基于新型分子識別機制的電位型傳感器技術(shù)研究
發(fā)布時間：2018-08-19 12:25
【摘要】：分子識別是化學(xué)及生物傳感得以實現(xiàn)的重要過程,傳統(tǒng)的離子選擇性電極依賴離子載體實現(xiàn)對目標(biāo)離子的高選擇性檢測。自上世紀(jì)六十年代開始,得益于生物化學(xué)及超分子化學(xué)的發(fā)展,多種高效的離子載體被發(fā)現(xiàn)、合成并用于構(gòu)建聚合物膜電位型傳感器。雖然上世紀(jì)九十年代低檢出限離子選擇性電極的發(fā)現(xiàn)進一步推動了該領(lǐng)域的發(fā)展,但是最近一二十年關(guān)于新型離子載體(尤其是陰離子載體)的報道較少。這一方面是由于該領(lǐng)域沒有及時將超分子化學(xué)的研究成果引入造成的,另一方面是因為發(fā)展陰離子及中性分子的載體/識別體確有難度。本論文從新型的分子識別機制出發(fā),分別利用共價鍵、配位鍵、氫鍵及特殊的化學(xué)反應(yīng)發(fā)展了幾類新型的電位型傳感器:1.基于硼酸寡聚反應(yīng)的電位型多元醇傳感器。葡萄糖氧化酶的性質(zhì)不穩(wěn)定,因而酶基傳感器的長期穩(wěn)定性欠佳。葡萄糖本身不能引起電位信號,并且缺乏能產(chǎn)生電位信號的高選擇性葡萄糖識別體,所以目前并沒有關(guān)于高選擇性電位型葡萄糖傳感器的報道。通過二硼酸與葡萄糖之間的可逆共價作用,兩種分子可以以首尾相接的形式形成線狀或環(huán)狀寡聚陰離子。利用該寡聚陰離子與聚陽離子魚精蛋白之間的靜電作用及魚精蛋白本身的電位響應(yīng),可實現(xiàn)葡萄糖的檢測。其它單糖因為只有一對順式二醇結(jié)構(gòu),不會和二硼酸形成寡聚陰離子,因而不會干擾葡萄糖的檢測。該方法可在沒有特異性識別體的情況下實現(xiàn)對葡萄糖的檢測,并可用于植物多酚的檢測。2.基于競爭分析的電位型磷酸根傳感器。可逆共價作用只發(fā)生在特定的官能團之間,因而上述方法有一定的局限性�？紤]到配位作用鍵能較強而且存在于大多數(shù)陰離子與金屬離子之間,我們利用配位作用構(gòu)建了競爭型磷酸根傳感器。以Cu2+-BPMP(雙(2,6-二(2-吡啶基甲基)氨基甲基)-4-甲基苯酚)或Zn2+-BPMP為分子識別體,以鄰巰基苯酚為指示分子,利用指示分子氧化反應(yīng)過程中產(chǎn)生的電位信號,我們實現(xiàn)了磷酸根的選擇性檢測。通過電位滴定實驗與競爭實驗測定了磷酸根、指示分子與分子識別體的結(jié)合常數(shù),進一步驗證了檢測原理。其它陰離子不能將指示分子從分子識別體中取代下來,因而不干擾磷酸根檢測。該方法可用于礦泉水、唾液、尿液等樣品中磷酸根含量的檢測。3.基于陽離子及中性銻烷的電位型氟離子傳感器。氟離子的水化能很強,需要發(fā)展強親和力的載體,將其從水相有效地萃取到膜相。以電中性及陽離子銻烷為氟離子載體,通過優(yōu)化離子交換劑的種類及用量,構(gòu)建了高選擇性氟離子電極。研究表明,這類電極對氟離子的選擇性明顯優(yōu)于只摻雜有陰離子交換劑的聚合物膜電極。采用雙層膜夾心法測定了離子載體與各種離子之間的結(jié)合常數(shù),該結(jié)合常數(shù)反映了電極的選擇性系數(shù)�；陉栯x子及電中性銻烷的氟離子電極具有優(yōu)良的響應(yīng)性能,可用于水溶液中氟離子濃度的測試,有一定的潛在應(yīng)用價值。4.電中性硫酚的電位響應(yīng)及其在電化學(xué)傳感中的應(yīng)用。對于大部分電中性分子來說,很難利用共價鍵及配位鍵發(fā)展與其相對應(yīng)的分子識別體。經(jīng)典的聚合物膜電極理論認為只有帶電物質(zhì)才能在聚合物膜上引起電位響應(yīng)。研究表明,電中性的表面活性劑、苯酚及硼酸等可以間接方式改變膜表面的電荷分布進而引起電位響應(yīng)。但是,這類電中性物質(zhì)能夠引起電位響應(yīng)的報道較少。我們發(fā)現(xiàn),電中性苯硫酚可在氫鍵作用下在陰離子交換劑摻雜的聚合物膜上引起電位響應(yīng)。通過均相的紫外滴定實驗及兩相萃取實驗,我們研究了苯硫酚與離子交換劑在均相及兩相溶液中結(jié)合性質(zhì),據(jù)此推測了它的電位響應(yīng)機理。該電極可作為一種簡單易行的手段檢測環(huán)境污染物苯硫酚。另外,利用苯硫酚氧化反應(yīng)過程中的信號變化,可發(fā)展高靈敏的電位型傳感平臺用于多種物質(zhì)的電化學(xué)檢測。5.免標(biāo)記、聚合放大型自由基反應(yīng)傳感器。以上幾種傳感方法針對的都是物理化學(xué)性質(zhì)比較穩(wěn)定的目標(biāo)物,但是對于化學(xué)性質(zhì)不穩(wěn)定的目標(biāo)物如自由基,很難發(fā)展一種與之相對應(yīng)的分子識別體。利用自由基反應(yīng)聚合乙烯型及芳香型單體的性質(zhì)及高靈敏聚離子電極,我們發(fā)展了針對自由基反應(yīng)的電位型傳感平臺。我們首先考察了經(jīng)RAFT反應(yīng)及FRP反應(yīng)產(chǎn)生的聚離子及其對應(yīng)的單體在聚合物膜電極上的響應(yīng)性能,研究發(fā)現(xiàn)聚離子電極對聚合物的靈敏度顯著高于對單體的靈敏度。利用葡萄糖氧化酶消除溶液中的氧氣,以自由基反應(yīng)聚合陽離子或陰離子單體,我們實現(xiàn)了對自由基引發(fā)劑(如辣根過氧化物酶、G-四聯(lián)體/核酸酶、Fenton反應(yīng))及猝滅劑(過氧化氫酶)的檢測�；陬愃频脑�,該傳感平臺可實現(xiàn)多種反應(yīng)及目標(biāo)物的高靈敏電位檢測。
[Abstract]:Molecular recognition is an important process for chemical and biological sensing. Traditional ion-selective electrodes rely on ion carriers to achieve high selective detection of target ions. Since the 1960s, thanks to the development of Biochemistry and supramolecular chemistry, a variety of efficient ion carriers have been discovered, synthesized and used to construct polymerization. Although the discovery of low detection limit ion selective electrodes in the 1990s has further promoted the development of this field, there have been few reports about new ion carriers (especially anionic carriers) in the last 20 years. This is due to the lack of timely introduction of supramolecular chemistry research results in this field. On the other hand, it is difficult to develop carriers / recognizers for anions and neutral molecules. In this paper, several novel potential sensors based on boric acid oligomerization have been developed by using covalent bonds, coordination bonds, hydrogen bonds and special chemical reactions, respectively. 1. Sensors. Glucose oxidase is unstable in nature, so the long-term stability of enzyme-based biosensors is poor. Glucose itself can not cause potential signals and lacks highly selective glucose recognizers that can produce potential signals. So there is no report on high selective potential glucose biosensors. Through boric acid and glucose Reversible covalent interactions between sugars allow the two molecules to form linear or cyclic oligomeric anions in the form of head-to-tail contact. The detection of glucose can be achieved by the electrostatic interaction between the oligomeric anion and polycationic protamine and the potential response of protamine itself. Other monosaccharides have only one pair of cis-diols, but no cis-diols. This method can be used to detect glucose without specific recognition body, and can be used to detect plant polyphenols. 2. Potential phosphate sensors based on competitive analysis. Reversible covalent interactions occur only between specific functional groups, so that they do not interfere with glucose detection. Considering that the coordination bond is strong and exists between most anions and metal ions, a competitive phosphate sensor is constructed by using the coordination interaction. Cu2 + - BPMP (bis (2,6-bis (2-pyridylmethyl) aminomethyl) - 4-methylphenol) or Zn2 + - BPMP are used as molecular recognizers and o-mercapto-BPMP as molecular recognizers. Phenol is used as an indicator molecule, and the selective detection of phosphate is realized by using the potential signals generated during the oxidation reaction of the indicator molecule. The binding constants of phosphate are determined by potentiometric titration and competitive experiments. The detection principle is further verified by indicating the binding constants between the indicator molecule and the molecular recognition molecule. This method can be used for the determination of phosphate in mineral water, saliva, urine and other samples. 3. Potential fluoride ion sensors based on cations and neutral antimony alkanes. Fluoride ions have strong hydration energy and need to develop strong affinity carriers to effectively extract them from aqueous phase. A highly selective fluoride ion electrode was constructed using electroneutral and cationic antimony alkane as fluoride ion carrier by optimizing the type and dosage of ion exchangers. The results showed that the selectivity of this kind of electrode to fluoride ion was obviously superior to that of polymer membrane electrode only doped with anion exchanger. The binding constant between the body and various ions reflects the selectivity coefficient of the electrode. The fluoride ion electrode based on cationic and electroneutral antimony alkane has excellent response performance and can be used to measure the concentration of fluoride ions in aqueous solution. It has a certain potential application value. 4. The potential response of electroneutral Thiophenol and its electrochemical transfer. The classical theory of polymer membrane electrode holds that only charged materials can induce potential response on polymer membranes. Studies have shown that electroneutral surfactants, phenols and boric acids can be indirect. However, there are few reports that these electroneutral substances can induce potential response. We found that electroneutral thiophenol can induce potential response on anion exchanger doped polymer membranes under hydrogen bonding. Homogeneous ultraviolet titration and two-phase extraction experiments were carried out. The binding properties of Thiophenol and ion exchanger in homogeneous and two-phase solutions were studied. The potential response mechanism of Thiophenol was deduced. The electrode can be used as a simple and easy method to detect thiophenol in environmental pollution. In addition, a highly sensitive potential sensing level can be developed by using the signal changes during the oxidation of thiophenol. Electrochemical detection of a variety of substances. 5. Label-free, polymerized amplified radical reaction sensors. The above-mentioned sensing methods are aimed at relatively stable physical and chemical properties of the target, but for unstable chemical properties such as free radicals, it is difficult to develop a corresponding molecular recognition. The properties of reactive polyethylene and aromatic monomers and highly sensitive polyion electrodes have been developed for the potentiometric sensing of free radical reactions. We first investigated the response of polyions and their corresponding monomers to polymer membrane electrodes via RAFT and FRP reactions, and found that polyion electrodes react with polymer membranes. Using glucose oxidase to eliminate oxygen in solution and to polymerize cationic or anionic monomers by free radical reaction, we have successfully detected free radical initiators (such as horseradish peroxidase, G-tetrad/nuclease, Fenton reaction) and quencher (catalase) based on similarity. The sensing platform can achieve high sensitivity potential detection for various reactions and targets.
【學(xué)位授予單位】：中國科學(xué)院煙臺海岸帶研究所
【學(xué)位級別】：博士
【學(xué)位授予年份】：2016
【分類號】：X830;TP212
本文編號：2191646
[Abstract]:Molecular recognition is an important process for chemical and biological sensing. Traditional ion-selective electrodes rely on ion carriers to achieve high selective detection of target ions. Since the 1960s, thanks to the development of Biochemistry and supramolecular chemistry, a variety of efficient ion carriers have been discovered, synthesized and used to construct polymerization. Although the discovery of low detection limit ion selective electrodes in the 1990s has further promoted the development of this field, there have been few reports about new ion carriers (especially anionic carriers) in the last 20 years. This is due to the lack of timely introduction of supramolecular chemistry research results in this field. On the other hand, it is difficult to develop carriers / recognizers for anions and neutral molecules. In this paper, several novel potential sensors based on boric acid oligomerization have been developed by using covalent bonds, coordination bonds, hydrogen bonds and special chemical reactions, respectively. 1. Sensors. Glucose oxidase is unstable in nature, so the long-term stability of enzyme-based biosensors is poor. Glucose itself can not cause potential signals and lacks highly selective glucose recognizers that can produce potential signals. So there is no report on high selective potential glucose biosensors. Through boric acid and glucose Reversible covalent interactions between sugars allow the two molecules to form linear or cyclic oligomeric anions in the form of head-to-tail contact. The detection of glucose can be achieved by the electrostatic interaction between the oligomeric anion and polycationic protamine and the potential response of protamine itself. Other monosaccharides have only one pair of cis-diols, but no cis-diols. This method can be used to detect glucose without specific recognition body, and can be used to detect plant polyphenols. 2. Potential phosphate sensors based on competitive analysis. Reversible covalent interactions occur only between specific functional groups, so that they do not interfere with glucose detection. Considering that the coordination bond is strong and exists between most anions and metal ions, a competitive phosphate sensor is constructed by using the coordination interaction. Cu2 + - BPMP (bis (2,6-bis (2-pyridylmethyl) aminomethyl) - 4-methylphenol) or Zn2 + - BPMP are used as molecular recognizers and o-mercapto-BPMP as molecular recognizers. Phenol is used as an indicator molecule, and the selective detection of phosphate is realized by using the potential signals generated during the oxidation reaction of the indicator molecule. The binding constants of phosphate are determined by potentiometric titration and competitive experiments. The detection principle is further verified by indicating the binding constants between the indicator molecule and the molecular recognition molecule. This method can be used for the determination of phosphate in mineral water, saliva, urine and other samples. 3. Potential fluoride ion sensors based on cations and neutral antimony alkanes. Fluoride ions have strong hydration energy and need to develop strong affinity carriers to effectively extract them from aqueous phase. A highly selective fluoride ion electrode was constructed using electroneutral and cationic antimony alkane as fluoride ion carrier by optimizing the type and dosage of ion exchangers. The results showed that the selectivity of this kind of electrode to fluoride ion was obviously superior to that of polymer membrane electrode only doped with anion exchanger. The binding constant between the body and various ions reflects the selectivity coefficient of the electrode. The fluoride ion electrode based on cationic and electroneutral antimony alkane has excellent response performance and can be used to measure the concentration of fluoride ions in aqueous solution. It has a certain potential application value. 4. The potential response of electroneutral Thiophenol and its electrochemical transfer. The classical theory of polymer membrane electrode holds that only charged materials can induce potential response on polymer membranes. Studies have shown that electroneutral surfactants, phenols and boric acids can be indirect. However, there are few reports that these electroneutral substances can induce potential response. We found that electroneutral thiophenol can induce potential response on anion exchanger doped polymer membranes under hydrogen bonding. Homogeneous ultraviolet titration and two-phase extraction experiments were carried out. The binding properties of Thiophenol and ion exchanger in homogeneous and two-phase solutions were studied. The potential response mechanism of Thiophenol was deduced. The electrode can be used as a simple and easy method to detect thiophenol in environmental pollution. In addition, a highly sensitive potential sensing level can be developed by using the signal changes during the oxidation of thiophenol. Electrochemical detection of a variety of substances. 5. Label-free, polymerized amplified radical reaction sensors. The above-mentioned sensing methods are aimed at relatively stable physical and chemical properties of the target, but for unstable chemical properties such as free radicals, it is difficult to develop a corresponding molecular recognition. The properties of reactive polyethylene and aromatic monomers and highly sensitive polyion electrodes have been developed for the potentiometric sensing of free radical reactions. We first investigated the response of polyions and their corresponding monomers to polymer membrane electrodes via RAFT and FRP reactions, and found that polyion electrodes react with polymer membranes. Using glucose oxidase to eliminate oxygen in solution and to polymerize cationic or anionic monomers by free radical reaction, we have successfully detected free radical initiators (such as horseradish peroxidase, G-tetrad/nuclease, Fenton reaction) and quencher (catalase) based on similarity. The sensing platform can achieve high sensitivity potential detection for various reactions and targets.
【學(xué)位授予單位】：中國科學(xué)院煙臺海岸帶研究所
【學(xué)位級別】：博士
【學(xué)位授予年份】：2016
【分類號】：X830;TP212
【參考文獻】
相關(guān)期刊論文 前1條
1 孫強;邱勇;劉臻;吳潔;陳軍浩;陳蕾蕾;馬薇薇;;SOX9在青少年特發(fā)性脊柱側(cè)凸患者骨髓間質(zhì)干細胞的表達及意義[J];中國脊柱脊髓雜志;2006年03期
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