Random End‐Switching Configurational Bias Monte Carlo for Long Chain Molecules

Summary: The exponential attrition of configurational bias Monte Carlo for long chains can be reduced to almost quadratic by a simple modification of the basic move. Each trial move begins on the side of the remaining sub chain opposite to the cut location. This type of move is akin to large‐scale reptation and in the limit of one‐segment cut is reptation. The extension is shown to require the same Rosenbluth weighting scheme as the original algorithm. Several examples are used to demonstrate the reliability and the improved performance of the proposed method.

     

A hereditarily indecomposable $ {mathcal{L}_{infty}} $-space that solves the scalar-plus-compact problem

We construct a hereditarily indecomposable Banach space with dual space isomorphic to ℓ ₁. Every bounded linear operator on this space is expressible as λI + K, with λ a scalar and K compact.     

Separation of major RNA-derived nucleotides by reversed-phase liquid chromatography

The effects of pH, ionic strength and amount of methanol in the eluent on the retention of 5'-, 3'- and 2'-ribonucleoside monophosphates on a reversed-phase high-performance liquid chromatographic system are described. The data were used to develop suitable separation protocols for synthetic nucleotide mixtures and applied to the separation of RNA nucleotides derived by alkaline hydrolysis.     

Transformations of poly(methoxy hexa(ethylene glycol) methacrylate)-b-(2-(diethylamino)ethyl methacrylate) block copolymer micelles upon metalation

Micelle transformations upon metalation (i.e., incorporation of metal compounds and metal nanoparticle formation) in poly(methoxy hexa(ethylene glycol) methacrylate)-block-poly((2-(diethylamino)ethyl methacrylate)), PHEGMA-b-PDEAEMA, solutions have been studied using transmission electron microscopy (TEM) and photon correlation spectroscopy (PCS). Three different methods for the formation of metalated micelles are compared: (A) dissolution of the block copolymers in pure water followed by incorporation of platinic acid (H(2)PtCl(6).6H(2)O), (B) micellization in acidic molecular solutions of block copolymers induced by interaction of the protonated amino groups with the PtCl(6)(2)(-) ions, and (C) incorporation of metal species in pH-induced micelles. The latter method leads to well-defined metalated micelles of 22-25 nm diameter containing nanoparticles with diameters of 1.3-1.5 nm. No nanoparticle aggregation is observed. Good agreement is obtained for the sizes of the platinic acid-containing micelles assessed by TEM and PCS.     

Coherence in electron transfer pathways

Central to the view of electron-transfer reactions is the idea that nuclear motion generates a transition state geometry at which the electron/hole amplitude propagates coherently from the electron donor to the electron acceptor. In the weakly coupled or nonadiabatic regime, the electron amplitude tunnels through an electronic barrier between the donor and acceptor. The structure of the barrier is determined by the covalent and noncovalent interactions of the bridge. Because the tunneling barrier depends on the nuclear coordinates of the reactants (and on the surrounding medium), the tunneling barrier is highly anisotropic, and it is useful to identify particular routes, or pathways, along which the transmission amplitude propagates. Moreover, when more than one such pathway exists, and the paths give rise to comparable transmission amplitude magnitudes, one may expect to observe quantum interferences among pathways if the propagation remains coherent. Given that the effective tunneling barrier height and width are affected by the nuclear positions, the modulation of the nuclear coordinates will lead to a modulation of the tunneling barrier and hence of the electron flow. For long distance electron transfer in biological and biomimetic systems, nuclear fluctuations, arising from flexible protein moieties and mobile water bridges, can become quite significant. We discuss experimental and theoretical results that explore the quantum interferences among coupling pathways in electron-transfer kinetics; we emphasize recent data and theories associated with the signatures of chirality and inelastic processes, which are manifested in the tunneling pathway coherence (or absence of coherence).     

Genericity and amalgamation of classes of Banach spaces

We study universality problems in Banach space theory. We show that if A is an analytic class, in the Effros-Borel structure of subspaces of C([0,1]), of non-universal separable Banach spaces, then there exists a non-universal separable Banach space Y, with a Schauder basis, that contains isomorphs of each member of A with the bounded approximation property. The proof is based on the amalgamation technique of a class C of separable Banach spaces, introduced in the paper. We show, among others, that there exists a separable Banach space R not containing L¹(0,1) such that the indices β and rND are unbounded on the set of Baire-1 elements of the ball of the double dual R∗∗ of R. This answers two questions of H.P. Rosenthal.We also introduce the concept of a strongly bounded class of separable Banach spaces. A class C of separable Banach spaces is strongly bounded if for every analytic subset A of C there exists Y∈C that contains all members of A up to isomorphism. We show that several natural classes of separable Banach spaces are strongly bounded, among them the class of non-universal spaces with a Schauder basis, the class of reflexive spaces with a Schauder basis, the class of spaces with a shrinking Schauder basis and the class of spaces with Schauder basis not containing a minimal Banach space X.     

Chaotic dynamics of semiconductor microring lasers

The complexity and dynamics of chaotic attractors generated in an InGaAsP-InP microring laser are calculated and evaluated by using a multimode rate equation model. Chaos originates from the continuous mutual injections from each mode to the other because of the bus waveguide's residual reflectivity at high values of the injection current. The data analysis of the filtered output power reveals high-dimensional chaos, and phase-dependent behavior is demonstrated.     

HPLC-ICP-MS and HPLC-ES-MS/MS characterization of synthetic seleno-arsenic compounds

Various toxicological and metabolic interactions have been reported to exist between arsenic and selenium. In the present study, synthetic seleno-arsenic compounds, potentially suitable for probing metabolic interactions between these two elements, were prepared and tentatively characterized by using high-performance liquid chromatography (HPLC)–electrospray tandem mass spectrometry and HPLC–inductively coupled plasma mass spectrometry. In analogy to the recently identified thio-arsenic species, which can be prepared from their corresponding oxo-arsenic species via reaction with H₂S, the seleno-arsenic compounds were also derived from oxo-arsenic compounds via reaction with H₂Se. Figure H₂Se bubbled into solutions containing oxo‐arsenosugars converts them into their seleno‐arsenosugar analogues.     

Improving on Nature: Making a Cyclic Heptapeptide Orally Bioavailable

The use of peptides in medicine is limited by low membrane permeability, metabolic instability, high clearance, and negligible oral bioavailability. The prediction of oral bioavailability of drugs relies on physicochemical properties that favor passive permeability and oxidative metabolic stability, but these may not be useful for peptides. Here we investigate effects of heterocyclic constraints, intramolecular hydrogen bonds, and side chains on the oral bioavailability of cyclic heptapeptides. NMR‐derived structures, amide H–D exchange rates, and temperature‐dependent chemical shifts showed that the combination of rigidification, stronger hydrogen bonds, and solvent shielding by branched side chains enhances the oral bioavailability of cyclic heptapeptides in rats without the need for N‐methylation.