基于石墨烯的膽固醇電化學(xué)傳感器的制備與性能研究
發(fā)布時(shí)間：2018-11-24 15:09
【摘要】：血清中高膽固醇水平與糖尿病、高血壓、動(dòng)脈粥樣硬化及冠心病等人類多發(fā)癥有關(guān),血清中膽固醇的含量已成為臨床診斷的一項(xiàng)重要指標(biāo)。傳統(tǒng)測(cè)定方法所用儀器復(fù)雜、檢測(cè)時(shí)間久、費(fèi)用較高、干擾因素多,電化學(xué)傳感器具有對(duì)目標(biāo)物有較高的識(shí)別能力,樣品用量少、響應(yīng)快,成本低、體積小,便于普及的優(yōu)點(diǎn),開發(fā)微型化、簡(jiǎn)便化、可大批量生產(chǎn)的測(cè)定膽固醇含量的電化學(xué)傳感器具有重要意義。石墨烯具有高的比表面積、良好的導(dǎo)電性、超高的機(jī)械強(qiáng)度及獨(dú)特的電學(xué)性質(zhì),基于石墨烯的納米復(fù)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(lǐng)域展現(xiàn)優(yōu)異性能,具有廣闊應(yīng)用前景。將石墨烯與導(dǎo)電聚合物材料、無(wú)機(jī)貴金屬材料結(jié)合,為新型的電化學(xué)傳感器和電化學(xué)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(xué)傳感器的制備與性能研究,主要研究?jī)?nèi)容如下:采用改進(jìn)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(duì)其還原制備還原的石墨烯材料,對(duì)石墨烯制備工藝進(jìn)行了優(yōu)化。運(yùn)用XRD、Raman、FTIR、SEM、TEM、AFM等手段對(duì)其進(jìn)行了微觀結(jié)構(gòu)表征,結(jié)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(guò)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(dǎo)電性的硫堇為導(dǎo)電介體,殼聚糖為粘結(jié)劑,負(fù)載膽固醇氧化酶和辣根過(guò)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(cè)膽固醇濃度的最佳工作條件為:測(cè)試體系的p H值取7.0,測(cè)試溫度取室溫。該傳感器具有較低的檢測(cè)限3.7×10-7M、較高的靈敏度24m AM-1cm-2、檢測(cè)范圍為2.0×10-6~4.6×10-4 M,且具有很強(qiáng)的抗干擾能力。該體系對(duì)膽固醇的檢測(cè)具有較低的檢測(cè)限3.7×10-7M、較高的靈敏度24m AM-1cm-2、檢測(cè)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(qiáng)的抗干擾能力,對(duì)葡萄糖、抗壞血酸、尿酸等干擾物質(zhì)分別只產(chǎn)生了0.15%、1.69%、2.19%的電流變化。采用分部電化學(xué)聚合方法合成石墨烯/聚吡咯/殼聚糖/膽固醇氧化酶/辣根過(guò)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(zhì)溶液,又研究了酶固定過(guò)程中戊二醛交聯(lián)時(shí)間對(duì)傳感器性能的影響,結(jié)果表明,運(yùn)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(zhì)的氧化石墨烯溶液中于0.2~0.9V范圍內(nèi)聚合18圈,最后負(fù)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(cè)范圍2.0×10-6~4.3×10-3 M,較低的檢測(cè)限1.8×10-7M。研究了基于石墨烯/鉑的無(wú)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(jìn)行反應(yīng)6h,使它們得到充分還原,合成石墨烯負(fù)載鉑的復(fù)合材料。石墨烯為鉑提供了大量的活性位點(diǎn),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(fù)合材料修飾到電極上,并用0.3%wt.戊二醛溶液進(jìn)行交聯(lián)3h,成功得制備出基于石墨烯/鉑的膽固醇無(wú)酶?jìng)鞲衅�。該傳感器具有更寬的檢測(cè)范圍2.9×10-3~6.9×10-3 M,更低的檢測(cè)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(cè),以及處理后食品中膽固醇的檢測(cè)。這對(duì)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(xué)位授予單位】：華南理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：O657.1;R446.11
本文編號(hào)：2354189
[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(xué)位授予單位】：華南理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：O657.1;R446.11
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