ELECTROCHEMISTRY, SPECTROELECTROCHEMISTRY OF (TPP)CO IN THE PRESENCE OF OH-ANIONS

In the presence of OH- anions, electrochemical redox reactions of cobalt tetraphenylporphyrin (TPP)Co were investigated in EtCl2 solution by thin-layer cyclic voltammetry and spectroelectrochemistry. In the pressence of OH-, OH- was axially coordinated to

ELECTROCHEMICAL AND IN-SITU SPECTROELECTROCHEMICAL STUDY OF (TETRAPHENYLPORPHINATO)MANGANESE(III) PERCHLORATE IN THE PRESENCE OF CHLORIDE ANIONS .2. OXIDATION PROCESSES

An investigation of electrode oxidation processes of (tetra-phenylporphinato) manganese (III) Perchlorate, (TPS)Mn(III)ClO4, was carried out during the titration of chloride anions by conventional cyclic voltammetry, thin-layer cyclic voltammetry and spectroelectrochemistry. It was demonstrated that in the presence of one equivalent amount of Cl-, the first one electron oxidation reaction corresponds to the Mn(III)I cation radical oxidation, and the second one electron oxidation corresponds to the cation radical/dication generation followed by an iso-porphyrin formation reaction, however in the presence of two equivalent amount of Cl-, the first one electron oxidation of Mn(III) gives Mn(IV) porphyrin and the second one electron oxidation generates cation radicals of Mn(IV) followed by an iso-porphyrin formation reactions. Mechanisms of these redox processes are postulated.

INVESTIGATION OF THE ELECTROCHEMICAL-BEHAVIOR OF TRYPTOPHAN BY IN-SITU CIRCULAR DICHROIC SPECTROELECTROCHEMISTRY

The electrochemical redox processes of tryptophan were studied by in situ circular dichroic (CD) spectroelectrochemistry with a long optical path length thin-layer cell. The oxidation of tryptophan at low concentrations in basic aqueous solution is a two-electron irreversible electrochemical process which results from an irreversible subsequent chemical reaction. A method of treatment of CD spectral data for the irreversible electrochemical reaction is suggested, from which the values E(p/2) = 0.46 V, alphan(alpha) = 0.313 and k0 = 2.4 x 10(-4) cm s-1 (the standard heterogeneous reaction rate constant for tryptophan oxidation) were obtained.

APPLICATIONS OF RAPID SCAN SPECTROELECTROCHEMISTRY - DETERMINATION OF HETEROGENEOUS ELECTRON-TRANSFER RATE-CONSTANT OF BILIVERDIN OXIDATION

The rapid scan spectrometer was used to determine the heterogeneous electron transfer rate parameters for the oxidation of Biliverdin in DMF by single potential step thin layer spectroelectrochemical techniques and yielded an average formal heterogeneous electron transfer rate constant K(s, h)0' = 2.45 (+/-0.12) x 10(-4) cm s-1, electrochemical transfer coefficient alpha = 0.694+/-0.008. The oxidation process of Biliverdin was also studied and the formal potential E0 = 0.637 V (vs. Ag/AgCl) was obtained.

SPECTROELECTROCHEMICAL STUDY OF BILIRUBIN IN DIMETHYL FORMAMIDE

The electrochemical reduction of bilirubin (BR) in dimethyl formamide (DMF) is discussed in detail. The kinetic study of the electroreduction process of BR results in values of 7.94 x 10(-6) cm2/s for the diffusion coefficient and about 10(-3) cm/s for the standard heterogeneous electrode reaction rate constant. Thin-layer spectroelectrochemical investigations of BR exhibit a blue shift and a red shift at E(pc) = -0.6 V and E(pc) = -0.85 V respectively. They also give values of E0' = -1.55 V and n = 1 for the reduction process, and E0' = -1.35 V and n = 1 for the oxidation process. It was found experimentally that as the potential changes from negative to positive, the sequential color changes are similar to those of some of the color components in visible light. A mechanism for BR electroreduction in DMF has been proposed.

DIRECT ELECTRON-TRANSFER REACTION OF HEMEPROTEINS PROMOTED BY METHYLENE-BLUE MODIFIED ELECTRODE

The heterogeneous electron transfer reaction of hemeproteins including hemoglobin, myoglobin and cytochrome C at Pt mesh electrode adsorbed methylene blue has been investigated. Thin-layer spectroelectrochemical technique was used for observing the electron transfer processes of three kinds of proteins, and the corresponding electrode rate constants were measured.

AMPEROMETRIC DETECTION AT A CARBON-FIBER ARRAY RING GLASSY-CARBON DISK ELECTRODE IN A WALL-JET CELL

A wall-jet cell incorporating a carbon fibre array ring/glassy-carbon disk electrode has been constructed, and characterized by the cyclic voltammetry and flow-injection techniques. The ring (composed of several microdisks) and glassy-carbon disk electrode, can be used separately for different purposes, e.g., detection in solution without a supporting electrolyte, collection/shielding detection with dual-electrode and voltammetric/amperometric detection with series dual-electrode. The electrode shows better collection and shielding effects than usual ring-disk electrode in quiescent solution and the series dual-electrode in a thin-layer flow-through cell. The detection limit at the ring electrode is comparable with that at a conventional-size electrode, and has been used in the mobile phase without a supporting electrolyte, proving to be a promising detector for normal-phase liquid chromatography.

THE REVERSIBLE ELECTRON-TRANSFER REACTION OF MYOGLOBIN AT BRILLIANT CRESYL BLUE MODIFIED PLATINUM GAUZE ELECTRODE

The electrochemical behavior of myoglobin at a Brilliant Cresyl Blue (BCB) modified platinum gauze electrode and spiral pt wire in the BCB solution in optically transparent thin layer cell base been investigated by using cyclic potential-absorbance method and double potential step chronoabsorptometry. The results reveal a reversible electron transfer resection of myoglobin. Exhaustive reductive and oxidative electrolyses are achieved at the modified platinum surface in 20 and 100s respectively. The formal h...

DETERMINATION OF PARAMETERS OF FAST CHEMICAL REACTION OF ALIZARIN RED S BY SPECTROELECTROCHEMICAL METHOD WITH LOPTLC

The rate constant of very fast chemical reaction generally can be measured by electrochemical methods, but can not by the thin layer electrochemical methods because of the influence of diffusion effect. Long optical path length thin layer cell (LOPTLC) with large ratio of electrode area to solution volume can be used to monitor the fist chemical reaction in situ with high sensitivity and accuracy. It enable the adsorption spectra to be measured without the influence of diffusion effect. In the present paper, a fast chemical reaction of Alizarin Red S (ARS) with its oxidative state has been studied. The reaction equilibrium constant (K) under different potentials can be determined by single step potential-absorption spectra in LOPTLC. An equilibrium constant of 7.94 x 10(5) l.mol(-1) for the chemical reaction has been obtained from the plot of lgK vs. (E - E-1(0)'). Rate constant (k) under different potentials can be measured by single step potential-chronoabsorptiometry. A rate constant of 426.6 l.mol(-1).s(-1) for the chemical reaction has been obtained from the plot of lgK vs. (E - E-1(0)') with (E - E-1(0)') = 0.

Construction of shuttle, expression vector of human tumor necrosis factor alpha (hTNF-alpha) gene and its expression in a cyanobacterium, Anabaena sp. PCC 7120

The construction of the shuttle, expression vector of human tumor necrosis factor alpha (hTNF-alpha) gene and its expression in a cyanobacterium Anabaena sp. PCC 7120 was reported. The 700-bp hTNF cDNA fragments have been recovered from plasmid pRL-rhTNF, then inserted downstream of the promoter PpsbA in the plasmid pRL439. The resultant intermediary plasmid pRL-TC has further been combined with the shuttle vector pDC-8 to get the shuttle, expression vector pDC-TNF. The expression of the rhTNF gene in Escherichia coil has been analyzed by SDS-PAGE and thin-layer scanning, and the results show that the expressed TNF protein with these two vectors is 16.9 percent (pRL-TC) and 15.0 percent (pDC-TNF) of the total proteins in the cells, respectively, while the expression level of TNF gene in plasmid pRL-rhTNF is only 11.8 percent. Combined with the participation of the conjugal and helper plasmids, pDC-TNF has been introduced into Anabaena sg PCC 7120 by triparental conjugative transfer, and the stable transgenic strains have been obtained. The existence of the introduced plasmid pDC-TNF in recombinant cyanobacterial cells has been demonstrated by the results of the agarose electrophoresis with the extracted plasmid samples and Southern blotting with alpha-(32)p labeled hTNF cDNA probes, while the expression of the hTNF gene in Anabaena sp. PCC 7120 has been confirmed by the results of Western blotting with extracted protein samples and human TNF-alpha monoclonal antibodies. The cytotoxicity assays using the mouse cancer cell line L929 proved the cytotoxicity of the TNF in the crude extracts from the transgenic cyanobacterium Anabaena sp. PCC 7120.

两株海藻内生真菌次生代谢产物及其生物活性研究

海洋微生物拥有丰富多样的次生代谢途径，其中海洋生物内生真菌次生代谢产物研究日益受到天然产物化学界的重视。本论文以菌丝体生物量、发酵产物重量、抗菌与细胞毒活性、薄层色谱分析结果以及高效液相色谱分析结果等为评价依据对采自青岛沿海的13株海藻内生真菌在四种液体培养基上的静置发酵产物进行了综合评价，并从中选择了黑曲霉Aspergillus niger EN-13（分离自褐藻囊藻Colpomenia sinuosa）和杂色曲霉A. versicolor EN-7（分离自褐藻鼠尾藻Sargassum thunbergii）两株真菌进行了30升规模发酵（分别采用GPYM培养基和PDB培养）和化学成分的研究，对分离得到的大部分化合物进行了初步的生物活性筛选。 发酵提取物采用常规的硅胶柱层析、反相硅胶柱层析，凝胶Sephadex LH-20柱层析、制备薄层层析、半制备高效液相色谱以及重结晶等分离手段，得到单体化合物。利用各种现代波谱技术(IR、UV、EI-MS、FAB-MS、HR-ESI-MS、1H-NMR、13C-NMR、DEPT、1H-1H COSY、HSQC、HMBC等)并结合化学方法从两种菌株发酵提取物中鉴定了55个化合物的结构。其中从菌株A. niger EN-13分离鉴定了31个化合物，发现9个新化合物，包括2个鞘酯类化合物（AN-1~2）、3个萘并-γ-吡喃酮类化合物（AN-3~5）、3个苯乙基取代的α-吡喃酮类化合物（AN-17, AN-19~20）和1个甾体Diels-Alder加成产物（AN-21），另有1个新的天然环二肽（AN-27）被分离鉴定；从菌株A. versicolor EN-7分离鉴定了24个化合物，发现2个新化合物，为蒽醌AV-12与AV-17，另外，从前一菌株（A. niger EN-13）中鉴定的2个新鞘酯类化合物（AN-1~2）在A. versicolor EN-7中也被再次分离到。 对大部分单体化合物进行了抗菌活性、DPPH自由基清除活性和细胞毒活性测试。结果显示新化合物AN-1、AN-5和AN-20具有弱或中等强度的抑制白色念珠菌生长的活性，AN-4、AN-5、AN-21显示了弱或中等强度的抑制黑曲霉生长的活性，AV-12、AV-17显示了弱的抑制大肠杆菌生长的活性。在DPPH自由基清除活性筛选中，AN-5显示了中等强度的活性，其EC50为109.3 mM，与阳性对照BHT相近（EC50为81.8 mM）。其它部分已知化合物在抗菌和DPPH自由基清除活性的筛选中也显示了弱或中等强度的活性。在针对人肝癌细胞株SMMC-7721和人肺腺癌细胞株A549的体外细胞毒活性筛选中，所测样品均未显示显著活性。

Hydrogen ion reduction in the process of iron rusting

Since the acceptance of the electrochemical rusting mechanism, oxygen reduction has been considered the main cathodic process, while H+ reduction has been overlooked for the past four decades because oxygen can be readily renewed due to the thin layer Of Solution film formed during atmospheric corrosion. This study shows that measurable hydrogen call be detected at the surface opposite to the corroding side of the specimen during wet-dry cycles, and a clear correlation exists between the quantities of hydrogen permeated through iron sheet and weight loss. Results Suggest the intrinsic importance of H+ reduction that merits further investigation. (c) 2004 Elsevier Ltd. All rights reserved.

三维VSP技术的研究及应用

Today, because of high petroleum consumption of our country, society steady development and difficulty increase in new resources exploration, deep exploitation of the existing oilfield is needed. More delicate reservoir imaging and description, such as thin layer identification, interlayer exploitation monitoring, subtle structure imaging, reservoir anisotropy recognition, can provide more detail evidence for new development adjustment scheme and enhanced oil recovery. Now, the people have already realized the 3D VSP technique more effective than the general methods in solving these aspects. But VSP technique especially 3D VSP develop slowly due to some reasons. Carrying out the research of VSP technique, it will be very useful to the EOR service. 3D VSP techniques include acquisition、data processing and interpretation. In this paper, the author carried out some researches around acquisition and processing. The key point of acquisition is the survey design, it is critical to the quality of the data and it will influence the reservoir recognition as follows. The author did detailed researches on the layout pattern of shot point and geophone. Some attributes relate to survey design such as reflectivity, incidence angle, observation area, reflection points distribution, fold, minimum well source distance, azimuth angle and so on are studied seriously. In this geometry design of 3D-VSP exploration in deviated wells, the main problems to be solved are: determining the center position of shots distribution, the effect of shots missing on coverage areas and coverage times，locating the shots and receivers of multi-wells. Through simulating and analyzing, the above problems are discussed and some beneficial conclusions are drawn. These will provide valuable references to actual survey design. In data processing, researches emphasize on those relatively key techniques such as wavefield separation, VSP-CDP imaging, the author carried out deep researches around these two aspects. As a result, variant apparent slowness wavefield separation method developed in this article suit the underground variant velocity field and make wavefield separation well, it can overcome reflection bending shortage aroused by conventional imaging method. The attenuateion range of underground seismic wave is very important for amplitude compensation and oil/gas identification.In this paper, seismic wave attenuateion mechanism is studied by 3D-VSP simulateion and Q-inversion technique. By testing with seismic data, the method of VSP data attenuateion and relationship of attenuateion attribute variant with depth is researched. Also the software of survey design and data processing is developed, it fill the gap of VSP area in our country. The technique developed applied successfully in SZXX-A Oilfield、QKYY-B Oilfield、A area and B area. The good results show that this research is valuable, and it is meaningful to the VSP technique development and application of offshore oil industry and other areas in our country.

砂泥岩薄互层储层预测方法与应用研究

With the deeply development of exploration and development in petroleum in China, new increasing reserves are found in old oil fields and the verge of the old ones through re-study of geological property. It is more and more important to discovery and develop thin layer or thin inter-bedded layers reservoirs. All of the targets are thin sand-shale inter-bedded reservoirs and the core technology is reservoir predictions between wells in thin sand-shale inter-bedded layers. The continuity of the thin sand-shale inter-bedded layers in space or separating and heterogeneity is the key of reservoir geology research. The seismic reflection, high resolution analysis method and inversion method to thin sand-shale inter-bedded layers are thorough discussed and deeply studied in this paper to try to find the methods and resolutions of reservoir geology research. The below is followed. 1. Based on the pre-research of other people, five models are created: the sand sphenoid body, interlay sandstone and interlay shale of the equal thickness, interlay sandstone of the equal thickness and interlay shale of the unequal thickness, interlay sandstone of the unequal thickness and interlay shale of the unequal thickness, interlay sandstone of the changing thickness in sequence and interlay shale of the changing thickness in sequence. Then the study of the forward modeling are conducted on the thin layer and thin inter-bedded layers geological characters and seismic reflections including amplitude, frequency, phase, wave shape and time-frequency responding in the domains of time and frequency. The affect of petro-physics difference of layers, single thin layer thickness, thickness of inter-bedded, layer number of inter-bedded, incident wavelet domain frequency and types, sample interval to seismic reflection characters, frequency spectrum and time-frequency respond of reflectivity is theoretically discussed. 2. Qualitatively analyzing the sedimentary rhythm of the thin inter-bedded layers in vertical orientation and computing the single layer thickness or the average thickness with the method of generalized S transform. Identifying the reflecting interface or lithology interface using the amplitude value of amplitude spectrum domain frequency. 3. Based on the seismic respond of thin sand-shale inter-bedded layers, bring out the high resolution analysis method of seismic data in thin sand-shale inter-bedded layers using wavelet analysis and the idea of affecting low and high frequency with middle frequency. Then analyzing the effect to the method and testing some wavelets in the method. This method is applied to the theoretical models and the field data. 4. Bring forward one improved very fast simulated annealing method (IVFSA) to resolve the problem nonlinearity and multi-parameters of the inversion in thin inter-bedded layers. And IVFSA is more productive and higher precision than general ways. 5. New target constrained function is used in the inversion based on the property of the inversion in thin inter-bedded layers. 6. Making the full use of geological and logging information, IVFSA and the new function are applied in the non-linear inversion to improve reservoir prediction and evaluation in thin inter-bedded formations combined with the idea of logging and seismic inversion. This method was applied to the field data and got good results.

边坡工程的极限分析上限法

Theory of limit analysis include upper bound theorem and lower bound theorem. To deal with slope stability analysis by limit analysis is to approximate the real solution from upper limit and lower limit. The most used method of limit analysis is upper bound theorem, therefore it is often applied to slope engineering in many cases. Although upper bound approach of limit analysis can keep away from vague constitutive relation and complex stress analyses, it also can obtain rigorous result. Assuming the critical surface is circular slip surface, two kinematically admissible velocity fields for perpendicular slice method and radial slice method can be established according to the limit analysis of upper bound theorem. By means of virtual work rate equation and strength reduction method, the upper-bound solution of limit analysis for homogeneous soil slope can be obtained. A log-spiral rotational failure mechanism for homogeneous slope is discussed from two different conditions which represent the position of shear crack passing the toe and below the toe. In the dissertition, the author also establishes a rotational failure mechanics with combination of different logarithmic spiral arcs. Furthermore, the calculation formula of upper bound solution for inhomogeneous soil slope stability problem can be deduced based on the upper bound approach of rigid elements. Through calculating the external work rate caused by soil nail, anti-slide pile, geotechnological grid and retaining wall, the upper bound solution of safety factor of soil nail structure slope, slip resistance of anti-slide pile, critical height of reinforced soil slope and active earth pressure of retaining wall can be obtained by upper bound limit analysis method. Taking accumulated body slope as subject investigated, with study on the limit analysis method to calculate slope safety factor, the kinematically admissible velocity fields of perpendicular slice method for slope with broken slip surface is proposed. Through calculating not only the energy dissipation rate produced in the broken slip surfaces and the vertical velocity discontinuity, but also the work rate produced by self-weight and external load, the upper bound solution of slope with broken slip surface is deduced. As a case study, the slope stability of the Sanmashan landslide in the area of the Three Gorges reservoir is analyzed. Based on the theory of limit analysis, the upper bound solution for rock slope with planar failure surface is obtained. By means of virtual work-rate equation, energy dissipation caused by dislocation of thin-layer and terrane can be calculated; furthermore, the formulas of safety factor for upper bound approach of limit analysis can be deduced. In the end, a new computational model of stability analysis for anchored rock slope is presented after taking into consideration the supporting effect of rock-bolts, the action of seismic force and fissure water pressure. By using the model, not only the external woke-rate done by self-weight, seismic force, fissure water pressure and anchorage force but also the internal energy dissipation produced in the slip surface and structural planes can be totally calculated. According to the condition of virtual work rate equation in limit state, the formula of safety factor for upper bound limit analysis can be deduced.