Balancing kinetic and thermodynamic control: the mechanism of carbocation cyclization by squalene cyclase

Molecular dynamics simulations with a combined quantum mechanical and molecular mechanical (QM/MM) potential have been carried out to investigate the squalene-to-hopene carbocation cyclization mechanism in squalene-hopene cyclase (SHC). The present study is based on free energy simulations by constructing the free energy surface for the cyclization steps along the reaction pathway. The picture that emerges for the carbocation cyclization cascade is a delicate balance of thermodynamic and kinetic control that ultimately favors the formation of the final hopanoids carbon skeleton. A key finding is that the five- to six-membered ring expansion process is not a viable reaction pathway for either C- or D-ring formation in the cyclization reaction. The only significant intermediate is the A/B-bicyclic cyclohexyl cation (III), from which two asynchronous concerted reaction pathways lead to, respectively, the 6,6,6,5-tetracyclic carbon skeleton and the 6,6,6,6,5-pentacyclic hopanoids. Experimentally, these two products are observed to have 1% and 99% yields, respectively, in the wild-type enzyme. We conclude that the product distribution in the wild-type enzyme is dictated by kinetic control of these two reaction pathways.     

Dithia-crown-annelated tetrathiafulvalene disulfides: synthesis, electrochemistry, self-assembled films, and metal ion recognition

The synthesis and electrochemistry of a series of tetrathiafulvalene (TTF) and dithia-crown-TTF derivatives attached with one or two disulfide group(s) 7a-f are reported. The self-assembled monolayers (SAMs) of these TTF disulfides on gold were prepared and characterized by reflection-absorption infrared spectroscopy. The SAMs are extremely stable under a wide variety of conditions and over extended periods of time and show remarkable electrochemical stability upon repeated potential scans. SAMs of the crown-TTF disulfides 7c,d,f can recognize alkali metal ions, and the process can be monitored following the electrochemical potential shift of the surface-confined TTF group.     

Capillary electrophoresis with amperometric detection of curcumin in Chinese herbal medicine pretreated by solid-phase extraction

In the present study, curcumin from Chinese herbal medicine turmeric was determined by capillary electrophoresis with amperometric detection (CE-AD) pretreated by a self-designed, simple, inexpensive solid-phase extraction (SPE) cartridge based on the material of tributyl phosphate resin. An average concentration factor of 9 with the recovery of > 80% was achieved when applied to the analysis of curcumin in extracts of tumeric. Under the optimized CE-AD conditions: a running buffer composed of 15 mM phosphate buffer at a pH 9.7, separation voltage at 16 kV, injection for 6 s at 9 kV and detection at 1.20 V, CE-AD with SPE exhibited low detection limit as 3 x 10(-8) mol/l (S/N = 3), high efficiency of 1.0 x 10(5) N, linear range of 7 x 10(-4) -3 x 10(-6) mol/l (r = 0.9986) for curcumin extracted from light petroleum. The method developed resulted in enhancement of the detection sensitivity and reduction of interference from sample matrix in complicated samples and exhibited the potential application for routine analysis, especially in food, because a relatively complete process of sample treatment and analysis was described.     

利用压电频移法测定水中的痕量亚硝酸盐

提出了利用压电频移法测定亚硝酸盐的方法。方法以碘离子与亚硝酸根之间的氧化还原反应为依据，通过测定由反应生成的碘所引起的压电晶体频率的变化，在被萃取水相中亚硝酸盐浓度为０．００９￣２．３ｍｇ／Ｌ范围内，频移值与浓度成正比：ΔＦ＝５．８＋２．５×１０＾３Ｃ（ｍｇ／Ｌ），ｒ＝０．９９０１。方法简便，用于天然水中亚硝酸盐的测定，结果令人满意。     

Thermal degradation of wood treated with guanidine compounds in air: Flammability study

Wood has been treated with guanidine phosphate, guanidine nitrate, guanidine carbonate and guanidine chloride to impart flame retardancy. The samples were subjected to differential thermal analysis (DTA) and thermogravimetry (TG) from ambient temperature to 800°C in air to study their thermal behaviors. From the resulting data, kinetic parameters for different stages of thermal degradation were obtained following the method of Broido. For the decomposition of wood and flame retardant wood, the activation energy was found to decrease from 116 to 54 kJ mol^–1; the char yield was found to increase from 5.6 to 34.9%, LOI from 18 to 41.5, which indicated that the flame retardancy of treated wood was improved. Effects of the different compounds on the degradation and flammability of wood have also been proposed.This revised version was published online in November 2005 with corrections to the Cover Date.     

钴膦簇合物的催化环丙烷化反应

本文首次利用碳基钴簇合物ＰｈＰＣｏ_３（ＣＯ）_９催化剂，在常压和－２０℃－０℃，用苯乙烯和重氮乙酸乙酯进行环丙烷化反应，合成了菊酸酯，重氮乙酸乙酯可全部转化，酯的选择性可达８５％。产物经减压分馏后，由ＩＲ和￣１ＨＮＭＲ分析，确证了产物为菊酸酯，表明了羰基钴簇合物对苯乙烯的环丙烷化反应有良好的催化性能，为四面体异核簇合物用于不对称催化反应打下了基础。     

Supramolecular assemblies of a naturally derived sophorolipid

Acidic sophorolipid (SL) molecules derived from yeasts represent a novel type of asymmetrical bolaamphiphiles due to their unique structural features that include an asymmetrical polar head size (disaccharide vs COOH), a kinked hydrophobic core (cis-9-octadecenoic chain), and a non-amide polar-nonpolar linkage. Light microscopy, small- and wide-angle X-ray scattering, FT-IR spectroscopy, and dynamic laser light scattering were used to investigate the supramolecular structures of the self-assembled aggregates of SL molecules at different pH values. In acidic conditions (pH < 5.5), giant twisted and helical ribbons of 5-11 microm width and several hundreds of micrometers length were observed for the first time. Increase in solution pH values slowed ribbon formation, decreased ribbon yield, and increased the helicity and entanglements of the giant ribbons. An interdigitated lamellar packing model of acidic SL-COOH molecules with a long period of 2.78 nm, stabilized by both the strong hydrophobic association between the cis-9-octadecenoic chains and strong disaccharide-disaccharide hydrogen bonding, is proposed. The neutralization of SL-COOH in water to SL-COONa produced clear solutions with the formation of short-range ordered aggregates. At concentrations below 1.0 mg/mL, the size of self-assembled aggregates increased as the concentration increased. At concentrations above 1.0 mg/mL, narrowly distributed micellar aggregates with a constant hydrodynamic radius (R(h)) of about 100 nm are formed. The large micelles show strong angular dependence with the fast mode appearing at scattering angle theta >/= 60 degrees.     

高效液相色谱检测Zn（Ⅱ）、Cd（Ⅱ）、Co（Ⅱ）、Pb（Ⅱ）、Ni（Ⅱ）、Cu（Ⅱ）、Hg（Ⅱ）

用双-(2-羟乙基)二硫代甲酸铵(HEDC)在反相液相色谱中作检测某些金属离子的衍生化试剂，HEDC的金属螯合物微溶于水，可直接水样注射于C18柱中进行检测，范围为0．006～10mg／L相对偏差1％～2％，检测波长254nm，金属汞的整合物在HPLC分析前进行浓缩富集检测限可低至0．06～25μg／L，相对偏差小于2％。     

Pre-Column Derivatization of Amines with 1,2-Benzo-3,4-Dihydrocarbazole-9-Isopropyl Chloroformate Followed by LC-Fluorescence and LC-APCI-MS

A pre-column derivatization method for the sensitive determination of amines using the labeling reagent 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl chloroformate (BCIC-Cl) followed by high-performance liquid chromatography with fluorescence detection has been developed. Identification of derivatives is carried out by high performance liquid chromatography/atmospheric pressure chemical ionization (LC-APCI-MS-MS). The chromophore of 2-(9-carbazole)-ethyl chloroformate (CEOC) reagent is replaced by 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl functional group, which results in a sensitive fluorescence derivatizing reagent BCIC-Cl. BCIC-Cl can easily and quickly label amines. Derivatives are stable enough to be efficiently analyzed by high-performance liquid chromatography and show an intense protonated molecular ion corresponding m/z [MH]⁺ under APCI in positive-ion mode. The collision-induced dissociation of protonated molecular ion formed a product at m/z 260 corresponding to the cleavage of CH₂-OCO bond. Studies on derivatization demonstrate excellent derivative yields over the pH 9.0–10.0. Maximal yields close to 100% are observed with a 3 to 4-fold molar reagent excess. In addition, the detection responses for BCIC derivatives are compared with those obtained using CEOC and FMOC as derivatization reagents. The ratios of I_BCIC/I_CEOC and I_BCIC/I_FMOC are, respectively, 1.23–3.14 and 1.25–3.08 for fluorescent (FL) responses (here, I is relative fluorescence intensity). Separation of the derivatized amines had been optimized on reversed-phase Eclipse XDB-C₈ column. Detection limits are calculated from 1.0 pmol injection, at a signal-to-noise ratio of 3, are 10.6–37.8 fmol. The mean interday accuracy ranges from 94 to 105% for fluorescence detection with the largest mean %CV<7.5. The mean interday precision for all standards is < 6.0% of the expected concentration. Excellent linear responses are observed with coefficients of > 0.9997. Revised: 12 December 2005 and 13 Febrauary 2006     

Electrical potential oscillation in an anionic surfactant system with barbitone in octanol as an oil phase

Studies were made on oscillations across a liquid membrane consisting of an oil layer, octanol containing barbitone, between two aqueous layers: one containing 8 mM SDS with alcohol and the other containing 0.1 M NaCl. The effects of various concentrations of chemical components in this system on the patterns of electrical oscillation were examined. The oscillations may be explained by the mechanism of repetitive formation and destruction of monolayer structures of the dodecyl sulfate anion at the interface between the organic and the aqueous phases, with the effect of proton penetration. This study of potential oscillation across a membrane containing a drug provides the possibility of further investigations in pharmacological activity.