首页|基于荧光猝灭原理的比率式光纤溶解氧传感器研究

基于荧光猝灭原理的比率式光纤溶解氧传感器研究

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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)32+)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405 nm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569 μm,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490 nm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0~20.05 mg·L-1溶解氧范围内,Stern-Volmer拟合度可达98.22%,灵敏度可达0.433 4/[O2],从饱和氮溶液到饱和氧溶液传感器的响应时间为12 s,从饱和氧溶液到饱和氮溶液传感器的恢复时间为144 s,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.
Study on Ratiometric Optical Fiber Dissolved Oxygen Sensor Based on Fluorescence Quenching Principle
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)32+)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 oxygen-sensitive 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 569 μm.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 605 and 409 nm 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 0~20.05 mg·L-1.The sensitivity can reach 0.433 4/unit[O2],and the response time from saturated oxygen solution to saturated nitrogen solution is 144s,and from saturated nitrogen solution to saturated oxygen solution is 12 s,introducing the asymmetric factor ASY to indicate the asymmetry of the sensing film.The optical stability and repeatability of the sensor were characterized.The photostability and repeatability of the sensor were tested,and the ratio type fiber optic sensor can overcome light source fluctuations and has stronger stability compared to single fluorescence intensity sensing.

Fluorescence quenching principleRuthenium complexExcitation spectrumRatiometric optical fiber sensorDissolved oxygenOrganic modified silicate

孟庆阳、张红霞、赵永昆、贾大功、刘铁根

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天津大学精密仪器与光电子工程学院,天津 300072

光电信息技术科学教育部重点实验室(天津大学),天津 300072

微光机电系统技术教育部重点实验室(天津大学),天津 300072

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

国家自然科学基金山东联合基金重点项目

U2006216

2024

光谱学与光谱分析
中国光学学会

光谱学与光谱分析

CSTPCD北大核心
影响因子:0.897
ISSN:1000-0593
年,卷(期):2024.44(9)