Calculations of and evidence for chain packing stress in inverse lyotropic bicontinuous cubic phases

Inverse bicontinuous cubic lyotropic phases are a complex solution to the dilemma faced by all self-assembled water-amphiphile systems: how to satisfy the incompatible requirements for uniform interfacial curvature and uniform molecular packing. The solution reached in this case is for the water-amphiphile interfaces to deform hyperbolically onto triply periodic minimal surfaces. We have previously suggested that although the molecular packing in these structures is rather uniform the relative phase behavior of the gyroid, double diamond, and primitive inverse bicontinuous cubic phases can be understood in terms of subtle differences in packing frustration. In this work, we have calculated the packing frustration for these cubics under the constraint that their interfaces have constant mean curvature. We find that the relative packing stress does indeed differ between phases. The gyroid cubic has the least packing stress, and at low water volume fraction, the primitive cubic has the greatest packing stress. However, at very high water volume fraction, the double diamond cubic becomes the structure with the greatest packing stress. We have tested the model in two ways. For a system with a double diamond cubic phase in excess water, the addition of a hydrophobe may release packing frustration and preferentially stabilize the primitive cubic, since this has previously been shown to have lower curvature elastic energy. We have confirmed this prediction by adding the long chain alkane tricosane to 1-monoolein in excess water. The model also predicts that if one were able to hydrate the double diamond cubic to high water volume fractions, one should destabilize the phase with respect to the primitive cubic. We have found that such highly swollen metastable bicontinuous cubic phases can be formed within onion vesicles. Data from monoelaidin in excess water display a well-defined transition, with the primitive cubic appearing above a water volume fraction of 0.75. Both of these results lend support to the proposition that differences in the packing frustration between inverse bicontinuous cubic phases play a pivotal role in their relative phase stability.     

Synthesis and intramolecular hydrogen bonding networks of 2,4,6-tri(o-hydroxyaryl)-1,3,5-triazines

Functionalized, triaryl substituted triazines were synthesized via the Friedel-Crafts arylation reaction. These conjugated triazines possess unique, intramolecular hydrogen bonding motifs, which provide tunable planarity.     

Recent progress in unconstrained nonlinear optimization without derivatives

We present an introduction to a new class of derivative free methods for unconstrained optimization. We start by discussing the motivation for such methods and why they are in high demand by practitioners. We then review the past developments in this field, before introducing the features that characterize the newer algorithms. In the context of a trust region framework, we focus on techniques that ensure a suitable “geometric quality” of the considered models. We then outline the class of algorithms based on these techniques, as well as their respective merits. We finally conclude the paper with a discussion of open questions and perspectives. Current reports available by anonymous ftp from the directory “pub/reports” on thales.math.fundp.ac.be. WWW: http://www.fundp.ac.be/ phtoint/pht/publications.html.     

The High‐Throughput Synthesis and Phase Characterisation of Amphiphiles: A Sweet Case Study

A new method for the discovery of amphiphiles by using high‐throughput (HT) methods to synthesise and characterise a library of galactose‐ and glucose‐containing amphiphilic compounds is presented. The copper‐catalysed azide–alkyne cycloaddition (CuAAC) “click” reaction between azide‐tethered simple sugars and alkyne‐substituted hydrophobic tails was employed to synthesise a library of compounds with systematic variations in chain length and unsaturation in a 24‐vial array format. The liquid–crystalline phase behaviour was characterised in a HT manner by using synchrotron small‐angle X‐ray scattering (SSAXS). The observed structural variation with respect to chain parameters, including chain length and degree of unsaturation, is discussed, as well as hydration effects and degree of hydrogen bonding between head groups. The validity of our HT screening approach was verified by resynthesising a short‐chain glucose amphiphile. A separate phase analysis of this compound confirmed the presence of numerous lyotropic liquid–crystalline phases.     

An exact penalty function for semi-infinite programming

This paper introduces a global approach to the semi-infinite programming problem that is based upon a generalisation of the ℓ₁ exact penalty function. The advantages are that the ensuing penalty function is exact and the penalties include all violations. The merit function requires integrals for the penalties, which provides a consistent model for the algorithm. The discretization is a result of the approximate quadrature rather than an a priori aspect of the model. This research was partially supported by Natural Sciences and Engineering Research Council of Canada grants A-8639 and A-8442. This paper was typeset using software developed at Bell Laboratories and the University of California at Berkeley.     

MAOS protocols for the general synthesis and lead optimization of 3,6-disubstituted-[1,2,4]triazolo[4,3-b]pyridazines

General, high-yielding MAOS protocols for the expedient synthesis of functionalized 3,6-disubstituted-[1,2,4]triazolo[4,3-b]pyridazines are described amenable to an iterative analog library synthesis strategy for the lead optimization of an M1 antagonist screening hit. Optimized compounds proved to be highly selective M1 antagonists.     

Role of the dopant in the superconductivity of diamond

We present an ab initio study of the recently discovered superconductivity of boron doped diamond within the framework of a phonon-mediated pairing mechanism. The role of the dopant, in substitutional position, is unconventional in that half of the coupling parameter lambda originates in strongly localized defect-related vibrational modes, yielding a very peaked Eliashberg alpha2F(omega) function. The electron-phonon coupling potential is found to be extremely large, and T(C) is limited by the low value of the density of states at the Fermi level. The effect of boron isotope substitution is explored.     

Experimental evidence of intermittent convection in the edge of magnetic confinement devices

Probe measurements in the PISCES linear device indicate the presence of plasma radially far from where it is produced. We show that this is mainly caused by large-scale structures of plasma with high radial velocity. Data from the Tore Supra tokamak show striking similarities in the shape of these intermittent events as well as the fluctuation density probability distribution and frequency spectrum. The fact that intermittent, large-scale events are so similar in linear devices and tokamaks indicates the universality of convective transport in magnetically confined plasmas.     

Suppression of temperature fluctuations and energy barrier generation by velocity shear

First measurements of temperature fluctuations in a region of high velocity shear show that absolute and normalized fluctuation levels are reduced across the shear layer, a result that is consistent with weak parallel electron thermal conduction in the electron temperature dynamics. The concomitant reduction of temperature, density, and electric field fluctuations reduces the anomalous conducted and convected heat fluxes.     

Superconductivity in doped sp3 semiconductors: the case of the clathrates

We present a joint experimental and theoretical study of the superconductivity in doped silicon clathrates. The critical temperature in Ba(8)@Si-46 is shown to strongly decrease with applied pressure. These results are corroborated by ab initio calculations using MacMillan's formulation of the BCS theory with the electron-phonon coupling constant lambda calculated from perturbative density functional theory. Further, the study of I(8)@Si-46 and of gedanken pure silicon diamond and clathrate phases doped within a rigid-band approach show that the superconductivity is an intrinsic property of the sp(3) silicon network. As a consequence, carbon clathrates are predicted to yield large critical temperatures with an effective electron-phonon interaction much larger than in C60.