A unique and highly efficient method for catalytic olefin aziridination

A facile, high yielding, and stereospecific method for olefin aziridination is described. This process capitalizes on the unique reactivity of sulfamate esters in combination with 1-2 mol % Rh2(tfacam)4 and PhI(OAc)2 as the terminal oxidant to promote N-atom transfer reactions. A range of structurally and electronically disparate alkenes are found to react under conditions that employ substrate as the limiting reagent and only a slight excess of H2NSO3CH2CCl3 as the nitrogen source. The product alkoxysulfonyl aziridines are useful intermediates that react smoothly with nucleophiles to generate 1,2-amine derivatives. Following aziridine ring-opening, the N-trichloroethoxysulfonyl group can be removed under mild reductive conditions (Zn(Cu)/AcOH-MeOH) to give the corresponding 1 degrees amine. The efficient and convenient performance of this chemistry should establish it as a useful tool for synthesis.     

Unique CO chemisorption properties of gold hexamer: Au6(CO)n- (n = 0-3)

Elucidating the chemisorption properties of CO on gold clusters is essential to understanding the catalytic mechanisms of gold nanoparticles. Gold hexamer Au(6) is a highly stable cluster, known to possess a D(3)(h) triangular ground state structure with an extremely large HOMO-LUMO gap. Here we report a photoelectron spectroscopy (PES) and quasi-relativistic density functional theory (DFT) study of Au(6)-CO complexes, Au(6)(CO)(n)(-) and Au(6)(CO)(n) (n = 0-3). CO chemisorption on Au(6) is observed to be highly unusual. While the electron donor capability of CO is known to decrease the electron binding energies of Au(m)(CO)(n)(-) complexes, CO chemisorption on Au(6) is observed to have very little effect on the electron binding energies of the first PES band of Au(6)(CO)(n)(-) (n = 1-3). Extensive DFT calculations show that the first three CO successively chemisorb to the three apex sites of the D(3)(h) Au(6). It is shown that the LUMO of the Au(6)-CO complexes is located in the inner triangle. Thus CO chemisorption on the apex sites (outer triangle) has little effect on this orbital, resulting in the roughly constant electron binding energies for the first PES band in Au(6)(CO)(n)(-) (n = 0-3). Detailed molecular orbital analyses lead to decisive information about chemisorption interactions between CO and a model Au cluster.     

Development and validation of a HPLC method for the determination of voriconazole in pharmaceutical formulation using an experimental design

A rapid and sensitive RP-HPLC method with UV detection (260 nm) for routine analysis of voriconazole in a pharmaceutical formulation (Vfend^®) was developed. Chromatography was performed with mobile phase containing a mixture of acetonitrile and water (50:50, v/v) with flow rate was of 1.0 ml min⁻¹. Quantitation was accomplished with internal standard method. The procedure was validated for linearity (correlation coefficient = 0.9999), accuracy, robustness and intermediate precision. Experimental design was used for validation of robustness and intermediate precision. To test robustness, three factors were considered. Percentage of acetonitrile in mobile phase, flow rate and p^H; an increase in the flow rate results in a decrease of the drug found concentration, while the percentage of organic modifier and p^H have no important effect on the response. For intermediate precision measure the variables considered were: analyst, equipment and number of days. The R.S.D. value (0.45%, n = 24) indicated a good precision of the analytical method. The proposed method was simple, highly sensitive, precise and accurate and retention time less than 4 min indicating that the method is useful for routine quality control.     

Hydrothermal Assisted Synthesis of Micro-Bricks Shaped WO3 for Electrochemical Oxidation of Paracetamol: A Microstructured Paracetamol Sensor

Russian Journal of Electrochemistry - A micro-bricks shaped tungsten oxide (WO3) was prepared by hydrothermal method. The prepared material was characterized by field emission scanning electron...     

Synthetic Antibody-Rhamnose Cluster Conjugates Show Potent Complement-Dependent Cell Killing by Recruiting Natural Antibodies

Monoclonal antibodies (mAbs) are one of the most rapidly growing drug classes used for the treatment of cancer, infectious and autoimmune diseases. Complement-dependent cytotoxicity (CDC) is one of the effector functions for antibodies to deplete target cells. We report here an efficient chemoenzymatic synthesis of structurally well-defined conjugates of a monoclonal antibody with a rhamnose- and an αGal trisaccharide-cluster to recruit natural anti-rhamnose and anti-αGal antibodies, respectively, to enhance the CDC-dependent targeted cell killing. The synthesis was achieved by using a modular antibody Fc-glycan remodeling method that includes site-specific chemoenzymatic Fc-glycan functionalization and subsequent click conjugation of synthetic rhamnose- and αGal trisaccharide-cluster to provide the respective homogeneous antibody conjugates. Cell-based assays indicated that the antibody-rhamnose cluster conjugates could mediate potent CDC activity for targeted cancer cell killing and showed much more potent efficacy than the antibody-αGal trisaccharide cluster conjugates for CDC effects.     

Synthesis and structural characterization of some titanium butoxides modified with chloroacetic acids

Reactions of Ti(OBu^s)₄ and Ti(OBuⁿ)₄ with chloroacetic acids (mono-, di-, and tri-) were carried out in toluene in 1:1 and 1:2 molar ratios at room temperature to generate new precursors of titania. These modified alkoxides/oxo-alkoxides were characterized by spectroscopic methods. A solution of Ti(OBuⁿ)₂(OOCCCl₃)₂ in toluene left for crystallization at ?30 °C yielded single crystals of the product Ti₆(μ₂-O)₂(μ₃-O)₂(μ₂-OC₄H₉)₂(OC₄H₉)₆(OOCCCl₃)₈. Single-crystal X-ray diffraction revealed the molecular structure to be composed of a hexanuclear unit in which two Ti₂O₁₀ units (made by two edge-sharing octahedra) are linked with two corner-sharing octahedra.     

Investigation on the effect of cottonseed oil blended with different percentages of octanol and suspended MWCNT nanoparticles on diesel engine characteristics

Journal of Thermal Analysis and Calorimetry - In the present work, a series of experiments were designed and conducted to prepare biodiesel from cottonseed oil and to blend it with octanol. The...     

A review on use of TRNSYS as simulation tool in performance prediction of desiccant cooling cycle

Journal of Thermal Analysis and Calorimetry - Solid desiccant-assisted cooling and dehumidification systems are becoming very popular nowadays for maintaining the required thermal comfort in...     

Correction to: Investigation on the effect of cottonseed oil blended with different percentages of octanol and suspended MWCNT nanoparticles on diesel engine characteristics

Journal of Thermal Analysis and Calorimetry - In the original publication of the article, the affiliations of the third, fourth and fifth authors were incorrectly published.