镍金属有机框架改性柔性纤维的制备及其多巴胺传感应用

Nickel-based metal-organic frameworks-modified flexible fiber:Preparation and its dopamine sensing application

功能纤维在可穿戴电子的应用中具有巨大的应用前景.但是,由于其成本高昂,且功能层与织物基材之间的黏合力很差,易导致功能层脱落,因此功能纤维在生物医学相关领域中的使用率很低.本文提出了一种高效的新策略,利用原子层沉积制备的氧化物薄膜来诱导自组装生长镍基金属有机框架(Ni-MOF-74),从而形成功能纤维复合结构(Ni-MOF-74-CF)及其平纹布.该复合结构中,自组装功能层黏附在纤维表面,形成多孔结构,从而增加反应活性位点、提高电子传导率,进而有效提高复合结构的电化学反应效率.在实现高灵敏多巴胺检测(在1~60μmol/L的宽线性范围内灵敏度高达434μA/(mmol L^(–1)cm^(2)))的同时,该结构具有良好的抗干扰性和实时响应特性.该结构有望应用于生物医学和可穿戴电子相关领域.此外,复合结构织物还具有良好的柔性,在大幅度(高达180°弯折、最小曲率半径为~1 mm)和多次(高达100次)形变下,其电化学传感性能依然保持稳定.

Functional fibers have huge application prospects in the field of wearable electronics.However,because of their high cost and the peeling off from the functional layer due to the poor adhesion between the functional layer and the fiber substrate,the use of functional fibers in biomedical-related fields is still scarce.The application of functional fibers in biomedicine has always been an important topic.The aim of this study is to develop an efficient method for preparing high-performance dopamine(DA)sensing composite functional fiber and apply the composite structure for accurate and sensitive detection of DA,which is closely related to many central nervous system diseases that have caused a great amount of human suffering,such as schizophrenia and Parkinson’s disease.Previous works have developed a variety of methods for DA detection,such as fluorescence spectroscopy,high performance liquid chromatography,capillary electrophoresis,ultraviolet-visible spectrophotometry,and liquid chromatography-electrospray tandem mass spectrometry,but they have disadvantages,such as high cost,complicated sample preparation,low sensitivity,and poor repeatability.Electrochemical detection is a simple,sensitive and environmentally friendly detection method,and DA has good electrochemical activity(oxidizable),so electrochemical technology can be used for the detection of DA.Existing research focuses electrochemical detection of DA on modification of glassy carbon electrodes with active materials,which is associated with complicated sample preparation process,poor portability,and is difficult to be applied to flexible materials.Therefore,a simple and low-cost method for preparing highperformance DA sensors has significant scientific and practical value.Herein,we proposed an efficient new strategy using oxide films prepared by atomic layer deposition(ALD)to induce self-assembly and growth of nickel-based metal-organic frameworks(Ni-MOF-74)to form functional composite fiber structures(Ni-MOF-74-CF)and corresponding textile.The high specific area and active site exposure of Ni-MOF-74 contribute to high DA sensitivity,and the electrochemical approach makes the sensing test simple,sensitive,and environmentally friendly.The fabrication of Ni-MOF-74-CF composite was conducted in a mild and simple way.Firstly,Zn O nanomembrane was deposited on CF and its corresponding plain cloth by ALD at a temperature of 150°C,and then formed a dense and conformal coating.Secondly,the as-prepared ALD-Zn O-CF was converted to Ni-MOF-74-CF via a wet chemistry approach.Thirdly,the electrochemical DA sensing tests with Ni-MOF-74-CF and its plain cloth were conducted.The characterization results show that Ni-MOF-74 was successfully synthesized on CF and this self-assembled functional layer closely adheres to the fiber surface to form a porous structure.Thus,the electrochemical reaction efficiency of this composite structure is improved.A high sensitivity of 434μA/(mmol L–1 cm2)to DA in a wide linear range of 1–60μmol/L was achieved,as well as good anti-interference and real-time response characteristics.Additionally,the composite structure displayed good flexibility.The corresponding plain cloth could recover after large(up to 180°-bending,minimum radius of curvature of~1 mm)and multiple(up to 100 times)deformations,and its electrochemical sensing performance remained stable,which is of importance for practical applications.Above all,this research provides a new preparation strategy for functional fibers which can be applied in biomedicine,wearable electronics,and related fields.This new preparation strategy has broad application prospects.