Irreversible capacity loss of graphite electrode in lithium-ion batteries

The irreversible capacity loss of the carbon electrode in lithium-ion batteries at the first cycle is caused mostly by surface film growth. We inspected an unknown irreversible capacity loss (UICL) of the natural graphite electrodes. The charge/discharge behavior of graphite and meso-phase carbon microbeads heat-treated at 2800 degrees C (MCMB28) as the materials of the carbon anode in the lithium-ion battery were compared. It was found that the capacity loss of the natural graphite electrode in the first cycle is caused not only by surface film growth, but also by irreversible lithium-ion intercalation on the new formed surface at the potential range of lithium intercalation, while the capacity loss of the MCMB28 electrode is mainly originated from surface film growth. The reason for the difference of their irreversible capacity losses of these two kinds of carbon material was explained in relation to their structural characteristics. (C) 1997 Published by Elsevier Science S.A.

Ansa-metallocene derivatives .2. Syntheses and structures of tetramethyldisiloxandiyl bis(1-indenyl and tetrahydroindenyl) zirconium dichlorides

The ansa-zirconocene derivative tetramethyldisiloxandiyl bis(1-indenyl) zirconium dichloride (1) has been prepared by the reaction of the dilithium salt of 1,3-bis(l-indenyl) tetramethyldisiloxane with ZrCl4 . 2THF, After catalytic hydrogenation, the corresponding tetrahydroindenyl complex (2) has been formed. Both 1 and 2 have been shown by H-1 NMR spectra to be the mixture of the cis(meso) and trans(rac) isomers, The pure trans isomers 1(l), 2(l) and cis isomer 2(c) were obtained by recrystallization, The crystal structures of 1(l) and 2(c) were determined by X-ray diffraction. Both crystals of 1(l) and 2(c) are monoclinics, belonging to space groups P2(1)/n(1(l)) and P2(1)/c(2(c)). In the unit cell of 2(c), one of the six-membered rings of the tetrahydroindenyl Ligands has two different conformations which have the same probabilities.

过氧化物模拟酶生物传感器——二茂铁衍生物为介体

本文用三种二茂铁衍生物—双羟基乙基二茂铁、单羟基已基二茂铁和羧基二茂铁为介体,在过氧化物模拟酶-meso-四(4-磺基苯)卟啉锰存在下,检测过氧化氢。以双羟基、单羟基已基二茂铁为介体时,获得了良好的结果。

过氧化物模拟酶在介体型生物传感器方面应用初探

meso-四(4-磺基苯)卟啉锰(Ⅲ)作为过氧化物模拟酶可催化H_2O_2与K_4Fe(CN)_6反应。电流响应与H_2O_2浓度在3.0×10~(-4)～1.0×10~(-3)mol/L范围内呈线性关系。重现性和回收率良好。抗坏血酸和DL-半胱氨酸干扰严重。

过氧化氢歧化模拟酶CoTPPS_4用于电化学传感器的初步研究

随着模拟酶研究的深入,模拟酶在生物传感器方面的应用研究也逐渐开展起来。Sigel和Saito分别报道,meso-四(4-磺基苯)卟啉(TPPS_4)及其钴络合物(CoTPPS_4)可以作为过氧化氢歧化酶的模拟酶,并能催化H_2O_2的分解,但未见将此模拟酶应用于生物传感器的报道。本文将CoTPPS_4修饰的阴离子交换树脂用尼龙网固定在原电池式氧电极上,由H_2O_2分解生成的O_2来定量H_2O_2。实验证明该模拟酶可以很好地应用于生物传感器。

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.

东北亚构造-盆地演化及油气资源控制作用

The oil and gas potential of Northeast Asia is enormous, but the degree of exploration is very low in Northeast Asia (the degree is below 3%-10%).The reasons are as follows: First, it is relatively difficult to study the oil and gas bearing basins(OGB), which are of multiple types, in different tectonic settings, with complex geologic frameworks and with long-term geologic evolution. Secondly, because of the non-equilibrium in development of economy and regional market, application of theories and techniques and the research levels in different countries, the conclusions are not conformable, and even contradictory. Thirdly, most of the former researches were limited to one territory or one basin, and lack of systematical and in-depth study on geotectonic evolution, classification of basins, and the evaluation of hydrocarbon resources. In this thesis, integrated study of the regional tectonic feature and basin features of Northeast Asia was done, to understand the basin evolution history and the controlling action on oil and gas. Then, new conclusions are and exploration proposals are as following: 1. Geotectonic evolution in Northeast Asia: The main structural motion system in Paleozoic Era was longitudinal, and in Meso-cenozoic was latitudinal with the Pacific Ocean. The whole evolution history was just the one of pulling-apart, cutting-out, underthrusting and collision of the Central Asia- Mongolia Ocean and the Pacific Ocean. 2. The evolution characteristics of basins in Northeast Asia: mainly developed from longitudinal paste-up, collision and relaxation rifting motion in Paleozoic-Early Mesozoic Era and from underthrust, accretion, and receding of subducted zone of the Pacific Ocean in Late Mesozoic Era-Cenozoic Era. 3. The research in basin classification of Northeast Asia: According to geotectonic system, the basins can be classified into three types: intracratonic, pericratonic and active zone basin. And they can be further classified into 18 different types according to genetic mechanism and dynamic features. 4. The master control factors of oil and gas accumulation in Northeast Asia: high quality cap-rock for craton and pericrationic basin, the effective source rock and high quality cap-rock for Mesozoic rifted basins, intra-arc, fore-arc and back-arc basins. Graded exploration potential of oil and gas for basin in Northeast Asia according to 7 factor, hereby, divided the oil and gas potential of basins into 5 levels. 5. Evaluation of hydrocarbon resources: The difference of resource potential among these basins is huge in Northeast Asia. The evaluation of Mesozoic rifted basin and Pacific Ocean basin showed that the large scale rifted basin and retroarc basin(including backarc marginal sea basin) have great resource potential. 6. The writer believes that the next step should pay more attention to the evaluation of petroleum resource in Far East part of Russia and trace them. On the other hand, according to integrated analysis of oil/gas resource potential and the operation difficulty in this area, suggests that East-Siberia basin, East-Gobi-Tamchag basin, Sakhalin basin, North-Okhotck basin, West-Kamchatka basin could be as cooperation priority basins in future.

化德群和土门群沉积岩碎屑锆石研究：对华北克拉通基底及元古宙盆地演化的指示意义

The Huade Group, consisting of low-grade and un-metamorphosed sedimentary rocks with no volcanic interlayer, is located at the northern margin of the North China craton and adjoining the south part of the Central Asian Orogenic Belt. It is east to the Paleo- to Meso-Proterozoic Bayan Obo and Zhaertai-Langshan rifts and northwest to the Paleo- to Neo-proterozoic Yanshan aulacogen, in which the typical Changcheng, Jixian and Qingbaikou systems are developed. The Huade Group are mainly composed of pebbly sandstones, sandstones, greywackes，shales，calc-silicate rocks and limestones, partly undergoing low-grade metamorphism and being changed to meta-sandstones, schists, phyllites, slates and crystalline limestones or marbles. The stratigraphic sequences show several cycles of deposition. Each of them developed coarse clastic rocks – interbedded fine clastic rocks and pelites from bottom upward or from coarse clastic rocks to interbedded fine clastic rocks and pelites to carbonate rocks. The Tumen Group outcrop sporadically around or west to the Tanlu faults in western Shandong. They are mainly composed of pebbly sandstones, sandstones, shales and limestones. This thesis deals with the characteristics of petrology, geochemistry and sedimentary of the Huade Group and the Tumen Group, and discusses the LA-ICP-MS and SIMS U-Pb ages, Hf isotope and trace element composition of the detrital zircons from 5 meta-sandstone samples of the Huade Group and 3 sandstone samples of the Tumen Group. The age populations of the detrital zircons from the Huade Group are mainly ~2.5 Ga and ~1.85 Ga, and there are also minor peaks at ~2.0 Ga, ~1.92 Ga and ~1.73 Ga. Most of the detrital zircon grains of 2.47-2.57 Ga and a few of 1.63-2.03 Ga have Hf crust model ages of 2.7-3.0 Ga, and most of the detrital zircon grains of 1.63-2.03 Ga have Hf crust model ages of 2.35-2.7 Ga, with a peak at 2.54 Ga. The main age peaks of the detrital zircons from the Tumen Group are ~2.5 Ga、~1.85 Ga, 1.57 Ga, 1.5 Ga, 1.33 Ga and 1.2 Ga. Different samples from the Tumen Group have distinct Hf isotopic characteristics. Detrital zircon grains of ~2.52 Ga from one sandstone sample have 2.7-3.2 Ga Hf crust model ages, whereas zircon grains of 1.73-2.02 Ga and 2.31-2.68 Ga from another sample have Hf crust model ages of 2.95-3.55 Ga. Detrital zircon grains of Mesoproterozoic ages have Paleoproterozoic (1.7-2.25 Ga) crust model ages. Through detailed analyses of the detrital zircons from the Huade and Tumen Group and comparison with those from the sedimentary rocks of similar sedimentary ages, the thesis mainly reaches the following conclusions: 1. The youngest age peaks of the detrital zircons of 1.73 Ga constrains the sedimentary time of the Huade Group from late Paleoproterozoic to Mesoproterozoic. 2. The age peaks of detrital zircons of the Huade Group correspond to the significant Precambrian tectonic-thermal events of the North China craton. The basement of the North China craton is the main provenance of the Huade Group, of which the intermediate to high grade metamorphic sedimentary rocks are dominant and provide mainly 1.85-1.92 Ga sediments. 3. The Huade basin belongs to the North China craton and it is suggested that the northern boundary of the North China craton should be north to the Huade basin. 4. The stratigraphic characteristics indicate the Huade Group formed in a stable shallow-hypabyssal sedimentary basin. The rock association and sedimentary time of the Huade Group are similar to those of the Banyan Obo Group and the Zhaertai Group, and they commonly constitute late Paleoproterozoic to Mesoproterozoic continental margin basins along the northern margin of the North China craton. 5. The continental margin basins would have initiated coeval with the Yanshan and Xiong’er aulacogens. 6. The ages of the detrital zircons from the Tumen Group and the Penglai Group at Shandong peninsula and the Yushulazi Group at south Liaoning are similar, so their sedimentary time is suggested to be Neoproterozoic，coeval with the Qingbaikou system. The detrital zircon ages of 1.0-1.2 Ga from the Tumen Group, the Penglai Group and the Yushulazi Group indicate that there have being 1.0-1.2 Ga magmatic activities at the eastern margin of the North China craton. 7. The U-Pb age populations of the detrital zircons from the late Paleoproterozoic to Neoproterozoic sedimentary rocks suggest that the main Precambrian tectonic-thermal events of the North China craton happened at ~2.5 Ga and ~1.85 Ga. But the events at 2.7 Ga and 1.2 Ga are also of great significance. Hf isotope characteristics indicate that the significant crust growth periods of the North China craton are 2.7-3.0 Ga and ~2.5 Ga.

长白山火山成因—物理机制和化学演化

This thesis is one of the contributions to NSFC project, “The Changbaishan Volcanism and its Links to the Northeast Asia Tectonic System”. The thesis presents our most recent works on Changbaishan Volcanism, on two aspects as (1) the chemical evolution of the Cenozoic volcanism and the physical links of magma genesis, (2) the Holocene activity of the Tianchi Volcano and risks of potential eruption. 1. Chemical evolution and physical links to the Changbaishan Volcanism Physical links to the Chanbaishan Volcanism, just like origins of most of the volcanisms in eastern China, has long been an enigma. A large scale of volcanic activity has dominated many places of eastern China in Meso-Cenozoic. Activity of these volcanisms in eastern China covers several quite different blocks, covers variety of tectonics, and covers a period of time over 200 million years. Such a large-scale and long-lived volcanism in a continental area challenges our knowledge on dynamics of the Earth’s interior. Some works on “Diwa” hypothesis and “lithospheric thinning” hypothesis present possible links between volcanisms and dynamic evolutions of the earth’s interior, but still cannot interpret where are the sources of the heat and fluid, which are essential to the volcanisms. Based on the study of this thesis, we suggest that dynamics of the deep subduction of western Pacific Plate is the critical factor to the Changbaishan Volcanism and volcanisms in NE China, and maybe even essential to most of the Meso-Cenozoic volcanisms in eastern China. In NE China, stagnant slabs flatted in the mantle transition zone (MTZ, ca. 660 km deep) transport and release significant hydrous fluid to the upper mantle. Metamorphism of the deep-subducted slabs and hence a series of mineral phases play an important role in the water transport, exchange, restore, and release. Dehydrated fluid of the wet slab ascending from the MTZ fertile the upper mantle, and also provide upward heat flow which is essential to the magma genesis. Then magma and volcanism occur with the deep subduction from Mesozoic to mordern time in eastern China. To discribe the exact chemical characteristics of the deep subduction releated volcanics is very difficult, because few researches has contributed to the chemical behaviors of fluid and trace elments in the very deep interior of the Earth, such 660 km deep, 410km or 350km where the fluid may ascend and react. However we can still find some chemical characteristics of oceanic subduction. Basalts of the Changbaishan Volcanism have siginficant characteristics of potassium rich, and even can be called a potassic igneous province. If there are only two possible ways, recycled continentical crust or oceanic crust, to fertile the mantle potossium element as we know now, it’s easy to attribute this to the deep-subducted of the west Pacific Plate. To the eastern China, fluid inclusions in mantle xenoliths from the Cenozic basalts also reveal potassium-rich characteristics. This reveals that the same potassium feritle agents may occur in the mantle sources of eastern China. 2. Holocene activiy of the Tianchi Volcano As one of the large volcanic center and complex volcanic cone, the Tianchi Volcano is a dangerous active volcano, with several Holocene eruptions. Among these eruptions, the Millennium Eruption is regardede as one of the biggist eruptions in the world in the last 2000 years. To estimate the potential danger of volcanic eruption, we discuss two essential factors, as (i) volcanic history of Holocene eruptions, including volcanic geolgy, chronnology and chemistry, (ii) state, evolution and relationship of the magma chambers in mantle and crust beneath the Tianchi Volcano.

土石混合体细观结构力学及其边坡稳定性研究

Soil-rock mixture (S-RM) refers to one extremely uneven loose rock and soil materials system with certain stone content. Its formation has started since Quaternary and it is composed of block stone, fine grained soil and pore with certain project scale and high strength. S-RM has extensive distribution in nature, especially in southwest China where the geotectonic background is complicated, the fracture activity is developed and the geomorphological characteristics of high mountain and steep gorge area are protuberant. This kind of complicated geologic body has developed wider in these areas. S-RM has obvious difference with the general soil or rock (rock mass) in physical and mechanical properties because its two components-“soil” and “rock-block” has extreme differences in physical and mechanical properties. The proposition of S-RM and its deep research are needed in the modern engineering construction. It is also the necessity in the modern development of rock and soil mechanics. The dissertation starts from the meso-structural characteristics of soil-rock and takes a systematic research on its meso-structural mechanics, deformation and failure mechanism and the stability of S-RM slope. In summary, it achieves the following innovative results and conclusions. There are various views on the conception of S-RM and its classification system. Based on the large number of field tests, the dissertation makes the conception and classification of S-RM more systematic. It systematically proposed the conception of meso-structural mechanics of S-RM. Thus the dissertation has laid a foundation for its deep study. With the fast development of the computer technology and digital image processing theory, digital image processing technology has been successfully applied in many fields and provided reliable technology support for the quantitative description of the structural characteristics of S-RM. Based on the digital image processing technology, the dissertation systematically proposes and developed the quantitative analysis method and quantitative index for the meso-structure of S-RM. The results indicate that the meso-structure such as its internal soil-rock granularity composition, the soil-rock shape and the orientability has obvious self-organization in the macro statistical level. The dissertation makes a systematic research on the physical mechanical properties, deformation and failure mechanism of S-RM based on large field test. It proposes the field test for the underwater S-RM and deduces the 3D data analysis method of in-situ horizontal push-shear test. The result indicates that S-RM has significant phenomenon of shear dilatancy in the shearing process, and its dilatancy will be more obvious with the increased proportion of rock or the decreased confining pressure. The proportion of rock has great effect on the strength of S-RM and rock-block, especially the spatial position of particles with comparatively big size has great effect on the shape and spatial position of the sample shear zone. The dissertation makes some improvements in the single ring infiltration test equipment and its application on the permeability of S-RM. The results indicate that the increasing of rock-block would make it more difficult for the soil to fill in the vacuity between the rock-block and the proportion would increase which would result in the increased permeability coefficient. The dissertation builds the real meso-structural model of S-RM based on the digital image processing technology. By using geometric reconstruction technology, it transfers the structural mode represented by Binary image into CAD format, which makes it possible to introduce the present finite element analysis software to take research on numerical experimental investigation. It systematically realizes leaping research from the image，geometric mode, to meso-structural mechanics numerical experiment. By using this method, the dissertation takes large scale numerical direct-shear test on the section of S-RM. From the mesoscopic perspective, it reveals three extended modes about the shear failure plane of S-RM. Based on the real meso-structural model and by using the numerical simulation test, the character and mechanics of seepage failure of S-RM are studied. At the same time, it builds the real structural mode of the slope based on the analysis about the slope crosssection of S-RM. By using the strength reduction method, it takes the research on the stability of S-RM and gets great achievements. The three dimensional geometric reconstruction technology of rock block is proposed, which provides technical support for the reconstruction of the 3D meso-structural model of S-RM. For the first time, the dissertation builds the stochastic structure model of two-dimensional and three-dimensional polygons or polyhedron based on the stochastic simulation technique of monte carlo method. It breaks the traditional research which restricted to the random generation method of regular polygon and develops the relevant software system (R-SRM2D/3D) which has great effect on meso-structural mechanics of S-RM. Based on the R-SRM software system which randomly generates the meso-structural mode of S-RM according to the different meso-structural characteristics, the dissertation takes a series of research on numerical test of dual axis and real three-axis, systematically analyses the meso destroy system, the effects of meso-structural characteristics such as on the stone content, size composition and block directionality on the macro mechanical behavior and macro-permeability. Then it proposes the expression of the upper and lower limit for the macro-permeability coefficient of the inhomogeneous geomaterials, such as S-RM. By using the strength reduction FEM, the dissertation takes the research on the stability of the slope structural mode of the randomly formed S-RM. The results indicate that generally, the stability coefficient of S-RM slope increases with the increasing of stone content; on the condition of the same stone content, the stability coefficient of slope will be different with different size composition and the space position of large block at the internal slop has great effect on the stability. It suggests that meso-structural characteristics, especially the space position of large block should be considered when analyzing the stability of this kind of slope and strengthening design. Taking Xiazanri S-RM slope as an example, the dissertation proposes the fine modeling of complicated geologic body based on reverse engineering and the generation method of FLAC3D mode. It resolves the bottleneck problem about building the fine structural mode of three-dimensional geological body. By using FLAC3D, the dissertation takes research on the seepage field and the displacement field of Xiazanri S-RM slope in the process of reservoir water level rising and decreasing. By using strength reduction method, it analyses the three-dimension stability in the process of reservoir water level rising and decreasing. The results indicate that the slope stability firstly show downward trend in the process of reservoir water level rising and then rebound to increase; the sudden drawdown of reservoir water level has great effect on the slope stability and this effect will increase with the sudden drawdown amplitude rising. Based on the result of the rock block size analysis of S-RM, and using R-SRM2D the stochastic structure model of Xiazanri S-RM slope is built. By using strength reduction method, the stability of the stochastic structure model is analysis, the results shows that the stability factor increases significantly after considering the block.

中国南方热带地区田洋玛珥湖24万年以来的气候变化及湖泊演变

A continuous long (224m) and high-resolution core TY2 was recovered from paleo-maar-lake Tianyang, tropical South China. Based on the diatom records of the upper 130-m core, this paper focuses on exploring climate change and the lake evolution history in tropical South China during the past 240ka. The most typical and unique characteristics of the diatom assemblages is that, Aulacoseira granulata was dominant or absolutely dominant species (80-90%) during most parts of the 130-m core, while Cyclotella stelligera var. tenuis and Fragilaria construens var. venter were subdominant species in only limited parts of the lower and upper core, respectively. Time scale is always the biggest problem for the study of TY2 core, so although diatom is seldom used for establishing time scale, here we attempt this by correlating the diatom-reconstructed temperature sequence with the time scale of ODP core 806B from Equatorial Western Pacific. Verified by the few most reliable ages from TY2 core and the parallel core TYl, a rather reasonable and reliable time scale was established. 01S 7/6 falls at the depth of 100m (ca. 194kaBP), OIS 6/5 at 75m (ca. 132kaBP), OIS 5/4 at 46m (ca. 75kaBP), OIS 4-3 at 35m (ca. 60kaBP). Qualitative and quantitative environmental reconstructions are made on the basis of diatom assemblage ecotype and EDDI dataset. Correlation of diatom-reconstructed temperature and moisture changes of Core TY2 with pollen-reconstructed temperature and rainfall sequence of Core TYl proves that the results are quite consistent in most periods. Thus the reconstruction results from diatom are quite reliable, and probably have a much higher resolution than pollen results. Combined with lithological and magnetic susceptibility variations, the diatom analysis reveals that, the general climate in tropical South China during the past 240ka was warm and wet. On the time scale of glacial-interglacial, warm and wet, cool and dry are not always synchronous. It was relatively warm-wet during the penultimate interglacial, cool-dry during the penultimate glacial, warm-dry during the last interglacial, and cooler-drier during the last glacial. In contrast, on the time scale of subglacial-subinterglacial scales, warm and dry, cool and wet corresponds very obviously, showing very clear 21-23 ka precession cycle. Analysis also shows that, the water of Tianyang paleo-maar-lake was generally warm, turbulent, turbid, meso-trophic, slightly alkaline, low conductivity and fresh during the past 240 kaBP, with small variations in some parts. Tianyang paleolake experienced shallow to semi-deep lake in OIS7d, open shallow lake in OIS7c-OIS5b, shallow coastal lake in OIS5a-OIS4c, swamp in OIS4b, and then completely dried up in OIS3c. The lake evolution was mainly controlled by temperature and precipitation changes in tropical China. While temperature and precipitation changes were probably controlled by the migrations of monsoon rainband and the evaporation rate, which was in turn controlled by the evolution of East Asian monsoon. Therefore, when the summer monsoon was strongest the climate was warm-dry, when stronger the climate was warm-wet; when the winter monsoon was strongest the climate was cool-dry, stronger cool-wet. This mechanism caused the warm-dry sub interglacial and cool-wet subglacial climate in the tropical South China.

大兴安岭南段中生代火山-侵入杂岩带的双层叠置构造体制兼论滇中武定、易门碳酸质火山岩年代、来源及矿库与找矿研究

These are two parts included in this report. In the first part, the zonation of the complexes in its series, lithofacies, the depth of magma source and chambers is discussed in detailed for the first time based on the new data of petrol-chemistry, isotopes, tectono-magma activity of Mesozoic volcano-plutonic complexes in the southern Great Hinggan Mts. Then, the genetic model of the zonality, double overlapped layer system, is proposed. The main conclusions are presented as follows: The Mesozoic volcanic-plutonic complexes in the southern Great Hinggan were formed by four stages of magma activity on the base of the subduction system formed in late Paleozoic. The Mesozoic magmatic activity began in Meso-Jurassic Epoch, flourished in late Jurassic Epoch, and declined in early Cretaceous Epoch. The complexes consist dominantly of acidic rocks with substantial intermediate rocks and a few mefic ones include the series of calc alkaline, high potassium calc alkaline, shoshonite, and a few alkaline. Most of those rocks are characterized by high potassium. The volcano-plutonic complexes is characterized by zonality, and can be divided mainly into there zones. The west zone, located in northwestern side of gneiss zone in Great Xinggan mountains, are dominated of high potassium basalts and basaltic andesite. The middle zone lies on the southeast side of the Proterozoic gneiss zone, and its southeast margin is along Huangganliang, Wushijiazi, and Baitazi. It composed of dominatly calc-alkaline, high potassium calc-alkaline rocks, deep granite and extrusive rhyolite. The east zone, occurring along Kesheketong Qi-Balinyou Qi-Balinzuo Qi, is dominated of shoshonite. In generally, southeastward from the Proterozoic gneiss zone, the Mesozoic plutons show the zones-mica granitites zone, hornblende-mica granitite zone, mica-hornblende granitite zone; the volcanic rocks also display the zones of calc alkaline-high potassium calc alkaline and shoshonites. In the same space, the late Paleozoic plutons also display the same zonality, which zones are combined of binary granite, granodiorite, quartz diorite and diorite southeast wards from the gneiss. Meso-Jurassic Epoch granite plutons almost distribute in the middle zone on the whole. Whereas late Jurassic Epoch volcanic rocks distribute in the west and east zone. This distribution of the volcano-plutonic complexes reveals that the middle zone was uplifted more intensively then the other zones in Meso-Jurassic and late Jurassic Epoches. Whole rock Rb-Sr isochron ages of the high potassium calc-alkaline volcanic rocks in the west zone, the calc-alkaline and high potassium calc-alkaline granite the middle zone, shoshonite in the east zone are 136Ma, 175Ma and 154Ma, respectively. The alkaline rocks close to the shoshonite zone is 143Ma and 126Ma. The isochron ages are comparable well with the K-Ar ages of the rocks obtained previously by other researchers. The compositions of Sr ans Nd isotopes suggest that the source of Mesozoic volcanic-plutonic complexes in Great Hinggan Mts. is mostly Paleo-Asia oceanic volcanic-sedimentary rocks, which probably was mixed by antiquated gneiss. The tectonic setting for Mesozoic magmatism was subductive continental margin. But this it was not directly formed by present west Pacific subduction. It actully was the re-working of the Paleozoic subduction system( which was formed during the Paleo-Asia ocean shortening) controlled by west Pacific subduction. For this reason, Although Great Hinggan Mts. is far away from west Pacific subduction zone, its volcanic arc still occurred echoing to the volcanic activities of east China, it, but the variation trend of potassium content in volcano-plutonic complexes of Great Hinggan is just reverse to ones of west Pacific. The primitive magmas occurred in the southern Great Hinggan Mts. Include high-potassium calc-alkaline basalt, high potassium calc-alkaline rhyolite, high potassium rhyolite, non-Eu negative anomaly trachy-rhyolite et al. Therefore, all of primitive magmas are either mafic or acid, and most of intermediate rocks occurring in the area are the products of Mesozoic acid magma contaminated by the Paleozoic volcanic- sedimentary rocks. The depth of those primitive magma sources and chambers gradually increase from northwest to southeast. This suggests that Paleozoic subduction still controlled the Mesozoic magmatism. In summary, the lithosphere tectonic system of the southern Great Hinggan Mts. controlling Mesozoic magmatism is a double overlapped layer system developing from Paleozoic subduction system. For this reason, the depth of crust of the southern Great Hinggan Mts. is thicker than that of its two sides, and consequently it causes regional negative gravity abnormity. The second part of this report shows the prolongation of the research work carried on in my doctor's period. Author presents new data about Rb-Sr and Sm-Nd isotopic compositions and ages, geochamical features, genesis mineralogy and ore deposit geology of the volcanic rocks in Kunyang rift. On the base of the substantial work, author presents a prospect of copper bearing magnetite ore deposit. The most important conclusions are as follows: 1. It is proved that all of these carbonatites controlled by a ringing structure system in Wuding-Lufeng basin in the central Yunnan were formed in the Mesoproterozoic period. Two stages could be identified as follows: in the first stage, carbonatitic volcanic rocks, such as lavas(Sm-Nd, 1685Ma), basaltic porphyrite dykes(Sm-Nd, 1645Ma), pyroclastic rocks and volcaniclastic sedimentary rocks, formed in the outer ring; in the second stage, carbonatitic breccias and dykes(Rb-Sr, 1048 Ma) did in the middle ring. The metamorphic age of the carbonatitic lavas (Rb-Sr, 893 Ma) in the outer ring was determined. The magma of carbonatitic volcanic rocks derived mainly form enriched mantle whose basement is depleted mantle that had been metasomated by mantle fluid and contaminated by Archaean lower crust. Carbonatitic spheres were discovered in ore bearing layers in Lishi copper mining in Yimen recently, which formed in calcite carbonatitic magma extrusion. This discovery indicates that the formation of copper ore deposit genesis relates to carbonatitic volcanic activity. The iron and copper ore deposits occurring in carbonatitic volcanic- sedimentary rocks in Kunyang rift results from carbonatitic magmatism. Author calls this kind of ore deposits as subaqueous carbonatitic iron-copper deposit. The magnetic anomaly area in the north of Lishi copper mining in Yimen was a depression more lower than its circumference. Iron and copper ores occurrig on the margin of the magnetic anomaly are volcanic hydrothermal deposit. The magnetic body causing the magnetic anomaly must be magnetite ore. Because the anomaly area is wide, it can be sure that there is a large insidious ore deposit embedding there.

Direct synthesis of highly ordered Fe-SBA-15 mesoporous materials under weak acidic conditions

Iron-substituted SBA-15 (Fe-SBA-15) materials have been synthesized via a simple direct hydrothermal method under weak acidic conditions. The powder X-ray diffraction (XRD), NZ sorption and transmission electron microscopy (TEM) characterizations show that the resultant materials have well-ordered hexagonal meso-structures. The diffused reflectance UV-vis and UV resonance Raman spectroscopy characterizations show that most of the iron ions exist as isolated framework species for calcined materials when the Fe/Si molar ratios are below 0.01 in the gel. The presence of iron species also has significant salt effects that can greatly improve the ordering of the mesoporous structure. Different iron species including isolated framework iron species, extraframework iron clusters and iron oxides are formed selectively by adjusting the pH values of the synthesis solutions and Fe/Si molar ratios. (c) 2005 Elsevier Inc. All rights reserved.

Development and assessment of new sensor systems in food packaging applications

The use of optical sensor technology for non-invasive determination of key quality pack parameters improved package/product quality. This technology can be used for optimization of packaging processes, improvement of product shelf-life and maintenance of quality. In recent years, there has been a major focus on O2 and CO2 sensor development as these are key gases used in modified atmosphere packaging (MAP) of food. The first and second experimental chapters (chapter 2 and 3) describe the development of O2, pH and CO2 solid state sensors and its (potential) use for food packaging applications. A dual-analyte sensor for dissolved O2 and pH with one bi-functional reporter dye (meso-substituted Pd- or Ptporphyrin) embedded in plasticized PVC membrane was developed in chapter 2. The developed CO2 sensor in chapter 3 was comprised of a phosphorescent reporter dye Pt(II)- tetrakis(pentafluorophenyl) porphyrin (PtTFPP) and a colourimetric pH indicator α-naphtholphthalein (NP) incorporated in a plastic matrix together with a phase transfer agent tetraoctyl- or cetyltrimethylammonium hydroxide (TOA-OH or CTA-OH). The third experimental chapter, chapter 4, described the development of liquid O2 sensors for rapid microbiological determination which are important for improvement and assurance of food safety systems. This automated screening assay produced characteristic profiles with a sharp increase in fluorescence above the baseline level at a certain threshold time (TT) which can be correlated with their initial microbial load and was applied to various raw fish and horticultural samples. Chapter 5, the fourth experimental chapter, reported upon the successful application of developed O2 and CO2 sensors for quality assessment of MAP mushrooms during storage for 7 days at 4°C.

Water exchange rates of water-soluble manganese(III) porphyrins of therapeutical potential.

The activation parameters and the rate constants of the water-exchange reactions of Mn(III)TE-2-PyP(5+) (meso-tetrakis(N-ethylpyridinium-2-yl)porphyrin) as cationic, Mn(III)TnHex-2-PyP(5+) (meso-tetrakis(N-n-hexylpyridinium-2-yl)porphyrin) as sterically shielded cationic, and Mn(III)TSPP(3-) (meso-tetrakis(4-sulfonatophenyl)porphyrin) as anionic manganese(iii) porphyrins were determined from the temperature dependence of (17)O NMR relaxation rates. The rate constants at 298 K were obtained as 4.12 x 10(6) s(-1), 5.73 x 10(6) s(-1), and 2.74 x 10(7) s(-1), respectively. On the basis of the determined entropies of activation, an interchange-dissociative mechanism (I(d)) was proposed for the cationic complexes (DeltaS(double dagger) = approximately 0 J mol(-1) K(-1)) whereas a limiting dissociative mechanism (D) was proposed for Mn(III)TSPP(3-) complex (DeltaS(double dagger) = +79 J mol(-1) K(-1)). The obtained water exchange rate of Mn(III)TSPP(3-) corresponded well to the previously assumed value used by Koenig et al. (S. H. Koenig, R. D. Brown and M. Spiller, Magn. Reson. Med., 1987, 4, 52-260) to simulate the (1)H NMRD curves, therefore the measured value supports the theory developed for explaining the anomalous relaxivity of Mn(III)TSPP(3-) complex. A magnitude of the obtained water-exchange rate constants further confirms the suggested inner sphere electron transfer mechanism for the reactions of the two positively charged Mn(iii) porphyrins with the various biologically important oxygen and nitrogen reactive species. Due to the high biological and clinical relevance of the reactions that occur at the metal site of the studied Mn(iii) porphyrins, the determination of water exchange rates advanced our insight into their efficacy and mechanism of action, and in turn should impact their further development for both diagnostic (imaging) and therapeutic purposes.