基于荧光淬灭作用的便携式溶解氧测量仪的研究
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摘要
氧气是人类生存和大部分化学反应不可或缺的成分，因此氧气的测量显得尤为重要。氧传感器在氧气的测量当中发挥着重要的作用，在环境保护、化工、医学、冶金和航空技术等领域有着广泛的应用。本文在新型光化学氧传感器的仪器开发方面进行了努力，发展了一种基于钌络合物荧光淬灭的便携式高性能全固态的溶解氧测量仪。
仪器的氧敏感光极探头采用吸附在硅胶上的钌(Ⅱ)络合物嵌入硅橡胶中制备成的氧气敏感膜，最大激发／发射波长分别为472nm／610nm时，分子氧可有效地淬灭敏感膜的荧光，测试结果为当溶解氧浓度分别在0-2mg／L和2-8mg／L时，敏感膜具有典型的Stern—Volmer响应曲线；从低溶解氧浓度到高溶解氧浓度的T_(95)响应时间约为5秒，从高溶解氧浓度到低溶解氧浓度为1分钟；此光极膜具有极好的重现性和光化学稳定性。激发光源和检测器分别采用高亮度的发光二极管和高灵敏的光敏二极管。敏感层涂覆在高通滤光片上，充分的利用空间，设计了结构紧凑合理的光极，达到了小型化、全固态的目的。
电路控制部分，硬件采用功能强大可编程的Microchip公司的PIC16F84系列芯片作为仪器的核心部件，计算、输出、控制功能均由此芯片完成，仪器还采用了稳定的数据放大、采集转换系统和大屏幕的液晶显示模块；软件部分，自编了汇编控制程序，程序包括单片机控制模块、采样模块、LCD输出控制模块、函数计算模块等。核心模块为函数计算模块，包括了测量子模块和校正子模块，其中的函数计算根据敏感膜的Stern—Vlomer响应曲线分析，将工作曲线分为两段。函数计算时取三个点(分别为0，2，8mg／L)的溶解氧浓度对应的电压值，求出每连续两点的斜率，由此函数可以求出任意测量范围内的未知样品的溶解氧浓度。控制软件中还加入了滤波程序，使数据更为稳定和平滑。
软硬件构成便携式高性能全固态的溶解氧测量仪。仪器可以精确测出氧气的溶解度参数，测量精度为0.1 mg／L，而且可对水中溶解氧进行实时在线监测，使用寿命长达一年。此测量仪具有体积小、携带和使用方便、能耗低、测量迅速等优点。
此外，还以四对溴苯基铂卟啉作为氧气传感器的响应性能进行了初步的试验。分子氧可以非常有效地淬灭四对溴苯基铂卟啉敏感膜的荧光，敏感膜的最大激发／发射波长为402／664nm。敏感膜的响应值非常好的符合Stern-Volmer方程。
纯氮气和纯氧气的荧光强度比值＊达到了 40倍。寿命大于 3个月。
The determination of molecular oxygen levels in solution is of great importance in environmental, biomedical, and industrial analyses. A hand held optode oxygen sensor has been fabricated, based on the fluorescence quenching of tris(4,7-diphenyl-l,10-phenanthroline) ruthenium(II) ditetrakis(4-chlorophenyl)borate in the presence of dissolved oxygen.
The developed hand-held dissolved oxygen optosensor based on All- Solid- State electronics and fluorescence quenching of a highly oxygen-sensitive luminescence complex. The oxygen-sensitive optode membrane was fabricated from Ruthenium(U) complex adsorbed on silica gel particles and embedded in a silicone-rubber film. The maximum EX/EM wavelength of the membrane is 472/610 nm, respectively. Oxygen in the surrounding medium quenches the fluorescence and is quantified by means of the Stem-Volmer expression at range of 0-2 or 2-8 mg/L. A responding time of T95=5s was obtained from high dissolved oxygen (DO) concentration to low DO concentration. High reversibility and photo stability of the oxygen sensitive membrane is demonstrated. The optode Excitation was achieved with an ultra-bright blue 472 nm light-emitting diode (LED), with emission monitored by a highly sensitive silicon photo diode(PD). The LED excitation and photodiode detection are employed in a trapeziform plastic configuration, with the oxygen-sen
sitive film coated on a 580nm long pass filter. The fluorescence intensity signal of the optode membrane was converted to the voltage signal, which was processed by a Single Chip Micyoco Controller microprocessor, PIC16F84. An assemble language program was developed for the unit control, data sampling, detection calculation and calibration. And the dissolved oxygen concentration was worked out and displayed on a liquid crystal display unit. The developed hand-held optosensor is pocketsize and low energy consuming, which provides on line dissolved oxygen measurement.
A novel fluorescence oxygen sensor with Pt-T(p-Br)PPH2 as its sensing material and
PVC polymer as support system is presented in the paper. When excited at the wavelength of 402nm and measured the emission at the wavelength of 664nm, the sensor shows a linear response to oxygen within the concentration range from 0 to 100% O2 with a ratio more than 40 of IN2 /IO2, where IN2 is the fluorescence intensity in 100% N2 and IO2, is the fluorescence intensity in 100% O2, respectively. The working curve is fit for the Stern-Volmer equation. The shell lifetime of the sensor was found to be longer than three months.
仪器的氧敏感光极探头采用吸附在硅胶上的钌(Ⅱ)络合物嵌入硅橡胶中制备成的氧气敏感膜，最大激发／发射波长分别为472nm／610nm时，分子氧可有效地淬灭敏感膜的荧光，测试结果为当溶解氧浓度分别在0-2mg／L和2-8mg／L时，敏感膜具有典型的Stern—Volmer响应曲线；从低溶解氧浓度到高溶解氧浓度的T_(95)响应时间约为5秒，从高溶解氧浓度到低溶解氧浓度为1分钟；此光极膜具有极好的重现性和光化学稳定性。激发光源和检测器分别采用高亮度的发光二极管和高灵敏的光敏二极管。敏感层涂覆在高通滤光片上，充分的利用空间，设计了结构紧凑合理的光极，达到了小型化、全固态的目的。
电路控制部分，硬件采用功能强大可编程的Microchip公司的PIC16F84系列芯片作为仪器的核心部件，计算、输出、控制功能均由此芯片完成，仪器还采用了稳定的数据放大、采集转换系统和大屏幕的液晶显示模块；软件部分，自编了汇编控制程序，程序包括单片机控制模块、采样模块、LCD输出控制模块、函数计算模块等。核心模块为函数计算模块，包括了测量子模块和校正子模块，其中的函数计算根据敏感膜的Stern—Vlomer响应曲线分析，将工作曲线分为两段。函数计算时取三个点(分别为0，2，8mg／L)的溶解氧浓度对应的电压值，求出每连续两点的斜率，由此函数可以求出任意测量范围内的未知样品的溶解氧浓度。控制软件中还加入了滤波程序，使数据更为稳定和平滑。
软硬件构成便携式高性能全固态的溶解氧测量仪。仪器可以精确测出氧气的溶解度参数，测量精度为0.1 mg／L，而且可对水中溶解氧进行实时在线监测，使用寿命长达一年。此测量仪具有体积小、携带和使用方便、能耗低、测量迅速等优点。
此外，还以四对溴苯基铂卟啉作为氧气传感器的响应性能进行了初步的试验。分子氧可以非常有效地淬灭四对溴苯基铂卟啉敏感膜的荧光，敏感膜的最大激发／发射波长为402／664nm。敏感膜的响应值非常好的符合Stern-Volmer方程。
纯氮气和纯氧气的荧光强度比值＊达到了 40倍。寿命大于 3个月。
The determination of molecular oxygen levels in solution is of great importance in environmental, biomedical, and industrial analyses. A hand held optode oxygen sensor has been fabricated, based on the fluorescence quenching of tris(4,7-diphenyl-l,10-phenanthroline) ruthenium(II) ditetrakis(4-chlorophenyl)borate in the presence of dissolved oxygen.
The developed hand-held dissolved oxygen optosensor based on All- Solid- State electronics and fluorescence quenching of a highly oxygen-sensitive luminescence complex. The oxygen-sensitive optode membrane was fabricated from Ruthenium(U) complex adsorbed on silica gel particles and embedded in a silicone-rubber film. The maximum EX/EM wavelength of the membrane is 472/610 nm, respectively. Oxygen in the surrounding medium quenches the fluorescence and is quantified by means of the Stem-Volmer expression at range of 0-2 or 2-8 mg/L. A responding time of T95=5s was obtained from high dissolved oxygen (DO) concentration to low DO concentration. High reversibility and photo stability of the oxygen sensitive membrane is demonstrated. The optode Excitation was achieved with an ultra-bright blue 472 nm light-emitting diode (LED), with emission monitored by a highly sensitive silicon photo diode(PD). The LED excitation and photodiode detection are employed in a trapeziform plastic configuration, with the oxygen-sen
sitive film coated on a 580nm long pass filter. The fluorescence intensity signal of the optode membrane was converted to the voltage signal, which was processed by a Single Chip Micyoco Controller microprocessor, PIC16F84. An assemble language program was developed for the unit control, data sampling, detection calculation and calibration. And the dissolved oxygen concentration was worked out and displayed on a liquid crystal display unit. The developed hand-held optosensor is pocketsize and low energy consuming, which provides on line dissolved oxygen measurement.
A novel fluorescence oxygen sensor with Pt-T(p-Br)PPH2 as its sensing material and
PVC polymer as support system is presented in the paper. When excited at the wavelength of 402nm and measured the emission at the wavelength of 664nm, the sensor shows a linear response to oxygen within the concentration range from 0 to 100% O2 with a ratio more than 40 of IN2 /IO2, where IN2 is the fluorescence intensity in 100% N2 and IO2, is the fluorescence intensity in 100% O2, respectively. The working curve is fit for the Stern-Volmer equation. The shell lifetime of the sensor was found to be longer than three months.
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