Selective esterifications of alcohols and phenols through carbodiimide couplings

Esterification of carboxylic acids capable of forming ketene intermediates upon treatment with carbodiimides permits the selective acylation of alcohols in the presence of phenols lacking strong electron-withdrawing groups. The selectivity of acylations involving highly acidic phenols could be reversed through the addition of catalytic amount of acid. Esterification of other carboxylic acids was found to proceed through the formation of symmetric anhydrides and provide the opposite chemoselectivity. In both cases the relative acylation rates of substituted phenols are consistent with a reaction mechanism involving an attack of phenolate anions on electrophilic intermediates such as ketenes and symmetric anhydrides, with the carbodiimides serving both as an activating reagent and as a basic catalyst.     

Investigation of micelle formation by fluorescence correlation spectroscopy

We show that noncovalently bound dye molecules can be used as labels in single-molecule fluorescence experiments for the determination of aggregate formation in standard surfactant systems. Aqueous solutions of sulfosuccinic acid bis(2-ethylhexyl) ester sodium salt, hexadecyltrimethylammonium chloride, and pentaethylene glycol monododecyl ether have been studied by fluorescence correlation spectroscopy using commercially available dyes. The translational diffusion coefficient and the critical micelle concentrations have been determined and compare well to values reported in the literature. The respective charges of the surfactant and of the dye molecule are crucial for the effectiveness of the presented method.     

Analysis of the decay of picosecond fluorescence in semiconductors: Criteria for the presumption of electroneutrality during the decay of an exponential electron-hole profile

When an exponential profile of electron-hole pairs is photogenerated (in a semiconductor) with a delta-function light pulse, unequal diffusion coefficients of holes and electrons (i.e. D_e≠ D_h) effect deviations from electroneutrality as electrons and holes diffuse into the bulk semiconductor. These deviations will in turn effect errors in the analysis of data (e.g. time resolved fluorescence) when using theory based on the presumption of electroneutrality. We deduce here the experimental conditions required for an effective electroneutrality to be maintained during the course of an experiment. Analyses were carried out using computer simulations without the presumption of electroneutrality and the analytic solution with the presumption of electroneutrality. The differences in the measured fluorescences predicted by the two computations are characterized as a function of a variety of experimental parameters and physical properties: intensity (of the excitation pulse), the absorption of the exciting and emitted light, the the ratio D_h/D_e, bulk dielectric constant of the semiconductor, bulk and surface recombination kinetics. It is shown that a conditon of adequate electroneutrality can be effectively attained when a well defined a minimum number of electron-hole pairs is generated; an upper limit of the number of e^?–k⁺ pairs is also established in order to avoid an intolerable temperature pulse.     

Eilatin as a bridging ligand in ruthenium(II) complexes: synthesis,crystal structures,absorption spectra,and electrochemical properties

The potential of the heptacyclic aromatic alkaloid eilatin (1), that features two nonequivalent binding sites, to serve as a bridging ligand is reported. The nonequivalency of the binding sites allowed the selective synthesis of both mono- and dinuclear complexes. The mononuclear Ru(II) complexes [Ru(dmbpy)(2)(eilatin)](2+) (2) and [Ru(tmbpy)(2)(eilatin)](2+) (3) in which eilatin selectively binds "head-on" were synthesized and employed as building blocks in the synthesis of the dinuclear complexes [[Ru(dmbpy)(2)](2)(mu-eilatin)](4+) (4) and [[Ru(tmbpy)(2)](2)(mu-eilatin)](4+) (5). Complete structure elucidation of the complexes in solution was accomplished by 1D and 2D NMR techniques. The X-ray structures of the mononuclear complex 3 and of the two dinuclear complexes 4 and 5 were solved, and absorption spectra and electrochemical properties of the complexes were explored. Both dinuclear complexes formed as racemic mixtures in a 3:1 diastereoisomeric ratio, the major isomer being the heterochiral one (Delta Lambda/Lambda Delta) as revealed by crystallography. The mononuclear complexes feature an exceptionally low energy MLCT band around 600 nm that shifted to over 700 nm upon the binding of the second Ru(II) center. The mononuclear complexes show one reversible oxidation and several reversible reduction waves, the first two reductions being substantially anodically shifted in comparison with [Ru(bpy)(3)](2+), attributed to the reduction of eilatin, and consistent with its low lying pi* orbital. The dinuclear complexes follow the same reduction trend, exhibiting several reversible reduction waves, and two reversible well-resolved metal centered oxidations due to the nonequivalent binding sites and to a significant metal-metal interaction mediated by the bridging eilatin.     

Two-Dimensional Crystallography of Amphiphilic Molecules at the Air–Water Interface

The advent of well-collimated, high-intensity synchrotron X-ray sources and the consequent development of surface-specific X-ray diffraction and fluorescence techniques have recently revolutionized the study of Langmuir monolayers at the air–liquid interface. These methods allowed for the first time the determination of the in-plane and vertical structure of such monolayers with a resolution approaching the atomic level. We briefly describe these methods, including grazing incidence X-ray diffraction, specular reflectivity, Bragg rods, standing waves, and surface fluorescence techniques, and review recent results obtained from them for Langmuir films. The methods have been successfully applied in the elucidation of the structure of crystalline aggregates of amphiphilic molecules such as alcohols, carboxylic acids and their salts, α-amino acids, and phospholipids at the water surface. In addition, it became possible to monitor by diffraction the growth and dissolution of the crystalline self-aggregates as well as structural changes occurring by phase transitions. Furthermore, the surface X-ray methods shed new light on the structure of the underlying ionic layer of attached solvent or solute species. Examples are given where singly or doubly charged ions bound to the two-dimensional (2D) crystal form either an ordered or diffuse counterionic layer. Finally, the surface diffraction methods provide data on transfer of structural information from 2D clusters to 3D single crystals, which had been successfully accomplished by epitaxial-like crystallization both in organic and inorganic crystals.     

Mononuclear and dinuclear complexes of dibenzoeilatin: synthesis, structure, and electrochemical and photophysical properties

This work describes a study of Ru(II) and Os(II) polypyridyl complexes of the symmetrical, fused-aromatic bridging ligand dibenzoeilatin (1). The synthesis, purification, and structural characterization by NMR of the mononuclear complexes [Ru(bpy)(2)(dbneil)](2+) (2), [Ru(tmbpy)(2)(dbneil)](2+) (3), and [Os(bpy)(2)(dbneil)](2+) (4), the homodinuclear complexes [[Ru(bpy)(2)](2)[micro-dbneil]](4+) (5), [[Ru(tmbpy)(2)](2)[micro-dbneil]](4+) (6), and [[Os(bpy)(2)](2)[micro-dbneil]](4+) (7), and the heterodinuclear complex [[Ru(bpy)(2)][micro-dbneil][Os(bpy)(2)]](4+) (8) are described, along with the crystal structures of 4, 6, and 7. Absorption spectra of the mononuclear complexes feature a low-lying MLCT band around 600 nm. The coordination of a second metal fragment results in a dramatic red shift of the MLCT band to beyond 700 nm. Cyclic and square wave voltammograms of the mononuclear complexes exhibit one reversible metal-based oxidation, as well as several ligand-based reduction waves. The first two reductions, attributed to reduction of the dibenzoeilatin ligand, are substantially anodically shifted compared to [M(bpy)(3)](2+) (M = Ru, Os), consistent with the low-lying pi orbital of dibenzoeilatin. The dinuclear complexes exhibit two reversible, well-resolved, metal-centered oxidation waves, despite the chemical equivalence of the two metal centers, indicating a significant metal-metal interaction mediated by the conjugated dibenzoeilatin ligand. Luminescence spectra, quantum yield, and lifetime measurements at room temperature in argon-purged acetonitrile have shown that the complexes exhibit (3)MLCT emission, which occurs in the IR-region between 950 and 1300 nm. The heterodinuclear complex 8 exhibits luminescence only from the Ru-based fragment, the intensity of which is less than 1% of that observed in the corresponding homodinuclear complex 5; no emission from the Os-based unit is observed, and an intramolecular quenching constant of k(q) > or = 3 x10(9) s(-)(1) is evaluated. The nature of the quenching process is briefly discussed.     

A complete set of invariants for finite groups and other results

For a finite group G and a set I ? {1, 2,…, n} let

${}_{\mathrm{G}}\text{(n,I) = ∑}{}_{\mathrm{g\; \in \; G}}\text{ε}{}_1\text{(g)?ε}{}_2\text{(g)???ε}{}_{\mathrm{n}}\text{(g)}$

,where

$\text{ε}{}_{\mathrm{i}}\text{(g)=g}\text{if}\text{i=∈ I,}$

$\text{ε}{}_{\mathrm{l}}\text{(g)=l}\text{if}\text{i=∈ I.}$

We prove, among other results, that the positive integers

$\text{tr}\text{(e}{}_{\mathrm{G}}\text{(n,I}{}_1\text{)+?+e}{}_{\mathrm{G}}\text{(n,I}{}_{\mathrm{r}}\text{))}{}^{\mathrm{k}}\text{:n,r,k,?1, I}{}_{\mathrm{j}}\text{?{1,…,n}, 1?|i}{}_{\mathrm{j}}\text{|?3}$

for 1 ? j ? r, I_j1 ∩ I_j2 ∩ I_j3 ∩ I_j4 = Ø for any 1 ? j₁ <j₂ <j₃ <j₄ ? r, determine G up to isomorphism. We also show that under certain assumptions finite groups are determined up to isomorphism by the number of their subgroups.     

An <Emphasis Type="Italic">m</Emphasis><Superscript>th</Superscript> Generation Model for Weak Ranking of Players in a Tournament

The problem of ranking players in a tournament has been studied by a number of authors. The methods developed for ranking players fall under two general headings—direct methods and rating methods. The present paper extends the tournament ranking problem in two directions. First, the usual definition of a tournament is broadened to include ties or draws. Thus, our model determines the best weak ranking of the players. Second, the ranking method presented takes account of player strength in that wins over strong players are valued higher than wins over weak players. To account for player strength, we evaluate both direct or first-order wins of players over opponents (i defeats j) and indirect or higher-order wins (i defeats k, who defeats j). A model which derives a composite score for each player, combining both direct and indirect wins, is used to obtain an overall ranking of the competitors.     

Phase transitions of p-type (Pb,Sn,Ge)Te-based alloys for thermoelectric applications

p-type (Pb,Sn,Ge)Te-based alloys for thermoelectric applications were prepared using Bridgman technique. Second-order, rhombohedral to cubic phase transitions are involved, as evaluated from anomalies in the temperature dependence values of Seebeck coefficient, electrical conductivity, heat flow and the elongation, in the vicinity of the phase transition temperature, T_c. The correlation between these anomalies in both the electronic and thermodynamic properties was interpreted by means of the relationship of Fermi energy to the chemical potential (or to the molar Gibbs free energy).     

Scattering from a long helix: Theory and simulation

We consider here the electromagnetic scattering by a long helical particle made from a thin (in comparison to the wavelength) wire. In contrast to several previous theoretical works, we adopt here the algorithm developed for scattering by a multi-layered fiber. In the present work, the helical particle is considered as a hollow cylinder with a thin non-homogeneous membrane for which periodical boundary conditions are imposed.