联用技术用于复杂体系中钙镁形态分析的研究
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摘要
传统分析化学只测定样品中待测元素的总量或总浓度,但是生物分析与毒性研究证明,环境中特定元素对生物的毒性或在生物体中的积累能力与该元素在环境中存在的形态密切相关。元素的形态不仅决定该元素在环境中的迁移转化规律,而且还决定该元素的生物可利用性和生物效应。因此形态分析对揭示元素在环境和生命科学中的迁移转化规律及其生物化学作用都具有重要意义。
     毛细管电泳(Capillary Electrophoresis,CE)是20世纪80年代迅速发展起来的一种新型分离分析技术。被认为是上世纪末在分离分析领域最具影响力的分支之一,也是该领域的公认前沿。毛细管电泳具有分离效率高、分析速度快、分析模式多、试剂用量少、应用范围广、易于自动化等优点,成为复杂体系中成分分析的重要分析方法之一。在生命科学、生物技术、临床医学、药物分析和环境科学等领域显示了极其重要的应用前景。
     微透析技术(Microdialysis,MD)是近年来发展起来的一种新的生物活体取样技术,它具有在体、原位取样,实时、在线检测等突出优点,可在清醒或麻醉的生物体内进行,特别适合于深部组织和重要器官的生化成分活体分析研究。微透析采样与毛细管联用对于生物样品的实时快速分离分析提供有效途径。微透析取样技术与现代分离分析技术联用已成为生物学、医学、药学研究的强有力手段。
     电感耦合等离子体原子发射光谱(Inductively coupled plasma atomic emission spectrometry,ICP-AES)具有检出限低、精密度高、选择性好、线性范围宽和多元素同时测定等特点,在痕量元素分析领域得到了广泛应用。将CE-ICP-AES结合起来,实现了高效分离与多元素选择性的测定。CE-ICP-AES联用技术在痕量元素形态分析,金属络合物分析,医药,生物,环境等方面开辟了一个新的领域。CE-ICP-AES联用技术结合了CE分离效能高和ICP-AES具有多元素同时测定和检出限低,线性范围宽等优点,为复杂样品的元素形态分析提供了一种强有力的分析手段。
     微透析是一种优良的采样技术,将MD-CE-ICP-AES结合起来,既实现MD与CE联用在微量样品的实时在线分离取样又实现了CE和ICP-AES的在线检测联用。微透析-毛细管电泳与电感耦合等离子体光谱联用应用于元素形态分析是一种很有发展前途的分离检测方法。它可以广泛应用于环保、食品、生物、临床和中医中药等领域,对揭示元素在环境和生命科学中的迁移转化规律及其生物化学作用都具有重要意义。它已成为当前环境科学、生物化学和生命科学领域中颇为活跃的前沿性课题。
     本论文将CE-ICP-AES联用技术应用于生物样品及中药等复杂体系中的形态分析,并对MD-CE与ICP-AES联用的建立及其在血液元素形态分析中的应用进行了研究,论文的主要研究内容及结果如下:
     1、建立了一种微透析采样、毛细管电泳分离及电感耦合等离子体原子发射光谱检测用于元素形态分析的新方法。在分离毛细管端口采用相转化法原位制备了聚醚砜透析膜,该系统具有避免样品稀释、在线微量取样等优点。实验设计并制作了MD-CE-ICP-AES联用接口。通过对载气流速、雾化效率、电泳条件及ICP-AES等实验条件的选择对其分析性能进行了优化,将此联用装置应用于无机离子Ca2+与CaEDTA2-及Mg2+与MgEDTA2-的透析采样与形态分析,从分离形态峰可以看出该接口装置用于形态分析的可行性,其峰面积RSD小于5%,检出限小于18μg·L~(-1)。
     2、首次用所建立的毛细管电泳与电感耦合等离子体原子发射光谱联用的方法,对大白鼠血浆中镁元素的形态进行了探讨,对游离态的镁进行了定量。实验优化条件为:融熔毛细管120cm×100μm(ID);缓冲溶液50mmol·L~(-1)NaAc-HAc(pH=5.5);电泳电压20kV。大白鼠血浆样品中Mg的形态主要有七种,通过标准Mg的迁移时间来定位表征血浆样品中游离镁的形态峰,其迁移时间的相对标准偏差小于3%,用峰面积积分来定量血浆样品中游离镁的含量为14.0mg·L~(-1),其相对标准偏差小于5%,采用以上联用技术对血浆样品中游离态的镁进行了回收测定,其回收率为95.8%~103.8%。
     3、首次将超声波应用于微透析与CE-ICP-AES联用技术,自行设计了超声透析装置,并将该联用技术用于大白鼠全血样品中Ca、Mg的形态分析。该方法比常规透析处理样品速度更快,更适用于生物样品的实时在线分离分析,操作简单,成本低廉,联用方便。为生物样品的快速分离分析提供新的分析手段。在缓冲溶液50mmol·L~(-1)Tris-HCl(pH=7.4),电泳电压18kV时对血液透析液中的钙镁元素进行了形态分析,分别得出钙镁以四种形态存在于血液透析液中,并以标准钙镁对透析样品中的游离钙镁形态进行了表征。
     4、建立微波萃取-毛细管电泳-电感耦合等离子体原子发射光谱联用方法,用于分析中草药艾纳香和石斛中Ca、Mg元素的形态。艾纳香中钙镁分别以四种形态存在,石斛中钙有六种形态,镁有三种形态,以标准钙镁对其中游离态的钙镁进行了表征。采用微波消解-电感耦合等离子体原子发射技术对中药中13种元素的总含量进行了检测分析,各元素的加标回收率为97%~106%,讨论了元素含量和形态对中药药理的影响,中药的形态分析对中药开发利用,相关药物的分析乃至医学研究具有重要意义。
It is a well-known fact that the toxicity, bioavailability, and transport properties of an element are highly dependent upon its chemical species. In the past, total quantification of an element was used to determine potential health hazards or benefits, but in recent years, more and more research groups have acknowledged that elemental quantification alone is not sufficient. To completely understand the ways in which particular elements will affect living organisms, it is necessary to determine the species within which the elements are found, and to quantify those species. Analysis performed to identify and/or quantify one or more distinct chemical species in a sample is known as speciation analysis.
     The capillary electrophoresis (CE) is developed rapidly in the eighties of the 20th century as a novel separation and analysis technology. It is considered to be one of the strongest influence branches of analysis field at the end of last century, as well as the frontier of this field. It has many advantages: high efficiency, quick analysis speed, many analysis modes, little reagent consumption, wide application, easy automation, etc. Thus it shows extremely important application to life sciences, biotechnology, clinical medicine, medicine analysis and environmental science and so on.
     Microdialysis(MD) is a membrane-based sampling technique, in which the driving force behind the separation is the concentration gradient alone-an electrical field or an ionic strength gradient across the membrane. It allows monitoring within a physiological environment with a minimum of disturbance to the animal. Microdialysis sampling is a technique that has been used for in vivo and in vitro monitoring of compounds of pharmaceutical, biomedical, and environmental interest.
     Inductively coupled plasma atomic emission spectrometry (ICP-AES) offers extending good advantages in terms of low detection limit, high precision, wide linear range and simultaneous multi-elements determination, widely used in trace-element analysis fields in recent years. CE coupled with ICP-AES has the individual advantages of capillary electrophoresis and inductively coupling plasma spectrometry, it realized the combination of efficient separation and element alternative measurement. It was considered as a powerful analytical method.
     Microdialysis sampling technique places a constraint on the analysis method because of providing the very small sample volume. On the other hand, microdialysis provides the advantage of clean samples that do not require cleanup prior to analysis. An on-line coupling of microdialysis sampling to CE analysis is described that uses the advantages of microcolumn separations to overcome the small volume limitation. The MD-CE and MD-CE coupled with ICP-AES have the advantages of microsampling and separate detection analysis.
     The hyphenation of microdialysis capillary electrophoresis and inductively coupling plasma spectrometry has become a kind of rising separation and detection method. It can be applied to environmental protection, food, biology, clinic and Chinese Traditional Medicine (CTM), etc. It is well known that the physiology, toxicity, biogeochemical behavior, environmental behavior and transformation of trace toxic elements are highly depended on their chemical speciation to some great extent. Speciation analysis has already become an active front subject in environmental sciences, biochemistry and life sciences at present.
     In this paper, the research has been carried on foundation of microdialysis capillary electrophoresis and inductively coupling plasma atomic emission spectrometry and their application to the speciation analysis of complex systems, such as biological samples (blood, plasma) and Chinese herbs. The main contents were described as fellow:
     1. A new method for making an interface of the microdialysis(MD)-capillary electrophoresis(CE) and inductively coupled plasma atomic emission spectrometry(ICP-AES) is introduced. The feasibility of this method and its application are tested. The analysis performance of the interface has been studied, such as nebulizer flow rate, efficiency of nebulization, precision, detection limit. The experimental result shows this interface has these advantages: on line analysis, good stability, high nebulisation efficiency and high precision, and to avoide diluting samples. The application of the developed MD-CE-ICP-AES for the speciation analysis of Ca~(2+), CaEDTA~(2-), Mg~(2+) and MgEDTA~(2-) is highlighted. The detection limit of these elements is lower than 18μg·L~(-1), RSD for those lower than 5%.
     2. A new method for speciation analysis of magnesium species and quantification of free magnesium concentrations in rat plasma was developed by on-line coupling capillary electrophoresis (CE) with inductively coupled plasma atomic emission spectrometry (ICP-AES). Baseline separation of magnesium speciation was achieved by CE-ICP-AES in a 120 cm length×100μm inside diameter (I.D.) fused-silica capillary at 20 kV using a solution of 50 mmol·L~(-1)NaAc-HAc (pH=5.5) as electrolyte buffer. The forms of magnesium in rat plasma have seven different species. The free Mg~(2+) in the plasma was identified by the spiked standard magnesium and free magnesium concentration by peak area is 14.0mg·L~(-1). The precisions (relative standard deviation, RSD, n=10) of migration time and peak area for the magnesium species were less than 5%. The recoveries of the free magnesium species in four samples were in the range of 95.8 to 103.8%.
     3. The analytical method for speciation analysis of the species of calcium and magnesium in rat blood was studied using ultrasonic-assisted dialysis coupled with inductively coupled plasma atomic emission spectrometry. Ultrasonic dialysis comparing with regular hemodialysis significantly improve the permeance of small molecular substances. The hyphenated technique is simple and convenient, which is fit for the separation and analysis of biological samples. The optimal separation of calcium and magnesium speciation was achieved by CE-ICP-AES in a 120 cm length×100μm inside diameter (I.D.) fused-silica capillary at 18 kV using a solution of 50 mmol·L~(-1)Tris-HCl (pH=7.4) as electrolyte buffer. The forms of calcium and magnesium in the dialysate of rat blood have four different species. Then the peak of free Ca~(2+) and Mg~(2+) in the dialysate was identified by the spiked standard species as them has the same retention time.
     4. Speciation analysis of Ca, Mg and determination of thirteen element in Blumea balsanifera and Dendrobium by Microwave Extraction and CE-ICP-AES. Using water as medium, the different species of calcium and magnesium was extracted from Chinese herb by microwave-asistant extraction. The speciation analysis of calcium and magnesium was studied by CE-ICP-AES. The results showed there were four and six species for Ca, four and three species for Mg in Blumea balsanifera and Dendrobium, respectively. And the free species of Ca, Mg were identified in the herbs. The contents of thirteen elements in the herbs have been determined by ICP-AES with microwave digestion. The recoveries of the Ca, Mg,etc. in the samples ranged from 97 to 106%. The results were in good agreement with the reference values.
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