Cui Xiaoli, Liu Guodong, Lin Yuehe
Pacific Northwest National Laboratory, Richland, Washington, USA.
Nanomedicine. 2005 Jun;1(2):130-5. doi: 10.1016/j.nano.2005.03.005.
Nanostructured, multivalent, manganese-oxide octahedral molecular sieves (OMS), including cryptomelane-type manganese oxides and todorokite-type manganese oxides, were synthesized and evaluated for chemical sensing and biosensing at low operating potential. Both cryptomelane-type manganese oxides and todorokite-type manganese oxides are nanofibrous crystals with subnanometer open tunnels that provide a unique property for sensing applications. The electrochemical and electrocatalytic performance of OMS for the oxidation of H2O2 have been compared. Both cryptomelane-type manganese oxides and todorokite-type manganese oxides can be used to fabricate sensitive H2O2 sensors. With glucose oxidase (GOx) as an enzyme model, amperometric glucose biosensors are constructed by bulk modification of carbon paste electrodes with GOx as a biocomponent and nanostructured OMS as a mediator. A Nafion thin film was applied as an immobilization/encapsulation and protective layer. The biosensors were evaluated as an amperometric glucose detector at phosphate buffer solution with a pH 7.4 at an operating potential of 0.3 V (vs Ag/AgCl). The biosensor is characterized by a well-reproducible amperometric response, linear signal-to-glucose concentration range up to 3.5 mmol/L and 1.75 mmol/L, and detection limits (S/N = 3) of 0.1 mmol/L and 0.05 mmol/L for todorokite-type manganese oxide and cryptomelane-type manganese oxide-modified electrodes, respectively. The biosensors based on OMS exhibit considerable good reproducibility and stability, and the construction and renewal are simple and inexpensive.
合成了纳米结构的多价锰氧化物八面体分子筛（OMS），包括隐钾锰矿型锰氧化物和钙锰矿型锰氧化物，并对其在低工作电位下的化学传感和生物传感性能进行了评估。隐钾锰矿型锰氧化物和钙锰矿型锰氧化物均为具有亚纳米级开放隧道的纳米纤维晶体，这为传感应用提供了独特的性能。比较了OMS对H2O2氧化的电化学和电催化性能。隐钾锰矿型锰氧化物和钙锰矿型锰氧化物均可用于制备灵敏的H2O2传感器。以葡萄糖氧化酶（GOx）作为酶模型，通过用GOx作为生物组分、纳米结构的OMS作为介质对碳糊电极进行本体修饰，构建了电流型葡萄糖生物传感器。应用Nafion薄膜作为固定/封装和保护层。在pH 7.4的磷酸盐缓冲溶液中，于0.3 V（相对于Ag/AgCl）的工作电位下，将该生物传感器作为电流型葡萄糖检测器进行评估。该生物传感器的特点是电流响应具有良好的重现性，线性信号-葡萄糖浓度范围分别高达3.5 mmol/L和1.75 mmol/L，钙锰矿型锰氧化物和隐钾锰矿型锰氧化物修饰电极的检测限（S/N = 3）分别为0.1 mmol/L和0.05 mmol/L。基于OMS的生物传感器具有相当好的重现性和稳定性，并且构建和更新简单且成本低廉。
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