SYNTHESIS OF TETRAPHENYLBUTADIENE LANTHANIDE METALLACYCLES

The cyclic derivatives of transition metals have been extensively investigated in recent years since they are believed to serve as key intermediates in various homogeneous catalytic processes of olefine and alkyne metathesis. The synthesis of the title compounds has not been reported before.

Dynamics of the buoyant plume off the Pearl River Estuary in summer

Field measurements of salinity, wind and river discharge and numerical simulations of hydrodynamics from 1978 to 1984 are used to investigate the dynamics of the buoyant plume off the Pearl River Estuary (PRE), China during summer. The studies have shown that there are four major horizontal buoyant plume types in summer: Offshore Bulge Spreading (Type I), West Alongshore Spreading (Type II), East Offshore Spreading (Type III), and Symmetrical Alongshore Spreading (Type IV). River mouth conditions, winds and ambient coastal currents have inter-influences to the transport processes of the buoyant plume. It is found that all of the four types are surface-advected plumes by analysing the vertical characteristic of the plumes, and the monthly variations of the river discharge affect the plume size dominantly. The correlation coefficient between the PRE plume size and the river discharge reaches 0.85 during the high river discharge season. A wind strength index has been introduced to examine the wind effect. It is confirmed that winds play a significant role in forming the plume morphology. The alongshore wind stress and the coastal currents determine the alongshore plume spreading. The impact of the ambient currents such as Dongsha Current and South China Sea (SCS) Warm Current on the plume off the shelf has also assessed. The present study has demonstrated that both the river discharge and wind conditions affect the plume evolution.

Physical mechanism and numerical simulations of surface layer temperature inversion in tropical ocean

The one-dimensional Kraus-Turner mixed layer model improved by Liu is developed to consider the effect of salinity and the equations of temperature and salinity under the mixed layer. On this basis, the processes of growth and death of surface layer temperature inversion is numerically simulated under different environmental parameters. At the same time, the physical mechanism is preliminarily discussed combining the observations at the station of TOGA-COARE 0 degrees N, 156 degrees E. The results indicate that temperature inversion sensitively depends on the mixed layer depth, sea surface wind speed and solar shortwave radiation, etc., and appropriately meteorological and hydrological conditions often lead to the similarly periodical occurrence of this inversion phenomenon.

Bacterial roles in the formation of high-molecular-weight dissolved organic matter in estuarine and coastal waters: Evidence from lipids and the compound-specific isotopic ratios

High-molecular-weight dissolved organic matter (HMW-DOM, > 1,000 Daltons) is actively involved in the global biogeochemical cycling of many elements, but its carbon sources and detailed formation pathways are still not well understood. In this study, we measured bulk stable carbon and nitrogen isotopic ratios, lipid composition, and compound-specific carbon isotopic ratios of HMW-DOM samples collected from four U.S. estuaries (Boston Harbor/Massachusetts Bay, Delaware/Chesapeake Bay, San Diego Bay, and San Francisco Bay). Analytical results show (1) a fraction of HMW-DOM (lipid associated) in estuarine and coastal waters is derived from bacteria and phytoplankton; (2) this fraction of HMW-DOM is formed by various release processes of bacterial membrane components and bacterial reworking of phytoplankton-derived material; (3) this fraction of HMW-DOM is generally present in all samples from different coastal systems despite variable organic matter inputs and environmental conditions, suggesting an important bacterial role in HMW-DOM formation.

Electrochemical, SEM/EDS and quantum chemical study of phthalocyanines as corrosion inhibitors for mild steel in 1 mol/l HCl

The inhibition effect of metal-free phthalocyanine (H2Pc), copper phthalocyanine (CuPc) and copper phthalocyanine tetrasulfuric tetrasodium salt (CuPc center dot S(4)center dot Na-4) on mild steel in I mol/l HCl in the concentration range of 1.0 X 10(-5) to 1.0 X 10(-3) mol/l was investigated by electrochemical test, scanning electron microscope with energy dispersive spectrometer (SEM/EDS) and quantum chemical method. The potentiodynamic polarization curves of mild steel in hydrochloric acid containing these compounds showed both cathodic and anodic processes of steel corrosion were suppressed, and the Nyquist plots of impedance expressed mainly as a capacitive loop with different compounds and concentrations. For all these phthalocyanines, the inhibition efficiency increased with the increase in inhibitor concentration, while the inhibition efficiencies for these three phthalocyanines with the same concentration decreased in the order Of CuPc center dot S(4)center dot Na-4 > CuPc > H2Pc according to the electrochemical measurement results. The SEM/EDS analysis indicated that there are more lightly corroded and oxidative steel surface for the specimens after immersion in acid solution containing 1.0 x 10(-3) mol/l phthalocyanines than that in blank. The quantum chemical calculation results showed that the inhibition efficiency of these phthalocyanines increased with decrease in molecule's LUMO energy, which was different from the micro-cyclic compounds. (c) 2005 Elsevier B.V. All rights reserved.

2,3,5-triphenyl-2H-tetrazolium chloride and 2,4,6-tri(2-pyridyl)-s-triazine on the corrosion of mild steel in HCl

Electrochemical measurement, quantum chemical method, and scanning electron microscopy (SEM) were performed to investigate the inhibitive effect of 2,3,5-triphenyl-2H-tetrazolium chloride (TTC) and 2,4,6-tri(2-pyridyl)-s-triazine(TPT) on the corrosion of mild steel in 1mol.L-1 HCl at room temperature. Impedance spectroscopy measurement showed that the polarization resistance increased and that double layer capacitance decreased with the increase in the inhibitive concentration, and the results of potentiodynamic polarization showed that the inhibitors suppressed both cathodic and anodic processes of steel corrosion without change in the mechanism. Higher the orbital density distribution strength of the lowest unoccupied molecular orbital, higher is the molecule dipole, and lower energy gap between the energy of the highest occupied molecular orbital and the energy of the lowest unoccupied molecular orbital resulted in higher inhibitory efficiency. The results of SEM analysis showed that the metal was protected from aggressive corrosion by the addition of TTC and TPT.

Electrochemical, quantum chemical and SEM investigation of the inhibiting effect and mechanism of ciprofloxacin, norfloxacin and ofloxacin on the corrosion for mild steel in hydrochloric acid

The inhibiting effect and mechanism of 1-cyclopropyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazinyl)-3-quinoline carboxylicacid(ciprofloxacin), 1-ethyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazinyl)-3-quinoline carboxylic acid (norfloxacin) and (-)-(S)-9-fluoro-2,3-dihydro-3-methyl-10-(4-methyl-1-piperazinyl)-7-oxo-7 H-pyrido(1,2,3-de)-1,4-benzoxazine-6 carboxylic acid (ofloxacin) on the corrosion of mild steel in 1 mol/L HCl have been studied using electrochemical method, quantum chemical method and SEM at 303 K. The potentiodynamic results showed that these compounds suppressed both cathodic and anodic processes of mild steel corrosion in 1 mol/L HCl. The impedance spectroscopy showed that R-p values increased, and C-dl values decreased with the rising of the working concentration. Quantum chemical calculation showed that there was a positive correlation between some inhibitors structure properties and the inhibitory efficiency. The inhibitors function through adsorption followed Langmuir isotherm, and chemisorption made more contribution to the adsorption of the inhibitors on the steel surface compared with physical adsorption. SEM analysis suggested that the metal had been protected from aggressive corrosion because of the addition of the inhibitors.

Electrochemical and quantum chemical study of purines as corrosion inhibitors for mild steel in 1 M HCl solution

The purines and its derivatives, such as, guanine, adenine, 2,6-diaminopurine, 6-thioguanine and 2,6-dithiopurine, were investigated as corrosion inhibitors for mild steel in 1 M HCl solution by weight loss measurements, electrochemical tests and quantum chemical calculations. The polarization curves of mild steel in the hydrochloric acid solutions of the purines showed that both cathodic and anodic processes of steel corrosion were suppressed. The Nyquist plots of impedance expressed mainly as a depressed capacitive loop with different compounds and concentrations. For all these purines, the inhibition efficiency increased by increasing the inhibitor concentration, and the inhibition efficiency orders are 2,6-dithiopurine > 6-thioguanine > 2,6-diaminopurine > adenine > guanine with the highest inhibiting efficiency of 88.0% for 10(-3) M 2,6-dithiopurine. The optimized structures of purines, the Mulliken charges, molecular orbital densities and relevant parameters were calculated by quantum chemical calculations. The quantum chemical calculation results inferred that the adsorption belong to physical adsorption, which might arise from the pi stacking between the pi electron of the purines and the metal surface. (C) 2008 Elsevier Ltd. All rights reserved.

黄铁矿热转变过程的岩石磁学研究

Pyrite is the most stable iron-sulfide in reduced environment, and plays an important role in geochemical iron-sulfur cycling of sediments. Thus, the presence of pyrite in sediments and rocks is an important indicator of sedimentary environments. Previous studies on the thermal products of pyrite showed that all of the products (e.g., pyrrhotite, magnetite, hematite) have strong capability of carrying remanence. To deepen our understanding of the environmental and paleomagnetic significances of pyrite, the mineral transformation processes of pyrite upon heating were systematically investigated in this study using intergrated rock magnetic experiments (in both argon and air atmospheres) and X-ray diffraction analysis. The room temperature susceptibility of the paramagnetic pyrite is about 2.68×10-5 SI. In argon atmosphere (reducing environment), pyrite was transformed into monoclinic stable single domain (SD) pyrrhotite above 440 C. The corresponding coercive force and remanence coercivity are about 20 mT and 30 mT, respectively. In contrast, in air atmosphere (oxidation environment), the intermediate thermal products of pyrite are magnetite and pyrrhotite, which were quickly further oxidated to SD hematite, which has coercivity of about 1400 mT. In addition, the hematite particles gradually grow from SD to PSD grain size region by multiple heating runs. The transformation processes of pyrite in oxidation atomosphere can be interpreted by three possible pathways: (1) pyrite→magnetite→hematite; (2) pyrite→pyrrhotite→magnetite→hematite; and (3) pyrite→pyrrhotite→hematite. Low-temperature magnetic experiments show no transitions for pyrite. Despite that low-temperature magnetic method is not suitable for identification of pyrite, it is clear in this study that the high-temperature thermomagnetic measurements (e.g.,  -T and J-T curves) are very sensitive to the presence of pyrite in sediments and rocks. Nevertheless, for the thermal treatment products, low-temperature magnetic measurements showed the 34 K transition of pyrrhotite and the 250 K Morine transition of hematite. Iron-sulfide has also been found on Martian meteorolites by other workers. Therefore, systematic study of rock magnetism of pyrite (and other iron-sulfides) and their products will have great significances for both paleomagnetism and planetary magnetism.

A study on reduction behaviors of the supported platinum-iron catalysts

The reduction behaviors of the supported platinum-iron catalysts and their comparison with supported iron catalysts were studied by TPR (temperature-programmed reduction)-in situ Fe-57 MBS (Mossbauer spectroscopy). The results indicated that the TPR processes of all Fe-containing catalysts were different from that of bulk alpha-Fe2O3. There were interactions between Pt, Fe and the gamma-Al2O3 or SiO2 support for the Pt-Fe/gamma-Al2O3 and Pt-Fe/SiO2 catalysts. All the iron-containing catalysts show that Fe3+ was highly dispersed on the support (gamma-Al2O3 and SiO2) before reduction. No Fe-0 was found in the reduction processes. The Fe3+ was reduced to Fe2+ in tetrahedral vacancy first for the reduction of the Pt-Fe/gamma-Al2O3 catalyst. No Fe2+ in octahedral vacancy was found in the reduction of the Pt-Fe/SiO2 catalyst. Adding Pt to Fe/support (gamma-Al2O3 or SiO2) could promote the reduction of the Fe species. (C) 1999 Elsevier Science B.V. All rights reserved.

The study of oxygen spillover and back spillover on Pt/TiO2 by a potential dynamic sweep method

Oxygen spillover and back spillover on Pt/TiO2 catalysts have been studied by a potential dynamic sweep method. The characteristics of I-V profiles of Pt/TiO2 electrodes in the three potential sweep regions are different from those of Pt and TiO2 electrodes. The catalytic role of Pt/TiO2 in oxygen spillover and back spillover is identified. It decreases, and the electrochemical oxygen adsorption (or desorption) increases with elevating temperature of hydrogen post-treatment of Pt/TiO2; to a certain extent (hydrogen post-treatment of Pt/TiO2 at 700 degrees C), the control step of oxygen electrode process (anodic oxidation or cathodic reduction) changes from oxygen diffusion to electrochemical oxygen adsorption or desorption, respectively. Increasing the amount of Pt supported on TiO2 enhances the processes of oxygen spillover and back spillover. (C) 1999 Elsevier Science B.V. All rights reserved.

A column method for determination of soil organic partition coefficients of eight pesticides

A column method was developed to conveniently and reliably determine the soil organic partition coefficients (K-oc) of three insecticides (methiocarb, azinphos-methyl, fenthion), four fungicides (triadimenol, fuberidazole, tebuconazole, pencycuron), and one herbicide (atrazine), in which real soil acted as a stationary phase and the water solution of pesticide as an eluent. The processes of sorption equilibrium were directly shown through a breakthrough curve(BTC). The log K-oc values are 1.69, 1.95, 2.25, 2.55, 2.69, 2.67, 3.10, and 3.33 for atrazine, triadimenol, methiocarb, fuberidazole, azinphos-methyl, tebuconazole, fenthion and pencycuron, respectively.

Chiral separation of enantiomers of amino acid derivatives by high-performance liquid chromatography on a norvancomycin-bonded chiral stationary phase

A novel norvancomycin-bonded chiral stationary phase (NVC-CSP) was synthesized by using the chiral selector of norvancomycin. The chiral separation of enantiomers of several dansyl-amino acids by high-performance liquid chromatography (HPLC) in the reversed-phase mode is described. The effects of some parameters, such as organic modifier concentration, column temperature, pH and flow rate of the mobile phase, on the retention and enantioselectivity were investigated. The study showed that ionic, as well as hydrophobic interactions were engaged between the analyte and macrocycle in this chromatographic system. Increasing pH of buffers usually improved the chiral resolution for dansyl-alpha-amino-n-butyric acid (Dns-But), dansyl-methionine (Dns-Met) and dansyl-threonine (Dns-Thr), but not for dansyl-glutamic acid (Dns-Glu) which contains two carboxylic groups in its molecular structure. The natural logarithms of selectivity factors (In alpha) of all the investigated compounds depended linearly on the reciprocal of temperature (1/T), most processes of enantioseparation were controlled enthalpically. Interestingly, the process of enantioseparation for dansyl-threonine was enthalpy-controlled at pH of 3.5, while at pH of 7.0, it was entropy-controlled according to thermodynamic parameters Delta(R,S)DeltaHdegrees and Delta(R,S)DeltaSdegrees afforded by Van't Hoff plots. In order to get baseline separation for all the solutes researched, norvancomycin was also used as a chiral mobile phase additive. In combination with the NVC-CSP remarkable increases in enanselectivity were observed for all the compounds, as the result of a "synergistic" effect. (C) 2003 Elsevier B.V. All rights reserved.