Hydroselenation of alkynes using NaBH4/BMIMBF4: easy access to vinyl selenides

A general and easy method for the synthesis of several vinyl selenides using NaBH₄ and BMIMBF₄ as a recyclable solvent is described. This efficient and improved method furnishes the corresponding vinyl chalcogenides preferentially with Z configuration. We also observed that when the same protocol was applied to phenyl acetylene, (E)-bis-phenylseleno styrene was obtained in good yield and with high selectivity.     

Copper(I) iodide-catalysed arylation of acetoacetate to yield 2-arylacetic acid esters

The C-C coupling reaction between ethyl acetoacetate and aryl halides in the presence of CuI is described. The effects of solvent, ligands such as vicinal diamines and amino acids, base and temperature are reported. The arylated acetoacetate ester is deacylated under the reaction conditions resulting in the generation of 2-arylacetic acid esters, constituting a mild alternative to direct arylation of carboxylate esters.     

Synthesis and characterization of water-soluble phenylene-vinylene-based singlet oxygen sensitizers for two-photon excitation

[reaction: see text] The synthesis and characterization of water-soluble singlet oxygen sensitizers with a phenylene-vinylene motif is presented. The principal motivation for this study was to better understand specific features of a water-soluble molecule that influence the photosensitized production of singlet oxygen upon nonlinear, two-photon excitation of that molecule. To achieve water solubility, sensitizers were synthesized with ionic as well as nonionic substituents. In the ionic approach, salts of N-methylated pyridine, benzothiazole, and 1-methyl-piperazine moieties were used, as were aryl-substituted sulfonic acid moieties. In the nonionic approach, aryl-substituted triethylene glycol moieties were used. Selected photophysical properties of the compounds synthesized were determined, including singlet oxygen quantum yields. Of the molecules examined, the most efficient singlet oxygen sensitizers had triethylene glycol units as the functional group that imparted water solubility. Molecules containing the ionic moieties did not make singlet oxygen in appreciable yield nor did they efficiently fluoresce. Rather, for these latter molecules, rapid charge-transfer-mediated non-radiative processes appear to dominate excited state deactivation.     

Effect of surface mobility on the particle sliding along a bubble or a solid sphere

The sliding velocity of glass beads on a spherical surface, made either of an air bubble or of a glass sphere held stationary, is measured to investigate the effect of surface mobility on the particle sliding velocity. The sliding process is recorded with a digital camera and analyzed frame by frame. The sliding glass bead was found to accelerate with increasing angular position on the collector's surface. It reaches a maximum velocity at an angular position of about 100 degrees and then, under certain conditions, the glass bead leaves the surface of the collector. The sliding velocity of the glass bead depends strongly on the surface mobility of a bubble, decreasing with decreasing surface mobility. By a mobile surface we mean one which cannot set up resistive forces to an applied stress on the surface. The sliding velocity on a rigid surface, such as a glass sphere, is much lower than that on a mobile bubble surface. The sliding velocity can be described through a modified Stokes equation. A numerical factor in the modified Stokes equation is determined by fitting the experimental data and is found to increase with decreasing surface mobility. Hydrophobic glass beads sliding on a hydrophobic glass sphere were found to stick at the point of impact without sliding if the initial angular position of the impact is less than some specific angle, which is defined as the critical sticking angle. The sticking of the glass beads can be attributed to the capillary contracting force created by the formation of a cavity due to spontaneous receding of the nonwetting liquid from the contact zone. The relationship between the critical sticking angle and the particle size is established based on the Yushchenko [J. Colloid Interface Sci. 96 (1983) 307] analysis.     

SOLVENT-INDUCED PHOTOREVERSIBLE REACTIONS OF C-PHYCOCYANIN FROM SYNECHOCOCCUS SP.

Abstract— C-phycocyanin from Synechococcus sp. ( Anacystis nidulans ) shows photoreversible absorption changes when dissolved in buffer containing 75% ethylene glycol (vol/vol). Irradiation with red light (638 nm) causes a 7.5% decrease in absorbance around the absorption maximum (620 m), while the absorbance around 500 nm increases. Subsequent irradiation with green light (500 nm) partially reverses this change. Final photoreversibility at around 620 nm amounts to ca. 2.5% of the maximum absorbance. These reactions are ascribed to two interconvertible species PC_r and PC_g, the former with a higher absorbance in the red. the latter in the green. The rate of dark reversion from PC_g to PC_r is strongly enhanced by ferricyanide. It is proposed that with this reagent, dark reversion occurs via an oxidized form of PC_g. Furthermore, ferricyanide in the presence of ethylene glycol is capable of reversibly oxidizing part of the chromophores of C-phycocyanin, presumably to a radical. In the absence of ethylene glycol, however, ferricyanide causes total irreversible bleaching of the pigment in the dark. The induced photoreversibility of C-phycocyanin is ascribed to the perturbing action on the protein structure by ethylene glycol in high concentrations. This solvent proved the most suitable perturbant of several compounds tested.     

Experimental studies on the applicability of the Kelvin equation to highly curved concave menisci

The thermodynamic properties of liquids trapped in microscopic pores are described in theory by the Kelvin equation, which relates the equilibrium meniscus curvature to the relative vapor pressure. We report here two series of experiments designed to test the validity of the Kelvin equation by direct measurement of the mean radius of curvature of the surface of cyclohexane condensed between crossed mica cylinders. In one series of experiments, the relative vapor pressure of the volatile cyclohexane was controlled by mixing it with a relatively involatile solute (n-dodecane or n-hexadecane). We found that the mean radius of curvature rapidly reached that predicted by the Kelvin equation at each relative vapor pressure of the volatile liquid, but that there was also a slow, but continuous, accumulation of the “involatile” solute at the point of condensation as the system approached true equilibrium. Such accumulation of very low vapor pressure materials may be one factor responsible for the discordant results reported by earlier workers. We find that the process of impurity buildup is complex, and suggest that studies of real porous systems may be affected by accumulation of “involatile” impurities through the vapor phase and by surface diffusion. The other series of experiments was designed to eliminate the impurity problem by maintaining the vapor pressure by temperature control of the pure liquid. The results from this series of experiments were not time dependent, and no evidence of contamination was found. The measured radii were within ±6% of those predicted by the Kelvin equation, for radii in the range 4–20 nm. We conclude that the thermodynamic basis of the Kelvin equation is valid in principle for menisci with radii as low as 4 nm.     

Quantitative electrochemical formation of phosphotungstate heteropolyanion blues

The optical and ESR spectra of electrochemically reduced phosphotungstate and polyphosphotungstate anions in phosphoric acid were examined as quantitative functions of W⁵⁺ concentration. The optical spectra obey Beer-Lambert laws and are similar to the spectra of reduced silicotungstate anions, indicating the secondary nature of the central cluster in the keggin structure with regard to interactions with the reduction electron. ESR spectra indicate an equivalent correspondence for the W⁵⁺ concentration and unpaired spins for the reduced polyphosphotungstate anion but for the reduced phosphotungstate anion monomer the unpaired spin concentration estimated by ESR was much lower than the W⁵⁺ concentration. Reacting reduced phosphotungstate anions with oxygen showed a I-electron reduction of the oxygen molecule with concomitant oxidation of W⁵⁺ to W⁶⁺ and possibly production of high-molecular-weight, polyanion clusters.     

There are uncountably many universal topological planes

We prove the existence of uncountably many nonisomorphic topological projective planes, each universal in the sense that it contains an isomorphic copy of every pseudoline arrangement.     

Developments in the use of chromatographic techniques in marine laboratories for the determination of halogenated contaminants and polycyclic aromatic hydrocarbons

Chromatography has been an important tool in marine laboratories. Since the 1960s, marine laboratories have been involved in the analysis of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs), and brominated flame retardants (BFRs). Column chromatography and liquid chromatography (LC) techniques have been used, mainly in the clean-up phase, while gas chromatography (GC) has been used extensively in the final determination of these contaminants. Developments have been observed from the use of packed GC columns, via capillary columns to the use of heart-cut multi-dimensional GC and comprehensive multi-dimensional GC. The progress made in interlaboratory studies and the availability of certified reference materials are discussed.     

Defect ordering in early transition-metal sulfides with the NaCl-type structure

The defect rock-salt type materials Zr_1?xS, Sc_1?xS, and Lu_1?xS have been shown to exhibit a complex variety of ordered superstructures. These superstructures are reviewed within the context of Landau's theory of symmetry and phase transitions, and it is concluded that there is a significant similarity in the transitions when they are considered from the point of view of reciprocal space.