A 3-D noninterpenetrating diamondoid network of a decanuclear copper(I) complex

The solvothermal reaction of CuCl(2).2H(2)O with pyridine-4-thiol and ethanol yielded a novel photoluminescent 3-D polymeric complex with an interesting decorated diamondoid network that is constructed of decanuclear copper(I) cluster units and mu(4)-Cl ligands. The in situ generation of CuSO(4).5H(2)O implies the spontaneous occurrence of desulfurization and redox reactions in the present system.     

Adsorption separation of terpene lactones from Ginkgo biloba L. extract using glass fiber membranes modified with octadecyltrichlorosilane

In this study porous glass fiber membranes were modified by reaction with octadecyl-trichlorosilane to form C18 hydrophobic membranes. The contact angle and the CH2 vibration bands at 2855 and 2920 cm(-1) found by FTIR measurements verified the successful immobilization of C18 groups on the glass fiber membranes. The resulting C18 hydrophobic membranes were used to adsorb terpene lactones from crude Ginkgo biloba L. extracts. In batch adsorption processes, the modified C18 membranes exhibited a better adsorption performance than commercial C18 solid phase extraction adsorbents. Different desorption solvents were tested and ethyl acetate was found to preferentially desorb terpene lactones from the modified C18 membranes. In flow adsorption experiments at 1 mL/min, terpene lactone contents higher than 6 wt% (the standardized content) could be achieved in the elution step using ethyl acetate.     

Total synthesis of crotophorbolone

As a natural diterpenoid, crotophorbolone possesses a challenging trans,trans-5/7/6 framework decorated with six contiguous stereogenic centers and is structurally and biogenetically related to tigliane-type diterpenoids with intriguing bioactivities such as phorbol and prostratin. Based on the convergent strategy, we completed an eighteen-step total synthesis of crotophorbolone starting from (−)-carvone and (+)-dimethyl-2,3-O-isopropylidene-l-tartrate. The key elements of the synthesis involve expedient installation of the six-membered ring and the five-membered ring with multiple functional groups at an early stage, cyclization of the seven-membered ring through alkenylation of the ketone between the five-membered ring and the six-membered ring, functional group-sensitive ring-closing metathesis and final selective introduction of hydroxyls at C₂₀ and C₄.

Convergent total synthesis of crotophorbolone was accomplished in 18 longest linear steps. Observation of unexpected thermodynamic stability of a cis,trans-5/7/6 tricycle would benefit synthetic design of tigliane- and daphnane-related diterpenoids.     

Reduction of 4-nitrophenol catalyzed by nitroreductase

The reduction of 4-nitrophenol catalyzed by nitroreductase in the presence of NADH was investigated in this paper.4-Amino- phenol and 4-bydroxylamino-phenol were found in the reductive products.The relationship between reaction time and the reductive ratio were studied.The similar reducing ratios of 4-nitrophenol were obtained under aerobic and anaerobic conditions.The results indicated that an oxygen-insensitive reaction was proceeded in the reduction of 4-nitrophenol and nitroreductase was an oxygen- insensitive enzyme.The reductive products of 4-nitrophenol were determined by HPLC and MS.     

Interfacial properties of self-organized TiO<Subscript>2</Subscript> nanotubes studied by impedance spectroscopy

The semiconductor properties of the interface TiO₂/electrolyte in high organized porous oxide structures were analyzed by means of impedance spectroscopy near the flat band potential. The impedance and capacitance studies performed on the as-anodized and thermally treated samples (anatase) indicate the presence of a duplex structure formed by (1) the oxide at the bottom of the pores and (2) the walls of pores with different donor densities and surface state concentrations.     

Multiple sprayer system for high-throughput electrospray ionization mass spectrometry

A multiple sprayer electrospray ion source for high-throughput analysis is described. The ion source is comprised of multiple electrospray capillaries, each with an ion lens located near the tip. The electric potentials applied to the ion lenses are used to control the sprayers. The use of ion lenses eliminates the need for mechanical blocking devices to selectively enable or disable the sprayers, and results in a less expensive and more reliable set-up. Sprayers can be enabled or disabled within approximately 50-250 ms when the lens potentials are controlled manually. For simultaneous operation of multiple electrospray capillaries, it is advantageous to orient the capillaries so that the spray from each passes directly in front of the entrance aperture of the mass spectrometer.     

Ab initio studies on the thermolysis of azetidine

The reaction mechanism of the thermolysis of azetidine to form ethylene and methylen-imine has been studied by ab initio SCF MO method at STO--3G and 3-21G levels. Two possible step-wise pathways are explored. One is the breaking of C--C bond as the first step, while the other is thebreaking of C--N bond. All the stationary points on the potential energy surface (PES) are fully optimiz-ed. MP2 / 3-21G single point calculations on all stationary points and MCSCF / STO-3G computationsfor some stationary points are also carried out. The calculations indicate that azetidine decomposesvia biradicaloid intermediates and the cleavage of C--N bond is preferable to that of C--C bond.     

甲烷在Mo/HZSM-5催化剂上的脱氢聚合反应

对不同Mo含量的Mo／HZSM－5催化剂的结构进行了表征，并对这些催化剂的甲烷非氧气氛下的转化反应进行了考察．催化剂的BET比表面积及酸性随Mo含量的增加而降低，当Mo含量大于5％时，Mo对ZSM－5分子筛的晶型有影响，并出现MoO3物相．甲烷在700℃时可高选择性地生成苯和乙烯，最佳Mo含量大约为2％．纯的MoO3或HZSM－5上该反应几乎不进行，因此，可能是分散的钼氧离子和分子筛的酸中心是甲烷转化的活性中心，只有二者的协同作用才能促进甲烷的转化．反应后催化剂中的钼物种被还原了．催化剂上的积炭可能是催化剂失活的主要原因之一，烧炭后催化剂活性基本恢复．     

Heat transfer from a rarefied plasma flow to a metallic or nonmetallic particle

Heat transfer from a plasma flow to a metallic or nonmetallic spherical particle is studied in this paper for the extreme case of free-molecule flow regime. Analytical expressions are derived for the heat flux due to, respectively, atoms, ions, and electrons and for the floating potential on the sphere exposed to a two-temperature plasma flow. It has been shown that the local or average heat flux density over the whole sphere is independent of the sphere radius and approximately in direct proportion to the gas pressure. The presence of a macroscopic relative velocity between the plasma and the sphere causes substantially nonuniform distributions of the local heat flux and enhances the total heat flux to the sphere. The heat flux is also enhanced by the gas ionization. Appreciable difference between metallic and nonmetallic spheres is found in the distributions along the oncoming flow direction of the floating potential and of the local heat flux densities due to ions and electrons. The total heat flux to the whole sphere is, however, almost the same for these different spheres. For a fixed value of the electron temperature, the heat flux decreases with increasing temperature ratio T_e/T_h.     

铋（Ⅲ）—溴邻苯三酚红配合物吸附波及其应用

铋（Ⅲ）－溴邻苯三酚红配合物吸附波及其应用＊刘家欣段友构黄诚朱苗力（吉首大学化学系湖南吉首４１６０００）匡向阳（永州市水文站湖南永州４２５０００）关键词铋溴邻苯三酚红配合物吸附波中图分类号Ｏ６５７．１４近年来，在某些有机试剂存在下用极谱法测定铋已有一...