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表面等离子体共振技术与聚合物光纤传感应用研究
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摘要
本论文的研究工作是在国家重点基础研究发展规划(No.2006CB302905)、国家自然科学基金重点项目(No.60736037))和面上项目(No.10704070)的资助下完成的。主要研究工作包括:表面等离子体共振技术传感应用研究以及聚合物光纤传感应用研究两方面。
     表面等离子体共振传感器具有灵敏度高、免标记、非破坏性和实时检测等优点,已被广泛应用于研究生物分子间的相互作用及浓度测量。随着研究的不断深入,表面等离子体共振技术将在疾病控制、药物开发、环境监测、食品安全以及国土安全等领域具有广阔的应用前景。但是表面等离子体共振传感器在实际应用中,仍然存在一些急需解决的问题,如价格昂贵,在检测低浓度小分子和大尺寸细胞方面受到限制、应用方式单一、无法进行野外实时远距离监测等。
     本论文中从传感器的结构出发,研究传感器的各个组成部分对总体性能的影响并且进行了参数的优化;设计了一种金银双层复合结构的芯片,并成功应用于商品化仪器系统上;研制了能够灵活应用,且具有高灵敏度的光纤SPR传感器。
     针对聚合物光纤应用于传感领域的问题,研究了偶氮掺杂聚合物光纤预制材料的光敏特性,并用双频光栅法在单模聚合物光纤上刻写了双折射长周期光纤光栅,讨论了将其应用于光纤SPR传感器中的可能性。从理论上分析了聚合物光纤光栅在温度、应力、应变等环境下的传感性能。建立了基于聚合物光纤的VCSEL自混合测速系统,分析了引入聚合物光纤后,对自混合信号产生的影响。本论文获得的成果主要有:
     1、研究Kretschmann耦合模型中,系统的各个组成部分对SPR传感器性能的影响,用于指导设计高性能、实用化的SPR传感器。提出了一种基于聚合物光纤的波长调制型SPR传感器。
     2、设计了一种基于金银双层金属复合结构的SPR芯片,利用转移矩阵方法,研究了金银不同厚度比例对SPR传感器性能的影响,并对芯片的结构进行了优化。加工了双层金属复合结构芯片,且将其成功应用于BIAcore3000仪器上研究磺胺甲恶唑和其抗体的相互作用。从波导理论出发,对长程表面等离子体的色散,损耗和场分布特征进行讨论,对设计新型的SPR传感芯片及其他光电子器件具有参考意义。
     3、从理论上详细讨论了影响光纤SPR传感器的因素,在理论的指导下构建了光纤SPR传感系统并进行了实验研究。在折射率为n=1.3945时,光纤SPR传感器的灵敏度指标为4778nm/RIU。从SPs场增强的角度,对待测样品折射率和介质保护膜影响SPR传感器灵敏度的原因进行了解释。分析了介质层对SPR共振曲线的调节作用,并简单讨论了可应用于液体和气体同时测量的双通道SPR传感器。
     4、分析了偶氮掺杂聚合物光纤预制材料的双折射弛豫过程和保留度问题,用于指导光敏聚合物光纤光栅纤芯材料的设计和筛选。用双频光栅法在单模聚合物光纤中刻写出双折射长周期光纤光栅,讨论将其用于光纤SPR传感器的可能性。从理论上分析了聚合物光纤光栅对温度、应力和应变的响应特性。
     5、建立了基于聚合物光纤的VCSEL自混合测速系统,系统结构简单且易于调节。在38-193mm/S范围内,实现了对流动液体内部速度的测量,测量误差小于1%。分析了聚合物光纤作为传光介质对VCSEL自混合测速信号的影响,首次观测到自混合信号的波形畸变和频谱展宽现象。
     本文创新点和特色:
     1、设计了金银双层金属复合结构芯片,首次将其应用于BIAcore3000仪器上用于研究生物分子间的相互作用。与传统的单层金膜芯片相比,这种新型的传感芯片能够获得更窄的共振峰和更高的灵敏度,同时仍具有金膜芯片的稳定性。
     2、研制了介质膜包覆的光纤SPR传感器,并从理论性上对多层结构的光纤SPR传感器性能优化进行分析。在折射率为n=1.3945时,获得光纤SPR传感器的灵敏度为4778nm/RIU。利用介质膜对SPR共振波长的调制特性,理论设计了用于液体和气体同时探测的双通道SPR传感器。
     3、首次报道了偶氮共聚型掺杂聚合物光纤的双折射效应,在低掺杂浓度下获得了72%的双折射保留度。并详细分析了浓度、间隔基和泵浦光功率等因素对该共聚材料双折射特性的影响.用双频光栅法在单模聚合物光纤上刻写了双折射长周期光栅,对红移和蓝移分离偏振峰的理论分析,表明该双折射光纤光栅在SPR传感方面具有潜在用途。
     4、首次建立了基于聚合物光纤的VCSEL自混合测速系统,系统结构简单且易于调节,无需使用频谱分析仪器,通过Labview软件和数据采集卡实现对液体流速的实时、快速测量。由于聚合物光纤与生物体有很好的兼容性,因此可将聚合物光纤作为一次性探针使用对血液流速进行测量。
The research work in this dissertation is supported by the National Key Basic Research Program of China(No.2006CB302905),the Key Program of National Natural Science Foundation of China(No.60736037) and the National Natural Science Foundation of China(No.10704070).The main work includes the researches on the applications of Surface Plasmon Resonance(SPR) sensing technique as well as Polymer Optical Fiber(POF).
     Surface Plasmon resonance sensors have been widely used in the studies of biomolecular interaction analysis and concentration measurement,due to their advantages in high sensitivity,label-free,non-destructive and real-time detection,etc. With further and deeper study in this field,surface plasmon resonance technology will certainly be applied in various areas,ranging from health-care,pharmaceuticals, environmental monitoring,and food safety to homeland security.But practically,there are still some limitations for the further development of SPR sensor,such as high cost of the chip,being unable to detect low concentrations of small molecules or large-sized cells,as well as not possible to be carded out with real-time and remote monitoring in the outdoor applications,etc.
     In this thesis,I analyzed the influences of the parameters of all SPR sensor components,and by optimization,I have made it possible to choose parameters to the best sensing performance.A piece of bimetallic chip combing gold and silver film is designed and fabricated,and then successfully utilized in the commercial SPR instrument.Also a fiber SPR sensor with flexibility and high-sensitivity is developed.
     The photosensitivity of polymer optical fiber performs is studied,and birefringence fiber grating is written in POF with double frequency grating method. The possibility of combining the birefringence grating and SPR technique is discussed. The sensing performances under the influences of temperature,stress,and strain by using POF grating are theoretically analyzed.A velocimetry system based on Polymer optical fiber and the VCSEL self-mixing effect is built up,and the influences of POF on self-mixing signals are discussed.
     The main research work and conclusions in this thesis are as following:
     1.Based on the Krestchmann SPR structure,I study how to choose the parameters of the SPR sensor's components in designing the sensor in order to achieve the best sensing performance.A wavelength modulation SPR sensor with POF is proposed.
     2.A bimetallic chip combing gold and silver film is designed,and the optimum thickness ratio of silver and gold is studied according to transfer matrix method. We fabricated the bimetallic chip,and applied it into the BIAcore3000 SPR instrument for researching the interactions between sulfamethoxazole and its antibody.The dispersion relationships,loss properties and field distribution of long-range surface plasmons(SPs) are discussed according to the waveguide theory.
     3.The birefringence process and reservation characteristic of azo doped POF is studied to guide the selection of core material in the POF grating.Birefringence fiber grating is written in POF with double frequency grating method,and the possibility of the birefringence grating applied in SPR Sensors is discussed.The polymer fiber gratings for sensing temperature,stress and strain is theoretically simulated.
     4.A simple and flexible velocimetry system based on POF and VCSEL self-mixing effect is established.The flow measurement inside the liquid at the range of 38-193mm/s is obtained,and the measurement error is less than 1%.The influences of POF on self-mixing signals are discussed,and the mixed-signal waveform distortion and spectrum broadening phenomenon is observed for the first time.
     Highlights of the dissertation are as following:
     1.A bimetallic chip of gold and silver is designed,and it has been successfully applied in the commercial BIAcore3000 instrument to study the interaction in biological molecules.Compared to the traditional single-layer gold film chip,this new type of sensor chip shows narrower resonance peak,higher sensitivity and still maintains the stability of single gold-film chips.
     2.Optical fiber SPR sensor with a dielectric protective film is developed,and its optimized parameters are discussed.The sensitivity of sensor at the refractive index of n=1.3945 is 4778nm/RIU.And a dual-channel fiber SPR sensor for measuring the gases and liquids is designed with the help of a dielectric layer.
     3.For us,it is the first time to report the birefringence effect in copolymer optical fiber.Residual birefringence of 72%is obtained in the material under low azo concentration.Many factors,causing the influences,such as azo concentration, spacer and pump optical power to the birefringence characteristics,are analyzed. Birefringence fiber grating is written in POF in double frequency grating method. Separate polarized peak is analyzed theoretically,which shows that the birefringence grating has great potential in the application of fiber SPR sensors.
     4.We build up the velocimetry system based on POF and VCSEL self-mixing effect for the first time.It is simple and easy to adjust the structure of our system.The real-time and rapid flow measurement could be carried out by using data acquisition card as well as Labview software instead of the expensive and bulky spectrum analysis instrument.Due to the fact that it has the advantages in flexibility,ease of handling,and perfect biocompatibility,the polymer fiber could be used as the disposable probe for measurement of blood flow velocity in vivo.
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