【作者】 徐岚；

【导师】 袁若；

【作者基本信息】 西南师范大学 ， 分析化学， 2005， 博士

【摘要】 选择对某些离子具有优先识别能力的有机化合物作为离子载体应用于聚氯乙烯（PVC）液膜离子性选择电极中,开发离子选择电极的应用范围,是电分析化学研究领域中的一个重要方向。将分子印迹聚合物作为敏感材料应用于化学传感器的设计,也是最近几年来化学传感器研究领域中一个十分具有前景的课题。本论文着重于设计、合成新型有机有机物,将其作为离子载体用于PVC溶剂聚合膜离子选择性电极的研究中,并将电极初步应用于实际样品分析。合成了以水杨酸分子为模板的印迹高聚物,并将其成功运用于电导型化学传感器的设计和研究。 一、本文第一部分设计合成了五类有机物或有机金属配合物,并将它们分别作为新型载体,制备和研究几种高选择性的PVC膜离子电极。 1.采用原料易得合成简单的新型水杨醛缩氨基酸Schiff’s碱二苄基锡（Ⅳ）五配位配合物[Sn（Ⅳ）-SIADBen]为载体研制阴离子选择电极,这类电极对常见阴离子具有明显的反Hofmeister选择行为,其选择性序列为:Sal>>ClO₄^->SCN^->PhCOO>I^-NO₃^->Cl^->NO₂-≈CH₃COO^->Citrate>SO₄^2-。在pH5.0的磷酸盐缓冲介质中,电位响应线性范围为1.0×10^-1～2.5×10^-6molI^-1,检测下限1.0×10^-5molI¹,斜率61±1.6mV/dec,出现超Nemstian响应现象。向PVC膜中加入脂溶性阴离子添加剂四苯基硼钠（NaTPB）后,电极电位选择性能和选择性得到明显提高,由此可推断出,这种五配位的有机锡化合物[Sn（Ⅳ）-SIADBen],遵循带正电荷载体的响应机理。采用交流阻抗,红外光谱和紫外光谱分析技术研究了电极的响应机理,并对超Nernstian现象进行了解释。将该电极用于药物检测,获得满意的结果。 2.在合成时,改变配合物[Sn（Ⅳ）-SIADBen]分子结构中的某些基团,即将与中心原子更多还原

【Abstract】 Ion-selective electrodes (ISEs) constructed by incorporating ion carriers into solvent polymetric membranes have been widely applied for the direct determination of several ionic species. Many of them showed potentiometric anion-selectivity sequences which differed from the Hofmeister pattern. The key components of the sensors are lipophilic complexing agents capable of reversibly binding ions. This thesis focuses on design and synthesis of several novel compounds and basic studies on solvent polymeric membrane ion-selective electrodes containing the compounds. The electrodes can be successfully applied to practice sample analysis. Recently, MIPs have drawn much attention because of their attractive advantages such as simple and economical preparation, predetermined selectivity and good recognition properties which are not affected by acid, base, heat or organic phase treatment. It is appropriate for MIPs to be used as the recognition components of chemical sensor. In this thesis, a conductometric chemical sensor based on salicylic acid imprinted polymer [P(SA)] has been described, which provides the possibility and basis of using the novel P(SA) based sensor for determination of the salicylic acid.Part I of the thesis deals with design of some novel carriers for poly(vinyl chloride) (PVC) membrane ion- electrode with high selectivity to Salicylate, Thiocyanate, Nitrite and Mercury( II) ion respectively.1. A novel poly(viny! chloride) membrane electrode with high selectivity toward salicylate(Sal) based on salicylal-imino acid Schiff base dibenyl complex of Sn(IV) [Sn(IV)-SIADBen] as ionophore was described. The influence on the electrode performances by lipophilic charged additives was studied. The results suggested that Sn(IV)-SIADBen acts onthe basis of a positively charged carrier mechanism. The influence of several other variables was investigated to optimize the potentiometric response and selectivity of the electrode. The electrode based on Sn(IV)-SIADBen, with 30.44 wt. % PVC, 64.55 wt. % plasticizer ( dioctyl phthalate, DOP ), 3.81 wt. % ionophore and 1.2 wt. % anionic additive exhibited a linear response for Sal" ion in concentration range 1.0x10"’ to 2.5><10’6 mol I"1 and displayed anti-Hofmeister selectivity sequence as follows: Salicylate ? Perchlorate > Thiocyanate > Benzoate > Iodide > Nitrate > Chloride > Nitrite-Acetate > Citrate > Sulfate. UV-Visible absorption spectra was used to examine the specific interaction of salicylate with the ionophore. The e! ;ci; ;J ? was ?p ’". ’ in the clinic medicine analysis and the results obtained were consistent with those obtained by conventional method.2. A Novel salicylate-selective electrode based on an organotin complex with salicylal Schiff base of amino acid salicyladehydeaminoacid-di-n-butyl-Sn(IV)[Sn(IV)-SAADB] as ionophore is described, which exhibits high selectivity for salicylate over many other common anions with an anti-Hoi’meisier selectivity sequence: Sal" ? SCN’ > PhCOO’> CIO4’ > V > NO3" > NO2" > Br’ > Cl" > CH3COO". The electrode based on Sn(IV)-SAADB, with 30.44 wt. % PVC, 65.45 wt. % plasticizer (diocty! phthalate, DOP), 3.81 wt. % ionophore and 0.3 wt. % anionic additive is linear in 6.0 x I0"6—1.0 x 10’1 mol I"1 with a detective limit of 2.0 x 10"6 mol I’1 and a slope of 62.0 ± 1.2 mV/decade of salicylate concentration in phosphate buffer solution of pH 5.5 at 25°C. The influence on the electrode performances by lipophilic charged additives was studied and the possible response mechanism is investigated by UV spectra. The electrode is applied to medicine analysis and the result obtained is satisfactory.3. A novel PVC membrane ion-selective electrode based on tribenzyltin(IV) dithiocarbamate [Sn(IV)-TBDTB] as neutral carrier was developed for thiocyanate (SCN") determination. The electrode exhibits a near-Nernstian response for SCN" with a slope of 62.2 ± 0.7 mV per decade over a wide concentration range l.Ox 10"1 ~ 2.Ox 10"6 mol I"1 and a detection limit of 9.2xlO"7mol I"1 in MES-NaOH buffer, pH 6.0, at 25°C. It shows a quite good selectivity for SCN" over a variety of other common anions and displays anti-Hofmeister selectivity sequence: SCN "> Sal " > I "> C1O4 ">Ac" >Br" > Cl" > NO3" > SO32" > SO42". The response mechanism is investigated via UV/Vis spectra and a.c. impedance technique which revealed that the excellent selectivity for thiocyanate was related to the unique interaction between the central tin(IV) ion and thiocyanate. The electrode has been used for direct determination of thiocyanate in wastewater with satisfactory results.更多还原