广范pH试纸的荧光pH传感特性及应用
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摘要
对广范pH试纸在pH值2.2~12.5范围内的荧光特性及基于试纸荧光的pH传感系统进行了探索。检测了不同pH缓冲液中浸渍过并晾干的pH试纸的光致发光,并分析了试纸荧光光谱的谱峰频移以及谱带重心频移。实验结果表明,pH试纸的荧光在实验pH区间的变化有明确的规律性,其中在弱酸碱性的pH值(4.0~9.0)范围内,谱带重心λ_B随pH值近似线性变化,相应的经验传感方程为λ_B=603.8-4.09pH。以pH为7对应的荧光谱带重心作参考,其相对灵敏度为0.71%/pH,实验系统的pH分辨力约为0.4。用该实验系统实际测试了稀的尿素水溶液及自来水的pH值,与商用电化学式pH计的结果一致,验证了实验方法及传感系统的通用性、实用性。该实验为pH检测提供了一种较比色读数更加精确客观、成本低廉、数据可靠、样品可保存可追溯的传感方法及测试系统。该系统还可以弥补广范pH试纸不能准确测试弱酸弱碱的不足。
The fluorescence pH sensing characteristics and applications of universal pH-indicator paper in the pH range of 2.2-12.5 were researched.In the experiment,pH-indicator paper strips were dipped into different pH buffer solutions first,then aired dry to be tested under light excitation.The fluorescence spectra were analyzed using peak shift and band barycenter shift.Experimental results indicate that the fluorescence of pH-indicator paper depends on the pH value of tested solution,and the dependence is repeatable.In the pH range of 4.0-9.0,the barycenter wavelength of the emission band is linearly dependent on pH value.As a consequence,pH sensing function ofλ_B=603.8-4.09pH is obtained.When a pH value of 7 is set as a reference,the relative sensitivity is determined as 0.71%/pH.Resolution of the experimental setup is determined as 0.4.The applications on urea solution and tap-water verify the merit of the sensing method and the corresponding system.The research can offer an optoelectronic method and corresponding experimental system for remote pH sensing.Moreover,the fluorescence pH test is more precise than the strip color judgment with naked eyes,particularly for acidulous or alkalescent solutions.
The fluorescence pH sensing characteristics and applications of universal pH-indicator paper in the pH range of 2.2-12.5 were researched.In the experiment,pH-indicator paper strips were dipped into different pH buffer solutions first,then aired dry to be tested under light excitation.The fluorescence spectra were analyzed using peak shift and band barycenter shift.Experimental results indicate that the fluorescence of pH-indicator paper depends on the pH value of tested solution,and the dependence is repeatable.In the pH range of 4.0-9.0,the barycenter wavelength of the emission band is linearly dependent on pH value.As a consequence,pH sensing function ofλ_B=603.8-4.09pH is obtained.When a pH value of 7 is set as a reference,the relative sensitivity is determined as 0.71%/pH.Resolution of the experimental setup is determined as 0.4.The applications on urea solution and tap-water verify the merit of the sensing method and the corresponding system.The research can offer an optoelectronic method and corresponding experimental system for remote pH sensing.Moreover,the fluorescence pH test is more precise than the strip color judgment with naked eyes,particularly for acidulous or alkalescent solutions.
引文
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[2]LI Y,ZHAO T,WANG C S,et al..Molecular basis of cooperativity in p H-triggered supramolecular self-assembly[J].Nat.Commun.,2016,7:13214.
[3]ZHOU K,LIU H,ZHANG S,et al..Multicolored p H-tunable and activatable fluorescence nanoplatform responsive to physiologic p H stimuli[J].J.Am.Chem.Soc.,2012,134(18):7803-7811.
[4]MARTZ T R,CARR J J,FRECH C R,et al..A submersible autonomous sensor for spectrophotometric p H measurements of natural waters[J].Anal.Chem.,2003,75(8):1844-1850.
[5]FUH M R S,BURGESS L W,HIRSCHFELD T,et al..Single fibre optic fluorescence p H probe[J].Analyst,1987,112(8):1159-1163.
[6]BENNA M,KBIR-ARIGUIB N,MAGNIA A,et al..Effect of p H on rheological properties of purified sodium bentonite suspensions[J].J.Colloid Interf.Sci.,1999,218(2):442-455.
[7]李冬冬,佘江波,彭波,等.微结构聚合物光纤化学修饰的p H值传感探头[J].应用激光,2012,32(5):398-402.LI D D,SHE J B,PENG B,et al..The chemical modification of microstructured polymer optical fiber and for p H determination[J].Appl.Laser,2012,32(5):398-402.(in Chinese)
[8]高潮,刘邦,郭永彩,等.5MN光纤布拉格光栅力值传感器[J].光学精密工程,2017,25(4):325-334.GAO C,LIU B,GUO Y C,et al..Five MN force sensor based on fiber Bragg grating[J].Opt.Precision Eng.,2017,25(4):325-334.(in Chinese)
[9]ZHANG W,LI Z,BAXTER G W,et al..Stress-and temperature-dependent wideband fluorescence of a phosphor composite for sensing applications[J].Experiment.Mechan.,2017,57(1):57-63.
[10]张巍巍,史凯兴,赵小兵,等.发光染料罗丹明B的荧光传感特性[J].光学精密工程,2017,25(3):591-596.ZHANG W W,SHI K X,ZHAO X B,et al..Multi-functional fluorescent sensing properties of rhodamine B[J].Opt.Precision Eng.,2017,25(3):591-596.(in Chinese)
[11]ZHANG W,WANG G,CAI Z,et al..Spectral analysis for broadband fluorescence:temperature sensing with the YAG∶Ce phosphor as an example[J].Opt.Mater.Express,2016,6(11):3482-3490.
[12]张巍巍,史凯兴.基于染料荧光多个特征的光纤温度传感器[J].仪器仪表学报,2016,37(11):2620-2627.ZHANG W W,SHI K X.A fiber optic temperature sensor based on multiple fluorescence characteristics of a dye[J]Chin.J.Sci.Instrum.,2016,37(11):2620-2627.(in Chinese)
[13]陈中师,王河林,隋成华,等.基于Cd Se/Zn S核壳量子点薄膜的荧光温度传感器[J].发光学报,2014,35(10):1215-1220.CHEN Z S,WANG H L,SUI C H,et al..Fluorescence temperature sensor based on Cd Se/Zn S core-shell quantum dots thin film[J].Chin.J.Lumin.,2014,35(10):1215-1220.(in Chinese)
[14]王书涛,郑亚南,王志芳,等.荧光光谱法和ABC-RBF神经网络在多环芳烃浓度检测中的应用[J].发光学报,2017,38(6):807-813.WANG S T,ZHENG Y N,WANG Z F,et al..Detection of the concentration of polycyclic aromatic hydrocarbon combining fluorescence spectra method with ABC-RBF neural network[J].Chin.J.Lumin.,2017,38(6):807-813.(in Chinese)
[15]ZHU X,JIN H,GAO C,et al..Ratiometric,visual,dual-signal fluorescent sensing and imaging of p H/copper ions in real samples based on carbon dots-fluorescein isothiocyanate composites[J].Talanta,2017,162:65-71.
[16]TAN J L,ZHANG M X,ZHANG F,et al..A novel“off-on”colorimetric and fluorescent rhodamine-based p H chemosensor for extreme acidity[J].Spectrochim.Acta Part A:Mol.Biomolecul.Spectrosc.,2015,140:489-494.
[17]ZHANG W,SHI K,SHI J,et al..Use of the fluorescence of rhodamine B for the p H sensing of a glycine solution[C].International Symposium on Optoelectronic Technology and Application 2016,International Society for Optics and Photonics,Beijing,China,2016:101553F-1-6.
[18]LIU L J,GUO P,CHAI L,et al..Fluorescent and colorimetric detection of p H by a rhodamine-based probe[J].Sens.Actuators B:Chem.,2014,194:498-502.
[19]GEORGIEV N I,DIMITROVA M D,KRASTEVA P V,et al..A novel water-soluble 1,8-naphthalimide as a fluorescent p H-probe and a molecular logic circuit[J].J.Lumin.,2017,187:383-391.
[20]ZHOU B,YANG S,NGUYEN T H,et al..Wireless sensor network platform for intrinsic optical fiber p H sensors[J].IEEE Sens.J.,2014,14(4):1313-1320.
[21]SAURA A V,BURGUETE M I,GALINDO F,et al..Novel fluorescent anthracene-bodipy dyads displaying sensitivity to p H and turn-on behaviour towards Cu(Ⅱ)ions[J].Org.Biomol.Chem.,2017,15(14):3013-3024.