Benefits of Anthocyanin-Rich Black Rice Fraction and Wood Sterols to Control Plasma and Tissue Lipid Concentrations in Wistar Kyoto Rats Fed an Atherogenic Diet

Background: This study reports on the relative effects of administrating a cyanidin-3-O-glucoside-rich black rice fraction (BRF), a standardized wood sterol mixture (WS), and a combination of both to lower plasma and target tissue lipid concentrations in Wistar Kyoto (WKY) rats fed atherogenic diets. Methods: Male WKY (n = 40) rats were randomly divided into five groups, which included a nonatherogenic control diet and atherogenic diets that included a positive control and atherogenic diets supplemented with BRF or WS, respectively, and a combination of both BRF + WS. Plasma and target tissue liver, heart and aorta cholesterol, and triacylglycerides (TAG) content were also measured. Results: Rats fed atherogenic diets exhibited elevated hyperlipidemia compared to counterparts fed nonatherogenic diets (p < 0.001); this effect was mitigated by supplementing the atherogenic diets with BRF and WS, respectively (p < 0.05). Combining BRF with WS to enrich the supplement lowered cholesterol similar to the WS effect (p < 0.05) and lowered TAG characteristic to the BRF effect (p < 0.05). Conclusions: Rats fed diets containing BRF or WS effectively mitigate the hypercholesterolemia and elevated TAG induced by feeding an atherogenic diet. The benefit of adding BRF + WS together is relevant to the lipid parameter measured and is target tissue-specific.     

Base stacking in cytosine dimer. A comparison of correlated ab initio calculations with three empirical potential models and density functional theory calculations

Ab initio MP2/6-31G* interaction energies were calculated for more than 80 geometries of stacked cytosine dimer. Diffuse polarization functions were used to properly cover the dispersion energy. The results of ab initio calculations were compared with those obtained from three electrostatic empirical potential models, constructed as the sum of a Lennard-Jones potential (covering dispersion and repulsion contributions) and the electrostatic term. Point charges and point multipoles of the electrostatic term were also obtained at the MP2/6-31G* level of theory. The point charge MEP model (atomic charges derived from molecular electrostatic potential) satisfactorily reproduced the ab initio data. Addition of π-charges localized below and above the cytosine plane did not affect the calculated energies. The model employing the distributed multipole analysis gave worse agreement with the ab initio data than the MEP approach. The MP2 MEP charges were also derived using larger sets of atomic orbitals: cc-pVDZ, 6-311 + G(2d, p), and aug-cc-pVDZ. Differences between interaction energies calculated using these three sets of point charges and the MP2/6-31G* charges were smaller than 0.8 kcal/mol. The correlated ab initio calculations were also compared with the density functional theory (DFT) method. DFT calculations well reproduced the electrostatic part of interaction energy. They also covered some nonelectrostatic short-range effects which were not reproduced by the empirical potentials. The DFT method does not include the dispersion energy. This energy, approximated by an empirical term, was therefore added to the DFT interaction energy. The resulting interaction energy exhibited an artifact secondary minimum for a 3.9-4.0 vertical separation of bases. This defect is inherent in the DFT functionals, because it is not observed for the Hartree-Fock + dispersion interaction energy.© 1996 John Wiley & Sons, Inc.     

Efficient algorithm for quantitative assessment of similarities among atoms in molecules

A new algorithm for quantitative assessment of similarity between two atoms in molecules is presented. Both the atomic similarity index and its derivatives with respect to the three Euler angles that describe the mutual orientation of the atoms under comparison are computed efficiently by taking advantage of the recently developed analytical representations for atomic zero-flux surfaces. The use of such representations makes it possible to substantially enhance the accuracy of the computed similarity indices without increasing the cost of their evaluation. Numerical tests involving oxygen atoms in several carbonyl compounds demonstrate the ability of the new algorithm to discern small changes in atomic similarity that are brought about by second-neighbor effects. Comparisons among hydrogen atoms in the acrolein molecule reveal the usefulness of the similarity index in detection and quantification of the effects of steric interactions on atomic shapes. © 1996 by John Wiley & Sons, Inc.     

Ring-opening of 1,2,3,4-tetramethyl-1,2,3,4-tetraphenylcyclotetrasilane in the presence of transition metal catalysts

Ring opening of 1,2,3,4-tetramethyl-1,2,3,4-tetraphenylcyclotetrasilane in the presence of various transition metal catalysts has been studied. Pd and Pt compounds are most active. Compounds with bulky ligands [e.g., Pd(PPh₃)₄] lead to the formation of “dimeric” cyclooctasilanes. Compounds with less bulky groups convert monomer to dimers and mixture of oligomers and polymers. Reactions with the all-trans monomer, tttt-(MePhSi)₄, result in the formation of stereoregular dimer, presumably all-trans, tttttttt-(MePhSi)₈, in high yields. Reactions in the presence of oxygen lead to the formation of polymers with inserted oxygen atoms in the main chain. © 1996 John Wiley & Sons, Inc.     

Stabilization of Catalytically Active Cu+ Surface Sites on Titanium–Copper Mixed‐Oxide Films

The oxidation of CO is the archetypal heterogeneous catalytic reaction and plays a central role in the advancement of fundamental studies, the control of automobile emissions, and industrial oxidation reactions. Copper‐based catalysts were the first catalysts that were reported to enable the oxidation of CO at room temperature, but a lack of stability at the elevated reaction temperatures that are used in automobile catalytic converters, in particular the loss of the most reactive Cu⁺ cations, leads to their deactivation. Using a combined experimental and theoretical approach, it is shown how the incorporation of titanium cations in a Cu₂O film leads to the formation of a stable mixed‐metal oxide with a Cu⁺ terminated surface that is highly active for CO oxidation.     

Au, Ge, and AuGe nanoparticles fabricated by laser ablation

A eutectic AuGe target immersed in distilled water was ablated by pulsed ultraviolet laser light. The structure of the ablated material was investigated by high-resolution transmission electron microscopy (HRTEM). The images show formation of nanowire structures of AuGe up to 100 nm in length, with widths of 5–10 nm. These nanostructures have Ge content significantly lower than the target material. Electron diffraction demonstrates that they crystallize in the α-AuGe structure. For comparison, laser ablation of pure Au and pure Ge targets was also performed under the same conditions. HRTEM shows that Ge forms spherical nanoparticles with a characteristic size of ~30 nm. Au forms spherical nanoparticles with diameters of ~10 nm. Similar to AuGe, it also forms chainlike structures with substantially lower aspect ratio.     

Local convergence of quasi-Newton methods for B-differentiable equations

We study local convergence of quasi-Newton methods for solving systems of nonlinear equations defined by B-differentiable functions. We extend the classical linear and superlinear convergence results for general quasi-Newton methods as well as for Broyden's method. We also show how Broyden's method may be applied to nonlinear complementarity problems and illustrate its computational performance on two small examples.