Erratum: Structure and Dynamics of Loosely Cross-Linked Ionic Microgel Dispersions in the Fluid Regime [Phys. Rev. Lett. 109, 048302 (2012)].

This corrects the article DOI: 10.1103/PhysRevLett.109.048302.

Dielectric spectroscopy of ionic microgel suspensions.

The determination of the net charge and size of microgel particles as a function of their concentration, as well as the degree of association of ions to the microgel backbone, has been pursued in earlier studies mainly by scattering and rheology. These methods suffer from contributions due to inter-particle interactions that interfere with the characterization of single-particle properties. Here we introduce dielectric spectroscopy as an alternative experimental method to characterize microgel systems. The advantage of dielectric spectroscopy over other experimental methods is that the polarization due to mobile charges within a microgel particle is only weakly affected by inter-particle interactions. Apart from electrode polarization effects, experimental spectra on PNIPAM-co-AA [poly(N-isopropylacrylamide-co-acrylic acid)] ionic microgel particles suspended in de-ionized water exhibit three well-separated relaxation modes, which are due to the polarization of the mobile charges within the microgel particles, the diffuse double layer around the particles, and the polymer backbone. Expressions for the full frequency dependence of the electrode-polarization contribution to the measured dielectric response are derived, and a theory is proposed for the polarization resulting from the mobile charges within the microgel. Relaxation of the diffuse double layer is modeled within the realm of a cell model. The net charge and the size of the microgel particles are found to be strongly varying with concentration. A very small value of the diffusion coefficient of ions within the microgel is found, due to a large degree of chemical association of protons to the polymer backbone.

Structure and dynamics of loosely cross-linked ionic microgel dispersions in the fluid regime.

We report a comprehensive experimental-theoretical study of the temperature- and concentration-dependent swelling behavior of weakly cross-linked PNiPAm ionic microgel particles in the deionized fluid phase. The particles swell reversibly when the dispersion is cooled from the collapsed state to lower temperatures. While the collapsed state shows no dependence on the microgel number density, the swelling at lower T is more pronounced at lower concentrations. The static pair correlations and short-time diffusion functions, and the concentration and temperature dependence of the microgel radius and effective charge, are studied using static and dynamic light scattering in combination with state-of-the-art analytical theoretical schemes based on a Yukawa-type effective pair potential and a core-shell model. We show that only such a combined, simultaneous fit of static and dynamic scattering functions allows for an unambiguous determination of the microgel radius and effective charge.

Synthesis and characterization of novel functional electrosterically stabilized colloidal particles prepared by emulsion polymerization using a strongly ionized amphiphilic diblock copolymer.

Amphiphilic diblock copolymers such as poly(styrene)-block-poly(styrene sulfonate) (PS-b-PSS) (Matsuoka, H.; Maeda, S.; Kaewsaiha, P.; Matsumoto, K. Langmuir 2004, 20, 7412), belong to a class of new polymeric surfactants that ionize strongly in aqueous media. We investigated their self-assembly behavior in aqueous solutions and used them as an emulsifier to prepare electrosterically stabilized colloidal particles of different diameters between 70 to 400 nm. We determined the size, size polydispersity, effective charge, total dissociable charge, structural ordering, and phase behavior using light scattering, transmission electron microscopy (TEM), small-angle neutron scattering (SANS), and potentiometric titration. These experiments clearly demonstrated that all of the synthesized particles were nearly monodisperse (polydispersity index

Structural ordering and phase behavior of charged microgels.

Recent theoretical phase diagrams for loosely cross-linked ionic microgels with a low monomer volume fraction (Gottwald; et al. Phys. Rev. Lett. 2004, 92 , 068301 ) have predicted a re-entrant order-disorder transition (i.e., fluid-FCC-BCC-fluid) as a function of concentration and so far there has been no experimental verifications of these theoretical predictions. Here, we present experimental results on phase behavior of loosely cross-linked charged poly(N-isopropylacrylamide co acrylic acid) (PNIPAm-co-AAc) microgesls with a low monomer volume fraction (approximately 0.003) for a wide range of concentrations (0.02-0.6 wt %) using static and dynamic light scattering methods. These microgel dispersions exhibit a short-range liquid order at low concentration (<0.03 wt %), a FCC crystalline order at intermediate concentrations (0.03- 0.3 wt %). In addition, we suggested a possible coexistence of BCC and FCC phases at higher concentration crystalline suspension (approximately 0.34 wt %). These results clearly demonstrate the experimental verification of above theoretical prediction below the overlap concentration and also reveal that the interaction potential between the microgel particles is of screened Coulomb repulsive type within these concentration ranges. At further higher concentration (approximately 0.57 wt %), we once again observed a disordered state and this disordered state from dynamic light scattering was confirmed to be a glass. These initial results are discussed in the light of previously reported results on the phase behavior of ionic microgel colloidal dispersions.

Synthesis and characterization of charged polystyrene-acrylic acid latex particles.

Novel, monodisperse charged colloidal particles of polystyrene cross linked with divinylbenzene and surface-grafted with acrylic acid were synthesized by emulsion polymerization and were characterized by estimating the dissociable surface charge by conductivity titration, the particle effective charge by conductivity verses particle concentration, and the particle size by dynamic light scattering and atomic force microscopy. The structural ordering and dynamics were investigated as a function of the volume fraction of the particles using static and dynamic light scattering, respectively. Furthermore, from the electrophoresis measurements, these particles are found to have a high salt tolerance due to increases in charge as a function of salt concentration.

Gas-solid coexistence in highly charged colloidal suspensions.

Aqueous suspensions of highly charged polystyrene particles with different volume fractions have been investigated for structural ordering and phase behavior using static light scattering (SLS) and confocal laser scanning microscope (CLSM). Under deionized conditions, suspensions of high-charge-density colloidal particles remained disordered whereas suspensions of relatively low charge density showed crystallization by exhibiting iridescence for the visible light. Though for the unaided eye crystallized suspensions appeared homogeneous, SLS measurements and CLSM observations have revealed their inhomogeneous nature in the form of the coexistence of voids with dense ordered regions. CLSM investigations on disordered suspensions showed their inhomogeneous nature in the form coexistence of voids with dense disordered (amorphous) regions. Our studies on highly charged colloids confirm the occurrence of gas-solid transition and are in accordance with predictions of Monte Carlo simulations using a pair-potential having a long-range attractive term [Mohanty, P. S.; Tata, B. V. R. J. Colloid Interface Sci. 2003, 264, 101]. On the basis of our experimental and simulation results, we argue that the reported reentrant disordered state [Yamanaka et al. Phys. Rev. Lett. 1998, 80, 5806 and Toyotama et al. Langmuir 2003, 19, 3236] in charged colloids observed at high charge densities is a gas-solid coexistence state.

Long-wavelength transverse modes in charged colloidal crystals.

The dynamics of closely index matched colloidal crystals of charged silica spheres dispersed in deionized ethylene glycol-water mixture is investigated using dynamic light scattering. At variance with the reports of phonon dispersion measurements on thin colloidal crystals, our observations on millimeter-sized crystals show unambiguous evidence for overdamped transverse modes turning propagative in the range of small wave numbers in agreement with the theory of hydrodynamic interactions in charged colloidal crystals.

Charge and salt-driven reentrant order-disorder and gas-solid transitions in charged colloids.

Monte Carlo simulations have been performed for aqueous charged colloidal suspensions as a function of effective charge density (sigma) on the particles and salt concentration C(s). We vary the effective charge density in our simulations over a range where a reentrant solid-liquid transition in suspensions of silica and polymer latex particles has been reported by Yamanaka et al. (Phys. Rev. Lett. 80 (1998) 5806). We show that at low ionic strengths a homogeneous liquid-like ordered suspension undergoes crystallization upon increasing sigma. Further increase in sigma resulted once again in a disordered state, which is in agreement with experimental observations. In addition to this reentrant order-disorder transition, we observe an inhomogeneous-to-homogeneous transition in our simulations when salt is added to the disordered inhomogeneous state. This inhomogeneous-to-homogeneous disordered transition is analogous to the solid-gas transition of atomic systems and has not yet been observed in charged colloids. The reported experimental observations on charged colloidal suspensions are discussed in the light of present simulation results.

Glass transition and dynamical heterogeneities in charged colloidal suspensions under pressure.

Constant-pressure Monte Carlo simulations have been performed to study the static and dynamical properties of a liquidlike ordered suspension of like-charged colloidal particles subjected to a sudden compression. We report for the first time a liquidlike ordered monodisperse suspension undergoing a glass transition at a very low volume fraction ( straight phi = 0.003) and existence of dynamical heterogeneities near the glass transition. Mobile particles have been identified using the non-Gaussian parameter for the self-part of the Van Hove correlation function, and they are found to form clusters. The pressure dependence of mean cluster size and the cluster-size distribution of the mobile particles are discussed.

The role of CP 47 in the evolution of oxygen and the binding of the extrinsic 33-kDa protein to the core complex of Photosystem II as determined by limited proteolysis.

In order to identify the domain within Photosystem II complexes that functions in the evolution of oxygen, we performed limited proteolysis with lysylendopeptidase of the core complex of Photosystem II which had been depleted of the extrinsic 33-kDa protein (Mn-stabilizing protein). The cleavage sites were estimated from the amino-terminal sequences of the degradation fragments, their apparent molecular masses and amino-acid compositions. Under certain conditions, the D2 protein was cleaved at Lys13; and a chlorophyll a-binding protein, CP 47, was cleaved at Lys227 and Lys389. Another chlorophyll a-binding protein, CP 43, was degraded more rapidly than CP 47. The oxygen-evolving activity and the capacity for rebinding of the 33-kDa protein to the core complex of Photosystem II decreased in parallel, with kinetics very similar to those of the cleavage of CP 47 at Lys389. These observations strongly suggest that the hydrophilic domain around Lys389 of CP 47, which are located on the lumenal side, is important in the binding of the 33-kDa protein and in maintaining the oxygen-evolving activity of the Photosystem II complex.

Glycinebetaine stabilizes the association of extrinsic proteins with the photosynthetic oxygen-evolving complex.

The photosynthetic oxygen-evolving activity of the photosystem 2 complex, prepared from spinach, was labile when the complex was exposed to high-salt conditions under which the extrinsic proteins were dissociated from the complex. Glycinebetaine prevented the dissociation of the 18-kDa and the 23-kDa extrinsic proteins from the photosystem 2 complex in the presence of 1 M NaCl. It also prevented the dissociation of the 33-kDa extrinsic protein from the complex in the presence of 1 M MgCl2 or 1 M CaCl2. The oxygen-evolving activity of the photosystem 2 complex was stabilized by glycinebetaine when the complex was subjected to treatment with NaCl and MgCl2.

Glycinebetaine enhances and stabilizes the evolution of oxygen and the synthesis of ATP by cyanobacterial thylakoid membranes.

Glycinebetaine (betaine), an osmoregulant in halophilic plants, stabilized the evolution of oxygen and the synthesis of ATP by thylakoid membranes from the cyanobacterium Synechocystis PCC6803 when it was present during the preparation and incubation of the thylakoid membranes. Moreover, betaine enhanced the evolution of oxygen and the synthesis of ATP when present during assays. When betaine at 1.0 M was present during the preparation of thylakoid membranes and during the measurement of activity, the rate of evolution of oxygen was equivalent to that of intact cells.