH 10 for the copolymer microgels with the highest AAA content, a significant shift of the volume phase transition temperature toward higher values is found. For higher AAA content, a change in pH from 8 to 10 can induce a change in radius of up to 100 nm making the particles interesting as pH controlled actuators.

General pathway toward crystalline-core micelles with tunable morphology and corona segregation.

We present a general mechanism for the solution self-assembly of crystalline-core micelles (CCMs) from triblock copolymers bearing a semicrystalline polyethylene (PE) middle block. This approach enables the production of nanoparticles with tunable dimensions and surface structures. Depending on the quality of the solvent used for PE, either spherical or worm-like CCMs can be generated in an easy and highly selective fashion from the same triblock copolymers via crystallization-induced self-assembly upon cooling. If the triblock copolymer stays molecularly dissolved at temperatures above the crystallization temperature of the PE block, worm-like CCMs with high aspect ratios are formed by a nucleation and growth process. Their length can be conveniently controlled by varying the applied crystallization temperature. If exclusively spherical micelles with an amorphous PE core are present before crystallization, confined crystallization within the cores of the preformed micelles takes place and spherical CCMs are formed. For polystyrene-block-polyethylene-block-poly(methyl methacrylate) triblock terpolymers a patch-like microphase separation of the corona is obtained for both spherical and worm-like CCMs due to the incompatibility of the PS and PMMA blocks. The structure of the patch-like corona depends on the selectivity of the employed solvent for the PS and PMMA corona blocks, whereby nonselective solvents produce a more homogeneous patch size and distribution. Annealing of the semicrystalline PE cores results in an increasingly uniform crystallite size distribution and thus core thickness of the worm-like CCMs.

Smart inorganic/organic hybrid microgels: Synthesis and characterisation

Responsive hybrid colloids containing both organic and inorganic components have been the subject of many investigations in recent years. These new materials combine the stimuli-responsiveness of some polymer-based colloids with the unique properties of inorganic nanoparticles. This article will review the different possible variations of such hybrid colloids. Moreover, synthetic approaches, methods of characterisation, and a few applications will be discussed. Due to the rather high number of recent publications dealing with hybrid materials based on a variety of polymers, we will mainly focus on responsive hybrid microgels made of poly(N-isopropyl-acrylamide) or poly(N-vinylcaprolactam) in aqueous media.

Packing Density Control in P(NIPAM-co-AAc) Microgel Monolayers: Effect of Surface Charge, pH, and Preparation Technique

In the present paper, thermosensitive coatings are prepared by deposition of P(NIPAM-co-AAc) microgel particles on precoated silicon wafers. The effect of pH, substrate precoating, and preparation technique is studied. The pH value is found to significantly influence the adsorption density, while the substrate surface charge is less important. Hence, the electrostatic contribution of the particle-particle interaction seems to play a more pronounced role for the adsorption density than at least the electrostatic part of the particle-surface interaction. For the latter, also nonelectrostatic contributions like hydrogen bonding and surface roughness play an important role. Immersion of the prepared polyelectrolyte/microgel layers in buffers leads to a reorganization of the adsorbed particles at the surface.

Phase structures of microemulsions

Microemulsions were subject to numerous studies during the last decades, mainly because of their potential with respect to applications, but they are also interesting model systems for statistical mechanics. This is due to their rather complicated phase behaviour and the fascinating microstructures encountered in microemulsion forming systems. In the present contribution new developments in the investigation and understanding of these microstructures will be outlined.

Multiresponsive Hybrid Colloids Based on Gold Nanorods and Poly(NIPAM-co-allylacetic acid) Microgels: Temperature- and pH-Tunable Plasmon Resonance

This work describes the control and manipulation of the optical properties of multiresponsive organic/inorganic hybrid colloids, which consist of thermo-responsive poly-(NIPAM-co-allylacetic acid) microgel cores and gold nanorods assembled on their surface. These composites are multifunctional, in the sense that they combine the interesting optical properties of the rod-shaped gold particles--exhibiting two well-differentiated plasmon modes--with the sensitivity of the copolymer microgel toward external stimuli, such as temperature or solution pH. It is shown that the collapse of the microgel core, induced by changes in either temperature or pH, enhances the electronic interactions between the gold nanorods on the gel surface, as a result of the subsequent increase of the packing density arising from the surface decrease of the collapsed microgel. Above a certain nanorod density, such interactions lead to remarkable red-shifts of the longitudinal plasmon resonance.

Stiffening Effect of Cholesterol on Disordered Lipid Phases: A Combined Neutron Spin Echo + Dynamic Light Scattering Analysis of the Bending Elasticity of Large Unilamellar Vesicles

In this study, the center-of-mass diffusion and shape fluctuations of large unilamellar 1-palmitoyl-2-oleyl-sn-glycero-phosphatidylcholine vesicles prepared by extrusion are studied by means of neutron spin echo in combination with dynamic light scattering. The intermediate scattering functions were measured for several different values of the momentum transfer, q, and for different cholesterol contents in the membrane. The combined analysis of neutron spin echo and dynamic light scattering data allows calculation of the bending elastic constant, kappa, of the vesicle bilayer. A stiffening effect monitored as an increase of kappa with increasing cholesterol molar ratio is demonstrated by these measurements.

Surface Plasmon Spectroscopy of Gold-Poly-N-isopropylacrylamide Core-Shell Particles

Highly uniform, core-shell microgels consisting of single gold nanoparticle cores and cross-linked poly-N-isopropylacrylamide (PNIPAM) shells were prepared by a novel, versatile protocol. The synthetic pathway allows control over the polymer shell thickness and its swelling behavior. The core-shell structure was investigated by electron microscopy and atomic force microscopy, whereas the swelling behavior of the shell was studied by means of dynamic light scattering and UV-vis spectroscopy. Furthermore, the latter method was used to investigate the optical properties of the hybrid particles. By modeling the scattering contribution from the PNIPAM shells, the absorption spectra of the gold nanoparticle cores could be recovered. This allows the particle concentration to be determined, and this in turn permits the calculation of the molar mass of the hybrid particles as well as the refractive index of the shells.