【摘要】：近年來,對惡性腫瘤的早期檢測成為研究的熱門問題,傳統(tǒng)的技術(shù)在惡性腫瘤早期檢測上存在一定的困難。核酸適配體是一種能夠靶向結(jié)合各種腫瘤標(biāo)志物,其不僅具有高的特異性識別的能力,還具有高的親和力以及修飾簡單、靶目標(biāo)物豐富、易于合成等諸多優(yōu)點(diǎn),從而提供了一種理想的腫瘤靶向識別分子。與此同時(shí),金屬-有機(jī)骨架(Metal-Organic Frameworks, MOFs)配合物是通過金屬離子或者金屬簇與有機(jī)配體之間通過配位鍵連接形成周期性的、無限網(wǎng)絡(luò)的聚合物多孔結(jié)構(gòu)。由于MOFs材料具有多孔結(jié)構(gòu)、孔隙易于調(diào)節(jié)、易于功能化、以及特殊的光磁電性能等諸多優(yōu)點(diǎn),使得其顯示出比傳統(tǒng)的純無機(jī)材料和純有機(jī)物質(zhì)更加豐富和優(yōu)異的物化性能,使其在氣體的儲存與分離、光電化學(xué)傳感器、催化劑等方面都具有很可觀的前景�；诖�,本論文以發(fā)展新型惡性腫瘤早期檢測方法為目標(biāo),通過金屬有機(jī)聚合物結(jié)合核酸適配體作為新型腫瘤靶向識別分子,并過電化學(xué)生物傳感器來放大信號,達(dá)到檢測腫瘤標(biāo)志物效果。并將合成的功能性MOFs應(yīng)用于過氧化氫(H202),抗壞血酸(AA)等小分子的檢測,具體包括以下幾個(gè)部分的內(nèi)容。(1)以硫堇類有機(jī)物硫堇(Thi)和1,8蒽二羧酸二甲酯(Dada)為配體,以過渡金屬銅和鈷為配位中心,合成兩種新型的金屬有機(jī)聚合物Cu-Dada以及Co-Thi。并確定分子式。并將Cu-Dada以及Co-Thi和Sgc8c結(jié)合生成Cu-Dada-Sgc8c以及Co-Thi-Sgc8c。(2) Cu-Dada-Sgc8c以及Co-Thi-Sgc8c構(gòu)建電化學(xué)生物傳感器檢測腫瘤標(biāo)志物蛋白絡(luò)氨酸激酶(PTK7K),實(shí)驗(yàn)結(jié)果表明Cu-Dada-Sgc8c檢測PTK7K的線性范圍為6.25×10-7-3.75×10-6mg mL-1,檢出限為 1.5×10-8 mgmL-1,靈敏度為 3.87mAmL mg-1 cm-2。Co-Thi-Sgc8c 檢測 PTK7K 線性范圍 1.25 ×10-5-2×10-4 mg mL-1,檢出限為 1.67×10-6mg mL-1,靈敏度為 1.66mA mL mg-1 cm-2。(3) Cu-Dada構(gòu)建電化學(xué)傳感器催化過氧化氫、抗壞血酸、亞硝酸鹽。實(shí)驗(yàn)結(jié)果表明,Cu-Dada/GCE檢測過氧化氫的線性范圍為5×10-7-2.6×10-3 M,靈敏度為199.6 mA mol-1 L cm-2,最低檢出限為2.6×10-7 M。利用碳納米管改性后,制成Cu-Dada/MWCNTs/GCE,該傳感器的線性范圍為5×10-7-1.8×10-1M,該傳感器的靈敏度為424.3 mA mol-1 L cm-2,最低檢出限為2.4×10-8M。Cu-Dada/GCE檢測抗壞血酸的線性范圍為 1.6×10-5-2.2×10-3M (R=0.997),靈敏度為 37.5 mAmol-1 Lcm-2,最低檢出限為1.37×10-6M。Cu-Dada/GCE檢測亞硝酸鈉的線性范圍為5×10-5-1.2×10-1M,該傳感器的靈敏度為2.1mAmol-1 Lcm-2,最低檢出限為1.6×10-5M。當(dāng)我們摻雜碳納米管改性制成Cu-Dada/MWCNTs/GCE后,性能有所提高,線性范圍為5×10-5-9.8×10-3 M,該傳感器的靈敏度為76 mA mol-1 Lcm-2,最低檢出限為7.3×10-6M。
[Abstract]:In recent years, the early detection of malignant tumors has become a hot issue, and the traditional technology has some difficulties in the early detection of malignant tumors. The aptamer of nucleic acid is a kind of target binding tumor marker, which not only has the ability of high specificity recognition, but also has many advantages, such as high affinity, simple modification, rich target material, easy synthesis and so on. This provides an ideal tumor target recognition molecule. At the same time, the metal-organic skeleton (Metal-Organic Frameworks, MOFs) complexes form periodic, infinite network polymer porous structures through the bonding of coordination bonds between metal ions or metal clusters and organic ligands. Due to its porous structure, easy adjustment of pores, easy functionalization, and special optomagnetoelectric properties, MOFs materials exhibit more abundant and excellent physical and chemical properties than traditional pure inorganic materials and pure organic materials. It has a promising future in gas storage and separation, photochemical sensors, catalysts and so on. Based on this, the aim of this paper is to develop a new method for early detection of malignant tumor, which uses organometallic polymer and nucleic acid aptamer as novel tumor target recognition molecules and over-electrochemical biosensor to amplify the signal. The effect of detecting tumor markers was achieved. The synthesized functional MOFs was applied to the detection of hydrogen peroxide (H202), ascorbic acid (AA) and other small molecules, including the following parts. (1) the ligand of thionine (Thi) and 1,8-anthracene dicarboxylate (Dada) were used as ligands. Two novel organometallic polymers, Cu-Dada and Co-Thi., were synthesized by using transition metal copper and cobalt as coordination centers. And determine the formula. Cu-Dada, Co-Thi and Sgc8c were combined to form Cu-Dada-Sgc8c, Co-Thi-Sgc8c. (2) Cu-Dada-Sgc8c and Co-Thi-Sgc8c to construct an electrochemical biosensor for the detection of tumor marker protein complex aminokinase (PTK7K). The linear range of Cu-Dada-Sgc8c for PTK7K detection was 6.25 脳 10-7-3.75 脳 10-6mg mL-1, and the detection limit was 1.5 脳 10-8 mgmL-1,. The linear range of 3.87mAmL mg-1 cm-2.Co-Thi-Sgc8c detection for PTK7K was 1.25 脳 10-5-2 脳 10-4 mg mL-1,. The detection limit was 1.67 脳 10-6mg mL-1,. The sensitivity was 1.66mA mL mg-1 cm-2. (3) Cu-Dada to construct electrochemical sensor to catalyze hydrogen peroxide. Ascorbic acid, nitrite. The experimental results show that the linear range of Cu-Dada/GCE is 5 脳 10-7-2.6 脳 10-3 Mand the minimum detection limit of 199.6 mA mol-1 L cm-2, is 2.6 脳 10-7 M. Modified by carbon nanotubes, The linear range of the sensor is 5 脳 10-7-1.8 脳 10-1M, the sensitivity of the sensor is 424.3 mA mol-1 L cm-2, the minimum detection limit of ascorbic acid is 2.4 脳 10-8M.Cu-Dada/GCE, the linear range is 1.6 脳 10-5-2.2 脳 10-3M (RV 0.997), the sensitivity is 37.5 mAmol-1 Lcm-2, minimum detection limit of nitrite is 1.37 脳 10-6M.Cu-Dada/GCE. The linear range of sodium is 5 脳 10 ~ (-5) to 1.2 脳 10 ~ (-1) M, and the sensitivity of the sensor is 1.6 脳 10 ~ (-5) M. the sensitivity of the sensor is 1.6 脳 10 ~ (-5) M. When we modified Cu-Dada/MWCNTs/GCE with carbon nanotubes, the linear range was 5 脳 10-5-9.8 脳 10-3 M.The sensitivity of the sensor was 76 mA mol-1 Lcm-2, and the minimum detection limit was 7.3 脳 10-6 M.The linear range of the sensor was 5 脳 10-5-9.8 脳 10-3 M.The sensitivity of the sensor was 7.3 脳 10-6M.
【學(xué)位授予單位】：南京師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O657.1;O641.4

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