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Advances in the Applications of Surface Enhanced Raman Scattering

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A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Analytical Chemistry".

Deadline for manuscript submissions: closed (31 May 2024) | Viewed by 17866

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Prof. Dr. Maurizio Muniz-Miranda

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Department of Chemistry, University of Florence, Via Lastruccia 3, I-50019 Sesto Fiorentino, Italy
Interests: metal nanoparticles; Raman spectroscopy; SERS; laser ablation in liquid; nanomedicine; heterogeneous catalysis; computational chemistry
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Dear Colleagues,

Nanoparticles have great capacity to adsorb molecules or ions, by virtue of their large surface development, establishing strong interactions with the “active sites” of the nanoparticle surface, seen as structural defects of the same surface with special chemical valences. The formation of surface complexes demonstrates the reactivity of the nanostructured surface, which can catalyze chemical reactions as well as interact with biological systems. From here, possible applications of the nanoparticles themselves are derived, especially in the field of heterogeneous catalysis for both chemical and photochemical reactions. In addition, nanoparticles composed of metals have particular optical properties due to the presence of “localized plasmons”. The strong localization of the electromagnetic field associated with the localized plasmons allows obtaining an enhancement of several orders of magnitude (usually up to 10⁷factors) of the Raman response in the so-called SERS (surface enhanced Raman scattering) effect, when molecules are adsorbed on nanostructured surfaces of metals with high optical reflectivity, such as Ag, Au, and Cu. In addition to this mechanism, a chemical enhancement contribution to the Raman signal of the adsorbed molecule can also be effective, due to the perturbation of the molecular polarizability because of the formation of chemical complexes of the molecule itself with the active sites of the metallic surface. Hence, by means of the SERS enhancement, Raman spectroscopy allows identifying, at trace level, reactants or products or byproducts of catalytic reactions, as well as pollutants. In this Special Issue, the interest is focused on the recent applications of the SERS spectroscopy, especially in the field of heterogeneous catalysis, sensoring, biomedicine, and environmental protection.

Prof. Dr. Maurizio Muniz-Miranda
Guest Editor

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Keywords

surface-enhanced Raman scattering
enhancement
applications
nanoparticles
plasmons

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Advances in the Applications of Surface Enhanced Raman Scattering, 2nd Edition in Molecules

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13 pages, 7103 KiB

Open AccessArticle

Controllable Construction of Aptamer-Modified Fe₃O₄@SiO₂-Au Core-Shell-Satellite Nanocomposites with Surface-Enhanced Raman Scattering and Photothermal Properties and Their Effective Capture, Detection, and Elimination of Staphylococcus aureus

by Yongdan Wang, Shengyi Wang, Yuhui Zou, Yuze Gao, Boya Ma, Yuhan Zhang, Huasong Dai, Jingmei Ma and Wenshi Zhao

Molecules 2024, 29(15), 3593; https://doi.org/10.3390/molecules29153593 - 30 Jul 2024

Viewed by 1031

Abstract

The early monitoring and inactivation of bacteria are of crucial importance in preventing the further spread of foodborne pathogens. Staphylococcus aureus (S. aureus), a prototypical foodborne pathogen, is widely present in the natural environment and has the capability to trigger a range of diseases at low concentrations. In this work, we designed Fe₃O₄@SiO₂-Au core–shell–satellite nanocomposites (NCs) modified with aptamer for efficient capture, high-sensitivity surface-enhanced Raman scattering (SERS) detection, and photothermal therapy (PTT) against S. aureus. Fe₃O₄@SiO₂-Au NCs with tunable Au nanocrystal nanogaps were prepared. By combining the finite-difference time-domain (FDTD) method and experimental results, we studied the electric field distribution of Fe₃O₄@SiO₂-Au under different Au nanogaps and ultimately obtained the optimal SERS substrate FSA-60. The modification of aptamer on the surfaces of FSA-60 could be used for the specific capture and selective detection of S. aureus, achieving a detection limit of as low as 50 cfu/mL. Furthermore, Apt-FSA-60 possessed excellent photothermal properties, demonstrating the strong photothermal killing ability against S. aureus. Therefore, Apt-FSA-60 is a promising high-sensitivity SERS substrate and efficient photothermal agent and is expected to be widely applied and promoted in future disease prevention and treatment. Full article

(This article belongs to the Special Issue Advances in the Applications of Surface Enhanced Raman Scattering)

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15 pages, 4642 KiB

Open AccessArticle

Magnetic Titanium Dioxide Nanocomposites as a Recyclable SERRS Substrate for the Ultrasensitive Detection of Histidine

by Hailin Wen, Miao Li, Chao-Yang Zhao, Tao Xu, Shuang Fu, Huimin Sui and Cuiyan Han

Molecules 2024, 29(12), 2906; https://doi.org/10.3390/molecules29122906 - 19 Jun 2024

Viewed by 715

Abstract

A highly sensitive, selective and recyclable histidine detection method based on magnetic Fe₃O₄@mTiO₂ (M-TiO₂) nanocomposites with SERRS was developed. Mesoporous M-TiO₂ nanoparticles were functionalized with 4-aminothiophenol and then coupled with histidine through an azo coupling reaction in 5 min, producing the corresponding azo compound. The strong and specific SERRS response of the azo product allowed for ultrasensitive and selective detection for histidine with an M-TiO₂ device loaded with Ag NPs due to the molecular resonance effect and plasmonic effect of Ag NPs under a 532 nm excitation laser. The sensitivity was further enhanced with the magnetic enrichment of M-TiO₂. The limit of detection (LOD) was as low as 8.00 × 10⁻¹² mol/L. The M-TiO₂ demonstrated applicability towards histidine determination in human urine without any sample pretreatment. Additionally, the M-TiO₂ device can be recycled for 3 cycles with the photodegradation of the azo product under UV irradiation due to TiO₂-assisted and plasmon-enhanced photocatalysis. In summary, a multifunctional and recyclable M-TiO₂ device was synthesized based on azo coupling and SERRS spectroscopy for ultra-sensitive and specific histidine sensing. In addition, the proposed system demonstrated the potential for the multiplex determination of toxic compounds in the fields of food safety, industrial production and environmental protection, which benefit from the fingerprint property and universality of SERRS. Full article

(This article belongs to the Special Issue Advances in the Applications of Surface Enhanced Raman Scattering)

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13 pages, 4428 KiB

Open AccessArticle

Photocatalytic Deposition of Au Nanoparticles on Ti₃C₂T_x MXene Substrates for Surface-Enhanced Raman Scattering

by Zhi Yang, Lu Yang, Yucun Liu and Lei Chen

Molecules 2024, 29(10), 2383; https://doi.org/10.3390/molecules29102383 - 18 May 2024

Cited by 2 | Viewed by 1535

Abstract

Surface-enhanced Raman scattering (SERS) is a promising technique for sensitive detection. The design and optimization of plasma-enhanced structures for SERS applications is an interesting challenge. In this study, we found that the SERS activity of MXene (Ti₃C₂T_x) can be improved by adding Au nanoparticles (NPs) in a simple photoreduction process. Fluoride-salt-etched MXene was deposited by drop-casting on a glass slide, and Au NPs were formed by the photocatalytic growth of gold(III) chloride trihydrate solutions under ultraviolet (UV) irradiation. The Au–MXene substrate formed by Au NPs anchored on the Ti₃C₂T_x sheet produced significant SERS through the synergistic effect of chemical and electromagnetic mechanisms. The structure and size of the Au-decorated MXene depended on the reaction time. When the MXene films were irradiated with a large number of UV photons, the size of the Au NPs increased. Hot spots were formed in the nanoscale gaps between the Au NPs, and the abundant surface functional groups of the MXene effectively adsorbed and interacted with the probe molecules. Simultaneously, as a SERS substrate, the proposed Au–MXene composite exhibited a wider linear range of 10⁻⁴–10⁻⁹ mol/L for detecting carbendazim. In addition, the enhancement factor of the optimized SERS substrate Au–MXene was 1.39 × 10⁶, and its relative standard deviation was less than 13%. This study provides a new concept for extending experimental strategies to further improve the performance of SERS. Full article

(This article belongs to the Special Issue Advances in the Applications of Surface Enhanced Raman Scattering)

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41 pages, 12277 KiB

Open AccessArticle

Highly Sensitive Measurement of Horseradish Peroxidase Using Surface-Enhanced Raman Scattering of 2,3-Diaminophenazine

by Evgeniy G. Evtushenko, Elizaveta S. Gavrilina, Alexandra D. Vasilyeva, Lyubov V. Yurina and Ilya N. Kurochkin

Molecules 2024, 29(4), 793; https://doi.org/10.3390/molecules29040793 - 8 Feb 2024

Viewed by 1381

Abstract

The development of various enzyme-linked immunosorbent assays (ELISAs) coupled with surface-enhanced Raman scattering (SERS) detection is a growing area in analytical chemistry due to their potentially high sensitivity. A SERS-based ELISA with horseradish peroxidase (HRP) as an enzymatic label, an o-phenylenediamine (oPD) substrate, and a 2,3-diaminophenazine (DAP) enzymatic product was one of the first examples of such a system. However, the full capabilities of this long-known approach have yet to be revealed. The current study addresses a previously unrecognized problem of SERS detection stage performance. Using silver nanoparticles and model mixtures of oPD and DAP, the effects of the pH, the concentration of the aggregating agent, and the particle surface chloride stabilizer were extensively evaluated. At the optimal mildly acidic pH of 3, a 0.93 to 1 M citrate buffer, and AgNPs stabilized with 20 mM chloride, a two orders of magnitude advantage in the limits of detection (LODs) for SERS compared to colorimetry was demonstrated for both DAP and HRP. The resulting LOD for HRP of 0.067 pmol/L (1.3 amol per assay) underscores that the developed approach is a highly sensitive technique. We suppose that this improved detection system could become a useful tool for the development of SERS-based ELISA protocols. Full article

(This article belongs to the Special Issue Advances in the Applications of Surface Enhanced Raman Scattering)

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18 pages, 5563 KiB

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Investigating Perampanel Antiepileptic Drug by DFT Calculations and SERS with Custom Spinning Cell

by Nicolò Simone Villa, Chiara Picarelli, Federica Iacoe, Chiara Giuseppina Zanchi, Paolo M. Ossi, Andrea Lucotti and Matteo Tommasini

Molecules 2023, 28(16), 5968; https://doi.org/10.3390/molecules28165968 - 9 Aug 2023

Cited by 3 | Viewed by 1214

Abstract

SERS, a clinical practice where medical doctors can monitor the drug concentration in biological fluids, has been proposed as a viable approach to therapeutic drug monitoring (TDM) of the antiepileptic drug Perampanel. The adoption of an acidic environment during the SERS experiments was found to be effective in enhancing the spectroscopic signal. In this work, we combine SERS experiments, conducted with a custom spinning cell in controlled acidic conditions, with DFT calculations aimed at investigating the possible protonated forms of Perampanel. The DFT-simulated Raman spectra of protonated Perampanel accounts for most of the observed SERS signals, thus explaining the effective role of protonation of the analyte. Our results suggest protonation as a viable approach to fostering SERS of alkaline drugs. Full article

(This article belongs to the Special Issue Advances in the Applications of Surface Enhanced Raman Scattering)

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18 pages, 6639 KiB

Open AccessArticle

Morphological and Compositional Analysis on Thermal Deposition of Supercritical Aviation Kerosene in Micro Channels

by Ao Sun, Cui Ye, Chenyang Yao, Lifeng Zhang, Ji Mi and Wenjun Fang

Molecules 2023, 28(11), 4508; https://doi.org/10.3390/molecules28114508 - 1 Jun 2023

Cited by 1 | Viewed by 1539

Abstract

The integration of active cooling systems in super or hypersonic aircraft using endothermic hydrocarbon fuels is considered an effective way to relieve the thermal management issues caused by overheating. When the temperature of aviation kerosene exceeds 150 °C, the oxidation reaction of fuel is accelerated, forming insoluble deposits that could cause safety hazards. This work investigates the deposition characteristic as well as the morphology of the deposits formed by thermal-stressed Chinese RP-3 aviation kerosene. A microchannel heat transfer simulation device is used to simulate the heat transfer process of aviation kerosene under various conditions. The temperature distribution of the reaction tube was monitored by an infrared thermal camera. The properties and morphology of the deposition were analyzed by scanning electron microscopy and Raman spectroscopy. The mass of the deposits was measured using the temperature-programmed oxidation method. It is observed that the deposition of RP-3 is highly related to dissolved oxygen content (DOC) and temperature. When the outlet temperature increased to 527 °C, the fuel underwent violent cracking reactions, and the structure and morphology of deposition were significantly different from those caused by oxidation. Specifically, this study reveals that the structure of the deposits caused by short-to-medium term oxidation are dense, which is different from long-term oxidative deposits. Full article

(This article belongs to the Special Issue Advances in the Applications of Surface Enhanced Raman Scattering)

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14 pages, 1614 KiB

Open AccessArticle

Comparison of Glyphosate Detection by Surface-Enhanced Raman Spectroscopy Using Gold and Silver Nanoparticles at Different Laser Excitations

by Lara Mikac, István Rigó, Marko Škrabić, Mile Ivanda and Miklós Veres

Molecules 2022, 27(18), 5767; https://doi.org/10.3390/molecules27185767 - 6 Sep 2022

Cited by 11 | Viewed by 2635

Abstract

Glyphosate is one of the most widely used pesticides in the world, but it has been shown to persist in the environment and therefore needs to be detected in food. In this work, the detection of glyphosate by surface-enhanced Raman scattering (SERS) using gold and silver nanoparticles and three different commonly used laser excitations (532, 632, and 785 nm wavelengths) of a Raman microscope complemented with a portable Raman spectrometer with 785 nm excitation is compared. The silver and gold nanosphere SERS substrates were prepared by chemical synthesis. In addition, colorimetric detection of glyphosate using cysteamine-modified gold and silver nanoparticles was also tested. The best results were obtained with Ag NPs at 532 nm excitation with a detection limit of 1 mM and with Au nanoparticles at 785 nm excitation with a detection limit of 100 µM. The SERS spectra of glyphosate with cysteamine-modified silver NPs improved the detection limits by two orders of magnitude for 532 nm excitation, i.e., up to 10 µM, and by one order of magnitude for 632 and 785 nm excitation wavelengths. Full article

(This article belongs to the Special Issue Advances in the Applications of Surface Enhanced Raman Scattering)

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10 pages, 1400 KiB

Open AccessCommunication

60-nt DNA Direct Detection without Pretreatment by Surface-Enhanced Raman Scattering with Polycationic Modified Ag Microcrystal Derived from AgCl Cube

by Jikai Mao, Lvtao Huang, Li Fan, Fang Chen, Jingan Lou, Xuliang Shan, Dongdong Yu and Jianguang Zhou

Molecules 2021, 26(22), 6790; https://doi.org/10.3390/molecules26226790 - 10 Nov 2021

Cited by 2 | Viewed by 2124

Abstract

Direct detection of long-strand DNA by surface-enhanced Raman scattering (SERS) is a valuable method for diagnosis of hereditary diseases, but it is currently limited to less than 25-nt DNA strand in pure water, which makes this approach unsuitable for many real-life applications. Here, we report a 60-nt DNA label-free detection strategy without pretreatment by SERS with polyquaternium-modified Ag microcrystals derived from an AgCl cube. Through the reduction-induced decomposition, the size of the about 3 × 3 × 3 μm³ AgCl cube is reduced to Ag, and the surface is distributed with the uniform size of 63 nm silver nanoparticles, providing a large area of a robust and highly electromagnetic enhancement region. The modified polycationic molecule enhances the non-specific electrostatic interaction with the phosphate group, thereby anchoring DNA strands firmly to the SERS enhanced region intactly. As a result, the single-base recognition ability of this strategy reaches 60-nt and is successfully applied to detect thalassemia-related mutation genes. Full article

(This article belongs to the Special Issue Advances in the Applications of Surface Enhanced Raman Scattering)

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Review

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19 pages, 1758 KiB

Open AccessReview

Advance in Detection Technique of Lean Meat Powder Residues in Meat Using SERS: A Review

by Qinghui Guo, Yankun Peng, Jianwei Qin, Kuanglin Chao, Xinlong Zhao and Tianzhen Yin

Molecules 2023, 28(22), 7504; https://doi.org/10.3390/molecules28227504 - 9 Nov 2023

Viewed by 1349

Abstract

Food that contains lean meat powder (LMP) can cause human health issues, such as nausea, headaches, and even death for consumers. Traditional methods for detecting LMP residues in meat are often time-consuming and complex and lack sensitivity. This article provides a review of the research progress on the use of surface–enhanced Raman spectroscopy (SERS) technology for detecting residues of LMP in meat. The review also discusses several applications of SERS technology for detecting residues of LMP in meat, including the enhanced detection of LMP residues in meat based on single metal nanoparticles, combining metal nanoparticles with adsorbent materials, combining metal nanoparticles with immunizing and other chemicals, and combining the SERS technology with related techniques. As SERS technology continues to develop and improve, it is expected to become an even more widely used and effective tool for detecting residues of LMP in meat. Full article

(This article belongs to the Special Issue Advances in the Applications of Surface Enhanced Raman Scattering)

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17 pages, 5745 KiB

Open AccessFeature PaperReview

Can DFT Calculations Provide Useful Information for SERS Applications?

by Maurizio Muniz-Miranda, Francesco Muniz-Miranda, Maria Cristina Menziani and Alfonso Pedone

Molecules 2023, 28(2), 573; https://doi.org/10.3390/molecules28020573 - 6 Jan 2023

Cited by 6 | Viewed by 2940

Abstract

Density functional theory (DFT) calculations allow us to reproduce the SERS (surface-enhanced Raman scattering) spectra of molecules adsorbed on nanostructured metal surfaces and extract the most information this spectroscopy is potentially able to provide. The latter point mainly concerns the anchoring mechanism and the bond strength between molecule and metal as well as the structural and electronic modifications of the adsorbed molecule. These findings are of fundamental importance for the application of this spectroscopic technique. This review presents and discusses some SERS–DFT studies carried out in Italy as a collaboration between the universities of Modena and Reggio-Emilia and of Florence, giving an overview of the information that we can extract with a combination of experimental SERS spectra and DFT modeling. In addition, a selection of the most recent studies and advancements on the DFT approach to SERS spectroscopy is reported with commentary. Full article

(This article belongs to the Special Issue Advances in the Applications of Surface Enhanced Raman Scattering)

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