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Plasmonic Nanoparticles in Chemical Analysis RSC Advances REVIEW View Article Online View Journal | View Issue Plasmonic nanoparticles in chemical analysis Jan Krajczewski, Karol Koła˛taj and Andrzej Kudelski* Cite this: RSC Adv.,2017,7, 17559 Many very sensitive analytical methods utilising specific properties of plasmonic metal nanoparticles have been developed. Some of these techniques are so sensitive that observation of the reliable signal even from a single molecule of the analyte is possible. In this review article we present the most important analytical techniques based on the plasmonic properties of selected metal nanoparticles and the basic theoretical background of these analytical techniques, including the mechanism of the interaction of the electromagnetic radiation with the plasmonic nanoparticles. The analytical techniques presented in this article include methods based on the change of the optical properties of plasmonic nanoparticles caused by analyte-induced aggregation, etching or the change of the growth of plasmonic nanoparticles, and techniques utilising increased efficiency of some optical processes in the proximity of the plasmonic nanoparticles, e.g. surface-enhanced Raman scattering (SERS), surface enhanced infra-red Received 23rd January 2017 absorption (SEIRA), and metal enhanced fluorescence (MEF). Recently, an observed increase in the Accepted 16th March 2017 Creative Commons Attribution-NonCommercial 3.0 Unported Licence. number of applications of techniques utilising surface plasmon resonance for the analysis of various DOI: 10.1039/c7ra01034f industrial, biological, medical, and environmental samples allows us to predict a large increase of the rsc.li/rsc-advances significance of these techniques in the near future. 1. Introduction intensive colour of suspensions of Ag and Au nanoparticles was the reason for using these materials in ancient times. For When electromagnetic radiation interacts with metal nano- example, in ancient Rome gold and silver nanoparticles were particles with a negative real and small positive imaginary used (of course without an understanding of the phenomenon) This article is licensed under a dielectric constant (e.g. silver and gold nanoparticles) it induces for dyeing glass and ceramics. Such use of nanoparticles a collective oscillation of surface conduction electrons called continued over time and many examples of stained glasses dyed surface plasmons.1–5 Excitation of surface plasmons leads to an using nanoparticles can be found in churches from the Middle enhanced electromagnetic eld at some places on the illumi- Ages. Various colours of glass were obtained by the formation of Open Access Article. Published on 20 March 2017. Downloaded 9/25/2021 2:38:33 AM. nated nanoparticles. Surface plasmons excited in silver and nanoparticles with different diameters. For example, red glass gold nanoparticles during their interaction with light are also oen contained ca. 20 nm gold nanoparticles, pink glass con- responsible for the bright colours of Ag and Au colloids. The tained ca. 30 nm gold nanoparticles and orange glass contained gold nanoparticles larger than 80 nm or silver nanoparticles. This method of glass dyeing is so durable that glass dyed Department of Chemistry, Faculty of Chemistry, University of Warsaw, Pasteur 1, centuries ago is still colourful. 02-093 Warsaw, Poland. E-mail: [email protected]; Fax: +48-225526434 Jan Krajczewski is pursuing his Karol Koła˛taj is pursuing his PhD at the University of War- PhD at the University of War- saw, Poland. His main research saw, Poland. His main research interest is surface-enhanced interest is shell-isolated Raman spectroscopy (SERS) nanoparticle-enhanced Raman and synthesis of various silver spectroscopy (SHINERS) and and gold nanoresonators. synthesis of electromagnetic nanoresonators for SHINERS measurements. This journal is © The Royal Society of Chemistry 2017 RSC Adv.,2017,7, 17559–17576 | 17559 View Article Online RSC Advances Review In this work some analytical applications of plasmonic metal plasma near nanoparticle's surface when the nanoparticle is nanoparticles are reviewed. We have focused on analytical irradiated – see Fig. 1a.9,10 applications based on the change of the plasmonic properties of Dislocation of metal electrons in the nanoparticle during Ag and Au nanoparticles caused by analyte-induced aggrega- irradiation leads to creation of the electric dipole and, as tion, etching or change of the grow of plasmonic nanoparticles, a consequence, to the additional electric eld near the and on the analytical methods utilising increase of the effi- nanoparticle's surface. The combined electric eld depends ciency of various optical processes in the proximity of gold and on the electric eld of the irradiating electromagnetic wave silver nanoparticles, such as surface-enhanced Raman scat- and on the eld created near nanoparticle's surface by the tering (SERS), surface enhanced infra-red absorption (SEIRA), surface plasmon resonance. For a spherical nanoparticle the and metal enhanced uorescence (MEF).6,7 We have also briey electric eld outside its surface is described by the following described the mechanism of the interaction of the electro- equation: magnetic wave with the plasmonic nanoobjects. All mentioned above plasmonic properties of gold and silver are only observed when gold and silver structures have sizes in the nanometers range (or the Au/Ag surface is nanostructured). The appearance of new functionalities of materials aer decreasing the size of its individual parts into the nanometers range is a realization of the futuristic concept of Richard Feynman presented in 1959 in the speech called: “There's Plenty of Room at the Bottom”.In this lecture Feynman described some new possibilities that comes from use of systems in the nanometric scale. Futuristic nanotechnology idea described in 1959 by Feynman is today's Creative Commons Attribution-NonCommercial 3.0 Unported Licence. reality and presented in this work applications of gold and silver nanoparticles is only a small part of the practical applications of nanomaterials. 2. Surface plasmon resonance (SPR) and distribution of electromagnetic field around spherical “plasmonic” This article is licensed under a nanoparticles Optical properties of nanoparticles from IB metals are very Open Access Article. Published on 20 March 2017. Downloaded 9/25/2021 2:38:33 AM. important for many of their applications. While a gold ingot is yellow and a silver ingot is greyish, colour of Au and Ag nano- particles strongly depends on their size and shape, and can have all colours of rainbow from red through green to violet.8 Silver and gold nanoparticles have their intensive and various colours because of plasmons excited on their surfaces. Metal can be considered as positively charged atomic nuclei surrounded by a plasma of free electrons from the conduction band. Surface plasmon resonance (SPR) is a collective oscillation of electron Fig. 1 (a) Schematic of plasmon oscillation in spherical plasmonic nanoparticle showing the displacement of the conduction electron Andrzej Kudelski is a professor at charge cloud relative to the nuclei. Reprinted with permission from ref. 10. Copyright 2003 American Chemical Society. (b) Electric field the University of Warsaw, enhancement contours around the silver trigonal prism for a plane that Poland. His area of expertise is is perpendicular to the trigonal axis and that passes midway through vibrational spectroscopy of the prism. The prism is illuminated by the light that have k along the molecules at metal surfaces, trigonal axis and E along the abscissa. The size of the prism: side length ¼ ¼ mainly SERS, SHINERS, SEROA 100 nm, thickness 16 nm. The wavelength of the excitation radiation: for the left image 770 nm, and for the right image 460 nm. and SEIRA spectroscopy and Reprinted with permission from ref. 10. Copyright 2003 American synthesis of electromagnetic Chemical Society. (c) Electromagnetic field distribution in the dimers nanoresonators for various consisting of two types of nanoparticles: (A) and (B) Silver nano- surface-enhanced vibrational particles (30 nm) with a thin silica layer (5 nm) and (C) and (D) silica spectroscopy. nanoparticles (30 nm) with a thin silver layer (5 nm) at two excitation wavelength (532 nm and 785 nm). Reprinted with permission from ref. 31. Copyright 2015 the Owner Societies of PCCP. 17560 | RSC Adv.,2017,7,17559–17576 This journal is © The Royal Society of Chemistry 2017 View Article Online Review RSC Advances " # 4 6 2 ~x 3x Csca ¼ 8p 3k a ½ðe À emÞ=ðe þ 2emÞ Eout ¼ Eo~x À aEo À x~x þ y~y þ z~z r3 r5 where k ¼ 2p/l and l is wavelength. As can be seen from 3 6 14 equations above Cabs scales with a while Csca scales with a . It where Eo is the magnitude of the external electric eld (pointing along the x-axis), a is the metal polarizability, x, y, z are Carte- means that absorption is more important for smaller nano- sian coordinates, r is the radial distance, and ~x, ~y, ~z are unit particles (for such nanoparticles scattering can be neglected) vectors.10,11 As can be seen, the rst part of the above equation is while for larger nanoparticles light scattering becomes 14 the electric eld of irradiating light and the second part is the dominant. electric eld from the induced dipole created on the nano- Surface plasmon resonance depends on many parameters of particle's surface. For a nanoparticle with a spherical geometry the nanoparticle, such as: its size and shape (Fig. 2 shows polarizability a can be expressed as: various
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