Glucose Sensor Based On Co-MOFs-modified Commercial Strip Electrodes
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摘要: 第三代葡萄糖传感器中氧化酶存在容易受温度、湿度、酸碱度等影响的缺点。因此，开发低成本、高灵敏度的葡萄糖催化剂具有广阔的应用前景。金属-有机框架(Metal-Origanic Frameworks, MOFs)因具有传质速度快、孔隙率可调和电子转移能力强等优点而受到广泛的关注。丝网印刷技术是一种低成本、批量化制备商业电极工艺。本文采用一种简单、经济的方法室温下成功地合成了Co-MOFs；采用丝网印刷技术将Co-MOFs涂敷在商业化条形银-碳电极上。作为生物传感器的催化剂，Co-MOFs纳米材料对葡萄糖表现出较高的电催化活性。测试结果表明，Co-MOFs基条形电极对葡萄糖检测的灵敏度为1393 nA·L/(mmol·cm2)，检测极限为0.58 μmol/L(S/N = 3)，线性范围为0.1-0.5 mmol/L。该工作对葡萄糖传感器中批量构筑多功能电极的设计具有一定的指导意义。Abstract: The oxidase catalyst in glucose sensors can be easily affected by temperature, humidity, PH. As a result, developing some catalysts with low cost and high sensitivity has a broad application prospect. Metal-organic Frameworks (MOFs) have attracted much attention because of their high mass transfer rate, adjustable porosity and strong electron transfer ability. The screen-printing technique has been used to fabricate commercial electrodes due to its low cost and batch preparation. Here, Co-MOFs were successfully synthesized by a simple and economical method at room temperature and coated on commercial strip silver-carbon electrode by screen-printing technique. As a biosensor catalyst, Co-MOFs nanomaterials exhibit high electrocatalytic activity for glucose. The results showed that the sensitivity of Co-MOFs-based strip electrode for glucose detection was 1393 nA·L/(mmol·cm2). The detection limit was 0.58 μmol/L (S/N = 3) and the linear range was 0.1-0.5 mmol/L. This work has certain guiding significance for the design of multi-function electrode in glucose sensor.
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Key words:
- Electrochemical sensor /
- Glucose Detection /
- Co-MOFs /
- Screen printing /
- Metal-organic framework
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图 2 Co-ZIF-67的(a)XRD图谱，(b)XPS全谱，(c)Co 2 p和(d)C 1 s精细谱
Figure 2. (a) XRD pattern, (b) XPS spectra, (c) Co 2 p and (d) C 1 s region of Co-ZIF-67.
图 3 Co-ZIF-67在不同放大倍数的SEM和TEM图
Figure 3. SEM and TEM images of Co-ZIF-67 at different magnifications.
图 4 Co-ZIF-67修饰电极在不同(a)PH值，(b)葡萄糖浓度，(c)扫速对葡萄糖的CV测试曲线；(d)扫速算术平方根与0.5 V电流之间的线性关系。
Figure 4. CV curves of Co-ZIF-67 modified electrodes (a) with different PH and (b) at different glucose concentrations. CV curves (c) at different scan rate and (d) corresponding linear relationship between current and scan rate1/2.
图 5 (a)Co-ZIF-67修饰电极在不同葡萄糖浓度中的DPV测试曲线；(b)每5支Co-ZIF-67修饰电极在0.55 V电位对不同浓度葡萄糖的平均电流响应信号;(c)Co-ZIF-67修饰电极对不同葡萄糖浓度的安培响应。(d)每5支电极对不同葡萄糖浓度的平均响应电流(取第15秒数值)。
Figure 5. (a) DPV curves of Co-ZIF-67 modified electrodes in the presence of glucose; (b) Linear relationship between average DPV current density response and different glucose concentrations of every five electrodes at 0.55 V; (c) Amperometric response of Co-ZIF-67 modified SPEs to different glucose concentration. (d) Corresponding linear curve of average current density of five electrodes in the 15 th second to glucose concentrations.
图 6 (a)干扰检查: 五支Co-ZIF-67修饰电极 对0.1 mmol/L 葡萄糖(GLU)，0.164 mol/L 艾考糊精(INN)，9 mmol/L 半乳糖(GAL)，30 mmol/L谷胱甘肽(GSH)和0.584 mol/L 麦芽糖(MAL) 的平均安培响应。(b)稳定性: 每5支Co-ZIF-67修饰电极在第1、4、7、10、13和16天内对0.1 mmol/L 葡萄糖的安培响应信号。(c)重现性: 10支Co-ZIP-67修饰电极对0.1 mmol/L 葡萄糖的响应。
Figure 6. (a) Interference examination: average amperometric responses of five CuO nanomaterials modified SPEs to 0.1 mmol/L Glucose(GLU), 0.164 mol/L Alcodextrin (Inn) , 9 mmol/L Galactose (GAL) , 30 mmol/L Glutathione (GSH) and 0.584 mol/L Maltose (MAL) . (b) Stability of every 5 Co-ZIF-67 modified electrodes to 0.1 mmol/L glucose on the 1 st, 4 th, 7 th, 10 th, 13 th and 16 th days. (c) Reproducibility of Co-ZIF-67 modified electrodes to 0.1 mmol/L glucose.
表 1 Co-ZIF-67修饰电极及其它电极的葡萄糖传感性能
Table 1. Glucose sensing performance of Co-ZIF-67-modified electrodes and other previously reported electrodes
Type of electrode Sensitivity (μA·L/(mmol·cm2) Detection limit (μmol/L) Linear range (mmol/L) Refs AgNPs/MOF-74(Ni) 1290 4.7 0.01-4 [27] NF/NiCo2O4NWs@Co3O4NPs 8163.2 — 0.001-1.7 [29] CuCo-MOF 6861 0.12 — [30] Ni2Co1-BDC/GCE 3925.3 0.29 0.0005-2.8995 [31] Ni/Co(HHTP)MOF/CC 3250 0.1 0.0003-2.312 [32] MIL-88 A@NiFe-PB 1963.2 0.12 0.005-1 [33] Ni3(HHTP)2/CNT 4774 4.1 0.004-3.9 [34] Co-MOFs/SPEs 1.393 0.58 0.1-0.5 This work Abbreviations: BTC: trimesic acid; CC: carbon cloth; BDC: 1,4-benzenedicarboxylic acid; GCE: glassy carbon electrode; HHTP: 2,3,6,7,10,11-hexahydroxytriphenylene; MIL:Materials from Institute Lavoisier; PB:Prussian Blue; CNT: carbon nanotubes; NP: nanoparticle; NF: nickel foam; NWs: nanowires; NPs: nanoparticles; SPEs: screen-printing electrodes 
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表 2 Co-ZIF-67修饰电极检测血清样品的葡萄糖含量(n = 3)
Table 2. Glucose detection in human serum samples using Co-ZIF-67 modified Ag-C electrodes (n = 3)
Samples Serum glucose (mmol/L) Added glucose (mmol/L) Detected glucose (mmol/L) RSD (%) Recovery rate (%) Human serum 0.12 0.18 0.29 6.20 93.97 0.28 0.39 4.37 101.5 0.36 0.47 3.90 98.97
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