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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. Trace Evidence Symposium Kansas City, Missouri August 11th, 2011 The following research was conducted at City College of New York Metropolitan Museum of Art New York, NY 1 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. Principle Investigators (left to right): Patrick Buzzini - Forensic & Investigative Science Program, West Virginia University Marco Leona - The Metropolitan Museum of Art, New York Philip Antoci - NYPD Crime Laboratory John Lombardi - Center for the Analysis of Structures and Interfaces, 2 City College of New York Why Raman Spectroscopy? Raman is non-destructive and allows in-situ detection Raman spectra may readily be obtained in aqueous solution (not possible with IR) Stokes and Anti-stokes Raman Spectrum of CCl4 virtual states o 0+ mn 0 Stokes mn Stokes Scattering 217 cm-1 mn mn Rayleigh Scattering - 217 - 312 312 217 460 Em E1n Em E0m Anti-Stokes Anti-Stokes Scattering 312 cm-1 IR Absorption 600 400 200 0 - 460 0- mn -200 -400 -600 -1 Raman Shift cm 460 cm-1 3 Why Raman Spectroscopy? Raman is non-destructive and allows in-situ detection Raman spectra may readily be obtained in aqueous solution (not possible with IR) Stokes and Anti-stokes Raman Spectrum of CCl4 virtual states o Stokes Anti-Stokes Normal Raman intensity is weak & fluorescence can contaminate spectrum mn mn Solution!! Rayleigh Stokes Scattering 217 cm-1 - 217 - 312 mn IR Anti-Stokes Scattering Scattering Surface Enhanced RamanAbsorption Scattering 312 cm-1 600 400 200 0 - 460 However….. 0+ mn 312 217 Em E1n Em E0m 0 460 0- mn -200 -400 -600 -1 (SERS) Raman Shift cm 460 cm-1 4 Surface Enhanced Raman Spectroscopy (SERS) Molecule in solution Silver Particle 5 Surface Enhanced Raman Spectroscopy (SERS) Surface Plasmon Resonance Molecules on silver surface Silver Particle 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. Factors that alter SERS intensity: • 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 6 Surface Enhanced Raman Spectroscopy (SERS) Surface Plasmon Resonance Molecules on silver surface Silver Particle SERS has its own set of challenges… • small number of compounds studied so far Advantages: • large difference in SERS efficiency even for closely • Highly sensitive: Very large enhancements of the Raman signal. This related compounds enables us to detect and identify extremely small quantities of trace • lack of searchable databases chemicals. • interferences dueSuppression to impurities or components • Suppresses fluorescence: ofmatrix fluorescence interference, (not a separation technique) impossible. which normally makes such identification • SERS still requires removing a sample - however Factors that alter SERS microscopic intensity: - from the object under analysis • Type of metal nanoparticle; usually silver • Size and shape of particle • Excitation wavelength enhanced electric field • Presence of ions such as Cl -, SO4 2-, NO37 Instrumentation City College of New York 488nm, 514 nm, 633 nm and 785 nm 488nm, 633 nm and 785 nm 488nm, 514 nm, 593 nm, 633 nm and 785 nm Ti-sapphire laser Dye laser The Metropolitan Museum of Art 8 Basic Steps to SERS 5 l of Ag colloids 1 l of 10-4-10-7 M aqueous dye 1 l of 0.5-0.1 M aggregate Raman Microscope DETECTOR SOURCE 488 nm 514.5 nm 632.8 nm 785 nm cutoff filter wavelength specific objective stage z focus course/fine x and y focus 9 Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos Current Research Projects Developing Methods • Need ways to acquire trace amounts of analyte in a “non-destructive manner” Gel Extraction • Need a reliable substrate to yield reproducible spectra SERS substrate Applications • Art History/Conservation Xanthene Dyes • Forensic Science: Controlled Substances SERS + Amphetamine • Forensic Science/Anthropology SERS of Tattoo Inks 10 Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos Gel Extraction Method 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 Filter Paper 11 Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos Gel Extraction Method Questioned Document Gel Size Area of Analysis 1 mm Extraction Materials Gel in extraction solvent Position of the (1% EDTA in a 1:1 H2O and DMF) Microscope Slide Gel Dispersive Raman Scope Gel Before Gel, post extraction After Ag NPs Gel with 5 l Ag NPs 12 Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos Gel Extraction Method SERS spectrum of Extracted Ink on hydroxy gel Identification of Ink Component Conclusion Multiple Extractions from SameisSample • The gel extraction method a fast, Area simple, versatile, and non Penmethod Extractfor extracting inks and dyes destructive • Coupled with SERS, it becomes a powerful tool for chemical analysis Methyl Violet First Extraction 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. Second Extraction 13 Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos Refining SERS Technique Microwave Silver NPs GOAL: Produce and Characterize Reproducible/Stable Ag surface for SERS Historic Method: AgNO3 (aq) + citrate Ag 0 Ag Nanoparticles (NP) reducing Lee-Miesel Silver NPs (AgNO3 + citrate) oxidizing broad absorption (FWHM > 120nm) broad size distribution (3 - 50 nm) not stable over time agent agent one hour Lee, P.C.; Meisel, D., J. Phys. Chem., 1982, 86, 3391-3395. Our Method: Microwave Reduction (Ag2SO4 + glucose + citrate) narrow absorption (FWHM ~ 50 nm) narrow size distribution (3 - 10 nm) stable over 5 - 12 months reproducible SERS spectra over time Leona, M., PNAS, 2009, 106 (35), 1475714762 Ag2SO4 (aq) + sugar (+ citrate) Ag 0 Ag NP oxidizing agent reducing agent 90 sec 14 Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos Microwave Silver NPs Historic Method: Lee-Miesel Silver NPs (AgNO3 + citrate) 1.5 lmax = 400 nm FWHM = 56 nm broad absorption (FWHM > 120nm) broad size distribution (3 - 50 nm) not stable over time via Lee-Miesel method with AgNO3 1.0 OD Our Method: Microwave Reduction (Ag2SO4 + glucose) via microwave reduction with AgSO4 narrow absorption (FWHM ~ 50 nm) narrow size distribution (3 - 10 nm) stable over 5 - 12 months reproducible SERS spectra over time lmax = 422 nm FWHM = 125 nm 0.5 0.0 200 300 400 500 600 700 800 Wavelength nm Lee-Miesel AgNO3 Lee-Miesel Microwave Ag2SO4 Microwave Ag2SO4 15 Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos Microwave Silver 1.4 measured n days after synthesis 1.0 1.2 0.8 1.0 0.6 0.4 0 days 7 days 14 days 145 days 0.8 SERS Model System: 4-mercaptopyridine Different Lots of Particles measured n days after synthesis OD OD 1.2 145 days 55 days 0 days 0.6 0.2 0.4 0.0 0.2 200 300 400 0.0 200 500 600 700 800 wavelength nm 300 400 500 600 700 800 wavelength nm 16 Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos SERS of Various Dyes Classes Dye Class Anthraquinones Publication Surface-enhanced Raman Spectroscopy study of the red dye laccaic acid Cañamares, M.V., et al., J. Raman Spectrosc., 2007, 38, 1259-1266. Surface Enhanced Raman Spectroscopy of Indanthrone and Flavanthrone Chang, J.; et al., J. Raman Spectrosc., 2009, 40, 1557-1563. Raman and Surface Enhanced Raman Spectra of Flavone and Several HydroxyDerivatives Teslova, T.; et al., J. Raman Spectroscopy, 2007, 38, 802-818. Flavones Raman and Surface Enhanced Raman Spectra of Chrysin, Apigenin and Luteolin Corredor, C.; et al., Vibrational Spectroscopy, 2009, 49, 190-195. Raman and Surface Enhanced Raman Spectra of 7 and 3’,4’ Hydroxyflavone Cañamares, M.V.; et al., Journal of ePreservationScience (Proceedings of the IRUG-8, Vienna Austria, Conference), 2009, 6, 81-88. Arylmethane DFT, SERS, and Single Molecule-SERS of Crystal Violet Cañamares, 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. Protoberberines Surface-enhanced Raman scattering of protoberberine alkaloids Cañamares, M.V.; et al., J. Raman Spectrosc., 2008, 39, 1907-1914. 17 Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos Art History Application GOAL: Characterize SERS spectrum of Halogenated Xanthene Dyes • • 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 Flourescein From Xanthene Dye Family 18 Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos Xanthene Dyes: A Spectroscopic Study Research Strategy: Fluorescein Acquire normal Raman spectrum of each dye normal Raman spectrum laser solid dye Acquire SERS spectrum of each dye Eosine Eythrosine laser solid dye Ag NP(aq) Assign Raman Bands to Vibrational Modes Generate SERS Library Phloxine dye on Ag(aq) SERS spectrum Rose Bengal 19 Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos Xanthene Dyes: A Spectroscopic Study Normal Raman spectra SERS spectra Eosine Erythrosine Phloxine Rose Bengal flourscein eosine erythrosine phloxine rosebengal 1800 1600 1400 1200 1000 800 1700 1600 1500 1400 1300 1200 1100 1000 900 800 -1 -1 Raman Shift cm Raman Shift cm • Spectra varies upon Halogenation • Should be able to differentiate in mixtures 20 Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos Surface-Enhanced Raman Scattering of Phenethylamines 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. Ecstacy Over 175 different Phenethylamines Phenethylamine The METH makeover wide variety of therapeutic classes, including but not limited to.. • • • • appetite depressants vascoconstrictors psychotropic drugs bronchodilators • antidepressants • Antiparkinson agents • neurotransmitters 21 Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos SERS of Phenethylamines GOAL: Acquire SERS of Amphetamines for trace analysis Research Strategy: Acquire normal Raman spectrum of Phenethylamines Phenethylamine normal Raman spectrum laser Amphetamine solid drug Acquire SERS spectrum of Phenethylamines, refining experimental conditions Methamphetamine laser SERS spectrum solid drug Ephedrine MDMA (Ecstasy) Ag NP(aq) drug on Ag(aq) 22 Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos 999 Normal Raman and SERS of Phenethylamine 619 1000 800 217 282 600 494 -1 Raman Shift cm 621 1200 1029 1400 1207 1605 1586 1600 342 492 619 740 817 778 899 942 1025 751 999 Phenethylamine 1002 1074 1204 1172 1137 1261 1313 1391 1454 1603 1583 1190 1179 1615 1600 1025 NR Phenethylamine SERS Phenethylamine 23 Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos SERS of Phenethylamine MDMA Ephedrine Methamphetamine Amphetamine Phenethylamine 1600 1400 1200 1000 800 600 -1 Raman Shift cm 24 Surface-Enhanced Raman Scattering of MDMA (Ecstasy) and Analogs Taplin, F.; O’Donnell, D.; Kubic, T.; Leona, M.; Lombardi, J.R., Forensic Science International - submitted Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos Raman Scattering of Tattoo Inks Anthropological Implications Pulled from the Headlines…. Worst tattoo ever? Amateur pranks friend by giving him obscene ink instead of yin-yang he asked for NY DAILY NEWS Tuesday, October 26th 2010, 4:28 PM 25 Extraction Method Separation Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos Raman Scattering of Tattoo Inks GOAL: Acquire SERS of Tattoo Inks • 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* Iron Works Brasil (10)- Brazil Skin Candy (17)- USA * 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. 26 Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos 12000 Tattoo Inks - Normal Raman Spectra 2000 4000 Overlay of Normal Raman Spectra to demonstrate differences RAW DATA Red Region (785nm) 200 400 600 5000 10000 12000 Raman Intensity 10000 15000 20000 Intensity Raman 6000 8000 10000 Vermelho-Iron Works Brasil Ingredients (according to packaging; translated): toxic pigment (mineral/organic) deionized water, surfactant, humectant, preservative NOTE: No color information provided 800 1000 1200 1400 1600 I Page 1/1 200 400 600 800 1000 1200 1400 1600 4000 C:\Users\Michelle\Documents\Administrative Documents\PhD DISSERTATION\The Metropolitan Museum of Art\9-01-2010 Tattoo Inks\IWB Vermelho9/1/2010 (Blue aggreg C:\Users\Michelle\Documents\Administrative Documents\PhD DISSERTATION\The Metropolitan Museum of Art\9-01-2010 Tattoo Inks\IWB Vermelho9/1/2010 (Red).2 2000 50x Raman Intensity 0 6000 8000 C:\Users\Michelle\Documents\Administrative Documents\PhD DISSERTATION\The Metropolitan Museum of Art\9-01-2010 Tattoo Inks\IWB Vermelho9/1/2010 (Red).2 RAW DATA Blue Aggregate (785nm) 200 400 600 Page 1/1 27 800 1000 1200 1400 1600 Refine Technique 2000 Application: Drugs Application: Tattoos 1364 Application: Dyes 1607 1395 1423 14541448 1459 1489 1513 1551 1333 1289 1120 1136 1204 1175 1222 1244 1014 1046 964 862 776 513492 538 574 611 374 265 209 424 107 730 Of the 38 major bands in Pigment Red 170, the red aggregate matched 30 bands 1165 A Closer Look at the Red Aggregate 144 4000 2000 Raman Intensity Raman Intensity 6000 8000 4000 6000 10000 8000 12000 10000 12000 Extraction Method Experimental Normal Raman Spectrum 200 400 Pigment Red 170 CI 12475 600 800 1000 Raman Shift cm-1 1200 1400 1600 Literature Normal Raman Spectrum 200 400 Documents\PhD 600 DISSERTATION\The 800 Metropolitan1000 1200 Tattoo Inks\IWB 1400Vermelho9/1/2010 1600 C:\Users\Michelle\Documents\Administrative Museum of Art\9-01-2010 (Red).2 IW Page 1/1 C:\Users\Michelle\Documents\Administrative Documents\PhD DISSERTATION\The Metropolitan Museum of Art\9-01-2010 Tattoo Inks\IWB Vermelho9/1/2010 (Red).2 Scherrer, N., Z., et al., Spectrochimica Acta Part A, 2009, Vol. 73, 505-524. 28 IW Refine Technique Application: Dyes Application: Drugs Application: Tattoos 1606 1434 1336 1363 1343 1143 1162 1184 1245 1289 1306 1106 1007 952 778 830 848 594 485 257 680 Of the 22 major bands in Pigment Blue 15:2, the blues aggregate matched 17 bands 1451 1490 748 145 A Closer Look at the Blue Aggregate 1526 12000 Raman IntensityRaman Intensity 4000 2000 6000 4000 8000 60001000080001200010000 Extraction Method Experimental Normal Raman Spectrum 200 400 600 800 Raman Shift 2000 Pigment Blue 15:2 C.I 74160 1000 1200 1400 1600 cm-1 Literature Normal Raman Spectrum C:\Users\Michelle\Documents\Administrative Documents\PhD DISSERTATION\The Metropolitan Museum of Art\9-01-2010 Tattoo Inks\IWB Vermelho9/1/2010 (Blue aggregate).2 200 400 600 800 1000 1200 1400 1600 Page 1/1 C:\Users\Michelle\Documents\Administrative Documents\PhD DISSERTATION\The Metropolitan Museum of Art\9-01-2010 Tattoo Inks\IWB Vermelho9/1/2010 (Blue aggregate).2 Scherrer, N., Z., et al., Spectrochimica Acta Part A, 2009, Vol. 73, 505-524. 29 Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos 1569 • • 1314 1236 SERS of Tattoo Inks High Fluorescence in Background Pigment not identifiable by Normal Dispersive Raman Normal Dispersive Raman Spectrum excited at 488 nm Razberry Creem Skin Candy Pigment Red 122 633 nm 785 nm 30 Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos Razberry Creem Skin 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 31 Extraction Method Refine Technique Application: Dyes Application: Drugs Application: Tattoos SERS Spectrum of Razberry Creem (Skin Candy) 488nm SERS Spectrum of Pigment Red 122 488nm 32 Research Summary Developing Methods Gel Extraction • Successfully extract and identify trace amounts • Methodology is system specific SERS substrate • Ag NP synthesis by microwave reduction yields reliable, reproducible surface • Stable for at least 5 months Applications Xanthene Dyes • Developing SERS Library • Future Work: Mixtures SERS + Phenethylamine • 5 Phenethylamines characterized SERS of Tattoo Inks • Tattoo Inks are heterogeneous, present challenge • Work is ongoing Other Areas of Research 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 33 Acknowledgments Prof. 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 Students Dane 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 Students Dr. Richard Livingstone – Graduate student Loes Vermeij – Undergraduate student Elizabeth Sefton – Undergraduate student, WVU Chara Themistokleous – Undergraduate student Faiza Anwar – Graduate student Funding Department of Justice (Award Number: 2009-DN-BX-K185) Center for Exploration of Nanostructures in Sensors and Energy Systems (CENSES) Xanthene Dyes Phenethylamines TLC + SERS and Ag NP Gel Extraction Tattoo Inks 34
