基于SPR技术的流动体系分析仪器检测器研究
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摘要
流动体系分析仪器是最常用的分析测试设备之一,检测器是流动体系分析仪器的关键部件之一,其性能直接影响到仪器的性能。传统的检测器在应用于流动体系分析仪器时往往具有局限性。发展通用、灵敏、便携、价廉的检测器对于微量物质的检测具有很强的实用价值,也是分析测试仪器领域研究的热门课题。表面等离子体共振(Surface Plasmon Resonance,SPR)检测技术是一种新型的光电检测技术,具有灵敏度高、样品无需标记、响应速度快、装置简单、价格低廉等特点,已在众多领域得到了广泛的应用。本文建立了一种基于SPR技术的检测器,并对其在流动体系分析仪器中的应用进行了实验研究。本文的主要研究内容和创新点包括:
1)构建了包括微型流通池、SPR传感器和电路系统在内的SPR检测器。
2)采用Visual C++和数据库技术编写了SPR检测器的工作站软件,用于数据的采集、处理、分析、显示、保存等。
3)研究了SPR光谱信号的数据处理方法。针对现有的动态基线一阶距分析方法存在的算法复杂费时等不足,提出了一种新颖的基于幅值的动态基线一阶距分析方法。该方法以SPR光谱信号幅度的一定比例加上光谱信号的最小值作为动态基线值。实验结果表明,基于幅值的动态基线一阶距分析方法不但可以有效降低光源光强波动的影响而且简单快速。
4)搭建了包括高压泵、进样器、SPR检测器在内的流动体系检测系统,通过实验分析了流速因素对检测器性能的影响,测试了所设计的检测器的噪声与漂移,同时将该检测系统应用于对盐类、糖类和无机小分子类物质的检测,分析其检测限。
5)搭建了包括高压泵、进样器、色谱分析柱、SPR检测器在内的高效液相色谱系统,对蔗糖和半乳糖的混合溶液进行了色谱分离检测。
Flow system analysis instrument is one of the most popular analytical testing instruments, detector is one of its key parts, and detector's performance influence the flow system analysis instrument's performance directly. Traditional detectors usually have limitations when they are used in flow system analysis instrument. Developing a universal, sensitive, easy-taking and low cost detector has strong practical values for the testing of trace substances and also is a hot research area of analytical testing instruments. Surface plasmon resonance (SPR) detection technique is a new photoelectric detection technique, and it has characteristics as high sensitivity, label-free, fast testing, simplicity, and low cost, and it has been widly used in many fields. This paper developed a new detector based on SPR technique, and experiments were taken about this SPR detector. The main research and innovative points include:
1) A new SPR detector including micro flow cell, SPR sensor and circuit was build.
2) SPR detector's workstation software was developed using visual C++ and database technique, and it was used for data collecting, processing, analysing, displaying and saving.
3) Research of data processing methods of SPR spectrum was developed. In order to improve the existing 1st moment analysis methods of dynamic baseline, a kind of 1st moment analysis method of dynamic baseline based on amplitude was proposed. The baseline of this method adjusts dynamically according to the minimum value. The results show 1st moment analysis method of dynamic baseline based on amplitude can reduce not only the influence of fluctuations in optical power on SPR spectrum signals but also the calculating time.
4) A kind of flow system detection instrument including high pressure pump, sampler and SPR detector was build. Using this instrument, the flow rate's influence on SPR detector was studied; noise and drift of SPR detector were tested. Using this instrument, salts, carbohydrates, inorganic small moleculars and their detection limits were detected.
5) A kind of high performance liquid chromatography system including high pressure pump, sampler, analytical column and SPR detector was build. Using this system, a chromatography of mixed solution of sucrose and galactose was got.
1)构建了包括微型流通池、SPR传感器和电路系统在内的SPR检测器。
2)采用Visual C++和数据库技术编写了SPR检测器的工作站软件,用于数据的采集、处理、分析、显示、保存等。
3)研究了SPR光谱信号的数据处理方法。针对现有的动态基线一阶距分析方法存在的算法复杂费时等不足,提出了一种新颖的基于幅值的动态基线一阶距分析方法。该方法以SPR光谱信号幅度的一定比例加上光谱信号的最小值作为动态基线值。实验结果表明,基于幅值的动态基线一阶距分析方法不但可以有效降低光源光强波动的影响而且简单快速。
4)搭建了包括高压泵、进样器、SPR检测器在内的流动体系检测系统,通过实验分析了流速因素对检测器性能的影响,测试了所设计的检测器的噪声与漂移,同时将该检测系统应用于对盐类、糖类和无机小分子类物质的检测,分析其检测限。
5)搭建了包括高压泵、进样器、色谱分析柱、SPR检测器在内的高效液相色谱系统,对蔗糖和半乳糖的混合溶液进行了色谱分离检测。
Flow system analysis instrument is one of the most popular analytical testing instruments, detector is one of its key parts, and detector's performance influence the flow system analysis instrument's performance directly. Traditional detectors usually have limitations when they are used in flow system analysis instrument. Developing a universal, sensitive, easy-taking and low cost detector has strong practical values for the testing of trace substances and also is a hot research area of analytical testing instruments. Surface plasmon resonance (SPR) detection technique is a new photoelectric detection technique, and it has characteristics as high sensitivity, label-free, fast testing, simplicity, and low cost, and it has been widly used in many fields. This paper developed a new detector based on SPR technique, and experiments were taken about this SPR detector. The main research and innovative points include:
1) A new SPR detector including micro flow cell, SPR sensor and circuit was build.
2) SPR detector's workstation software was developed using visual C++ and database technique, and it was used for data collecting, processing, analysing, displaying and saving.
3) Research of data processing methods of SPR spectrum was developed. In order to improve the existing 1st moment analysis methods of dynamic baseline, a kind of 1st moment analysis method of dynamic baseline based on amplitude was proposed. The baseline of this method adjusts dynamically according to the minimum value. The results show 1st moment analysis method of dynamic baseline based on amplitude can reduce not only the influence of fluctuations in optical power on SPR spectrum signals but also the calculating time.
4) A kind of flow system detection instrument including high pressure pump, sampler and SPR detector was build. Using this instrument, the flow rate's influence on SPR detector was studied; noise and drift of SPR detector were tested. Using this instrument, salts, carbohydrates, inorganic small moleculars and their detection limits were detected.
5) A kind of high performance liquid chromatography system including high pressure pump, sampler, analytical column and SPR detector was build. Using this system, a chromatography of mixed solution of sucrose and galactose was got.
引文
[1]云自厚、欧阳津、张晓彤。液相色谱检测方法(第二版)。北京:化学工业出版社,2004,1-146
[2]朱岩。离子色谱仪器。北京:化学工业出版,2006,1-68 152-165
[3]李彤。高效液相色谱仪器系统。北京:化学工业出版社,2004,1-150
[4]中国教育在线http://www.eol.cn/
[5]徐卉。玉米中维生素和植物激素的毛细管液相色谱分离检测[硕士学位论文]。汕头,汕头大学,2008,1-50
[6]徐卉、贾丽、柳亚玲。毛细管液相色谱法分离植物内源激素。分析试验室,2009,28(2):30-33
[7]马继平、丁明玉。毛细管离子色谱进展。分析化学评述与进展特刊,2006,34:272-277
[8]林秉承、秦建华。微流控芯片实验室的历史、现状和发展前景[会议论文]。2008,第八届全国微纳生物化学分离分析会议论文集CMSB2008,1-1。
[9]林秉承。微流控芯片实验室及其功能化。中国药科大学学报 2003,34(1):1-6
[10]Wood R W.On a remarkable case of uneven distribution of light in a diffraction grating spectrum.Philosophical Magazine,1902,4:392-402
[11]Homola Jiri,Yee Sinclair S.,Gauglitz Gunter.Surface plasmon resonance sensors:review.Sensors and Actuators B-Chemical.1999,54(1-2):3-15
[12]Dhesingh Ravi Shankaran,K.Vengatajalabathy Gobi,Norio Miura.Recent advancements in surface plasmon resonance immunosensors for detection of small molecules of biomedical,food and environmental interest.Sensors and Actuators B,2007,121(1):158-177
[13]Jir Homola.Surface plasmon resonance sensors for detection of chemical and biological species.Chemical Reviews,2008,108(2):462-493
[14]随森芳、肖才德、杨军。表面等离体激元共振生物传感器。上海:上海科学技术出版社,2008,1-23 197-268
[15]魏景艳,牟颖,许海波,胡鑫,宋大千,刘霞,张寒琦,金钦汉,罗贵民。用多克隆抗体构建的夹心免疫传感器检测心肌肌钙蛋白Ⅰ。高等学校化学学报,2003,24(12):2161-2164
[16]Xing-Zheng Wu,Masamitsu Nakagawa,Chiaki Nagamori,Katsumi Uchiyama,Toshiyuki Hobo.Detection Method Based on a Surface Plasmon Resonance and Its Application to Flow Injection Analysis and Liquid Chromatography.Bulletin of the Chemical Society of Japan,1996,69:1969-1974
[17]Cepria G,Castillo J R.Surface plasmon resonance-based detection An alternative to refractive index detection in high-performance liquid chromatography.Journal of Chromatography A,1997,759:27-35
[18]Rebecca J.Whelan and Richard N.Zare.Surface plasmon resonance Detection for Capillary Electrophoresis Separation.Analytical Chemistry,2003,75:1542-1547
[19]Ming Du and Feimeng Zhou.Postcolumn Renewal of Sensor Surfaces for High-Performance Liquid Chromatography-Surface Plasmon Resonance Detection.Analytical Chemistry,2008,80:4225-4230
[20]Kyung M B,Donghyun K S June K.Investigation of the sensitivity enhancement of nanoparticle based surface plasmon resonance biosensors using rigorous coupled wave analysis.Plasmonics in Biology and Medicine,2005,5703(Bellingham):61-70
[21]Chen F C,Chen S J,Hu W P,Lin G Y,Huang K T.Nanoparticle-enhanced ultrahigh-resolution surface plasmon resonance biosensors.Plasmonics in Biology and Medicine,2004,5327(Bellingham):140-147
[22]赵晓军、陈焕文、宋大千。表面等离子体子共振传感器1:基本原理。分析仪器,2000,4:1-8。
[23]Kazuyoshi Kurihara and Koji Suzuki.Therorectical Understanding of an Absorption-Based Surface Plasmon Resonance Sensor Based on Kretchmann's Theory.Analytical Chemistry,2002,74:696-701
[24]Texas Instruments.TSPR1A170100 SpreetaTM liquid sensor[K].Texas Instruments Incorporated,1999
[25]T.M.Chinowskya,J.G.Quinnb,D.U.Bartholomewb.Performance of the Spreeta 2000 integrated surface plasmon resonance affinity sensor.Sensor and Actuators B,2003,695:1-9
[26]Sahin K(O|¨),G(o|¨)n(u|¨)l T S.Temperature Effects on Surface Plasmon Resonance:Design Considerations for an Optical Temperature Sensor.Journal of Ligthwave Technology,2003,21(3):805-813
[27]Colin J.Alleyne,Andrew G.Kirk,Wei-Yin Chien and Paul G.Charette.Numerical method for high accuracy index of refraction estimation for spectro-angular surface plasmon resonance systems[J].Optical Society of America,2008,16(24):19493-19503
[28]David J.Kruglinkski(潘爱民、王国印).Visual C++技术内幕(第四版).北京:清华大学出版社,1998,1-810
[29]侯俊杰。深入浅出MFC第二版。武汉:华中科技大学出版社,2001,1:587
[30]Bruce Eckel.C++编程思想 第1卷:标准C++导引。北京:机械工业出版社,2002,1:479
[31]谭浩强。C++程序设计。北京:清华大学出版社,2004,1:486
[32]严蔚敏,吴伟民.数据结构:C语言版[M].北京:清华大学出版社,1996,1:334
[33]李长林,高洁,李长林,高洁编.Visual C++串口通信技术与典型实例。北京:清华大学出版社,2006,1:367
[34]Abraham Silberschartz,Henry F.Korth,S.Sudarshan.数据库系统概念。北京:机械工业出版社,2006,1:468
[35]龙帅。深入浅出SQL Server数据库开发。北京:中国青年出版社,2006,1:361
[36]Sandy Owega,Daniel Poitras.Local similarity matching algorithm for determining SPR angle in surface plasmon resonance sensors[J].Sensors and Actuators B,2007,123:35-41
[37]张雪娇。基于SPR传感技术的生物检测方法与实验研究[硕士学位论文]。杭州,浙江大学,2007,48-51
[38]Knut Johansen,Ralph Stalberg,Ingemar Lundstr(o|¨)m and Bo Liedberg.Surface plasmon resonance:instrumental resolution using photo diode arrays[J]. Measurement Science and Technology,2000,11(11):1630-1638.
[39]Timothy M.Chinowsky,Linda S.Jung,Sinclair S.Yee.Optimal linear data analysis for surface plasmon resonance biosensors[J].Sensors and Actuators B,1999,54:89-97
[40]Petr Tobi?ska,Ji?r'i Homola.Advanced data processing for SPR biosensors[J].Sensors and Actuators B,2005,107:162-169
[41]黄显,栗大超,徐可欣,于海霞,黄福祥,胡小唐。基于微型表面等离子共振生物传感器的葡萄糖浓度测量技术[J]。传感技术学报,1999,19(5):11814-11819
[42]Garet G Nenninger,Marek Piliarik,Ji?r'i Homola.Data analysis for optical sensors based on spectroscopy of surface plasmons[J].Measurement Science and Technology,2002,13:2038-2046.
[43]C.Thirstrup,W.Zong.Data analysis for surface plasmon resonance sensors using dynamic baseline algorithm[J].Sensors and Actuators B,2005,106:796-802.
[2]朱岩。离子色谱仪器。北京:化学工业出版,2006,1-68 152-165
[3]李彤。高效液相色谱仪器系统。北京:化学工业出版社,2004,1-150
[4]中国教育在线http://www.eol.cn/
[5]徐卉。玉米中维生素和植物激素的毛细管液相色谱分离检测[硕士学位论文]。汕头,汕头大学,2008,1-50
[6]徐卉、贾丽、柳亚玲。毛细管液相色谱法分离植物内源激素。分析试验室,2009,28(2):30-33
[7]马继平、丁明玉。毛细管离子色谱进展。分析化学评述与进展特刊,2006,34:272-277
[8]林秉承、秦建华。微流控芯片实验室的历史、现状和发展前景[会议论文]。2008,第八届全国微纳生物化学分离分析会议论文集CMSB2008,1-1。
[9]林秉承。微流控芯片实验室及其功能化。中国药科大学学报 2003,34(1):1-6
[10]Wood R W.On a remarkable case of uneven distribution of light in a diffraction grating spectrum.Philosophical Magazine,1902,4:392-402
[11]Homola Jiri,Yee Sinclair S.,Gauglitz Gunter.Surface plasmon resonance sensors:review.Sensors and Actuators B-Chemical.1999,54(1-2):3-15
[12]Dhesingh Ravi Shankaran,K.Vengatajalabathy Gobi,Norio Miura.Recent advancements in surface plasmon resonance immunosensors for detection of small molecules of biomedical,food and environmental interest.Sensors and Actuators B,2007,121(1):158-177
[13]Jir Homola.Surface plasmon resonance sensors for detection of chemical and biological species.Chemical Reviews,2008,108(2):462-493
[14]随森芳、肖才德、杨军。表面等离体激元共振生物传感器。上海:上海科学技术出版社,2008,1-23 197-268
[15]魏景艳,牟颖,许海波,胡鑫,宋大千,刘霞,张寒琦,金钦汉,罗贵民。用多克隆抗体构建的夹心免疫传感器检测心肌肌钙蛋白Ⅰ。高等学校化学学报,2003,24(12):2161-2164
[16]Xing-Zheng Wu,Masamitsu Nakagawa,Chiaki Nagamori,Katsumi Uchiyama,Toshiyuki Hobo.Detection Method Based on a Surface Plasmon Resonance and Its Application to Flow Injection Analysis and Liquid Chromatography.Bulletin of the Chemical Society of Japan,1996,69:1969-1974
[17]Cepria G,Castillo J R.Surface plasmon resonance-based detection An alternative to refractive index detection in high-performance liquid chromatography.Journal of Chromatography A,1997,759:27-35
[18]Rebecca J.Whelan and Richard N.Zare.Surface plasmon resonance Detection for Capillary Electrophoresis Separation.Analytical Chemistry,2003,75:1542-1547
[19]Ming Du and Feimeng Zhou.Postcolumn Renewal of Sensor Surfaces for High-Performance Liquid Chromatography-Surface Plasmon Resonance Detection.Analytical Chemistry,2008,80:4225-4230
[20]Kyung M B,Donghyun K S June K.Investigation of the sensitivity enhancement of nanoparticle based surface plasmon resonance biosensors using rigorous coupled wave analysis.Plasmonics in Biology and Medicine,2005,5703(Bellingham):61-70
[21]Chen F C,Chen S J,Hu W P,Lin G Y,Huang K T.Nanoparticle-enhanced ultrahigh-resolution surface plasmon resonance biosensors.Plasmonics in Biology and Medicine,2004,5327(Bellingham):140-147
[22]赵晓军、陈焕文、宋大千。表面等离子体子共振传感器1:基本原理。分析仪器,2000,4:1-8。
[23]Kazuyoshi Kurihara and Koji Suzuki.Therorectical Understanding of an Absorption-Based Surface Plasmon Resonance Sensor Based on Kretchmann's Theory.Analytical Chemistry,2002,74:696-701
[24]Texas Instruments.TSPR1A170100 SpreetaTM liquid sensor[K].Texas Instruments Incorporated,1999
[25]T.M.Chinowskya,J.G.Quinnb,D.U.Bartholomewb.Performance of the Spreeta 2000 integrated surface plasmon resonance affinity sensor.Sensor and Actuators B,2003,695:1-9
[26]Sahin K(O|¨),G(o|¨)n(u|¨)l T S.Temperature Effects on Surface Plasmon Resonance:Design Considerations for an Optical Temperature Sensor.Journal of Ligthwave Technology,2003,21(3):805-813
[27]Colin J.Alleyne,Andrew G.Kirk,Wei-Yin Chien and Paul G.Charette.Numerical method for high accuracy index of refraction estimation for spectro-angular surface plasmon resonance systems[J].Optical Society of America,2008,16(24):19493-19503
[28]David J.Kruglinkski(潘爱民、王国印).Visual C++技术内幕(第四版).北京:清华大学出版社,1998,1-810
[29]侯俊杰。深入浅出MFC第二版。武汉:华中科技大学出版社,2001,1:587
[30]Bruce Eckel.C++编程思想 第1卷:标准C++导引。北京:机械工业出版社,2002,1:479
[31]谭浩强。C++程序设计。北京:清华大学出版社,2004,1:486
[32]严蔚敏,吴伟民.数据结构:C语言版[M].北京:清华大学出版社,1996,1:334
[33]李长林,高洁,李长林,高洁编.Visual C++串口通信技术与典型实例。北京:清华大学出版社,2006,1:367
[34]Abraham Silberschartz,Henry F.Korth,S.Sudarshan.数据库系统概念。北京:机械工业出版社,2006,1:468
[35]龙帅。深入浅出SQL Server数据库开发。北京:中国青年出版社,2006,1:361
[36]Sandy Owega,Daniel Poitras.Local similarity matching algorithm for determining SPR angle in surface plasmon resonance sensors[J].Sensors and Actuators B,2007,123:35-41
[37]张雪娇。基于SPR传感技术的生物检测方法与实验研究[硕士学位论文]。杭州,浙江大学,2007,48-51
[38]Knut Johansen,Ralph Stalberg,Ingemar Lundstr(o|¨)m and Bo Liedberg.Surface plasmon resonance:instrumental resolution using photo diode arrays[J]. Measurement Science and Technology,2000,11(11):1630-1638.
[39]Timothy M.Chinowsky,Linda S.Jung,Sinclair S.Yee.Optimal linear data analysis for surface plasmon resonance biosensors[J].Sensors and Actuators B,1999,54:89-97
[40]Petr Tobi?ska,Ji?r'i Homola.Advanced data processing for SPR biosensors[J].Sensors and Actuators B,2005,107:162-169
[41]黄显,栗大超,徐可欣,于海霞,黄福祥,胡小唐。基于微型表面等离子共振生物传感器的葡萄糖浓度测量技术[J]。传感技术学报,1999,19(5):11814-11819
[42]Garet G Nenninger,Marek Piliarik,Ji?r'i Homola.Data analysis for optical sensors based on spectroscopy of surface plasmons[J].Measurement Science and Technology,2002,13:2038-2046.
[43]C.Thirstrup,W.Zong.Data analysis for surface plasmon resonance sensors using dynamic baseline algorithm[J].Sensors and Actuators B,2005,106:796-802.