Density functional theory study of the mechanism of the proline-catalyzed intermolecular aldol reaction

Transition structures associated with the C-C bond-formation step of the proline-catalyzed intermolecular aldol reaction between acetone and isobutyraldehyde have been studies using density functional theory methods at the B3LYP/6-31G** computational level. A continuum model has been selected to represent solvent effects. For this step, which is the stereocontrolling and rate-determining step, four reactive channels corresponding to the syn and anti arrangement of the active methylene of the enamine relative to the carboxylic acid group of l-proline and the re and si attack modes to both faces of the aldehyde carbonyl group have been analyzed. The B3LYP/6-31G** energies are in good agreement with experiment, allowing us to explain the origin of the catalysis and stereoselectivity for these proline-catalyzed aldol reactions. Received: 2 April 2002 / Accepted: 18 July 2002 / Published online: 11 October 2002 Acknowledgements. This work was supported by research funds provided by the Ministerio de Educación y Cultura of the Spanish Government by DGICYT (project PB98–1429). All the calculations were performed on a Cray–Silicon Graphics Origin 2000 of the Servicio de Informática de la Universidad de Valencia. We are most indebted to this center for providing us with computer capabilities. Correspondence to: L. R. Domingo e-mail: domingo@utopia.uv.es     

Simultaneous hydrogen and peroxide production by photocatalytic water splitting

Photocatalytic oxidation of water is a promising method to realize large-scale H₂O₂ production without a hazardous and energy-intensive process. In this study, we introduce a Pt/TiO₂(anatase) photocatalyst to construct a simple and environmentally friendly system to achieve simultaneous H₂ and H₂O₂ production. Both H₂ and H₂O₂ are high-value chemicals, and their separation is automatic. Even without the assistance of a sacrificial agent, the system can reach an efficiency of 7410 and 5096 μmol g^–1 h^–1 (first 1 h) for H₂ and H₂O₂, respectively, which is much higher than that of a commercial Pt/TiO₂(anatase) system that has a similar morphology. This exceptional activity is attributed to the more favorable two-electron oxidation of water to H₂O₂, compared with the four-electron oxidation of water to O₂.     

Microstructure and electrical properties of BaTiO<Subscript>3</Subscript> and (Ba,Sr)TiO<Subscript>3</Subscript> ferroelectric thin films on nickel electrodes

Nickel thin films have been sputtered on standard Si/SiO₂ substrates with TiO₂ as an adhesive layer. The thermal stability of these substrates was analyzed. SEM images show an increase in grain size with annealing temperature. They were found to be stable till 800°C, beyond which the nickel layer disintegrated. These substrates were used for deposition of BaTiO₃ and (Ba,Sr)TiO₃ dielectric thin films under a reducing atmosphere. The dielectric thin films were processed with various pyrolysis and annealing temperatures in order to optimize the dielectric properties. Increased pyrolysis temperatures showed an increase in the grain size. Results on these nickelised substrates were finally compared with dielectric films deposited on platinized silicon substrates under identical conditions but crystallized in an oxygen atmosphere.     

Fabrication of lead titanate single crystalline nanowires by hydrothermal method and their characterization

Single crystalline nanowires of lead titanate (PbTiO₃) were fabricated by hydrothermal method at 200°C using lead acetate and n-tetrabutyl titanate as starting materials, where sodium hydroxide was served as a mineralizer. Crystalline phases, microstructure and optical properties of PbTiO₃ nanowires were investigated. The PbTiO₃ nanowires were uniform and continuous along the long axis, and were composed of single crystalline PbTiO₃ with a tetragonal perovskite structure. The diameter of a single nanowire was around 12 nm and the length reached up to 3 μm. The chemical composition of the samples and the valence states of elements were determined by X-ray photoelectron spectroscopy (XPS). The ultraviolet/visible absorption spectroscopic investigation suggested that the absorption edge of optical transition of the first excitonic state occurred at around 320 nm. A blue-green light emission peaking at about 471 nm (2.63 eV) is observed at room temperature, and the intensity of this emission increased with increasing excitation wavelength. Oxygen vacancies are responsible for the light emission of PbTiO₃ nanowires.     

Studies on stereoselective approaches to β-carboline derivatives

Transformation of β-carboline derivatives into optically active entities were studied and the de and ee values of the resulted compounds were detected. Dedicated to Professor Károly Lempert on his 80th birthday.     

A Theoretical Study on the Conductivity of Carbon Doped BNNT

From the changes in energy band, density of state (DOS) and electronic structure calculated by the DFT/B3LYP method, the conductivity of carbon doped boron‐nitride nanotube (BNNT), which is formed by C‐C bond substituting B‐N bond, was discussed. The results indicate that the substitution will strengthen the conductivity of the tube, and its semi‐conductivity might be adjusted by controlling the substitution.     

Substituent effects on monoboronic acid sensors for saccharides based on N-phenyl-1,8-naphthalenedicarboximides

In the course of our investigations on new monoboronic acid saccharide sensors with C(0) spacers, a series of probes 1-6 based on 1,8-naphthalenedicarboximide were synthesized. Sensor 1 displays features typical of PET monoboronic acid sensors and shows high selectivity to fructose. Sensor 2 exhibits a novel dual emission and remarkable sensitivity for glucose relative to fructose and galactose through subtle changes in pH. Sensor 3 displays significantly enhanced fluorescence in the presence of galactose at low pH. Although probes 4-6 exhibit unique properties such as high quantum yield (Phi(F) = 0.407) and excellent solubility in water, they did not show significant change in fluorescence intensity in the presence of monosaccharides. The effects of substituent on all six probes lend support to the proposed photoelectrochemical model.     

A Novel Preprocessing Algorithm for Three-Way HPLC Data

Orthogonal signal correction (OSC) was a data preprocessing algorithm. It ensured that the filtered information was irrelevant to concentration data while using it to filter the noise from the original data. This paper extended the OSC application range from two-way data to three-way data. Two drug data sets, Enoxacin, Norfloxacin, Ciprofloxacin and Betamethasone, cortisone acetate, prednisone acetate, showed that the application of the OSC algorithm to three-way HPLC data was feasible and needed further research.     

A molecular docking model of SARS-CoV S1 protein in complex with its receptor, human ACE2

The exact residues within severe acute respiratory syndrome coronavirus (SARS-CoV) S1 protein and its receptor, human ACE2, involved in their interaction still remain largely undetermined. Identification of exact amino acid residues that are crucial for the interaction of S1 with ACE2 could provide working hypotheses for experimental studies and might be helpful for the development of antiviral inhibitor. In this paper, a molecular docking model of SARS-CoV S1 protein in complex with human ACE2 was constructed. The interacting residue pairs within this complex model and their contact types were also identified. Our model, supported by significant biochemical evidence, suggested receptor-binding residues were concentrated in two segments of S1 protein. In contrast, the interfacial residues in ACE2, though close to each other in tertiary structure, were found to be widely scattered in the primary sequence. In particular, the S1 residue ARG453 and ACE2 residue LYS341 might be the key residues in the complex formation.     

Synthesis and crystallization kinetics of the novel ion exchanger Na<Subscript>4</Subscript>Ti<Subscript>4</Subscript>Si<Subscript>3</Subscript>O<Subscript>10</Subscript> for cesium removal

Thermodynamics and crystallization kinetics of the hydrothermal synthesis of Na₄Ti₄Si₃O₁₀ (NaTS) were systemically studied by both experiments and model simulation. Experimental results showed that the curve of crystallinity with time was a characteristic signmoid in the shape that indicated the crystallization of Na₄Ti₄Si₃O₁₀ was a typical spontaneous nucleation process on the laboratory scale. Crystallization of NaTS belongs to the liquid-liquid transformation mechanism and the reaction is endothermic (ΔH = 15.3 kJ/mol). A mathematic model of crystallization kinetics was developed to simulate the synthesis of NaTS. Runge-Kutta and simplex methods were adopted to solve the partial differential equations. Model results fitted well with the experimental data and showed that the synthesis process belongs to spontaneous nucleation and crystal growth. Moreover, the very small crystal growth constant (5.6·10⁻⁷) and gel dissolution constant (7.0·10⁻⁷) indicate they are the rate-limiting steps of the whole synthesis process.