Structure Elucidation and Theoretical Investigation of Key Steps in the Biogenetic Pathway of Schisanartane Nortriterpenoids by Using DFT Methods

Rubrifloradilactone C (4), a novel bioactive nortriterpenoid, along with four other nortriterpenoids (1-3, 5) were isolated from Schisandra rubriflora. The structure of 4 was determined by extensive NMR spectral analysis, computational evidence by using t

Synthesis, photoluminescence, and theoretical studies of novel Cu(I) complex

A novel diimine Cu(I)complex [Cu(ABPQ)(DPEphos)]BF4 [ABPQ and DPEphos are acenaphtho[1,2-b]bipyrido[2,3-h:3,2-f]quinoxaline and bis(2-(diphenylphosphanyl)phenyl) ether, respectively] is synthesized, and its photophysical properties are experimentally and theoretically characterized. The emission bands centered at ca. 400/470 and 550 nm of [Cu(ABPQ)(DPEphos)]BF4 are attributed to the ligand-centered pi -> pi* transition and the metal-to-ligand charge transfer d pi(Cu) -> pi*(N-N) transition, respectively. The luminescence quantum yield of [Cu(ABPQ)(DPEphos)]BF4 in CHCl3 is found to be about five times higher than that of [Cu(Phen)(DPEphos)]BF4.

Synthesis, photophysical properties, and theoretical studies on pyrrole-containing bromo Re(I) complex

Two bromo rhenium(I) carbonyl complexes with the formula of [Re(CO)(3)(L)Br], where L = 1,10-phenanthroline (Phen-Re) and 5-(1H-pyrrol-1-yl)-1,10-phenanthroline (Pyph-Re), were successfully synthesized with the aim to analyze the effect of the pyrrole (Py) moiety on the photophysical properties of Pyph-Re. It was found that the triplet metal-to-ligand charge-transfer d pi (Re) --> pi*(N-N) emission of Phen-Re and Pyph-Re centered at ca. 527 nm with the luminescence quantum yield (LQY) of 0.015 and ca. 578 nm with the LQY of 0.011, respectively. At the same time, the geometrical structures of the ground state and the absorption spectral properties of Phen-Re and Pyph-Re were also calculated with the 6-31G* basis set employed on C, H, N, O, and Br atoms, and LANL2DZ adopted on Re atom.

Immunosensor Interface Based on Physical and Chemical Immunogylobulin G Adsorption onto Mixed Self-Assembled Monolayers

An immunosensor interface based on mixed hydrophobic self-assembled monolayers (SAMs) of methyl and carboxylic acid terminated thiols with covalently attached human Immunoglobulin G (hIgG), is investigated. The densely packed and organised SAMs were characterised by contact angle measurements and cyclic voltammetry. The effect of the non-ionic surfactant, Tween 20, in preventing nonspecific adsorption is addressed by ellipsometry during physical and covalent hIgG immobilization on pure and mixed SAMs, respectively. It is clearly demonstrated that nonspecific adsorption due to hydrophobic interactions of hIgG on methyl ended groups is totally inhibited, whereas electrostatic/hydrogen bonding interactions with the exposed carboxylic groups prevail in the presence of surfactant. Results of ellipsometry and Atomic Force Microscopy, reveal that the surface concentration of covalently immobilized hIgG is determined by the ratio of COOH/CH3-terminated thiols in SAM forming solution. Moreover, the ellipsometric data demonstrates that the ratio of bound anti-hIgG/hIgG depends on the density of hIgG on the surface and that the highest ratio is close to three. We also report the selectivity and high sensitivity achieved by chronoamperometry in the detection of adsorbed hIgG and the reaction with its antibody.

Experimental Verification And Theoretical Analysis Of The Relationships Between Hardness, Elastic Modulus, And The Work Of Indentation

The relationship between hardness (H), reduced modulus (E-r), unloading work (W-u), and total work (W-t) of indentation is examined in detail experimentally and theoretically. Experimental study verifies the approximate linear relationship. Theoretical analysis confirms it. Furthermore, the solutions to the conical indentation in elastic-perfectly plastic solid, including elastic work (W-e), H, W-t, and W-u are obtained using Johnson's expanding cavity model and Lame solution. Consequently, it is found that the W-e should be distinguished from W-u, rather than their equivalence as suggested in ISO14577, and (H/E-r)/(W-u/W-t) depends mainly on the conical angle, which are also verified with numerical simulations. (C) 2008 American Institute of Physics.

Experimental and theoretical study on numerical density evolution of short fatigue cracks

Fatigue testing was performed using a kind of triangular shaped specimen to obtain the characteristics of numerical density evolution for short cracks at the primary stage of fatigue damage. The material concerned is a structural alloy steel. The experimental results show that the numerical density of short cracks reaches the maximum value when crack length is slightly less than the average grain diameter, indicating grain boundary is the main barrier for short crack extension. Based on the experimental observations and related theory, the expressions for growth velocity and nucleation rate of short cracks have been proposed. With the solution to phase space conservation equation, the theoretical results of numerical density evolution for short cracks were obtained, which were in agreement with our experimental measurements.

EXPERIMENTAL AND THEORETICAL STUDY OF BINARY DROPLET HEAD-ON COLLISIONS IN MEMS

The experimental and theoretical investigations into the head-on collision between a landing droplet with another one resting on the PDMS substrate were addressed in this talk. The colliding process of the two droplets was recorded with highspeed camera. Four different responses after collision were observed in our experiments: complete rebound, coalescence, partial rebound with conglutination, and coalescence accompanied by conglutination. The contact time between the two colliding droplets was found to be in the range of 10-20 milliseconds. For the complete bouncing case, Hertz contact model was applied to estimate the contact time of the binary head-on colliding droplets with both the droplets considered as elastic bodies. The estimated contact time was in good agreement with the experimental result.

Physical and thermal properties of P2O5-Al2O3-BaO-La2O3 glasses

The physical and thermal properties Of P2O5-Al2O3-BaO-La2O3 glasses were investigated. The effects of glass compositions on the transition temperature, thermal expansion coefficient, density, hardness and refractive index of glasses were studied. The highest hardness of the glasses is 4143.891 MPa and the lowest thermal expansion coefficient of the glasses is 71.770 x 10(-7)/° C. A phosphate glass with high mechanical strength and good thermal characteristic is obtained.

Effect of F- ions on physical and spectroscopic properties of Yb3+-doped TeO2-based glasses

The effects of F- ions on physical and spectroscopic properties of the Yb3+ in tellurite glass system are investigated. The results show that the glass system takes on good thermal stability with the content of ZnF2 lower than 15 mol%, both the emission cross-section and the fluorescence lifetime of Yb3+ ions increase evidently which indicate that such oxyfluoride tellurite glass system is a promising laser host matrix for high power generation. FT-IR spectra were used to analyze the effect of F- ions on the structure of tellurite glasses and OH- groups in this glass system. Analysis demonstrates that addition of fluoride decreases the symmetry of the structure of tellurite glasses which increases the emission cross-section and removes the OH- groups, and which improves the measured fluorescence lifetime of Yb3+ ions. (c) 2004 Elsevier B.V. All rights reserved.

Identification of triosephosphate isomerase (TIM) genes from Microcystis (Cyanobacteria : Chroococcales) and theoretical analyses of the potential of cyanobacterial TIM as a target for designing specific inhibitors

The genes encoding triosephosphate isomerase (TIM) in three species of Microcystis (M. aeruginosa, M. viridis and M. wesenbergii) were investigated. Reverse transcriptase-polymerase chain reaction indicated that they were transcribed in the cells. Analyses showed that their DNA and deduced amino acid sequences were highly conserved between all the three species, only a single nonsynonymous substitution was seen at position 31, from an Asp in M. aeruginosa and M. viridis to Glu in M. wesenbergii. Sequence alignment of these with 12 other known cyanobacterial TIM sequences showed that all the cyanobacterial TIMs had a very high level of amino acid identity (over 50% between each two). Comparison of the cyanobacterial TIMs with other reported TIMs (from diverse lineages of the three Domains) showed that they possessed common active-site residues and sequence motifs. All cyanobacterial TIMs have two common cysteine residues (Cys127 and Cys176), and the Cys176 is almost cyanobacteria-specific with only one exception in Streptomyces coelicolor. Both secondary structure alignment and comparative modelling of Synechocystis sp. TIM showed that Cys176 was located at the hinge region of the flexible loop-6 and might therefore be critical to the movement of TIM's loop-6, which is important to the function of the enzyme. Thus, the cyanobacterial TIM-specific Cys176 may be a potential site for the discovery of suitable drugs against cyanobacteria, and such drugs may have utility in controlling water blooms due to cyanobacteria.

Numerical and theoretical analysis of the crosstalk in linear optical amplifiers

The dynamic characteristics, including the crosstalk and relaxation oscillation, of linear optical amplifiers (LOAs) are investigated by small-signal analysis under an averaging carrier density approximation and compared with the results of numerical simulation. The good agreement between the numerical simulation and the small-signal analysis indicated the averaging carrier density is an appropriate approximation for analyzing LOAs. Theoretical analyzes also show that the dynamic properties of the vertical laser fields dominate the dynamic performance of LOAs. Based on the small-signal analysis, a concise equation for the crosstalk under high bit rate was derived, which can be applied to measure the differential gain of LOAs.