Cyclization of citronellal to p-menthane-3,8-diols in water and carbon dioxide

A clean process has been developed for the synthesis of p-menthane-3,8-diols from cyclization of citronellal in CO2-H2O medium without any additives. With the addition of CO2, the reaction rate could be enhanced about 6 times for the cyclization of citronellal in H2O, because CO2 dissolved into water and formed carbonic acid inducing an increase of the acidity. Although, the reaction conversion in CO2-H2O is slightly lower compared to that obtained with sulfuric acid as catalyst, CO2-H2O could replace the sulfuric acid at a relative higher reaction temperature. The reaction kinetics studies showed that the hydration of isopulegols to p-menthane-3,8-diols is a reversible reaction. The equilibrium constant and the maximum equilibrium yield obtained in CO2-H2O at a range of CO2 pressures are similar to that with sulfuric acid catalyst.

中国北方风成堆积的风化作用与环境变迁—U-Th、~(10)Be及元素地球化学的研究

The surface of the Earth is continuously undergoing changes as a result of weathering-erosion, plate tectonics and volcanic processes. Continental weathering-erosion with its complex rock-water interactions is the central process of global biochemical cycling of elements, and affects the long-term ocean atmosphere budget of carbon dioxide both through the consumption of carbonic acid during silicate weathering and through changes in the weathering and burial rates of organic carbon. Rates of the weathering-erosion depend on a variety of factors, in particular rock properties and chemical composition, climate (especially rainfall), structure, and elevation. They are quite variable on a regional scale. Thus, environmental changes in a region could be indicated by the history of weathering-erosion in the region. Recent attention has focused on increased silicate weathering of tectonically uplifted areas in the India-Asia collision zone as a possible cause for falling atmospheric CO_2 levels in the Cenozoic era. The wind blown dust deposits in the Loess Plateau is derived from the arid and semiarid regions in northwestern China, in turn, where the deposits have been derived from the Qinghai-Xizang Plateau and the high mountains around. Therefore, geochemistry of the wind blown loess-paleosol and red clay sequences may provide insight both to paleoenvironmental changes on the Loess Plateau, and to the uplift and weathering-erosion histories of the Qinghai-Xizang Plateau. In this paper, uranium-thorium series nuclides and cosmogenic ~(10)Be have been employed as tracers of weathering intensities and histories of the dust sediments in the Loess Plateau. Major elements, such as Na, Al, Fe etc., are also used to estimate degree of chemical alteration of the dust sediments and to rebuild the history of weathering on the Loess Plateau. First of all, using a low-level HPGe γ-ray detector, we measured U and Th series nuclides in 170 loess and paleosol samples from five sites in the Loess Plateau, going back 2.6 Ma. The results show that ~(238)U activities are disequilibrium with its daughter nuclide ~(230)Th in young loess-paleosol sequence, indicating that weathering was happened both in dust deposition site and in dust source regions. Using concentrations of ~(238)U and ~(232)Th in the samples, we estimated the amounts of ~(238)U leached out of from paleosols due to weathering. Further, based on analyses of ~(230)Th in paleosols deposited in the past ca. 140 ka, we determined when the paleosols weathered in the source regions. We conclude that most of the weathering in the dust-source regions may have occurred during the interglacials before dust deposition.

CLONING AND QUANTITATIVE ANALYSIS OF THE CARBONIC ANHYDRASE GENE FROM PORPHYRA YEZOENSIS

Carbonic anhydrase (CA), an enzyme that catalyzes the interconversion of CO2 and HCO3-, has a critical role in inorganic carbon acquisition in many kingdoms, including animals, plants, and bacteria. In this study, the full-length cDNA of the CA gene from Porphyra yezoensis Ueda (denoted as PyCA) was cloned by using an expressed sequence tag (EST) and rapid amplification of cDNA ends (RACE). The nucleotide sequence of PyCA consists of 1,153 bp, including a 5' untranslated region (UTR) of 177 bp, a 3' UTR of 151 bp, and an open reading frame (ORF) of 825 bp that can be translated into a 274-amino-acid putative peptide with a molecular mass (M) of 29.8 kDa and putative isoelectric point (pI) of 8.51. The predicted polypeptide has significant homology to the beta-CA from bacteria and unicellular algae, such as Porphyridium purpureum. The mRNA in filamentous thalli, leafy thalli, and conchospores was examined, respectively, by real-time fluorescent quantitative PCR (qPCR), and the levels of PyCA are different at different stages of the life cycle. The lowest level of mRNA was observed in leafy thalli, and the level in filamentous thalli and in the conchospores was 4-fold higher and 10-fold higher, respectively.

An Amino Acid Substitution Matrix for Protein Conformation Identification

Amino acid substitution matrices play an essential role in protein sequence alignment, a fundamental task in bioinformatics. Most widely used matrices, such as PAM matrices derived from homologous sequences and BLOSUM matrices derived from aligned segments of PROSITE, did not integrate conformation information in their construction. There are a few structure-based matrices, which are derived from limited data of structure alignment. Using databases PDB_SELECT and DSSP, we create a database of sequence-conformation blocks which explicitly represent sequence-structure relationship. Members in a block are identical in conformation and are highly similar in sequence. From this block database, we derive a conformation-specific amino acid substitution matrix CBSM60. The matrix shows an improved performance in conformational segment search and homolog detection.

Preparation And Tribology Studies of Alkyl Carboxylic Acid Monolayer Films on Pei-Coated Glass Substrate

首次在涂敷PEI的玻璃表面上制备了癸酸及全氟癸酸的单分子层膜。研究了成膜机理及摩擦特性。结果表明。脱水剂DCCD促进了癸酸或全氟癸酸与PEI酞胺化的反应。导致两种羧酸在PEI表面产生了靠化学键（酞胺键）连接的稳定的单分子层膜,摩擦、磨损实验表明。单分子层有机膜的摩擦特性受膜的组成、表面能及有序性和堆积密度的重要影响。表面能越低,有序性和堆积密度越高。摩擦系数越低。与碳氢化合物相比。碳氟化合物形成的有序膜具有更高的强度和抗磨性能。

Preparation and Tribological Studies of Stearic Acid Self-Assembled Monolayers on Polymer-Coated Silicon Surface

We present a good alternative method to improve the tribological properties of polymer films by chemisorbing a long-chain monolayer on the functional polymer surface. Thus, a novel self-assembled monolayer is successfully prepared on a silicon substrate coated with amino-group-containing polyethyleneimine (PEI) by the chemical adsorption of stearic acid (STA) molecules. The formation and structure of the STA-PEI film are characterized by means of contact-angle measurement and ellipsometric thickness measurement, and of Fourier transformation infrared spectrometric and atomic force microscopic analyses. The micro- and macro-tribological properties of the STA-PEI film are investigated on an atomic force microscope (AFM) and a unidirectional tribometer, respectively. It has been found that the STA monolayer about 2.1-nm thick is produced on the PEI coating by the chemical reaction between the amino groups in the PEI and the carboxyl group in the STA molecules to form a covalent amide bond in the presence of N,N'-dicyclohexylcarbodiimide (DCCD) as a dehydrating regent. By introducing the STA monolayer, the hydrophilic PEI polymer surface becomes hydrophobic with a water contact angle to be about 105degrees. Study of the time dependence of the film formation shows that the adsorption of PEI is fast, whereas at least 24 h is needed to generate the saturated STA monolayer. Whereas the PEI coating has relatively high adhesion, friction, and poor anti-wear ability, the STA-PEI film possesses good adhesive resistance and high load-carrying capacity and anti-wear ability, which could be attributed to the chemical structure of the STA-PEI thin film. It is assumed that the hydrogen bonds between the molecules of the STA-PEI film act to stabilize the film and can be restored after breaking during sliding. Thus, the self-assembled STA-PEI thin film might find promising application in the lubrication of micro-electromechanical systems (MEMS).

Effects of Molecular Length, Ortientation and Amino Acid Mutation on Kinetics of Selectin/Ligand interactions

Receptor/ligand interactions are basic issues to cell adhesion, which are important to many physiological and pathological processes such as lymphocyte-mediated cytotoxicity, tumor metastasis and inflammatory reactionl. Selectin/carbohydrate ligand bindings have been found to mediate the fast rolling of leukocytes on activated endothelial monolayer. Kinetic rate and binding affinity constants are essential determinants of cell adhesion...