Characterization of protein adducts formed by toxic alkaloids by nano‐scale liquid chromatography with mass spectrometry

Betel quid chewing is associated with cytotoxicity, genotoxicity and carcinogenicity in diseases such as oral cancer, liver cirrhosis, hepatocellular carcinoma and diabetes mellitus. Arecoline and arecaidine, which are the main alkaloids in the areca nut, are potential exposure biomarkers in habitual betel quid users. This study developed a method of detecting arecoline‐ and arecaidine‐protein adducts by mass spectrometry (MS). First, bovine serum albumin was used to predict and confirm the binding sites of proteins modified by arecoline or arecaidine. Cells were then treated with arecoline to identify new protein adducts after cellular metabolic processing. Finally, human plasma was used to model long‐term exposure to arecoline and arecaidine. Following isolation proteins were tryspin digested. The peptides afforded were separated and analyzed by nano‐scale liquid chromatography with MS using an LTQ Orbitrap mass spectrometer. The experimental findings showed that cysteine is the predominant amino acid in protein adduct formation. The goal of this study was to establish a screening platform for identifying novel protein adducts that form covalent bonds with arecoline or arecaidine. Use of this strategy to survey new protein‐toxic adducts may help to identify novel biomarkers of betel nut exposure. Copyright © 2012 John Wiley & Sons, Ltd.     

Formation of Columnar Liquid Crystals on the Basis of Unconventional Triazine‐Based Dendrimers by the C3‐Symmetric Approach

Two series of unconventional triazine‐based dendrimers with C₂ symmetry and C₃ symmetry were prepared. The newly prepared C₃‐symmetrical dendrimers were characterized by ¹H and ¹³C NMR spectroscopy, mass spectrometry, and elemental analysis. Differential scanning calorimetry, polarizing microscopy, and powder XRD showed that the C₃‐symmetrical dendrimers display columnar liquid‐crystalline phases during thermal treatment, but the C₂‐symmetrical dendrimers were not observed to behave correspondingly. The molecular conformations of C₃‐ and C₂‐symmetrical dendrimers were obtained by computer simulation with the MM2 model of the CaChe program in the gas phase. The simulation results reasonably explain the different mesogenicities of C₃‐ and C₂‐symmetric dendrimers. This new strategy should be applicable to other types of unconventional dendrimers with rigid frameworks for displaying columnar liquid‐crystalline behavior.     

Relating the Composition of PtxRu100−x/C Nanoparticles to Their Structural Aspects and Electrocatalytic Activities in the Methanol Oxidation Reaction

A controlled composition‐based method—that is, the microwave‐assisted ethylene glycol (MEG) method—was successfully developed to prepare bimetallic Pt_xRu_100?x/C nanoparticles (NPs) with different alloy compositions. This study highlights the impact of the variation in alloy composition of Pt_xRu_100?x/C NPs on their alloying extent (structure) and subsequently their catalytic activity towards the methanol oxidation reaction (MOR). The alloying extent of these Pt_xRu_100?x/C NPs has a strong influence on their Pt d‐band vacancy and Pt electroactive surface area (Pt ECSA); this relationship was systematically evaluated by using X‐ray absorption (XAS), scanning electron microscopy (SEM) coupled with energy dispersive X‐ray spectroscopy (EDX), transmission electron microscopy (TEM), density functional theory (DFT) calculations, and electrochemical analyses. The MOR activity depends on two effects that act in cooperation, namely, the number of active Pt sites and their activity. Here the number of active Pt sites is associated with the Pt ECSA value, whereas the Pt‐site activity is associated with the alloying extent and Pt d‐band vacancy (electronic) effects. Among the Pt_xRu_100?x/C NPs with various Pt:Ru atomic ratios (x=25, 50, and 75), the Pt₇₅Ru₂₅/C NPs were shown to be superior in MOR activity on account of their favorable alloying extent, Pt d‐band vacancy, and Pt ECSA. This short study brings new insight into probing the synergistic effect on the surface reactivity of the Pt_xRu_100?x/C NPs, and possibly other bimetallic Pt‐based alloy NPs.     

Thermal,mechanical, and morphological properties of novolac‐type phenolic resin blended with fullerenol polyurethane and linear polyurethane

Fullerenol polyurethane (C₆₀‐PU) and linear polyurethane (linear‐PU) modified phenolic resins were prepared in this study. Phenolic resin/C₆₀‐PU and phenolic resin/linear‐PU blends show good miscibility as a result of the intermolecular hydrogen bonding existing between phenolic resin and PU modifiers. DSC and thermogravimetric analysis methods were used to study the thermal properties of phenolic resin blended with different types of PUs. The intermolecular hydrogen bonding that existed between phenolic resin and C₆₀‐PU was investigated by Fourier transform infrared spectroscopy. The morphology and mechanical properties of phenolic resin/C₆₀‐PU and phenolic resin/linear‐PU blends were also investigated. The char yield of the modified phenolic resins decreased with increasing PU modifier content. Significant improvement in the toughness of the modified phenolic resins was observed. The improvements of impact strength were 27.4% for the phenolic resin/linear‐PU system and 54.3% for the phenolic resin/C₆₀‐PU system, respectively, both with 3 phr linear‐PU and C₆₀‐PU content. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2436–2443, 2001     

A theoretical study on the mechanism, regiochemistry, and stereochemistry of hydrosilylation catalyzed by cationic ruthenium complexes

Density functional calculations have been carried out to understand the anti-addition stereochemistry and Markovnikov regiochemistry of the hydrosilylation of terminal alkynes and the endo-dig product of intramolecular hydrosilylation of homopropargyl alcohols catalyzed by cationic cyclopentadienyl-ruthenium complexes. It has been found that hydride or silyl insertion is concerted with the oxidative addition of the H-Si bond. Hydride insertion is much more favorable than silyl insertion. Such a hydride insertion nicely reproduces the observed regioselectivity, while silyl insertion would predict the opposite result. The hydride insertion leads to the formation of a eta(2)-vinylruthenium intermediate for the reaction of acetylene or a metallacyclopropene intermediate for the reaction of propyne. In the formation of both intermediates, there is a C(alpha)-C(beta) bond rotation so that the transferring hydride becomes anti to the silyl group. This is followed by a facile reductive alpha-silyl migration transition state, which results in the overall anti-addition stereochemistry. The proposed mechanism also rationalizes the observed regio- and stereochemistry of the intramolecular reaction.     

Organic peroxide assisted transition metal hydrosilylation catalysis

Summary The catalytic activity of rhodium complexes for the hydrosilylation of substrates such as alkenes, 1,3-dienes, 1-alkynes, or ketones, is enhanced by the addition of organic oxidizing agents, such ast-butyl hydroperoxide, hydrogen peroxide, orm-chloroperbenzoic acid. Similar enhancement is found for the Group VIA hexacarbonyls in the hydrosilylation of 1,3-dienes.     

Numerical study of flow and thermal behaviour of lid‐driven flows in cavities of small aspect ratios

Numerical study has been performed to investigate the effects of cavity shape on flow and heat transfer characteristics of the lid‐driven cavity flows. Dependence of flow and thermal behaviour on the aspect ratio of the cavities is also evaluated. Three types of the cross‐sectional shape, namely, circular, triangular, and rectangular, and four aspect ratios, 0.133, 0.207, 0.288, and 0.5, are taken into account to construct twelve possible combinations; however, attention is focused on the small‐aspect‐ratio situations. Value of the Reynolds number considered in this study is varied between 100 and 1800. For the cases considered in this study a major clockwise vortex driven by the moving lid prevailing in the cavity is always observed. When the Reynolds number is fixed, the rectangular cavity produces strongest lid‐driven flow, and the triangular cavity weakest. For the cases at small aspect ratio and low Reynolds number, the streamlines appear symmetric fore‐and‐aft with respect to the central line at x/L = 0.5. Data for the local and average Nusselt numbers are also provided. For rectangular cavities, it is observed that case 1/5R produces the highest average Nusselt number at any Reynolds number. Among the twelve possible geometric cases considered herein, the highest and lowest average Nusselt numbers are found with cases 1/6T and 1/2C, respectively. Copyright © 2006 John Wiley & Sons, Ltd.     

Synthesis,characterization, and properties of novel ladderlike phosphorus‐containing polysilsesquioxanes

Novel ladderlike polysilsesquioxanes that contain phosphorus were successfully synthesized by the sol–gel method. The polysilsesquioxanes were characterized by Fourier transform infrared spectroscopy, ²⁹Si NMR, and X‐ray diffraction. The characterizations demonstrated that the polymer possesses a typical ladderlike structure. The thermogravimetric and differential scanning calorimetric data revealed that the polysilsesquioxanes possess excellent thermal stability. A kinetic analysis of thermal degradation showed that the activation energy of thermal degradation is 187 kJ/mol, according to Kissinger's method. The activation energy of thermal degradation normally increases with conversion (from 171 to 309 kJ/mol) according to Ozawa's method. The average activation energy, calculated by Ozawa's method, was 209 kJ/mol. The scanning electron microscopic photograph and Si and P mappings of ladderlike polysilsesquioxanes showed that the particles were uniformly dispersed at the molecular level and that the sizes of the polysilsesquioxane particles were less than 100 nm. The ultraviolet–visible spectra of the ladderlike polysilsesquioxanes revealed no absorbance in the range of 400–800 nm. Ladderlike polysilsesquioxanes possess excellent optical transparency and excellent flame retardance. This transmittance may be used as a criterion for identifying the formation of a homogeneous phase. These polymers have great potential in waveguide applications. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1371–1379, 2003