Abstract
Ag nanorod arrays/dielectrics/mirror-structured multilayer thin films are well-known, sensitive surface-enhanced Raman scattering (SERS) substrates that enhance the Raman scattering cross section by the interference of light. However, it is difficult to extract biomarkers directly from human skin using these solid substrates. To overcome this problem, we propose a multilayer thin-film flake dispersion gel by centrifugal mixing of the multilayer thin film and hydroxyethyl cellulose (HEC) gel. The multilayer thin film was prepared by serial bideposition using the dynamic oblique angle deposition technique. The mixing process was optimized to obtain flakes of ~ 10 μm so that the optical properties of the multilayer film can be preserved, and there is no risk of adverse effects on humans. The SERS characteristics of the flakes dispersion gel were tested using 4, 4′-bipyridine (BPY). The BPY molecules diffused through the highly porous gel within seconds, producing significant SERS signals. The multilayer thin-film flakes dispersion gel showed a SERS signal approximately 20 times better than the gel-dispersed Ag nanorod arrays without a multilayer film structure. These SERS active flakes dispersion gel can be used directly on the skin surface to collect body fluids from sweat, for biomarker sensing.
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References
Banholzer MJ, Millstone JE, Qin L, Mirkin CA (2008) Rationally designed nanostructures for surface-enhanced Raman spectroscopy. Chem Soc Rev 37:885–897. https://doi.org/10.1039/b710915f
Bochenkov V, Baumberg J, Noginov M, Benz F, Aldewachi H, Schmid S, Podolskiy V, Aizpurua J, Lin K, Ebbesen T, Kornyshev AA (2015) Applications of plasmonics: general discussion. Faraday Discuss 178:435. https://doi.org/10.1039/c5fd90025e
Cinel NA, Cakmakyapan S, Butun S et al (2015) E-Beam lithography designed substrates for surface enhanced Raman spectroscopy. Photonics Nanostructures—Fundam Appl 15:109–115. https://doi.org/10.1016/j.photonics.2014.11.003
Deng CY, Zhang GL, Zou B et al (2013) Local electric field enhancement of neighboring Ag nanoparticles in surface enhanced raman scattering. Adv Mater Res 760–762:801–805. https://doi.org/10.4028/www.scientific.net/AMR.760-762.801
Doherty B, Presciutti F, Sgamellotti A et al (2014) Monitoring of optimized SERS active gel substrates for painting and paper substrates by unilateral NMR profilometry. J Raman Spectrosc 45:1153–1159. https://doi.org/10.1002/jrs.4542
Fan M, Andrade GFS, Brolo AG (2011) A review on the fabrication of substrates for surface enhanced Raman spectroscopy and their applications in analytical chemistry. Anal Chim Acta 693:7–25. https://doi.org/10.1016/j.aca.2011.03.002
Fukuoka T, Kumar S, Namura K, Suzuki M (2019) Jellylike Flexible Sensors Containing Pre-aggregated Gold Nanoparticles for Plasmonic Sensing of Repellants. In: Okinawa Colloids. Okinawa
Gibbs JG, Mark AG, Lee T-C et al (2014) Nanohelices by shadow growth. Nanoscale 6:9457–9466. https://doi.org/10.1039/c4nr00403e
Harper MM, McKeating KS, Faulds K (2013) Recent developments and future directions in SERS for bioanalysis. Phys Chem Chem Phys 15:5312–5328. https://doi.org/10.1039/c2cp43859c
Hughes J, Izake EL, Lott WB et al (2014) Ultra sensitive label free surface enhanced Raman spectroscopy method for the detection of biomolecules. Talanta 130:20–25. https://doi.org/10.1016/j.talanta.2014.06.012
Jain PK, Lee KS, El-Sayed IH, El-Sayed MA (2006) Calculated absorption and scattering properties of gold nanoparticles of different size, shape, and composition: applications in biological imaging and biomedicine. J Phys Chem B 110:7238–7248. https://doi.org/10.1021/jp057170o
Jiang T, Goel P, Zhao H et al (2020) Internal structure tailoring in 3D nanoplasmonic metasurface for surface-enhanced Raman spectroscopy. Part Part Syst Charact 37:1900345. https://doi.org/10.1002/ppsc.201900345
Joo SW (2004) Surface-enhanced Raman scattering of 4,4′-bipyridine on gold nanoparticle surfaces. Vib Spectrosc 34:269–272. https://doi.org/10.1016/j.vibspec.2003.12.006
Kosuda KM, Bingham JM, Wustholz KL, et al (2016) Nanostructures and Surface-Enhanced Raman Spectroscopy. Elsevier Ltd
Kruszewski S (1998) Enhancement mechanisms in the SERS phenomenon. In: Proc. SPIE 3320, Tenth Polish-Czech-Slovak Optical Conference: Wave and Quantum Aspects of Contemporary Optics. International Society for Optics and Photonics, p 281
Kumar S, Goel P, Singh DP, Singh JP (2014) Highly sensitive superhydrophobic Ag nanorods array substrates for surface enhanced fluorescence studies. Appl Phys Lett 104:023107. https://doi.org/10.1063/1.4861836
Kumar S, Lodhi DK, Goel P et al (2015) A facile method for fabrication of buckled PDMS silver nanorod arrays as active 3D SERS cages for bacterial sensing. Chem Commun 51:12411–12414. https://doi.org/10.1039/C5CC03604F
Kumar S, Lodhi DK, Singh JP (2016) Highly sensitive multifunctional recyclable Ag–TiO 2 nanorod SERS substrates for photocatalytic degradation and detection of dye molecules. RSC Adv 6:45120–45126. https://doi.org/10.1039/C6RA06163J
Kumar S, Goel P, Singh JP (2017) Flexible and robust SERS active substrates for conformal rapid detection of pesticide residues from fruits. Sensors Actuators B Chem 241:577–583. https://doi.org/10.1016/J.SNB.2016.10.106
Kumar S, Namura K, Suzuki M (2019) Proposal for a gel-based SERS sensor. Proc SPIE 10894:1089414. https://doi.org/10.1117/12.2506951
Kumar S, Doi Y, Namura K, Suzuki M (2020a) Plasmonic nanoslit arrays fabricated by serial bideposition: optical and surface-enhanced Raman scattering study. ACS Appl Bio Mater 3:3226–3235. https://doi.org/10.1021/acsabm.0c00215
Kumar S, Kumar P, Das A, Pathak CS (2020b) Surface-Enhanced Raman Scattering: Introduction and Applications. In: Chee K (ed) Charged Particle Scattering. IntechOpen
Lucht S, Murphy T, Schmidt H, Kronfeldt H-D (2000) Optimized recipe for sol-gel-based SERS substrates. J Raman Spectrosc 31:1017–1022. https://doi.org/10.1002/1097-4555(200011)31:113.0.CO;2-V
Mosier-Boss PA (2017) Review of SERS substrates for chemical sensing. Nanomaterials 7:142. https://doi.org/10.3390/nano7060142
Moskovits M (1985) Surface-enhanced spectroscopy. Rev Mod Phys 57:783–826. https://doi.org/10.1103/RevModPhys.57.783
Namura K, Imafuku S, Kumar S et al (2019) Direction control of quasi-stokeslet induced by thermoplasmonic heating of a water vapor microbubble. Sci Rep 9:4770. https://doi.org/10.1038/s41598-019-41255-5
Petry R, Schmitt M, Popp J (2003) Raman spectroscopy–a prospective tool in the life sciences. ChemPhysChem 4:14–30. https://doi.org/10.1002/cphc.200390004
Pu H, Xiao W, Sun DW (2017) SERS-microfluidic systems: a potential platform for rapid analysis of food contaminants. Trends Food Sci Technol 70:114–126. https://doi.org/10.1016/j.tifs.2017.10.001
Rajput A, Kumar S, Singh JP (2017) Vertically standing nanoporous Al-Ag zig-zag silver nanorod arrays for highly active SERS substrates. Analyst 142:3959–3966. https://doi.org/10.1039/c7an00851a
Schlücker S (2014) Surface-enhanced raman spectroscopy: concepts and chemical applications. Angew Chemie—Int Ed 53:4756–4795. https://doi.org/10.1002/anie.201205748
Schneider CA, Rasband WS, Eliceiri KW (2012) NIH Image to ImageJ: 25 years of image analysis. Nat Methods 9:671–675
Shen Y, Cheng X, Li G et al (2016) Highly sensitive and uniform surface-enhanced Raman spectroscopy from grating-integrated plasmonic nanograss. Nanoscale Horizons 1:290–297. https://doi.org/10.1039/c6nh00059b
Shin K, Ryu K, Lee H et al (2013) Au nanoparticle-encapsulated hydrogel substrates for robust and reproducible SERS measurement. Analyst 138:932–938. https://doi.org/10.1039/c2an35862j
Sivashanmugan K, Squire K, Tan A et al (2019) Trace detection of tetrahydrocannabinol in body fluid via surface-enhanced Raman scattering and principal component analysis. ACS Sens 4:1109–1117. https://doi.org/10.1021/acssensors.9b00476
Strekas TC, Diamandopoulos PS (1990) Surface-enhanced Raman spectroscopy of bipyridines and phenylpyridines. J Phys Chem 94:1986–1991. https://doi.org/10.1021/j100368a049
Suzuki M, Maekita W, Wada Y, et al (2005) Surface enhanced raman scattering on physically self-assembled Ag nanorod arrays. In: Materials Research Society Symposium Proceedings. pp 217–222
Suzuki M, Maekita W, Wada Y et al (2006) In-line aligned and bottom-up Ag nanorods for surface-enhanced Raman spectroscopy. Appl Phys Lett 88:203121. https://doi.org/10.1063/1.2205149
Suzuki M, Imai Y, Tokunaga H, et al (2008a) Tailoring coupling of light to local plasmons by using Ag nanorods/dielectric layer/mirror sandwich structures. In: Proc. SPIE 7041, Nanostructured Thin Films
Suzuki M, Maekita W, Wada Y et al (2008) Ag nanorod arrays tailored for surface-enhanced Raman imaging in the near-infrared region. Nanotechnology 19:265304. https://doi.org/10.1088/0957-4484/19/26/265304
Varsanyi G (1969) Assignments for vibrational spectra of seven hundred benzene derivatives, 1st edn. Akademiai KiadoÌ, Budapest
Xu K, Zhang C, Lu TH et al (2017) Hybrid metal-insulator-metal structures on Si nanowires array for surface enhanced Raman scattering. Guangdian Gongcheng/Opto-Electronic Eng 44:185–191. https://doi.org/10.3969/j.issn.1003-501X.2017.02.006
Yang J, Shen D, Zhou L et al (2014) Mesoporous silica-coated plasmonic nanostructures for surface-enhanced Raman scattering detection and photothermal therapy. Adv Healthc Mater 3:1620–1628. https://doi.org/10.1002/adhm.201400053
Yao S, Zhou C, Chen D (2013) A highly porous PVA dried gel with gold nanoparticles embedded in the network as a stable and ultrasensitive SERS substrate. Chem Commun 49:6409–6411. https://doi.org/10.1039/c3cc42726a
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The authors thank Dr. Kosuke Ishikawa of Kyoto University for assisting us with the SEM observations.
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This work was supported by JST COI Grant Number JPMJCE1307.
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Kumar, S., Kanagawa, M., Namura, K. et al. Multilayer thin-film flake dispersion gel for surface-enhanced Raman spectroscopy. Appl Nanosci 13, 155–163 (2023). https://doi.org/10.1007/s13204-020-01562-0
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DOI: https://doi.org/10.1007/s13204-020-01562-0