On the role of softness in ionic microgel interactions.

Thermoresponsive microgels are a popular model system to study phase transitions in soft matter, because temperature directly controls their volume fraction. Ionic microgels are additionally pH-responsive and possess a rich phase diagram. Although effective interaction potentials between microgel particles have been proposed, these have never been fully tested, leading to a gap in our understanding of the link between single-particle and collective properties. To help resolve this gap, four sets of ionic microgels with varying crosslinker density were synthesised and characterised using light scattering techniques and confocal microscopy. The resultant structural and dynamical information was used to investigate how particle softness affects the phase behaviour of ionic microgels and to validate the proposed interaction potential. We find that the architecture of the microgel plays a marked role in its phase behaviour. Rather than the ionic charges, it is the dangling ends which drive phase transitions and interactions at low concentration. Comparison to theory underlines the need for a refined theoretical model which takes into consideration these close-contact interactions.

Controlling the morphology of microgels by ionic stimuli.

Stimuli-responsive microgels have attracted much interest for their use as vehicles for drug delivery or as the building blocks of adaptive materials. Ionic microgel particles, including popular poly(NIPAM-co-acrylic acid), show strong mechanical responsiveness to many external stimuli, including changes in ionic strength or acidity. In this work, we demonstrate that combining multiple ionic stimuli can enable detailed control over the morphology of microgels. To this extent, we analyze the particle morphology in various surroundings with light-scattering techniques. First, we find strong indications of an inverted density profile in the core of the particles. Secondly, we show that the swelling of this hydrogel core and the corona of dangling polymer ends can be targeted separately by a combination of deionization and deprotonation steps. Hence, this work represents an advance in tailoring particle morphologies after synthesis in a predictable fashion.

Efficient configurational-bias Monte-Carlo simulations of chain molecules with "swarms" of trial configurations.

The pruned-enriched Rosenbluth method (PERM) is a popular and powerful Monte-Carlo technique for sampling flexible chain polymers of substantial length. In its original form, however, the method cannot be applied in Markov-chain Monte-Carlo schemes, which has rendered PERM unsuited for systems that consist of many chains. The current work builds on the configurational-bias Monte-Carlo (CBMC) method. The growth of a large set of trial configurations in each move is governed by simultaneous pruning and enrichment events, which tend to replace configurations with a low statistical weight by clones of stronger configurations. In simulations of dense brushes of flexible chains, a gain in efficiency of at least three orders of magnitude is observed with respect to CBMC and one order of magnitude with respect to recoil-growth approaches. Moreover, meaningful statistics can be collected from all trial configurations through the so-called "waste-recycling" Monte Carlo scheme.

Deswelling behaviour of ionic microgel particles from low to ultra-high densities.

The swelling of ionic microgel particles is investigated at a wide range of concentrations using a combination of light, X-ray and neutron scattering techniques. We employ a zero-average contrast approach for small-angle neutron scattering experiments, which enables a direct determination of the form factor at high concentrations. The observed particle size initially decreases strongly with the particle concentration in the dilute regime but approaches a constant value at intermediate concentrations. This is followed by a further deswelling at high concentrations above particle overlap. Theory and experiments point at a pivotal contribution of dangling polymer ends to the strong variation in size of ionic microgels, which presents itself mainly through the hydrodynamics properties of the system.

Swelling of micro-hydrogels with a crosslinker gradient.

A heterogeneous distribution of crosslinker in micro-hydrogels (microgels) results in a non-uniform polymer density inside the particles. Identifying the morphology of the hydrogel backbone enables a bottom-up approach towards the structural and rheological properties of microgel systems. On a local level we use a Flory-Rehner inspired model that focuses on highly swollen networks, characterized by a Poisson's ratio of 1/4. Our ab initio calculations take account for the nonuniform distribution of crosslinker species during the synthesis of poly(N-isopropylacylamide) (PNIPAM) microgels, yet the method is also applicable to other microgel architectures. We recover a single-particle density profile that is in close agreement with SAXS data. Comparison with experimental data confirms that the surface of the cross-linked particle is decorated with dangling polymers ends of considerable size.

Liquid Crystal Phase Transition in Epitaxial Monolayers of DNA-Functionalized Nanoparticle Superlattices.

Epitaxial growth of DNA-functionalized nanoparticles is used to grow extended superlattices with a preferred orientation for optimizing the physical properties of metamaterials for real applications. Like any solid in nature, superlattices can contain different kinds of structural defects, which significantly alter their physical properties. Further development of these materials requires a deeper understanding of, as well as precise control over, structural defect formation. Here we use Monte Carlo simulations to conduct a systematic study of the equilibrium structures of the adsorbed nanoparticle monolayers by changing the binding energies of different attachment sites. The simulations show two main results. First, the structural defects form one-dimensional clusters with an exponential length distribution. Second, these linear defects exhibit spontaneous symmetry breaking and undergo a liquid crystal phase transition. Subsequently, a mean-field approach is introduced to provide theoretical descriptions for the system. Our theory matches with the simulation results. We anticipate that this theoretical framework will be highly applicable to other two-dimensional assemblies. Our work demonstrates that defects can be engineered to design two-dimensional superlattices with interesting physical properties.

Anomalous system-size dependence of electrolytic cells with an electrified oil-water interface.

Manipulation of the charge of the dielectric interface between two bulk liquids not only enables the adjustment of the interfacial tension but also controls the storage capacity of ions in the ionic double layers adjacent to each side of the interface. However, adjusting this interfacial charge by static external electric fields is difficult since the external electric fields are readily screened by ionic double layers that form in the vicinity of the external electrodes. This leaves the liquid-liquid interface, which is at a macroscopic distance from the electrodes, unaffected. In this study we show theoretically, in agreement with recent experiments, that control over this surface charge at the liquid-liquid interface is nonetheless possible for macroscopically large but finite closed systems in equilibrium, even when the distance between the electrode and interface is orders of magnitude larger than the Debye screening lengths of the two liquids. We identify a crossover system-size below which the interface and the electrodes are effectively coupled. Our calculations of the interfacial tension for various electrode potentials are in good agreement with recent experimental data.

Effective charges and virial pressure of concentrated macroion solutions.

The stability of colloidal suspensions is crucial in a wide variety of processes, including the fabrication of photonic materials and scaffolds for biological assemblies. The ionic strength of the electrolyte that suspends charged colloids is widely used to control the physical properties of colloidal suspensions. The extensively used two-body Derjaguin-Landau-Verwey-Overbeek (DLVO) approach allows for a quantitative analysis of the effective electrostatic forces between colloidal particles. DLVO relates the ionic double layers, which enclose the particles, to their effective electrostatic repulsion. Nevertheless, the double layer is distorted at high macroion volume fractions. Therefore, DLVO cannot describe the many-body effects that arise in concentrated suspensions. We show that this problem can be largely resolved by identifying effective point charges for the macroions using cell theory. This extrapolated point charge (EPC) method assigns effective point charges in a consistent way, taking into account the excluded volume of highly charged macroions at any concentration, and thereby naturally accounting for high volume fractions in both salt-free and added-salt conditions. We provide an analytical expression for the effective pair potential and validate the EPC method by comparing molecular dynamics simulations of macroions and monovalent microions that interact via Coulombic potentials to simulations of macroions interacting via the derived EPC effective potential. The simulations reproduce the macroion-macroion spatial correlation and the virial pressure obtained with the EPC model. Our findings provide a route to relate the physical properties such as pressure in systems of screened Coulomb particles to experimental measurements.

'Soft' amplifier circuits based on field-effect ionic transistors.

Soft materials can be used as the building blocks for electronic devices with extraordinary properties. We introduce a theoretical model for a field-effect transistor in which ions are the gated species instead of electrons. Our model incorporates readily-available soft materials, such as conductive porous membranes and polymer-electrolytes to represent a device that regulates ion currents and can be integrated as a component in larger circuits. By means of Nernst-Planck numerical simulations as well as an analytical description of the steady-state current we find that the responses of the system to various input voltages can be categorized into ohmic, sub-threshold, and active modes. This is fully analogous to what is known for the electronic field-effect transistor (FET). Pivotal FET properties such as the threshold voltage and the transconductance crucially depend on the half-cell redox potentials of the source and drain electrodes as well as on the polyelectrolyte charge density and the gate material work function. We confirm the analogy with the electronic FETs through numerical simulations of elementary amplifier circuits in which we successfully substitute the electronic transistor by an ionic transistor.

Crystallization and reentrant melting of charged colloids in nonpolar solvents.

We explore the crystallization of charged colloidal particles in a nonpolar solvent mixture. We simultaneously charge the particles and add counterions to the solution with aerosol-OT (AOT) reverse micelles. At low AOT concentrations, the charged particles crystallize into body-centered-cubic (bcc) or face-centered-cubic (fcc) Wigner crystals; at high AOT concentrations, the increased screening drives a thus far unobserved reentrant melting transition. We observe an unexpected scaling of the data with particle size, and account for all behavior with a model that quantitatively predicts both the reentrant melting and the data collapse.

Metabolic response to green tea extract during rest and moderate-intensity exercise.

BACKGROUND: Green tea catechins have been hypothesized to increase energy expenditure and fat oxidation by inhibiting catechol-O-methyltransferase (COMT) and thus promoting more sustained adrenergic stimulation. Metabolomics may help to clarify the mechanisms underlying their putative physiological effects. OBJECTIVE: The study investigated the effects of 7-day ingestion of green tea extract (GTE) on the plasma metabolite profile at rest and during exercise. METHODS: In a placebo-controlled, double-blind, randomized, parallel study, 27 healthy physically active males consumed either GTE (n=13, 1200 mg catechins, 240 mg caffeine/day) or placebo (n=14, PLA) drinks for 7 days. After consuming a final drink (day 8), they rested for 2 h and then completed 60 min of moderate-intensity cycling exercise (56% ± 4% VO(2)max). Blood samples were collected before and during exercise. Plasma was analyzed using untargeted four-phase metabolite profiling and targeted profiling of catecholamines. RESULTS: Using the metabolomic approach, we observed that GTE did not enhance adrenergic stimulation (adrenaline and noradrenaline) during rest or exercise. At rest, GTE led to changes in metabolite concentrations related to fat metabolism (3-ß-hydroxybutyrate), lipolysis (glycerol) and tricarboxylic acid cycle (TCA) cycle intermediates (citrate) when compared to PLA. GTE during exercise caused reductions in 3-ß-hydroxybutyrate concentrations as well as increases in pyruvate, lactate and alanine concentrations when compared to PLA. CONCLUSIONS: GTE supplementation resulted in marked metabolic differences during rest and exercise. Yet these metabolic differences were not related to the adrenergic system, which questions the in vivo relevance of the COMT inhibition mechanism of action for GTE.

No effect of 1 or 7 d of green tea extract ingestion on fat oxidation during exercise.

PURPOSE: The aim of this study was to investigate the effects of 1 and 7 d of green tea extract (GTE) ingestion on whole body fat oxidation during moderate-intensity exercise. METHODS: Thirty-one men completed two exercise trials (60-min cycle, 50% Wmax). After the baseline trial (day 0), subjects were randomly assigned to one of three conditions involving a week supplementation of the following: 1) 7 d of placebo, 2) 6 d of placebo followed by 1 d of GTE (GTE1), and 3) 7 d of GTE ingestion (GTE7). The morning after the supplementation week, subjects consumed an additional supplement and completed a second exercise trial (day 8). V˙O2 and V˙CO2 measurements were taken during exercise to calculate whole body fat oxidation rates. Blood samples, for analysis of plasma fatty acids (FA), glycerol, and epigallocatechin gallate, were collected at rest and during exercise. RESULTS: On day 8, the plasma kinetics and maximal plasma concentrations of epigallocatechin gallate were similar in the GTE1 and GTE7 group (206 ± 28 and 216 ± 25 ng·mL, respectively). One day of GTE ingestion did not affect markers of lipolysis during the exercise bout. Seven days of GTE ingestion significantly increased plasma glycerol during exercise (P = 0.045) and plasma FA during exercise (P = 0.020) as well as at rest (P = 0.046). However, fat oxidation did not change in any of the groups. CONCLUSIONS: There was no effect of 1 d of GTE ingestion on markers of lipolysis or fat oxidation during exercise. Seven days of GTE ingestion increased lipolysis, indicated by increased plasma FA and glycerol concentrations, but did not result in significant changes in fat oxidation.

Electrostatic interactions between Janus particles.

In this paper we study the electrostatic properties of "Janus" spheres with unequal charge densities on both hemispheres. We introduce a method to compare primitive-model Monte Carlo simulations of the ionic double layer with predictions of (mean-field) nonlinear Poisson-Boltzmann theory. We also derive practical Derjaguin Landau Verwey Overbeek (DLVO)-like expressions that describe the Janus-particle pair interactions by mean-field theory. Using a large set of parameters, we are able to probe the range of validity of the Poisson-Boltzmann approximation, and thus of DLVO-like theories, for such particles. For homogeneously charged spheres this range corresponds well to the range that was predicted by field-theoretical studies of homogeneously charged flat surfaces. Moreover, we find similar ranges for colloids with a Janus-type charge distribution. The techniques and parameters we introduce show promise for future studies of an even wider class of charged-patterned particles.

Charge reversal of moisturous porous silica colloids by take-up of protons.

The net charge of porous Stöber silica colloids is studied using a modified Poisson-Boltzmann theory in a spherical cell, with a focus on the case of water-filled porous silica particles suspended in a non-aqueous solvent. We show that the silica's usual negative surface charge, due to deprotonisation of the Si-OH group, is counteracted by an excess uptake of protons in the water-filled pores of the particle at low enough pH. A small volume fraction of pores suffices to induce a point of zero charge at pH≈4. Based on the difference in Donnan potential between the porous medium and the solvent a relation can be constructed that describes the location of the point of zero charge analytically. The accuracy of this relation is confirmed by numerical calculations. For Stöber silica in water we find a charge reversal below pH≈3, which is in this case solely a result of the selective uptake of cations in the porous network.

Phase diagrams of colloidal spheres with a constant zeta-potential.

We study suspensions of colloidal spheres with a constant zeta-potential within Poisson-Boltzmann theory, quantifying the discharging of the spheres with increasing colloid density and decreasing salt concentration. We use the calculated renormalized charge of the colloids to determine their pairwise effective screened-Coulomb repulsions. Bulk phase diagrams in the colloid concentration-salt concentration representation follow, for various zeta-potentials, by a mapping onto published fits of phase boundaries of point-Yukawa systems. Although the resulting phase diagrams do feature face-centered cubic and body-centered cubic phases, they are dominated by the (re-entrant) fluid phase due to the colloidal discharging with increasing colloid concentration and decreasing salt concentration.

Effects of catechin enriched green tea on body composition.

Obesity is a major health problem in the developed and developing world. Many "functional" foods and ingredients are advocated for their effects on body composition but few have consistent scientific support for their efficacy. However, an increasing amount of mechanistic and clinical evidence is building for green tea (GT). This experiment was therefore undertaken to study the effects of a high-catechin GT on body composition in a moderately overweight Chinese population. In a randomized placebo-controlled trial, 182 moderately overweight Chinese subjects, consumed either two servings of a control drink (C; 30 mg catechins, 10 mg caffeine/day), one serving of the control drink and one serving of an extra high-catechin GT1 (458 mg catechins, 104 mg caffeine/day), two servings of a high-catechin GT2 (468 mg catechins, 126 mg caffeine/day) or two servings of the extra high-catechin GT3 (886 mg catechins, 198 mg caffeine/day) for 90 days. Data were collected at 0, 30, 60, and 90 days. We observed a decrease in estimated intra-abdominal fat (IAF) area of 5.6 cm(2) in the GT3 group. In addition, we found decreases of 1.9 cm in waist circumference and 1.2 kg body weight in the GT3 group vs. C (P < 0.05). We also observed reductions in total body fat (GT2, 0.7 kg, P < 0.05) and body fat % (GT1, 0.6%, P < 0.05). We conclude that consumption of two servings of an extra high-catechin GT leads to improvements in body composition and reduces abdominal fatness in moderately overweight Chinese subjects.

Macronutrient distribution over a period of 23 years in relation to energy intake and body fatness.

The distribution of the four macronutrients is associated with energy intake and body fatness according to short-term interventions. The present study involves macronutrient distribution in relation to energy intake and body fatness over a period of 23 years in individuals who have ad libitum access to food. Eight follow-up measurements have been performed in 168 men and 182 women who participate in the Amsterdam Growth and Health Longitudinal Study. From the age of 13 years onwards, dietary intake, physical activity and the thickness of four skinfolds have been assessed. Body fatness was assessed using dual-energy X-ray absorptiometry at the age of 36 years. Generalised estimating equation regression analyses showed that energy percentages (En%) from protein and (in men) carbohydrates were inversely related to energy intake, while the En% from fat was positively related with energy intake. The men and women with high body fatness at the age of 36 years had a 1 En% higher protein intake, and the women with high body fatness had a 2 En% lower alcohol intake at the age of 32 and 36 years. The apparent inconsistent relationships between protein and energy intake and protein and body fatness can in women be explained by reverse causation and underreporting, as in women, low energy intake could not be explained by low physical activity. In conclusion, high intake of protein and (in men) carbohydrate, and low intake of fat are inversely related to total energy intake. High body fatness at the age of 36 years is related to a higher protein intake and, in women, to a lower alcohol intake.

Health potential for functional green teas?

Obesity is a major health problem in the developed and developing world. Many "functional" foods and ingredients are advocated for their effects on body composition but few have consistent scientific support for their efficacy. However, an increasing amount of mechanistic and clinical evidence is building for green tea. The tea plant is naturally rich in a group of antioxidants known as catechins. Unlike black tea, green tea production involves little processing and fermentation and therefore, green tea brews are rich in catechins. Green tea has been suggested to have a number of potential health benefits in areas such as cardiovascular disease, cancer prevention, glucose homeostasis and dental health. Although there is some promising evidence in all of these areas, more data from human intervention trials are needed. A lot of attention has lately been focused on the beneficial effects of green tea on body composition and particularly visceral fat, which has been shown to have a strong link with different components of the metabolic syndrome such as cardiovascular disease and type 2 diabetes. Most, but not all, of the positive results come from a number Asian studies, in which overweight subjects (men and women) consumed green tea for approximately 12 weeks. Finally, green tea may also have measurable acute effects on energy metabolism and fat oxidation and in particular during physical activity, as evidenced by other studies specifically looking at these endpoints. Small cumulative effects on energy metabolism could also be responsible for the longer-tem effects of green tea on body composition, and these long-term effects may also be most apparent in the context of moderate physical activity. However, more research is needed to further clarify the exact mechanisms of action and to extrapolate these findings to non-Asian populations.

The effects of hydralazine on lipolysis in subcutaneous adipose tissue in humans.

Recent evidence from animal research and in vitro experiments indicates that changes in dietary calcium intake could cause changes in lipolysis through alterations of the intracellular calcium concentration in adipocytes. The objective of the study was to examine whether the calcium antagonist hydralazine affects blood flow and lipolysis in subcutaneous abdominal adipose tissue in vivo in humans. Three different concentrations of hydralazine (12.2, 24.4, and 48.8 micromol/L) were locally administered in adipose tissue using the microdialysis technique to assess effects on lipolysis and blood flow in subcutaneous adipose tissue in the abdominal region. Subjects from the general community were studied ambulatorily at a university hospital. Eight healthy men (age, 33.1 +/- 3.3 years; body mass index, 24.2 +/- 0.2 kg/m(2)) were recruited by local announcement. Subcutaneous adipose tissue in the abdominal region was perfused with increasing concentrations of hydralazine. The main outcome measures were adipose tissue lipolysis and blood flow. Hydralazine had no effect on ethanol outflow-inflow ratios, but significantly increased interstitial glycerol concentration at the highest concentration (P < .05). The present results indicate that hydralazine increases lipolysis in abdominal subcutaneous adipose tissue in healthy lean subjects, but hydralazine had no significant effects on local blood flow in adipose tissue.

The effects of increasing serum calcitriol on energy and fat metabolism and gene expression.

OBJECTIVE: Evidence from a number of investigations indicates that calcium intake could be inversely related to body weight through alterations in the 1,25-OH(2)-D(3) metabolism. The objective of this study was to test whether energy and substrate metabolism and adipose tissue enzyme mRNA expression can be altered by changes in serum 1,25-OH(2)-D(3) through oral cholecalciferol supplementation in non-obese human subjects. RESEARCH METHODS AND PROCEDURES: An intervention study was used with a treatment period of 7 days. During this intervention, energy expenditure (EE) and substrate metabolism were measured using indirect calorimetry at t = 0, 1, 3, and 7 days, and blood samples were obtained at t = -1, 0, 1, 2, 3, 5 and 7 days. Fat biopsies were obtained at t = 0 and 7 days for determination of expression of genes involved in lipolytic and lipogenic pathways. Subjects from the general community were studied in an ambulatory setting at a university hospital. Ten healthy young men (age, 28 +/- 3 years; BMI, 25.5 +/- 0.5 kg/m(2)) were recruited by local announcement, and all completed the study. All subjects received 2000 IU cholecalciferol/d for 7 days, and they were instructed to consume a low-cholecalciferol, low-calcium diet. EE, fat oxidation, and adipose tissue enzyme mRNA were the main outcome measures. RESULTS: Despite a significant increase in serum 1,25-OH(2)-D(3) concentration at t = 5 and 7 days, no significant differences in substrate and energy metabolism nor mRNA concentrations of different lipid metabolism-related proteins were observed. DISCUSSION: Seven-day supplementation with 2000 IU cholecalciferol/d together with a decrease in dietary calcium intake does not affect EE or substrate metabolism nor gene expression of proteins related to fat metabolism, despite a significant increase in serum 1,25-OH(2)-D(3) concentration.