New Cu-based catalysts supported on TiO2 films for Ullmann S(N)Ar-type C-O coupling reactions

New routes for the preparation of highly active TiO(2)-supported Cu and CuZn catalysts have been developed for C-O coupling reactions. Slurries of a titania precursor were dip-coated onto glass beads to obtain either structured mesoporous or non-porous titania thin films. The Cu and CuZn nanoparticles, synthesized using a reduction by solvent method, were deposited onto calcined films to obtain a Cu loading of 2 wt%. The catalysts were characterized by inductively coupled plasma (ICP) spectroscopy, temperature-programmed oxidation/reduction (TPO/TPR) techniques, (63)Cu nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction (XRD), scanning and transmission electron microscopy (S/TEM-EDX) and X-ray photo-electron spectroscopy (XPS). The activity and stability of the catalysts obtained have been studied in the C-O Ullmann coupling of 4-chloropyridine and potassium phenolate. The titania-supported nanoparticles retained catalyst activity for up to 12 h. However, catalyst deactivation was observed for longer operation times due to oxidation of the Cu nanoparticles. The oxidation rate could be significantly reduced over the CuZn/TiO(2) catalytic films due to the presence of Zn. The 4-phenoxypyridine yield was 64% on the Cu/nonporous TiO(2) at 120 °C. The highest product yield of 84% was obtained on the Cu/mesoporous TiO(2) at 140 °C, corresponding to an initial reaction rate of 104 mmol g(cat) (-1) s(-1). The activation energy on the Cu/mesoporous TiO(2) catalyst was found to be (144±5) kJ mol(-1), which is close to the value obtained for the reaction over unsupported CuZn nanoparticles (123±3 kJ mol(-1)) and almost twice the value observed over the catalysts deposited onto the non-porous TiO(2) support (75±2 kJ mol(-1)).     

Effect of doping concentration and annealing temperature on luminescence properties of Y2O3:Eu3+ nanophosphor prepared by colloidal precipitation method

Eu³⁺ doped Y₂O₃ nanophosphors have been synthesized using the simple colloidal precipitation method. Doping of Eu³⁺ ions in host yttria lattice has been achieved through slow re-crystallization process under wet-chemical conditions followed by annealing at high temperatures (300–1400 °C). The nanophosphors were characterized by using powder X-ray diffraction (XRD), thermogravimetric analysis (TGA), atomic force microscopy (AFM) and spectrofluorometer techniques. XRD analysis reveals formation of pure cubic phase of Y₂O₃ in samples annealed at 700 °C or above. Further, the XRD data was successfully used to retrieve the crystallite size and size distribution from powder samples using the FW((1/5)/(4/5))M method. Crystallite size (11–50 nm) extracted from XRD has been found to be consistent with AFM measurements. The PL emission spectra of nanophosphors show bright red emission at 612 nm due to hypersensitive electric dipole (ED) ⁵D₀–⁷F₂ transition of Eu³⁺ ions in Y₂O₃ lattice. Further, photoluminescence studies indicate that optimum value of the Eu³⁺ to get best luminescence properties is 12 at%. Surface conjugations of these nanophosphors with water soluble dextran biomolecules have also been performed. Surface conjugated rare earth nanophosphors have great potential for bio-applications.     

Synthesis of selenoxo peptides and oligoselenoxo peptides employing LiAlHSeH

Synthesis of selenoxo peptides by the treatment of N(α)-protected peptide esters with a combination of PCl(5) and LiAlHSeH is delineated. The method is simple, high-yielding, and free from racemization. Thus obtained selenoxo peptides are used as units for N-terminal chain extension through N(α)-deprotection/coupling to yield peptide-selenoxo peptide hybrids. Multiple selenation is demonstrated by conversion of two peptide bonds of tripeptides into selenoxo peptide bonds. Amino acid derived arylamides are also converted into aryl selenoamides. C(6)H(5)-CSeNH-Val-OMe 8f is obtained as single crystal, and its structure was determined through X-ray diffraction study.     

HPLC Bioassay of Elvitegravir using a Molecularly Imprinted Polymer Based Solid Phase Extraction in RAT Plasma: Application to Pharmacokinetic Studies

Journal of Analytical Chemistry - A water-compatible molecularly imprinted polymer (MIP) was prepared for specific extraction of HIV-1 integrase inhibitor elvitegravir (EVG). It was prepared by a...     

Concentration Dependence of Room Temperature Magnetic Ordering in Dilute Fe: Ge1 − x Te x Alloy

Hyperfine interaction techniques like Mossbauer spectroscopy are very sensitive tools to study the local probe interactions in dilute magnetic semiconductors. We report here a Mossbauer study on the concentration dependence in Fe_0.008Ge_{1 − x} Te _x for x = 0, 0.008, 0.016, 0.03 and 0.05. At room temperature magnetic interactions were observed for all concentrations of Te and the population of magnetic site was found to increase gradually with the Te concentration. A constant magnetic hyperfine field of 136 KOe was found. A quadrupole doublet due to the FeTe₂ compound phase was also seen.     

Cytotoxic Oligomers and Fibrils Trapped in a Gel‐like State of α‐Synuclein Assemblies

α‐Synuclein (α‐Syn) aggregation is associated with Parkinson's disease (PD) pathogenesis. In PD, the role of oligomers versus fibrils in neuronal cell death is debatable, but recent studies suggest oligomers are a proximate neurotoxin. Herein, we show that soluble α‐Syn monomers undergo a transformation from a solution to a gel state on incubation at high concentration. Detailed characterization of the gel showed the coexistence of monomers, oligomers, and short fibrils. In vitro, the gel was highly cytotoxic to human neuroblastoma cells. The individual constituents of the gel are short‐lived species but toxic to the cells. They comprise a structurally heterogeneous population of α‐helical and β‐sheet‐rich oligomers and short fibrils with the cross‐β motif. Given the recent evidence of the gel‐like state of the protein associated with neurodegenerative diseases, the gel state of α‐Syn in this study represents a mechanistic and structural model for the in vivo toxicity of α‐Syn in PD.     

Mesoporous Co3O4 Nanobundle Electrocatalysts

Tailoring metal oxide nanostructures with mesoporous architectures is vital to improve their electrocatalytic performance. Herein, we demonstrate the synthesis of 2D mesoporous Co₃O₄ (meso‐Co₃O₄) nanobundles with uniform shape and size by employing a hard‐template method. In this study, the incipient wetness impregnation technique has been chosen for loading metal precursor into the silica hard template (SBA‐15). The results reveal that the concentration of a saturated precursor solution plays a vital role in mesostructured ordering, as well as the size and shape of the final meso‐Co₃O₄ product. The optimized precursor concentration allows us to synthesize ordered meso‐Co₃O₄ with four to seven nanowires in each particle. The meso‐Co₃O₄ structure exhibits excellent electrocatalytic activity for both glucose and water oxidation reactions.     

Structure-Activity Relations for Imidazo-pyridine-Type Inhibitors of β-D-Glucosidases

The triazole 7 and the known gluco- and manno-configurated imidazoles 10 and 11 have been prepared by annulation of the azole ring to the aldonothiolactam 14 in a Hg(OAc)₂-promoted reaction with either hydrazine-carbaldehyde or aminoacetaldehyde dimethyl acetal. Depending upon the reaction conditions, the synthesis of the imidazoles yielded mostly the gluco-imidazole 19 or a mixture of the gluco/manno epimers 19/20 . In contrast to the triazole 4, the isomeric triazole 7 proved a good inhibitor of retaining β-glucosidases from sweet almonds and from Caldocellum saccharolyticum. This observation and the qualitative correlation between basicity and inhibitory power of the tetrahydropyridoazoles provide further evidence for the hypothesis of the ‘lateral protonation’ of glycosides by (some) retaining β-glucosidases.