Development of durable carbon black/titanium dioxide supported macrocycle catalysts for oxygen reduction reaction

Carbon black and titanium dioxide supported iron tetraphenylporphyrin (FeTPP/TiO2/C) catalysts for oxygen reduction reaction (ORR) were prepared by sol-gel and precipitation methods followed by a heat-treatment at temperatures of 400-1000 degrees C. The FeTPP/C and TiO2/C were also studied for comparison. The FeTPP/TiO2/C pyrolyzed at 700 degrees C exhibits significantly improved stability while maintaining high activity towards ORR in comparison with the FeTPP/C counterpart. The electrochemical study combined with XRD, XPS, and SEM/EDX analyses revealed that the appropriate dispersion of TiO2 on the surface of FeTPP/TiO2/C catalysts, which depending on heat-treatment temperature, plays a crucial role in determining the activity and stability of catalysts.

THE FORMATION MECHANISM OF THE VITRIFIED SLAG IN A PLASMA ARC REACTOR FOR HAZARDOUS WASTE TREATMENT

Various hazardous wastes with additives have been vitrified to investigate the formation mechanism of the glassy slag by a 30 kW DC plasma-arc reactor developed by the Institute of Mechanics, Chinese Academy of Sciences. The average temperature in the reaction area is controlled at 1500°C. The chemical compositions of three sorts of fly ashes are analyzed by XRF (X-Ray Fluorescence). Fly ashes with vitrifying additives can be vitrified to form glassy slag, which show that the ratio of the whole oxygen ions to the whole network former ions in glass (R) is appropriate in the range of 2~3 to form durable vitrified slag. In this experiment, the arc power is controlled below 5 kW to inhibit waste evaporation. To enhance the effects of heat transfer to wastes, ferrous powder has been added into the graphite crucible, which aggregates as ingot below the molten silicate after vitrification. The slag fails to form glass if the quenching rate is less than 1 K/min. Therefore, the slag will break into small chips due to the sharp quenching rate, which is more than 100 K/sec.

无指盘臭蛙皮肤抗菌肽Odorgrin A和Odorgrin C基因表达载体的构建及其在毕赤酵母中的表达

研究背景与目的：近二十年来，抗生素的广泛使用以及一些不当应用导致临床上出现大量的耐药性病原菌，所以不易产生耐药性的抗菌肽就成为目前研究的热点。本课题组此前的研究表明无指盘臭蛙（Odorrana grahami）皮肤抗菌肽具有广谱抗菌活性，但对真核细胞没有毒性，因此有成为新型药物的潜力。本研究采用毕赤酵母真核表达系统来生物合成抗菌肽Odorgrin A和Odorgrin C，为大量获取抗菌肽资源提供技术支撑。 方法：依照Odorgrin A和C的氨基酸序列、采用酵母偏爱密码子分别设计并化学合成了相应的目的基因序列。目的片段从合成质粒上用Xho Ι和EcoR Ι双酶切下后，与经同样限制酶完全酶切pPIC9K载体所获得的两个大片段直接连接，并转化至大肠杆菌DH5α。用PCR扩增、酶切及测序检测，鉴定正确的重组质粒。提取大量表达载体pPIC9K - Odo A和C并使之线性化后经电击法分别转化毕赤酵母（Pichia pastoris）GS115宿主菌，用营养缺陷型筛选、遗传霉素抗性筛选、PCR扩增和测序检测，鉴定并筛选出对G418具高抗性的Odorgrin A和C重组酵母菌。用甲醇对之进行诱导表达，SDS - PAGE电泳及反相层析检测表达产物，并做抑菌活性检测。 成果：PCR扩增、酶切及测序等结果表明表达载体pPIC9K - Odo A和C构建成功。营养缺陷型筛选、遗传霉素抗性筛选、PCR扩增和测序等证实pPIC9K - Odo A和C已整合入酵母基因组中。SDS - PAGE电泳及反相层析结果表明抗菌肽Odorgrin A和C成功地获得了分泌表达。而抑菌活性实验则检测到部分阳性克隆菌诱导分泌表达的抗菌肽Odorgrin A和C都对测试菌的生长具有较高（>94%）的抑制率。 结论：无指盘臭蛙皮肤抗菌肽Odorgrin A和Odorgrin C基因的表达载体都构建成功，并且都在毕赤酵母系统中获得了成功表达。 Background ＆ Objective: In the recent twenty years, a lot of pathogenic bacteria have come forth in clinic with durable trait derived from making use of and abusing the traditional antibiotics. Therefore, studying antimicrobial peptides, not be easy to be invalidated by durable bacteria, are becomimg popular and important. The skin antimicrobial peptides of Odorrana grahami with broad spectrum antibacterial activity and no toxicity to eukaryotic cell, discovered by previous research work of our workgroup, are looked forward to being potential medication. Pichia pastoris expressional system was used for biosynthesis antimicrobial peptides Odorgrin A and Odorgrin C in this study, for producing abundant antimicrobial peptides. Methods: The foreign fragments which included Odorgrin A or Odorgrin C gene according to their amino acid sequence respectively were synthesized based on the biased codon usage of yeast. The DNA fragments, obtained from the plasmids containing them by digested with Xho Ι and EcoR Ι, were directly ligated with the two bigger fragments obtained from the vector pPIC9K by digested with the same restriction enzymes. And then they were transformed into Escherichia coli DH5α to be selected and amplified positive colonies. The recombinants were testified by using PCR amplification, enzymes digestion and sequencing of the foreign fragment. After the expressional vector pPIC9K - Odo A and pPIC9K - Odo C were linearized, they were transformed into Pichia pastoris GS115 strain by the electroporation. Then the positive colonies which were of the highest geneticin resistant were selected through auxotrophic screening, genetic resistant screening, PCR amplification and sequencing of the inserted fragment. Methanol was used to induce the recombinant yeasts to express the foreign gene. SDS-PAGE electrophoresis, reversed phase chromatography and antibacterial activity experiment were used to testify the expressional products. Results: The evidences of PCR, enzymes digestion and sequence analysis confirmed that the expressional vector pPIC9K - Odo A and pPIC9K - Odo C have been constructed correctly. The results of auxotrophic screening, of genetic resistant screening, of PCR and sequencing of the foreign fragment showed that Odorgrin A and Odorgrin C gene have been homologous integrated with the Pichia pastoris genome. And it was also testified that antimicrobial peptides Odorgrin A and Odorgrin C have been expressed successfully by using SDS - PAGE electrophoresis, reversed phase chromatography and antibacterial activity experiment. Conclusion: The expressional vector of the skin antimicrobial peptides Odorgrin A and Odorgrin C gene of Odorrana grahami have been constructed correctly and both of the genes have been expressed successfully in Pichia pastoris system in this study.

Nafion/PTFE composite membranes for fuel cell applications

Porous polytetrafluoroethylene (PTFE) membranes were used as support material for Nafion((R))/PTFE composite membranes. The composite membranes were synthesized by impregnating porous PTFE membranes with a self-made Nafion solution. The resulting composite membranes were mechanically durable and quite thin relative to traditional perfluorosulfonated ionomer membranes (PFSI); we expect the composite membranes to be of low resistance and cost. In this study, we used three kinds of porous PTFE films to prepare Nafion/PTFE composite membranes of different thickness. Scanning electron micrographs and oxygen permeabilities showed that Nafion resin is distributed uniformly in the composite membrane and completely plug the micropores, there is a continuous thin Nation film present on the PTFE surface. The variation in water content of the composite and Nafion 115 membranes with temperature was determined. At the same temperature, water content of the composite membranes was smaller than that of the Nafion 115. In both dry and wet conditions, maximum strength and break strength of C-325(#) and C-345(#) were larger than those of Nafion 112 due to the reinforcing effect of the porous PTFE films. And the PEMFC performances and the lifetime of the composite membranes were also tested on the self-made apparatus. Results showed that the bigger the porosity of the substrate PTFE films, the better the fuel cell performance; the fuel cell performances of the thin composite membranes were superior to that of Nation 115 membrane; and after 180 h stability test at 500 mA/cm(2), the cell voltage showed no obvious drop. (C) 2002 Published by Elsevier Science B.V.

Facile preparation of amperometric laccase biosensor with multifunction based on the matrix of carbon nanotubes-chitosan composite

The carbon nanotubes-chitosan (CNTs-CS) composite provides a suitable biosensing matrix due to its good conductivity, high stability, and good biocompatibility. Enzymes can be firmly incorporated into the matrix without the aid of other cross-linking reagents. The composite is easy to form insoluble film in solution above pH 6.3. Based on this, a facilely fabricated amperometric biosensor by entrapping laccase into the CNTs-CS composite film has been developed. At pH 6.0, the fungi laccase incorporated into the composite film remains better catalytic activity than that dissolved in solution. The system is in favor of the accessibility of substrate to the active site of laccase, thus the affinity to substrates is improved greatly, such as 2,2'-azino-bis-(3-ethylbenzthiazoline-6-sulfonic acid) diammonium salt (ABTS), catechol, and 0, with K. values of 19.86 mu M, 9.43 mu M, and 3.22 mM, respectively. The major advantages of the as-prepared biosensor are: detecting different substrates (ABTS, catechol, and 02), possessing high affinity and sensitivity, durable long-term stability, and facile preparation procedure. On the other hand, the system can be applied in fabrication of biofuel cells as the cathodic catalysts based on its good electrocatalysis for oxygen reduction.

Corrosion behaviour of hot dip zinc and zinc-aluminium coatings on steel in seawater

A comparative investigation of hot dip Zn-25Al alloy, Zn-55Al-Si and Zn coatings on steel was performed with attention to their corrosion performance in seawater. The results of 2-year exposure testing of these at Zhoushan test site are reported here. In tidal and immersion environments, Zn-25Al alloy coating is several times more durable than zinc coating of double thickness. At long exposure times, corrosion rate for the Zn-25Al alloy coating remains indistinguishable from that for the Zn-55Al-Si coating of similar thickness in tidal zone, and is two to three times lower than the latter in immersion zone. The decrease in tensile strength suggested that galvanized and Zn-55Al-Si coated steel suffer intense pitting corrosion in immersion zone. The electrochemical tests showed that all these coatings provide cathodic protection to the substrate metal; the galvanic potentials are equal to - 1,050, - 1,025 and - 880 mV (SCE) for zinc, Zn-25Al alloy and Zn-55Al-Si coating, respectively, which are adequate to keep the steel inside the immunity region. It is believed that the superior performance of the Zn-25Al alloy coating is due to its optimal combination of the uniform corrosion resistance and pitting corrosion resistance. The inferior corrosion performance by comparison of the Zn coating mainly results from its larger dissolution rate, while the failure of the Zn-55Al-Si coating is probably related to its higher susceptibility to pitting corrosion in seawater.

松辽盆地南部大情字井地区CO2埋存体地质格架及储层建模

Increasing attentions have been paid to the subsurface geological storage for CO2 in view of the huge storage capacity of subsurface reservoirs. The basic requirement for subsurface CO2 storage is that the CO2 should be sequestrated as supercritical fluids (physical trapping), which may also interact with ambient reservoir rocks and formation waters, forming new minerals (chemical trapping). In order to the effective, durable and safe storage for CO2, enough storage space and stable sealing caprock with strong sealing capacity are necessitated, in an appropriate geological framework. Up till now, hydrocarbon reservoirs are to the most valid and appropriate CO2 storage container, which is well proven as the favorable compartment with huge storage capacity and sealing condition. The thesis focuses on two principal issues related to the storage and sealing capacity of storage compartment for the Qingshankou and Yaojia formations in the Daqingzijing block, Southern Songliao Basin, which was selected as the pilot well site for CO2-EOR storage. In the operation area, three facies, including deltaic plain, deltaic front and subdeep-deep lake facies associations, are recognized, in which 11 subfacies such as subaqueous distributary channel, river- mouth bar, interdistributary bay, sheet sandbody, crevasse splay and overflooding plain are further identified. These subfacies are the basic genetic units in the reservoir and sealing rocks. These facies further comprise the retrogradational and progradational depositional cycles, which were formed base- level rise and fall, respectively. During the regressive or lake lowstand stage, various sands including some turbidites and fans occurred mostly at the bottom of the hinged slope. During the progradation stage, these sands became smaller in size and episodically stepped backwards upon the slope, with greatly expanded and deeped lake. However, most of Cretaceous strata in the study area, localized in the basin centre under this stage, are mainly composed of grey or grizzly siltstones and grey or dark grey mudstones intercalated with minor fine sandstones and purple mudstones. On the base of borehole and core data, these siltstones are widespread, thin from 10 to 50 m thick, good grain sorting, and have relative mature sedimentary structures with graded bedding and cross- lamination or crossbeds such as ripples, which reflect strong hydrodynamic causes. Due to late diagenesis, pores are not widespread in the reservoirs, especially the first member of Qingshankou formation. There are two types of pores: primary pore and secondary cores. The primary pores include intergranular pores and micropores, and the secondary pores include emposieus and fracture pores. Throat channels related to pores is also small and the radius of throat in the first, second and third member of Qingshankou formation is only 0.757 μm, 0.802 μm and 0.631 μm respectively. In addition, based on analyzing the probability plot according to frequency of occurrence of porosity and permeability, they appear single- peaked distribution, which reflects strong hetero- geneity. All these facts indicate that the conditions of physical property of reservoirs are not better. One reason may be provided to interpret this question is that physical property of reservoirs in the study area is strong controlled by the depositional microfacies. From the statistics, the average porosity and permeability of microfacies such as subaqueous distributary channel, channel mouth bar, turbidites, is more than 9 percent and 1md respectively. On the contrary, the average porosity and permeability of microfacies including sand sheet, flagstone and crevasse splay are less than 9 percent and 0.2md respectively. Basically, different hydrodynamic environment under different microfacies can decide different physical property. According to the reservoir models of the first member of Qingshankou formation in the No. well Hei47 block, the character of sedimentary according to the facies models is accord to regional disposition evolution. Meantime, the parameter models of physical property of reservoir indicate that low porosity and low permeability reservoirs widespread widely in the study area, but the sand reservoirs located in the channels are better than other places and they are the main sand reservoirs. The distribution and sealing ability of fault- fractures and caprock are the key aspects to evaluate the stable conditions of compartments to store CO2 in the study area. Based on the core observation, the fractures widespread in the study area, especially around the wells, and most of them are located in the first and second member of Qingshankou formation, almost very few in the third member of Qingshankou formation and Yaojia formation instead. In addition, analyzing the sealing ability of eleven faults in the three-dimensional area in the study area demonstrates that most of faults have strong sealing ability, especially in the No. well Hei56 and Qing90-27. To some extent, the sealing ability of faults in the No. well Hei49, Qing4-6 and Qing84-29 are worse than others. Besides, the deposition environment of most of formations in the study area belongs to moderately deep and deep lake facies, which undoubtedly take advantage to caprocks composed of mudstones widespread and large scale under this deposition environment. In the study area, these mudstones distribute widely in the third member of Qingshankou formation, Yaojia and Nenjiang formation. The effective thickness of mudstone is nearly ~550m on an average with few or simple faults and fractures. In addition, there are many reservoir beds with widely- developed insulated interbeds consist of mudstones or silty mudstone, which can be the valid barrier to CO2 upper movement or leakage through diffusion, dispersion and convection. Above all, the closed thick mud caprock with underdeveloped fractures and reservoir beds can be taken regard as the favorable caprocks to provide stable conditions to avoid CO2 leakage.