Flow injection determination of dopamine based on inhibited electrochemiluminescence of luminol

A flow injection method has been developed for the determination of dopamine based on its inhibition of the electrochemiluminescence of luminol. This method is simple and sensitive for dopamine detection. Under the selected experimental conditions, the decreased electrochemiluminescent intensity is linear with dopamine concentration in the range of 5.0 x 10(-8)-1.0 x 10(-5) mol/L with a detection limit of 30 nmol/L. The relative standard deviation of eleven determinations is 1.9% for 1.0 x 10(-6) mol/L dopamine. The proposed method has been applied to the detection of dopamine in pharmaceutical injections with satisfactory results.

STUDIES ON INCREASING THE ACTIVITY OF SELENIUM-CONTAINING ABZYME .1. SYNTHESIS, CHARACTERIZATION AND PROPERTIES OF HAPTEN AND ANTIGEN

The thiol group of glutathione (GSH) reacts specifically with 2,4-di-ni-trochlorobenzene to give S-substituted dinitrophenyl glutathione (GSH-S-DNP); two carboxyl groups of GSH-S-DNP were further esterified by n-butanol to produce the hapten, multisubstrate analog GSH-S-DNP Butyl Ester (GSH-S-DNP BE). The primary structure of the hapten was characterized by the free. amino group analysis, H-1 NMR, IR determinations and the elemental analysis. The hapten was then conjugated to bovine serum albumin (BSA) in the presence of glutaraldehyde. The reaction mixture was purified by Ultrogel AcA54 colum chromatography to give the antigen. On an average, 25 haptens were bound to each BSA molecule. Electrophoresis analysis showed that the average molecular weight of the antigen was 87 KD. CD spectrum showed that the a-helix content of the antigen increased.

STUDY OF THE CHLORINATION REACTION OF Li2CO3 WITH NH4Cl

The chlorination reaction of Li2CO3 with NH4Cl has been studied in detail by a series of thermal analysis methods. When NH4Cl/Li2CO3 mole ratio equals 4, Li2CO3 can be transformed into LiCl quantitatively in a stream of Ar gas flow. All residual NH4Cl is decomposed completely at 400 degrees C and carried away from the reaction cell by Ar gas.Analysis by X-Ray diffraction and Ion Chromatography show that there are almost no NH4Cl remained in The LiCl product. It is interested that the chlorination reaction can be applied to the determinations of phase diagram by thermal analysis method and the preparation of Al-Li alloy by electrolysis in molten salt.

Early expressed genes showing a dichotomous developing pattern in the lancelet embryo

Lancelets (amphioxus), although showing the most similar anatomical features to vertebrates, never develop a vertebrate-like head but rather several structures specific to this animal. The lancelet anatomical specificity seems to be traceable to early developmental stages, such as the vertebrate dorsal and anterior-posterior determinations. The BMP and Wnt proteins play important roles in establishing the early basis of the dorsal structures and the head in vertebrates. The early behavior of BMP and Wnt may be also related to the specific body structures of lancelets. The expression patterns of a dpp-related gene, Bbbmp2/4, and two wnt-related genes, Bbwnt7 and Bbwnt8, have been studied in comparison with those of brachyury and Hnf-3 beta class genes The temporal expression patterns of these genes are similar to those of vertebrates; Bbbmp2/4 and Bbwnt8 are first expressed in the invaginating primitive gut and the equatorial region. respectively, at the initial gastrula stage. However, spatial expression pattern of Bbbmp2/4 differs significantly from the vertebrate cognates. It is expressed in the mid-dorsal inner layer of gastrulae and widely in the anterior region, in which vertebrates block BMP signaling, The present study suggests that the lancelet embryo may have two distinct developmental domains from the gastrula stage, the domains of which coincide later with the lateral diverticular and the somitocoelomic regions. The embryonic origin of the anterior-specific structures in lancelets corresponds to the anterior domain where Bbbmp2/4 is continuously expressed.

Clay mineral distributions in the southern Yellow Sea and their significance

To better understand the characteristics of the clay minerals in the southern Yellow Sea, the X-ray quantitative determinations have been carried out for the surface samples obtained from the Yellow Sea. With newly compiled clay mineral synoptic maps, the depositional processes were described for four main clay minerals (illite, chlorite, kaolinite and smectite). The analysis shows that most clay minerals are of terrigenous source with the Huanghe River acting as the major sediment supplier. Besides, the source of muddy sediments in the Yellow Sea was also discussed. As for the central Yellow Sea mud (CYSM), the sediments in its northern part mainly come from the Huanghe River, and those in the rest are of multi-origin. Very similarly, a large amount of sediments in the northern part of the southeastern Yellow Sea Mud (SEYSM) derive from the Keum River and Yeong-san River, while those in the southern part are of multi-origin.

华北克拉通孔玆岩系中石榴子石花岗岩的成因：熔体与残留相混合机制的研究

The most widespread rock associations in the Western Block of North China Craton are khondalites distributed mainly in Jining, Liangcheng and Datong. A large quantitiy of garnet-bearing granites are contained in the khondalites. A great deal of research has been carried out on them by previous researchers. Studies of these garnet-bearing granites consist essentially of structural characteristics, petrography and geochemistry, and finally geochronological determinations. Summing up these researches, it will not be difficult to see that all of these authors have regarded these large numbers of garnets (up to 20%) contained in granites as crystallized products from magmas, but they have not proved this from petrological perspective. Theoretically, there are possibly three kinds of petrogenesis as to these garnets. The first one is that they have been transferred to the granites from khondalites by melt when anatexis happened to khondalites, and they, in essence, are residual metamorphic garnets; The second one is that when the khondalites were being melted, these garnets were produced from biotite dehydration melting, and the newly formed garnets intruded together with the melt and eventually molded the garnet-bearing granites. Garnets of this possible kind either showed independent crystals, or garnets from khondalites took place secondary growth under favorable temperature and pressure conditions for their crystallization; The last possibility is that these garnets were crystallized from magmas in which suitable pressure, temperature and composition were available. These garnets, generally, should be fine-grained. The aim of this study is, through examining the mineral chemistry of the garnets and the whole rock chemistry, to ascertain under which kind of mechanism, in the world, did these garnets form? Besides, we try to calculate the temperatures under which khondalites began melting and reactions of the garnets and the cooled melts happened by garnet-biotite thermometry. The whole rock chemistry analyses of the garnet-bearing granites tell us that all the samples are strongly peraluminous (A/CNK greater than 1.1) on the A/NK vs. A/CNK plot. On the SiO2-K2O plot, the granites are mainly constrained to be high-K calc-alkaline and calc-alkaline series, consistent with previous researches. On the ACF（（Al2O3-Na2O-K2O）-FeO(T)-CaO） discrimination plot, all the six garnet-bearing granite samples drop into the area of S-type granites. The relationship between CaO/Na2O and SiO2 shows that the overwhelming majority of garnet-bearing granites have a CaO/Na2O value over 0.3, revealing that they probably come from metagreywacke precursors or mediate-felsic orthogeneisses compositionally similar to them. Detailed EPMA analyses conducted on the garnets contained in the garnet-bearing granites show that all the garnets are dominated by almandine and pyrope, which occupy 92-96% (Weight Percentage) of each garnet analyzed, typical of granulite facies. Their chemical composition is entirely different from those crystallized in magmas, but extremely similar to those of typical granulite facies metapelites in khondalites and typical granulites, indicating all the garnets to be metamorphogenic. In addition, REEs distribution patterns of the garnets are totally different from typical biotite granites and peraluminous granites. In other words, both LREE and HREE of our garnets are evidently lower than those from these two kinds of rocks. Moreover, compared to the REE pattern of the garnets from typical amphibolites, LREE content of our garnets is obviously higher and HREE content is a little lower. However, REE patterns of our garnets are completely in harmony with those of garnets from typical granulites. So, the REE patterns of garnets, again, prove that all the garnets we studied are metamorphogenic. Biotites appear in two forms, being as inclusions in the garnet and as selvages immediately adjacent to the garnet, respectively. Two reactions and their corresponding temperatures, with the help of petrography and Garnet-Biotite geothermometers, could be obtained, which are Bt+ Pl+ Qtz→Kfs+ Opx+ Grt+ melt as positive reaction and Kfs+ Grt+ melt→Bt+ Pl+ Qtz as reverse reaction, respectively. Summing up the discussion above, we declare that the garnet-bearing granites distributed in the Western Block of North China Craton are the mixture of melts and restites resulted from biotite dehydration melting. The garnets contained in the restites are the products from biotite dehydration melting and restites from the khondalites, respectively.

流体地球化学：成因、流动和流体-岩石相互作用及塔里木盆地实例研究

Geofluid in sedimentary basins is related to petroleum generation, migration, accumulation and preservation, and is a topic of geological frontier. By integrating the multi-discipline methods of petroleum geochemistry, sedimentology, hydrogeology, petroleum geology and experimental geochemistry, the thesis has carried out experiments of microcline dissolution in solutions with organic acids, crude oil, brines with high total dissolved solids (TDS), and has dealt with Al distribution between the crude oil and the brines after the experiments. Cases for study includes Central Tarim, Hetianhe Gas Field and Kucha forland basin with data containing fluid chemistry and isotopic compositions, thin sections of sandstones and carbonates, homogenization temperatures and salinities of fluid inclusions, isotopic compositions of bulk rock and autigenic minerals. The aims are to elucidate fluid origin and flow in the three areas, effect of hydrocarbon emplacement on diagenesis, and to show occurrence of microbe-mediated, and thermochemical sulfate reduction in the Tarim Basin. Microcline dissolution experiments show that after 100 hour, part of the dissolved Al distributes in the crude oil, and the Al concentrations in the crude oil rise when organic acids are added. The result can be used to explain that most oilfield waters in the Tarim Basin are characterized by less than 3mg/L Al. Crude oil added to the solutions can enhance microcline dissolution, which is also observed in the case - Silurian sandstones with early crude oil emplacement in the Central Tarim. Al and Si have higher concentrations in the experiments of oxalic acid than of acetic acid under the same pH conditions, suggesting that there exist Al-oxalate and Si-oxalate complexes. Presence of acetate can enhance the activity of Ca and Al, but Al concentrations have not been increased significantly due to formation of small Al-acetate complex during the experiments. Relationships between δD and δ~(18)O in conjunction with chemistry of oilfield waters show that the waters are evaporated connate waters, which subsequently mixed with meteoric water, and were influenced by water-rock interactions such as salt dissolution, dolomitization of calcite, albitization of feldspar. In the Hetianhe Gas Field where salt dissolution took place, δD and δ~(18)O values can be used to trace nicely meteoric water recharge area and flow direction, but TDS can not. Part of the waters have high TDS but very light δD and δ~(18)O. When combined with paleo-topography, or fluid potentials, meteoric water is suggested to flow eastward in the Hetianhe Gas Field, which is the same with the Central Tarim. Whist in the Kuche forland basin, meteoric water may have permeated Cambrian-Ordovician strata. Relationship between ~(87)Sr/~(86)Sr and 1/Sr can be used to indicate migration and mixing of brines from carbonate strata (low ~(87)Sr/~(86)Sr ratio but high Sr content), clastic strata (high ~(87)Sr/~(86)Sr ratio but low Sr content) and crystalline basement (high ~(87)Sr/~(86)Sr ratio and heavy δ~(18)O value). Using this approach, it can be found that ~(87)Sr-depleted brine from Ordovician carbonates have migrated up to and mixed with ~(87)Sr-enriched waters from Silurian and Carboniferous sandstones, and that Silurian brines have mixed with meteoric water. In the Kuche forland basin, brines from the Cambrian and Ordovician carbonates have higher ~(87)Sr/~(86)Sr ratios than those from the overlying sandstones, when combined with chemistry, δ~(15)N and ~3He/~4He ratios of the coexisting natural gases, suggesting that the brines were derived from the basement. There exists some debate on the effect of hydrocarbon emplacement on mineral diagenesis. Case-study from Silurian sandstones in the Central Tarim show that quartz has kept overgrowing secondarily when oil saturation was decreased by meteoric water flushing subsequently to hydrocarbon emplacement. Silicon precipitates on the water-wet quartz surface, leading to decreased Si concentration close to the surface. A Si grads can result in Si diffusion, which supplies Si for quartz overgrowth. Hydrocarbon oxidation-sulfate reduction is an important type of organic-inorganic interaction. Not only can it make secondary alteration of hydrocarbons, but generate H_2S and CO_2 gases which can improve reservoir property. Thermochemical sulfate reduction took place at the temperatures more than 125 ℃ to 140 ℃ in the Cambrian-Ordovician carbonates, the products - H_2S and CO_2 gases migrated up to the Silurian, and precipitated as pyrite and calcite, respectively. The pyrite has an average δ~(34)S value close to those of Ordovician seawater and anhydrite, and calcite has δ~(13)C value as low as -21.5‰. In the Hetianhe Gas Field, sulfate reduction bacteria carried by meteoric water flowing eastward may have preferentially depleted ~(12)C of light hydrocarbon gases, and results in heavier δ~(13)C values of the residual hydrocarbon gases and higher molar CO_2 in the natural gases in the west than in the east. Coexisting pyrite has δ~(34)S values as low as -24.9‰.

释光测年实验室的建立与沉积物释光测年技术研究

The main research projects reported in this paper are the establishment of a luminescence (OSL/TL) dating laboratory in The Institute of Geology and Geophysics, CAS, and studies on OSL dating technique and protocol of sediments from North China. These projects have been suggested in order to fit in with the needs of research developments in environmental changes, in particular the aridity and desertification in North China. A new luminescence dating laboratory in which there are a Rise TL/OSL-DA-15B/C reader with Sr-90 beta source, a set of Little More Tape 9022 alpha and beta irradiators, three set of Daybreak 583 intelligent alpha counters and sample preparation system has been set up in the Institute in June 2001. The courses of the establishment of a new laboratory involved a series of technical works, besides making a suitable choice of the equipment, as follows: installing and testing TL/OSL reader, calibrating the dose rate of the beta and alpha sources in the irradiators with the standard sources, testing and calibrating the count rates of the thick source alpha counting in the alpha counters with a standard sample, and then dating of the know age samples to check and examine the OSL/TL dating system. All data obtained from above calibrations and tests show that the established OSL/TL system, including the used equipment in it, can be used to determine age of the geological and archaeological samples with an error of equivalent dose (De) of less than 5%. The OSL dates of several sediment samples obtained from the system are good agreement with those from the OSL dating laboratory in Hong Kong University and ~(14)C dates within 1 - 2 standard deviations. The studies on OSL dating technique and protocol of sediment samples being in progress involve the De determinations with single aliquot regeneration (SAR) (Murray and Wintle, 2000) of the coarse grain quartz from sand dune samples and comparison of the De determinations obtained from SAR with those measured by using multiple aliquot regeneration of loess fine grains. The preliminary results from these research works are shown as follows. The very low natural equivalent dose (De) of about 0.012 - 0.03 Gy, corresponding age of less than 10 years, for BLSL (blue light stimulated luminescence) of the coarse grain quartz from modern sand dune samples in Horqin sand fields has been determined with both the SAR and multiple aliquot regeneration (MAR) techniques. This imply that the BLSL signal zeroing of the quartz could be reached before burying of the sand in Horqin sand fields. The De values and ages of the coarse grain quartz measured with SAR protocol are in good agreement with those obtained from multiple aliquot technique for the modern sand dune samples, but the errors of De from the MAR is greater than those from the SAR. This may imply that the higher precision of age determination for younger sand dune samples could be achieved with the SAR of coarse grain quartz. The MAR combining with "Australian Slide method" may be a perfect choice for De measurements of loess fine grain samples on the basis of analysis of De values obtained from the SAR and from the MAR. The former can be employed to obtain a reliable age estimate of loess sample as older as approximately SO ka BR There is a great difference between De determinations from the (post-IR) OSL of the SAR (Roberts and Wintle, 2001) and those from independent or expected estimates for the older samples. However, the age estimates obtained from the (post-IR) OSL of the SAR are mostly closed to the independent age determinations for the younger (age less than 10 ka) fine grain samples. It may be suggested that the (post-IR) OSL of the SAR protocol of the fine grain fraction would be a suitable choice to dating of the younger samples, but may be unsuitable for the older samples.

富硫流体的成因与硫酸盐还原作用研究

Origins of H_2S, thiols, thiophenes in natural gases and sulphur-enriched oils are complicated and thus some debates exist on them. The post-doctoral research is based upon oil- and gas-field data. Cases for study include Triassic Jianglingjiang Formation natural gases, Wolonghe Field, Sichuan Basin, Paleozoic oils and bitumen, Central Tarim, gases reserviored nearby Carboniferious - Ordovician unconformity, Hetianhe Field, Tarim Basin and sulphur-enriched oils in Tertiary reserviors in Jinxian Sag, Bohai Bay Basin. We have carried out analyses on the oils and gases for chemistry, δ~(13)C, δ~(34)S, and molecular composition of biomarkers, analyzed authigenetic pyrite forδ~(34)S, formation water for chemistry and δD and δ~(18)O along with petroleum system and burial history analyses, The aims are to assess the origins of the H2S and authigenetic pyrite, to discuss the possibility of reduced sulphur incorporation into hydrocarbons and to determine the mechanisms of hydrocarbon secondary alteration in the above four cases by comparison. The research shows that the reduced sulphur in the four cases is the result of thermochemical and biological sulphate reduction., TSR and BSR, respectively. No evidence indicates an origin of decomposition of organic matter or mantle - derived H2S in the cases. Elevated H_2S contents (up to 32%) in the Triassic Jialingjiang Formation are considered to result from TSR while relatively low H_2S (up to 2000ppm) in the Hetianhe Field resulted from BSR. However, it is not the case for the Central Tarim where relatively low H2S but abundant authigenetic pyrite occurr. Part of the H_2S in the Central Tarim reservoirs has reacted with iron released from clay minerals to precipitate pyrite. Thus, reduced sulphur δ~(34)S and reservoir temperatures rather than the H2S amount are reliable parameters to distinguish between TSR and BSR. TSR in Sichuan Basin Triassic Jialingjiang Formation and Central Tarim Paleozoic reservoirs are showed to take place at more than 125℃. the H2S and authigenetic pyrite have δ~(34)S close to parent anhydrite. In contrast, BSR in the reservoirs near the Carboniferous - Ordovician unconformity in the Hetianhe Field and in the Tertiary in the Jinxian Sag took place at temperatures less than 80℃with sulphide δ~(34)S as light as -24.9‰ and -12.5‰, anhydrite δ~(34)S as heavy as +26‰and +3 5-+40‰, respectively. Chemistry and isotopic composition of the natural gases change as the result of sulphate reduction. It has been observed that relative composition of light hydrocarbon gases is changed along with a rise in H_2S and CO_2. TSR in the Triassic Jialingjiang Formation and BSR in the Hetianhe Field result in a greater degree of preferential depletion of methane than larger molecular hydrocarbon gases. As TSR or BSR proceeds, hydrocarbon gases evolved to heavier carbon isotope as the result of kinetic isotopic fractionation, i.e., selective anaerobic oxidation of ~(12)C. Using the model of residual methane (Whiticar, 1999) to describe the relationship among the proportion of methane oxidation, isotopic shift and fraction factor, about 30% methane is calculated to have been oxidized during BSR in the western part of the Hetianhe Field. From the above, it can be concluded that in the area where H_2S is abundant, empiricalδ~(13)C -Ro relationships do not work. Sulphate reduction results in a rise in sulphur content, gravity and viscosity of an oil as well as changes in δ~(13)C and δ~(34)S. On special conditions, the reduced sulphur from sulphates might be incorporated into oils, i.e., the increasing sulphur is derived from secondarily reduced sulphur. A positive correlative relationship exists between sulphur content and δ~(34)S in the oils in Paleozoic reservoirs in Central Tarim, indicating that enhanced sulphur is ~(34)S-enriched, originated from TSR. The Jinxian oil with the highest sulphur content has the lightest δ~(34)S, suggesting part of the sulphur in the oil is ~(34)S-depleted, originated from BSR. In the Jinxian oil with increasing sulphur content, asphaltenes shows higher content and more negative δ~(13)C, and saturates shows evidence of biodegradetion and a decreasing content and a positive δ~(13)C shift. Thus, asphaltenes have δ~(13)C values closer to saturates. All the above indicate that the reduced sulphur has been incorporated into biodegradated saturates to generate new asphaltenes with relatively light δ~(13)C of saturates. Thiols and thiophenes in natural gases in the Triassic Jialingjiang Formation may result from reaction of H_2S with hydrocarbon. In the Jialingjiang Formation hydrocarbon gases are dominated by methane thus have a high dryness coefficient and thiols are showed to be positively related to H_2S content, suggesting that the thiols may result from H_2S reaction with short chain hydrocarbons. In contrast, high thiophenes occur in wet gases in Jurassic reservoirs with their source rock from sulphur - depleted type I kerogen, indicating that thiophenes may be a product of reaction of H2S with longer chain hydrocarbons.

辽河盆地东部凹陷热历史及其与油气关系

This dissertation focuses on the basin geothermal history, tectonothermal evolution and the relationship between geothermal field evolution and hydrocarbon generation. Based on the research of present-day geothermal field, geothermal history of Eastern Subdepression of Liaohe Basin was reconstructed with available data from drillings, loggings, seismic cross-sections, BHTs and thermal indicators. 12 heat flow density values were calculated. Ranging from 45.7 mW/m~2 to 70.0 mW/m~2, the mean value of these determinations exhibits 58.0(±5.83mW/m~22). The heat flow density in the uplift and ramp is greater than that in the sag. The main factors affecting the heat flow density are the morphostructure of basement and thickness of sedimentary cover. The Subdepression experienced a much higher heat flow period from 43 Ma to about 25 Ma. The heat flow increased gradually from Sha3 stage to Dongying stage, and reached the peak at the late of Dongying stage, then cooled down. Structural subsidence analysis shows that the subsidence of Eastern Subdepression can be divided into two phases: earlier (25-43Ma) initial (rift) and late (since 25Ma) thermal subsidence. The lower present-day heat flow and the higher palaeo-heat flow corresponding to structural subsidence stage as well as the typical rift subsidence style in Eastern Subdepression provide with some insights to the tectonic-thermal evolution of the basin. The source rocks of Sha3 member began to generate oil in the Shal stage, and entered oil-window at the late of Dongying stage. The source rocks of Shal began to generate oil at the late of Dongying stage, and being at the stage of lower maturation-maturation now. Most of Dongying source rocks are not mature now. The late of Dongying stage is the critical time for the oil system.

Synthesis and characterization of gallium-based perovskite-type dense membrane with oxygen semipermeability

La0.15Sr0.85Ga0.3Fe0.7O3-delta (LSGFO) and La0.15Sr0.85Co0.3Fe0.7O3-delta (LSCFO) mixed oxygen-ion and electron conducting oxides were synthesized by using a combined EDTA and citrate complexing method, and the corresponding dense membranes were fabricated. The properties of the oxide powders and membranes were characterized with combined SEM, XRD, H-2-TPR, O-2-TPD techniques, mechanical strength and oxygen permeation measurement. The results showed that LSGFO had much higher thermochemical stability than LSCFO due to the higher valence stability of Ga3+. After the temperature-programmed reduction by 5% H-2 in Ar from 20 degreesC to 1020 degreesC, the basic perovskite structure of LSGFO was successfully preserved. LSGFO also favors the oxygen vacancy formation better than LSCFO. Oxygen permeation measurement demonstrated that LSGFO had higher oxygen permeation flux than LSCFO, but they had similar activation energy for oxygen transportation, with a value of 110 and 117 kJ . mol(-1), respectively The difference in oxygen permeation fluxes was correlated with the difference in oxygen vacancy concentrations for the two materials.