The chemical fingerprint of hair melanosomes by infrared nano-spectroscopy

Stanic, Vesna; Maia, Francisco Carlos Barbosa; Freitas, Raul de Oliveira; Montoro, Fabiano Emmanuel; Evans-Lutterodt, Kenneth

doi:10.1039/C8NR03146K

Title: The chemical fingerprint of hair melanosomes by infrared nano-spectroscopy

Journal Article · 16 July 2018 · Nanoscale

DOI: https://doi.org/10.1039/C8NR03146K · OSTI ID:1477957

^[1];

^[2];

^[3]

Brazilian Synchrotron Light Lab., Campinas (Brazil)
Brazilian National Nanotechnology Lab., Campinas (Brazil)
Brookhaven National Lab. (BNL), Upton, NY (United States)

In situ characterization of the chemical and structural properties of black and white sheep hair was performed with a spatial resolution of 25 nm using infrared nano-spectroscopy. Comparing data sets from two types of hair allowed us to isolate the keratin FTIR fingerprint and so mark off chemical properties of the hair's melanosomes. From a polarization sensitive analysis of the nano-FTIR spectra, we showed that keratin intermediate filaments (IFs) present anisotropic molecular ordering. In stark contrast with white hair which does not contain melanosomes, in black hair, we spatially resolved single melanosomes and achieved unprecedented assignment of the vibrational modes of pheomelanin and eumelanin. The in situ experiment presented here avoids harsh chemical extractive methods used in previous studies. Lastly, our findings offer a basis for a better understanding of the keratin chemical and structural packing in different hair phenotypes as well as the involvement of melanosomes in hair color and biological functionality.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012704

OSTI ID:: 1477957

Report Number(s):: BNL--209180-2018-JAAM

Journal Information:: Nanoscale, Journal Name: Nanoscale Journal Issue: 29 Vol. 10; ISSN NANOHL; ISSN 2040-3364

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (60)

Isolation of melanosomes from keratinous structures: current state of the art Borovansk�, J.; Hach, P. Archives of Dermatological Research, Vol. 279, Issue 1 https://doi.org/10.1007/BF00404359	journal	November 1986
Bacteria or melanosomes? A geochemical analysis of micro-bodies on a tadpole from the Oligocene Enspel Formation of Germany Barden, Holly E.; Bergmann, Uwe; Edwards, Nicholas P. Palaeobiodiversity and Palaeoenvironments, Vol. 95, Issue 1 https://doi.org/10.1007/s12549-014-0177-5	journal	November 2014
Synchrotron X-ray muprobe and its application to human hair analysis Iida, Atsuo; Noma, Takashi Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 82, Issue 1 https://doi.org/10.1016/0168-583X(93)95092-J	journal	July 1993
Scanning probe optical microscopy using a metallic probe tip Kawata, S.; Inouye, Y. Ultramicroscopy, Vol. 57, Issue 2-3 https://doi.org/10.1016/0304-3991(94)00159-K	journal	February 1995
Lipids in keratinized tissues Fraser, R. D. B.; MacRae, T. P.; Rogers, G. E. Journal of Molecular Biology, Vol. 7, Issue 1 https://doi.org/10.1016/S0022-2836(63)80021-2	journal	July 1963
Evidence for various calcium sites in human hair shaft revealed by sub-micrometer X-ray fluorescence Mérigoux, C.; Briki, F.; Sarrot-Reynauld, F. Biochimica et Biophysica Acta (BBA) - General Subjects, Vol. 1619, Issue 1 https://doi.org/10.1016/S0304-4165(02)00441-5	journal	January 2003
Infrared spectroscopy of proteins Barth, Andreas Biochimica et Biophysica Acta (BBA) - Bioenergetics, Vol. 1767, Issue 9 https://doi.org/10.1016/j.bbabio.2007.06.004	journal	September 2007
Chemical imaging of biological tissue with synchrotron infrared light Miller, Lisa M.; Dumas, Paul Biochimica et Biophysica Acta (BBA) - Biomembranes, Vol. 1758, Issue 7 https://doi.org/10.1016/j.bbamem.2006.04.010	journal	July 2006
Degradation of the ethyl glucuronide content in hair by hydrogen peroxide and a non-destructive assay for oxidative hair treatment using infra-red spectroscopy Ammann, Dominic; Becker, Roland; Kohl, Anka Forensic Science International, Vol. 244 https://doi.org/10.1016/j.forsciint.2014.07.029	journal	November 2014
Fifty years of fibrous protein research: A personal retrospective Parry, David A. D. Journal of Structural Biology, Vol. 186, Issue 3 https://doi.org/10.1016/j.jsb.2013.10.010	journal	June 2014
Three-dimensional architecture of macrofibrils in the human scalp hair cortex Harland, Duane P.; Walls, Richard J.; Vernon, James A. Journal of Structural Biology, Vol. 185, Issue 3 https://doi.org/10.1016/j.jsb.2014.01.010	journal	March 2014
Microspectroscopic soft X-ray analysis of keratin based biofibers Späth, Andreas; Meyer, Markus; Semmler, Sonja Micron, Vol. 70 https://doi.org/10.1016/j.micron.2014.12.003	journal	March 2015
Individual colour patches as multicomponent signals Grether, Gregory F.; Kolluru, Gita R.; Nersissian, Karen Biological Reviews, Vol. 79, Issue 3 https://doi.org/10.1017/S1464793103006390	journal	January 1999
Nano-FTIR chemical mapping of minerals in biological materials Amarie, S.; Keilmann, F.; Zaslansky, P. Microscopy and Microanalysis, Vol. 18, Issue S2 https://doi.org/10.1017/s1431927612002012	journal	July 2012
Infrared Vibrational Nanospectroscopy by Self-Referenced Interferometry Pollard, Benjamin; Maia, Francisco C. B.; Raschke, Markus B. Nano Letters, Vol. 16, Issue 1 https://doi.org/10.1021/acs.nanolett.5b02730	journal	December 2015
Amplitude- and Phase-Resolved Nanospectral Imaging of Phonon Polaritons in Hexagonal Boron Nitride Shi, Zhiwen; Bechtel, Hans A.; Berweger, Samuel ACS Photonics, Vol. 2, Issue 7 https://doi.org/10.1021/acsphotonics.5b00007	journal	June 2015
Infrared Fingerprints of Natural 2D Talc and Plasmon–Phonon Coupling in Graphene–Talc Heterostructures Barcelos, Ingrid D.; Cadore, Alisson R.; Alencar, Ananias B. ACS Photonics, Vol. 5, Issue 5 https://doi.org/10.1021/acsphotonics.7b01017	journal	April 2018
Infrared and Water Sorption Studies of the Hydration Structure and Mechanism in Natural and Synthetic Melanin Bridelli, Maria Grazia; Crippa, Pier Raimondo The Journal of Physical Chemistry B, Vol. 114, Issue 29 https://doi.org/10.1021/jp101833k	journal	July 2010
Protein Secondary Structure Imaging with Ultrabroadband Multiplex Coherent Anti-Stokes Raman Scattering (CARS) Microspectroscopy Bito, Kotatsu; Okuno, Masanari; Kano, Hideaki The Journal of Physical Chemistry B, Vol. 116, Issue 4 https://doi.org/10.1021/jp210914x	journal	January 2012
Nano-FTIR Absorption Spectroscopy of Molecular Fingerprints at 20 nm Spatial Resolution Huth, Florian; Govyadinov, Alexander; Amarie, Sergiu Nano Letters, Vol. 12, Issue 8 https://doi.org/10.1021/nl301159v	journal	July 2012
Near-field probing of vibrational absorption for chemical microscopy Knoll, B.; Keilmann, F. Nature, Vol. 399, Issue 6732 https://doi.org/10.1038/20154	journal	May 1999
Hyperspectral infrared nanoimaging of organic samples based on Fourier transform infrared nanospectroscopy Amenabar, Iban; Poly, Simon; Goikoetxea, Monika Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14402	journal	February 2017
Structural analysis and mapping of individual protein complexes by infrared nanospectroscopy Amenabar, Iban; Poly, Simon; Nuansing, Wiwat Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3890	journal	December 2013
Vibrational nano-spectroscopic imaging correlating structure with intermolecular coupling and dynamics Pollard, Benjamin; Muller, Eric A.; Hinrichs, Karsten Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4587	journal	April 2014
Photonic crystals cause active colour change in chameleons Teyssier, Jérémie; Saenko, Suzanne V.; van der Marel, Dirk Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7368	journal	March 2015
Infrared-spectroscopic nanoimaging with a thermal source Huth, F.; Schnell, M.; Wittborn, J. Nature Materials, Vol. 10, Issue 5 https://doi.org/10.1038/nmat3006	journal	April 2011
3D spectral imaging with synchrotron Fourier transform infrared spectro-microtomography Martin, Michael C.; Dabat-Blondeau, Charlotte; Unger, Miriam Nature Methods, Vol. 10, Issue 9 https://doi.org/10.1038/nmeth.2596	journal	August 2013
Opto-nanomechanical spectroscopic material characterization Tetard, L.; Passian, A.; Farahi, R. H. Nature Nanotechnology, Vol. 10, Issue 10 https://doi.org/10.1038/nnano.2015.168	journal	August 2015
Tip-enhanced infrared nanospectroscopy via molecular expansion force detection Lu, Feng; Jin, Mingzhou; Belkin, Mikhail A. Nature Photonics, Vol. 8, Issue 4 https://doi.org/10.1038/nphoton.2013.373	journal	January 2014
Local structure of human hair spatially resolved by sub-micron X-ray beam Stanić, Vesna; Bettini, Jefferson; Montoro, Fabiano Emmanuel Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep17347	journal	November 2015
Elemental characterisation of melanin in feathers via synchrotron X-ray imaging and absorption spectroscopy Edwards, Nicholas P.; van Veelen, Arjen; Anné, Jennifer Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep34002	journal	September 2016
Graphene/h-BN plasmon–phonon coupling and plasmon delocalization observed by infrared nano-spectroscopy Barcelos, Ingrid D.; Cadore, Alisson R.; Campos, Leonardo C. Nanoscale, Vol. 7, Issue 27 https://doi.org/10.1039/C5NR01056J	journal	January 2015
Theory of infrared nanospectroscopy by photothermal induced resonance Dazzi, A.; Glotin, F.; Carminati, R. Journal of Applied Physics, Vol. 107, Issue 12 https://doi.org/10.1063/1.3429214	journal	June 2010
Structure, function, and self-assembly of single network gyroid (I4132) photonic crystals in butterfly wing scales Saranathan, V.; Osuji, C. O.; Mochrie, S. G. J. Proceedings of the National Academy of Sciences, Vol. 107, Issue 26 https://doi.org/10.1073/pnas.0909616107	journal	June 2010
Ultrabroadband infrared nanospectroscopic imaging Bechtel, H. A.; Muller, E. A.; Olmon, R. L. Proceedings of the National Academy of Sciences, Vol. 111, Issue 20 https://doi.org/10.1073/pnas.1400502111	journal	May 2014
Chemical, experimental, and morphological evidence for diagenetically altered melanin in exceptionally preserved fossils Colleary, Caitlin; Dolocan, Andrei; Gardner, James Proceedings of the National Academy of Sciences, Vol. 112, Issue 41 https://doi.org/10.1073/pnas.1509831112	journal	September 2015
The Structure of Hair, Muscle, and Related Proteins Pauling, L.; Corey, R. B. Proceedings of the National Academy of Sciences, Vol. 37, Issue 5 https://doi.org/10.1073/pnas.37.5.261	journal	May 1951
Oxygen impact on the electronic and vibrational properties of black phosphorus probed by synchrotron infrared nanospectroscopy Grasseschi, D.; Bahamon, D. A.; Maia, F. C. B. 2D Materials, Vol. 4, Issue 3 https://doi.org/10.1088/2053-1583/aa8210	journal	August 2017
Colour-producing β-keratin nanofibres in blue penguin ( Eudyptula minor ) feathers D'Alba, Liliana; Saranathan, Vinodkumar; Clarke, Julia A. Biology Letters, Vol. 7, Issue 4 https://doi.org/10.1098/rsbl.2010.1163	journal	February 2011
Near-field microscopy by elastic light scattering from a tip Keilmann, Fritz; Hillenbrand, Rainer Philosophical Transactions of the Royal Society of London. Series A: Mathematical, Physical and Engineering Sciences, Vol. 362, Issue 1817 https://doi.org/10.1098/rsta.2003.1347	journal	April 2004
Investigating the origins of nanostructural variations in differential ethnic hair types using X-ray scattering techniques Wade, M.; Tucker, I.; Cunningham, P. International Journal of Cosmetic Science, Vol. 35, Issue 5 https://doi.org/10.1111/ics.12061	journal	June 2013
Contributions to the chemistry of human hair. 1. Analyses of cystine, cysteine and cystine oxides in untreated human hair Hilterhaus-Bong, Sabine; Zahn, Helmut International Journal of Cosmetic Science, Vol. 9, Issue 3 https://doi.org/10.1111/j.1467-2494.1987.tb00467.x	journal	June 1987
Secondary structure estimation and properties analysis of stretched Asian and Caucasian hair Zhou, A. J.; Liu, H. L.; Du, Z. Q. Skin Research and Technology, Vol. 21, Issue 1 https://doi.org/10.1111/srt.12169	journal	July 2014
Infrared vibrational nanocrystallography and nanoimaging Muller, Eric A.; Pollard, Benjamin; Bechtel, Hans A. Science Advances, Vol. 2, Issue 10 https://doi.org/10.1126/sciadv.1601006	journal	October 2016
Nanoscale simultaneous chemical and mechanical imaging via peak force infrared microscopy Wang, Le; Wang, Haomin; Wagner, Martin Science Advances, Vol. 3, Issue 6 https://doi.org/10.1126/sciadv.1700255	journal	June 2017
Fossil Evidence for Evolution of the Shape and Color of Penguin Feathers Clarke, J. A.; Ksepka, D. T.; Salas-Gismondi, R. Science, Vol. 330, Issue 6006 https://doi.org/10.1126/science.1193604	journal	September 2010
Scanning Interferometric Apertureless Microscopy: Optical Imaging at 10 Angstrom Resolution Zenhausern, F.; Martin, Y.; Wickramasinghe, H. K. Science, Vol. 269, Issue 5227 https://doi.org/10.1126/science.269.5227.1083	journal	August 1995
Precise colocalization of interacting structural and pigmentary elements generates extensive color pattern variation in Phelsuma lizards Saenko, Suzanne V.; Teyssier, Jérémie; van der Marel, Dirk BMC Biology, Vol. 11, Issue 1 https://doi.org/10.1186/1741-7007-11-105	journal	January 2013
Polarization Properties in Apertureless-Type Scanning Near-Field Optical Microscopy Ishibashi, Takayuki; Cai, Yongfu Nanoscale Research Letters, Vol. 10, Issue 1 https://doi.org/10.1186/s11671-015-1062-5	journal	September 2015
Midinfrared absorption measured at a λ/400 resolution with an atomic force microscope Houel, Julien; Homeyer, Estelle; Sauvage, Sébastien Optics Express, Vol. 17, Issue 13 https://doi.org/10.1364/OE.17.010887	journal	January 2009
Near-field imaging and nano-Fourier-transform infrared spectroscopy using broadband synchrotron radiation Hermann, Peter; Hoehl, Arne; Patoka, Piotr Optics Express, Vol. 21, Issue 3 https://doi.org/10.1364/OE.21.002913	journal	January 2013
Characterization of semiconductor materials using synchrotron radiation-based near-field infrared microscopy and nano-FTIR spectroscopy Hermann, Peter; Hoehl, Arne; Ulrich, Georg Optics Express, Vol. 22, Issue 15 https://doi.org/10.1364/OE.22.017948	journal	January 2014
Nanoscale plasmonic phenomena in CVD-grown MoS_2 monolayer revealed by ultra-broadband synchrotron radiation based nano-FTIR spectroscopy and near-field microscopy Patoka, Piotr; Ulrich, Georg; Nguyen, Ariana E. Optics Express, Vol. 24, Issue 2 https://doi.org/10.1364/OE.24.001154	journal	January 2016
Broadband near-field infrared spectromicroscopy using photothermal probes and synchrotron radiation Donaldson, Paul M.; Kelley, Chris S.; Frogley, Mark D. Optics Express, Vol. 24, Issue 3 https://doi.org/10.1364/OE.24.001852	journal	January 2016
Low-aberration beamline optics for synchrotron infrared nanospectroscopy Freitas, Raul O.; Deneke, Christoph; Maia, Francisco C. B. Optics Express, Vol. 26, Issue 9 https://doi.org/10.1364/OE.26.011238	journal	January 2018
Local infrared microspectroscopy with subwavelength spatial resolution with an atomic force microscope tip used as a photothermal sensor Dazzi, A.; Prazeres, R.; Glotin, F. Optics Letters, Vol. 30, Issue 18 https://doi.org/10.1364/OL.30.002388	journal	January 2005
Nano-Scale Morphology of Melanosomes Revealed by Small-Angle X-Ray Scattering Gorniak, Thomas; Haraszti, Tamas; Garamus, Vasyl M. PLoS ONE, Vol. 9, Issue 3 https://doi.org/10.1371/journal.pone.0090884	journal	March 2014
Nano-FTIR chemical mapping of minerals in biological materials Amarie, Sergiu; Zaslansky, Paul; Kajihara, Yusuke Beilstein Journal of Nanotechnology, Vol. 3 https://doi.org/10.3762/bjnano.3.35	journal	January 2012
Abnormal pigmentation within cutaneous scars: A complication of wound healing Chadwick, Sarah; Heath, Rebecca; Shah, Mamta Indian Journal of Plastic Surgery, Vol. 45, Issue 02 https://doi.org/10.4103/0970-0358.101328	journal	May 2012
Nano-scale morphology of melanosomes revealed by small-angle X-ray scattering Gorniak, T.; Haraszti, T.; Garamus, V. M. Karlsruhe https://doi.org/10.5445/ir/1000049234	text	January 2014

Cited By (1)

Modern Scattering‐Type Scanning Near‐Field Optical Microscopy for Advanced Material Research Chen, Xinzhong; Hu, Debo; Mescall, Ryan Advanced Materials https://doi.org/10.1002/adma.201804774	journal	April 2019

Similar Records

Pheomelanin pigment remnants mapped in fossils of an extinct mammal

Journal Article · 2019 · Nature Communications · OSTI ID:1532396

Manning, Phillip L.; Edwards, Nicholas P.; Bergmann, Uwe; +12 more

Effects of ultraviolet-visible irradiation in the presence of melanin isolated from human black or red hair upon Ehrlich ascites carcinoma cells

Journal Article · 1983 · Cancer Res.; (United States) · OSTI ID:5428899

Menon, I A; Persad, S; Ranadive, N S; +1 more

Estimate of the melanin content in human hairs by the inverse Monte-Carlo method using a system for digital image analysis

Journal Article · 2006 · Quantum Electronics (Woodbury, N.Y.) · OSTI ID:21456923

Bashkatov, A N; Genina, Elina A; Kochubei, V I; +1 more

Related Subjects

36 MATERIALS SCIENCE

Title: The chemical fingerprint of hair melanosomes by infrared nano-spectroscopy

Citation Formats

References (60)

Cited By (1)

Similar Records

Related Subjects