Surface Enhanced Raman

Spectroscopy
Presented by: Eden Almakias
CHEM 495
March 21st 2016

Presentation Outline
Introduction and background information
SERS theory
Applications of SERS
Conclusions
References

Basics of Raman Spectroscopy

Raman spectroscopy is a technique which uses inelastic light
scattering to obtain information about molecular structures.

Incident light interacts with the analyte electron cloud,

momentarily exciting the molecule to a virtual state.

As light scatters off the molecule, some energy is lost (or

gained), resulting in a shift in the wavelength (Raman shift).

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

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

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

History of Raman Spectroscopy

In the mid-1920s Indian physicists C.V. Raman and K.S. Krishnan
used simple experiments to investigate light scattering in liquids.

They observed that a portion of the scattered light was shifted to a

lower energy (colour change).
This phenomenon occurred consistently in approximately 60 of the
different liquids investigated.

Initial experiments using sunlight and visual observation

C.V. Raman with his quartz spectrograph

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

http://chemwiki.ucdavis.edu/Core/Physical_Chemistry/Spectroscopy/Vibrational_Spectroscopy/Raman_Spectro
scopy/Resonant_vs._Nonresonant_Raman_Spectroscopy

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What is SERS?
The Raman effect is relatively weak since only 1/106
photons scatter inelastically.

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

Raman signals are greatly enhanced (up to a factor of 1011).

This technique therefore counteracts one of the weak points

of Raman spectroscopy (low sensitivity).

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Discovery of SERS
SERS was first observed by Martin Fleischmann, Patrick J.
Hendra and A. J. McQuillan at the University of Southampton

(1973).
The original purpose of their research was to investigate the
adsorption of pyridine on a roughened silver electrode using
Raman spectroscopy.

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

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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 the large
surface area of the silver electrode.

In 1977, two research groups independently calculated that the

surface area cannot account for the observations.
One group proposed an electromagnetic enhancement while the
other proposed a chemical enhancement (still under debate).

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

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Factors influencing Enhancement

=E
Magnitude of induced
dipole in scattering
molecule

Determines intensity
of Raman signal

Polarizability tensor of
scattering molecule
Magnitude of the
applied electric field

Influenced by local
electromagnetic
environment

Intrinsic property of the

scattering molecule
(bond lengths, density etc)

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

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Chemical Enhancement

Chem. Soc. Rev., 2012, 41, 70857107

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Electromagnetic Enhancement
Incoming light of the appropriate frequency is able to produce
a localized surface plasmon resonance (LSPR) in the metal

surface.
This local electric oscillation supplements the electric field of
the incoming radiation and increases the magnitude of the
field experienced by the scattering molecule.

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

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Angew. Chem. Int. Ed. 2014, 53, 2 42

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SERS Substrates

Anal Bioanal Chem (2012) 403:2754

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Illustration of SERS effect: Single Molecule Detection

rhodamine 6G

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

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Application of SERS: monitoring of chemical

syntheses in micro-droplets
Researchers at the university of Leipzig used SERS to
monitor dynamic chemical processes in a microfluidic device.

The reaction which they investigated was the Hantzsch

synthesis of 2-aminothiazoles.

Chem. Commun., 2015, 51, 85888591

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Chem. Commun., 2015, 51, 85888591

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By monitoring the characteristic Raman peaks of the

reactants and products the researchers were able to
follow the progress of the reaction as a function of time

Chem. Commun., 2015, 51, 85888591

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Application of SERS: A ultrasensitive analytical

method for the quantitation of hydrazine
Hydrazine is a highly toxic compound used in many industrial
processes including the synthesis of pesticides and

pharmaceuticals (120,000 tons produced annually) .

Researchers at the university of Notre Dame used SERS to
develop a method for the detection and quantification of
hydrazine at a sub-nanomolar level.

Anal. Chem. 2015, 87, 64606464

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Anal. Chem. 2015, 87, 64606464

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Anal. Chem. 2015, 87, 64606464

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Anal. Chem. 2015, 87, 64606464

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Application of SERS: A platform for the imaging

of cancer cells (SERS-microscopy)
Researchers at the university of Osnabruck have developed
gold nanoparticles wrapped with a SERS active self assemble

monolayer.
By coating these particles with silica and conjugating anti-p63
antibodies, the particles were able to image the locations of
p63 (tumor suppressor) in prostate biopsies.

J. Biophotonics 4, No. 6, 453463 (2011)

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J. Biophotonics 4, No. 6, 453463 (2011)

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J. Biophotonics 4, No. 6, 453463 (2011)

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J. Biophotonics 4, No. 6, 453463 (2011)

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J. Biophotonics 4, No. 6, 453463 (2011)

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Conclusions
SERS is a very versatile and effective tool which can be used in
many different areas of research.

Since it is a relatively new technique, there are still areas which can
be optimized (e.g. design of better substrates and reporter
molecules)

Current trends in research show that SERS will definitely develop

as researchers explore its potential.

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Anal Bioanal Chem (2012) 403:2754

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References
1) The Raman Effect: A Unified Treatment of the Theory of Raman Scattering by Molecules. Derek A. Long
2) http://www.acs.org/content/dam/acsorg/education/whatischemistry/landmarks/ramaneffect/the-raman-effect-

commemorative-booklet.pdf
3) Principles of Surface-Enhanced Raman Spectroscopy Eric C. Le Ru and Pablo G. Etchegoin
4) Chem. Commun., 2015, 51, 85888591

5) Anal. Chem. 2015, 87, 64606464

6) J. Biophotonics 4, No. 6, 453463 (2011)
7) Anal Bioanal Chem (2012) 403:2754