【作者】 邹小军；

【导师】 常希俊；

【作者基本信息】 兰州大学 ， 分析化学， 2009， 博士

【摘要】 随着工业生产的发展,环境中重金属的污染日趋严重,已经影响到人类的正常生活。解决这一问题的方法在于提高对重金属检测的灵敏度以加强环境监测的控制,并寻找合适的吸附剂净化或回收进入环境的重金属离子。固相萃取方法（SPE）因简单、操作条件灵活等特点已在金属元素富集上得到了广泛的应用。SPE方法的发展趋势是寻找新的吸附剂,尤其是具有特殊性能的吸附剂,以实现从复杂基体中预富集和分离被分析物的目的。在已报道研究工作的基础上,本论文从合成新的吸附剂入手,进行了如下创新性工作:（1）合成了一种新型的吸附剂聚烯丙基硫脲,并将其作为固相萃取吸附剂应用于溶液中贵金属离子Au³⁺和Pd⁴⁺的预富集和分离,用电感耦合等离子体原子发射光谱进行测定。研究了影响吸附性能的各试验参数,寻找出了最佳试验条件。在最佳条件下,吸附剂对Au³⁺和Pd⁴⁺的最大吸附容量分别为3.23和3.84 mmolg^-1。实际样品中痕量的Au³⁺和Pd⁴⁺用聚烯丙基硫脲富集分离后经电感耦合等离子体原子发射光谱法测定,取得了满意的分析结果。（2）以CPS为偶联剂,用磺胺修饰的硅胶作为作为固相萃取吸附剂应用于溶液中的Cu²⁺、Zn²⁺和Ni²⁺离子的预富集和分离,用电感耦合等离子体原子发射光谱进行测定。优化了影响吸附效果的各项试验参数,得到吸附剂对Cu²⁺、Zn²⁺和Ni²⁺最大吸附容量分别为34.91、19.07和23.62 mg g^-1。方法的检出限分别为1.60、0.50和0.61 ng mL。方法用于标准参照物和不同水样中Cu²⁺、Zn²⁺和Ni²⁺离子的测定,取得了满意的结果。（3）用1-吡咯烷二硫代羧酸铵盐修饰的活性炭作为固相萃取吸附剂应用于溶液中的Cr³⁺和Pb²⁺的预富集和分离,用电感耦合等离子体原子发射光谱进行测定。优化了影响吸附效果的各项试验参数,得到吸附剂对Cr³⁺和Pb²⁺最大吸附能力分别为39.4和49.9 mg g^-1。方法用于标准参照物和不同水样中Cr³⁺和Pb²⁺的测定,取得了满意的结果。（4）用桑色素修饰的纳米二氧化硅作为固相萃取吸附剂应用于溶液中的Cd²⁺、Cu²⁺、Ni²⁺、Pb²⁺、Zn²⁺的预富集和分离,用电感耦合等离子体原子发射光谱进行测定。优化了影响吸附效果的各项试验参数,得到吸附剂对Cd²⁺、Cu²⁺、Ni²⁺、Pb²⁺、Zn²⁺的最大吸附容量分别为22.36、36.8、40.37、33.21、25.99 mg g^-1。方法用于标准参照物、生物样品及不同水样中Cd²⁺、Cu²⁺、Ni²⁺、Pb²⁺、Zn²⁺的测定,取得了满意的结果。另外,使用高效液相色谱法对多粘菌素B相关物质进行了分析。使用C₁₈色谱柱,流动相为20%乙腈:80%硫酸钠溶液（称取4.46克无水硫酸钠至1000ml纯化水中,用磷酸调节pH至2.3）,在215nm检测波长下利用制备用高效液相色谱仪分离多粘菌素B样品,并用高分辨质谱对分离的十个样品进行了结构分析,完成了某公司的课题。更多还原

【Abstract】 With the development of industrial production,heavy metal residues in theenvironment is getting more and more serious,which is known to cause severedamage to human health and aquatic life.To solve these problems,we must improvethe sensitivity of detection in order to strengthen the control,or find suitableadsorbent to recovery heavy metal ions in environment.Solid-phase extraction （SPE） method is currently being widely used inpreconcentration and separation of trace elements because it can provide moreflexible working conditions and simple operation.The trend of SPE method is to findnew adsorbent,especially of which has good performance in achieving ablity ofpreconcentration and separation analyte from complex matrices.Based on the research works of reference literature reported,some creativeworks were carried out in this dissertation as follows:（1） A new solid-phase extractant,poly-allylthiourea was prepared for selectiveseparation and enrichment of trace Au³⁺ and Pd⁴⁺ from aqueous solution.Thedetermination of metal ions in aqueous solutions was carried out by inductivelycoupled plasma optical emission spectrometry （ICP-AES）.Several parameters,suchas distribution coefficient and adsorption capacity of the chelating resin,pH and timeof uptake and striping,volume of sample and eluent,were evaluated using modelsolutions.The effects of electrolytes and cations on the enrichment were alsoinvestigated.At optimal conditions,the maximum extraction capacity of new sorbentwas 3.23 and 3.84 mmol g^-1 for Au³⁺ and Pd⁴⁺,respectively.The adsorption behaviorof target ions on the sorbent could be described by Langmuir adsorption isothermequation.The developed method was applied to the separation and enrichment oftrace Au³⁺ and Pd⁴⁺ in synthetic samples with satisfactory results.（2） A new chelating matrix was prepared by immobilizing sulfanilamide （SA） onsilica gel （SG） surface modified with 3-chloropropyltrimethoxysilane as a sorbent forthe solid-phase extraction （SPE） of Cu²⁺,Zn²⁺ and Ni²⁺.The determination of metalions in aqueous solutions was carried out by inductively coupled plasma opticalemission spectrometry （ICP-AES）.Experimental conditions for effective sorption of trace levels of Cu²⁺,Zn²⁺ and Ni²⁺ were optimized with respect to differentexperimental parameters.The maximum sorption capacity of the sorbent at optimumconditions was found to be 34.91,19.07 and 23.62 mg g^-1 for Cu²⁺,Zn²⁺ and Ni²⁺,respectively.The detection limit of the method was found to be 1.60,0.50 and 0.61 ngmL^-1 for Cu²⁺,Zn²⁺ and Ni²⁺,respectively.The method was applied to the recovery ofCu²⁺,Zn²⁺ and Ni²⁺ from the certified reference material （GBW 08301,river sediment）and to the simultaneous determination of these cations in different water samples withsatisfactory results.（3） A new method that utilizes 1-pyrrolidine dithio carboxylic acid ammoniumsalt-modified activated carbon （AC-PDCA） as a solid phase extractant has beendeveloped for simultaneous preconcentration of trace Cr³⁺ and Pb²⁺ prior to themeasurement by inductively coupled plasma optical emission spectrometry（ICP-AES）.Experimental conditions for effective adsorption of trace levels of Cr³⁺and Pb²⁺ were optimized with respect to different experimental parameters.Themaximum static adsorption capacity of the sorbent at optimum conditions was foundto be 39.4 and 49.9 mg g^-1 for Cr³⁺ and Pb²⁺,respectively.The prepared sorbent assolid-phase extractants were successfully applied for the preconcentration of traceCr³⁺ and Pb²⁺ in natural and certified samples with satisfactory results.（4） Morin was successfully used as a chemical modifier to improve the reactivityof the nanometer SiO₂ surface in terms of selective binding and extraction of heavymetal ions.This new functionalized nanometer SiO₂ （nanometer SiO₂-morin） wasused as an effective sorbent for the solid phase extraction （SPE） of Cd²⁺,Cu²⁺,Ni²⁺,Pb²⁺,Zn²⁺ in solutions prior to its determination by inductively coupled plasmaatomic emission spectrometry （ICP-AES）.Experimental conditions for effectiveadsorption of trace levels of metal ions were optimized with respect to differentexperimental parameters.The maximum static adsorption capacity of the sorbent atoptimum conditions was found to be 22.36,36.8,40.37,33.21 and 25.99 mg g^-1 forCd²⁺,Cu²⁺,Ni²⁺,Pb²⁺,Zn²⁺,respectively.The procedure was validated by analyzingthe certified reference river sediment material （GBW 08301,China）.The resultsobtained were in good agreement with standard values.The prepared sorbent assolid-phase extractants were successfully employed in the separation andpreconcentration of trace Cd²⁺,Cu²⁺,Ni²⁺,Pb²⁺,Zn²⁺ from the biological and naturalwater samples. In addition,an extract of Polymyxin B was analyzed by a validated highperformance liquid chromatography （HPLC） method based on reverse phase （RP）column separations.The components were separated preparatively on a C₁₈ stationaryphase by using 215nm detection.The mobile phase comprises acetonitrile-sodiumsulphate （dissolve 4.46 g of anhydrous sodium sulphate in 900 ml of water,adjust topH 2.3 with dilute phosphoric acid and dilute to 1000 mL with water） （20:80）.Tenpolymyxin B components were isolated and characterized using Accurate-MassQ-TOF.These were investigated and characterized by a number of instrumentaltechniques including:HPLC spectrometry;high resolution mass spectrometry;isolation of compounds by preparative scale HPLC,etc.更多还原