View O'Donnell Surface‐Enhanced Raman Spectroscopy Presentation
Transcript of View O'Donnell Surface‐Enhanced Raman Spectroscopy Presentation
Surface Enhanced Raman Spectroscopy (SERS) and Databases
for the Characterization of Dyes
Deanna O’Donnell, Ph.D.
The following research was conducted at
City College of New YorkMetropolitan Museum of Art
New York, NY
Trace Evidence SymposiumKansas City, Missouri
August 11th, 2011
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Research Objectives• To validate SERS in a forensic context, and show the conditions under which
Raman spectroscopy and especially SERS contribute to the value of forensic science.
• To compare both SERS and normal Raman spectra, and to explore the conditions in which each may be of value.
• To validate certain specialized SERS techniques
• To provide useful protocols for use of field workers
• To provide a searchable database for rapid and reliable field use.
Patrick Buzzini - Forensic & Investigative Science Program,West Virginia University
Marco Leona - The Metropolitan Museum of Art, New YorkPhilip Antoci - NYPD Crime LaboratoryJohn Lombardi - Center for the Analysis of Structures and Interfaces,
City College of New York 2
Principle Investigators (left to right):
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Why Raman Spectroscopy?
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Anti-Stokes
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Stokes
Raman Shift cm-1
Stokes and Anti-stokes Raman Spectrum of CCl4
217 cm-1 312 cm-1 460 cm-1
E1
E0
StokesScattering
Anti-StokesScattering
RayleighScattering
0- mn 0+ mn0
virtualstates
mn mn
Em m
Em nmn
IR Absorption
Raman is non-destructive and allows in-situ detectionRaman spectra may readily be obtained in aqueous solution (not possible with IR)
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Why Raman Spectroscopy?
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Anti-Stokes
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Stokes
Raman Shift cm-1
Stokes and Anti-stokes Raman Spectrum of CCl4
217 cm-1 312 cm-1 460 cm-1
E1
E0
StokesScattering
Anti-StokesScattering
RayleighScattering
0- mn 0+ mn0
virtualstates
mn mn
Em m
Em nmn
IR Absorption
Raman is non-destructive and allows in-situ detectionRaman spectra may readily be obtained in aqueous solution (not possible with IR)
However…..Normal Raman intensity is weak & fluorescence can contaminate spectrum
Solution!!Surface Enhanced Raman Scattering (SERS)
Surface Enhanced Raman Spectroscopy (SERS)
Silver Particle
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Molecule in solution
Silver Particle
Molecules on silver surface
Surface Plasmon Resonance
Advantages:• Highly sensitive: Very large enhancements of the Raman signal. This
enables us to detect and identify extremely small quantities of trace chemicals.
• Suppresses fluorescence: Suppression of fluorescence interference, which normally makes such identification impossible.
• Type of metal nanoparticle; usually silver• Size and shape of particle• Excitation wavelength• Presence of ions such as Cl -, SO4
2-, NO3- enhanced electric field
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Surface Enhanced Raman Spectroscopy (SERS)
Factors that alter SERS intensity:
Silver Particle
Molecules on silver surface
Surface Plasmon Resonance
Advantages:• Highly sensitive: Very large enhancements of the Raman signal. This
enables us to detect and identify extremely small quantities of trace chemicals.
• Suppresses fluorescence: Suppression of fluorescence interference, which normally makes such identification impossible.
• Type of metal nanoparticle; usually silver• Size and shape of particle• Excitation wavelength• Presence of ions such as Cl -, SO4
2-, NO3- enhanced electric field
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Surface Enhanced Raman Spectroscopy (SERS)
Factors that alter SERS intensity:
SERS has its own set of challenges…• small number of compounds studied so far• large difference in SERS efficiency even for closely
related compounds• lack of searchable databases• interferences due to impurities or matrix components
(not a separation technique)• SERS still requires removing a sample - however
microscopic - from the object under analysis
Instrumentation
The Metropolitan Museum of Art
City College of New York
488nm, 633 nm and 785 nm
488nm, 514 nm, 633 nm and 785 nm
488nm, 514 nm, 593 nm, 633 nm
and 785 nmTi-sapphire laser
Dye laser
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x and y focus
stage
objective
cutoff filterwavelength
specific
z focuscourse/fine
DETECTORSOURCE
488 nm514.5 nm632.8 nm785 nm
Raman Microscope
Basic Steps to SERS
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5 l of Ag colloids 1 l of 10-4-10-7 M aqueous dye
1 l of 0.5-0.1 M aggregate
Current Research Projects
• Need ways to acquire trace amounts of analyte in a “non-destructive manner”Gel Extraction
• Need a reliable substrate to yield reproducible spectraSERS substrate
Developing Methods Applications
• Art History/Conservation
Xanthene Dyes
• Forensic Science: Controlled Substances
SERS + Amphetamine
• Forensic Science/Anthropology
SERS of Tattoo Inks
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Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos
Gel Extraction Method
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GOAL: Develop Non-Destructive Gel Extraction Method
Idea
• Ink or dye can be extracted from a medium using a hydroxy gel
• The gel extracts such a small amount of dye that it leaves the test subject virtually unchanged
o Important in trace analysis
• The extracted dye can then be analyzed and identified using normal Raman spectroscopy or SERS
Model System
• Ball Point Pen Ink on Whatman FilterPaper
Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos
Gel Extraction Method
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Questioned Document Extraction Materials
Gel in extraction
solvent(1% EDTA in
a 1:1 H2O and DMF)
Gel Size
1 mm
Position of the Gel
Gel
Microscope Slide
Gel, post extraction
Area of Analysis
Before
After
Gel with 5 l Ag NPsAg NPs
Dispersive Raman Scope
Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos
Gel Extraction Method
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SERS spectrum of Extracted Ink on hydroxy gel
Identification of Ink Component
Pen Extract
Methyl Violet
Multiple Extractions from Same Sample Area
First Extraction
Second Extraction
Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos
Conclusion• The gel extraction method is a fast, simple, versatile, and non
destructive method for extracting inks and dyes • Coupled with SERS, it becomes a powerful tool for chemical
analysis
Nondestructive Identification of Natural and Synthetic Organic Colorants in Works of Art by Surface Enhanced Raman Scattering, Leona, M.; Decuzzi, P.; Kubic, T.A.; Gates, G.; Lombardi , J.R., Anal. Chem., 2011, 83(11), 3990–3993.
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GOAL: Produce and Characterize Reproducible/Stable Ag surface for SERS
Historic Method:Lee-Miesel Silver NPs (AgNO3 + citrate)
broad absorption (FWHM > 120nm)broad size distribution (3 - 50 nm)not stable over time
Our Method:Microwave Reduction (Ag2SO4 + glucose + citrate)
narrow absorption (FWHM ~ 50 nm)narrow size distribution (3 - 10 nm)stable over 5 - 12 monthsreproducible SERS spectra over time
Refining SERS TechniqueMicrowave Silver NPs
AgNO3 (aq) + citrate Ag 0 Ag Nanoparticles (NP) oxidizing
agent
reducing agent
one hour
Ag2SO4 (aq) + sugar (+ citrate) Ag 0 Ag NP
90 sec
oxidizing agent
reducing agent
Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos
Leona, M., PNAS, 2009, 106 (35), 14757-14762
Lee, P.C.; Meisel, D., J. Phys. Chem., 1982, 86, 3391-3395.
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Historic Method:Lee-Miesel Silver NPs (AgNO3 + citrate)
broad absorption (FWHM > 120nm)broad size distribution (3 - 50 nm)not stable over time
Our Method:Microwave Reduction (Ag2SO4 + glucose)
narrow absorption (FWHM ~ 50 nm)narrow size distribution (3 - 10 nm)stable over 5 - 12 monthsreproducible SERS spectra over time
Microwave Silver NPs
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Wavelength nm
via microwave reduction
with AgSO4
via Lee-Miesel method
with AgNO3
lmax = 400 nmFWHM = 56 nm
lmax = 422 nmFWHM = 125 nm
Lee-MieselAgNO3
MicrowaveAg2SO4
Lee-Miesel
MicrowaveAg2SO4
Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos
Microwave Silver
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SERS Model System:4-mercaptopyridine
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Different Lots of Particles
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Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos
SERS of Various Dyes Classes
Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos
Dye Class Publication
Protoberberines
Arylmethane
Surface-enhanced Raman Spectroscopy study of the red dye laccaic acidCañamares, M.V., et al., J. Raman Spectrosc., 2007, 38, 1259-1266.
Surface Enhanced Raman Spectroscopy of Indanthrone and FlavanthroneChang, J.; et al., J. Raman Spectrosc., 2009, 40, 1557-1563.
Raman and Surface Enhanced Raman Spectra of Flavone and Several Hydroxy-Derivatives
Teslova, T.; et al., J. Raman Spectroscopy, 2007, 38, 802-818.
Raman and Surface Enhanced Raman Spectra of Chrysin, Apigenin and LuteolinCorredor, C.; et al., Vibrational Spectroscopy, 2009, 49, 190-195.
Raman and Surface Enhanced Raman Spectra of 7 and 3’,4’ HydroxyflavoneCañamares, M.V.; et al., Journal of ePreservationScience (Proceedings of the IRUG-8, Vienna Austria, Conference), 2009, 6, 81-88.
DFT, SERS, and Single Molecule-SERS of Crystal VioletCañamares, M.V.; et al., J. Phys. Chem. C, 2008, 112, 20295-20300.
Application of Raman spectroscopy and surface-enhanced Raman scattering to the analysis of synthetic dyes found in ballpoint pen ink
Geiman, I.; et al., J. Forensic Sci., 2009, 54, 947-952.
Surface-enhanced Raman scattering of protoberberine alkaloidsCañamares, M.V.; et al., J. Raman Spectrosc., 2008, 39, 1907-1914.
Flavones
Anthraquinones
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Art History Application
• Want to Identify Dyes in Art
o Art Conservation
o Art History
o Archeology
• large number of dye classes
o we have investigated 10 dyes classes (75 dyes total)
• Van Gogh was known to use Xanthene Dyes
GOAL: Characterize SERS spectrum of Halogenated Xanthene Dyes
FlouresceinFrom Xanthene Dye Family
Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos
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Xanthene Dyes: A Spectroscopic Study
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Eythrosine
Rose Bengal
Eosine
Phloxine
Fluorescein
Research Strategy:
Acquire normal Raman spectrum of each dye
Acquire SERS spectrum of each dye
laser
solid dye
solid dye
Ag NP(aq)
laser
dye on Ag(aq)
normal Raman
spectrum
SERSspectrum
Assign Raman Bands to Vibrational Modes
Generate SERS Library
Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos
SERS spectra
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Xanthene Dyes: A Spectroscopic Study
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Eosine
Erythrosine
Phloxine
Rose Bengal
Raman Shift cm-1
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Raman Shift cm-1
flourscein
eosine
erythrosine
phloxine
rosebengal
Normal Raman spectra
• Spectra varies upon Halogenation• Should be able to differentiate in
mixtures
Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos
Surface-Enhanced Raman Scattering of Phenethylamines
Ecstacy
Phenethylamine
Over 175 different Phenethylamines
Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos
The METH makeover
Previous SERS work on Controlled Substances:“Surface-Enhanced Raman Spectroscopy for Trace Identification of Controlled Substances: Morphine, Codeine, and Hydrocodone”Rana, V.; Cañamares, M.V.; Kubic, T.; Leona, M.; Lombardi, J.R.; Journal of Forensic Sciences, 2010, 55(1), 200-207.
wide variety of therapeutic classes, including but not limited to..
• appetite depressants• vascoconstrictors• psychotropic drugs • bronchodilators
• antidepressants• Antiparkinson agents• neurotransmitters 21
SERS of Phenethylamines
Research Strategy:
Acquire normal Raman spectrum of Phenethylamines
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GOAL: Acquire SERS of Amphetamines for trace analysis
Phenethylamine
MDMA (Ecstasy)
Ephedrine
Amphetamine
Methamphetamine
Acquire SERS spectrum of Phenethylamines, refining experimental conditions
laser
solid drug
solid drug
Ag NP(aq)
laser
drug on Ag(aq)
normal Raman
spectrum
SERSspectrum
Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos
Normal Raman and SERS of Phenethylamine
Phenethylamine
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SERS Phenethylamine 1
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Raman Shift cm-1
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Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos
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Raman Shift cm-1
MDMA
Ephedrine
Methamphetamine
Amphetamine
Phenethylamine
SERS of Phenethylamine
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Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos
Surface-Enhanced Raman Scattering of MDMA (Ecstasy) and AnalogsTaplin, F.; O’Donnell, D.; Kubic, T.; Leona, M.; Lombardi, J.R., Forensic Science International - submitted
Raman Scattering of Tattoo Inks
Pulled from the Headlines….
Worst tattoo ever? Amateur pranks friend by giving him obscene ink instead of yin-yang he asked forNY DAILY NEWSTuesday, October 26th 2010, 4:28 PM
Anthropological Implications
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Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos
Extraction Method Separation Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos
GOAL: Acquire SERS of Tattoo Inks
Raman Scattering of Tattoo Inks
Skin Candy (17)- USA
Iron Works Brasil (10)- Brazil
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• Most work on Tattoo inks in the past have used Absorption Spectroscopy, IR, XRD and SEM.
• Some work has been done using Dispersive Raman looking at carbonous materials in tattoos*
* Poon, K.; I. Dadour, I.; McKinley, A., J. of Raman Spectroscopy, 2008, 39, 1227-1237.
Poon, K.W.C., M.S./Ph.D. Thesis, The University of Western Australia, 2008.
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RAW DATARed Region (785nm)
RAW DATABlue Aggregate (785nm)
50x
Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos
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Vermelho-Iron Works BrasilIngredients (according to packaging; translated): toxic pigment (mineral/organic) deionized water, surfactant, humectant, preservativeNOTE: No color information provided
Tattoo Inks - Normal Raman Spectra
Overlay of Normal Raman Spectra to demonstrate differences
Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos
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A Closer Look at the Red Aggregate
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Raman Shift cm-1
Experimental Normal Raman Spectrum
Literature Normal Raman SpectrumPigment Red 170CI 12475
Scherrer, N., Z., et al., Spectrochimica Acta Part A, 2009, Vol. 73, 505-524.
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Of the 38 major bands in Pigment Red 170, the red aggregate matched 30 bands
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Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos
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A Closer Look at the Blue Aggregate
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Raman Shift cm-1
Of the 22 major bands in Pigment Blue 15:2, the blues aggregate matched 17 bands
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Pigment Blue 15:2C.I 74160
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Scherrer, N., Z., et al., Spectrochimica Acta Part A, 2009, Vol. 73, 505-524.
Experimental Normal Raman Spectrum
Literature Normal Raman Spectrum
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633 nm 785 nm
Razberry CreemSkin Candy
Pigment Red 122
Normal Dispersive Raman Spectrum excited at 488 nm
Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos
SERS of Tattoo Inks
• High Fluorescence in Background• Pigment not identifiable by Normal
Dispersive Raman
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Razberry CreemSkin Candy
Pigment Red 122
SERS Spectrum excited at 488nm
Note: Enhancement of three weak bands ( 1568, 1316 and 1238 cm-1) and additional peaks resolved
Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos
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SERS Spectrum of Pigment Red 122488nm
SERS Spectrum of Razberry Creem (Skin Candy)488nm
Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos
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Research Summary
Gel Extraction• Successfully extract and identify
trace amounts• Methodology is system specificSERS substrate• Ag NP synthesis by microwave
reduction yields reliable,reproducible surface
• Stable for at least 5 months
Developing Methods ApplicationsXanthene Dyes• Developing SERS Library• Future Work: MixturesSERS + Phenethylamine• 5 Phenethylamines characterizedSERS of Tattoo Inks• Tattoo Inks are heterogeneous,
present challenge• Work is ongoing
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TLC + SERS
• SERS can improve detection limit beyond visible detection
• Separation and Identification of complex mixtures
SERS of Dye/Drug mixtures
• Engineered Mixtures and Real Samples
Other Areas of Research
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AcknowledgmentsProf. John Lombardi – research advisor (CCNY)
Dr. Marco Leona – research advisor (Metropolitan Museum of Art)
Patrick Buzzini - collaborator (West Virginia University)
Phillip Antoci - collaborator (NYPD Crime Labs)
Current StudentsDane Christie – Undergraduate student (CCNY)
Federica Pozzi - Graduate Student (Metropolitan Museum of Art)Francis Taplin – Graduate student (John Jay)
Peter Decuzzi – Graduate student (John Jay)
Michelle Miranda – Graduate student (John Jay)Kathryn Luppino - Undergraduate student (CCNY)
Yi Pan – Graduate student (CCNY)
Former StudentsDr. Richard Livingstone – Graduate studentLoes Vermeij – Undergraduate student
Elizabeth Sefton – Undergraduate student, WVU
Chara Themistokleous – Undergraduate student
Faiza Anwar – Graduate student
FundingDepartment of Justice (Award Number: 2009-DN-BX-K185)Center for Exploration of Nanostructures in Sensors and Energy Systems (CENSES)
TLC + SERS and Ag NP Gel Extraction
Phenethylamines
Xanthene Dyes
Tattoo Inks