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Raman Spectroscopy Analysis of Surfaces
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Raman Spectroscopy Analysis of Surfaces

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

Deadline for manuscript submissions: 31 January 2025 | Viewed by 6378

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 total Raman scattering cross-section is ca. 10−29 cm2 per molecule, whereas typical cross-sections for absorption in ultraviolet and infrared regions are ca. 10−18 and 10−21 cm2 per molecule, respectively. Therefore, to record conventional Raman spectra, analytical concentrations greater than 0.01M are usually required. However, by utilizing special nano-resonators constructed from plasmonic metals, Raman scattering cross-sections (in an effect called surface-enhanced Raman spectroscopy—SERS) can be significantly increased, e.g., to 10−14 cm2 per molecule, making possible observations of Raman spectra even of a single molecule. This Special Issue of Molecules will attempt to cover the recent advances in SERS analysis of surfaces, including the characterization of various interfaces and selected analytical applications of SERS spectroscopy. 

Dr. Andrzej Kudelski
Guest Editor

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Keywords

  • Raman spectroscopy
  • characterization of various interfaces
  • SERS spectroscopy
  • applications

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Published Papers (5 papers)

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Research

12 pages, 10543 KiB  
Article
Hollow Gold–Silver Nanorods—A New, Very Efficient Nanomaterial for Surface-Enhanced Raman Scattering (SERS) Measurements
by Aleksandra Michałowska and Andrzej Kudelski
Molecules 2024, 29(19), 4540; https://doi.org/10.3390/molecules29194540 - 25 Sep 2024
Viewed by 685
Abstract
Anisotropic plasmonic nanoparticles usually generate SERS enhancement factors that are significantly larger than those generated by spherical plasmonic nanostructures, so the former are usually preferred as substrates for SERS measurements. Gold nanorods are one of the most commonly used anisotropic nanomaterials for SERS [...] Read more.
Anisotropic plasmonic nanoparticles usually generate SERS enhancement factors that are significantly larger than those generated by spherical plasmonic nanostructures, so the former are usually preferred as substrates for SERS measurements. Gold nanorods are one of the most commonly used anisotropic nanomaterials for SERS experiments. Unfortunately, even a slight contamination of the surfactant used in the process of the synthesis of gold nanorods has a significant impact on the geometry of the resulting nanostructures. In this work, using easily formed silver nanorods as templates, hollow AuAg nanorods are formed by means of a silver–gold galvanic exchange reaction (in this process, nanostructures with a cavity inside form because one gold atom replaces three silver atoms). Hollow AuAg nanorods are highly active during SERS measurements—for shorter wavelengths of the excitation radiation, they display greater SERS activity than Au nanorods. To our knowledge, this is the first example of the use of hollow plasmonic nanorods for SERS measurements. Elemental mapping of the rods showed that the silver, some of which remained after the galvanic replacement, is mainly located close to the internal cavity that was formed, whereas the gold is mainly located at the outermost regions of the nanostructure. This explains the high chemical stability of these nanostructures. Full article
(This article belongs to the Special Issue Raman Spectroscopy Analysis of Surfaces)
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13 pages, 4429 KiB  
Article
Photo-Thermal Conversion and Raman Sensing Properties of Three-Dimensional Gold Nanostructure
by Feng Shan, Jingyi Huang, Yanyan Zhu and Guohao Wei
Molecules 2024, 29(18), 4287; https://doi.org/10.3390/molecules29184287 - 10 Sep 2024
Viewed by 631
Abstract
Three-dimensional plasma nanostructures with high light–thermal conversion efficiency show the prospect of industrialization in various fields and have become a research hotspot in areas of light–heat utilization, solar energy capture, and so on. In this paper, a simple chemical synthesis method is proposed [...] Read more.
Three-dimensional plasma nanostructures with high light–thermal conversion efficiency show the prospect of industrialization in various fields and have become a research hotspot in areas of light–heat utilization, solar energy capture, and so on. In this paper, a simple chemical synthesis method is proposed to prepare gold nanoparticles, and the electrophoretic deposition method is used to assemble large-area three-dimensional gold nanostructures (3D-GNSs). The light–thermal water evaporation monitoring and surface-enhanced Raman scattering (SERS) measurements of 3D-GNSs were performed via theoretical simulation and experiments. We reveal the physical processes of local electric field optical enhancement and the light–thermal conversion of 3D-GNSs. The results show that with the help of the efficient optical trapping and super-hydrophilic surface properties of 3D-GNSs, they have a significant effect in accelerating water evaporation, which was increased by nearly eight times. At the same time, the three-dimensional SERS substrates based on gold nanosphere particles (GNSPs) and gold nanostar particles (GNSTs) had limited sensitivities of 10−10 M and 10−12 M to R6G molecules, respectively. Therefore, 3D-GNSs show strong competitiveness in the fields of solar-energy-induced water purification and the Raman trace detection of organic molecules. Full article
(This article belongs to the Special Issue Raman Spectroscopy Analysis of Surfaces)
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14 pages, 4572 KiB  
Article
Analysis of Structural Heterogeneity in Low-Rank Coal and Its Pyrolyzed Char Using Multi-Point Scanning Micro-Raman Spectroscopy
by Yaqi Gao, Chong Zou, Yuan She, Zhengyan Huang and Siqi Li
Molecules 2024, 29(10), 2361; https://doi.org/10.3390/molecules29102361 - 17 May 2024
Viewed by 842
Abstract
Understanding the changes in carbon structure during the mid–low-temperature pyrolysis of low-rank coal is important for efficient utilization. Raman spectroscopy is commonly used to analyze the structural order of carbonaceous materials, but traditional methods may overlook the heterogeneity of coal/char. This research explores [...] Read more.
Understanding the changes in carbon structure during the mid–low-temperature pyrolysis of low-rank coal is important for efficient utilization. Raman spectroscopy is commonly used to analyze the structural order of carbonaceous materials, but traditional methods may overlook the heterogeneity of coal/char. This research explores the heterogeneity of char structure derived from low-rank coal at 700 °C through multi-point micro-Raman analysis. The analysis of parameters such as area (A), intensity (I), full width at half maximum (FWHM/W), and peak position (P) reveals that the carbon structure becomes less ordered as coal transforms into char due to the deposition of small molecules on the surface. The study emphasizes the benefits of multi-point detection for gaining in-depth insights into the structural evolution of carbonaceous materials. The increased standard deviation of Raman parameters indicates diverse structural characteristics resulting from pyrolysis at this temperature, which traditional methods may not capture effectively. The mapping method used in this research visually illustrates the distribution of carbon structures in the region. Full article
(This article belongs to the Special Issue Raman Spectroscopy Analysis of Surfaces)
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12 pages, 3702 KiB  
Article
Fabrication and Application of Ag@SiO2/Au Core–Shell SERS Composite in Detecting Cu2+ in Water Environment
by Meizhen Zhang, Lin Meng, Kelgenbaev Kalyinur, Siyuan Dong, Xinyi Chang, Qian Yu, Rui Wang, Bo Pang and Xianming Kong
Molecules 2024, 29(7), 1503; https://doi.org/10.3390/molecules29071503 - 27 Mar 2024
Viewed by 1364
Abstract
A sensitive and simple method for detecting Cu2+ in the water source was proposed by using surface-enhanced Raman scattering spectroscopy (SERS) based on the Ag@SiO2/Au core–shell composite. The Ag@SiO2 SERS tag was synthesized by a simple approach, in which [...] Read more.
A sensitive and simple method for detecting Cu2+ in the water source was proposed by using surface-enhanced Raman scattering spectroscopy (SERS) based on the Ag@SiO2/Au core–shell composite. The Ag@SiO2 SERS tag was synthesized by a simple approach, in which Ag nanoparticles were first embedded with Raman reporter PATP and next coated with a SiO2 shell. The Ag@SiO2 nanoparticles had strong stability even in a high-concentration salty solution, and there were no changes to their properties and appearance within one month. The Ag@SiO2/Au composite was fabricated through a controllable self-assemble process. L-cysteine was decorated on the surface of a functionalized Ag@SiO2/Au composite, as the amino and carboxyl groups of it can form coordinate covalent bond with Cu2+, which shows that the Ag@SiO2/Au composite labelled with L-cysteine has excellent performance for the detection of Cu2+ in aqueous media. In this study, the SERS detection of Cu2+ was carried out using Ag@SiO2 nanoparticles, and the limit of detection (LOD) as low as 0.1 mg/L was achieved. Full article
(This article belongs to the Special Issue Raman Spectroscopy Analysis of Surfaces)
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16 pages, 3200 KiB  
Article
Electrochemical Shell-Isolated Nanoparticle-Enhanced Raman Spectroscopy of Imidazole Ring Functionalized Monolayer on Smooth Gold Electrode
by Agnė Zdaniauskienė, Martynas Talaikis, Tatjana Charkova, Rita Sadzevičienė, Linas Labanauskas and Gediminas Niaura
Molecules 2022, 27(19), 6531; https://doi.org/10.3390/molecules27196531 - 3 Oct 2022
Cited by 2 | Viewed by 2201
Abstract
The imidazole ring (Im) of histidine side chains plays a unique role in the function of proteins through covalent bonding with metal ions and hydrogen bonding interactions with adjusted biomolecules and water. At biological interfaces, these interactions are modified because of the presence [...] Read more.
The imidazole ring (Im) of histidine side chains plays a unique role in the function of proteins through covalent bonding with metal ions and hydrogen bonding interactions with adjusted biomolecules and water. At biological interfaces, these interactions are modified because of the presence of an electric field. Self-assembled monolayers (SAMs) with the functional Im group mimic the histidine side chain at electrified interfaces. In this study, we applied in-situ shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) to probe the structure and hydrogen bonding of Im-functionalized SAM on smooth Au at the electrochemical interface. The self-assembly of molecules on the Au induced the proton shift from N1 atom (Tautomer-I), which is the dominant form of Im in the bulk sample, to N3 atom (Tautomer-II). The impact of electrode potential on the hydrogen bonding interaction strength of the Im ring was identified by SHINERS. Temperature-Raman measurements and density functional theory (DFT) analysis revealed the spectral marker for Im ring packing (mode near 1496–1480 cm−1) that allowed us to associate the confined and strongly hydrogen bonded interfacial Im groups with electrode polarization at −0.8 V. Reflection adsorption IR (RAIR) spectra of SAMs with and without Im revealed that the bulky ring prevented the formation of a strongly hydrogen bonded amide group network. Full article
(This article belongs to the Special Issue Raman Spectroscopy Analysis of Surfaces)
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