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.

SOME NEWER CONCEPTS OF ETHYLENE ALPHA-OLEFIN COPOLYMERIZATION ON HETEROGENEOUS ZIEGLER-NATTA CATALYSTS

Unsteady diffusion kinetic, recently advanced by this laboratory, is applied to the examination of some polymerization and molecular chain structure problems. Hitherto deemed "anomalous" phenomena, such as the faster rate of copolymerization of ethylene/alpha-olefin than the homopolymerization of ethylene and the enrichment in the incorporation of a higher alpha-olefin in its copolymerization with ethylene by a lower alpha-olefin, are reasonably explained by unsteady diffusion of monomers. Molecular chain structure of copolymers, such as compositional heterogeneity and its dependence on comonomer incorporation originates from the difference in diffusion coefficients of the monomers. A copolymer composition equation taking into consideration the unsteady diffusion was developed. In cases where simulated curves were compared with experimental curves, good agreements were found.

Molecular determination of oxytetracycline-resistant bacteria and their resistance genes from mariculture environments of China

Aims: To assess the diversity of antibiotic-resistant bacteria and their resistance genes in typical maricultural environments. Methods nand Results: Multidrug-resistant bacteria and resistance genes from a mariculture farm of China were analysed via cultivation and polymerase chain reaction (PCR) methods. Oxytetracycline (OTC)-resistant bacteria were abundant in both abalone and turbot rearing waters, accounting for 3.7% and 9.9% of the culturable microbes. Multidrug resistance was common, with simultaneous resistance to OTC, chloramphenicol and ampicillin the most common resistance phenotype. 16S rDNA sequence analyses indicate that the typical resistant isolates belonged to marine Vibrio, Pseudoalteromonas or Alteromonas species, with resistance most common in Vibrio splendidus isolates. For OTC resistance, tet(A), tet(B) and tet(M) genes were detected in some multidrug-resistant isolates, with tet(D) being the most common molecular determinant. For chloramphenicol resistance, cat II was common, and floR was also detected, especially in marine Pseudoalteromonas strains. Conclusions: There is the risk of multidrug-resistant bacteria contamination in mariculture environments and marine Vibrio and Pseudoalteromonas species serve as reservoirs of specific antibiotic resistance determinants. Significance and Impact of the Study: This paper and similar findings from Korea and Japan indicate the potential for widespread distribution of antibiotic resistance genes in mariculture environments from the East Asian region of the world.

Diversity and spatial distribution of amoA-encoding archaea in the deep-sea sediments of the tropical West Pacific Continental Margin

The ecological characteristics of the deep-sea amoA-encoding archaea (AEA) are largely unsolved. Our aim was to study the diversity, structure and distribution of the AEA community in the sediments of the tropical West Pacific Continental Margin, to develop a general view of the AEA biogeography in the deep-sea extreme environment. Archaeal amoA clone libraries were constructed. Diverse and novel amoA sequences were identified, with the Bohol Sea, Bashi Strait and Sibuyan Sea harbouring the highest and the Bicol Shelf the lowest AEA diversity. Phylogenetic and statistical analyses illustrate a heterogeneous distribution of the AEA community, probably caused by the differential distribution of the terrestrial or estuarine AEA in the various sampling sites. The deep-sea sedimentary environments potentially harbour diverse and novel AEA in the tropical West Pacific Continental Margin. The stations in the Philippine inland seas (including station 3043) may represent AEA assemblages with various terrestrial influences and the stations connected directly to the open Philippine Sea may represent marine environment-dominant AEA assemblages. Our study indicates the potential importance of geological and climatic events in the transport of terrestrial micro-organisms to the deep-sea sedimentary environments, almost totally neglected previously.

Modern sedimentary environments and dynamic depositional systems in the southern Yellow Sea

Based on analyses of more than 600 surface sediment samples together with large amounts of previous sedimentologic and hydrologic data, the characteristics of modern sedimentary environments and dynamic depositional systems in the southern Yellow Sea (SYS) are expounded, and the controversial formation mechanism of muddy sediments is also discussed. The southern Yellow Sea shelf can be divided into low-energy sedimentary environment and high-energy sedimentary environment; the low-energy sedimentary environment can be further divided into cyclonic and anticyclonic ones, and the high-energy environment is subdivided into high-energy depositional and eroded environments. In the shelf low-energy environments, there developed muddy depositional system. In the central part of the southern Yellow Sea, there deposited the cold eddy sediments under the actions of a meso-scale cyclonic eddy (cold eddy), and in the southeast of the southern Yellow Sea, an anticyclonic eddy muddy depositional system (warm eddy sediment) was formed. These two types of sediments showed evident differences in grain size, sedimentation rate, sediment thickness and mineralogical characteristics. The high-energy environments were covered with sandy sediments on seabed; they appeared mainly in the west, south and northeast of the southern Yellow Sea. In the high-energy eroded environment, large amounts of sandstone gravels were distributed on seabed. In the high-energy depositional environment, the originally deposited fine materials (including clay and fine silt) were gradually re-suspended and then transported to a low-energy area to deposit again. In this paper, the sedimentation model of cyclonic and anticyclonic types of muddy sediments is established, and a systematic interpretation for the formation cause of muddy depositional systems in the southern Yellow Sea is given.

PCBs and its coupling with eco-environments in Southern Yellow Sea surface sediments

In this paper, the spatial distribution and source of the PCBs in surface sediments of the Southern Yellow Sea (SYS) and influencing factors, such as the sediment characteristics (components, relative proportions and total organic carbon contents), and hydrodynamic conditions were analyzed. PCB concentrations in the surface sediments ranged from 518-5848 pg/g, with average values of 1715 pg/g decreasing sharply compared to last year. In the study area, the PCB pollution level in the middle area was the highest, followed by that of the east coast and the west coast, respectively. Although the PCB level in the coastal areas was lower than that in the middle areas, it was proven in our study that the Yellow Sea obtained PCBs by virtue of river inputs. There was a positive and pertinent correlation between the clay proportion and PCB concentrations, and the increase of the PCB concentrations was directly proportional to the increase of TOC contents, with r = 0.61, but it was contrary to the sediment grain size. Consequently, the factors controlling PCB distribution had direct or indirect relationships with sediment grain size; moreover, the hydrodynamic conditions determined the sediment components and grain size. In conclusion, hydrodynamic conditions of the Yellow Sea were the most important influencing factors effecting the distribution of PCBs in the surface sediments of the SYS. (C) 2007 Elsevier Ltd. All rights reserved.

Behavioural responses by yaks in different physiological states (lactating, dry or replacement heifers), when grazing natural pasture in the spring (dry and germinating) season on the Qinghai-Tibetan plateau

Using heterogeneous vegetation in alpine grassland through grazing is a necessary component of deintensification of livestock systems and conservation of natural environments. However, better understanding of the dynamics of animal feeding behaviour would improve pasture and livestock grazing managements, particularly in the early part of the spring season when forage is scarce. The changes in behaviour may improve the use of poor pastures. Then, enhancing management practices may conserve pasture and improve animal productivity. Grazing behaviour over 24 In periods by yaks in different physiological states (lactating, dry and replacement heifers) was recorded in the early, dry and later, germinating period of the spring season. Under conditions of inadequate forage, the physiological state of yaks was not the primary factor affecting their grazing and ruminating behaviour. Forage and sward state affected yaks' grazing and ruminating behaviour to a greater extent. Generally, yaks had higher intake and spent more time grazing and ruminating during the later part of the spring season, following germination of forage, than during the earlier dry part of the season. However, the live weight of yaks was less during pasture germination than during the early dry part of the season because the herbage mass is low, and the yaks have to expend much energy to seek feed at this particular time. (c) 2007 Elsevier B.V. All rights reserved.

东海陆架盆地西南部烟囱构造与油气运聚关系研究

In recent years, chimney structure has been proved one of important indicators and a useful guide to major petroleum fields exploration through their exploration history both at home and abroad. Chimney structure, which has been called "gas chimney" or "seismic chimney", is the special fluid-filled fracture swarm, which results from the boiling of active thermal fluid caused by abruptly decreasing of high pressure and high temperature in sedimentary layers of upper lithosphere. Chimney structure is well developed in continental shelf basin of East China Sea, which indicates the great perspectives of petroleum resources there. However, the chimney structure also complicated the petroleum accumulation. So the study of chimney structure on its formation, its effect on occurrence and distribution of petroleum fields is very important not only on theoretical, but also on its applied research. It is for the first time to make a clear definition of chimney structure in this paper, and the existence and practical meaning of chimney structure are illustrated. Firstly, on the viewpoint of exploration, this will amplify exploration area or field, not only in marine, but also on continent. Secondly, this is very important to step-by-step exploration and development of petroleum fields with overpressure. Thirdly, this will provide reference for the study on complex petroleum system with multi-sources, commingled sources and accumulation, multi-stage accumulations, and multi-suits petroleum system in the overlay basin. Fourthly, when the thermal fluid enters the oceanic shallow layer, it can help form gas hydrate under favorable low-temperature and high-pressure conditions. Meanwhile, the thermal fluid with its particular component and thermal content will affect the physical, chemical and ecological environments, which will help solving the problem of global resources and environment. Beginning from the regional tectonic evolution characteristics, this paper discussed the tectonic evolution history of the Taibei depression, then made an dynamical analysis of the tectonic-sedimentary evolution during the Mesozoic and Cenozoic for the East China Sea basin. A numerical model of the tectonic-thermal evolution of the basin via the Basin-Mod technique was carried out and the subsidence-buried history and thermal history of the Taibei depression were inverse calculated: it had undergone a early rapid rift and sag, then three times of uplift and erosion, and finally depressed and been buried. The Taibei depression contains a huge thick clastic sedimentary rock of marine facies, transitional facies and continental facies on the complex basement of ante-Jurassic. It is a part of the back-arc rifting basins occurred during the Mesozoic and Cenozoic. The author analyzed the diagenesis and thermal fluid evolution of this area via the observation of cathodoluminescence, scanning electron microscope and thin section, taking advantage of the evidences of magma activities, paleo-geothermics and structural movement, the author concluded that there were at least three tectonic-thermal events and three epochs of thermal-fluid activities; and the three epochs of thermal-fluid activities were directly relative to the first two tectonic-thermal events and were controlled by the generation and expulsion of hydrocarbon in the source rock simultaneously. Based on these, this paper established the corresponding model between the tectonic-thermal events and the thermal-fluid evolution of the Taibei Depression, which becomes the base for the study on the chimney structures. According to the analyses of the gas-isotope, LAM spectrum component of fluid inclusion, geneses of CO_2 components and geneses of hydrocarbon gases, the author preliminarily verified four sources of the thermal fluid in the Taibei Depression: ① dehydration of mud shale compaction, ② expulsion of hydrocarbon in the source rock; ③ CO_2 gas hydro-thermal decomposition of carbonatite; ④magma-derived thermal fluid including the mantle magma water and volatile components (such as H_2O, CO_2, H_2S, SO_2, N_2 and He etc.). On the basis of the vitrinite reflectance (Ro), homogenization temperature of fluid inclusion, interval transit time of major well-logging, mud density of the wells, measured pressure data and the results of previous studies, this paper analyzed the characteristics of the geothermal fields and geo-pressure fields for the various parts in this area, and discussed the transversal distribution of fluid pressure. The Taibei depression on the whole underwent a temperature-loss process from hot basin to cold basin; and locally high thermal anomalies occurred on the regional background of moderate thermal structure. The seal was primarily formed during the middle and late Paleocene. The overpressured system was formed during the middle and late Eocene. The formation of overpressured system in Lishui Sag underwent such an evolutionary process as "form-weaken-strengthen-weaken". Namely, it was formed during the middle and late Eocene, then was weakened in the Oligocene, even partly broken, then strengthened after the Miocene, and finally weakened. The existence of the thermal fluid rich in volatile gas is a physical foundation for the boiling of the fluid, and sharply pressure depletion was the major cause for the boiling of the fluid, which suggests that there exists the condition for thermal fluid to boil. According to the results of the photoelastic simulation and similarity physical experiments, the geological condition and the formation mechanism of chimnestructures are summarized: well compartment is the prerequisite for chimney formation; the boiling of active thermal fluid is the original physical condition for chimney formation; The local place with low stress by tension fault is easy for chimney formation; The way that thermal fluid migrates is one of the important factors which control the types of chimney structures. Based on where the thermal fluid come from and geometrical characteristics of the chimney structures, this paper classified the genetic types of chimney structures, and concluded that there existed three types and six subtypes chimney structures: organic chimney structures generated by the hydrocarbon-bearing thermal fluid in middle-shallow layers, inorganic and commingling-genetic chimney structures generated by thermal fluid in middle-deep layers. According to the seismic profiles interpretations, well logging response analysis and mineralogical and petrological characteristics in the study area, the author summarized the comprehensive identification marks for chimney structures. Especially the horizon velocity analysis method that is established in this paper and takes advantage of interval velocity anomaly is a semi-quantitative and reliable method of chimney structure s identification. It was pointed out in this paper that the occurrence of the chimney structures in the Taibei depression made the mechanism of accumulation complicated. The author provided proof of episodic accumulation of hydrocarbon in this area: The organic component in the boiling inclusion is the trail of petroleum migration, showing the causality between the boiling of thermal fluid and the chimney structures, meanwhile showing the paroxysmal accumulation is an important petroleum accumulation model. Based on the evolutionary characteristics of various types of chimney structures, this paper discussed their relationships with the migration-accumulation of petroleum respectively. At the same time, the author summarized the accumulating-dynamical models associated with chimney structures. The author analyzed such accumulation mechanisms as the facies state, direction, power of petroleum migration, the conditions of trap, the accumulation, leakage and reservation of petroleum, and the distribution rule of petroleum. The author also provides explanation for such practical problems the existence of a lot of mantle-derived CO_2, and its heterogeneous distribution on plane. By study on and recognition for chimney structure, the existence and distribution of much mantle-derived CO_2 found in this area are explained. Caused by tectonic thermal activities, the deep magma with much CO_2-bearing thermal fluid migrate upward along deep fault and chimney structures, which makes two wells within relatively short distance different gas composition, such as in well LF-1 and well LS36-1-1. Meanwhile, the author predicted the distribution of petroleum accumulation belt in middle-shallow layer for this area, pointed out the three favorable exploration areas in future, and provided the scientific and deciding references for future study on the commingling-genetic accumulation of petroleum in middle-deep layer and the new energy-gas hydrate.

Heterogeneous asymmetric hydrogenation of ethyl pyruvate on chirally modified Pt/Al2O3 catalyst with fixed-bed reactor

The enantioselective hydrogenation of ethyl pyruvate on the cinchonidine modified Pt/Al2O3 catalyst was investigated using a high-pressure reaction system with a fixed-bed reactor for the purpose to produce the,chiral product without separating the catalyst from the reaction system. The reaction was also investigated in a batch reactor for comparison. About 60% e. e. and 90% e. e. were obtained with the fixed-bed reactor and the batch reactor respectively, demonstrating the possibility for the heterogeneous asymmetric hydrogenation in the fixed-bed reactor. Some adsorbed chiral modifier, cinchonidine, can be slowly removed from the surface of Pt/Al2O3 under the continuous flow reaction, as a result, the e, e, values drops with the reaction time in the fixed-bed reactor. The enantio-selectivity is higher in the fixed-bed reactor, but lower in the batch reactor when ethanol was used as solvent than that when acetic acid as solvent. CO was used as molecular probe to characterize the adsorption of cinchonidine an the catalyst surface by IR spectroscopy, A red shift observed in IR spectra of coadsorbed CO with cinchonidine suggests that the cinchonidine adsorption is mainly through the pi -interaction with platinum surface and donating electron to the platinum surface.

Ligand modified real heterogeneous catalysts for fixed-bed hydroformylation of propylene

A novel ligand modified heterogeneous catalyst has been developed for hydroformylation of propylene, which showed excellent activity, selectivity and stability and need not be separated from the product after reaction in a fixed-bed reactor. The coordination bonds between triphenyl phosphine (PPh3) and Rh/SiO2 were confirmed by means of thermogravimetric (TG), solid-state P-31 NMR, XPS and FT-IR. Two types of active species for hydroformylation were formed, which were proved by in situ FT-IR techniques. The problem of metal leaching was greatly reduced by directly fastening Rh particles on the support, and the active Rh species that was responsible for the outstanding performance of propylene hydroformylation was tightly bound by the very strong metal-metal bonds. No sign of deactivation was observed over a period of more than 1000 h on the condition that PPh3 was added at 300-350 h of time on stream. (c) 2005 Elsevier B.V. All rights reserved.

Heterogeneous enantioselective epoxidation catalyzed by Mn(salen) complexes grafted onto mesoporous materials by phenoxy group

Three chiral Mn(salen) complexes were immobilized into different mesoporous material via phenoxy group by a simplified method and they show high activity and enantioselectivity for asymmetric epoxidation of various substituted unfunctional olefins. The heterogeneous Mn(salen) catalysts show comparable ee values for asymmetric epoxidation of styrene and 6-cyano-2,2-dimethylchromene and much higher ee values for epoxidation of a-methylstyrene (heterogeneous 79.7% ee versus homogeneous 26.4% ee) and cis-beta-methylstyrene (heterogeneous 94.9% ee versus homogeneous 25.3% ee for cis-epoxide) than the homogeneous catalysts. These heterogeneous catalysts also remarkably alter the cis/trans ratio of epoxides for asymmetric epoxidation of cis-beta-methylstyrene (heterogeneous 21 versus homogeneous 0.38). The axial tether group does not make a big effect on ee values and the increase in ee value and change in cis/trans ratio are mainly attributed to the axial immobilization mode and the support effect of heterogeneous catalysts. The catalysts keep constant ee values for the recycle tests of eight times for asymmetric epoxidation of a-methylstyrene. And several possibilities were proposed to elucidate the difference in ee values of heterogeneous catalysts from homogeneous catalysts. (c) 2005 Elsevier B.V. All rights reserved.