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.

Structure and short-time dynamics in suspensions of charged silica spheres in the entire fluid regime.

We present an experimental study of short-time diffusion properties in fluidlike suspensions of monodisperse charge-stabilized silica spheres suspended in dimethylformamide. The static structure factor S(q), the short-time diffusion function D(q), and the hydrodynamic function H(q) have been probed by combining x-ray photon correlation spectroscopy experiments with static small-angle x-ray scattering. Our experiments cover the full liquid-state part of the phase diagram, including de-ionized systems right at the liquid-solid phase boundary. We show that the dynamic data can be consistently described by the renormalized density fluctuation expansion theory of Beenakker and Mazur over a wide range of concentrations and ionic strengths. In accordance with this theory and Stokesian dynamics computer simulations, the measured short-time properties cross over monotonically, with increasing salt content, from the bounding values of salt-free suspensions to those of neutral hard spheres. Moreover, we discuss an upper bound for the hydrodynamic function peak height of fluid systems based on the Hansen-Verlet freezing criterion.

Collective diffusion in charge-stabilized suspensions: concentration and salt effects.

The authors present a joint experimental-theoretical study of collective diffusion properties in aqueous suspensions of charge-stabilized fluorinated latex spheres. Small-angle x-ray scattering and x-ray photon correlation spectroscopy have been used to explore the concentration and ionic-strength dependence of the static and short-time dynamic properties including the hydrodynamic function H(q), the wave-number-dependent collective diffusion coefficient D(q), and the intermediate scattering function over the entire accessible range. They show that all experimental data can be quantitatively described and explained by means of a recently developed accelerated Stokesian dynamics simulation method, in combination with a modified hydrodynamic many-body theory. In particular, the behavior of H(q) for de-ionized and dense suspensions can be attributed to the influence of many-body hydrodynamics, without any need for postulating hydrodynamic screening to be present, as it was done in earlier work. Upper and lower boundaries are provided for the peak height of the hydrodynamic function and for the short-time self-diffusion coefficient over the entire range of added salt concentrations.

Diffusion and microstructural properties of solutions of charged nanosized proteins: experiment versus theory.

We have reanalyzed our former static small-angle x-ray scattering and photon correlation spectroscopy results on dense solutions of charged spherical apoferritin proteins using theories recently developed for studies of colloids. The static structure factors S(q), and the small-wave-number collective diffusion coefficient D(c) determined from those experiments are interpreted now in terms of a theoretical scheme based on a Derjaguin-Landau-Verwey-Overbeek-type continuum model of charged colloidal spheres. This scheme accounts, in an approximate way, for many-body hydrodynamic interactions. Stokesian dynamics computer simulations of the hydrodynamic function have been performed for the first time for dense charge-stabilized dispersions to assess the accuracy of the theoretical scheme. We show that the continuum model allows for a consistent description of all experimental results, and that the effective particle charge is dependent upon the protein concentration relative to the added salt concentration. In addition, we discuss the consequences of small ions dynamics for the collective protein diffusion within the framework of the coupled-mode theory.

Off pump coronary artery bypass grafting in EuroSCORE high and low risk patients.

OBJECTIVE: Off pump coronary artery bypass grafting (OPCAB) is claimed to reduce the operative morbidity and mortality in high risk patients. It was the aim of the study to compare the outcome of OPCAB patients classified as high- and low risk according to the EuroSCORE. METHODS: Medical records of patients undergoing off pump coronary artery bypass grafting (n=126) at our institution between 1998 and 2001 were retrospectively reviewed. We classified them into two subgroups: low risk (EuroSCORE < or = 5, n=72, male 58 (81%), female 14 (19%), age 61 (37-78) years) and high risk (EuroSCORE >5, n=54, male 32 (59%), female 22 (41%), age 73 (42-83) years). RESULTS: EuroSCORE high risk patients showed significantly higher rates of blood transfusion (70 vs 31%; P<0.0001), intraaortic balloon pump insertion (16 vs 3%; P=0.013), atrial fibrillation (43 vs 22%; P=0.014), and renal failure (13 vs 3%; P=0.028). ICU length of stay was significantly longer in the high risk group (25 vs 22 h; P=0.002). There was also a higher perioperative mortality in the high risk group (9 vs 0%; P=0.008). CONCLUSION: From these data we conclude that using off pump coronary artery bypass grafting results as predicted by the EuroSCORE can be achieved. OPCAB is safe for low risk patients. Major complications seem to occur preferentially in the high risk group.

Extraanatomical coronary artery bypass grafts on the beating heart for management of the severely atherosclerotic ascending aorta.

BACKGROUND: Crossclamping a severely atherosclerotic ascending aorta carries a significant risk of stroke in coronary artery bypass grafting. Besides other techniques aortic no touch concepts are increasingly applied for management of this problem. METHODS: Out of 407 patients undergoing epiaortic scanning during coronary artery bypass grafting 38 (9.3%) exhibited severe ascending aortic atherosclerosis. 22 of these patients (18 male, 4 female, age 72 (57-79) years, Parsonnet Score 11 (0-18), Euro Score 8 (2-13), McSPI Stroke Risk Index 6 (1-30) %) were operated on using a beating heart and aortic no touch technique. All patients received at least one internal mammary artery (IMA) in situ graft and additional extraanatomical bypass conduits: venous Y-graft from the IMA (n=14), arterial Y-graft from the IMA (n=3), vein graft from the axillary artery (n=3), vein graft from the IMA stump (n=2), vein graft from the innominate artery (n=2). RESULTS: No stroke occurred. The rate of perioperative myocardial infarction (CKMB rt; 50 U/l) was 5/22. Median ICU length of stay was 54 (15-1245) h. Hospital mortality was 2/22. Pre- and postoperative angina class (CCSC) were 3.3 +/- 0.9 and 1.4 +/- 0.9 respectively (p<0.001). After a median follow up period of 8 months 3 deaths, one stroke, and one myocardial infarction occurred. On 3D multislice CT scan reconstructions which were performed in 13 patients during the first postoperative year all IMA grafts to the LAD and 11 out of 13 extraanatomical vein grafts were shown to be patent. CONCLUSION: Performance of beating heart extraanatomical coronary artery bypass grafts for management of a heavily diseased ascending aorta can result in a very low stroke rate despite a considerable stroke risk. The complexity of the procedures may be reflected by a relatively high rate of perioperative myocardial infarctions. Perioperative mortality as well as short term patency of extraanatomical bypass grafts seem to be acceptable.

Dynamic scaling and freezing criteria in quasi-two-dimensional dispersions.

We report on a Brownian dynamics simulation study of quasi-two-dimensional dispersions of colloidal spheres interacting by long-range electrostatic and dipolar magnetic forces. The calculated dynamic correlation functions are shown to obey dynamic scaling in terms of a characteristic relaxation time related to the mean particle distance and, due to hydrodynamic interactions, to the particle size. The dynamical freezing criterion of Löwen [Phys. Rev. E 53, R29 (1996)] is shown to be equivalent to a two-dimensional static freezing criterion.

Rotational tracer diffusion in binary colloidal sphere mixtures.

We demonstrate that tracer/host size asymmetry and electrostatic interactions strongly affect rotational self-diffusion in binary mixtures of charged colloidal tracer and host spheres. Tracer diffusion coefficients, measured with time-resolved phosphorescence anisotropy, are compared with calculations of rotational diffusion including two- and three-particle hydrodynamic interactions. We also show that the inverse dependence of the rotational diffusion coefficient on the suspension viscosity is approached only at large size ratios.

Stokesian dynamics study of quasi-two-dimensional suspensions confined between two parallel walls

We present a Stokesian dynamics (SD) computer simulation study of the static and dynamical properties of a monolayer of spherical colloidal particles restricted to diffuse in the midplane between two parallel walls. SD simulations account for hydrodynamic interactions (HI's) among the particles, and between particles and walls. Three different types of systems are studied: first, a monolayer of neutral spheres and neutral hard walls; second, particles interacting by a repulsive Yukawa-type potential of range depending on the wall separation. As a third system, the interesting case of charged particles between charged parallel walls with a longer-range attractive part in the pair potential is investigated, using the experimentally determined effective pair potential of Acuna-Campa et al. [Phys. Rev. Lett. 80, 5802 (1998)]. Various measurable quantities are calculated in dependence of the particle concentration and the wall distance: short- and long-time self-diffusion coefficients, radial distribution functions and static structure factors, hydrodynamic functions, mean squared displacements, and van Hove real-space correlation functions. We assess the importance of HI's by comparing our results with simulation results where HI's are fully or partially disregarded. Some of our results are also compared with experimental data, and good agreement is found. Remarkable effects are investigated, like the hydrodynamic enhancement of self-diffusion for the case of strongly charged particles, and the strong increase of the hydrodynamic function at small wave numbers.

Sedimentation of Strongly and Weakly Charged Colloidal Particles: Prediction of Fractional Density Dependence.

We report on calculations of the reduced sedimentation velocity U/U0 in homogenous suspensions of strongly and weakly charged colloidal spheres as a function of particle volume fraction φ. For dilute suspensions of strongly charged spheres at low salinity, U/U0 is well represented by the parametric form 1 - pφalpha with a fractional exponent alpha = 13 and a parameter p approximately 1.8, which is essentially independent from the macroion charge Z. This nonlinear volume fraction dependence can be quantitatively understood in terms of a model of effective hard spheres with φ-dependent diameter. For weakly charged spheres in a deionized solvent, we show that the exponent alpha can be equal to 12, if an expression for U/U0 given by Petsev and Denkov (1992, J. Colloid Interface Sci. 149, 329) is employed. We further show that the range of validity of this expression is limited to very small values of φ and Z, which are probably not accessible in sedimentation experiments. The presented results might also hold for other systems such as spherical proteins or ionic micelles. Copyright 1999 Academic Press.

Optical Polydispersity and Contrast Variation Effects in Colloidal Dispersions.

We present a theoretical study on the effect of refractive index variations on static and dynamic light scattering in size-polydisperse suspensions of sterically and charge-stabilized colloidal particles with an internal optical structure (core-shell model) and size-dependent refractive indices. The equilibrium microstructure and the short-time dynamics of these optically, size-, and interaction-polydisperse systems are calculated using hypernetted chain and Percus-Yevick integral equation schemes. Our calculations show that, close to an index matching point, the scattered intensity I(k), the measurable structure factor SM(k), and the measurable hydrodynamic function HM(k) become very sensitive to the refractive index contrast with respect to the solvent. For this purpose, various definitions of index matching points are analyzed, and the strong relative enhancement of the incoherent part of the scattered intensity close to the matching points is discussed. For charge-stabilized systems we show that the anomalous behaviour of I(k) and HM(k) in the matching regime of the solvent refractive index can be well described by a simple approximative scheme, which can be easily implemented. Consequences of our study for scattering experiments aimed to determine particle sizes or structural properties of colloidal dispersions are discussed. Copyright 1998 Academic Press.