Effect of counterion substitution on the viscosity anomaly in AOT microemulsions

AOT-based water-in-oil microemulsions display an anomalous maximum in the viscosity with X, the water to surfactant ratio. Several explanations for this phenomenon have been offered. In this work, we investigate viscosity and droplet interactions in Ca(AOT)(2)/water/n-decane and KAOT/water/n-decane microemulsions and compare our results with the commonly studied NaAOT/water/oil system. The Ca(AOT)(2) system demonstrates a maximum in relative viscosity and droplet attraction near X=15, similar to the NaAOT system, although the maximum occurs at a higher value of X in the Ca(AOT)(2) system. By contrast, the viscosity and interparticle interactions in the KAOT system do not strongly depend on the amount of water in the system. We attribute the differences in behavior between the two systems to different hydration characteristics of the counterion, and we believe that our results are consistent with a previously proposed model that attributes interdroplet attractions to charge fluctuations and surfactant exchange. Our findings support the connection between the viscosity anomaly and interparticle interactions.     

Nanoparticle-reinforced associative network hydrogels

ABA triblock copolymers in solvents selective for the midblock are known to form associative micellar gels. We have modified the structure and rheology of ABA triblock copolymer gels comprising poly(lactide)-poly(ethylene oxide)-poly(lactide) (PLA-PEO-PLA) through addition of a clay nanoparticle, laponite. Addition of laponite particles resulted in additional junction points in the gel via adsorption of the PEO corona chains onto the clay surfaces. Rheological measurements showed that this strategy led to a significant enhancement of the gel elastic modulus with small amounts of nanoparticles. Further characterization using small-angle X-ray scattering and dynamic light scattering confirmed that nanoparticles increase the intermicellar attraction and result in aggregation of PLA-PEO-PLA micelles.     

The effect of pharmaceuticals on the nanoscale structure of PEO-PPO-PEO micelles

We present results on the effects of various hydrophobic drugs and additives on the micellar structure of Pluronic F127 solutions. Small-angle neutron scattering experiments on 5wt% F127 solutions were used to measure micelle core size (R(1)), micelle corona size (R(2)), intermicellar interaction distance (R(int)), polydispersity (sigma), and aggregation number (N(agg)); dynamic light scattering was used to measure critical micelle concentration (CMC); and ultraviolet spectroscopy was used to measure drug solubility and apparent micelle-water partition coefficient (K(mw)). The core and corona size were found to generally increase in the presence of the drugs, as did R(int). Both sigma and N(agg) were found to decrease in the presence of most of the drugs, and the CMC was found to vary considerably with no clear correlation. A design of experiments (DOE) approach was used to analyze the results and build empirical correlations. All of the parameters from the SANS experiments were found to depend strongly on drug solubility, with a weak dependence on K(mw) in most cases. The aggregation number, however, was found to depend strongly on both K(mw) and solubility. The correlations can be used to roughly predict the structural parameters of F127 micelles for other hydrophobic drugs.     

Characterization of enantiospecific chemisorption on chiral Cu surfaces vicinal to Cu(111) and Cu(100) using density functional theory

Surfaces of simple fcc metals such as Cu with nonzero and unequal Miller indices are intrinsically chiral. Density functional theory (DFT) calculations are a useful way to study the enantiospecific adsorption of small chiral molecules on these chiral metal surfaces. We report DFT calculations of seven chiral molecules on several structurally distinct chiral Cu surfaces. These surfaces include two surfaces with (111)-oriented terraces and one with (100)-oriented terraces. Calculations are also described on a surface that was modified to mimic the surface structures that typically appear on real metal surfaces following thermally driven fluctuations in step edges. Our results provide initial information on how variation in the surface structure of intrinsically chiral metal surfaces can affect the enantiospecific adsorption of small molecules on these surfaces.     

Design,Synthesis, and Biomedical Applications of Glycotripods for Targeting Trimeric Lectins

In the last decades, various efforts have been made to synthesize optimal glycotripods for targeting trimeric glycoproteins like asialoglycoprotein receptor, hemagglutinin, and langerin. All these trimeric glycoproteins have sugar binding pockets which are highly selective for a particular carbohydrate ligand. Optimized glycotripods are high affinity binders and have been used for delivering drugs or even applied as drug candidates. The selection of the tripodal base scaffold together with the length and flexibility of the linker between the scaffold and sugar residue, as important design parameters are discussed in this review.     

The Prenucleation Equilibrium of the Parathyroid Hormone Determines the Critical Aggregation Concentration and Amyloid Fibril Nucleation

Nucleation and growth of amyloid fibrils were found to only occur in supersaturated solutions above a critical concentration (c_crit). The biophysical meaning of c_crit remained mostly obscure, since typical low values of c_crit in the sub-μM range hamper investigations of potential oligomeric states and their structure. Here, we investigate the parathyroid hormone PTH₈₄ as an example of a functional amyloid fibril forming peptide with a comparably high c_crit of 67±21 μM. We describe a complex concentration dependent prenucleation ensemble of oligomers of different sizes and secondary structure compositions and highlight the occurrence of a trimer and tetramer at c_crit as possible precursors for primary fibril nucleation. Furthermore, the soluble state found in equilibrium with fibrils adopts to the prenucleation state present at c_crit. Our study sheds light onto early events of amyloid formation directly related to the critical concentration and underlines oligomer formation as a key feature of fibril nucleation. Our results contribute to a deeper understanding of the determinants of supersaturated peptide solutions. In the current study we present a biophysical approach to investigate c_crit of amyloid fibril formation of PTH₈₄ in terms of secondary structure, cluster size and residue resolved intermolecular interactions during oligomer formation. Throughout the investigated range of concentrations (1 μM to 500 μM) we found different states of oligomerization with varying ability to contribute to primary fibril nucleation and with a concentration dependent equilibrium. In this context, we identified the previously described c_crit of PTH₈₄ to mark a minimum concentration for the formation of homo-trimers/tetramers. These investigations allowed us to characterize molecular interactions of various oligomeric states that are further converted into elongation competent fibril nuclei during the lag phase of a functional amyloid forming peptide.     

Efficient derivative-free variants of Hansen-Patrick’s family with memory for solving nonlinear equations

In this paper, we present a new tri-parametric derivative-free family of Hansen-Patrick type methods for solving nonlinear equations numerically. The proposed family requires only three functional evaluations to achieve optimal fourth order of convergence. In addition, acceleration of convergence speed is attained by suitable variation of free parameters in each iterative step. The self-accelerating parameters are estimated from the current and previous iteration. These self-accelerating parameters are calculated using Newton’s interpolation polynomials of third and fourth degrees. Consequently, the R-order of convergence is increased from 4 to 7, without any additional functional evaluation. Furthermore, the most striking feature of this contribution is that the proposed schemes can also determine the complex zeros without having to start from a complex initial guess as would be necessary with other methods. Numerical experiments and the comparison of the existing robust methods are included to confirm the theoretical results and high computational efficiency.     

Angular distributions of light projectile fragments in deep inelastic Pb + Em interactions at 160 A GeV

The nuclear emulsion was exposed at CERN by the lead projectile at 160 A GeV. The angles between any pair of fragments with Z = 2-4 have been measured in the emulsion plane for the events which did not contain heavy fragments. The constant characterizing the normal angle (J) distribution of the fragment momentum projection onto the emulsion plane with respect to initial projectile momentum p₀ is found to be C_J = (0.37 - 0.02) mrad. Corresponding value C₀ = (121 - 6) MeV/c of nucleon momentum distribution in the lead nucleus coincides with that expected from Fermi momentum distribution for this nucleus. The peak in the pair-angle distribution of double-charged fragments, ⁸Be M 2!, is presented for the region of small angles (<0.1 mrad). The fraction of !-particles coming from the decay of the ground state ⁸Be is found to be (13 - 2)% of their whole number.     

Multicomponent effective medium-correlated random walk theory for the diffusion of fluid mixtures through porous media

Molecular transport in nanoconfined spaces plays a key role in many emerging technologies for gas separation and storage, as well as in nanofluidics. The infiltration of fluid mixtures into the voids of porous frameworks having complex topologies is common place to these technologies, and optimizing their performance entails developing a deeper understanding of how the flow of these mixtures is affected by the morphology of the pore space, particularly its pore size distribution and pore connectivity. Although several techniques have been developed for the estimation of the effective diffusivity characterizing the transport of single fluids through porous materials, this is not the case for fluid mixtures, where the only alternatives rely on a time-consuming solution of the pore network equations or adaptations of the single fluid theories which are useful for a limited type of systems. In this paper, a hybrid multicomponent effective medium-correlated random walk theory for the calculation of the effective transport coefficients matrix of fluid mixtures diffusing through porous materials is developed. The theory is suitable for those systems in which component fluxes at the single pore level can be related to the potential gradients of the different species through linear flux laws and corresponds to a generalization of the classical single fluid effective medium theory for the analysis of random resistor networks. Comparison with simulation of the diffusion of binary CO(2)/H(2)S and ternary CO(2)/H(2)S/C(3)H(8) gas mixtures in membranes modeled as large networks of randomly oriented pores with both continuous and discrete pore size distributions demonstrates the power of the theory, which was tested using the well-known generalized Maxwell-Stefan model for surface diffusion at the single pore level.     

Search for universal extra dimensions in pp collisions

We present a search for Kaluza-Klein (KK) particles predicted by models with universal extra dimensions (UED) using a data set corresponding to an integrated luminosity of 7.3 fb(-1), collected by the D0 detector at a pp center-of-mass energy of 1.96 TeV. The decay chain of KK particles can lead to a final state with two muons of the same charge. This signature is used to set a lower limit on the compactification scale of R(-1)>260 GeV in a minimal UED model.