查看“︁表面增强拉曼光谱”︁的源代码

{{Translating|[[:en:Surface-enhanced Raman spectroscopy]]||time=2017-4-25}}
[[File:sers.jpg|thumb|right|250px]]
'''表面增强拉曼光谱'''（{{lang-en|Surface-enhanced Raman spectroscopy}}）或'''表面增强拉曼散射'''（{{lang-en|surface-enhanced Raman scattering (SERS)}}），是一种通过吸附在粗糙[[金属]]表面上的[[分子]]或[[等离子体]][[磁性]][[二氧化硅]]纳米管等[[纳米结构]]增强[[拉曼散射]]的表面敏感技术<ref>Xu, X., Li, H., Hasan, D., Ruoff, R. S., Wang, A. X. and Fan, D. L. (2013), Near-Field Enhanced Plasmonic-Magnetic Bifunctional Nanotubes for Single Cell Bioanalysis. Adv. Funct. Mater.. {{DOI|10.1002/adfm.201203822}}</ref>，其增强因子可高达<math>{10}^{10}-{10}^{11}</math><ref>{{Cite journal|last1=Blackie|first1=Evan J.|last2=Le Ru|first2=Eric C.|last3=Etchegoin|first3=Pablo G.|title=Single-Molecule Surface-Enhanced Raman Spectroscopy of Nonresonant Molecules|journal=J. Am. Chem. Soc.|volume=131|issue=40|pages=14466–14472|date=2009|doi=10.1021/ja905319w|pmid=19807188}}</ref><ref>{{Cite journal|last1=Blackie|first1=Evan J.|last2=Le Ru|first2=Eric C.|last3=Meyer|first3=Matthias|last4=Etchegoin|first4=Pablo G.|title=Surface Enhanced Raman Scattering Enhancement Factors: A Comprehensive Study|journal=J. Phys. Chem. C|volume=111|pages=13794–13803|date=2007|doi=10.1021/jp0687908|issue=37}}
</ref>，这意味着该技术可以检测单个分子<ref>{{cite journal|doi=10.1126/science.275.5303.1102|pmid=9027306|date=1997|last1=Nie|first1=S|last2=Emory|first2=SR|title=Probing Single Molecules and Single Nanoparticles by Surface-Enhanced Raman Scattering|volume=275|issue=5303|pages=1102–6|journal=Science}}</ref><ref>{{Cite journal|last1=Le Ru|first1=Eric C.|last2=Meyer|first2=Matthias|last3=Etchegoin|first3=Pablo G.|title=Proof of Single-Molecule Sensitivity in Surface Enhanced Raman Scattering (SERS) by Means of a Two-Analyte Technique|journal=J. Phys. Chem. B|volume=110|pages=1944–1948|date=2006|doi=10.1021/jp054732v|issue=4|pmid=16471765}}</ref>。
==历史==
1973年，英国[[南安普敦大学]]化学系的[[马丁·弗莱舍曼]]，[[帕特里克·J·亨德拉]]和[[A.詹姆斯·麦奎伦]]发现了吸附在电化学粗糙[[银]]上的吡啶的表面增强拉曼光谱<ref>{{cite journal|last=Fleischmann|first=M.|authorlink=Martin Fleischman|author2=PJ Hendra|author3=AJ McQuillan|last-author-amp=yes|title=Raman Spectra of Pyridine Adsorbed at a Silver Electrode|journal=[[Chemical Physics Letters]]|volume=26|issue=2|pages=163–166|date=15 May 1974|doi=10.1016/0009-2614(74)85388-1|bibcode = 1974CPL....26..163F }}</ref>。这篇论文被引用超过4000次。1977年，两个团队分别注意到散射物质的浓度无法解释增强信号，并且每个团队分别提出了一种增强信号的产生机理，这两种机理现在仍被接受。[[让马尔]]和[[凡·瓦拉赫]]提出是电磁效应<ref>{{cite journal|last=Jeanmaire|first=David L.|author2=Richard P. van Duyne |title=Surface Raman Electrochemistry Part I.  Heterocyclic, Aromatic and Aliphatic Amines Adsorbed on the Anodized Silver Electrode|journal=[[Journal of Electroanalytical Chemistry]]|volume=84|pages=1–20|date=1977|doi=10.1016/S0022-0728(77)80224-6}}</ref>，而[[阿尔布雷希]]和[[克赖顿]]提出是电荷转移效应<ref>{{cite journal|last=Albrecht|first=M. Grant|author2=J. Alan Creighton |title=Anomalously Intense Raman Spectra of Pyridine at a Silver Electrode|journal=[[Journal of the American Chemical Society]]|volume=99|pages=5215–5217|date=1977|doi=10.1021/ja00457a071|issue=15}}</ref>。[[橡树岭国家实验室]]健康科学研究室的[[鲁弗斯·里奇]]，预测了表面等离子体的存在<ref>{{cite journal|title=Technical Highlights. New Probe Detects Trace Pollutants in Groundwater|journal=[[Oak Ridge National Laboratory Review]]|volume=26|issue=2|url=http://www.ornl.gov/info/ornlreview/rev26-2/text/tecmain.html|deadurl=yes|archiveurl=https://web.archive.org/web/20100115025603/http://www.ornl.gov/info/ornlreview/rev26-2/text/tecmain.html|archivedate=2010年1月15日|df=|access-date=2017年4月25日}}</ref>。
==机理==
表面增强拉曼光谱的确切机理仍然在争论中。有两种机理基本不同的理论，实验中仍无法准确地区分它们。电磁理论提出机理是局部表面[[等离子体]]的[[激发]]，而化学理论提出是[[电荷转移配合物]]的形成。化学理论仅适用于表面已形成[[化学键]]的物质，所以不能解释所有观察到的增强信号，而电磁理论可以应用于试样只是[[物理吸附]]在表面的情况下。最近的研究表明，当激发分子远离承载金属纳米颗粒的表面，导致表面等离子体现象时，表面增强拉曼现象也可以发生<ref name=Kukushkin>{{cite journal|last1=Kukushkin|first1=V. I.|last2=Van’kov|first2=A. B.|last3=Kukushkin|first3=I. V.|title=Long-range manifestation of surface-enhanced Raman scattering|journal=JETP Letters|volume=98|issue=2|date=2013|pages=64–69|issn=0021-3640|doi=10.1134/S0021364013150113}}</ref>。这一观察有力支撑了表面增强拉曼光谱的电磁理论。2015年对表面增强拉曼光谱更强大的扩展技术——[[多相和多成分超灵敏表面增强拉曼散射]]（{{lang-en|Slippery Liquid-Infused Porous SERS (SLIPSERS)}}）<ref>{{Cite journal|title=Ultrasensitive surface-enhanced Raman scattering detection in common fluids|url=http://www.pnas.org/content/113/2/268|last=Yang|first=Shikuan|last2=Dai|first2=Xianming|date=2016-01-12|journal=Proceedings of the National Academy of Sciences|issue=2|doi=10.1073/pnas.1518980113|volume=113|pages=268–273|language=en|issn=0027-8424|pmc=4720322|pmid=26719413|last3=Stogin|first3=Birgitt Boschitsch|last4=Wong|first4=Tak-Sing|access-date=2017-05-02|archive-date=2020-06-27|archive-url=https://web.archive.org/web/20200627135208/https://www.pnas.org/content/113/2/268|dead-url=no}}</ref>的研究进一步支持了电磁理论<ref>{{Cite web|url=http://www.kurzweilai.net/single-molecule-detection-of-contaminants-explosives-or-diseases-now-possible|title=Single-molecule detection of contaminants, explosives or diseases now possible KurzweilAI|accessdate=2017-05-02|last=http://helldesign.net|work=www.kurzweilai.net|language=en-US|archive-date=2021-01-26|archive-url=https://web.archive.org/web/20210126140807/https://www.kurzweilai.net/single-molecule-detection-of-contaminants-explosives-or-diseases-now-possible|dead-url=no}}</ref>。
===電磁理論===
當特定表面的[[電場]]加強時，物質[[吸附]]在該平面上的[[拉曼光譜學|拉曼光譜]]的強度會增加。當一束光打至金屬表面，被擊中的金屬表面將會激發出[[電漿子]]。另外，只有當電漿子的震動方向與金屬表面垂直時才會發生拉曼散射；反之，拉曼散射不會發生。因此，表面增強拉曼光譜(SERS)實驗需要使用粗糙的金屬表面或者使用經過排列的[[纳米微粒]](nano-particle)才能有效地加強拉曼光譜。

===化學理論===

==应用==
银纳米棒制备的表面增强拉曼光谱的底物被用于检测低丰度的[[生物分子]]的存在，因此可以检测体液中的[[蛋白质]]<ref>Rapid Identification by Surface-Enhanced Raman Spectroscopy of Cancer Cells at Low Concentrations Flowing in a Microfluidic Channel
Alessia Pallaoro, Mehran R. Hoonejani, Gary B. Braun, Carl D. Meinhart, and Martin Moskovits
ACS Nano 2015 9 (4), 4328-4336
DOI: 10.1021/acsnano.5b00750</ref><ref>{{cite journal|last=Yang|first=J|display-authors=etal|title=Surface-Enhanced Raman Spectroscopy Based Quantitative Bioassay on Aptamer-Functionalized Nanopillars Using Large-Area Raman Mapping|journal=ACS Nano|date=May 2013|volume=7|issue=6|pages=5350–5359|url=http://www.silmeco.com/media/10763/ACSNano-SERS-large-area-mapping.pdf|doi=10.1021/nn401199k|author=|access-date=2017-04-25|archive-url=https://web.archive.org/web/20160304031326/http://www.silmeco.com/media/10763/ACSNano-SERS-large-area-mapping.pdf|archive-date=2016-03-04|dead-url=yes}}</ref><ref name="Han 2014">{{cite journal|last=Han|first=YA|author2=Ju J |author3=Yoon Y |author4=Kim SM |title=Fabrication of cost-effective surface enhanced Raman spectroscopy substrate using glancing angle deposition for the detection of urea in body fluid|journal=Journal of Nanoscience and Nanotechnology|date=May 2014|volume=14|issue=5|pages=3797–9|doi=10.1166/jnn.2014.8184 |pmid=24734638}}</ref><ref name="Li 2014">{{cite journal|last=Li|first=D|author2=Feng S |author3=Huang H |author4=Chen W |author5=Shi H |author6=Liu N |author7=Chen L |author8=Chen W |author9=Yu Y |author10=Chen R |title=Label-free detection of blood plasma using silver nanoparticle based surface-enhanced Raman spectroscopy for esophageal cancer screening|journal=Journal of Nanoscience and Nanotechnology|date=March 2014|volume=10|issue=3|pages=478–84|doi=10.1166/jbn.2014.1750 |pmid=24730243}}</ref>。该技术已用于检测[[尿素]]和游离在人[[血清]]中的[[血浆]]标签，并且可以成为[[癌症]]检测和筛选下一代技术<ref name="Han 2014" /><ref name="Li 2014" />。表面增强拉曼光谱具有的分析纳米尺度混合物的组成的能力，使其应用于[[环境分析]]、[[药学]]、[[材料科学]]、[[艺术]]和[[考古]]研究、[[法医学]]、[[药物]]和[[爆炸物]]检测、[[食品质量]]分析<ref>Andreou, C., Mirsafavi, R., Moskovits, M., & Meinhart, C. D. (2015). Detection of low concentrations of ampicillin in milk. The Analyst, 140(15), 5003–5005. doi:10.1039/c5an00864f</ref>和单藻类细胞的检测<ref>{{cite journal|last=Deng|first=Y|author2=Juang Y |title=Black silicon SERS substrate: Effect of surface morphology on SERS detection and application of single algal cell analysis|journal=Biosensors and Bioelectronics|date=March 2014|volume=53|pages=37–42|url=http://dx.doi.org/10.1016/j.bios.2013.09.032|doi=10.1016/j.bios.2013.09.032}}</ref><ref>{{cite techreport |first=Eric |last=Hoppmann |display-authors=etal |title=Trace detection overcoming the cost and usability limitations of traditional SERS technology |institution=Diagnostic anSERS |date=2013 |url=https://www.diagnosticansers.com/documentation/P-SERS-Whitepaper-v1.0.pdf |access-date=2017-04-25 |archive-url=https://web.archive.org/web/20160305081044/https://www.diagnosticansers.com/documentation/P-SERS-Whitepaper-v1.0.pdf |archive-date=2016-03-05 |dead-url=yes }}</ref><ref>{{cite journal|journal=Applied Optics|doi=10.1364/AO.49.004362|author1=Wackerbarth H|author2=Salb C|author3=Gundrum L|author4=Niederkrüger M|author5=Christou K|author6=Beushausen V|author7=Viöl W|title=Detection of explosives based on surface-enhanced Raman spectroscopy|date=2010|volume=49|issue=23|pages=4362–4366|url=https://www.osapublishing.org/ao/abstract.cfm?uri=ao-49-23-4362|16=|access-date=2017-04-25|archive-date=2018-06-01|archive-url=https://web.archive.org/web/20180601231946/https://www.osapublishing.org/ao/abstract.cfm?uri=ao-49-23-4362|dead-url=no}}</ref>。表面增强拉曼光谱与等离子体传感结合，可用于生物分子相互作用的高灵敏度的定量检测<ref name="Nanoscale2016">{{cite journal|last1=Xu|first1=Zhida|last2=Jiang|first2=Jing|last3=Wang|first3=Xinhao|last4=Han|first4=Kevin|last5=Ameen|first5=Abid|last6=Khan|first6=Ibrahim|last7=Chang|first7=Te-Wei|last8=Liu|first8=Logan|title=Large-area, uniform and low-cost dual-mode plasmonic naked-eye colorimetry and SERS sensor with handheld Raman spectrometer|journal=Nanoscale|date=2016|volume=8|pages=6162–6172|doi=10.1039/C5NR08357E|url=http://pubs.rsc.org/en/content/articlelanding/2016/nr/c5nr08357e#!divAbstract|access-date=2017-04-25|archive-date=2018-09-20|archive-url=https://web.archive.org/web/20180920014647/http://pubs.rsc.org/en/Content/ArticleLanding/2016/NR/C5NR08357E#!divAbstract|dead-url=no}}</ref>。
==参考文献==
{{reflist}}
[[分类:表面化学]]
[[分类:拉曼光谱学]]