重金屬配合物光電功能材料在生化分析中的應(yīng)用研究
發(fā)布時(shí)間:2018-04-19 23:02
本文選題:電化學(xué)傳感器 + 光致電化學(xué)分析; 參考:《青島科技大學(xué)》2017年碩士論文
【摘要】:電化學(xué)生物傳感器具有操作簡單、靈敏度高、消耗低廉等優(yōu)點(diǎn),在相關(guān)疾病的診斷、環(huán)境檢測等方面有著非常重要的應(yīng)用。監(jiān)測電化學(xué)信號最常用的是計(jì)時(shí)庫侖法,它能夠定量地測定電活性物質(zhì)或表面活性物質(zhì)在電極表面的吸附量,并且可以容易地得到實(shí)驗(yàn)數(shù)據(jù),信噪比極好。本論文就采用此方法構(gòu)建了電化學(xué)生物傳感器用于腺苷的檢測。光致電化學(xué)作為電化學(xué)的一個(gè)分支,目前正在逐步的發(fā)展。作為一種新型的分析檢測方法,它的光信號與電信號是分開的,所以背景信號的干擾比其它方法要小,因此它在分析檢測領(lǐng)域的應(yīng)用將會(huì)越來越廣泛。光電傳感器的靈敏度取決于采用材料的光電轉(zhuǎn)化效率,所以設(shè)計(jì)開發(fā)新型高效光電材料成為目前越來越重要的研究方向。本課題以設(shè)計(jì)高效的光電材料為出發(fā)點(diǎn),通過引入光敏基團(tuán)設(shè)計(jì)合成高效的銥配合物光電材料,研究其光電性質(zhì),結(jié)合納米材料的信號放大,來構(gòu)建高選擇性、高靈敏度的光電傳感器,用于生物活性分子的檢測。主要研究工作包括以下內(nèi)容:(1)以鏈置換DNA聚合和滾環(huán)擴(kuò)增(RCA)作為放大手段,構(gòu)建了高效的免標(biāo)記電化學(xué)生物傳感器,用于腺苷的檢測。腺苷會(huì)引發(fā)自催化DNA聚合/剪切過程,同時(shí)釋放大量的ssDNA。然后這些釋放的ss DNA可作為引物啟動(dòng)RCA聚合反應(yīng),在電極表面形成長DNA聚合物以吸附大量電活性指示劑Ru(NH3)63+,實(shí)現(xiàn)CC的信號放大。這兩種放大手段聯(lián)用使得傳感器的靈敏度大大提高,檢測限低至0.032 nM,并且它還對不同種類的核苷表現(xiàn)出高度的選擇性和良好的重現(xiàn)性。(2)以香豆素-L(C_L)為主配體,4-(2-吡啶基)苯甲醛(hpba)為輔助配體合成了光電材料[Ir(C_L)(hpba)_2]PF_6(Ir-1),并對其進(jìn)行了紫外可見吸收光譜、熒光光譜及光電性質(zhì)研究。結(jié)果表明,Ir-1在450 nm處有較強(qiáng)的光吸收。以氧氣作為電子受體時(shí),光電材料可以產(chǎn)生穩(wěn)定的還原電流。再分別以氧氣、三乙醇胺、抗壞血酸等作為電子供受體,對其信號的影響進(jìn)行了討論,通過對比發(fā)現(xiàn),抗壞血酸作為電子供體,開啟電壓為-2 V時(shí),光電流最大,且暗電流小。將其作為信號物質(zhì)構(gòu)建成光致電化學(xué)生物傳感器,用于檢測DNA。在最佳條件下,這種生物傳感器檢出限低至9.0 fmol L-1(3σ)。(3)以香豆素-6(C_6)為主配體,二吡啶并[3,2-a:2',3'-c]吩嗪(dppz)為輔助配體合成了光電材料[Ir(C_6)2(dppz)]PF_6(Ir-2),并對其進(jìn)行了紫外可見吸收光譜、熒光光譜及光電性質(zhì)的研究。研究表明,Ir-2在480 nm處有較強(qiáng)的光吸收。當(dāng)氧氣作為電子受體時(shí),可以產(chǎn)生穩(wěn)定的還原電流。對比不同偏置電壓發(fā)現(xiàn),偏置電壓為0 V時(shí),檢測到的光電流大,且關(guān)光時(shí)的暗電流小。分別以氧氣、三乙醇胺、抗壞血酸等作為電子供受體,對其信號的影響進(jìn)行了討論,通過對比發(fā)現(xiàn),氧氣作為電子受體,開啟電壓為0 V時(shí),光電流最大,且暗電流小。
[Abstract]:Electrochemical biosensor has many advantages, such as simple operation, high sensitivity, low consumption and so on. It has very important applications in the diagnosis of related diseases and environmental detection. The most commonly used method for monitoring electrochemical signals is the time-coulomb method, which can quantitatively determine the adsorption of electroactive substances or surface active substances on the electrode surface, and can easily obtain experimental data. The signal-to-noise ratio (SNR) is excellent. In this paper, electrochemical biosensor was constructed to detect adenosine. Photochemistry, as a branch of electrochemistry, is developing step by step. As a new analysis and detection method, its optical signal and electrical signal are separated, so the interference of background signal is smaller than other methods, so it will be more and more widely used in the field of analysis and detection. The sensitivity of the photoelectric sensor depends on the photoelectric conversion efficiency of the materials, so the design and development of new and efficient optoelectronic materials has become more and more important research direction. Based on the design of high efficiency optoelectronic materials, the high selectivity of iridium complexes was constructed by introducing Guang Min group to design and synthesize high efficiency iridium complex optoelectronic materials, studying its photoelectric properties and combining with the signal amplification of nanomaterials. A highly sensitive photoelectric sensor for the detection of bioactive molecules. The main research work includes the following contents: (1) High efficiency non-label electrochemical biosensor was constructed by using chain displacement DNA polymerization and ring-amplification method as amplification method, which can be used for the detection of adenosine. Adenosine can initiate an autocatalytic DNA polymerization / shearing process and release a large amount of ssDNA. Then these ss DNA can be used as primers to initiate RCA polymerization and form long DNA polymers on the electrode surface to adsorb a large number of electroactive indicator Ru(NH3)63 to amplify CC signal. The combination of these two amplifiers greatly improves the sensitivity of the sensor. The detection limit was as low as 0.032 nm, and it also showed high selectivity and good reproducibility for different nucleosides. UV-Vis absorption spectra, Study on fluorescence spectrum and photoelectric properties. The results show that Ir-1 has strong light absorption at 450 nm. When oxygen is used as the electron acceptor, the photovoltaic material can produce a stable reduction current. The effects of oxygen, triethanolamine and ascorbic acid as electron donor receptors were discussed. It was found that ascorbic acid was the electron donor and the opening voltage was 2 V, the photocurrent was the largest and the dark current was small. It was used as signal material to construct photochemical biosensor to detect DNA. Under the optimum conditions, the detection limit of this biosensor is as low as 9.0 fmol L-1dppz. 3) the main ligand of this biosensor is coumarin -6C6), and the photovoltaic material [IRC62dppz)] PF6Ir-2n has been synthesized and characterized by UV-Vis absorption spectra. Study on fluorescence spectrum and photoelectric properties. The results show that Ir-2 has strong light absorption at 480 nm. When oxygen acts as an electron receptor, a steady reduction current is produced. When the bias voltage is 0 V, the detected photocurrent is large and the dark current is small when the light is turned off. The effects of oxygen, triethanolamine and ascorbic acid as electron donor receptors are discussed respectively. It is found that the photocurrent is the largest and the dark current is small when oxygen is used as the electron receptor and the opening voltage is 0 V.
【學(xué)位授予單位】:青島科技大學(xué)
【學(xué)位級別】:碩士
【學(xué)位授予年份】:2017
【分類號】:TB34;O657.1
【參考文獻(xiàn)】
相關(guān)期刊論文 前1條
1 羅先金 ,宋健 ,程侶柏 ,黃德音;Preparation of some new coumarin dyes[J];Science in China(Series B);2001年05期
,本文編號:1775107
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