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基于納米氧化鋅復(fù)合材料的光電化學(xué)生物傳感特性的研究

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  本文關(guān)鍵詞: 光電化學(xué) ZnO PLD 腫瘤標(biāo)志物 上轉(zhuǎn)換發(fā)光 出處:《吉林大學(xué)》2017年碩士論文 論文類型:學(xué)位論文


【摘要】:作為三大死亡殺手的癌癥已成為疾病死因之首,且發(fā)病率和死亡率不斷增加,嚴(yán)重威脅人類健康。但是癌癥卻并非等于死亡,癌癥的早期檢測(cè)對(duì)于臨床診斷及治療非常重要,而一般的檢測(cè)方法和手段,難以進(jìn)行早期準(zhǔn)確檢測(cè)。光電化學(xué)生物分析法可以對(duì)蛋白,核酸等與癌癥相關(guān)生物物質(zhì)進(jìn)行低濃度的快速精確測(cè)定。此外,光電化學(xué)生物分析利用光學(xué)信號(hào)為激發(fā)信號(hào),實(shí)行光電流的檢測(cè),兼具光學(xué)與電化學(xué)檢測(cè)的優(yōu)勢(shì),能夠?qū)崿F(xiàn)腫瘤標(biāo)志物的高靈敏度檢測(cè)。ZnO是第三代寬帶隙半導(dǎo)體材料,具有優(yōu)異的熱學(xué)、化學(xué)性能,密度低,生物相容性好,光化學(xué)穩(wěn)定性好等優(yōu)點(diǎn),ZnO納米材料在光電化學(xué)生物分析中表現(xiàn)出優(yōu)異的發(fā)展前景。另一方面,單獨(dú)的納米氧化鋅電極對(duì)光的利用率低,只能吸收光譜中相當(dāng)少部分的紫外光,而且易發(fā)生光生電子-空穴的復(fù)合,不利于制備高靈敏度的傳感器,我們將采用基于納米氧化鋅的復(fù)合電極材料,制備具有優(yōu)異傳感性能的光電化學(xué)生物傳感器。在此基礎(chǔ)上,利用稀土離子具有深的穿透深度,大的斯托克斯位移,低的背景噪聲與低毒性等優(yōu)點(diǎn)。采用980nm激光器激發(fā)稀土材料,產(chǎn)生紫外光與可見光,從而激發(fā)納米復(fù)合電極材料,這樣避免了紫外光在光電化學(xué)生物檢測(cè)系統(tǒng)中的影響。本文中,我們采用光電化學(xué)的檢測(cè)手段,以基于氧化鋅納米復(fù)合材料為光電極,對(duì)腫瘤的標(biāo)志物進(jìn)行高靈敏快速檢測(cè)。我們首先以模板法制備了三維大孔的納米氧化鋅材料電極,以激光脈沖沉積的方法制備了結(jié)構(gòu)完整均勻的納米氧化鋅薄膜電極,然后分別利用窄帶隙半導(dǎo)體材料(Ag_2S,CdS)進(jìn)行復(fù)合,成功的制備了ZnO/Ag_2S復(fù)合電極與ZnO/CdS復(fù)合電極。在增加吸收光的同時(shí),都能夠?qū)崿F(xiàn)兩種電極結(jié)構(gòu)的能級(jí)匹配,抑制光生載流子的復(fù)合,從而制備了低成本,高靈敏度,低檢測(cè)限,寬檢測(cè)范圍,穩(wěn)定性與特異性好的光電化學(xué)生物傳感器,同時(shí)運(yùn)用不同的激發(fā)光源,對(duì)腫瘤標(biāo)志物甲胎蛋白進(jìn)行了有效檢測(cè)。(1)首先利用膠體晶體模板法在FTO玻璃上制備了三維大孔納米氧化鋅材料電極,然后利用連續(xù)離子層吸附反應(yīng)在氧化鋅反蛋白石大孔結(jié)構(gòu)的框架與表面修飾了無毒的Ag_2S納米粒子(NPs),制備了FTO/ZnO/Ag_2S復(fù)合電極,在氙燈的照射下對(duì)腫瘤標(biāo)志物甲胎蛋白實(shí)現(xiàn)了低濃度無酶的光電化學(xué)高靈敏度檢測(cè),復(fù)合電極的檢測(cè)限低達(dá)8pg/mL,線性范圍為0.05ng/mL-200ng/mL。(2)采用激光脈沖沉積(PLD)的方法,依次在FTO玻璃基片上沉積了NaYF_4:Yb,Tm,ZnO,CdS,制備成FTO/NaYF_4:Yb,Tm/ZnO/CdS復(fù)合薄膜電極,在980nm激光的照射下,實(shí)現(xiàn)了低濃度甲胎蛋白的高靈敏度檢測(cè),檢測(cè)的線性范圍為0.01ng/mL-200ng/mL,檢測(cè)限為5 pg/mL。采用窄帶隙的納米材料與氧化鋅材料電極復(fù)合,提高了光的利用率,抑制了載流子的復(fù)合,從而制備出高靈敏度的生物傳感器。我們對(duì)于兩種結(jié)構(gòu)氧化鋅復(fù)合電極的光電性能進(jìn)行了研究,并且采用不同的光源應(yīng)用于檢測(cè)腫瘤標(biāo)志物甲胎蛋白。三維大孔的ZnO電極相對(duì)PLD方法制備的ZnO薄膜電極具有更高、更快的光電響應(yīng),更好的靈敏度。引入稀土離子的FTO/NaYF_4:Yb,Tm/ZnO/CdS復(fù)合薄膜電極,在980nm的激光激發(fā)下,ZnO/CdS能夠最大的利用稀土的上轉(zhuǎn)換發(fā)光,此光電化學(xué)檢測(cè)系統(tǒng)對(duì)甲胎蛋白有更低的檢測(cè)限和更寬的檢測(cè)范圍,該傳感器對(duì)于未來光電化學(xué)生物應(yīng)用與體內(nèi)檢測(cè)有更好的應(yīng)用前景。
[Abstract]:As the three leading cause of death of cancer has become the first cause of disease, and the incidence and mortality increased, a serious threat to human health. But cancer is not equal to death, the early detection of cancer is very important for clinical diagnosis and treatment, detection methods and means in general, it is difficult to early detection of photoelectric chemical and biological analysis. Method for protein, nucleic acid and cancer related biological material for fast and accurate determination of low concentration. In addition, the photoelectric chemical and biological analysis by using optical signal as excitation signal, the detection of photocurrent, optical and electrochemical detection, high sensitivity detection of.ZnO can realize the tumor markers is the third generation wide band gap semiconductor material and have excellent thermal, chemical properties, low density, good biocompatibility, good photochemical stability, ZnO nano materials in photoelectrochemical biology Exhibit excellent prospects for development analysis. On the other hand, the low utilization rate of nano Zinc Oxide electrode alone to light, can only absorb ultraviolet light is less part of the spectrum, but also prone to electron - hole recombination, is not conducive to the preparation of high sensitivity of the sensor, we will use Zinc Oxide's nano composite electrode materials based on the photoelectrochemical biosensor preparation has excellent sensing performance. On this basis, with the penetration depth of deep utilization of rare earth ions, large Stokes shift, background noise and the advantages of low toxicity. Using 980nm laser excitation of rare earth materials, produce ultraviolet and visible light, so as to stimulate the nano composite electrode material, so to avoid the effect of UV in the photoelectric chemical and biological detection system. In this paper, we use the photoelectric detection means, based on the Zinc Oxide nano composite material for optical Electrode, markers of cancer by high sensitive and rapid detection. We first by template method to prepare nano electrode materials Zinc Oxide 3D macroporous, the method of pulsed laser deposition of nanometer thin film electrode structure of Zinc Oxide perfect preparation, and then use a narrow bandgap semiconductor materials (Ag_2S, CdS) compound, successful preparation of ZnO/Ag_2S composite electrode and ZnO/CdS composite electrode. The increase in the absorption of light at the same time, are able to achieve level two electrode structures, and inhibit the recombination of photogenerated charge carriers and thus produce low cost, the preparation of high sensitivity, low detection limit, wide detection range, photoelectrochemical biosensor with good stability and specificity at the same time, using different excitation sources, the tumor markers were effective detection. (1) first on FTO glass was prepared using three-dimensional macroporous oxide nano colloidal crystal template method The zinc electrode materials, and then use the SILAR in frame and surface Zinc Oxide inverse opal macroporous structure modified Ag_2S nanoparticles (NPs), non-toxic FTO/ZnO/Ag_2S composite electrode was prepared under Xe lamp irradiation on tumor markers can detect the photoelectrochemical high sensitivity of low concentration and no enzyme. The detection limit as low as 8pg/mL composite electrode, the linear range of 0.05ng/mL-200ng/mL. (2) by pulsed laser deposition (PLD) method, turn on the FTO glass substrate were deposited on NaYF_4:Yb, Tm, ZnO, CdS, FTO/ were prepared in NaYF_4:Yb, Tm/ZnO/CdS composite film electrode in 980nm laser irradiation, to achieve a high the sensitivity of detection of low concentration of AFP, the linear range of detection was 0.01ng/mL-200ng/mL, the detection limit is 5 pg/mL. with narrow band gap of nano materials and composite materials Zinc Oxide electrode, improves the utilization rate of light, suppression The recombination, thus preparing biosensor with high sensitivity. We studied the photoelectric properties of two kinds of structure of Zinc Oxide composite electrodes, and the use of different light source application in the detection of tumor markers. ZnO electrode 3D macroporous relative PLD method for preparing ZnO thin film electrode has a higher photoelectric, faster response, better sensitivity. The introduction of rare earth ions FTO/NaYF_4:Yb, Tm/ZnO/CdS composite film electrodes, under 980nm excitation, ZnO/CdS to maximum utilization of rare earth upconversion luminescence, the photoelectric detection system has lower detection limit and wide range of detection of AFP, the application prospect of this sensor have a better future for Photoelectrochemical applications and biological detection in vivo.

【學(xué)位授予單位】:吉林大學(xué)
【學(xué)位級(jí)別】:碩士
【學(xué)位授予年份】:2017
【分類號(hào)】:R730.4;TP212

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