Growth and structure of aggregates of heat-denatured β-Lactoglobulin

Summary The aggregation of the globular protein β-lactoglobulin after heat-denaturation was studied in aqueous solution at pH 7 using static and dynamic light scattering. The structure of the aggregates is self-similar with fractal dimension 2.0. Size exclusion chromatography and dynamic light scattering measurements show that the aggregates have a broad size distribution. Initially clusters of about 85 proteins and 15 nm radius are formed which are the elementary units of the larger fractal aggregates. At low ionic strength the formation of the larger aggregates is impeded by electrostatic interactions.
The structure of the aggregates is independent of the concentration and the temperature. The rate of aggregation has an Arrhenius temperature dependence with an activation energy of about 350 kJ/mol weakly dependent on the concentration. The apparent reaction order of the aggregation is 1.5. In the mixture both variants A and B have the same aggregation rate. The gel time increases with decreasing concentration and diverges at about 0.7g L⁻¹. At lower concentration the aggregate growth stagnates when all protein has aggregated.     

ORDERING TRANSITIONS IN LIQUID CRYSTALS PERMIT IMAGING OF SPATIAL AND TEMPORAL PATTERNS FORMED BY PROTEINS PENETRATING INTO LIPID-LADEN INTERFACES

Recent studies have reported that full monolayers of L-α-dilaurylphosphatidylcholine (L-DLPC) and D-α-dipalmitoylphosphatidylcholine (D-DPPC) formed at interfaces between thermotropic liquid crystals (LCs) and aqueous phases lead to homeotropic (perpendicular) orientations of nematic LCs and that specific binding of proteins to these interfaces (such as phospholipase A ₂ binding to D-DPPC) can trigger orientational ordering transitions in the liquid crystals. We report on the nonspecific interactions of proteins with aqueous-LC interfaces decorated with partial monolayer coverage of L-DLPC. Whereas nonspecific interactions of four proteins (cytochrome c, bovine serum albumin, immunoglobulins, and neutravidin) do not perturb the ordering of the LC when a full monolayer of L-DLPC is assembled at the aqueous-LC interface, we observe patterned orientational transitions in the LC that reflect penetration of proteins into the interface of the LC with partial monolayer coverage of L-DLPC. The spatial patterns formed by the proteins and lipids at the interface are surprisingly complex, and in some cases the protein domains are found to compartmentalize lipid within the interfaces. These results suggest that phospholipid-decorated interfaces between thermotropic liquid crystals and aqueous phases offer the basis of a simple and versatile tool to study the spatial organization and dynamics of protein networks formed at mobile, lipid-decorated interfaces.     

Lattice Monte Carlo simulations as link between ab-initio calculations and macroscopic behavior of dopants and defects in silicon

In this work, we show that lattice Monte Carlo simulations can be used to span the time and distance scales between underlying atomistic processes and macroscopic diffusion behavior. We use ab- initio calculations of binding energies versus configuration to calculate hopping rates of vacancies for use in lattice Monte Carlo (LMC) simulations of diffusion and aggregation in silicon. The LMC simulations consider the biased nature of vacancy hop frequencies in the neighborhood of dopants, with interactions up to sixth-nearest- neighbor distances included. We use these simulations to investigate the expected macroscopic diffusion behavior, as well as the process by which dopant/defect aggregation occurs. Specific phenomena investigated include collective behavior leading to greatly enhanced diffusivity at high doping levels, the time dependence of effective diffusivity due to the formation of dopant/vacancy clusters, and dopant fluxes in the presence of a vacancy gradient.     

The effect of binary cosolvent systems (glycerol–sucrose mixtures) on the heat-induced gelation mechanism of bovine serum albumin

The influence of cosolvent composition on the thermal denaturation and gelation of bovine serum albumin (BSA) has been studied. Cosolvent composition was varied by changing the ratio of glycerol to sucrose in 40 wt% cosolvent solutions containing BSA. Differential scanning calorimetry measurements on 0.5 wt% BSA solutions showed that the thermal denaturation temperature of the protein increased with increasing sucrose content. Temperature scanning dynamic shear rheology and turbidity measurements on 4 wt% BSA solutions showed that the gelation temperature and final gel strength increased with increasing sucrose concentration. These observations were attributed to the fact that sucrose was more effective than glycerol at increasing the thermal stability and attraction between globular BSA molecules through a steric exclusion effect. The molecular origin of these effects is the tendency for the system to minimize the contact area of the protein molecules with the surrounding cosolvent solution.     

Theoretical calculations of the structure and UV-vis absorption spectra of hydrated C60 fullerene

A combined Monte Carlo simulation with semiempirical quantum mechanics calculations has been performed to investigate the structure of hydrated fullerene (C₆₀HyFn) and the influence of hydration on its UV-vis spectra. The statistical information of the C₆₀ fullerene aqueous solution (C₆₀FAS) is obtained from NPT ensemble including one C₆₀ fullerene immerses in 898 water molecules. To obtain an efficient ensemble average, the auto-correlation function of the energy has been calculated. The analyzed center-of-mass pair-wise radial distribution function indicates that, on average, there are 65 and 151 water molecules around the first and second hydration shells, respectively, of a single C₆₀ molecule. To calculate the average UV-vis transition energies of C₆₀HyFn, only the statistically uncorrelated configurations are used in the quantum mechanical calculations (INDO/CIS). These involve hundreds of supramolecular structures containing one C₆₀ fullerene surrounded by the first hydration shell. The calculated average transitions at 268 and 350 nm are in very good agreement with the experimental prediction.     

EXTRACTIVE DISTILLATION WITH AQUEOUS SOLUTIONS OF HYDROTROPES

The effect of hydrotropes on vapor-liquid equilibrium of a mixture provides a potential technique of extractive distillation for systems which are difficult or impossible to separate by normal rectification. Various hydrotropes, such as sodium toluate, sodium toluence sulfonate, sodium cymcnc sulfonate, sodium mesitylene sulfonate and sodium salicylate, in aqueous solutions have been tested for the separation of close-boiling point mixtures, such as p-cresol/2,6-xylenol, isopropanol/ fm-butanol, and wc-butanol/rert-butanol. The changes in the relative volatility increase with the concentration of hydrotrope and with the hydrotrope to solute ratio.     

Aggregation in sensor networks: an energy–accuracy trade-off

Wireless ad hoc sensor networks (WASNs) are in need of the study of useful applications that will help the researchers view them as distributed physically coupled systems, a collective that estimates the physical environment, and not just energy-limited ad hoc networks. We develop this perspective using a large and interesting class of WASN applications called aggregation applications. In particular, we consider the challenging periodic aggregation problem where the WASN provides the user with periodic estimates of the environment, as opposed to simpler and previously studied snapshot aggregation problems. In periodic aggregation our approach allows the spatial–temporal correlation among values sensed at the various nodes to be exploited towards energy-efficient estimation of the aggregated value of interest. Our approach also creates a system level energy vs. accuracy knob whereby the more the estimation error that the user can tolerate, the less is the energy consumed. We present a distributed estimation algorithm that can be applied to explore the energy–accuracy subspace for a subclass of periodic aggregation problems, and present extensive simulation results that validate our approach. The resulting algorithm, apart from being more flexible in the energy–accuracy subspace and more robust, can also bring considerable energy savings for a typical accuracy requirement (fivefold decrease in energy consumption for 5% estimation error) compared to repeated snapshot aggregations.     

Preparation of Silica Nanostructured Spheres by Sol Spray Drying

Silica nanostructured spheres were obtained by spray drying of silica sol prepared in situ. Their morphologies were significantly affected by the aggregation of the primary particles in the sol. They had the mode of the pore sizes which was about the same order as Laser Particle Size Analyzer (LPA) diameter. Increasing the mixing ratio of the larger particles (20 nm) to smaller ones (7 nm) decreased the Brunauer, Emmett and Teller (BET) specific surface area, as expected. Pore volume decreased with the pore size distribution broadened and the mean pore diameter was not affected by the increase, due to the decrease in aggregation of the primary particles. Either the increase in the drying temperature and use of ethanol as a cosolvent made the agglomerates hollower, the larger of which with thinner shell transformed to doughnut type agglomerates, due to the structural and hydrodynamic instabilities.     

Characterization of α-carrageenan solution behavior by field-flow fractionation and multiangle light scattering

The salt mediated molecular conformation change of alpha (α)-carrageenan was studied in 0.1 M solutions of NaCl, NaI, and KCl. Asymmetric Field-Flow Fractionation with multiangle laser light scattering (AFFF/MALLS) detection was used to determine the average molecular weight, radius of gyration, and hydrodynamic radius which were in turn used to calculate the molecular density. In the presence of 0.1 M NaCl, an inert salt that does not promote gelation, α-carrageenan has a denser structure compared to κ-carrageenan of a similar molecular weight. A distinct and dramatic increase in the molecular weight (factor of 2) was observed for α-carrageenan in 0.1 M NaI compared to 0.1 M NaCl. This combined with only a slight change in the radius of gyration, suggests intermolecular interaction to a more compact structure (e.g., coaxial helices). A similar increase in molecular weight is observed in 0.1 M KCl, accompanied with an approximate 50% increase in the radius of gyration as well as an increase in polydispersity. This may also be attributed to intermolecular interaction with helix formation (coaxial or lateral) or may be due to K⁺ cations interacting with naturally occurring residual ι-carrageenan in the sample. As previously reported for other carrageenans the random coil to helix transition of α-carrageenan appears to be stabilized by K⁺ cation or I⁻ anion in an aqueous environment.