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    Surface Enhanced Raman

    Spectroscopy

    Presented by: Eden Almakias

    CHEM 495

    March 21st 2016

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    Presentation Outline

    Introduction and background information

    SERS theory

     Applications of SERS

    Conclusions

    References

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    Basics of Raman Spectroscopy

    Raman spectroscopy is a technique which uses in

    scattering to obtain information about molecular st

    Incident light interacts with the analyte electron clo

    momentarily exciting the molecule to a “virtual” sta

     As light scatters off the molecule, some energy is

    gained), resulting in a shift in the wavelength (Ram

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    The Raman Effect: A Unified Treatment of the Theory of Raman Scattering by Mole

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    http://bwtek.com/raman-theory-of-raman-scattering/ 

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    The Raman Effect: A Unified Treatment of the Theory of Raman Scattering by Mole

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    History of Raman Spectroscopy

    In the mid-1920’s Indian physicists C.V. Raman and K.

    used simple experiments to investigate light scattering

    They observed that a portion of the scattered light was

    lower energy (colour change).

    This phenomenon occurred consistently in approximat

    different liquids investigated.

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    Initial experiments using sunlight and visual observatio

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    C.V. Raman with his quartz spectrograph

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    The Raman Effect: A Unified Treatment of the Theory of Raman Scattering by Mole

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    http://chemwiki.ucdavis.edu/Core/Physical_Chemistry/Spectroscopy/Vibrational_Spectroscopy/Ram

    scopy/Resonant_vs._Nonresonant_Raman_Spectroscopy 

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    What is SERS?

    The Raman effect is relatively weak since only ≈ 1

    photons scatter inelastically.

    By using a metal (usually Ag or Au) surface, the in

    Raman signals are greatly enhanced (up to a facto

    This technique therefore counteracts one of the w

    of Raman spectroscopy (low sensitivity).

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    Discovery of SERS

    SERS was first observed by Martin Fleischmann,

    Hendra and A. J. McQuillan at the University of So

    (1973).

    The original purpose of their research was to inves

    adsorption of pyridine on a roughened silver electr

    Raman spectroscopy.

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    Principles of Surface-Enhanced Raman Spectroscopy Eric C. Le Ru and Pablo G. E

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     Abstract of original paper describing SERS.

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    Explanation for SERS effect

    The researchers attributed the enhanced intensity to th

    surface area of the silver electrode.

    In 1977, two research groups independently calculated

    surface area cannot account for the observations.

    One group proposed an electromagnetic enhancemen

    other proposed a chemical enhancement (still under de

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    Principles of Surface-Enhanced Raman Spectroscopy Eric C. Le Ru and Pablo G. E

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    Factors influencing Enhancement

    µ = E ·α

    Magnitude of induced

    dipole in scattering

    molecule Magnitude of the

    applied electric field

    Polariza

    scatterin

    Determines intensity

    of Raman signalInfluenced by local

    electromagnetic

    environment

    Intrinsic pro

    scattering m

    (bond leng

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    The Raman Effect: A Unified Treatment of the Theory of Raman Scattering by Mole

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    Chemical Enhancement

    Chem. Soc. Rev

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    Electromagnetic Enhancement

    Incoming light of the appropriate frequency is able

    a localized surface plasmon resonance (LSPR) in

    surface.

    This local electric oscillation supplements the elec

    the incoming radiation and increases the magnitud

    field experienced by the scattering molecule.

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    Principles of Surface-Enhanced Raman Spectroscopy Eric C. Le Ru and Pablo G. E

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     Angew. Chem. In

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    19 SERS S b t t

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    19 SERS Substrates

     Anal Bioanal

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    Illustration of SERS effect: Single Molecule Detectio

    rhodamine 6G

    Principles of Surface-Enhanced Raman Spectroscopy Eric C. Le Ru and Pablo G. E

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     Application of SERS: monitoring of chem

    syntheses in micro-droplets

    Researchers at the university of Leipzig used SER

    monitor dynamic chemical processes in a microflu

    The reaction which they investigated was the Han

    synthesis of 2-aminothiazoles.

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    Chem. Commun

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    Chem. Commun

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    By monitoring the characteristic Ram

    reactants and products the research

    follow the progress of the reaction as

    Chem. Commun

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     Application of SERS: A ultrasensitive an

    method for the quantitation of hydrazine

    Hydrazine is a highly toxic compound used in man

    processes including the synthesis of pesticides an

    pharmaceuticals (120,000 tons produced annually

    Researchers at the university of Notre Dame used

    develop a method for the detection and quantificat

    hydrazine at a sub-nanomolar level.

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     Anal. Ch

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     Anal. Ch

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     Anal. Ch

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     Anal. Ch

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     Application of SERS: A platform for the

    of cancer cells (SERS-microscopy)

    Researchers at the university of Osnabruck have d

    gold nanoparticles wrapped with a SERS active se

    monolayer.

    By coating these particles with silica and conjugat

    antibodies, the particles were able to image the lo

    p63 (tumor suppressor) in prostate biopsies.

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    J. Biophotonics

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    J. Biophotonics

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    J. Biophotonics

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    J. Biophotonics

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    J. Biophotonics

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    Conclusions

    SERS is a very versatile and effective tool which can bmany different areas of research.

    Since it is a relatively new technique, there are still are

    be optimized (e.g. design of better substrates and rep

    molecules)

    Current trends in research show that SERS will definite

    as researchers explore its potential.

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     Anal Bioanal

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    R f

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    References

    1) The Raman Effect: A Unified Treatment of the Theory of Raman Scattering by Molecules. Derek A

    2) http://www.acs.org/content/dam/acsorg/education/whatischemistry/landmarks/ramaneffect/the-ra

    commemorative-booklet.pdf 

    3) Principles of Surface-Enhanced Raman Spectroscopy Eric C. Le Ru and Pablo G. Etchegoin

    4) Chem. Commun., 2015, 51, 8588—8591

    5)  Anal. Chem. 2015, 87, 6460−6464

    6) J. Biophotonics 4, No. 6, 453 –463 (2011)

    7)  Anal Bioanal Chem (2012) 403:27 –54

    http://www.acs.org/content/dam/acsorg/education/whatischemistry/landmarks/ramaneffect/the-raman-effect-commemorative-booklet.pdfhttp://www.acs.org/content/dam/acsorg/education/whatischemistry/landmarks/ramaneffect/the-raman-effect-commemorative-booklet.pdfhttp://www.acs.org/content/dam/acsorg/education/whatischemistry/landmarks/ramaneffect/the-raman-effect-commemorative-booklet.pdfhttp://www.acs.org/content/dam/acsorg/education/whatischemistry/landmarks/ramaneffect/the-raman-effect-commemorative-booklet.pdf