环境中金属离子的荧光探测及可修复研究
摘要
近年来,超分子概念的不断深入再加上纳米材料作为固体载体的应用,制备功能化杂化荧光材料引起了人们的广泛关注。它也在分子识别、材料化学和纳米科技之间建立起一座桥梁。由于纳米网状和三维结构可重复构造,以及仿生化学在杂化材料内的出现,使得在三维网络结构中制备功能性的材料成为研究的热点。近年来,采用高分子化合物作为固体载体也逐渐激起了化学家们的兴趣。本论文主要包括以下几个方面的内容：
1.水溶液中识别汞离子的荧光探针及环境修复研究：制备高选择性的荧光探针是一项富有挑战性的工作,基于Hg2+对硫原子有强烈的结合能力,一个以蛋氨酸甲酯为离子载体的化学传感器RM被设计合成并予以结构表征。可用于水溶液中高选择性的识别Hg2+,其他碱金属、碱土金属、过渡金属和重金属对其基本都没有影响,可适用的pH值范围为4-9,对环境中ppb(十亿分之一)级的Hg2+也有荧光响应。将RM固定在多孔的功能化分子筛SBA-15上,制成有机-无机杂化的固体材料RMS,它同样也可以用于水溶液中高选择性高灵敏度的识别汞离子。荧光滴定实验证实RMS的荧光强度与汞离子的量具有很好的线性关系,这说明它可用于实时并定量检测Hg2+。通过ICP(电感耦合等离子发射光谱)实验,证实固体探针RMS可吸附水中约70.4%的Hg2+,因此,RMS在环境修复上有潜在的应用价值。
2.水溶液中识别Fe3+的荧光探针及环境修复研究：目前为止,由于Fe3+的顺磁性、配体水溶性差以及其他金属离子的干扰,制备高选择性、水溶性的Fe3+荧光探针成为一大挑战。两个基于香豆素和氨基葡萄糖的荧光探针CG1、CG2被设计合成出来,并研究了CG1、CG2在水溶液中识别Fe3+的性质以及取代基对于它们荧光性质的影响。我们又设计合成了水溶性探针CO1和CO2,它们在水中对Fe3+也有很好的响应,而且相对于CG1、CG2灵敏度更高。为了实现材料化的目的,我们利用具有良好成膜性和对金属具有很好螯合能力的壳聚糖,将香豆素负载在高分子化合物壳聚糖上,制成了固体探针CC1和CC2。利用ICP(电感耦合等离子发射光谱)实验,证实固体探针CC1可用于吸附水中61.4%的Fe3+,CC1是一个潜在的处理Fe3+的固体吸附剂,可用于环境中处理污水,进而达到修复环境的目的。
Very recently, the combination of nanomaterials used as solid supports and supramolecular concepts has led to the development of hybrid materials with improved functionalities. It can bridge the gaps between molecular chemistry, materials science and nanotechnology, Because of the reversible building of nanometersized networks and 3D architectures as well as biomimetic and gated chemistry in hybrid nanomaterials, the development of advanced functional protocols in three dimensional frameworks has become the hot topic. On the other hand, macromolecular compounds used as solid supports have compelled many investigators to work with it.
A new rhodamine B based on chemosensor rhodamine-B methionine methyl ester (RM) was synthesized and structural characterized. It can be used for the selective detection of Hg2+in aqueous solution and was not affected by alkali and alkali-earth, transition and heavy metals, RM can detect Hg2+in a large pH range from 4 to 9, excellent sensitivity to Hg2+level lower to ppb(part per billion). Inorganic-organic hybrid fluorescence chemosensor RMS was prepared by immobilizing RM to the mesoporous silica material SBA-15 via triethoxysilane groups, the fluorescent intensity shows well-fitted linearity with the concentration of Hg2+in aqueous solution, according to ion chromatography (ICP),70.4%of Hg2+being extracted by RMS, suggesting the possibility of RMS for potential application in environmental restoration.
A new glucose-based CG1 and CG2 have been synthesized by glucosamine and coumarin for the recognition of Fe3+. Both CG1 and CG2 result in fluorescent enhancement in the presence of Fe3+in aqueous solution. Chemically modified chitosan CO1 and CO2 were also synthesized by chitosan oligosaccharide and coumarin, they can also be used to recognize Fe3+in aqueous solution. We observed that addition of Fe3+to aqueous solution of CO1 and CO2 increase the fluorescence intensity larger compared with CG1 and CG2. Besides, chitosan can adsorb metal ions and can be used as membrane material, so solid material CC1 and CC2 were prepared to adsorb Fe3+, according to ion chromatography (ICP),61.4%of Fe3+being extracted by CC1. CC1 is a potencially adsorbent for Fe3+and can be used in environmental cleanup.
1.水溶液中识别汞离子的荧光探针及环境修复研究：制备高选择性的荧光探针是一项富有挑战性的工作,基于Hg2+对硫原子有强烈的结合能力,一个以蛋氨酸甲酯为离子载体的化学传感器RM被设计合成并予以结构表征。可用于水溶液中高选择性的识别Hg2+,其他碱金属、碱土金属、过渡金属和重金属对其基本都没有影响,可适用的pH值范围为4-9,对环境中ppb(十亿分之一)级的Hg2+也有荧光响应。将RM固定在多孔的功能化分子筛SBA-15上,制成有机-无机杂化的固体材料RMS,它同样也可以用于水溶液中高选择性高灵敏度的识别汞离子。荧光滴定实验证实RMS的荧光强度与汞离子的量具有很好的线性关系,这说明它可用于实时并定量检测Hg2+。通过ICP(电感耦合等离子发射光谱)实验,证实固体探针RMS可吸附水中约70.4%的Hg2+,因此,RMS在环境修复上有潜在的应用价值。
2.水溶液中识别Fe3+的荧光探针及环境修复研究：目前为止,由于Fe3+的顺磁性、配体水溶性差以及其他金属离子的干扰,制备高选择性、水溶性的Fe3+荧光探针成为一大挑战。两个基于香豆素和氨基葡萄糖的荧光探针CG1、CG2被设计合成出来,并研究了CG1、CG2在水溶液中识别Fe3+的性质以及取代基对于它们荧光性质的影响。我们又设计合成了水溶性探针CO1和CO2,它们在水中对Fe3+也有很好的响应,而且相对于CG1、CG2灵敏度更高。为了实现材料化的目的,我们利用具有良好成膜性和对金属具有很好螯合能力的壳聚糖,将香豆素负载在高分子化合物壳聚糖上,制成了固体探针CC1和CC2。利用ICP(电感耦合等离子发射光谱)实验,证实固体探针CC1可用于吸附水中61.4%的Fe3+,CC1是一个潜在的处理Fe3+的固体吸附剂,可用于环境中处理污水,进而达到修复环境的目的。
Very recently, the combination of nanomaterials used as solid supports and supramolecular concepts has led to the development of hybrid materials with improved functionalities. It can bridge the gaps between molecular chemistry, materials science and nanotechnology, Because of the reversible building of nanometersized networks and 3D architectures as well as biomimetic and gated chemistry in hybrid nanomaterials, the development of advanced functional protocols in three dimensional frameworks has become the hot topic. On the other hand, macromolecular compounds used as solid supports have compelled many investigators to work with it.
A new rhodamine B based on chemosensor rhodamine-B methionine methyl ester (RM) was synthesized and structural characterized. It can be used for the selective detection of Hg2+in aqueous solution and was not affected by alkali and alkali-earth, transition and heavy metals, RM can detect Hg2+in a large pH range from 4 to 9, excellent sensitivity to Hg2+level lower to ppb(part per billion). Inorganic-organic hybrid fluorescence chemosensor RMS was prepared by immobilizing RM to the mesoporous silica material SBA-15 via triethoxysilane groups, the fluorescent intensity shows well-fitted linearity with the concentration of Hg2+in aqueous solution, according to ion chromatography (ICP),70.4%of Hg2+being extracted by RMS, suggesting the possibility of RMS for potential application in environmental restoration.
A new glucose-based CG1 and CG2 have been synthesized by glucosamine and coumarin for the recognition of Fe3+. Both CG1 and CG2 result in fluorescent enhancement in the presence of Fe3+in aqueous solution. Chemically modified chitosan CO1 and CO2 were also synthesized by chitosan oligosaccharide and coumarin, they can also be used to recognize Fe3+in aqueous solution. We observed that addition of Fe3+to aqueous solution of CO1 and CO2 increase the fluorescence intensity larger compared with CG1 and CG2. Besides, chitosan can adsorb metal ions and can be used as membrane material, so solid material CC1 and CC2 were prepared to adsorb Fe3+, according to ion chromatography (ICP),61.4%of Fe3+being extracted by CC1. CC1 is a potencially adsorbent for Fe3+and can be used in environmental cleanup.
引文
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