NH<sub>2</sub>-MIL-101(Fe) Mimetic Peroxidase-Based Determination of Glucose

Lu WAN; Yu-ming HUANG; Ping FENG

doi:10.13718/j.cnki.xdzk.2019.03.012

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The material of NH₂-MIL-101(Fe) metal-organic framework was found to be able to catalyze the oxidization of 3, 3', 5, 5'-tetramethylbenzidine (TMB) by H₂O₂ to produce a blue product, showing intrinsic peroxidase-like activity. Furthermore, the NH₂-MIL-101(Fe) was found to exhibit good robustness in a wide temperature range from 4 to 80℃ and in a wide pH range from 2 to 10. In a study reported herein, a new method for the detection of glucose was developed when combined with glucose oxidase. Under optimal conditions, the absorbance at 652 nm showed linear response with glucose concentrations in the range from 0.75 μmol/L to 50 μmol/L with a detection limit of 0.75 μmol/L. The proposed method was applied to determine the content of glucose in human serum samples and satisfactory results were obtained.

Corresponding author: Yu-ming HUANG ;

Received Date: 26/07/2018

Available Online: 20/03/2019

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Abstract: The material of NH₂-MIL-101(Fe) metal-organic framework was found to be able to catalyze the oxidization of 3, 3', 5, 5'-tetramethylbenzidine (TMB) by H₂O₂ to produce a blue product, showing intrinsic peroxidase-like activity. Furthermore, the NH₂-MIL-101(Fe) was found to exhibit good robustness in a wide temperature range from 4 to 80℃ and in a wide pH range from 2 to 10. In a study reported herein, a new method for the detection of glucose was developed when combined with glucose oxidase. Under optimal conditions, the absorbance at 652 nm showed linear response with glucose concentrations in the range from 0.75 μmol/L to 50 μmol/L with a detection limit of 0.75 μmol/L. The proposed method was applied to determine the content of glucose in human serum samples and satisfactory results were obtained.

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天然酶是一类生物催化剂，可高效、专一催化生化反应，而且反应条件温和.然而，天然酶易变性失活，提纯困难，价格昂贵，储藏和使用不便，成本高，所以模拟酶的研究应运而生.目前已有大量利用卟啉、主体试剂、印迹高分子、膜体系及配合物等作为模拟酶的报道^[1].近年来，纳米材料模拟酶的研究引起广泛关注，各种各样的纳米材料，如金属氧化物、金属硫化物、金属纳米微粒及碳材料等均具有模拟酶特性^[2].

金属有机框架(MOFs)材料具有良好的孔结构、较大的比表面积等特性，在气体储存、化学催化以及药物传输等方面显示出良好的应用前景^[3-4].本研究利用NH₂-MIL-101(Fe)作为催化剂，发现它能显著催化H₂O₂氧化TMB，产生蓝色反应，使体系的吸光度显著增加，表现出过氧化物模拟酶特性，而且在较宽的温度(4~80 ℃)及pH值(2~10)范围内保持其模拟酶活性，据此，结合葡萄糖氧化酶，建立了测定血清中葡萄糖的新方法.

1. 实验方法与材料

1.1. 仪器及试剂

UV-2450型紫外-可见分光光度计(岛津，苏州). 3，3，5，5-四甲基联苯胺(TMB)和葡萄糖氧化酶(GOx)均购买于Sigma-Aldrich上海有限公司. FeCl₃·6H₂O、N，N-二甲基甲酰胺(DMF)、H₂O₂、盐酸、氢氧化钠、NaAc、HA、无水乙醇、葡萄糖、果糖、乳糖和麦芽糖均购自重庆泰兴化学试剂公司. 2-氨基对苯二甲酸(NH₂-H₂BDC)购自TCI化成工业发展有限公司(上海).玻璃仪器用体积分数为10%的硝酸溶液浸泡24 h，使用前用超纯水清洗干净.

1.2. NH₂-MIL-101(Fe)的合成

根据文献方法制备NH₂-MIL-101(Fe) ^[5]，将0.225 g NH₂-H₂BDC与0.675 g FeCl₃·6H₂O分别溶于一定量的DMF中，搅拌至完全溶解后，放入反应釜中加热至110 ℃，反应24 h，然后冷却至室温，并用DMF、乙醇交替洗涤，最后在60 ℃下真空干燥，即得NH₂-MIL-101(Fe).

1.3. 测定方法

取0.5 mL质量浓度为20 mg/L的NH₂-MIL-101(Fe)、0.25 mL浓度为1 mmol/L的TMB溶液及0.25 mL不同浓度的H₂O₂加入浓度为0.2 mol/L的NaAc缓冲溶液(pH=4)中，定容至5 mL后，在30 ℃水浴中孵育20 min，冷却至室温后，用紫外-可见分光光度计进行测定，记录652 nm处的吸光度.以吸光度变化值ΔA=A-A₀进行定量(A₀和A分别为未加入和加入H₂O₂时的吸光度).

葡萄糖测定：在系列比色管中依次加入0.1 mL质量浓度为1 g/L的GOx、0.5 mL醋酸钠缓冲液(pH=7)及0.1 mL不同浓度的葡萄糖溶液，在37 ℃水浴条件下孵育30 min后，按照前面检测H₂O₂的过程进行比色测定.

1.4. NH₂-MIL-101(Fe)的耐受性

将NH₂-MIL-101(Fe)在不同温度(4，8，15，20，25，30，40，50，60，70，80 ℃)和pH值(2，3，4，5，6，7，8，9，10)条件下孵育2 h后，按照1.3节的条件进行测定，考察NH₂-MIL-101(Fe)作为模拟酶的耐受性.

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NH₂-MIL-101(Fe) Mimetic Peroxidase-Based Determination of Glucose

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NH₂-MIL-101(Fe) Mimetic Peroxidase-Based Determination of Glucose

Corresponding author: Yu-ming HUANG ;