基于荧光猝灭原理的比率式光纤溶解氧传感器研究  

Study on Ratiometric Optical Fiber Dissolved Oxygen Sensor Based on Fluorescence Quenching Principle

作　　者：孟庆阳 张红霞[1,2] 赵永昆 贾大功[1,2,3] 刘铁根[1,2,3] MENG Qing-yang;ZHANG Hong-xia;ZHAO Yong-kun;JIA Da-gong;LIU Tie-gen(College of Precision Instrument and Optoelectronics Engineering,Tianjin University,Tianjin 300072,China;Key Laboratory of Opto-Electronics Information Technology(Tianjin University),Ministry of Education,Tianjin 300072,China;Key Laboratory of Micro Opto-electro Mechanical System Technology(Tianjin University),Ministry of Education,Tianjin 300072,China)

机构地区：[1]天津大学精密仪器与光电子工程学院,天津300072 [2]光电信息技术科学教育部重点实验室(天津大学),天津300072 [3]微光机电系统技术教育部重点实验室(天津大学),天津300072

出　　处：《光谱学与光谱分析》2024年第9期2445-2449,共5页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金山东联合基金重点项目(U2006216)资助。

摘　　要：溶解氧浓度的准确测定在医疗应用、海洋监测、工农业生产等领域中,起到至关重要的作用。本篇论文提出了一种比率式光纤溶解氧传感器,以四乙氧基硅烷(TEOS)和正辛基三乙氧基硅烷(Octyl-triEOS)为前驱体的有机改性硅酸盐(ORMOSILs)作为载体基质,选用三(4,7-联苯-1,10-邻菲啰啉)二氯化钌(Ru(dpp)_(3)^(2+))为氧敏感染料,选用7-氨基-4-(三氟甲基)香豆素(AFC)为参比染料。吸收光谱表明,氧敏感染料和参比染料可以被中心波长为405nm的光源激发。发射光谱表明,氧敏感染料和参考染料的发射波长没有光谱重叠,因此可以使用比率法测量溶解氧浓度。通过溶胶-凝胶工艺制备的ORMOSILs将氧敏感染料和参比染料固定在塑料光纤端部,从而形成复合氧敏感薄膜,对传感膜的厚度和疏水性进行了表征,传感膜的厚度为569μm,水接触角为81°。将该传感器在水溶液中进行了测试,在光源激发下,氧敏感染料和参考染料在605和490nm处有明显的发射峰,随着溶解氧浓度的增加,氧敏感染料的荧光强度降低,而参比染料的荧光强度稳定在某一数值,通过测量氧敏感染料与参比染料的比率,达到检测氧浓度的目的。采用Stern-Volmer方程对溶解氧浓度和荧光强度比进行线性拟合,该传感器在0~20.05mg·L^(-1)溶解氧范围内,Stern-Volmer拟合度可达98.22%,灵敏度可达0.4334/[O_(2)],从饱和氮溶液到饱和氧溶液传感器的响应时间为12s,从饱和氧溶液到饱和氮溶液传感器的恢复时间为144s,引入非对称因子ASY表明传感时间的不对称性。对传感器的光稳定性和重复性进行了测试,比率式光纤传感器可以克服光源波动,相对单荧光强度传感有更强的稳定性。The accurate measurement of dissolved oxygen concentration plays a crucial role in medical applications,marine monitoring,industrial and agricultural production,and other fields.A ratiometric optical fiber dissolved oxygen sensor is proposed.Organic modified silicates(ORMOSILs)using tetraethoxysilane(TEOS)and triethoxyoctylsilane(Octyl-triEOS)as precursors as carrier matrices,tris(4,7-diphenyl-1,10-phenanthrolin)ruthenium(II)dichloride complex(Ru(DPP)_(3)^(2+))as the oxygen-sensitive dye,7-amino-4-(trifluoromethyl)coumarin(AFC)as the reference dye.The absorption spectrum indicates that the oxygen-sensitivedye and reference dye can be excited by a light source with a central wavelength of 405nm.The emission spectrum indicates no spectral overlap between the emission wavelengths of the oxygen-sensitivedye and the reference dye so that the ratio method can measure the dissolved oxygen concentration.ORMOSILs prepared by-the sol-gel process fix oxygensensitive dyes and reference dyes on the end of plastic optical fiber to form composite oxygen-sensitive films.The thickness and hydrophobicity of the sensing film were characterized,with a thickness of 569μm.The water contact angle is 81°.The sensor was tested in an aqueous solution.Under the excitation of a light source,there were obvious emission peaks at 605and 409nm for the oxygen-sensitivedye and reference dye.Oxygen has a quenching effect on the fluorescence of oxygen-sensitive dyes.As the concentration of dissolved oxygen increases,the fluorescence intensity of oxygen-sensitive dye gradually decreases.The fluorescence intensity of the reference dye remains stable at a certain value,and the purpose of detecting oxygen concentration is achieved by measuring the ratio of oxygen-sensitive dyes to the reference dye.The linear relationship between the fluorescence intensity of the ruthenium complex and the concentration of dissolved oxygen is described by the Stern-Volmer equation.The calibration curve of the sensor was 98.22%in the range of 0~20.05mg·L^(-1).The sens

关 键 词：荧光猝灭原理 钌络合物 激发光谱 比率式光纤传感器 溶解氧 有机改性硅酸盐 

分 类 号：O436[机械工程—光学工程]