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A special issue of Nanomaterials (ISSN 2079-4991). This special issue belongs to the section "Nanophotonics Materials and Devices".

Deadline for manuscript submissions: closed (12 February 2023) | Viewed by 24173

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Dr. Karolína Šišková

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Guest Editor

Department of Biophysics, Faculty of Science, Palacký University Olomouc, Olomouc, Czech Republic
Interests: noble metal and iron-containing nanoparticles; preparation and physicochemical characterization of nanoparticles; infrared absorption spectroscopy; Raman spectroscopy; surface-enhanced Raman spectroscopy; laser ablation

Special Issue Information

Dear colleagues,

Surface-enhanced Raman spectroscopy (SERS) and surface enhanced resonance Raman spectroscopy (SERRS), known for almost half a century, are currently widely employed either for monitoring of species in trace concentrations in different environments, or for in situ chemical mapping, including in vivo application. Due to the great improvement in instrumentation and special design of nanomaterials, very low detection limits and increased reproducibility of SERS/SERRS signals have been achieved. This Special Issue of Nanomaterials is therefore focused on the innovative preparation of nanostructures and nanocomposites for SERS applications. We welcome contributions in the form of reviews, full-length articles, and communications.

Mostly, noble metal nanostructures of various shapes, sizes, compositions, and surface functionalizations are successfully synthesized and used for SERS/SERRS. On the other hand, syntheses of nanocomposites serving as good enhancers of Raman scattered light from the molecules being in close vicinity to noble metal nanosurfaces are more challenging because of the lower reproducibility of SERS/SERRS signals. Such nanocomposites can comprise noble metal nanostructures embedded in a functional matrix or being combined with another nanosubstrate which possesses useful properties (e.g., magnetic).

Dr. Karolína Šišková
Guest Editor

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Keywords

nanocomposite synthesis
synthesis of noble metal nanostructure
preparation of nanomaterials
SERS
SERRS
chemical mapping
nanomaterial design
functional nanocomposites
functional nanostructures

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Published Papers (7 papers)

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Research

11 pages, 1752 KiB

Open AccessArticle

Gold Nanocolumnar Templates for Effective Chemical Sensing by Surface-Enhanced Raman Scattering

by Grégory Barbillon, Christophe Humbert, María Ujué González and José Miguel García-Martín

Nanomaterials 2022, 12(23), 4157; https://doi.org/10.3390/nano12234157 - 24 Nov 2022

Cited by 6 | Viewed by 2038

Abstract

Herein, we investigate the chemical sensing by surface-enhanced Raman scattering regarding two templates of gold nanocolumns (vertical and tilted) manufactured by glancing angle deposition with magnetron sputtering. We selected this fabrication technique due to its advantages in terms of low-cost production and ease of implementation. These gold nanocolumnar structures allow producing a high density of strongly confined electric field spots within the nanogaps between the neighboring nanocolumns. Thiophenol molecules were used as model analytes since they have the principal property to adsorb well on gold surfaces. Regarding chemical sensing, the vertical (tilted) nanocolumnar templates showed a detection threshold limit of 10 nM (20 nM), an enhancement factor of 9.8 × 10

^{8}

(4.8 × 10

^{8}

), and a high quality of adsorption with an adsorption constant

K_{a d s}

of 2.0 × 10

^{6}

^{- 1}

(1.8 × 10

^{6}

^{- 1}

) for thiophenol molecules. Full article

(This article belongs to the Special Issue SERS/SERRS-Active Nanostructures and Nanocomposites)

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Figure 1

15 pages, 3648 KiB

Open AccessEditor’s ChoiceArticle

Surface-Enhanced Raman Spectroscopy Chips Based on Silver Coated Gold Nanostars

by Miriam Parmigiani, Benedetta Albini, Giovanni Pellegrini, Marco Genovesi, Lorenzo De Vita, Piersandro Pallavicini, Giacomo Dacarro, Pietro Galinetto and Angelo Taglietti

Nanomaterials 2022, 12(20), 3609; https://doi.org/10.3390/nano12203609 - 14 Oct 2022

Cited by 14 | Viewed by 4656

Abstract

Surface-enhanced Raman scattering (SERS) is becoming widely used as an analytical tool, and the search for stable and highly responsive SERS substrates able to give ultralow detection of pollutants is a current challenge. In this paper we boosted the SERS response of Gold nanostars (GNS) demonstrating that their coating with a layer of silver having a proper thickness produces a 7-fold increase in SERS signals. Glass supported monolayers of these GNS@Ag were then prepared using simple alcoxyliane chemistry, yielding efficient and reproducible SERS chips, which were tested for the detection of molecules representative of different classes of pollutants. Among them, norfloxacin was detected down to 3 ppb, which is one of the lowest limits of detection obtained with this technique for the analyte. Full article

(This article belongs to the Special Issue SERS/SERRS-Active Nanostructures and Nanocomposites)

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Graphical abstract

16 pages, 3542 KiB

Open AccessArticle

Thermally Stable Magneto-Plasmonic Nanoparticles for SERS with Tunable Plasmon Resonance

by Lina Mikoliunaite, Martynas Talaikis, Aleksandra Michalowska, Jorunas Dobilas, Voitech Stankevic, Andrzej Kudelski and Gediminas Niaura

Nanomaterials 2022, 12(16), 2860; https://doi.org/10.3390/nano12162860 - 19 Aug 2022

Cited by 19 | Viewed by 2982

Abstract

Bifunctional magneto-plasmonic nanoparticles that exhibit synergistically magnetic and plasmonic properties are advanced substrates for surface-enhanced Raman spectroscopy (SERS) because of their excellent controllability and improved detection potentiality. In this study, composite magneto-plasmonic nanoparticles (Fe₃O₄@AgNPs) were formed by mixing colloid solutions of 50 nm-sized magnetite nanoparticles with 13 nm-sized silver nanoparticles. After drying of the layer of composite Fe₃O₄@AgNPs under a strong magnetic field, they outperformed the conventional silver nanoparticles during SERS measurements in terms of signal intensity, spot-to-spot, and sample-to-sample reproducibility. The SERS enhancement factor of Fe₃O₄@AgNP-adsorbed 4-mercaptobenzoic acid (4-MBA) was estimated to be 3.1 × 10⁷ for a 633 nm excitation. In addition, we show that simply by changing the initial volumes of the colloid solutions, it is possible to control the average density of the silver nanoparticles, which are attached to a single magnetite nanoparticle. UV-Vis and SERS data revealed a possibility to tune the plasmonic resonance frequency of Fe₃O₄@AgNPs. In this research, the plasmon resonance maximum varied from 470 to 800 nm, suggesting the possibility to choose the most suitable nanoparticle composition for the particular SERS experiment design. We emphasize the increased thermal stability of composite nanoparticles under 532 and 442 nm laser light irradiation compared to that of bare Fe₃O₄ nanoparticles. The Fe₃O₄@AgNPs were further characterized by XRD, TEM, and magnetization measurements. Full article

(This article belongs to the Special Issue SERS/SERRS-Active Nanostructures and Nanocomposites)

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Graphical abstract

21 pages, 6769 KiB

Open AccessArticle

Distinctly Different Morphologies of Bimetallic Au-Ag Nanostructures and Their Application in Submicromolar SERS-Detection of Free Base Porphyrin

by Iveta Vilímová and Karolína Šišková

Nanomaterials 2021, 11(9), 2185; https://doi.org/10.3390/nano11092185 - 26 Aug 2021

Cited by 4 | Viewed by 2675

Abstract

Core-shell Au-Ag nanostructures (Au-AgNSs) are prepared by a seed-meditated growth, i.e., by a two-step process. The synthetic parameters greatly influence the morphologies of the final bimetallic Au-AgNSs, their stability and application potential as surface-enhanced Raman scattering (SERS) substrates. Direct comparison of several types of Au NPs possessing different surface species and serving as seeds in Au-AgNSs synthesis is the main objective of this paper. Borohydride-reduced (with varying stages of borohydride hydrolysis) and citrate-reduced Au NPs were prepared and used as seeds in Au-AgNSs generation. The order of reactants in seed-mediated growth procedure represents another key factor influencing the final Au-AgNSs characteristics. Electronic absorption spectra, dynamic light scattering, zeta potential measurements, energy dispersive spectroscopy and transmission electron microscopy were employed for Au-AgNSs characterization. Subsequently, possibilities and limitations of SERS-detection of unperturbed cationic porphyrin, 5,10,15,20-tetrakis(1-methyl-4-pyridyl)21H,23H-porphine (TMPyP), were investigated by using these Au-AgNSs. Only the free base (unperturbed) SERS spectral form of TMPyP is detected in all types of Au-AgNSs. It reports about a well-developed envelope of organic molecules around each Au-AgNSs which prevents metalation from occuring. TMPyP, attached via ionic interaction, was successfully detected in 10 nM concentration due to Au-AgNSs. Full article

(This article belongs to the Special Issue SERS/SERRS-Active Nanostructures and Nanocomposites)

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Graphical abstract

14 pages, 3487 KiB

Open AccessArticle

Improved Surface-Enhanced-Raman Scattering Sensitivity Using Si Nanowires/Silver Nanostructures by a Single Step Metal-Assisted Chemical Etching

by Ioannis Kochylas, Spiros Gardelis, Vlassis Likodimos, Konstantinos P. Giannakopoulos, Polycarpos Falaras and Androula G. Nassiopoulou

Nanomaterials 2021, 11(7), 1760; https://doi.org/10.3390/nano11071760 - 6 Jul 2021

Cited by 22 | Viewed by 3501

Abstract

In this study, we developed highly sensitive substrates for Surface-Enhanced-Raman-Scattering (SERS) spectroscopy, consisting of silicon nanowires (SiNWs) decorated by silver nanostructures using single-step Metal Assisted Chemical Etching (MACE). One-step MACE was performed on p-type Si substrates by immersion in AgNO₃/HF aqueous solutions resulting in the formation of SiNWs decorated by either silver aggregates or dendrites. Specifically, dendrites were formed during SiNWs’ growth in the etchant solution, whereas aggregates were grown after the removal of the dendrites from the SiNWs in HNO₃ aqueous solution and subsequent re-immersion of the specimens in a AgNO₃/HF aqueous solution by adjusting the growth time to achieve the desired density of silver nanostructures. The dendrites had much larger height than the aggregates. R6G was used as analyte to test the SERS activity of the substrates prepared by the two fabrication processes. The silver aggregates showed a considerably lower limit of detection (LOD) for SERS down to a R6G concentration of 10⁻¹³ M, and much better uniformity in terms of detection in comparison with the silver dendritic structures. Enhancement factors in the range 10⁵–10¹⁰ were calculated, demonstrating very high SERS sensitivities for analytic applications. Full article

(This article belongs to the Special Issue SERS/SERRS-Active Nanostructures and Nanocomposites)

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Graphical abstract

10 pages, 1234 KiB

Open AccessArticle

SERS-Active Pattern in Silver-Ion-Exchanged Glass Drawn by Infrared Nanosecond Laser

by Ekaterina Babich, Vladimir Kaasik, Alexey Redkov, Thomas Maurer and Andrey Lipovskii

Nanomaterials 2020, 10(9), 1849; https://doi.org/10.3390/nano10091849 - 16 Sep 2020

Cited by 9 | Viewed by 3844

Abstract

The irradiation of silver-to-sodium ion-exchanged glass with 1.06-μm nanosecond laser pulses of mJ-range energy results in the formation of silver nanoparticles under the glass surface. Following chemical removal of ~25-nm glass layer reveals a pattern of nanoparticles capable of surface enhancement of Raman scattering (SERS). The pattern formed when laser pulses are more than half-overlapped provides up to ~10⁵ enhancement and uniform SERS signal distribution, while the decrease of the pulse overlap results in an order of magnitude higher but less uniform enhancement. Full article

(This article belongs to the Special Issue SERS/SERRS-Active Nanostructures and Nanocomposites)

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12 pages, 4651 KiB

Open AccessArticle

Numerical Investigation on Multiple Resonant Modes of Double-Layer Plasmonic Grooves for Sensing Application

by Shuwen Chu, Qiao Wang, Li Yu, Huixuan Gao, Yuzhang Liang and Wei Peng

Nanomaterials 2020, 10(2), 308; https://doi.org/10.3390/nano10020308 - 11 Feb 2020

Cited by 12 | Viewed by 3120

Abstract

A high-performance multi-resonance plasmonic sensor with double-layer metallic grooves is theoretically constructed by introducing a polymethyl methacrylate groove with a numerical simulation method. Multiple resonance wavelengths can be generated at the oblique incidence, and the number and feature of resonant mode for sensing detection is different for various incident angles. Specifically, at the incident angle of 30°, the reflection spectrum exhibits two resonant dips, in which the dip at the wavelength of 1066 nm has an extremely narrow line width of ~4.5 nm and high figure of merit of ~111.11. As the incident angle increases, the electric dipole mode gradually weakens, but the surface plasmon resonance and cavity resonance mode are enhanced. Therefore, for an incident angle of 65°, three resonance dips for sensing can be generated in the reflection spectrum to realize three-channel sensing measurement. These double-layer plasmonic grooves have potential in the development of advanced biochemical surface plasmon polariton measurements. Full article

(This article belongs to the Special Issue SERS/SERRS-Active Nanostructures and Nanocomposites)

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