抑制容器荧光干扰的双轴共焦拉曼检测方法
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摘要
为消除拉曼光谱检测中样品装载容器的荧光背景干扰,利用样品拉曼信号光与容器产生的荧光不共焦的特性,设计了一种双轴共焦的检测光路结构。实验结果表明:来自容器的荧光干扰幅度出现数量级的衰减,拉曼信号光幅度下降了约30%;双轴共焦拉曼检测方法能够避免传统共轴共焦检测方法中拉曼信号光和荧光混合接收的问题,解决了荧光干扰对拉曼信号动态检测范围的限制,实现了对荧光材料容器装载样品拉曼信号的有效检测。
Aimed at eliminating the fluorescence interference from containers of the sample in the detection of Raman spectroscopy,a dual-axis confocal detection scheme is proposed based on the characteristic that the fluorescence generated by the container and the Raman signal of the sample are not confocal. The experimental results show that the fluorescence interference signals from the container are reduced by an order of magnitude,and the intensity of Raman signal decreases by about 30%. The dual-axis confocal Raman detection scheme can solve the mixed reception problem of Raman signal and fluorescence in the conventional coaxial confocal Raman detection scheme,solve the limitation of the dynamic detection range of Raman signal caused by the fluorescence interference,and achieve the effective detection of Raman signal of the material in fluorescent material containers.
Aimed at eliminating the fluorescence interference from containers of the sample in the detection of Raman spectroscopy,a dual-axis confocal detection scheme is proposed based on the characteristic that the fluorescence generated by the container and the Raman signal of the sample are not confocal. The experimental results show that the fluorescence interference signals from the container are reduced by an order of magnitude,and the intensity of Raman signal decreases by about 30%. The dual-axis confocal Raman detection scheme can solve the mixed reception problem of Raman signal and fluorescence in the conventional coaxial confocal Raman detection scheme,solve the limitation of the dynamic detection range of Raman signal caused by the fluorescence interference,and achieve the effective detection of Raman signal of the material in fluorescent material containers.
引文
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[2]Hu J,Hu J M.Applications progress of Raman techniques in analytical chemistry[J].Chinese Journal of Analytical Chemistry,2000,28(6):764-771.胡军,胡继明.拉曼光谱在分析化学中的应用进展[J].分析化学,2000,28(6):764-771.
[3]Wang J Y,Wang M,Liu L,et al.Raman spectroscopy in archaeology[J].The Journal of Light Scattering,2006,18(2):130-133.王吉有,王闵,刘玲,等.拉曼光谱在考古中的应用[J].光散射学报,2006,18(2):130-133.
[4]Fang X Q,Peng Y K,Li Y Y,et al.Rapid and quantitative detection method of sodium benzoate in carbonated beverage based on surface-enhanced Raman spectroscopy[J].Acta Optica Sinica,2017,37(9):0930001.房晓倩,彭彦昆,李永玉,等.基于表面增强拉曼光谱快速定量检测碳酸饮料中苯甲酸钠的方法[J].光学学报,2017,37(9):0930001.
[5]Mosier-Boss P A,Lieberman S H,Newbery R,et al.Fluorescence rejection in Raman spectroscopy by shifted-spectra,edge detection,and FFT filtering techniques[J].Applied Spectroscopy,1995,49(5):630-638.
[6]Chen S.Research on background deduction algorithm of Raman spectrum and its application[D].Changsha:Central South University,2011.陈珊.拉曼光谱背景扣除算法及其应用研究[D].长沙:中南大学,2011.
[7]Wang H,Wang Y Z,Zhao Y,et al.Latest methods of fluorescence suppression in Raman spectroscopy[J].Spectroscopy and Spectral Analysis,2017,37(7):2050-2056.王欢,王永志,赵瑜,等.拉曼光谱中荧光抑制技术的研究新进展综述[J].光谱学与光谱分析,2017,37(7):2050-2056.
[8]Yang G Y,Li L,Chen H,et al.Baseline correction method for Raman spectra based on generalized Whittaker smoother[J].Chinese Journal of Lasers,2015,42(9):0915003.杨桂燕,李路,陈和,等.基于广义Whittaker平滑器的拉曼光谱基线校正方法[J].中国激光,2015,42(9):0915003.
[9]Zhao F,Peng Y K.Measurement of iodine value of pork's subcutaneous adipose tissue by interval partial least square and Raman spectroscopy[J].Chinese Journal of Lasers,2017,44(11):1111001.赵芳,彭彦昆.区间偏最小二乘法结合拉曼光谱测定猪肉皮下脂肪的碘值[J].中国激光,2017,44(11):1111001.
[10]Li F.Key techniques for suppression of fluorescence interference by frequency shift Raman excitation[D].Xiamen:Xiamen University,2014.李帆.移频拉曼激发法抑制荧光干扰关键技术研究[D].厦门:厦门大学,2014.
[11]Wu J L,Fan X G,Xu Y J,et al.Raman spectrum measuring device excited by multi-wavelength laser frequency shift excitation:201510057825[P].2015-05-06.吴景林,范贤光,许英杰,等.一种多波长激光频移激发的拉曼光谱测量装置:201510057824.7[P].2015-05-06.
[12]Mou T T,Xiong S J,Zhao X,et al.Portable dualwavelength fluorescence Raman spectrometry detection system:201521113688.0[P].2016-09-28.牟涛涛,熊胜军,赵喜,等.便携式双波长消荧光拉曼光谱检测系统:201521113688.0[P].2016-09-28.
[13]Matousek P,Clark I P,Draper E R,et al.Subsurface probing in diffusely scattering media using spatially offset Raman spectroscopy[J].Applied Spectroscopy,2005,59(4):393-400.
[14]Matousek P.Inverse spatially offset Raman spectroscopy for deep noninvasive probing of turbid media[J].Applied Spectroscopy,2006,60(11):1341-1347.
[15]Yin L,Cai S W,Jiang X B,et al.A portable adjustable Raman probe:201410061973.6[P].2014-05-07.殷磊,蔡圣闻,姜晓冰,等.一种便携式可调节的拉曼探头:201410061973.6[P].2014-05-07.
[16]An Y.Research on the optical machine system of handheld Ramans pectrometer[D].Changchun:Changchun Institute of Optics,Fine Mechanics and Physics,Chinese Academy of Sciences,2014.安岩.手持式拉曼光谱仪的光机系统技术研究[D].长春:中国科学院长春光学精密机械与物理研究所,2014.
[17]Xiao X M.Comparison between two different Raman confocal techniques[J].Modern Scientific Instruments,2005(3):17-20.肖新民.拉曼光谱仪的两种共焦显微术的对比[J].现代科学仪器,2005(3):17-20.
[18]Wang Y J.Research on measurement and control technology of laser confocal Raman spectrometer[D].Beijing:Beijing Institute of Technology,2016.王雅杰.激光共焦拉曼光谱仪测控技术研究[D].北京:北京理工大学,2016.
[19]Watanabe J,Kinoshita S,Kushida T.Fluorescence rejection in Raman-spectroscopy by a gated singlephoton counting method[J].Review of Scientific Instruments,1985,56(6):1195-1198.
[20]Martyshkin D V,Ahuja R C,Kudriavtsev A,et al.Effective suppression of fluorescence light in Raman measurements using ultrafast time gated charge coupled device camera[J].Review of Scientific Instruments,2004,75(3):630-635.