【摘要】：血清中高膽固醇水平與糖尿病、高血壓、動脈粥樣硬化及冠心病等人類多發(fā)癥有關,血清中膽固醇的含量已成為臨床診斷的一項重要指標。傳統(tǒng)測定方法所用儀器復雜、檢測時間久、費用較高、干擾因素多,電化學傳感器具有對目標物有較高的識別能力,樣品用量少、響應快,成本低、體積小,便于普及的優(yōu)點,開發(fā)微型化、簡便化、可大批量生產的測定膽固醇含量的電化學傳感器具有重要意義。石墨烯具有高的比表面積、良好的導電性、超高的機械強度及獨特的電學性質,基于石墨烯的納米復合材料在電子器件、生物材料、傳感器材料和催化劑載體等領域展現(xiàn)優(yōu)異性能,具有廣闊應用前景。將石墨烯與導電聚合物材料、無機貴金屬材料結合,為新型的電化學傳感器和電化學生物傳感器的開發(fā)提供了新的思路。本論文主要是基于石墨烯的膽固醇電化學傳感器的制備與性能研究,主要研究內容如下:采用改進的Hummers方法,制備氧化石墨,用超聲剝離的方法制備氧化石墨烯,然后用水合肼對其還原制備還原的石墨烯材料,對石墨烯制備工藝進行了優(yōu)化。運用XRD、Raman、FTIR、SEM、TEM、AFM等手段對其進行了微觀結構表征,結果表明,超聲剝離13h可以合成薄的、理想的石墨烯材料。制備了石墨烯/硫堇/殼聚糖/膽固醇氧化酶/辣根過氧化物酶膽固醇生物傳感器。以合成的石墨烯為載體,具有良好導電性的硫堇為導電介體,殼聚糖為粘結劑,負載膽固醇氧化酶和辣根過氧化物酶作為催化劑,制備出了基于石墨烯/硫堇的膽固醇生物傳感器,檢測膽固醇濃度的最佳工作條件為:測試體系的p H值取7.0,測試溫度取室溫。該傳感器具有較低的檢測限3.7×10-7M、較高的靈敏度24m AM-1cm-2、檢測范圍為2.0×10-6~4.6×10-4 M,且具有很強的抗干擾能力。該體系對膽固醇的檢測具有較低的檢測限3.7×10-7M、較高的靈敏度24m AM-1cm-2、檢測范圍為2.0×10-6~4.6×10-4 M,表觀米氏常數(shù)KapM為4.9×10-5M,且具有很強的抗干擾能力,對葡萄糖、抗壞血酸、尿酸等干擾物質分別只產生了0.15%、1.69%、2.19%的電流變化。采用分部電化學聚合方法合成石墨烯/聚吡咯/殼聚糖/膽固醇氧化酶/辣根過氧化物酶膽固醇生物傳感器,研究了恒電位法聚合聚吡咯的工藝以及篩選了循環(huán)伏安法聚石墨烯的適合的電解質溶液,又研究了酶固定過程中戊二醛交聯(lián)時間對傳感器性能的影響,結果表明,運用恒電位聚合法于0.75V電位下聚合180s,再用循環(huán)伏安法在含Li Cl O4為電解質的氧化石墨烯溶液中于0.2~0.9V范圍內聚合18圈,最后負載酶后于0.3%wt.戊二醛溶液中交聯(lián)2h為最佳制備工藝。該方法所制得的基于石墨烯/聚吡咯的膽固醇生物傳感器,具有較寬的檢測范圍2.0×10-6~4.3×10-3 M,較低的檢測限1.8×10-7M。研究了基于石墨烯/鉑的無酶膽固醇傳感器。采用共沉淀法,利用弱還原劑乙二醇,與氯鉑酸和氧化石墨烯溶液在100℃高溫下進行反應6h,使它們得到充分還原,合成石墨烯負載鉑的復合材料。石墨烯為鉑提供了大量的活性位點,使其均勻分散,納米鉑也使石墨烯克服了自身的卷曲和層間堆疊等不足。用0.03M氯鉑酸合成的石墨烯/鉑復合材料修飾到電極上,并用0.3%wt.戊二醛溶液進行交聯(lián)3h,成功得制備出基于石墨烯/鉑的膽固醇無酶傳感器。該傳感器具有更寬的檢測范圍2.9×10-3~6.9×10-3 M,更低的檢測限8.3×10-8M。以上方法制備的基于石墨烯的膽固醇傳感器,可用于血清中游離膽固醇或總膽固醇的檢測,以及處理后食品中膽固醇的檢測。這對膽固醇傳感器的研究具有重大意義和發(fā)展前景。
[Abstract]:The high cholesterol level in the serum is related to the human multiple diseases such as diabetes, hypertension, atherosclerosis and coronary heart disease, and the content of cholesterol in the serum has become an important index of clinical diagnosis. The traditional measuring method has the advantages of complex instrument, long detection time, high cost and multiple interference factors, The electrochemical sensor capable of mass production for measuring the content of cholesterol is of great significance. The graphene has high specific surface area, good electrical conductivity, high mechanical strength and unique electrical property, and the graphene-based nano composite material has excellent performance in the fields of electronic devices, biological materials, sensor materials and catalyst carriers, and has wide application prospect. the combination of the graphene with the conductive polymer material and the inorganic noble metal material provides a new idea for the development of a novel electrochemical sensor and an electrochemical biosensor. This paper is mainly based on the preparation and performance of the graphene-based cholesterol electrochemical sensor. The main contents are as follows: the modified Hummers method is adopted to prepare the oxidized graphite, and the graphene oxide is prepared by the method of ultrasonic stripping. and then the reduced graphene material is reduced and prepared by using the water-bonding agent, and the preparation process of the graphene is optimized. The microstructural characterization was carried out by means of XRD, Raman, FTIR, SEM, TEM and AFM. The results show that the ultrasonic stripping 13h can be used to synthesize a thin, ideal graphene material. a graphene/ thiocyanate/ chitosan/ cholesterol oxidase/ horseradish peroxidase cholesterol biosensor is prepared. The graphene/ sulfur-based cholesterol biosensor is prepared by using the synthesized graphene as a carrier, a sulfur atom with good electrical conductivity as a conductive mediator, a chitosan as an adhesive, a load cholesterol oxidase and a horse radish peroxidase as a catalyst, The optimum working conditions for detecting the concentration of cholesterol are: the p H value of the test system is 7.0, and the test temperature is room temperature. The sensor has a low detection limit of 3. 7-10-7M, a high sensitivity of 24m AM-1cm-2, a detection range of 2.0-10-6-4. 6-10-4M, and has strong anti-interference capability. The system has a low detection limit of 3. 7-10-7M, a high sensitivity of 24m AM-1 cm-2, a high sensitivity of 24m AM-1 cm-2, a detection range of 2.0-10-6-4, 6-10-4 M, an apparent m-constant KapM of 4. 9-10-5M, and has strong anti-interference ability, The current changes of uric acid, such as uric acid, were only 0.15%, 1.69% and 2.19%, respectively. The synthesis of graphene/ poly-graphene/ chitosan/ cholesterol oxidase/ horseradish peroxidase cholesterol biosensor by a partial electrochemical polymerization method, a process for the polymerization of polygraphene by a constant potential method, and a suitable electrolyte solution for screening the polygraphene of the cyclic voltammetry, The effect of glutaraldehyde cross-linking time on the performance of the sensor was also studied. The results show that the polymerization of 180s under the potential of 0. 75V by the method of constant potential polymerization, and the cyclic voltammetry is used to polymerize the 18-ring in the range of 0. 2-0. 9V in the graphene solution containing Li-Cl _ 4 as the electrolyte. The final load of the enzyme was 0.3% by weight. and the cross-linking of the glutaraldehyde solution for 2h is the optimal preparation process. The method has the advantages of wide detection range of 2.0, 10-6-4, 3-10-3M, and low detection limit of 1. 8-10-7M. The enzyme-free cholesterol sensor based on graphene/ platinum was studied. By adopting the co-precipitation method, the weak reducing agent ethylene glycol, the chloroplatinic acid and the graphene oxide solution are reacted at a high temperature of 100 DEG C for 6h, so that they are fully reduced, and the composite material of the graphene supported platinum is synthesized. The graphene provides a large number of active sites for platinum, so that the graphene is uniformly dispersed, and the nano-platinum also overcomes the defects that the graphene overcomes the defects of the curling and the interlayer stack, and the like. The graphene/ platinum composite synthesized with 0. 03M chloroplatinic acid was modified to the electrode and used with 0.3% wt. The glutaraldehyde solution was cross-linked for 3h, and a graphene/ platinum-based cholesterol-free sensor was successfully prepared. The sensor has a wider detection range of 2. 9-10-3-6. 9-10-3M, and a lower detection limit of 8.3-10-8M. The graphene-based cholesterol sensor prepared by the method can be used for detecting the free cholesterol or total cholesterol in the serum, and detecting the cholesterol in the food after treatment. This study of cholesterol sensor is of great significance and development prospect.
【學位授予單位】：華南理工大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：O657.1;R446.11

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