The Crystal Structures of Two Calcium(II) Complexes with Pyrazine- 2,6-Dicarboxylate and Water Ligands

The structure of catena-{bis[(μ-aqua)(diaqua)(pyrazine-2,6-dicarboxylato-O,N-μ-O')](calcium(II)} consists of dimeric units composed of two calcium(II) ions, two ligand molecules and six water molecules. The calcium ions are bridged by two bidentate oxygen atoms, each donated by one carboxylic group of the ligand. The Ca(II) ion is also coordinated by one oxygen atom of the second carboxylate group and the hetero-ring nitrogen atom belonging to the same ligand molecule. Both calcium ions in a dimer are bridged to the Ca(II) ions in adjacent dimers by a pair of water molecules forming infinite molecular ribbons. In addition, each Ca(II) ion is coordinated by three water molecules; one of them is used for bridging the adjacent dimer. The coordination polyhedron around the Ca(II) ion is a pentagonal bipyramid with two apices above and one apex below the equatorial plane. The same molecular pattern is observed in the structure of catena-{bis[(μ-aqua)(diaqua)(pyrazine-2,6-dicarboxylato-O,N-μ-O')](calcium(II)} dihydrate which, in addition, contains two solvation water molecules per unit cell. In both compounds the molecular ribbons are held together by extended systems of hydrogen bonds.     

Stability of caffeic acid phenethyl amide (CAPA) in rat plasma

A validated C₁₈ reverse‐phase HPLC method with UV detection at 320 nm was developed and used for the stability evaluation of caffeic acid phenethyl amide (CAPA) and caffeic acid phenethyl ester (CAPE) in rat plasma. CAPA is the amide derivative of CAPE, a naturally occurring polyphenolic compound that has been found to be active in a variety of biological pathways. CAPA has been shown to protect endothelial cells against hydrogen peroxide‐induced oxidative stress to a similar degree to CAPE. CAPE has been reported to be rapidly hydrolyzed in rat plasma via esterase enzymes. CAPA is expected to display a longer half‐life than CAPE by avoiding hydrolysis via plasma esterases. The stability of CAPA and CAPE in rat plasma was investigated at three temperatures. The half‐lives for CAPA were found to be 41.5, 10 and 0.82 h at 25, 37 and 60 °C, respectively. The half‐lives for CAPE were found to be 1.95, 0.35 and 0.13 h at 4, 25 and 37 °C, respectively. The energy of activation was found to be 22.1 kcal/mol for CAPA and 14.1 kcal/mol for CAPE. A more stable compound could potentially extend the beneficial effects of CAPE. Copyright © 2011 John Wiley & Sons, Ltd.     

CdTe纳米棒的合成和性质

用半胱氨酸和巯基乙酸的混合配体作为修饰剂制备了高发光水溶性CdTe纳米棒,同时研究了CdTe纳米棒与高半胱氨酸,酪氨酸,脯氨酸,半胱氨酸,胱氨酸等5种氨基酸之间的相互作用,实验发现CdTe纳米棒纵横比和光致发光可以由回流时间来控制.     

液相色谱法检测化妆品中3种防腐剂

建立了化妆品中防腐剂水杨酸、苯甲酸和山梨酸的高效液相色谱检测方法.试样经乙醇和硫酸处理后,由C18反相色谱柱进行分离,紫外检测器进行检测,用外标法定量.实验结果表明,该方法简便、高效,测定结果准确,适用于化妆品中水杨酸、苯甲酸和山梨酸含量的同时检测.     

Effect of High Pressure on Acid Phosphatase in Milk

Acid phosphatase activity was measured in whole milk, skim milk, acid and rennet wheys before and after subjecting samples to high hydrostatic pressures for 10 min. Whole and skim milks exhibited a significant drop in activity following treatment at pressures in excess of 200 MPa. While rennet whey exhibited similar characteristics, acid whey was more pressure resistant and required pressures in excess of 500 MPa before exhibiting a net loss in activity. Most of the activity was lost in the first 10 min of pressurisation.     

Characterizing the Memory Effect on the amylose tris(3,5-dimethylphenyl) carbamate stationary phase

Acid/base modifiers are sometimes used as additives in normal phase elution on columns packed with CHIRALPAK^® AD^®. They affect enantioseparations in ways that are not understood for the lack of systematic studies, which makes the scale-up of preparative separations difficult to predict. Once a column has been exposed to these modifiers, the selectivity of certain pairs of enantiomers may change, for the better or the worse. Numerous molecules that are affected by this phenomenon are listed in the literature. We selected five of them, the selectivity of which changes as more acidic or basic solutions are percolated through the column. The selectivity of ketoprofen, 4-chlorophenylalanine methyl and ethyl esters improves as a solution of Ethanesulfonic Acid is percolated through the column. The selectivity of Propranolol HCl and Tröger’s base increases as a solution of diisopropylamine is percolated through the column. Each one of these five compounds is inversely affected by the percolation of the opposite acid/base solution. We used trans-Stilbene Oxide (tso) as a “standard” to determine the columns stability because no Memory Effect is observed for it (its retention, enantioselectivity, and resolution remain constant). Karl Fisher titrations showed that only slight changes in the water content of the mobile phase occurred, and that a unique water to polymer moiety ratio is important. Analytical studies of the stationary phase suggest that slow protonation/deprotonation of water attached to the carbamate moiety may be responsible for the acid/base Memory Effect. Finally, we showed that the Memory Effect can be minimized by percolating through the column a sufficiently concentrated solution of the appropriate acid or base. Thus, columns that were unreliable for method development, due to the Memory Effect, can now be used. As a result, the need to store several CHIRALPAK AD columns, specific for each condition of the Memory Effect, is eliminated.     

Flexible soft glass capillary columns vs. flexible fused silica capillary columns for gas chromatography-a critique

The gas chromatographic use of flexible thin walled soft glass capillary columns coated with non-polar stationary phases is compared to similar columns made of fused silica glass. With non-polar soft glass columns, the use of surface roughening viagaseous HCI followed by a Carbowax 20 M pretreatment gave adsorptive phenomena, and thermal instability. With very polar soft glass columns where a variety of cyanopropyl silicone phases were coated directly onto the NaCI crystal matrix, adsorptive effects were again prominent and frequent break-down in film stability with time, was also observed. These undesirable effects were due to the presence of metal oxides in the soft glass. Attempts to remove these materials from the thin walled soft glass surface by means of acid leaching produced significant brittleness. This deleterious result was further increased by attempts at high temperature silylation or polysiloxane deactivation. In sharp contrast, the fused silica surface was essentially free of metal oxides and the surface silanol groups are easily neutralized by silylation or polysiloxane deactivation techniques. No brittleness was observed following these procedures. An increasing series of high molecular weight, viscous, polymeric vinyl containing non-polar and highly polar stationary phases have been produced which readily wet the surface of the fused silica and are easily crosslinked in the presence of free radical generators. These columns are essentially free of all the problems noted with flexible thin walled soft glass. When all of the parameters involved in the fabrication of a glass capillary column are assessed, it appears at this time, that the flexible fused silica glass column with cross linked phases approaches the “ideal” capillary column.     

The nanoscale description of acid penetration to the gold colloids encapsulated in silica sol–gel matrix

Various sizes of gold nano colloidal particles ranging from 5 nm to 100 nm of size were encapsulated in a silica based sol–gel, and these surfaces were exposed to a pH 1 acid solution. This enabled us to observe the process of solvent intrusion and interaction with gold colloids by the absorption spectrum as a function of time. The rate was analyzed by a single exponential analytical function, and the maximum rate was found for gold colloid of 15 nm size. The least acid interaction and colour change was observed for the size of 60 nm. It was speculated that the surface of these gold colloids were homogeneously covered by the sodium tetra-borate buffer which insulated silica gel layer, thus avoiding direct contact of the acid with the surface of the gold colloid. This study confirmed that the nano scale dopant size affects the rate of solvent penetration into a sol–gel cavity.     

Conformation, activity and proteolytic stability of acid phosphatase on clay minerals and soil colloids from an Alfisol

The present study was carried out to investigate the conformation, enzymatic activity and proteolytic stability of acid phosphatase on montmorillonite, kaolinite and soil colloids from an Alfisol by means of circular dichroism (CD) spectroscopy, isothermal titration microcalorimetry (ITC) and biochemical assay, respectively. The results showed that the secondary structure of phosphatase was changed from disordered type to ordered form during adsorption/desorption cycle, organic substance and 2:1-clay mineral in Brown Soil benefited the formation of ordered structure. Enzymatic activity of phosphatase was inhibited while the proteolytic stability was promoted after the interaction with active particles from permanent charge soil. The decrease of enzymatic activity and the increase of proteolytic stability resulted by montmorillonite and organic colloid were both greater than that by kaolinite and inorganic colloid, which was in consistent with the extent of structural change induced by different colloid particles. Thus, one of the most significant factors responsible for the variation of enzymatic activity and proteolytic stability might be the hiding or even damage of active sites and the irrecognition of cleavage sites in enzyme molecules induced by the formation of ordered structure. The information obtained in this study is of crucial significance for the understanding of the behavior and fate of extracellular enzymes in soils with permanent charges.     

Some Information Theoretic Ideas Useful in Statistical Inference

In this paper we discuss four information theoretic ideas and present their implications to statistical inference: (1) Fisher information and divergence generating functions, (2) information optimum unbiased estimators, (3) information content of various statistics, (4) characterizations based on Fisher information. This paper was written while the first author was visiting the University of Cyprus, Department of Mathematics and Statistics.