Determination of 30 free fatty acids in two famous Tibetan medicines by HPLC with fluorescence detection and mass spectrometric identification

A simple and sensitive high-performance liquid chromatographic (HPLC) method with fluorescence detection and mass spectrometric identification has been developed for analysis of 30 long-chain and short-chain free Fatty acids (FFAs). The fatty acids were derivatized to their esters with 1-[2-(p-toluenesulfonate)ethyl]-2-phenylimidazole-[4,5-f]-9,10-phenanthrene (TSPP) in N,N-dimethylformamide (DMF) at 90 degrees C with anhydrous K2CO3 as catalyst. A mixture Of C-1-C-30 fatty acids was completely separated within 60 min by gradient elution on a reversed-phase C-8 column. Qualitative identification of the acids was performed by atmospheric-pressure chemical ionization mass spectrometry (APCI-MS) in positive-ion mode. The fluorescence excitation and emission wavelengths were 260 and 380 nm, respectively. Quantitative determination of the 30 acids in two Tibetan medicines Gentiana straminea and G. dahurica was performed. The results indicated that the medicines contained many FFAs. Linear correlation coefficients for the FFA derivatives were > 0.9991. Relative standard deviations (RSDs, n = 6) for the fatty acid derivatives were < 3%. Detection limits (at a signal-to-noise ratio of 3:1) were 3.1-38 fmol. When the fatty acid derivatives were determined in the two real samples results were satisfactory and the sensitivity and reproducibility of the method were good.

Influence of grazing intensity on performance of perennial grass mixtures in the alpine region of the Tibetan Plateau

Effects of grazing intensity on leaf photosynthetic rate (Pn), specific leaf area (SLA), individual tiller density, sward leaf area index (LAI), harvested herbage DM, and species composition in grass mixtures (Clinelymus nutans + Bromus inermis, Elymus nutans + Bromus inermis + Agropyron cristatum and Elymus nutans + Clinelymus nutans + Bromus inermis + Agropyron cristatum) were studied in the alpine region of the Tibetan Plateau. Four grazing intensities (GI), expressed as feed utilisation rates (UR) by Tibetan lambs were imposed as follows: (1) no grazing; (2) 30% UR as light grazing; (3) 50% UR as medium grazing; and (4) 70% UR as high grazing. Leaf Pn rate and tiller density of grasses increased (P < 0.05), while sward LAI and harvested herbage DM declined (P < 0.05) with the increments of GI, although no effect of GI on SLA was observed. With increasing GI, Elymus nutans and Clinelymus nutans increased but Bromus inermis and Agropyron cristatum decreased in swards, LAI and DM contribution. Whether being grazed or not, Elymus nutans + Clinelymus nutans + Bromus inermis + Agropyron cristatum was the most productive sward among the grass mixtures. Thus, two well-performed grass species (Elymus nutans and Clinelymus nutans) and the most productive mixture of four species should be investigated further as the new feed resources in the alpine grazing system of the Tibetan Plateau. Light grazing intensity of 30% UR was recommended for these grass mixtures when swards, LAI, herbage DM harvested, and species compatibility were taken into account.

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.

中国东部上第三系硬粘土的工程地质特性及边坡开挖工程环境效应研究

The engineering geological properties of Neogene hard clays and related engineering problems are frontiers in the fields of Engineering Geology, Soil Mechanics and Rock Mechanics. Recently, it has been recognized that Neogene hard clay is the intermediate type of material between the soil and the rock. Many aspects of them, such as sampling, testing, calculating and engineering process, are special, which could not be researched by means of theories and methods of traditional Soil Mechanics of Rock Mechanics. In order to get real knowledge and instruct the engineering practice, intersect studying of multiple disciplines, including Engineering Geology, Soil Mechanics and Rock Mechanics, etc., is necessary. Neogene hard clay is one of the important study objects of regional problem rocks & soils in our country, which extensively distributed in China, especially in Eastern China. Taking the related areas along the middle line of the Project of Transferring Water from the South to the North (e.g. Nanyang basin, Fangcheng-Baofeng area and Handan-Yongnian area), South-west of Shandong, Xu-Huai area and Beijing area, etc. as main study areas, the paper divided Neogene hard clays into reduction environment dominated origin and oxidation environment dominated origin, which distributed on areas western and eastern to Mount Taihangshan respectively. Intermediate types are also existed in some areas, which mainly distribute near the edges of depositional basins; they are usually of transitions between diluvial and lacustrine deposits. As to Neogene hard clays from Eastern China, the clay particle content is high, and montmorillonite or illite/montmorillonite turbostratic mineral is the dominating clay mineral. The content of effective montmorillonite is very high in each area, which is the basis for the undesirable engineering properties of Neogene hard clays. For hard clays from the same area, the content of effective montmorillonite in gray-greenish hard clay is much higher than that in purple-brownish or brown-yellowish hard clay, which is the reason why the gray-greenish hard clay usually has outstanding expansive property. On the other hand, purple-brownish or brown-yellowish hard clay has relatively less montmorillonite, so its property is better. All of these prove that the composition (clay mineral) of Neogene hard clay is the control factor for the engineering properties. Neogene hard clays have obvious properties such as fissured, overconsolidated and expansive, which are the main reasons that many engineering problems and geological harzards usually occur in Neogene hard clays. The paper systematically elaborates the engineering properties of Neogene hard clays from Eastern China, analyses the relationships between engineering properties and basic indexes. The author introduces the ANN method into the prediction of engineering property indexes of hard clays, which provides a new way for quantitatively assessment and prediction of engineering property indexes. During investigation in the field, the author found that there exists obvious seam-sheared zone between different hard clays in Miocene Xiacaowan formation in Xu-Huai area. Similar phenomenon also exists near the borderline between Neogene hard clays and underlying coal measures in the Southwest of Shandong province, which could be observed in the cores. The discovery of seam-sheard zone has important theoretical and practical significance for engineering stability analysis and revealing the origin of fissures in Neogene hard clays. The macrostructure, medium structure and microstructure together control the engineering properties of hard clays. The author analyses and summarizes the structural effects on hard clays in detail. The complex of the strength property of hard clays is mostly related to the characteristics of fissures, which is one of the main factors that affect the choice of shear strength parameters. So structure-control theory must be inseparably combined with composition-control theory during the engineering geological and rock/soil mechanics research of hard clays. The engineering properties, such as fissured, overconsolidated and expansive, control the instability of engineering behaviors of Neogene hard clays under the condition of excavation, i.e. very sensitive to the change of existence environment. Based on test data analysis, the author elaborates the effects of engineering environment change on the engineering properties. Taking Nanyang basin as example, the author utilizes FEM to study the effects of various factors on stability of cutting canal slopes, than sets forth the characteristics, development laws and formation mechanism of the deformation and failure of hard clay canal slopes, summarizes the protection and reinforcement principles, as well as the protection and remedy steps. On the basis of comparison of engineering properties of domestic and foreign Neogene muddy deposits, in the view of whole globe and associated with the geological characteristics of China, the paper demonstrates that the intermediate type of the material between the soil and the rock, named "hard clay/soft rock", which can not be separated abruptly, really exists in China. The author has given a preliminary classification based on its geological origin and distribution law, which is very significant for promoting the mixture of Engineering Geology, Soil Mechanics and Rock Mechanics. In the course of large scales engineering construction in China, many engineering experiences and testing data are gained, summarizing these testing results and automatically managing them with computer technology are very necessary. The author develops a software named "Hard Clay-Soft Rock Engineering Geological Information Management and Analysis System (HRGIMS)", realizes the automatic and visual management of geo-engineering information, on the basis of information management, the functions of test data analysis and engineering property prediction are strengthened. This system has well merits for practice and popularization.

温度、压力耦合背景下多相流体运移的数学模型研究

The Mathematical modeling of multiphase fluid flow is an important aspect of basin simulation, and also is a topic of geological frontier. Based on coupling relation of temperature, pressure and fluid flow, this dissertation discusses the modeling which conform to geological regularities of fluid migration. The modeling that is multi-field and multiphase includes heat transport equation, pressure evolvement equation, solution transport equation and fluid transport equation. The finite element method is effective numerical calculation methods. Author applies it to solve modeling and implements the finite element program, and the modeling is applied to Ying-Qiong Basin. The channels of fluid vertical migration are fault, fracture and other high penetrability area. In this thesis, parallel fracture model and columnar channel model have been discussed, and a characteristic time content and a characteristic space content been obtained to illustrate the influences of stratigraphic and hydrodynamic factors on the process. The elliptoid fracture model is established and its approximately solution in theory is gotten. Three kinds of modeling are applied to analyze the transient variation process of fluid pressure in the connected permeable formations. The elliptoid fracture model is the most similar geology model comparing with the other fracture models so the research on this fracture model can enhance the understanding to fluid pressure. In the non-hydrodynamic condition, because of the difference between water density and nature gas density, nature gas can migrate upon by float force. A one-dimension mathematical model of nature gas migration by float force is established and also applied to analyze the change in the saturation of gas. In the process of gas migration its saturation is non-continuous. Fluid flow is an important factor which influences the distribution of the temperature-field, the change of temperature can influence fluid property (including density, viscidity, and solubility),a nd the temperature field has coupling relations to the fluid pressure field. In this dissertation one-dimension and two-dimension thermal convection modeling is developed and also applied to analyze convective and conductive heat transfer. Author has established one-dimension and two-dimension mathematical modeling in which fluid is a mixture of water and nature gas based on the coupling relation between temperature and pressure, discussed mixture fluid convection heat transfer in different gas saturation, and analyzed overpressure form mechanism. Based on geothermal abnormity and pore pressure distribution in Dongfong 1-1, Yinggehai Basin, South China Sea, one-dimension mathematical modeling of coupling temperature and pressure is established. The modeling simulates the process that fluid migrates from deep to shallow and overpressure forms in shallow. When overpressure is so large that fractures appear and overpressure is released. As deep fluid flow to shallow, the high geothermal then forms in shallow. Based on the geological characteristics in Ya13-1, two-dimension mathematical modeling of coupling temperature and pressure is established. Fluid vertically flows in fault and then laterally migrates in reservoir. The modeling simulates the geothermal abnormity and pore pressure distribution in reservoir.

A novel silica-based column packing for reversed-phase HPLC of basic compounds

A novel bonded phase for reversed-phase HPLC was synthesized in two steps. Octylamine was first reacted with beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (beta -ECTS) and then the intermediate product was coupled onto porous silica. The prepared packing was characterized by elemental analysis, solid-state C-13 NMR and Fourier transform infrared (FT-IR). Chromatographic evaluations were carried out by using a mixture of organic compounds including acidic, basic and neutral analytes and methanol-water as binary mobile phase. The results showed that the stationary phase has excellent chromatographic properties and is resistant to hydrolysis between pH = 2 similar to 8. It can be used efficiently for the separation of basic compounds.

Simple derivatization method for sensitive determination of fatty acids with fluorescence detection by high-performance liquid chromatography using 9-(2-hydroxyethyl)-carbazole as derivatization reagent

A simple and sensitive method for the determination of short and long-chain fatty acids using high-performance liquid chromatography with fluorimetric detection has been developed. The fatty acids were derivatized to their corresponding esters with 9-(2-hydroxyethyl)-carbazole (HEC) in acetonitrile at 60 degreesC with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride as a coupling agent in the presence of 4-dimethylaminopyridine (DMAP). A mixture of esters of C-1-C-20 fatty acids was completely separated within 38 min in conjunction with a gradient elution on a reversed-phase C-18 column. The maximum fluorescence emission for the derivatized fatty acids is at 365 nm (lambda (ex) 335 nm). Studies on derivatization conditions indicate that fatty acids react proceeded rapidly and smoothly with HEC in the presence of EDC and DMAP in acetonitrile to give the corresponding sensitively fluorescent derivatives. The application of this method to the analysis of long chain fatty acids in plasma is also investigated. The LC separation shows good selectivity and reproducibility for fatty acids derivatives. The R.S.D. (n = 6) for each fatty acid derivative are <4%. The detection limits are at 45-68 fmol levels for C-14-C-20 fatty acids and even lower levels for

A gas chromatographic analysis of light hydrocarbons on a column packed with modified silica gel

A one-meter long column packed with silica gel is used to separate light hydrocarbons. The silica gel has been modified with several kinds of gas chromatography stationary phases. Among these, PEG 2000 shows fairly good effect when using 80-100 meshes silica gel for the separation of mixture of methane, ethane, ethylene, acetylene, propane, propylene and n-, i-butane. The different behavior of silica gel between batch to batch is also found. When silica gel is coated with a small amount of Al2O3 prepared with sol-gel method, better resolution has been observed on a 2-meter column compared with the non-modified silica gel.

Preparation of chitooligosaccharides from chitosan by a complex enzyme

Chitosan of 24% degree of acetylation was depolymerized by a mixture of cellulase, alpha amylase, and proteinase to give the title oligosaccharides. The removal of products by membrane separation permitted yield maximization of products having degree of polymerization in the 3-10 range. (C) 1999 Elsevier Science Ltd. All rights reserved.