Water dispersible ZnS:Mn nanocrystals were synthesized by capping the surface of the nanocrystals with four kinds of aminoacids ligands: arginine, cystein, histidine, and methionine. The aminoacids capped ZnS:Mn nanocrystal powders were characterized by XRD, HR-TEM, EDXS, and FT-IR spectroscopy. The optical properties of the aminoacids capped ZnS:Mn colloidal nanocrystals were also measured by UV/Vis and solution photoluminescence (PL) spectroscopies in aqueous solvents. The solution PL spectra showed broad emission peaks around 575 nm (orange light emissions) with PL efficiencies in the range of 4.4 to 7.1%. The measured particle sizes for the aminoacid capped ZnS:Mn nanocrystals by HR-TEM images were in the range of 5.3 to 11.7 nm.

We report a novel method to synthesize nanocomposites composed of titania nanoparticles and phosphotungstate ions with various composition ratios ranging from W/Ti = 12/10 to 12/500 by inducing the electrostatic interaction between the positively charged protonated titania sol-particles and the negatively charged phosphotungstate anions to flocculate and precipitate. The precipitates showed varied features depending on the composition. The precipitate from the tungsten-richest W/Ti = 12/10 reaction is amorphous in its powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and Raman spectroscopy data. This material shows the Type II adsorption characteristics in its N2-adsorption isotherm, but with quite low surface area of 34 m2/g. To the contrary, the precipitates from the titanium-richer reactions (W/Ti = 12/50- 12/500) are composed of anatase nanoparticles of 2-6 nm by XRD, TEM and Raman and show the Type I adsorption characteristics. The surface area linearly increases with the titanium content from 131 m2/g for W/ Ti = 12/50 to 228 m2/g for 12/500. The precipitate from the reaction with the intermediate composition W/Ti = 12/20 is composed of anatase nanoparticles and does not have any pore accessible to N2. With the wide variety of the physical properties of the precipitates, the present method can be a novel, viable means to tailor synthesis of nanocomposite materials. A formation mechanism of the precipitates is based on the electrostatic interactions between the titania nanoparticles and phosphotungstate ions.

Conducting Polypyrrole-lead titanate (PPy/PbTiO3) composites have been prepared by in situ deposition technique by placing different wt.% of fine grade powder of PbTiO3 (10, 20, 30, 40, and 50%) during polymerization of pyrrole. The composites formed were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA), and these data indicate that PbTiO3 particles are dominating with an increase in crystallinity as well as thermal stability of the composites. The results on the low frequency dielectric studies which are obtained in the form of pressed pellet state are interpreted in terms of Maxwell Wagner polarization, which are responsible for the dielectric relaxation mechanism and frequency dependence of conductivity.

Acetohydroxyacid synthase (AHAS, EC 2. 2. 1. 6) is the enzyme that catalyses the first step in the common pathway of the biosynthesis of the branched chain amino acids, valine, leucine and isoleucine. For the first time, the AHAS gene from Bacillus anthracis was cloned into the expression vector pET28a(+), and was expressed in the E. coli strain BL21(DE3). The purified enzyme was checked on 12% SDS-PAGE to be a single band with molecular weight of 65 kDa. The optimum pH and temperature for B. anthracis AHAS was at pH 7.5 and 37 oC, respectively. Kinetic parameters of B. anthracis were as follows: Km for pyruvate, K0.5 for ThDP and Mg2+ was 4.8, 0.28 and 1.16 mM respectively. AHAS from B. anthracis showed strong resistance to three classes of herbicides, Londax (a sulfonylurea), Cadre (an imidazolinone), and TP (a triazolopyrimidine). These results indicated that these herbicides could be used in the search for new anti-bacterial drugs.

Based on the hit compound 4 derived from focused library, a series of furo[2,3-d]pyrimidines were designed, synthesized and evaluated for the inhibitory activity against Akt1 kinase. And their structure-activity relationships were investigated. Of these compounds, 3a having 2-thienyl and methyl groups at R1 and R2 showed the most potent activity with an IC50 value of 24 μ M. Introduction of the thienyl groups at C-5 and C- 6 positions significantly improved potency compared to furyl and phenyl groups.

Hydrogen gas and carbon nanotubes along with nanocarbon were produced from commercial natural gas using fixed bed catalyst reactor system. The maximum amount of carbon (491 g/g of catalyst) formation was achieved on 25% Ni, 3% Cu supported catalyst without formation of CO/CO2. Pure carbon nanotubes with length of 308 nm having balloon and horn type shapes were also formed at 673 K. Three sets of catalysts were prepared by varying the concentration of Ni in the first set, Cu concentration in the second set and doping with K in the third set to investigate the effect on stabilization of the catalyst and production of carbon nanotubes and hydrogen by copper and potassium doping. Particle size analysis revealed that most of the catalyst particles are in the range of 20-35 nm. All the catalysts were characterized using powder XRD, SEM/EDX, TPR, CHN, BET and CO-chemisorption. These studies indicate that surface geometry is modified electronically with the formation of different Ni, Cu and K phases, consequently, increasing the surface reactivity of the catalyst and in turn the Carbon nanotubes/H2 production. The addition of Cu and K enhances the catalyst dispersion with the increase in Ni loadings and maximum dispersion is achieved on 25% Ni: 3% Cu/Al catalyst. Clearly, the effect of particle size coupled with specific surface geometry on the production of hydrogen gas and carbon nanotubes prevails. Addition of K increases the catalyst stability with decrease in carbon formation, due to its interaction with Cu and Ni, masking Ni and Ni:Cu active sites.

It was demonstrated that Y[N(TMS)2]3, the neutral yttrium-diamine complex 13 and yttrium-NPS complexes 15 are efficient precatalysts for intramolecular hydroamination of aminoalkynes involving primary amines. Complex 13 and 15 were quantitatively prepared in situ by direct metalation of the ligands 4 and 9 with 1 equiv of Y[N(TMS)2]3 in benzene-d6 at 120 oC for 5 days and 10 days, respectively, via elimination of (TMS)2NH. 5-Exo- and 6-exo-dig intramolecular hydroamination of aminoalkynes using catalyst 12 and 13 proceeded smoothly to give nitrogen-contained cyclic products in good to excellent yields in all cases. In the case of 7- exo-dig intramolecular hydroamination, the desired product was produced in 41% and 48% yields despite the gem-dimethyl effect. However, treatment of catalyst 15 with aminoalkynes (19 and 22) having a methyl substituent at the carbon adjacent to triple bond and 6-exo-dig intramolecular hydroamination of 21 failed to give the desired products. Zirconium-catalyzed intramolecular hydroamination of aminoallenes (25, 27, and 31) with 5 mol% 16 afforded 2-(trans-1-propenyl)pyrrolidine, 2-isopropylenepyrrolidine, and 2-(trans-1- propenyl)piperidine in 96%, 95%, and 93% yield, respectively. However, subjecting 25 to 5 mol% 15 was unsuccessful to produce the desired product.

Pseudo-first-order rate constants (kobs) for the reaction of N-benzylphthalimide (NBPT) with HO- have been determined at 2.0 × 10?4 M NBPT, 1.0 × 10?3 and 2.0 × 10?3 M NaOH as well as varying concentrations of cetyltrimethylammonium bromide ([CTABr]T = 0.0-1.7 × 10?1 M). The effects of [CTABr]T ? CMC (with CMC representing the critical micelle concentration of CTABr) on kobs have been analyzed in terms of Berezin's pseudophase (BPP) model and pseudophase ion-exchange (PIE) model. Although both models give the best observed data fit with least-squares values not significantly different from each other, the calculated values of KS from BPP model appear to be more reliable compared to those from PIE model because the values of KS from BPP model are similar to the corresponding KS values determined spectrophotometrically.

Molecular modeling study has been performed to assist in the design of PTP1B inhibitors using FlexX. FlexX dockings with 19 test ligands, whose structures have been determined by X-ray crystallography, were successful in reproducing the experimental conformations within the protein. An increase in biological activity is observed as hydrophobic character of formylchromone derivatives increases. Most ligands bind to the activesite regions of the protein successfully in two different score runs. The Drug score run gave better results than the FlexX score run based on the score, rank, binding modes and bond distance of docked structures. Consensus values from the CScore scoring function are between 3 and 5, suggesting that the scoring scheme is reliable. All formylchromone inhibitors considered in this work show unidirectional binding modes in the active site pocket, which is contrary to the bidirectional X-ray results by Malamas et al. and amino acid residues responsible for such orientation are identified to help further development of the inhibitors.

In a previous study, a catalyst (A) was discovered for oxidative decarboxylation of melanin-concentrating hormone (MCH). To explain the catalytic action and to predict the structure of a new catalyst with improved activity, docking simulations were carried out for the complex formed between A and MCH. The simulations suggested that the three terminal groups of A form a hydrophobic pocket and that van der Waals interactions between the hydrophobic pocket and MCH play a role in stabilizing the MCH-A complex. Consequently, a new catalyst (B) was designed and synthesized in expectation of improved catalytic activity resulting from enhanced van der Waals interactions. The new catalyst, however, showed slightly lower catalytic activity. Lack of the accurate solution structure of MCH may be one of the factors associated with difficulties in prediction of improvement in catalytic activity by purely theoretical means. The results, however, revealed that variation of the acyl portion of the hydroxyproline portion may lead to improved catalysts.

Valerophenone shows a dramatic shift of photoreactivity by a cyclopropyl group at alpha position to the carbonyl group. By the minor change of structure, the diastereoselectivity of the Yang photocyclization is reversed and the ratio of cyclization to elimination products increases significantly.

New unsymmetrical trans-stilbenes have been prepared by the sequential coupling reactions of bromobenzenesulfonate with formylarylboronic acids, benzylphosphonates and arylmagnesium bromides and characterized. The nickel-catalyzed reactions of stilbenesulfonates with aryl Grignard reagents produced the corresponding stilbenes via the nucleophilic aromatic substitution of the neopentyloxysulfonyl group by aryl nucleophiles. The great chemoselectivity of the alkyloxysulfonyl group allows the stepwise construction of unsymmetrical trans-stilbenes possessing terphenyl moieties. This procedure appears to be a promising and conceptually straightforward route for the parallel synthesis of various unsymmetrical stilbenes as well as other highly conjugated hydrocarbons.

A simple and convenient method for the addition of TMSCN to carbonyl compounds is described. NbCl5 is found to possess a strong Lewis acid property to transform carbonyl compounds smoothly to the corresponding cyanosilylether in high yields (up to 99 %) in solvent- free conditions.

We have developed an electrochemical immunosensor that combines the electrocatalytic property of carbon nanotube and the low background current of indium tin oxide (ITO) electrode. A partial monolayer of carboxylated single-walled carbon nanotube (CCNT) is covalently formed on an ITO electrode modified with amine-terminated phosphonic acid. Nonspecifically adsorbed avidin on the hydrophobic sidewalls of CCNT is used to immobilize biotinylated antibody and to reduce the nonspecific binding to CCNT. The biotinylated antimouse IgG bound on avidin and the antimouse IgG conjugated with alkaline phosphatase (ALP) sandwiches a target mouse IgG. ALP catalyzes the conversion of p-aminophenyl phosphate monohydrate into p-aminophenol, which is electrocatalytically oxidized to p-quinone imine on CCNT surface. Moderate electrocatalytic electrode obtained with the combination of CCNT and ITO allows low detection limit (0.1 ng/ mL).

A series of new organic semiconductors hexyl end-capped thiophene-anthracene oligomers containing the anthracene moiety in the center of the oligomers are synthesized. The target oligomers have been obtained by Stille coupling reactions as key step reactions. The synthesized thiophene-anthracene oligomers were characterized by 1H-NMR, 13C-NMR and high-resolution mass spectroscopy, respectively. All of the oligomers are soluble in chlorinated solvents. Their optical, thermal and electrochemical properties were measured. The hexyl end-capped oligomers and their unsubstituted oligomers exhibit the same absorption behavior in dilute toluene solution. Hexyl end-capped bis-terthienylanthracene oligomer is observed to show liquid crystalline mesophase at 166 oC in heating process. The thermal analyses as well as the electrochemical measurement data indicate that the designed materials show better thermal and oxidation stability than the corresponding oligothiophenes without anthracene core. Fluorescence lifetimes and fluorescence quantum yields of the thiophene-anthracene oligomers are measured to be 10-14 ps and 3.4-9.9 × 10?3 which are much shorter and lower than those of oligothiophenes respectively.

A shake-flask method was used to determine the n-octanol/water partition coefficients of sulfamethazine, sulfadimethoxine, sulfamethoxydiazine, sulfamonomethoxine, sulfamethoxazole, sulfaquinoxaline and sulfachloropyrazine from (298.15 to 333.15) K. The results showed that the n-octanol/water partition coefficient of each sulfonamide decreased with the increase of temperature. Based on the fluid phase equilibrium theory, the thermodynamic relationship of n-octanol/water partition coefficient depending on the temperature is proposed, and the changes of enthalpy, entropy, and the Gibbs free energy function for sulfonamides partitioning in n-octanol/ water are determined, respectively. Sulfonamides molecules partitioning in n-octanol/water is mainly an enthalpy driving process, during which the order degrees of system increased. The temperature effect coefficient of n-octanol/water partition coefficient is discussed. The results show that its magnitude is the same as that of values in the literature.

The three major active isoflavonoids (calycosin-7-O-β -glucoside, isomucronulatol 7-O-β-glucoside, formononetin) and two main saponins (astragaloside I, astragaloside IV) in an extract of Radix Astragali were determined using rapid, sensitive, reliable HPLC/UV and LC-ESI-MS/MS methods. The separation conditions employed for HPLC/UV were optimized using a phenyl-hexyl column (4.6 × 150 mm, 5 μm) with the gradient elution of acetonitrile and water as the mobile phase at a flow rate of 1.0 mL/min and a detection wavelength of 230 nm. The specificity of the peaks was determined using a triple quadrupole tandem mass spectrometer equipped with an electrospray ionization (ESI) source that was operated in multiple reaction monitoring (MRM) in the positive mode. These methods were fully validated with respect to the linearity, accuracy, precision, recovery and robustness. The HPLC/UV method was applied successfully to the quantification of three major isoflavonoids in the extract of Radix Astragali. The results indicate that the established HPLC/UV and LC-ESI-MS/MS methods are suitable for the quantitative analysis and quality control of multi-components in Radix Astragali.