Experimental and theoretical characterization of arsenite in water: insights into the coordination environment of As-O

Long-term exposure to arsenic in drinking water has been linked to cancer of the bladder, lungs, skin, kidney, nasal passages, liver, and prostate in humans. It is therefore important to understand the structural aspects of arsenic in water, as hydrated arsenic is most likely the initial form of the metalloid absorbed by cells. We present a detailed experimental and theoretical characterization of the coordination environment of hydrated arsenite. XANES analysis confirms As(III) is a stable redox form of the metalloid in solution. EXAFS analysis indicate, at neutral pH, arsenite has a nearest-neighbor coordination geometry of approximately 3 As-O bonds at an average bond length of 1.77 A, while at basic pH the nearest-neighbor coordination geometry shifts to a single short As-O bond at 1.69 A and two longer As-O bonds at 1.82 A. Long-range ligand scattering is present in all EXAFS samples; however, these data could not be fit with any degree of certainty. There is no XAS detectable interaction between As and antimony, suggesting they are not imported into cells as a multinuclear complex. XAS results were compared to a structural database of arsenite compounds to confirm that a 3 coordinate As-O complex for hydrated arsenite is the predominate species in solution. Finally, quantum chemical studies indicate arsenite in solution is solvated by 3 water molecules. These results indicate As(OH)3 as the most stable structure existing in solution at neutral pH; thus, ionic As transport does not appear to be involved in the cellular uptake process.     

Preparation of a novel diphosphine-palladium macrocyclic complex possessing a molecular recognition site. Oxidative addition studies

A disphosphine-palladium(0) complex capable of recognising barbiturates has been prepared. Oxidative addition studies with a barbitiurate:aryl iodide conjugate provided new Pd(ii) complexes where the positioning of the Pd-bound aryl group is controlled by the molecular recognition event.     

Wavelength beam combining of ytterbium fiber lasers

Wavelength beam combining of five ytterbium fiber lasers is demonstrated in a master-oscillator power-amplifier configuration at combined powers up to 6 W. The combined beam profile has an M2 value of 1.14, which is equal to that of an individual fiber. Beam steering in one dimension over 140 resolvable spots is also demonstrated.     

A metal-centered hydrophobic pocket recognizing pyridine over piperidine

Two external spaces of an inorganic tennis ball are a novel type of metal-centered hydrophobic pocket where two hydrophobic trans-(+/-)-1,2-diaminocyclohexane groups stand perpendicularly to and around the metal coordination plane. The space recognizes pyridine over piperidine, and a novel supramolecule was obtained using such pyridine recognition properties.     

Aziridines as a protecting and directing group. Stereoselective synthesis of (+)-bromoxone

[reaction: see text] The directing ability of an aziridine group for the epoxidation of adjacent double bonds is demonstrated. The aziridine group is also used to effectively protect a double bond in a cycloenone system for a short synthesis of the title compound.     

Efficient asymmetric synthesis of the vasopeptidase inhibitor BMS-189921

[reaction: see text] An efficient asymmetric synthesis of the vasopeptidase inhibitor BMS-189921 was accomplished. Two short enantioselective syntheses of the common key intermediate (S)-alpha-aminoazepinone 6b were developed. Olefin 3 was converted to 6b via asymmetric hydrogenation. Alternatively, enyne 12 was converted to racemic alpha-aminoazepinone 15b, which was transformed to 6b by a practical dynamic resolution.     

The kinetics of homogeneous nucleation of silver nanoparticles stabilized by polymers

The formation of Ag nanoparticles synthesized by homogeneous nucleation, stabilized by polymers (PVA and PVP) was monitored by UV–Vis spectrophotometry and transmission electron microscopy. Our aim was to differentiate between the two main phases of particle formation, i.e. nucleation and growth and to characterize their rates with the help of appropriate kinetic equations. Time resolved spectrophotometric measurements revealed that particle formation is an autocatalytic process: a slow, continuous nucleation phase (3–5 min) is followed by a rapid, autocatalytic growth phase where the maximal particle size is 5–7 nm. By freezing the reaction mixture, the process of particle growth can be followed from 5 to 40 min on TEM pictures. The first order rate constants were calculated and they are strongly depend on the polymer concentration. If the growing particles are attached by PEI to the surface of a solid support, the formation of silver nanoparticles can also be followed by atomic force microscopy (AFM) and we can control the particle growth on mica surface. The cross section analysis of the pictures show, that the particle growing process can be also monitored at solid–liquid interface.     

Arbitrage valuation and bounds for sinking-fund bonds with multiple sinking-fund dates

The paper tackles the problem of pricing, under interest-rate risk, a default-free sinking-fund bond which allows its issuer to recurrently retire part of the issue by (a) a lottery call at par, or (b) an open market repurchase. By directly modelling zero-coupon bonds as diffusions driven by a single-dimensional Brownian motion, a pricing formula is supplied for the sinking-fund bond based on a backward induction procedure which exploits, at each step, the martingale approach to the valuation of contingent-claims. With more than one sinking-fund date, however, the pricing formula is not in closed form, not even for simple parametrizations of the process for zerocoupon bonds, so that a numerical approach is needed. Since the computational complexity increases exponentially with the number of sinking-fund dates, arbitrage-based lower and upper bounds are provided for the sinking-fund bond price. The computation of these bounds is almost effortless when zero-coupon bonds are as described by Cox, Ingersoll and Ross. Numerical comparisons between the price of the sinking-fund bond obtained via Monte Carlo simulation and these lower and upper bounds are illustrated for different choices of parameters.