Optical properties of cadmium sulfide nanocrystal film prepared by electrochemical synthesis at liquid-liquid interface

Dendritic nanocrystalline CdS film was deposited at liquid-liquid interface of surfactants and an electrolyte containing 4 mmol L⁻¹ cadmium chloride (CdCl₂) and 16 mmol L⁻¹ thioacetamide (CH₃CSNH₂) with an initial pH value of 5 at 15 °C by electrochemical synthesis. The nanofilm was characterized by transmission electron microscopy (TEM), field emission scanning electron microscope (FE-SEM), atomic force microscopy (AFM), ultraviolet visible (UV-vis) absorption spectroscopy and fluorescence spectroscopy. The surface morphology and particle size of the nanofilm were investigated by AFM, SEM and TEM, and the crystalline size was 30-50 nm. The thickness of the nanofilm calculated by optical absorption spectrum was 80 nm. The microstructure and composition of the nanofilm was investigated by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), showing its polycrystalline structure consisting of CdS and Cd. Optical properties of the nanofilm were investigated systematically by UV-vis absorption and fluorescence spectroscopy. A λ_onset blue shift compared with bulk CdS was observed in the absorption spectra. Fluorescence spectra of the nanofilm indicated that the CdS nanofilm emitted blue and green light. The nanocomposites film electrode will bring about anodic photocurrent during illumination, showing that the transfer of cavities produces photocurrent.     

A ring-closing metathesis approach to a synthesis of the B ring of eleutherobin

A short and efficient RCM route is reported for the construction of the key nine-membered B ring of eleutherobin starting from the readily available 1,2,5,6-diisopropylidene-d-glucose.     

Effects of vitrification suppression on structure morphology, conductivity and dielectric properties of vanadium phosphate glasses

Vitrification suppression in the (V₂O₅)_1−x (P₂O₅)_x glasses where x=0.10, 0.15, 0.20, and 0.25 was controlled by changing the rate of quenching glasses. The structure variations occurring in the glasses were detected by differential thermal analysis and optical microscope. The results implied the separation and growth of V₂O₅ orthorhombic microcrystal in the samples with x=0.10 and 0.15 whereas other samples did not illustrate remarkable changes in their microstructure. However, in temperature range between 300 and 473 K a semiconducting behavior for all samples appears during the study of electrical conductivity-temperature dependence. A decrease in conductivity values accompanied with some variations in activation energies by reducing quenching rate was observed. The conductivity results suggested that the conduction occurs by the phonon assisted hopping of a small polaron between V⁴⁺ and V⁵⁺ states at relatively higher temperature range above θ_D/2. Whereas at relatively low temperatures the conduction may occur by electron jumping between filled and empty states at Fermi level in the disordered matrix besides polaronic conduction. Reasonable values for the density of localized states, carrier concentration and carrier mobility were estimated and discussed. Also, dielectric constant and dielectric loss were studied as a function of frequency at different temperatures confirming the structure variations in the glass system.     

EPR investigations of oxidation effects in (V1−xMox)2−δO3

Electron paramagnetic resonance (EPR) investigations has been carried out on the new family of molybdenum doped vanadium sesquioxides (V_1−xMo_x)_2−δO₃. The oxidation effects were monitored from the rate of paramagnetic V⁴⁺ created when the sample is exposed to the air. The effects of the oxidation time, sample temperature, and annealing at 1000 °C under a diluted hydrogen atmosphere on the EPR signal features are analyzed. The V⁴⁺ concentration in the oxidized samples is determined and the relaxation effects driven by the conduction electrons are pointed out from the thermal behaviour of the EPR line features. EPR spectra of all the oxidized samples also reveal a small ferromagnetic contribution strongly correlated with the V⁴⁺ content.     

Total synthesis of (±) maculalactone A, maculalactone B and maculalactone C and the determination of the absolute configuration of natural (+) maculalactone A by asymmetric synthesis

Maculalactones A, B and C from the marine cyanobacterium Kyrtuthrix maculans are amongst the only compounds based on the tribenzylbutyrolactone skeleton known in nature and (+) maculalactone A from the natural source possesses significant biological activity against various marine herbivores and marine settlers. We now report a concise synthesis of racemic maculalactone A in five steps from inexpensive starting materials. Maculalactones B and C were synthesized by a minor modification to this procedure, and the synthetic design also permitted an asymmetric synthesis of maculalactone A to be achieved in around 85% ee. The (+) and (−) enantiomers of maculalactone A were assigned, respectively, to the S and R configurations on the basis of the chiral selectivity expected for catecholborane reduction of an unsymmetrical ketone in the presence of Corey's oxazoborolidine catalyst. Surprisingly, it appeared that natural (+) maculalactone A was biosynthesized in K. maculans in a partially racemic form, comprising ca. 90-95% of the (S) enantiomer and 5-10% of its (R) enantiomer. Coincidentally therefore, the percentage enantiomeric excess of the product obtained from asymmetric synthesis almost exactly matched that found in nature.     

Synthesis and applications of chiral bis-THF in asymmetric synthesis

The synthesis of enantiopure bis-THF is described, starting from d-mannitol. Bis-THF is used as chiral ligand for organolithium reagents in four different reactions. The enantioselectivity provided by this ligand is moderate, and the asymmetric induction is in line with the expected model.     

Ti(IV)/BINOL-catalyzed asymmetric aldol reaction of a masked acetoacetic ester: pronounced influence of catalyst concentration on nonlinear effects

Initial concentration of enantioenriched or enantiopure catalysts proved to be an important factor for the achievement of a more pronounced amplification of ee's in the Ti(IV)/BINOL-catalyzed aldol reaction of an O-silyldienolate.     

Stereoselective migration of sterically hindered organoboranes in cyclic and acyclic systems. A stereoselective allylic C-H activation reaction

The thermal migration of cyclic and acyclic organoboranes were studied. In most cases, a stereoselective 1,2-dyotropic migration was observed, allowing the stereocontrol of three contiguous chiral centers. Scope and limitations of this thermal migration are presented.