查找:                      转第 显示法宝之窗 隐藏相关资料 下载下载 收藏收藏 打印打印 转发转发 小字 小字 大字 大字
【期刊名称】 《刑事技术》
基于表面等离子体共振原理的传感技术在物证检验中的应用
【英文标题】 Application of Surface Plasmon Resonance Sensing Methodologies in Evidence Analysis
【作者】 王霄崔勐陈彭波刘艳曹艳萍郝红霞
【作者单位】 西北政法大学公安学院{博士,讲师}陕西省西安市公安局刑侦局技术处陕西省西安市公安局刑侦局技术处西北政法大学公安学院西北政法大学公安学院
【分类】 司法鉴定学【中文关键词】 表面等离子体共振;传感;物证检验
【英文关键词】 surface plasmon resonance (SPR); sensing analysis methodologies; evidence analysis
【文章编码】 1008-3650(2019)06-0524-06
【文献标识码】 A DOI: 10.16467/j.1008-3650.2019.06.011
【期刊年份】 2019年【期号】 6
【页码】 524
【摘要】

表面等离子体共振(surface plasmon resonance, SPR)是一种物理光学现象。基于表面等离子体共振原理发展的各种分析检测方法具有响应快、免标记、灵敏度高等诸多特点,可在天然条件下实现无损原位、实时动态的测量,已被广泛应用于物理、化学、生物学、医学、法庭科学等领域。本文简要介绍了表面等离子体共振原理及基于该原理所衍生出的不同分析方法,对其在物证检验中的重要应用进行了综述,并对目前存在的关键问题加以分析,同时指出了该技术应用于实际办案可能的发展方向。

【英文摘要】

Surface plasmon resonance (SPR) is an optical phenomenon of physics. The SPR-based detection methodologies play an important role of efficient tools in forensic analysis thanks to their well-known advantages of sensitivity, selectivity, easy functioning, rapid detection, affordability and capability of miniaturization and automation. With the merit of non-destructive, in-situ, real-time and dynamic measurement in natural conditions, the relevant technology has been widely used into biology, medicine, chemistry and forensic science. Numerous reporting applications of SPR can be found about forensic researches in the most qualified journals of analytical chemistry/biochemistry, angewandte chemie, analytica chimica acta, biosensors and bioelectronics among others. This article reviews the most widespread SPR-based sensing methodologies and their applications for evidence analysis, enumerating with elucidation into the SPR sensors of SPR/SPRi, fiber optic and the localized. The advantages and existing problems of SPR in evidence analysis have also been discussed although significant improvements have been achieved in recent years by the combination of SPR with mass spectrometry (MS) that pushed their wider usage into complex forensic analysis and real cases.

【全文】法宝引证码CLI.A.1283715    
  
  

物证检验主要研究证明物证的形成、组分、结构及内在的变化规律,一般需利用灵敏度较高的仪器分析方法方可实现分析检测{1-3}。表面等离子体共振(surface plasmon resonance , SPR)是一种物理光学现象,基于该原理所发展的分析检测方法均具有操作便捷、灵敏度高、设备微型等诸多特点,现已广泛应用于化学、医学、环境科学、物证检验等领域,发展迅速,已然成为一类十分重要的生物传感分析技术{4}。

SPR现象的产生缘于等离子体,金属的原子核可视作正离子,其核外电子可视作在原子核周围运动的自由电子气,电磁场(比如光波)作用后会产生表面等离子体波,其沿着金属与电介质的分界面传播。要实现波矢的匹配要求特定的耦合条件,SPR传感根据耦合条件的不同可分为不同类型{5-6}。本文拟就在物证检验领域最常用的三种SPR传感分析方法作出简要介绍,分别是Kretschmann构型的SPR/SPRi传感器(surface plasmon resonance imaging, SPRi)、光纤SPR传感及局域SPR传感。这三种SPR传感方法的共同特点是无须标记、检测灵敏度高,无须各组分的纯化,设备可小型化,可实时原位检测各种生物分子或颗粒物,并且SPRi能够满足高通量的分析检测要求{7}。本文在对上述三种方法原理介绍的同时将其在物证检验领域的一些重要应用一并加以概述,包括毒素、爆炸物、非法药物、农残及环境污染物的检测和指纹的分析研究,并对该技术在物证检验方面的发展前景提出问题并辅以展望。

1原理

1.1 Kretschmann结构的SPR/SPRi传感器

Kretschmann结构的SPR/SPRi传感器是目前已被普及推广的商品化仪器。其灵敏度高、操作方便、检测快速,已被广泛应用于医学、化学、生物学、法庭科学等领域{8}。要实现表面等离子体共振通常需要不同的耦合条件,Kretschmann耦合结构的SPR/SPRi传感器是其中的一种,该方法的核心部分主要依靠金属薄膜(如金膜)。当外部光源与等离子体波的波矢匹配即发生光吸收现象,此时即发生表面等离子体共振效应,所产生的光吸收会随金属外表周围介质的差异而发生变化,如介电常数和折射率不同即会产生不同强度的光信号,因此可用于金属外表面样品的实时分析。 SPR与SPRi的分析原理相同,SPR用于单一样品分析,SPRi则适合批量样品的分析{9-10}。

1.2光纤SPR传感

光纤SPR是基于SPR原理发展的一种分析检测方法,其灵敏度与传统的Kretschmann结构SPR仪器相比较有很大的提升。光纤SPR装置通常小巧灵活、经济廉价、易于搭建,便于一般的实验室应用普及,值得推广。光纤在传输光的过程当中,耦合进入的光在纤芯内表面会发生全内反射,若在光纤的石英纤芯表面镀上一层金属膜,就能够成为SPR测量的关键部件。与Kretschmann结构SPR传感器类似,当反射光的波矢与金属薄膜产生的表面等离子体波波矢相匹配即会发生SPR现象{11-12}。

1.3局域SPR传感

金属纳米颗粒的表面等离子体波通常很容易被远场光激发,此后形成局域化的表面等离子体振荡现象,即局域SPR,在消光光谱中会产生局域SPR峰。其中金纳米颗粒由于比表面积大、体积小、容易修饰而最为常用。其具有良好的光学可调性和生物相容性,特殊的光学性质使其能够作为性能优良的识别传感探针。其局域SPR吸收光谱会随着颗粒尺寸、形状、表面的介电性质及微环境等因素的不同而发生相应的改变。这种纳米技术的检测方法成本低廉,操作简便,已被用来研究许多生物分子的相互作用和识别过程{13}。

2物证检验中的应用

2.1毒素检测

在毒素分析检测中,对被污染的藻类或贝类所产生的毒素研究已成为全球关注的热点。岩沙海葵毒素是已知毒性最强的毒素之一,食用受其污染的海鲜食物严重危害人类健康甚至会导致死亡。Yakes等{14}结合抗原抗体的免疫反应,利用SPR分析检测了岩沙海葵毒素,检出限为2.8 ng/mL。冈田酸(OA)和鳍藻属毒素-1(DTX-1)是产生于浮游植物中的亲脂性海洋生物毒素,多聚集于贝类物质。Stewart等{15}利用SPR方法结合免疫反应对其加以分析,检出限为31μg/kg每贻贝,线性测定范围为31~174μg/kg。 Fonfria等{16}检测了软骨藻酸,检出限为10 nM,线性范围为13~200 nM。近年来,与微囊藻毒素(一种蓝藻的次生代谢产物)相关的案例在我国频频出现且危害严重。李莹等{17}构建的SPR分析方法对微囊藻毒素的检测限低于1μg/L,满足行业标准中对于饮用水和地表水中微囊藻毒素最低检测含量的要求(1.0μg/L)。同时这种SPR的芯片检测方法具有设备便携、样品前处理简单、成本低等优点,有望用于现场检测。Herranz等{18}也利用SPR分析了饮用水中的微囊藻毒素,结合竞争性抑制反应,首先将微囊藻毒素自组装固定在芯片表面,之后对抗体浓度、缓冲溶液、封闭溶液及芯片再生溶液等实验条件加以优化,所构建方法的线性检测范围、检出限及IC50分别为0.2~2.0μg/L, (73±8)ng/L和(0.67±0.09)μg/L。该SPR芯片可在1 h内同时实现四组测试,且芯片反复再生重复利用40次无明显的结合能力损失。该方法同样满足行业标准中微囊藻毒素最低检测含量的要求。核酸适配体是一类单链寡核苷酸,能特异性结合靶标分子。Zhu等{19}通过将赭曲霉毒素A (OTA)适配体固定在SPR传感芯片上实现对OTA的检测,检出限为0.005 ng/mL。Park等{20}将OTA适配体修饰在金纳米棒表面,当金纳米棒-适配体复合物与赭曲霉毒素A结合后会导致适配体结构的变化,这种微环境的改变导致金纳米棒表面折射率的改变,可宏观表现为最大吸收波长的红移或蓝移。该方法对OTA的线性检测范围为0.0001~10μmol/L,检出限低于1 nmol/L。Bai等{21}首先将SPR传感芯片用链霉亲和素加以修饰,之后将适配体固定在修饰后的传感芯片上,实现了对禽流感病毒的分析检测。 Gupta等{22}结合分子印迹技术检测了葡萄球菌肠毒素B(SEB),实验中将3-氨基苯基硼酸通过原位聚合的方法固定在金膜表面,该方法的线性检测范围和检出限分别为3.2~25.6 fM和0.05 fM。同时也对动力学进行了一定研究,所得到的平衡常数KD和吉布斯自由能?G分别为24 fM和-77.54 kJ/mol。

2.2爆炸物检测

在爆炸案件中,案件现场的爆炸物一般是以痕量存在于庞杂基体中。对于此类微痕量爆炸物的检测,发展灵敏度高、特异性好且高通量的快速检测方法显得十分必要{23}。爆炸物的种类繁多,在检测工作中有诸多困难,其中以三硝基甲苯(TNT)的研究最为久远,SPR方法在其中表现出显著的优势。 Kawaguchi等{24}将M-TNT Ab(TNT单克隆抗体)固定于SPR传感芯片表面,结合竞争性抑制结合法,可检测到pg/mL水平的TNT。进一步结合局域SPR技术,引入纳米金进行信号放大,其线性检测范围可以降低到0.01~100 ng/mL,使检测信号被放大了四倍之多。同样的,Shankaran等{25}利用抗原抗体免疫反应,结合竞争性抑制作用实验,对TNT的检出限和线性测定范围分别为0.09 ng/mL和0.09~1000 ng/mL,检测用时约为22 min。在SPR实验中,芯片的非特异性吸附是普遍存在的一个问题。Nagatomo等北大法宝

  ······

法宝用户,请登录后查看全部内容。
还不是用户?点击单篇购买;单位用户可在线填写“申请试用表”申请试用或直接致电400-810-8266成为法宝付费用户。
【注释】                                                                                                     
【参考文献】

{1}王俭,王景翰,王彦吉,等.仪器分析与法庭化学[J].生命科学仪器,2003, 1(2):17-20.(WANG Jian, WANG Jinghan, WANG Yanji, et al. Instrumental analysis and forensic chemistry[J]. Life Science Instruments, 2003, 1(2):17-20.)

{2}王彦吉,王景翰,王俭,等.法庭化学与化学[J].化学通报,2002(10):688-691.(WANG Yanji, WANG Jinghan, WANG Jian, et al. Forensic chemistry and chemistry[J]. Chemistry, 2002(10):688-691.)

{3}庞松颖.浅谈微量物证的应用[J].中国公共安全(学术版),2012(3):107-109.(PANG Songying. Discussion about trace evidence[J]. China Public Security (Academy Edition), 2012(3):107-109.)

{4}谭俊鹏,郝红霞,杨瑞琴. SPR传感器检测痕量炸药的研究进展[J].刑事技术,2016, 41(5):345-351.(TAN Junpeng, HAO Hongxia, YANG Ruiqin. Advances in the application of SPR sensor for determining trace explosive[J]. Forensic Science and Technology, 2016, 41(5):345-351.)

{5}WILLE TS K A, VAN DUYNE R P. Localized surface plasmon resonance spectroscopy and sensing [J]. Annual Review of Physical Chemistry, 2007, 58:267-297.

{6}HOMO LA J. Surface plasmon resonance sensors for detection of chemical and biological species [J]. Chemical Reviews, 2008, 108(2):462-493.

{7}陈义.高通微量分析[J].化学进展,2005, 17(4):573-580.(CHEN Yi. High throughput microanalysis[J]. Progress in Chemistry, 2005, 17(4):573-580.)

{8}WANG X, XU J, LIU C, et al. Specific interaction of platinated DNA and proteins by surface plasmon resonance imaging [J].Rsc Advances, 2016, 6(26):21900-21906.

{9}王霄,许吉英,陈义.生物分子相互作用动力学的表面等离子体共振研究方法[J].化学进展,2015, 27(5):550-558.(WANG Xiao, XU Jiying, CHEN Yi. Surface plasmon resonance methodology for interaction kinetics of biomolecules[J].Progress in Chemistry, 2015, 27(5):550-558.)

{10}刘巍,陈义.表面等离子体共振成像法用于糖蛋白分析[J].高等学校化学学报,2008, 29(9):1744-1746.(LIU Wei, CHEN Yi. Glycoproteins analysis by surface plasmon resonance absorption and imaging[J]. Chemical Journal of Chinese Universities, 2008, 29(9):1744-1746.)

{11}SCIA CCA B, FRANCOIS A, HOFFMANN P, et al. Multiplexing of radiative-surface plasmon resonance for the detection of gastric cancer biomarkers in a single optical fiber[J]. Sensors and Actuators B-Chemical, 2013, 183:454-458.

{12}SHRI VASTAV A M, MISHRA S K, GUPTA B D. Surface Plasmon Resonance-Based Fiber Optic Sensor for the Detection of Ascorbic Acid Utilizing Molecularly Imprinted Polyaniline Film[J]. Plasmonics, 2015, 10(6):1853-1861.

{13}WONG C L, OLIVO M. Surface plasmon resonance imaging sensors: a review [J]. Plasmonics, 2014, 9(4):809-824.

{14}YAKE S B J, DEGRASSE S L, POLI M, et al. Antibody characterization and immunoassays for palytoxin using an SPR biosensor[J]. Analytical and Bioanalytical Chemistry, 2011, 400(9):2865-2869.

{15}STEWA RT L D, HESS P, CONNOLLY L, et al. Development and single-laboratory validation of a pseudofunctional biosensor immunoassay for the detection of the okadaic acid group of toxins[J]. Analytical Chemistry, 2009, 81(24):10208-10214.

{16}FONF RIA E S, VILARINO N, CAMPBELL K, et al. Paralytic shellfish poisoning detection by surface plasmon resonancebased Biosensors in shellfish matrixes[J]. Analytical Chemistry, 2007, 79(16):6303-6311.

{17}李莹,钟金钢,马骁,等.表面等离子体共振免疫传感器用于快速检测微囊藻毒素的研究[J].食品工业科技,2017, 38(5):304-314.(LI Ying, ZHONG Jingang, MA Xiao, et al. Research of the surface plasmon resonance immunosensor for rapid detection of microcystin[J]. Science and Technology of Food Industry, 2017, 38(5):304-314.)

{18}HERR ANZ S, BOCKOVA M, DOLORES MARAZUELA M, et al. An SPR biosensor for the detection of microcystins in drinking water[J]. Analytical and Bioanalytical Chemistry, 2010, 398(6):2625-2634.

{19}ZHU Z , PENG M, ZUO L, et al. An aptamer based surface plasmon resonance biosensor for the detection of ochratoxin A in wine and peanut oil [J]. Biosensors & Bioelectronics, 2015, 65:320-326.

{20}PARK J H, BYUN J Y, MUN H, et al. A regeneratable, labelfree, localized surface plasmon resonance (LSPR) aptasensor for the detection of ochratoxin A[J]. Biosensors & Bioelectronics, 2014, 59:321-327.

{21}BAI H , WANG R, HARGIS B, et al. A SPR aptasensor for detection of avian influenza virus H5N1[J]. Sensors, 2012, 12(9):12506-12518.

{22}GUPT A G, SINGH P K, BOOPATHI M, et al. Molecularly imprinted polymer for the recognition of biological warfare agent staphylococcal enterotoxin B based on surface plasmon resonance[J]. Thin Solid Films, 2010, 519(3):1115-1121.

{23}姜红,徐建新.爆炸案件中爆炸残留物的检验及应用[J].中国人民公安大学学报(自然科学版),2007(1):10-14.(JANG Hong, XU Jianxin. Inspection and application of explosive residues in explosion cases[J]. Journal of Chinese People’s Public Security University (Science and Technology Edition), 2007(1):10-14.)

{24}KAWA GUCHI T, SHANKARAN D R, KIM S J, et al. Surface plasmon resonance immunosensor using Au nanoparticle for detection of TNT[J]. Sensors and Actuators B-Chemical, 2008, 133:467-472.

{25}SHAN KARAN D R, GOBI K V, SAKAI T, et al. Surface plasmon resonance immunosensor for highly sensitive detection of 2, 4, 6-trinitrotoluene[J]. Biosensors & Bioelectronics, 2005, 20:1750-1756.

{26}NAGA TOMO K, KAWAGUCHI T, MIURA N, et al. Development of a sensitive surface plasmon resonance immunosensor for detection of 2, 4-dinitrotoluene with a novel oligo (ethylene glycol)-based sensor surface[J]. Talanta, 2009, 79(4):1142-1148.

{27}LARS SON A, ANGBRANT J, EKEROTH J, et al. A novel biochip technology for detection of explosives-TNT: Synthesis, characterisation and application [J]. Sensors and Actuators B-Chemical, 2006, 113:730-748.

{28}EHRE NTREICH F?ERSTER E, ORGEL D, KRAUSEGRIEP A, et al. Biosensor-based on-site explosives detection using aptamers as recognition elements[J]. Analytical and Bioanalytical Chemistry, 2008, 391(5):1793-1800.

{29}CENN AMO N, D’AGOSTINO G, GALATUS R, et al. Sensors based on surface plasmon resonance in a plastic optical fiber for the detection of trinitrotoluene[J]. Sensors and Actuators B-Chemical, 2013, 188:221-226.

{30}GUO W, LI X, WEI T. Applications of surface plasmon resonance technique in gas sensing [J]. Progress in Chemistry, 2008, 20(1):155-162.

{31}JIANG Y, ZHAO H, ZHU N, et al. A simple assay for direct colorimetric visualization of trinitrotoluene at picomolar levels using gold nanoparticles [J]. Angewandte Chemie International Edition, 2008, 47(45):8601-8604.

{32}LIN D , LIU H, QIAN K, et al. Ultrasensitive optical detection of trinitrotoluene by ethylenediamine-capped gold nanoparticles[J]. Analytica Chinaica Acta, 2012, 744:92-98.

{33}袁博,苗翠英,翟博.国内外毒物、毒品检验现状及发展趋势[J].中国人民公安大学学报(自然科学版),2004(2):48-51.(YUAN Bo, MIAO Cuiying, ZHAI Bo. Current situation and development trend of toxic and drug testing home and abroad[J]. Journal of Chinese People’s Public Security University (Science and Technology Edition), 2004(2):48-51.)

{34}DILLO N P P, DALY S J, MANNING B M, et al. Immunoassay for the determination of morphine-3-glucuronide using a surface plasmon resonance-based biosensor[J]. Biosensors & Bioelectronics, 2003, 18:217-227.

{35}VIKH OLM LUNDIN I, AUER S, HELLGREN A C. Detection of 3, 4-methylenedioxymethamphetamine (MDMA, ecstasy) by displacement of antibodies[J]. Sensors and Actuators BChemical, 2011, 156:28-34.

{36}KLEN KAR G, LIEDBERG B. A microarray chip for labelfree detection of narcotics [J]. Analytical and Bioanalytical Chemistry, 2008, 391:1679-1688.

{37}MAUR IZ E, CALLE A, MANCLUS J J, et al. Multi-analyte SPR immunoassays for environmental biosensing of pesticides [J].Analytical and Bioanalytical Chemistry, 2007, 387:1449-1458.

{38}SHRI VASTAV A M, USHA S P, GUPTA B D. Fiber optic profenofos sensor based on surface plasmon resonance technique and molecular imprinting[J]. Biosensors & Bioelectronics, 2016, 79:150-157.

{39}SAMSO NOVA J V, USKOVA N A, ANDRESYUK A N, et al. Biacore biosensor immunoassay for 4-nonylphenols: assay optimization and applicability for shellfish analysis[J]. Chemosphere, 2004, 57(8):975-985.

{40}CHAN G Y H, CHANG T C, KAO E F, et al. Detection of protein A produced by Staphylococcus aureus with a fi beropticbased biosensor[J]. Bioscience, Biotechnology and Biochemistry, 1996, 60(10):1571-1574.

{41}刘小桃.表面等离子体共振技术在环境污染物监测中的应用研究[J].低碳世界,2016(9):19-20.(LIU Xiaotao. Application of surface plasmon resonance technology in environmental pollution monitoring[J]. Low Carbon World, 2016(9):19-20.)

{42}张婷,杨瑞琴.指纹中化学成分免疫分析技术热点研究[J].刑事技术,2015, 40(1):24-27.(ZHANG Ting, YANG Ruiqin. Research progress of immunological technique in analysis of fingerprints’ contents[J]. Forensic Science and Technology, 2015, 40(1):24-27.)

{43}刘鸣禹.纳米技术在刑事侦查潜指纹鉴定中的应用[J].生物物理学报,2012, 28(12):945-951.(LIU Mingyu. Application and recent progress of nanotechnology for latent fingerprint detection[J]. Acta Biophysica Sinica, 2012, 28(12):945-951.)

{44}吴逸川,姚曼文,方湘怡.应用SPRI技术检测指纹上的化学品残留[J].传感器与微系统,2015, 34(6):37-42.(WU Yichuan, YAO Manwen, FANG Xiangyi. Application of SPRi technology in detecting of chemical residual in fingerprint[J]. Transducer and microsystem Technologies, 2015, 34(6):37-42.)

{45}李莹,钟金钢,张永林.基于表面等离子体共振成像的指纹采集[J].中国激光,2006, 33(8):1143-1147.(LI Ying, ZHONG Jingang, ZHANG Yonglin. Fingerprint image acquisition based on surface plasmon resonance imaging[J]. Chinese Journal of Lasers, 2006, 33(8):1143-1147.)

{46}ZHAN G Y, LI X, NIE H, et al. Interface for online coupling of surface plasmon resonance to direct analysis in real time mass spectrometry[J]. Analytical Chemistry, 2015, 87(13):65056509.

©北大法宝:(www.pkulaw.cn)专业提供法律信息、法学知识和法律软件领域各类解决方案。北大法宝为您提供丰富的参考资料,正式引用法规条文时请与标准文本核对
欢迎查看所有产品和服务。法宝快讯:如何快速找到您需要的检索结果?    法宝V5有何新特色?
扫码阅读
本篇【法宝引证码CLI.A.1283715      关注法宝动态:  

法宝联想
【相似文献】

热门视频更多