Visualizing the solubilization of supported lipid bilayers by an amphiphilic peptide

The effect of the presequence peptide of cytochrome c oxidase subunit IV (p25) on supported phospholipid bilayers (SPBs) was visualized using atomic force microscopy (AFM). The presequence was found to cause the complete disruption of supported bilayers containing neutral lipids. At relatively low concentrations of presequence, the peptide was found to bind to the membrane, coalescing to form microdomains within the liquid-crystalline bilayer that were located predominantly at bilayer-mica boundaries. Further increases in peptide concentration resulted in the formation of holes within the SPB that were spanned by an interpenetrating network of narrower regions of the bilayer, which, at higher applied peptide concentrations, were observed to disappear through a budding process, ultimately leading to the formation of spherical structures at yet higher peptide concentrations. Within this paper, the impact the presequence has upon the structure and order of the membrane is discussed, as is the potential implication of this apparent solubilization process on the translocation of cytochrome c oxidase into the inner mitochondrial membrane.     

Security of quantum bit string commitment depends on the information measure

Unconditionally secure nonrelativistic bit commitment is known to be impossible in both the classical and the quantum world. However, when committing to a string of n bits at once, how far can we stretch the quantum limits? In this Letter, we introduce a framework of quantum schemes where Alice commits a string of n bits to Bob, in such a way that she can only cheat on a bits and Bob can learn at most b bits of information before the reveal phase. Our results are twofold: we show by an explicit construction that in the traditional approach, where the reveal and guess probabilities form the security criteria, no good schemes can exist: a + b is at least n. If, however, we use a more liberal criterion of security, the accessible information, we construct schemes where a = 4log2(n) + O(1) and b = 4, which is impossible classically. Our findings significantly extend known no-go results for quantum bit commitment.     

Biased tug-of-war, the biased infinity Laplacian, and comparison with exponential cones

We prove that if ${U\subset \mathbb {R}^n}$ is an open domain whose closure ${\overline U}$ is compact in the path metric, and F is a Lipschitz function on ?U, then for each ${\beta \in \mathbb {R}}$ there exists a unique viscosity solution to the β-biased infinity Laplacian equation $$\beta |\nabla u| + \Delta_\infty u=0$$ on U that extends F, where ${\Delta_\infty u= |\nabla u|^{-2} \sum_{i,j} u_{x_i}u_{x_ix_j} u_{x_j}}$ . In the proof, we extend the tug-of-war ideas of Peres, Schramm, Sheffield and Wilson, and define the β-biased ${\epsilon}$ -game as follows. The starting position is ${x_0 \in U}$ . At the kth step the two players toss a suitably biased coin (in our key example, player I wins with odds of ${\exp(\beta\epsilon)}$ to 1), and the winner chooses x _k with ${d(x_k,x_{k-1}) < \epsilon}$ . The game ends when ${x_k \in \partial U}$ , and player II pays the amount F(x _k ) to player I. We prove that the value ${u^{\epsilon}(x_0)}$ of this game exists, and that ${\|u^\epsilon - u\|_\infty \to 0}$ as ${\epsilon \to 0}$ , where u is the unique extension of F to ${\overline{U}}$ that satisfies comparison with β-exponential cones. Comparison with exponential cones is a notion that we introduce here, and generalizing a theorem of Crandall, Evans and Gariepy regarding comparison with linear cones, we show that a continuous function satisfies comparison with β-exponential cones if and only if it is a viscosity solution to the β-biased infinity Laplacian equation.     

Enantioselective Rhodium‐Catalyzed Atom‐Economical Macrolactonization

A highly attractive route toward macrolactones, which form the cyclic scaffold of a multitude of diverse natural compounds, is described. Although many chemical approaches to this structural motif have been explored, an asymmetric variant of the cyclization is unprecedented. Herein we present an enantioselective macrolactonization through an intramolecular atom‐economical rhodium‐catalyzed coupling of ω‐allenyl‐substituted carboxylic acids. The use of a modified diop ligand, chiral DTBM‐diop, led to high enantioselectivity (up to 93 % ee). The reaction tolerated a large variety of functionalities, including α,β‐unsaturated carboxylic acids and depsipeptides, and provided the desired macrocycles with very high enantio‐ and diastereoselectivity.     

Neutron Compton scattering investigation of sodium hydride: from bulk material to encapsulated nanoparticulates in amorphous silica gel

In this study we utilize neutron Compton scattering (NCS) to determine differences in nuclear momentum distributions in NaH, both as bulk material and encapsulated as nanoscale particles (from 20 to 50 nm in diameter) within an amorphous silica-gel matrix (SiGNaH). In addition, elemental Na dispersed in such a matrix is also studied (SiGNa). Data treatment and fitting of experimental spectra yields comparison of the nuclear Compton profiles and radial momentum distributions for the proton in both bulk NaH and nanoscale SiGNaH, with resultant proton kinetic energies being in agreement with previous inelastic neutron studies of bulk NaH. Slight differences in proton radial momentum distributions for bulk and nanoscale systems are witnessed and discussed. The technique of stoichiometric-fixing is applied to the backscattering spectra of each system in order to examine changes in the Na profile width, and NCS is shown to be sensitive to the chemical environment change of this heavier nucleus. Examination of the Si and O profile widths in the gel samples also supports this method.     

Chiral analytical method development and application to pre‐clinical pharmacokinetics of pinocembrin

An analytical method enabling the detection and quantification of the individual enantiomers of racemic (±) pinocembrin is required to fully characterize its pharmacokinetic disposition. Direct resolution of the enantiomers of pinocembrin was achieved using a novel and simple reversed‐phase high‐performance liquid chromatography method with electrospray ionization and detection by mass spectrometry in rat serum. A Chiralcel® AD‐RH column was employed to perform baseline separation with electrospray positive‐mode ionization with selected ion monitoring detection. The standard curves were linear from 0.5 to 100 µg/mL for each enantiomer. The limit of quantification was 0.5 µg/mL. The assay was applied successfully to stereoselective serum disposition of pinocembrin enantiomers in rats. Pinocembrin enantiomers were detected in serum. Both enantiomers had a serum half‐life of ~15 min in rats. Similar values of volume of distribution between the enantiomers were also observed: 1.76 L/kg for S‐pinocembrin and 1.79 L/kg for R‐pinocembrin. Total clearance was 5.527 L//h/kg for S‐pinocembrin and 5.535 L/h/kg for R‐pinocembrin, and the area under the curve was 1.821 µg h/mL for S‐pinocembrin and 1.876 µg h/mL for R‐pinocembrin. The large volume of distribution coupled with the short serum half‐life suggests extensive distribution of pinocembrin into the tissues. Copyright © 2012 John Wiley & Sons, Ltd.     

Scanning force microscopy based rapid force curve acquisition on supported lipid bilayers: experiments and simulations using pulsed force mode.

In situ pulsed force mode scanning force microscopy (PFM-SFM) images of phase separated solid-supported lipid bilayers are discussed with the help of computer simulations. Simultaneous imaging of material properties and topography in a liquid environment by means of PFM-SFM is severely hampered by hydrodynamic damping of the cantilever. Stiffness and adhesion images of solid-supported membranes consisting of cholesterol, sphingomyelin, and 1,2-dioleyl-phosphatidylcholine obtained in aqueous solution exhibit contrast inversion of adhesion and stiff. ness images depending on parameters such as driving frequency, amplitude, and trigger setting. Simulations using a simple harmonic oscillator model explain experimental findings and give a deeper insight into the way PFM-SFM experiments have to be performed in order to obtain interpretable results and hence pave the way for reliable material contrast imaging at high speed.     

New fluorescent probes for testing combinatorial catalysts with phosphodiesterase and esterase activities

Combinatorial development of new catalysts with phosphodiesterase and esterase activities requires specific fluorescent probes for rapid visual detection of hydrolytic activity. Such fluorescent probes have been synthesized with special attention to solubility in water and stability towards spontaneous hydrolysis at a given pH. The probes reported here include compound 5 based on a fluorescein fluorophore, compound 12 for FRET-detection of phosphodiester hydrolysis and compound 25 based on a quinolinium fluorophore.