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Title: Raman scattering and red fluorescence in the photochemical transformation of dry tryptophan particles

Abstract

Tryptophan is a fluorescent amino acid common in proteins. Its absorption is largest for wavelengths λ ≲ 290 nm and its fluorescence emissions peak around 300–350 nm, depending upon the local environment. Here we report the observation of red fluorescence near 600 nm emerging from 488-nm continuous-wave (CW) laser photoexcitation of dry tryptophan (Trp) particles. With an excitation intensity below 0.5 kW/cm2, dry Trp particles yield distinctive Raman scattering peaks in the presence of relatively weak and spectrally broad emissions with λ ~500–700 nm, allowing estimation of particle temperature at low excitation intensities. When the photoexcitation intensity is increased to 1 kW/cm2 or more for a few minutes, fluorescence intensity dramatically increases by more than two orders of magnitude. The fluorescence continues to increase in intensity and gradually shift to the red when photoexcitation intensity and the duration of exposure are increased. The resulting products absorb at visible wavelengths and generate red fluorescence with λ ~ 650–800 nm with 633-nm CW laser excitation. In conclusion, we attribute the emergence of orange and red fluorescence in the Trp products to a photochemical transformation that is instigated by weak optical transitions to triplet states in Trp with 488-nm excitation and which maymore » be expedited by a photothermal effect.« less

Authors:
 [1];  [2];  [2];  [3];  [2]
  1. U.S. Army Research Lab., Adelphi, MD (United States); Michigan State Univ., East Lansing, MI (United States)
  2. U.S. Army Research Lab., Adelphi, MD (United States)
  3. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-CA), Livermore, CA (United States); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1266213
Grant/Contract Number:  
HDTRA1619734; HDTRS1518237; DMR-0955944; W911NF-12-2-0019; AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
Optics Express
Additional Journal Information:
Journal Volume: 24; Journal Issue: 11; Journal ID: ISSN 1094-4087
Publisher:
Optical Society of America (OSA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; scattering; Raman; spectroscopy, fluorescence and luminescence; photochemistry

Citation Formats

Lai, Chih Wei, Schwab, Mark, Hill, Steven C., Santarpia, Joshua, and Pan, Yong -Le. Raman scattering and red fluorescence in the photochemical transformation of dry tryptophan particles. United States: N. p., 2016. Web. doi:10.1364/OE.24.011654.
Lai, Chih Wei, Schwab, Mark, Hill, Steven C., Santarpia, Joshua, & Pan, Yong -Le. Raman scattering and red fluorescence in the photochemical transformation of dry tryptophan particles. United States. https://doi.org/10.1364/OE.24.011654
Lai, Chih Wei, Schwab, Mark, Hill, Steven C., Santarpia, Joshua, and Pan, Yong -Le. Thu . "Raman scattering and red fluorescence in the photochemical transformation of dry tryptophan particles". United States. https://doi.org/10.1364/OE.24.011654. https://www.osti.gov/servlets/purl/1266213.
@article{osti_1266213,
title = {Raman scattering and red fluorescence in the photochemical transformation of dry tryptophan particles},
author = {Lai, Chih Wei and Schwab, Mark and Hill, Steven C. and Santarpia, Joshua and Pan, Yong -Le},
abstractNote = {Tryptophan is a fluorescent amino acid common in proteins. Its absorption is largest for wavelengths λ ≲ 290 nm and its fluorescence emissions peak around 300–350 nm, depending upon the local environment. Here we report the observation of red fluorescence near 600 nm emerging from 488-nm continuous-wave (CW) laser photoexcitation of dry tryptophan (Trp) particles. With an excitation intensity below 0.5 kW/cm2, dry Trp particles yield distinctive Raman scattering peaks in the presence of relatively weak and spectrally broad emissions with λ ~500–700 nm, allowing estimation of particle temperature at low excitation intensities. When the photoexcitation intensity is increased to 1 kW/cm2 or more for a few minutes, fluorescence intensity dramatically increases by more than two orders of magnitude. The fluorescence continues to increase in intensity and gradually shift to the red when photoexcitation intensity and the duration of exposure are increased. The resulting products absorb at visible wavelengths and generate red fluorescence with λ ~ 650–800 nm with 633-nm CW laser excitation. In conclusion, we attribute the emergence of orange and red fluorescence in the Trp products to a photochemical transformation that is instigated by weak optical transitions to triplet states in Trp with 488-nm excitation and which may be expedited by a photothermal effect.},
doi = {10.1364/OE.24.011654},
journal = {Optics Express},
number = 11,
volume = 24,
place = {United States},
year = {Thu May 19 00:00:00 EDT 2016},
month = {Thu May 19 00:00:00 EDT 2016}
}

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Works referenced in this record:

Aerosol Fluorescence Spectrum Analyzer for Rapid Measurement of Single Micrometer-Sized Airborne Biological Particles
journal, January 1998

  • Pinnick, Ronald G.; Hill, Steven C.; Nachman, Paul
  • Aerosol Science and Technology, Vol. 28, Issue 2
  • DOI: 10.1080/02786829808965514

Autofluorescence of atmospheric bioaerosols – fluorescent biomolecules and potential interferences
journal, January 2012

  • Pöhlker, C.; Huffman, J. A.; Pöschl, U.
  • Atmospheric Measurement Techniques, Vol. 5, Issue 1
  • DOI: 10.5194/amt-5-37-2012

Real-time measurement of fluorescence spectra from single airborne biological particles
journal, January 1999


Detection and characterization of biological and other organic-carbon aerosol particles in atmosphere using fluorescence
journal, January 2015


Spectroscopic Methods for Analysis of Protein Secondary Structure
journal, January 2000


Protein secondary structure from deep-UV resonance Raman spectroscopy
journal, January 2006

  • Huang, Cheng-Yen; Balakrishnan, Gurusamy; Spiro, Thomas G.
  • Journal of Raman Spectroscopy, Vol. 37, Issue 1-3
  • DOI: 10.1002/jrs.1440

Raman spectroscopy of proteins: from peptides to large assemblies
journal, January 2005

  • Tuma, Roman
  • Journal of Raman Spectroscopy, Vol. 36, Issue 4
  • DOI: 10.1002/jrs.1323

Separation and isolation of trace impurities in l-tryptophan by high-performance liquid chromatography
journal, February 1993


UV Resonance Raman excitation profiles of the aromatic amino acids
journal, June 1986

  • Asher, Sanford A.; Ludwig, Michael.; Johnson, Craig R.
  • Journal of the American Chemical Society, Vol. 108, Issue 12
  • DOI: 10.1021/ja00272a005

Tryptophan UV resonance Raman excitation profiles
journal, June 1990

  • Sweeney, Joyce A.; Asher, Sanford A.
  • The Journal of Physical Chemistry, Vol. 94, Issue 12
  • DOI: 10.1021/j100375a009

Two-dimensional stimulated ultraviolet resonance Raman spectra of tyrosine and tryptophan: a simulation study: 2D stimulated UVRR spectra of Tyr and Trp
journal, March 2013

  • Ren, Hao; Biggs, Jason D.; Mukamel, Shaul
  • Journal of Raman Spectroscopy, Vol. 44, Issue 4
  • DOI: 10.1002/jrs.4210

Surface-enhanced Raman scattering
journal, January 1998

  • Campion, Alan; Kambhampati, Patanjali
  • Chemical Society Reviews, Vol. 27, Issue 4
  • DOI: 10.1039/a827241z

Surface-Enhanced Raman Spectroscopy
journal, September 2005

  • Haynes, Christy L.; McFarland, Adam D.; Van Duyne, Richard P.
  • Analytical Chemistry, Vol. 77, Issue 17
  • DOI: 10.1021/ac053456d

Surface-enhanced Raman scattering study of L-tryptophan
journal, February 2009

  • Aliaga, A. E.; Osorio-Román, I.; Leyton, P.
  • Journal of Raman Spectroscopy, Vol. 40, Issue 2
  • DOI: 10.1002/jrs.2099

Excited state chemistry of aromatic amino acids and related peptides. III. Tryptophan
journal, May 1975

  • Bent, D. V.; Hayon, E.
  • Journal of the American Chemical Society, Vol. 97, Issue 10
  • DOI: 10.1021/ja00843a004

Excited state chemistry of aromatic amino acids and related peptides. I. Tyrosine
journal, May 1975

  • Bent, D. V.; Hayon, E.
  • Journal of the American Chemical Society, Vol. 97, Issue 10
  • DOI: 10.1021/ja00843a002

Excited state chemistry of aromatic amino acids and related peptides. II. Phenylalanine
journal, May 1975

  • Bent, D. V.; Hayon, E.
  • Journal of the American Chemical Society, Vol. 97, Issue 10
  • DOI: 10.1021/ja00843a003

Mechanisms of Tryptophan Fluorescence Shifts in Proteins
journal, May 2001


Tryptophan fluorescence as a reporter for structural changes in photoactive yellow protein elicited by photo-activation
journal, January 2013

  • Hospes, Marijke; Hendriks, Johnny; Hellingwerf, Klaas J.
  • Photochem. Photobiol. Sci., Vol. 12, Issue 3
  • DOI: 10.1039/C2PP25222H

Intrinsic Tryptophan Fluorescence in the Detection and Analysis of Proteins: A Focus on Förster Resonance Energy Transfer Techniques
journal, December 2014

  • Ghisaidoobe, Amar; Chung, Sang
  • International Journal of Molecular Sciences, Vol. 15, Issue 12
  • DOI: 10.3390/ijms151222518

Absorption, fluorescence, and fluorescence excitation spectra of free molecules of indole and its derivatives
journal, March 2007


Photochemistry of proteins: a Review
journal, January 1984


Origin of the doublet at 1360 and 1340 cm−1 in the Raman spectra of tryptophan and related compounds
journal, January 1986

  • Harada, Issei; Miura, Takashi; Takeuchi, Hideo
  • Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 42, Issue 2-3
  • DOI: 10.1016/0584-8539(86)80193-3

Characterization of individual tryptophan side chains in proteins using Raman spectroscopy and hydrogen-deuterium exchange kinetics
journal, January 1988

  • Miura, Takashi; Takeuchi, Hideo; Harada, Issei
  • Biochemistry, Vol. 27, Issue 1
  • DOI: 10.1021/bi00401a015

Tryptophan Raman bands sensitive to hydrogen bonding and side-chain conformation
journal, October 1989

  • Miura, Takashi; Takeuchi, Hideo; Harada, Issei
  • Journal of Raman Spectroscopy, Vol. 20, Issue 10
  • DOI: 10.1002/jrs.1250201007

Ultraviolet resonance Raman characterization of photochemical transients of phenol, tyrosine, and tryptophan
journal, March 1986

  • Johnson, Craig R.; Ludwig, Michael.; Asher, Sanford A.
  • Journal of the American Chemical Society, Vol. 108, Issue 5
  • DOI: 10.1021/ja00265a010

Raman scattering of L-tryptophan enhanced by surface plasmon of silver nanoparticles: vibrational assignment and structural determination
journal, February 2009

  • Chuang, Chi-Hung; Chen, Yit-Tsong
  • Journal of Raman Spectroscopy, Vol. 40, Issue 2
  • DOI: 10.1002/jrs.2097

Raman structural markers of tryptophan and histidine side chains in proteins
journal, January 2003


Identification of epidermal L-tryptophan and its oxidation products by in vivo FT-Raman Spectroscopy further supports oxidative stress in patients with vitiligo
journal, September 2008

  • Rokos, Hartmut; Wood, John M.; Hasse, Sybille
  • Journal of Raman Spectroscopy, Vol. 39, Issue 9
  • DOI: 10.1002/jrs.1968

Tryptophan degradation during heat treatments: Part 1—The degradation of free tryptophan
journal, January 1983


Essential on the Photophysics and Photochemistry of the Indole Chromophore by Using a Totally Unconstrained Theoretical Approach
journal, October 2011

  • Giussani, Angelo; Merchán, Manuela; Roca-Sanjuán, Daniel
  • Journal of Chemical Theory and Computation, Vol. 7, Issue 12
  • DOI: 10.1021/ct200646r

Photochemistry of the model phototropic system involving flavines and indoles. III. A spectroscopic study of the polarized luminescence of indoles
journal, August 1969

  • Song, Pill-Soon; Kurtin, William E.
  • Journal of the American Chemical Society, Vol. 91, Issue 17
  • DOI: 10.1021/ja01045a052

Temperature dependence of tryptophan and tyrosine luminescence in poly(vinyl alcohol) films
journal, January 1981

  • Sakurovs, R.; Ghiggino, Kp
  • Australian Journal of Chemistry, Vol. 34, Issue 7
  • DOI: 10.1071/CH9811367

Studies on the Photo Degradation of Tryptophan
journal, June 1965


Characterisation of photo-oxidation products within photoyellowed wool proteins: tryptophan and tyrosine derived chromophores
journal, January 2006

  • Dyer, J. M.; Bringans, S. D.; Bryson, W. G.
  • Photochemical & Photobiological Sciences, Vol. 5, Issue 7
  • DOI: 10.1039/b603030k

Photoreactivity of Amino Acids: Tryptophan-induced Photochemical Events via Reactive Oxygen Species Generation
journal, January 2007

  • Igarashi, Naoko; Onoue, Satomi; Tsuda, Yoshiko
  • Analytical Sciences, Vol. 23, Issue 8
  • DOI: 10.2116/analsci.23.943

Photodegradation of tryptophan in wool
journal, December 1997


Fluorescence of N'-formylkynurenine and of protein exposed to sunlight
journal, August 1972


Metallic-like photoluminescence and absorption in fused silica surface flaws
journal, April 2009

  • Laurence, Ted A.; Bude, Jeff D.; Shen, Nan
  • Applied Physics Letters, Vol. 94, Issue 15
  • DOI: 10.1063/1.3119622

Quasi-continuum photoluminescence: Unusual broad spectral and temporal characteristics found in defective surfaces of silica and other materials
journal, February 2014

  • Laurence, Ted A.; Bude, Jeff D.; Shen, Nan
  • Journal of Applied Physics, Vol. 115, Issue 8
  • DOI: 10.1063/1.4866422

Raman spectroscopic characterization of some commercially available carbon black materials
journal, January 1995


Phonon linewidths and electron-phonon coupling in graphite and nanotubes
journal, April 2006


Carbonization behavior of l-tryptophan and gluten
journal, December 2006

  • Nishikawa, Goro; Shioya, Masatoshi; Iwashita, Norio
  • Journal of Materials Science, Vol. 42, Issue 6
  • DOI: 10.1007/s10853-006-1213-2

Spectroscopic Evaluation and Classification of the Normal, Aging, and Cataractous Lens. (With 1 color plate)
journal, January 1976

  • Lerman, Sidney; Borkman, Raymond
  • Ophthalmic Research, Vol. 8, Issue 5
  • DOI: 10.1159/000264841

Ultraviolet Radiation and Cataract
journal, June 2000

  • Balasubramanian, D.
  • Journal of Ocular Pharmacology and Therapeutics, Vol. 16, Issue 3
  • DOI: 10.1089/jop.2000.16.285

Works referencing / citing this record:

Real-time sensing of bioaerosols: Review and current perspectives
journal, September 2019