Ultrasensitive Optical Fingerprinting of Biorelevant Molecules by Means of SERS-Mapping on Nanostructured Metasurfaces

Elizaveta Kozhina; Sergey Bedin; Alexander Martynov; Stepan Andreev; Alexey Piryazev; Yuri Grigoriev; Yulia Gorbunova; Andrey Naumov

doi:10.3390/bios13010046

Ultrasensitive Optical Fingerprinting of Biorelevant Molecules by Means of SERS-Mapping on Nanostructured Metasurfaces

Biosensors (Basel). 2022 Dec 28;13(1):46. doi: 10.3390/bios13010046.

Authors

Elizaveta Kozhina^{1

2}, Sergey Bedin^{2

3

4}, Alexander Martynov⁵, Stepan Andreev³, Alexey Piryazev^{6

7}, Yuri Grigoriev⁴, Yulia Gorbunova^{5

8}, Andrey Naumov^{2

3

9}

Affiliations

¹ Laboratory of Plasmonics, Skolkovo Institute of Science and Technology, Bolshoy Boulevard 30, bld. 1, 121205 Moscow, Russia.
² Department of Advanced Photonics and Sensorics, Lebedev Physical Institute RAS, Troitsk Branch, Fizicheskaya Str. 11, 108840 Moscow, Troitsk, Russia.
³ Laboratory of Physics of Advanced Materials and Nanostructures, Moscow State Pedagogical University, Malaya Pirogovskaya St. 1-1, 119991 Moscow, Russia.
⁴ Laboratory for the Growth of Thin Films and Inorganic Nanostructures Center of Crystallography and Photonics of RAS, Leninskiy Prosp. 59, 119333 Moscow, Russia.
⁵ Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninskiy Prosp., 31 Building 4, 119071 Moscow, Russia.
⁶ Department of Chemistry, Moscow State University, Leninskie Gory, 1, 119991 Moscow, Russia.
⁷ Research Center of Genetics and Life Sciences, Research Direction-Biomaterials, Sirius University of Science and Technology, 1 Olympic Ave, 354340 Sochi, Russia.
⁸ Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskiy Prosp., 31, 119991 Moscow, Russia.
⁹ Laboratory for Spectroscopy of Electronic Spectra of Molecules, Institute for Spectroscopy RAS, Fizicheskaya Str. 5, 108840 Moscow, Troitsk, Russia.

Abstract

The most relevant technique for portable (on-chip) sensors is Surface Enhanced Raman Scattering (SERS). This strategy crashes in the case of large (biorelevant) molecules and nano-objects, whose SERS spectra are irreproducible for "homeopathic" concentrations. We suggested solving this problem by SERS-mapping. We analyzed the distributions of SERS parameters for relatively "small" (malachite green (MG)) and "large" (phthalocyanine, H₂Pc*) molecules. While fluctuations of spectra for "small" MG were negligible, noticeable distribution of spectra was observed for "large" H₂Pc*. We show that the latter is due to a random arrangement of molecules with respect to "hot spot" areas, which have limited sizes, thus amplifying the lines corresponding to vibrations of different molecule parts. We have developed a method for engineering low-cost SERS substrates optimized for the best enhancement efficiency and a measurement protocol to obtain a reliable Raman spectrum, even for a countable number of large molecules randomly distributed over the substrate.

Keywords: Raman mapping; SERS; biosensing; nanowires; numerical simulations; track-etched membranes.

MeSH terms

Metal Nanoparticles* / chemistry
Nanostructures* / chemistry
Rosaniline Dyes
Spectrum Analysis, Raman / methods

Substances

malachite green
Rosaniline Dyes

Grants and funding

This research was funded by the Ministry of Education of Russia and Ministry (project State number AAAA-A20-120061890084-9 “Physics of nanostructured materials: fundamental research and applications in materials science, nanotechnology and photonics” and Russian Ministry of Science and Education grant No. 075-15-2021-1353. The experimental technique for spectral analysis of complex organic macromolecules is developed for the purposes of RFBR project number 20-03-00923. SEM images using the equipment of the Center for Collective Use of the Federal Research Center “Crystallography and Photonics of the Russian Academy of Sciences” The authors are members of the Leading Scientific School of the Russian Federation (grant of the President of the Russian Federation NSh-776.2022.1.2).