膨胀土化学改性实验研究

Expansive soil is a kind of typical unsaturated soil with characteristics of high swelling-shrinking deformation, cracks and over consolidation. It is very harmful to civil engineering, As a new processing method deal with expansive soil, Chemistry treatment has widespread applied in developed countries such as Europe and America, and also gained remarkable result. Based on the embankment filling soil improving testing projects in Meng-Xin freeway, this paper proposed a new processing method to expansive soil embankment wrapped with PAS-treated soil, experimental study of expansive soil chemical improved by PAS is been carried out. The water content change is the external factor which causes expansive soil to have swelling-shrinkage deformation. this reflected that the soil body swelling-shrinkage characteristic mainly depends on its mineral ingredient and the soil-water mutual function. This paper takes expansive soil as one kind of ordinary high plastic clay from angle of clay-water mutual function explained the expansive soil swelling-shrinkage deformation mechanism on microscopic. And take this swelling-shrinkage mechanism as the master line, Cooperates with the China Academy of Chemistry, we developed the new method PAS treatment, trough ionic exchange, joint, package and flocculation, the stronger static electricity function weakened the level through adsorption and the stronger static electricity function, PAS can weakened the negative charge repulsion between levels, causes the electric potential to reduce, diffusion layer thickness to be thinner, and improves the water affinity performance of expansive soil effectively. Moreover the space network architecture compromised with PAS and soil enhanced the joint strength between the clay particles , enable the soil body to have comparatively high strength and the distortion rate. pointed proposed the PAS modified principle. Combine with the construction of experimented road, this paper sums up and presents the construction craft and technology requirement of PAS treatment to expansive soil embankment. Through many experimental studied the basic physical property, the intensity characteristic and water stability changes of expansive soil and PAS-treated soil. The results of study indicate that adding lime into the expansive soil can reduce the content of clay gain obviously, reduce the plasticity notably, increase the strength greatly, control the property of swelling and shrinking effectively, and can meliorate the stability of sucking water clearly. Simultaneity PAS don’t change the cultivate capacity of the soil, the modified slope of the embankment can adopt plant fixed slope method as ecology protection. Finally the processing effect of use different treatment has analyzed through numerical simulation, summarized the PAS chemical wrapping treatment process in the actual project application, and appraised its processing effect and the project efficiency. The research indicated that PAS chemical treatment is one effective method to improve expansive soil. Compare with long-distance replacement, especially in the high plastic expansive soil massive distribution area, PAS treatment has the very greatly economical superiority to be promoted. The study in the paper not only afforded technique method to Meng-Xin expressway construction but also important for improvement of the expressway construction theory in swelling soil areas. Key words: PAS; expansive soil; swelling-shrinkage deformation mechanism; wrapping embankment; chemical modified treatment.

典型人类活动对边坡变形及稳定性的影响研究

China is a mountainous country in which geological hazards occurred frequently, especially in the east of China. Except the geology, topography and extreme climate, the large scale human activities have become a major factor to landslides. Typical human activities which induced landslides are fill, cut and underground mining. On the topic of the deformation mechanism and slope stability, taking three different man-made slopes as examples, deformation mechanism and slope stability were studied by several methods, such as field work, numerical modeling and monitor. The details are as following: (1) The numerical modeling approach advantages over other conventional methods such as limit methods, so the numerical modeling is the major tool in this thesis. So far, there is no uniform failure criterion for numerical simulation. The failure criterion were summarized and analyzed firstly, subsequently the appropriate criterion was determinated. (2) Taking 220kV Yanjin transformation substation fill slope as example, the deformable characteristic, unstable mode and laboratory tests were studied systematically. The results show: the slope deformation was probably caused by a combination effect of unfavorable topographic, geological and hydro geological conditions, and external loading due to filling. It was concluded that the creep deformation of the slope was triggered by external loading applied at the back of the slope. In order to define the calculating parameters, a set of consolidated drained (CD) tests, consolidated undrained (CU) tests, repeated direct shear tests and UCS tests were carried out. The stability of the slope before and after reinforcement was assessed using 3D numerical modeling and shear strength reduction technique. The numerical modeling results showed: the factor of safety (FOS) of the slope was 1.10 in the natural state, and reduced to 1.03 after fill, which was close to the critical state and it caused creeping slip or deformation under rainfall. The failure surface in the slope is in active shear failure, whereas tensile failure occurs at the slope crest. After the site was reinforced with piles, the FOS was 1.27. Therefore, the slope is stable after reinforcement measures were taken. (3) The cut slope stability is a complex problem. Taking the left cut slope of Xiangjiaba as example in this thesis, the deformation and slope stability were studied systematically by numerical modeling and monitor methods. The numerical results show: the displacement is gradually increasing along with the cutting, and the largest displacement is 27.5mm which located at the bench between the elevation 340 and 380. Some failure state units distribute near the undermining part and there is no linked failure state occurred from crest to bottom during cutting. After cutting, some failure units appeared at the ground surface between elevation 340 and 360. The increasing tense stress made the disturbed rock failed. The slope is stable after cutting by the monitor method, such as surface monitor, multipoint displacement meter, inclinometer and anchor cable tensometer. (4) The interaction between underground mining and slope stability is a common situation in mountainous. The slope deformation mechanism induced by underground mining may contributed significantly to slope destabilization. The Mabukan slope in xiangjiaba was analyzed to illustrate this. Failure mechanism and the slope stability were presented by numerical modeling and residual deformation monitor. The results show: the roof deformed to the free face and the floor uplift lightly to the free face. The subsidence basin is formed, but the subsidence and the horizontal movement is small, and there is no failure zone occurred. When the underground mining is going on, the roof deformation, subsidence and the horizontal movements begin increasing. The rock deformation near the free face is larger than the ground surface, and the interaction between these coal seams appeared. There are some tensile failures and shear failures occurred on the roof and floor, and a majority of failure is tensile failure. The roof deformation, subsidence and the horizontal movements increased obviously along with the underground mining. The failure characteristic is shear failure which means the tensile stress transformed to the compressive stress. So the underground mining will induced tensile stress first which lead to structure crack, subsequently the compressive stress appeared which result in slippage. The crest was subjected to horizontal tension which made the rock crack along with the joint. The long term residual deformation monitor demonstrates that the slope is stable after the underground mining stopped.

非饱和膨胀土力学特性及其工程处置研究

The unsaturated expansive soil is a hotspot and difficulty in soil mechanics inland and outland. The expansive soil in our China is one of the widest in distributing and greatest in area, and the disaster of expansive soil happens continually as a result. The soil mechanics test, monitor, numerical simulation and engineering practice are used to research swell and shrinkage characteristic, edge strength characteristic and unsaturated strength characteristic of Mengzi expansive soil. The seep and stability of the slope for expansive soil associated with fissure are analyzed and two kinds of new technique are put forward to be used in expansive soil area, based on disaster mechnics proposed of the slope.The technique of reinforcement in road embankment is optimized also. Associated with engineering geology research of Mengzi expansive soil, mineral composition, chemical composition, specific area and cation content, dissolubility salt and agglutinate, microcosmic fabric characteristic, cause of formation and atmosphere effect depth are analyzed to explain the intrinsic cause and essence of swell and shrinkage for expansive soil. The rule between swell-shrinkage and initial state, namely initial water content, initial dry density and initial pressure, can be used to construction control. Does Response model is fit to simulate the rule, based on ternary regression analysis. It has great meaning to expansive soil engineering in area with salt or alkali. The mechanics under CD, CU and GCU of expansive soil is researched by edge surface theory to explain the remarkable effect of consolidation pressure, initial dry density, initial water content, cut velocity, drainage and reinforcement to the edge strength characteristic. The infirm hardening stress strain curves can be fitted with hyperbola model and the infirm softening curves can be fitted with exponential model. The normalization theory can be used to reveal the intrinsic unity of the otherness which is brought by different methods to the shear strength of the same kinds of samples. The unsaturated strain softening characteristic and strength envelope of remolding samples are researched by triaxial shear test based on suction controlled, the result of which is simulated by exponential function. The strength parameters of the unsaturated samples are obtained to be used in the unsaturated seep associated with rainfall. The elasticity and plasticity characters of expansive soil are researched to attain the model parameters by using modified G-A model. The humidification destroy characteristic of expansive soil is discussed to research the disaster mechanism of the slope with the back pressure increasing and suction decreasing under bias pressure consolidation. The indoor and outdoor SWCCs are measured to research the effect factors and the rule between different stress and filling environment. The moisture absorption curves can express the relationship between suction and water content in locale. The SWCCs of Mengzi expansive soil are measured by GDS stress path trixial system. The unsaturated infiltration function is gained to research seep and stability of the slope of expansive soil. The rainfall infiltration and ability of slope considering multifarious factors are studied by analyzing fissure cause of Mengzi expansive soil. The mechanism of the slope disaster is brought forward by the double controlling effect between suction and fissure. Two new kinds of technique are put forward to resolve disaster of expansive soil and the technique of reinforcement on embankment is optimized, which gives a useful help to solving engineering trouble.

中国大中型气田天然气成藏物理化学模拟研究

Natural gas pays more important role in the society as clean fuel. Natural gas exploration has been enhanced in recent years in many countries. It also has prospective future in our country through "85" and "95" national research. Many big size gas fields have been discovered in different formations in different basins such as lower and upper Paleozoic in Erdos basin, Tertiary system in Kuche depression in Tarim basin, Triassic system in east of Sichuan basin. Because gas bearing basins had been experienced multiple tectogenesis. The characteristics of natural gases usually in one gas field are that they have multiple source rocks and are multiple maturities and formed in different ages. There has most difficult to research on the gas-rock correlation and mechanism of gas formation. Develop advanced techniques and methods and apply them to solve above problems is necessary. The research is focused on the critical techniques of geochemistry and physical simulation of gas-rock correlation and gas formation. The lists in the following are conclusions through research and lots of experiments. I 8 advanced techniques have been developed or improved about gas-rock correlation and gas migration, accumulation and formation. A series of geochemistry techniques has been developed about analyzing inclusion enclave. They are analyzing gas and liquid composition and biomarker and on-line individual carbon isotope composition in inclusion enclave. These techniques combing the inclusion homogeneous temperature can be applied to study on gas-rock correlation directly and gas migration, filling and formation ages. Technique of on-line determination individual gas carbon isotope composition in kerogen and bitumen thermal pyrolysis is developed. It is applied to determine the source of natural is kerogen thermal degradation or oil pyrolysis. Method of on-line determination individual gas carbon isotope composition in rock thermal simulation has being improved. Based on the "95"former research, on-line determination individual gas carbon isotope composition in different type of maceral and rocks thermal pyrolys is has been determined. The conclusion is that carbon isotope composition of benzene and toluene in homogenous texture kerogen thermal degradation is almost same at different maturity. By comparison, that in mixture type kerogen thermal pyrolysis jumps from step to step with the changes of maturity. This conclusion is a good proof of gas-rock dynamic correlation. 3. Biomarker of rock can be determined directly through research. It solves the problems such as long period preparing sample, light composition losing and sample contamination etc. It can be applied to research the character of source rock and mechanism of source rock expulsion and the path of hydrocarbon migration etc. 4. The process of hydrocarbon dynamic generation in source rock can be seen at every stage applying locating observation and thermal simulation of ESEM. The mechanism of hydrocarbon generation and expulsion in source rock is discussed according to the experiments. This technique is advanced in the world. 5. A sample injection system whose character is higher vacuum, lower leaks and lower blank has been built up to analyze inert gas. He,Ar,Kr and Xe can be determined continuously on one instrument and one injection. This is advanced in domestic. 7. Quality and quantity analysis of benzene ring compounds and phenolic compounds and determination of organic acid and aqueous gas analysis are applied to research the relationship between compounds in formation water and gas formation. This is another new idea to study the gas-rock correlation and gas formation. 8. Inclusion analysis data can be used to calculate the Paleo-fluid density, Paleo-geothermal gradient and Paleo-geopressure gradient and then to calculate the Paleo-fluid potential. It's also a new method to research the direction of hydrocarbon migration and accumulation. 9. Equipment of natural gas formation simulation is produced during the research to probe how the physical properties of rock affect the gas migration and accumulation and what efficiency of gas migrate and factors of gas formation and the models of different type of migration are. II study is focused on that if the source rocks of lower Paleozoic generated hydrocarbon and what the source rocks of weathered formation gas pool and the mechanism of gas formation are though many advanced techniques application. There are four conclusions. 1.The maturity of Majiagou formation source rocks is higher in south than that in north. There also have parts of the higher maturity in middle and east. Anomalous thermal pays important role in big size field formation in middle of basin. 2. The amount of gas generation in high-over maturity source rocks in lower Paleozoic is lager than that of most absorption of source rocks. Lower Paleozoic source rocks are effective source rocks. Universal bitumen exists in Ordovician source rocks to prove that Ordovician source rocks had generated hydrocarbon. Bitumen has some attribution to the middle gas pool formation. 3. Comprehensive gas-rock correlation says that natural gases of north, west, south of middle gas field of basin mainly come from lower Paleozoic source rocks. The attribution ratio of lower Paleozoic source rocks is 60%-70%. Natural gases of other areas mainly come from upper Paleozoic. The attribution ratio of upper Paleozoic source rocks is 70%. 4. Paleozoic gases migration phase of Erdos basin are also interesting. The relative abundance of gasoline aromatic is quite low especially toluene that of which is divided by that of methyl-cyclohexane is less than 0.2 in upper Paleozoic gas pool. The migration phase of upper Paleozoic gas may be aqueous phase. By comparison, the relative abundance of gasoline aromatic is higher in lower Paleozoic gas. The distribution character of gasoline gas is similar with that in source rock thermal simulation. The migration phase of it may be free phase. IH Comprehensive gas-rock correlation is also processed in Kuche depression Tarim basin. The mechanism of gas formation is probed and the gas formation model has been built up. Four conclusions list below. 1. Gases in Kuche depression come from Triassic-Jurassic coal-measure source rocks. They are high-over maturity. Comparatively, the highest maturity area is Kelasu, next is Dabei area, Yinan area. 2. Kerogen thermal degradation is main reason of the dry gas in Kuche depression. Small part of dry gas comes from oil pyrolysis. VI 3.The K12 natural gas lays out some of hydro-gas character. Oil dissolved in the gas. Hydro-gas is also a factor making the gas drier and carbon isotope composition heavier. 4. The mechanism and genesis of KL2 gas pool list as below. Overpressure has being existed in Triassic-Jurassic source rocks since Keche period. Natural gases were expulsed by episode style from overpressure source rocks. Hetero-face was main migration style of gas, oil and water at that time. The fluids transferred the pressure of source rocks when they migrated and then separated when they got in reservoir. After that, natural gas migrated up and accumulated and formed with the techno-genesis. Tectonic extrusion made the natural gas overpressure continuously. When the pressure was up to the critical pressure, the C6-C7 composition in natural gas changed. The results were that relative abundance of alkane and aromatic decreased while cycloalkane and isoparaffin increased. There was lots of natural gas filling during every tectonic. The main factors of overpressure of natural gas were tectonic extrusion and fluid transferring pressure of source rocks. Well preservation was also important in the KL2 gas pool formation. The reserves of gas can satisfy the need of pipeline where is from west to east. IV A good idea of natural gas migration and accumulation modeling whose apparent character is real core and formation condition is suggested to model the physical process of gas formation. Following is the modeling results. 1. Modeling results prove that the gas accumulation rule under cap layer and gas fraction on migration path. 2. Natural gas migration as free phase is difficult in dense rock. 3. Natural gases accumulated easily in good physical properties reservoirs where are under the plugging layer. Under the condition of that permeability of rock is more than 1 * 10~(-3)μm~(-1), the more better the physical properties and the more bigger pore of rock, the more easier the gas accumulation in there. On the contrary, natural gas canonly migrate further to accumulate in good physical properties of rock. 4. Natural gas migrate up is different from that down. Under the same situation, the amount of gas migration up is lager than that of gas migration down and the distance of migration up is 3 times as that of migration down. 5. After gas leaks from dense confining layer, the ability of its dynamic plug-back decreased apparently. Gas lost from these arils easily. These confining layer can confine again only after geology condition changes. 6. Water-wetted and capillary-blocking rocks can't block water but gases generally. The result is that water can migrate continuously through blocking rocks but the gases stay under the blocking rocks then form in there. The experiments have proved the formation model of deep basin gas.

孤北洼陷沙三-沙四段隐蔽油藏形成机制及其预测

Based on the study of sequence stratigraphy, modern sedimentary, basin analysis, and petroleum system in Gubei depression, this paper builds high resolution sequence stratigraphic structure, sedimentary system, sandbody distribution, the effect of tectonic in sequence and sedimentary system evolution and model of tectonic-lithofacies. The pool formation mechanism of subtle trap is developed. There are some conclusions and views as follows. 1.With the synthetic sequence analysis of drilling, seismic, and well log, the highly resolution sequence structure is build in Gubei depression. They are divided two secondary sequences and seven three-order sequences in Shahejie formation. They are include 4 kinds of system traces and 7 kinds of sedimentary systems which are alluvial fan, under water fan, alluvial fan and fan-delta, fan-delta, lacustrine-fan, fluvial-delta-turbidite, lakeshore beach and bar, and deep lake system. Sandbody distribution is show base on third order sequence. 2.Based on a lot of experiment and well log, it is point out that there are many types of pore in reservoir with the styles of corrosion pore, weak cementing, matrix cementing, impure filling, and 7 kinds of diagenetic facies. These reservoirs are evaluated by lateral and profile characteristics of diagenetic facies and reservoir properties. 3.The effect of simultaneous faulting on sediment process is analyzed from abrupt slope, gentle slope, and hollow zone. The 4 kinds of tectonic lithofacies models are developed in several periods in Gubei depression; the regional distribution of subtle trap is predicted by hydro accumulation characteristics of different tectonic lithofacies. 4.There are 4 types of compacting process, which are normal compaction, abnormal high pressure, abnormal low pressure and complex abnormal pressure. The domain type is normal compaction that locates any area of depression, but normal high pressure is located only deep hollow zone (depth more than 3000m), abnormal low pressures are located gentle slope and faulted abrupt slope (depth between 1200~2500m). 5.Two types dynamic systems of pool formation (enclosed and partly enclosed system) are recognized. They are composed by which source rocks are from Es3 and Es4, cap rocks are deep lacustrine shale of Esl and Es3, and sandstone reservoirs are 7 kinds of sedimentary system in Es3 and Es4. According to theory of petroleum system, two petroleum systems are divided in Es3 and Es4 of Gubei depression, which are high or normal pressure self-source system and normal or low pressure external-source system. 6.There are 3 kinds of combination model of pool formation, the first is litholgical pool of inner depression (high or normal pressure self-source type), the second is fault block or fault nose pool in marginal of depression (normal type), the third is fault block-lithological pool of central low lifted block (high or normal pressure type). The lithological pool is located central of depression, other pool are located gentle or abrupt slope that are controlled by lithological, faulting, unconfirmed. 7.This paper raise a new technique and process of exploration subtle trap which include geological modeling, coring description and logging recognition, and well log constrained inversion. These are composed to method and theory of predicting subtle trap. Application these methods and techniques, 6 hydro objects are predicted in three zone of depression.

陡坡带砂砾岩体油气成藏模式研究——以东营凹陷西北部陡坡带为例

Based on the study of sequence stratigraphy, modern sedimentary, basin analysis, and petroleum system in abrupt slop of depression, this paper builds sedimentary system and model, sandy bodies distribution, and pool-forming mechanism of subtle trap. There are some conclusions and views as follows. By a lot of well logging and seismic analysis, the author founded up the sequence stratigraphic of the abrupt slope, systematically illustrated the abrupt slope constructive framework, and pointed out that there was a special characteristics which was that south-north could be divided to several fault block and east-west could be carved up groove and the bridge in studying area. Based all these, the author divided the studying area to 3 fault block zone in which because of the groove became the basement rock channel down which ancient rivers breathed into the lake, the alluvial fan or fan delta were formed. In the paper, the author illustrated the depositional system and depositional model of abrupt slope zone, and distinguished 16 kinds of lithofacies and 3 kinds of depositional systems which were the alluvial fan and fan-delta system, lake system and the turbidite fan or turbidity current deposition. It is first time to expound completely the genetic pattern and distributing rule of the abrupt slope sandy-conglomeratic fan bodies. The abrupt slope sandy-conglomeratic fan bodies distribute around the heaves showing itself circularity shape. In studying area, the sandy-conglomeratic fan bodies mainly distribute up the southern slope of Binxian heave and Chenjiazhuang heave. There mainly are these sandy-conglomeratic fan body colony which distributes at a wide rage including the alluvial fan, sub-water fluvial and the turbidite fan or the other turbidity current deposition in the I fault block of the Wangzhuang area. In the II fault block there are fan-delta front and sub-water fluvial. And in the Binnan area, there mainly are those the alluvial fan (down the basement rock channel) and the sandy-conglomeratic fan body which formed as narrowband sub-water fluvial (the position of bridge of a nose) in the I fault block, the fan-delta front sandy-conglomeratic fan body in the H fault block and the fan-delta front and the turbidity current deposition sandy-conglomeratic fan body in the m fault block. Based on the reservoir outstanding characteristics of complex classic composition and the low texture maturity, the author comparted the reservoir micro-structure of the Sha-III and Sha-IV member to 4 types including the viscous crude cementation type, the pad cementation type, the calcite pore-funds type and the complex filling type, and hereby synthetically evaluated 4 types sandy- conglomeratic fan body reservoir. In the west-north abrupt slope zone of Dongying Depression, the crude oil source is belonging to the Sha-III and Sha-IV member, the deep oil of Lijin oilfield respectively come from the Sha-III and Sha-IV member, which belongs to the autogeny and original deposition type; and the more crude oil producing by Sha-IV member was migrated to the Wangzhuan area and Zhengjia area. The crude oil of Binnan oil-field and Shanjiasi oil-field belongs to mixed genetic. It is the first time to illustrate systematically the genetic of the viscous crude that largely being in the studying area, which are that the dissipation of the light component after pool-forming, the biological gradation action and the bath-oxidation action, these oil accumulation belonging to the secondary viscous crude accumulation. It is also the first time to compart the studying area to 5 pool-forming dynamical system that have the characteristic including the common pressure and abnormal pressure system, the self-fountain and other-fountain system and the closing and half-closing system etc. The 5 dynamical systems reciprocally interconnected via the disappearance or merger of the Ethology and the fluid pressure compartment zone, the fault and the unconformity surface, hereby formed duplicated pattern oil-gas collecting zone. Three oil-gas pool-forming pattern were founded, which included the self-fountain side-direction migrated collecting pattern, the self-fountain side-direction ladder-shape pool-forming pattern and the other-fountain pressure releasing zone migrated collecting pattern. A series of systemic sandy-conglomeratic fan bodies oil-gas predicting theory and method was founded, based on the groove-fan corresponding relation to confirm the favorable aim area, according as the characteristic of seismic-facies to identify qualitatively the sandy-conglomeratic fan bodies or its scale, used the temporal and frequency analysis technique to score the interior structure of the sandy- conglomeratic fan bodies, applied for coherent-data system analysis technology to describe the boundary of the sandy-conglomeratic fan bodies, and utilized the well logging restriction inversion technique to trace quantificational and forecast the sandy-conglomeratic fan bodies. Applied this technique, totally 15 beneficial sandy-conglomeratic fan bodies were predicted, in studying area the exploration was preferably guided, and the larger economic benefit and social benefit was acquired.

A study on the ignition process for the catalytic partial oxidation of methane to synthesis gas by MS-TPSR technique

The ignition processes for the catalytic partial oxidation of methane (POM) to synthesis gas over oxidic nickel catalyst (NiO/Al2O3), reduced nickel catalyst (Ni-0/Al2O3), and Pt-promoted oxidic nickel catalyst (Pt-NiO/Al2O3) were studied by the temperature-programmed surface reaction (TPSR) technique. The complete oxidation of methane usually took place on the NiO catalyst during the CH4/O-2 reaction, even with a pre-reduced nickel catalyst, and Ni-0 is inevitably first oxidized to NiO if the temperature is below the ignition temperature. It is above a certain temperature that Ni-0 is formed again, which leads to the start of the POM. The POM can be initiated at a much lower temperature on a Pt-NiO catalyst because of Pt promotion of the reduction of NiO. The POM in a fluidized bed can be easily initiated due to the addition of Pt.

On the evaluation of diffusivities in gels using the diffusion cell technique

Modeling of the gel-immobilized cell system requires accurate measurement of diffusion coefficients. Three methods of the quasi-steady-state (QSS) method, the time-lag (TL) method and a variant quasi-steady-state (VQSS) method were critically assessed and compared for the evaluation of diffusivities using the diffusion cell technique. Experimental data from our laboratory were used for the analysis of the influence of crucial theoretical assumptions not being fulfilled in each method. The results highlighted a risk in obtaining highly variable diffusion coefficients by not validating the QSS and the accuracy of the measurements. In the TL method, the estimation of diffusivities based on the plot intercept that was mostly used in the literature, results in a many fold lower value when compared to that based on the plot slope. The comparison with the QSS and VQSS methods confirmed similar diffusivity obtained by the TL method based on the plot slope. It thus suggested that the correct estimation of diffusivities by the TL method could be based on the plot slope only. Furthermore, the errors associated with the solute mass in the gel, the sample withdrawal and the non-negligible concentration changes in the chambers were also discussed. It is concluded that diffusion cell technique has to be employed cautiously for a correct evaluation of diffusivities. (C) 2001 Elsevier Science B.V. All rights reserved.

Drug-protein interaction studied by technique of microdialysis combined with high performance liquid chromatography

Drug-protein binding is an important process in determining the activity and fate of a pharmaceutical agent once it has entered the body. This review examines the method of microdialysis combined with high-performance liquid chromatography (HPLC) that has been developed;by ours to study such interactions, in which the microdialysis was applied to sample the free drug in the mixed solution of drug with protein, and HPLC to quantify the concentration of free drug in the microdialysate. This technique has successfully been used for determining various types of binding interactions between the low affinity drugs, high affinity drugs and enantiomers to HSA. For the case of competitive binding of two drugs to a protein in solution, a displacement equation has been derived and examined with four nonsteroidal anti-inflammatory drugs and HSA as model drugs and protein, respectively. Microdialysis with HPLC was adopted to determine simultaneously the free solute and displacing agent in drug-protein solutions. The method is able to locate the binding site and determine affinity constants even up to 10(7) L/mol accurately.

Application of liquid pre-column capillary electrophoresis technique to the study of interaction between drug enantiomers and human serum albumin

Based on the chiral separation of several basic drugs, dimetindene, tetryzoline, theodrenaline and verapamil, the liquid pre-column capillary electrophoresis (LPC-CE) technique was established. It was used to determine free concentrations of drug enantiomers in mixed solutions with human serum albumin (HSA). To prevent HSA entering the CE chiral separation zone, the mobility differences between HSA and drugs under a specific pH condition were employed in the LPC. Thus, the detection confusion caused by protein was totally avoided. Further study of binding constants determination and protein binding competitions was carried out. The study proves that the LPC technique could be used for complex media, particularly the matrix of protein coexisting with a variety of drugs.