【作者】 李春艳；

【导师】 俞汝勤； 沈国励；

【作者基本信息】 湖南大学 ， 分析化学， 2008， 博士

【摘要】 以有机化合物为载体的化学传感的研究是一个十分活跃的领域,寻找具有高选择性的新型有机分子识别载体用于化学传感研究是一项非常有意义的工作。本文在广泛查阅相关文献的基础上,结合本实验室原有的工作基础,针对传感器在灵敏度和选择性等方面存在的问题,设计并合成了一系列新型的荧光探针分子和离子选择性电极的载体分子,并将它们用于pH、金属阳离子和阴离子的检测中。具体内容如下:1.设计并合成了可咯化合物为荧光载体的化学传感器用于pH测定。本文合成了一种新化合物,10-(4-氨基)-5,15-二(1,3,5-三甲基苯基)可咯,并以该化合物作为载体固定在溶胶-凝胶膜中,制备成光化学传感器用于对溶液pH值的测量。该传感器的构建是基于可咯具有多步的质子化和去质子化的性质,从而引起可咯荧光值对溶液pH值的响应。由于10-(4-氨基)-5, 15-二(1, 3, 5-三甲基苯基)可咯具有多个质子活性中心,因此基于它的传感器对pH的响应范围比5, 10, 15, 20-四苯基卟啉和5, 10, 15-三(五氟苯基)可咯的要宽得多。基于10-(4-氨基)-5, 15-二(1, 3, 5-三甲基苯基)可咯的传感器对pH响应的线性范围是2.17-10.30。该传感器表现出良好的可逆性和重现性,常见的阳离子对其检测pH无明显的干扰。2.设计并合成了以卟啉衍生物为载体的比率型荧光分子探针用于生物相关离子Zn2+的测定。本文设计并合成了一个含有2-(氧基甲基)吡啶单元的卟啉衍生物,并将其制成荧光探针用于识别金属离子。通常情况下,卟啉化合物被用来识别重金属离子,而该卟啉化合物却可以用来制备比率型传感器识别锌离子。比率型荧光信号的实现是基于卟啉的金属化,2-(氧基甲基)吡啶单元的协同作用促进了金属离子进入卟啉环,即化合物可以与锌离子形成配合物(配合比为1:1,结合常数K为1.04×105),这为锌离子荧光探针的构建提供了理论基础。我们考察了这个锌离子荧光探针的响应特性,锌离子响应的线性范围是3.2×10-7到1.8×10-4 M,检测下限为5.5×10-8 M。实验结果表明,在中性条件下(pH 4.0-8.0),该化合物对锌的响应几乎不受pH的影响。此外,该探针对锌离子具有很好的选择性。3.设计并合成了以萘酐-蒽双荧光团化合物为载体的双增强荧光分子探针用于Hg2+的测定。首次设计并合成了2-(N-丁基-1,8-萘酰亚胺-4-哌嗪基-甲基)-6-(蒽-9-甲基-哌嗪基-甲基)吡啶,并将其制成荧光分子探针用于有毒离子Hg(II)的测定,其中萘酐-蒽荧光染料作为荧光基团,含氮的2,6-二(哌嗪基-1-甲基)吡啶作为识别基团。此探针基于著名的光致电子转移(PET)机理,实现了单激发,双发射的检测Hg(II)。2,6-二(哌嗪基-1-甲基)吡啶单元可以与Hg(II)形成配合物(配合比为1:1),导致了该化合物的两个发射峰的荧光强度增强,这为汞离子荧光探针的构建提供了基础。我们考察了这个Hg(II)荧光探针的响应特性。Hg(II)响应的线性范围是2.4×10-7到8.6×10-5 M,检测下限为4.6×10-8 M。实验结果表明,在中性条件下(pH 5.0-8.0),该化合物对汞的响应几乎不受pH的影响。并且该探针对汞离子具有良好的选择性。4.设计并合成了以萘酐-卟啉双荧光团化合物为载体的比率型荧光分子探针用于有毒离子Hg2+的测定。首次合成了萘酐-卟啉双荧光团化合物,并将其制成比率型荧光分子探针用于有毒离子Hg(II)的测定。比率信号的实现是基于该化合物能够和汞离子发生配位作用,并且化合物的两个荧光基团(萘酐和卟啉)具有相同的激发波长,不同的发射波长(两个发射波长之间的距离较宽,为125 nm),这为汞离子荧光探针的构建提供了理论基础。汞离子响应的线性范围是7.8×10-7到1.2×10-4 M,检测下限为8.0×10-8 M。实验结果表明,在中性条件下(pH 4.0-8.0),该化合物对汞的响应几乎不受pH的影响。并且该探针对汞离子具有很好的选择性。5.设计并合成了以多取代酚-钌吡啶化合物为荧光探针用于Co2+的测定。酰胺键连接的2,6-二{[(2-羟基-5-叔丁基苄基)(吡啶-2-亚甲基)胺基]亚甲基}-4-甲基苯酚和钌三联吡啶配合物被首次用作在乙醇/水(1:1,v/v)溶液中识别二价钴离子。其中钌三联吡啶作为荧光基团,多取代苯酚作为识别基团。多取代苯酚可以与钴离子形成配合物(配合比为1:1,结合常数K为2.5×105),这为钴离子荧光探针的构建提供了理论基础。我们考察了这个钴离子荧光探针的响应特性。钴离子响应的线性范围是1.0×10-7到5.0×10-4 M,检测下限为5×10-8 M。实验结果表明,在中性条件下(pH 4.5-9.5),该化合物对钴的响应几乎不受pH的影响。此外,在金属阳离子中,除了铜离子,该探针对钴离子具有良好的选择性。该探针被用在水样中钴离子的测定。6.研制了基于酰胺键联接的双卟啉的铅离子选择性电极。首次合成了化合物酰胺键联氧杂蒽双卟啉(ADPX),并将其用于铅离子选择性电极的制备。其中ADPX作为PVC膜的载体,2-硝基苯基辛基酯(o-NPOE)作为增塑剂,四苯硼钠(NaTPB)为添加剂。考察了膜组分对电极性能的影响,得到了最佳的组分配比,即ADPX: NaTPB: o-NPOE: PVC的质量比为3:3:65:32。电极表现出良好的响应特性,线性响应范围是从2.6×10-6到1.0×10-1 M。在中性条件下(pH 4.5-7.5),电极的响应几乎不受pH的影响。另外,电极表现出对铅离子良好的选择性,并将其初步用于铅离子的滴定分析。7.研制了基于酰胺键联接的金属双卟啉的硫氰酸根离子选择性电极。首次合成了化合物酰胺键联氧杂蒽双锰卟啉(Mn2Cl2ADPX),并将其用于硫氰酸根离子选择性电极的制备。其中Mn2Cl2ADPX作为PVC膜的载体,2-硝基苯基辛基酯(o-NPOE)作为增塑剂。考察了膜组分对电极性能的影响,得到了最佳的组分配比,即Mn2Cl2ADPX: o-NPOE: PVC的质量比为3:65:32。电极表现出良好的响应特性,线性响应范围是从2.4×10-6到1.0×10-1 M。在中性条件下(pH 3.0-8.0),电极的响应几乎不受pH的影响。另外,电极表现出对硫氰酸根离子良好的选择性,并将其初步用于人体尿液中SCN-的测定,获得了满意的结果。更多还原

【Abstract】 In recent years, the research on chemical sensors based on organic dyes remains very active and searching for new fluorophores to improve sensitivity and selectivity of chemical sensors is still a challenge for the analytical research efforts. In this thesis, a series of novel fluorescent probes and ion-selective carriers were designed and synthesized to determine pH, metal ions and anions. The contents of this thesis are presented as follows:1. The synthesis of a new compound, 10-(4-aminophenyl)-5,15-dimesitylcorrole, and its application for preparation of optical chemical pH sensors are described. The dye was immobilized in a sol–gel glass matrix and exposed to aqueous buffer solutions. The response of the sensor was studied which is based on the fluorescence intensity changing of corrole owing to multiple steps of protonation and deprotonation. Due to the presence of several proton sensitive centers, 10-(4-Aminophenyl)-5,15-dimesitylcorrole based optode shows wider response range toward pH than that of tetraphenylporphyrin(TPPH2) and 5,10,15-tris(pentafluorophenyl)corrole(H3(tpfc)). It shows a linear pH response in the range of 2.17-10.30. The effect of the composition of the sensor membrane has been studied and the experimental conditions are optimized. The optode shows good reproducibility and reversibility, and common co-existing inorganic ions did not show obvious interference to its pH measurement.2. A porphyrin derivative containing two 2-(oxymethyl)pyridine units has been designed and synthesized as chemosensor for recognition of metal ions. Unlike many common porphyrin derivatives that show response to different heavy metal ions, the porphyrin derivative exhibits unexpected ratiometric fluorescence response to Zn2+ with high selectivity. The response of the novel chemosensor to zinc was based on the porphyrin metallation with cooperating effect of 2-(oxymethyl)pyridine units. The change of fluorescence of the porphyrin derivative was attributed to the formation of an inclusion complex between porphyrin ring and Zn2+ by 1:1 complex ratio (K= 1.04×105), which has been utilized as the basis of the fabrication of the Zn2+-sensitive fluorescent chemosensor. The analytical performance characteristics of the proposed Zn2+-sensitive chemosensor were investigated. The sensor can be applied to the quantification of Zn2+ with a linear range covering from 3.2×10?7 to 1.8×10?4 M and a detection limit of 5.5×10?8 M. The experimental results show that the response behavior of the porphyrin derivative to Zn2+ is pH-independent in medium condition (pH 4.0–8.0) with excellent selectivity for Zn2+ over transition metal cations.3. 2-{[(N-butyl-1,8-naphthalimide-4-yl)piperazine]methyl}-6-{[(anthracene-9- yl)-methyl-piperazine]-methyl}pyridine has been designed and synthesized to recognize Hg(II) in EtOH/H2O(1:1,v/v) solution, with naphthalimides-anthracene dyad selected as the fluorophore and a nitrogen-containing 2,6-bis(piperazine-1-yl-methyl) pyridine as the receptor. The new chemosensor for mercury was based on the well-known photoinduced electron-transfer (PET) mechanism and provided single-excitation, dual-emission detection. The dual fluorescence emission enhancement of the compound was attributed to the formation of an inclusion complex between 2,6-bis(piperazine-1-yl-methyl)pyridine unit and Hg(II) with a 1:1 complex ratio, which has been utilized as the basis of the fabrication of the Hg(II)-sensitive fluorescent chemosensor. The analytical performance characteristics of the proposed Hg(II)-sensitive chemosensor were investigated. The sensor can be applied to the quantification of Hg(II) with a linear range covering from 2.4×10-7 to 8.6×10-5 M and a detection limit of 4.6×10-8 M. The experimental results show that the response behavior of the compound to Hg(II) is pH independent in medium condition (pH 5.0-8.0). And the proposed Hg(II)-sensitive chemosensor showed excellent selectivity for Hg(II) over other metal cations.4. The synthesis of a novel fluoroionophore containing naphthalimide and porphyrin and its application as a HgII-sensitive ratiometric fluorescent chemosensor are described. The realization of ratiometric signaling is based on developing a new stategy with two fluorophores (naphthalimide and porphyrin) in one molecule having the same excitation wavelength. The response of the chemosensor is based on the fluorescence ratiometric change of the compound by coordination with HgII and large shift between the two emission maxima (125 nm) with single excitation wavelength. The compound-based chemosensor shows a linear response toward HgII in the concentration range from 7.8×10-7 to 1.2×10-4 M with a detection limit of 8.0×10-8 M, and a working pH range from 4.0 to 8.0. The chemosensor shows excellent selectivity for HgII over other transition metal cations. Based on this, a highly sensitive and selective method for the determination of mercury was developed.5. An amide-linked 2,6-bis{[(2-hydroxy-5-tert-butylbenzyl)(pyridyl-2-methyl)- amino]-methyl}-4-methylphenol-ruthenium (II) tris(bipyridine) 2PF6- complex was first used to recognize Co(II) in EtOH/H2O(1:1,v/v) solution, with the ruthenium (II) tris(bipyridine) moiety selected as a fluorophore and the multi-substituted phenol unit chosen as a receptor. The fluorescence quenching of the compound was attributed to the formation of an inclusion complex between multi-substituted phenol unit and Co(II) by 1:1 complex ratio(K= 2.5×105), which has been utilized as the basis of the fabrication of the Co(II)-sensitive fluorescent chemosensor. The analytical performance characteristics of the proposed Co(II)-sensitive chemosensor were investigated. The sensor can be applied to the quantification of Co(II) with a linear range covering from 1.0×10-7 to 5.0×10-5 M and a detection limit of 5×10-8 M. The experimental results show that the response behavior of the compound to Co(II) is pH independent in medium condition(pH 4.5-9.5) with excellent selectivity for Co(II) over transition metal cations except Cu(II). And the chemosensor has been used for determination of Co(II) in water samples.6. The synthesis of a new compound, amide-linked diporphyrin xanthene(ADPX), and its application for preparation of lead(II) ion selective electrodes are described. The electrode was prepared with a PVC membrane combining ADPX as an electroactive material, 2-nitrophenyl octyl ether (o-NPOE) as a plasticizer and sodium tetraphenylborate (NaTPB) as an additive in the percentage ratio of 3:3:65:32 (ADPX: NaTPB: o-NPOE: PVC, w:w). The electrode exhibited linear response with a near Nernstian slope of 28.2 mV per decade within the concentration range of 3.2×10-6 to 1.0×10-1 M lead ions, with a working pH range from 4.5 to 7.5, and a fast response time of less than 30s. Selectivity coefficients for Pb(II) relative to a number of interfering ions were investigated. The electrode is highly selective for Pb2+ ions over a large number of cations. Several electroactive materials and solvent mediators have been compared and the experimental conditions were optimized. The sensor was applied as indicator electrode in titration of Pb(II) with potassium chromate solution with satisfactory results.7. The synthesis of a new compound, amide-linked manganese diporphyrin xanthene(Mn2Cl2ADPX), and its application for preparation of thiocyanate selective electrodes are described. The electrode was prepared with a PVC membrane combining Mn2Cl2ADPX as an electro active material, 2-nitrophenyl octyl ether (o-NPOE) as a plasticizer in the percentage ratio of 3:65:32 (ADPX: o-NPOE: PVC, w:w). The electrode exhibited linear response within the concentration range of 2.4×10-6 to 1.0×10-1 M SCN-, with a working pH range from 3.0 to 8.0 and a fast response time of less than 60s. Several electro active materials and solvent mediators have been compared and the experimental conditions were optimized. Selectivity coefficients for SCN- relative to a number of interfering ions were investigated. The electrode exhibits anti-Hofmeister selectivity toward SCN- with respect to common co-existing anions. The electrode was applied to the determination of SCN- in body urine with satisfactory results.更多还原