研發導電高分子結合鉻離子載體雙環己酮草酰二腙與修飾5-硫基-2-硝基苯甲酸之金奈米粒子以電化學方法偵測生物樣品中鉻離子含量

Application of PEDOT：OABCH and TNBA-capped gold nanoparticles in electrochemical detection of chromium ion in biofluids

廖彥誠(Yen-Chen Liao)

指導教授 ： 吳立真

國立暨南國際大學/科技學院/應用化學系/碩士(2011年)

摘要

電鍍與皮革工廠排放含鉻廢水影響周遭環境與生物體內鉻殘留量。生物體內含有許多還原劑，將攝入體內的鉻離子還原至三價鉻陽離子，其為最穩定的狀態。因此偵測生樣品內三價鉻離子含量為重要課題。而目前檢測生物樣品中鉻離子含量的方法為塞曼石磨爐原子光譜法(ZFGAAS)以及感應耦合電漿質譜儀(ICP-MS)，其偵測極限可達1.44 nM，但其儀器昂貴，樣品製備不易，因而發展出其他較簡便便宜的偵測方法。其中，電化學偵測最廣泛被研究。，目前以電化學方法偵測三價鉻離子以離子選擇電極最普遍，其原理是利用聚氯乙烯(PVC)攙和塑化劑(Platicizer)與離子載體(Ionophore)，其利用離子載體對三價鉻離子專一性吸附使兩電極間產生電位差，由電位差的大小定量。而本實驗將此概念應用於網版印刷電極(Screen-printed carbon electrode, SPCE)上。將電極表面以十二烷基硫酸鈉(SDS)為助溶劑鉻三架離子載體雙環己酮草酰二腙(OABCH)溶於水中，溶液中並含有導電高分子單體3,4-亞乙二氧基噻吩(EDOT)。電沉積過程中，PEDOT膜內鑲嵌OABCH，以吸附Cr3+。接著，加入修飾5-硫基-2-硝基苯甲酸(TNBA)之金奈米粒子，利用TNBA的硝基與羧基與Cr3+吸附。電極上吸附的金奈米粒子，經在酸性條件下給予1.2 V電位氧化金奈米粒子後，以方波伏安法偵測其還原電流。本實驗中探討在修飾網版印刷碳三電極過程中，EDOT在含有OABCH以及SDS的環境中，對電極表面性質影響。也針對SDS對電極表面電性改變作探討，並找出EDOT與OABCH在系統中的最佳濃度，以及所處適合的酸鹼度環境。此方法偵測極限為1.028 μM，線性範圍為3 μM ~ 100μL。本方法偵測添加Cr3+自來水樣品中回收率佳，可應用於廢水檢測，此方法其儀器攜帶簡便，可於取樣地點即時檢測。當將Cr3+添加於生物樣品內時，回收率僅添加量的30 %，需更進一步針對去除蛋白質的方法做改善，以達準確偵測生物樣品內三價鉻離子之目的。

關鍵字

三價鉻陽離子 ； 雙環己酮草酰二腙5-硫基-2-硝基苯甲酸 ； 金奈米粒子

並列摘要

A PEDOT:Ionophore modified screen-printed electrode was developed as a trivalent chromium (Cr3+) sensor. Cr3+ plays an important role in biological systems such as glucose metabolism and DNA impairment. Several electrochemical approaches for Cr3+ determination are proposed. Among which, ion-selective electrode (ISE) has been widely applied. The applications of this ionophore doped PVC film electrode coupled with voltmeter on waste water management and water pollution draw significant attention recently. In the present study, we developed a sandwich assay employing PEDOT:Ionophore modified screen-printed carbon electrode (SPCE) coupled with 5-thio-(2-nitrobenzoic acid) capped gold nanoparticles (TNBA-AuNPs) as signal sources to measure Cr3+ concentration in biofluids. EDOT was dissolved with the aid of SDS to form polymer by electrodeposition with oxalic acid bis(cyclohexylidene hydrazide) (OABCH), an ionophore of Cr3+, doped. Cr3+ incubated on the surface of the modified electrode to be adsorbed by ionophore. TNBA-AuNPs were then added to interact with Cr3+-OABCH complexes. TNBA-AuNPs was dissolved by 0.1 M nitric acid and gold was detected by anodic stripping square wave voltammetry. Parameters included the reaction pH of Cr3+ for ionophore selectivity, and the concentrations of ionophore, SDS, and EDOT for detection limit were discussed. This system possessed a LOD of Cr3+ was 1.028×10-6 M by this method. The linear range of this mithod are between 3 μM and 100 μM. This system provides potential applications in blood Cr3+ determination for healthcare monitoring.

並列關鍵字

Chromium ； PEDOT ； OABCH ； Ionophore ； Ion-selective electrode ； Gold nanoparticles

參考文獻

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