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Nanomaterials
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Nanomaterials for Surface Enhanced Raman Spectroscopy
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Nanomaterials for Surface Enhanced Raman Spectroscopy

A special issue of Nanomaterials (ISSN 2079-4991). This special issue belongs to the section "Nanofabrication and Nanomanufacturing".

Deadline for manuscript submissions: closed (30 September 2021) | Viewed by 27234

Special Issue Editor

Dr. Andrzej Kudelski

E-Mail Website
Guest Editor
Faculty of Chemistry, University of Warsaw, 1 Pasteur St., 02-093 Warsaw, Poland
Interests: synthesis of new nanomaterials for Raman spectroscopy analysis of surfaces; photochemical synthesis and reconstruction of silver nanostructures including their so-called plasmon-driven transformation; application of surface enhanced Raman spectroscopy for DNA detection
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

For many decades, Raman spectroscopy has not been considered a useful analytical tool because of the very low efficiency of “normal” Raman scattering (the typical cross-section for Raman scattering is 11 and 8 orders of magnitude smaller than the typical cross-sections for absorption in ultraviolet and infrared). However, by utilizing special electromagnetic resonators constructed from plasmonic metals, the Raman scattering cross-sections could be increased by many orders of magnitude, making possible the observation of good-quality Raman spectra of even a single molecule. This effect is called SERS (surface-enhanced Raman scattering). Crucial to obtaining strong SERS signal is the application of an efficient SERS substrate. This Special Issue of Nanomaterials will attempt to cover the recent advances in nanomaterials for SERS spectroscopy, concerning not only their synthesis, but also simulations of the obtained local SERS enhancement factors and the applications of new nanomaterials in chemical and biochemical SERS analysis.

Dr. Andrzej Kudelski
Guest Editor

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Keywords

  • multifunctional materials
  • plasmonic nanostructures
  • surface-enhanced Raman spectroscopy
  • SERS sensors
  • SERS biosensors
  • shell-isolated nanoparticle-enhanced Raman spectroscopy
  • SERS substrates
  • tip-enhanced Raman spectroscopy

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Published Papers (6 papers)

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Research

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15 pages, 21220 KiB  
Article
Genetic Algorithm-Driven Surface-Enhanced Raman Spectroscopy Substrate Optimization
by Buse Bilgin, Cenk Yanik, Hulya Torun and Mehmet Cengiz Onbasli
Nanomaterials 2021, 11(11), 2905; https://doi.org/10.3390/nano11112905 - 29 Oct 2021
Cited by 2 | Viewed by 3745
Abstract
Surface-enhanced Raman spectroscopy (SERS) is a highly sensitive and molecule-specific detection technique that uses surface plasmon resonances to enhance Raman scattering from analytes. In SERS system design, the substrates must have minimal or no background at the incident laser wavelength and large Raman [...] Read more.
Surface-enhanced Raman spectroscopy (SERS) is a highly sensitive and molecule-specific detection technique that uses surface plasmon resonances to enhance Raman scattering from analytes. In SERS system design, the substrates must have minimal or no background at the incident laser wavelength and large Raman signal enhancement via plasmonic confinement and grating modes over large areas (i.e., squared millimeters). These requirements impose many competing design constraints that make exhaustive parametric computational optimization of SERS substrates prohibitively time consuming. Here, we demonstrate a genetic-algorithm (GA)-based optimization method for SERS substrates to achieve strong electric field localization over wide areas for reconfigurable and programmable photonic SERS sensors. We analyzed the GA parameters and tuned them for SERS substrate optimization in detail. We experimentally validated the model results by fabricating the predicted nanostructures using electron beam lithography. The experimental Raman spectrum signal enhancements of the optimized SERS substrates validated the model predictions and enabled the generation of a detailed Raman profile of methylene blue fluorescence dye. The GA and its optimization shown here could pave the way for photonic chips and components with arbitrary design constraints, wavelength bands, and performance targets. Full article
(This article belongs to the Special Issue Nanomaterials for Surface Enhanced Raman Spectroscopy)
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12 pages, 2117 KiB  
Article
Gold-Deposited Nickel Foam as Recyclable Plasmonic Sensor for Therapeutic Drug Monitoring in Blood by Surface-Enhanced Raman Spectroscopy
by Saiqa Muneer, Daniel K. Sarfo, Godwin A. Ayoko, Nazrul Islam and Emad L. Izake
Nanomaterials 2020, 10(9), 1756; https://doi.org/10.3390/nano10091756 - 6 Sep 2020
Cited by 21 | Viewed by 4030
Abstract
A sensitive and recyclable plasmonic nickel foam sensor has been developed for surface-enhanced Raman spectroscopy (SERS). A simple electrochemical method was used to deposit flower-shaped gold nanostructures onto nickel foam substrate. The high packing of the gold nanoflowers onto the nickel foam led [...] Read more.
A sensitive and recyclable plasmonic nickel foam sensor has been developed for surface-enhanced Raman spectroscopy (SERS). A simple electrochemical method was used to deposit flower-shaped gold nanostructures onto nickel foam substrate. The high packing of the gold nanoflowers onto the nickel foam led to a high enhancement factor (EF) of 1.6 × 1011. The new SERS sensor was utilized for the direct determination of the broad-spectrum β-lactam carbapenem antibiotic meropenem in human blood plasma down to one pM. The sensor was also used in High Performance Liquid Chromatography (HPLC)-SERS assembly to provide fingerprint identification of meropenem in human blood plasma. Moreover, the SERS measurements were reproducible in aqueous solution and human blood plasma (RSD = 5.5%) and (RSD = 2.86%), respectively at 200 µg/mL (n = 3), and successfully recycled using a simple method, and hence, used for the repeated determination of the drug by SERS. Therefore, the new sensor has a strong potential to be applied for the therapeutic drug monitoring of meropenem at points of care and intensive care units. Full article
(This article belongs to the Special Issue Nanomaterials for Surface Enhanced Raman Spectroscopy)
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16 pages, 4225 KiB  
Article
Gold Nanorod Assemblies: The Roles of Hot-Spot Positioning and Anisotropy in Plasmon Coupling and SERS
by Priyanka Dey, Verena Baumann and Jessica Rodríguez-Fernández
Nanomaterials 2020, 10(5), 942; https://doi.org/10.3390/nano10050942 - 14 May 2020
Cited by 30 | Viewed by 4202
Abstract
Plasmon-coupled colloidal nanoassemblies with carefully sculpted “hot-spots” and intense surface-enhanced Raman scattering (SERS) are in high demand as photostable and sensitive plasmonic nano-, bio-, and chemosensors. When maximizing SERS signals, it is particularly challenging to control the hot-spot density, precisely position the hot-spots [...] Read more.
Plasmon-coupled colloidal nanoassemblies with carefully sculpted “hot-spots” and intense surface-enhanced Raman scattering (SERS) are in high demand as photostable and sensitive plasmonic nano-, bio-, and chemosensors. When maximizing SERS signals, it is particularly challenging to control the hot-spot density, precisely position the hot-spots to intensify the plasmon coupling, and introduce the SERS molecule in those intense hot-spots. Here, we investigated the importance of these factors in nanoassemblies made of a gold nanorod (AuNR) core and spherical nanoparticle (AuNP) satellites with ssDNA oligomer linkers. Hot-spot positioning at the NR tips was made possible by selectively burying the ssDNA in the lateral facets via controlled Ag overgrowth while retaining their hybridization and assembly potential at the tips. This strategy, with slight alterations, allowed us to form nanoassemblies that only contained satellites at the NR tips, i.e., directional anisotropic nanoassemblies; or satellites randomly positioned around the NR, i.e., nondirectional nanoassemblies. Directional nanoassemblies featured strong plasmon coupling as compared to nondirectional ones, as a result of strategically placing the hot-spots at the most intense electric field position of the AuNR, i.e., retaining the inherent plasmon anisotropy. Furthermore, as the dsDNA was located in these anisotropic hot-spots, this allowed for the tag-free detection down to ~10 dsDNA and a dramatic SERS enhancement of ~1.6 × 108 for the SERS tag SYBR gold, which specifically intercalates into the dsDNA. This dramatic SERS performance was made possible by manipulating the anisotropy of the nanoassemblies, which allowed us to emphasize the critical role of hot-spot positioning and SERS molecule positioning in nanoassemblies. Full article
(This article belongs to the Special Issue Nanomaterials for Surface Enhanced Raman Spectroscopy)
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13 pages, 2495 KiB  
Article
Synthesis of Monolayer Gold Nanorings Sandwich Film and Its Higher Surface-Enhanced Raman Scattering Intensity
by Liqiu Zhang, Tiying Zhu, Cheng Yang, Ho Young Jang, Hee-Jeong Jang, Lichun Liu and Sungho Park
Nanomaterials 2020, 10(3), 519; https://doi.org/10.3390/nano10030519 - 13 Mar 2020
Cited by 4 | Viewed by 3922
Abstract
Most previous studies relating to surface-enhanced Raman spectroscopy (SERS) signal enhancement were focused on the interaction between the light and the substrate in the x-y axis. 3D SERS substrates reported in the most of previous papers could contribute partial SERS enhancement [...] Read more.
Most previous studies relating to surface-enhanced Raman spectroscopy (SERS) signal enhancement were focused on the interaction between the light and the substrate in the x-y axis. 3D SERS substrates reported in the most of previous papers could contribute partial SERS enhancement via z axis, but the increases of the surface area were the main target for those reports. However, the z axis is also useful in achieving improved SERS intensity. In this work, hot spots along the z axis were specifically created in a sandwich nanofilm. Sandwich nanofilms were prepared with self-assembly and Langmuir-Blodgett techniques, and comprised of monolayer Au nanorings sandwiched between bottom Ag mirror and top Ag cover films. Monolayer Au nanorings were formed by self-assembly at the interface of water and hexane, followed by Langmuir-Blodgett transfer to a substrate with sputtered Ag mirror film. Their hollow property allows the light transmitted through a cover film. The use of a Ag cover layer of tens nanometers in thickness was critical, which allowed light access to the middle Au nanorings and the bottom Ag mirror, resulting in more plasmonic resonance and coupling along perpendicular interfaces (z-axis). The as-designed sandwich nanofilms could achieve an overall ~8 times SERS signals amplification compared to only the Au nanorings layer, which was principally attributed to enhanced electromagnetic fields along the created z-axis. Theoretical simulations based on finite-difference time-domain (FDTD) method showed consistent results with the experimental ones. This study points out a new direction to enhance the SERS intensity by involving more hot spots in z-axis in a designer nanostructure for high-performance molecular recognition and detection. Full article
(This article belongs to the Special Issue Nanomaterials for Surface Enhanced Raman Spectroscopy)
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Review

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20 pages, 1471 KiB  
Review
Strategies for SERS Detection of Organochlorine Pesticides
by Rebeca Moldovan, Bogdan-Cezar Iacob, Cosmin Farcău, Ede Bodoki and Radu Oprean
Nanomaterials 2021, 11(2), 304; https://doi.org/10.3390/nano11020304 - 25 Jan 2021
Cited by 39 | Viewed by 6017
Abstract
Organochlorine pesticides (OCPs) embody highly lipophilic hazardous chemicals that are being phased out globally. Due to their persistent nature, they are still contaminating the environment, being classified as persistent organic pollutants (POPs). They bioaccumulate through bioconcentration and biomagnification, leading to elevated concentrations at [...] Read more.
Organochlorine pesticides (OCPs) embody highly lipophilic hazardous chemicals that are being phased out globally. Due to their persistent nature, they are still contaminating the environment, being classified as persistent organic pollutants (POPs). They bioaccumulate through bioconcentration and biomagnification, leading to elevated concentrations at higher trophic levels. Studies show that human long-term exposure to OCPs is correlated with a large panel of common chronic diseases. Due to toxicity concerns, most OCPs are listed as persistent organic pollutants (POPs). Conventionally, separation techniques such as gas chromatography are used to analyze OCPs (e.g., gas chromatography coupled with mass spectrometry (GC/MS)) or electron capture detection (GC/ECD). These are accurate, but expensive and time-consuming methods, which can only be performed in centralized lab environments after extensive pretreatment of the collected samples. Thus, researchers are continuously fueling the need to pursue new faster and less expensive alternatives for their detection and quantification that can be used in the field, possibly in miniaturized lab-on-a-chip systems. In this context, surface enhanced Raman spectroscopy (SERS) represents an exceptional analytical tool for the trace detection of pollutants, offering molecular fingerprint-type data and high sensitivity. For maximum signal amplification, two conditions are imposed: an efficient substrate and a high affinity toward the analyte. Unfortunately, due to the highly hydrophobic nature of these pollutants (OCPs,) they usually have a low affinity toward SERS substrates, increasing the challenge in their SERS detection. In order to overcome this limitation and take advantage of on-site Raman analysis of pollutants, researchers are devising ingenious strategies that are synthetically discussed in this review paper. Aiming to maximize the weak Raman signal of organochlorine pesticides, current practices of increasing the substrate’s performance, along with efforts in improving the selectivity by SERS substrate functionalization meant to adsorb the OCPs in close proximity (via covalent, electrostatic or hydrophobic bonds), are both discussed. Moreover, the prospects of multiplex analysis are also approached. Finally, other perspectives for capturing such hydrophobic molecules (MIPs—molecularly imprinted polymers, immunoassays) and SERS coupled techniques (microfluidics—SERS, electrochemistry—SERS) to overcome some of the restraints are presented. Full article
(This article belongs to the Special Issue Nanomaterials for Surface Enhanced Raman Spectroscopy)
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25 pages, 11886 KiB  
Review
Substrates for Surface-Enhanced Raman Scattering Formed on Nanostructured Non-Metallic Materials: Preparation and Characterization
by Jan Krajczewski, Robert Ambroziak and Andrzej Kudelski
Nanomaterials 2021, 11(1), 75; https://doi.org/10.3390/nano11010075 - 31 Dec 2020
Cited by 29 | Viewed by 4156
Abstract
The efficiency of the generation of Raman spectra by molecules adsorbed on some substrates (or placed at a very close distance to some substrates) may be many orders of magnitude larger than the efficiency of the generation of Raman spectra by molecules that [...] Read more.
The efficiency of the generation of Raman spectra by molecules adsorbed on some substrates (or placed at a very close distance to some substrates) may be many orders of magnitude larger than the efficiency of the generation of Raman spectra by molecules that are not adsorbed. This effect is called surface-enhanced Raman scattering (SERS). In the first SERS experiments, nanostructured plasmonic metals have been used as SERS-active materials. Later, other types of SERS-active materials have also been developed. In this review article, various SERS substrates formed on nanostructured non-metallic materials, including non-metallic nanostructured thin films or non-metallic nanoparticles covered by plasmonic metals and SERS-active nanomaterials that do not contain plasmonic metals, are described. Significant advances for many important applications of SERS spectroscopy of substrates based on nanostructured non-metallic materials allow us to predict a large increase in the significance of such nanomaterials in the near future. Some future perspectives on the application of SERS substrates utilizing nanostructured non-metallic materials are also presented. Full article
(This article belongs to the Special Issue Nanomaterials for Surface Enhanced Raman Spectroscopy)
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