Novel Insights to Raman Spectroscopy: Advances and Prospects

A special issue of Applied Sciences (ISSN 2076-3417). This special issue belongs to the section "Optics and Lasers".

Deadline for manuscript submissions: closed (30 November 2019) | Viewed by 25895

Special Issue Editor

Department of Physics, University of Pavia, 27100 Pavia, Italy
Interests: raman and sers spectroscopies; nanomaterials; optical; electronic; vibrational and structural properties of oxide-based advanced materials for sensors; energetics and spintronics; smart materials and advanced methods for biomedical and cultural heritage applications

Special Issue Information

Dear Colleagues,

Recently, Raman Spectroscopy (RS) has received increasingly attention from a large portion of the scientific community. Nowadays, it is easy to find a Raman spectrum as a key element in the search for solutions to different research, analytical, and industrial problems. This widespread usage of RS has been determined by the development of modern and highly efficient instrumentations, allowing one to perform RS in hard environments and for the solution to complex scientific problems once hardly faced by RS. In parallel, the discovery and exploitation of Surface Enhanced Raman Scattering (SERS) allows for a rare combination of sensitivity and specificity using a non-contact method, leading to several successful applications in a variety of fields, including electrochemistry, catalysis, biology, medicine, art conservation, materials science, and biochemical optical sensing. Accordingly, the possibility offered by nanotechnology has stimulated researchers to deepen the basic physics underlying SERS or other enhanced RS, and encouraged scientific dialogue on the reasons for the observed results.

The present Special Issue is devised as a collection of articles reporting concise reviews of recently obtained results in different scientific and industrial fields, in which novel insights concerning RS and SERS have produced a step forward in terms of knowledge.

Prof. Dr. Pietro Galinetto
Guest Editor

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Published Papers (7 papers)

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Research

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11 pages, 2607 KiB  
Article
DNA-Related Modifications in a Mixture of Human Lympho-Monocyte Exposed to Radiofrequency Fields and Detected by Raman Microspectroscopy Analysis
by Maria Lasalvia, Giuseppe Perna and Vito Capozzi
Appl. Sci. 2019, 9(18), 3700; https://doi.org/10.3390/app9183700 - 06 Sep 2019
Cited by 1 | Viewed by 1963
Abstract
Human exposure to electromagnetic fields (EMFs) has risen considerably during the last decades, because of the industrial and technical development and the consequent increase of artificial EMFs sources. In particular, blood is largely involved in the environmental EMF exposure, because it is located [...] Read more.
Human exposure to electromagnetic fields (EMFs) has risen considerably during the last decades, because of the industrial and technical development and the consequent increase of artificial EMFs sources. In particular, blood is largely involved in the environmental EMF exposure, because it is located everywhere in the human body. Lympho-monocyte cells are blood components that protect the human organism against infections. In this study, we investigate biochemical changes in lympho-monocyte cells extracted from human peripheral blood after exposure to EMFs at 1.8 GHz frequency and 200 V/m electric field strength for times ranging from 5 to 20 h inside a reverberation chamber. Some mixtures of cells, coming from many human subjects, were exposed and successively investigated by means of Raman micro-spectroscopy technique and principal components analysis. The spectral analysis was able to detect variations of the biochemical composition of the nucleus of exposed cells. Such modifications are mainly detectable as an intensity decrease of some DNA and nucleic acid Raman peaks with respect to the intensity of some protein peaks and they were most evident in the case of 20 h exposed samples. These results were in agreement with the increase of reactive oxygen species (ROS) production, observed in the exposed cells. Overall, the obtained results point out that EMFs exposure may induce modifications of the DNA in some blood cells of long-term exposed people. Full article
(This article belongs to the Special Issue Novel Insights to Raman Spectroscopy: Advances and Prospects)
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18 pages, 2804 KiB  
Article
Comparison of Raman and Mid-Infrared Spectroscopy for Real-Time Monitoring of Yeast Fermentations: A Proof-of-Concept for Multi-Channel Photometric Sensors
by Robert Schalk, Annabell Heintz, Frank Braun, Giuseppe Iacono, Matthias Rädle, Norbert Gretz, Frank-Jürgen Methner and Thomas Beuermann
Appl. Sci. 2019, 9(12), 2472; https://doi.org/10.3390/app9122472 - 17 Jun 2019
Cited by 13 | Viewed by 6059
Abstract
Raman and mid-infrared (MIR) spectroscopy are useful tools for the specific detection of molecules, since both methods are based on the excitation of fundamental vibration modes. In this study, Raman and MIR spectroscopy were applied simultaneously during aerobic yeast fermentations of Saccharomyces cerevisiae [...] Read more.
Raman and mid-infrared (MIR) spectroscopy are useful tools for the specific detection of molecules, since both methods are based on the excitation of fundamental vibration modes. In this study, Raman and MIR spectroscopy were applied simultaneously during aerobic yeast fermentations of Saccharomyces cerevisiae. Based on the recorded Raman intensities and MIR absorption spectra, respectively, temporal concentration courses of glucose, ethanol, and biomass were determined. The chemometric methods used to evaluate the analyte concentrations were partial least squares (PLS) regression and multiple linear regression (MLR). In view of potential photometric sensors, MLR models based on two (2D) and four (4D) analyte-specific optical channels were developed. All chemometric models were tested to predict glucose concentrations between 0 and 30 g L−1, ethanol concentrations between 0 and 10 g L−1, and biomass concentrations up to 15 g L−1 in real time during diauxic growth. Root-mean-squared errors of prediction (RMSEP) of 0.68 g L−1, 0.48 g L−1, and 0.37 g L−1 for glucose, ethanol, and biomass were achieved using the MIR setup combined with a PLS model. In the case of Raman spectroscopy, the corresponding RMSEP values were 0.92 g L−1, 0.39 g L−1, and 0.29 g L−1. Nevertheless, the simple 4D MLR models could reach the performance of the more complex PLS evaluation. Consequently, the replacement of spectrometer setups by four-channel sensors were discussed. Moreover, the advantages and disadvantages of Raman and MIR setups are demonstrated with regard to process implementation. Full article
(This article belongs to the Special Issue Novel Insights to Raman Spectroscopy: Advances and Prospects)
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11 pages, 617 KiB  
Article
Authenticity and Concentration Analysis of Extra Virgin Olive Oil Using Spontaneous Raman Spectroscopy and Multivariate Data Analysis
by Shiyamala Duraipandian, Jan C. Petersen and Mikael Lassen
Appl. Sci. 2019, 9(12), 2433; https://doi.org/10.3390/app9122433 - 14 Jun 2019
Cited by 45 | Viewed by 4852
Abstract
Adulteration of extra virgin olive oil (EVOO) with cheaper edible oils is of considerable concern in the olive oil industry. The potential of Raman spectroscopy combined with multivariate statistics has been investigated for evaluating the authenticity (or purity) and concentration of EVOO irrespective [...] Read more.
Adulteration of extra virgin olive oil (EVOO) with cheaper edible oils is of considerable concern in the olive oil industry. The potential of Raman spectroscopy combined with multivariate statistics has been investigated for evaluating the authenticity (or purity) and concentration of EVOO irrespective of it being adulterated with one or more adulterants. The adulterated oil samples were prepared by blending different concentrations of EVOO (10–100% v/v) randomly with cheaper edible oils such as corn, soybean and rapeseed oil. As a result, a Raman spectral database of oil samples (n = 214 spectra) was obtained from 11 binary mixtures (EVOO and rapeseed oil), 16 ternary mixtures (EVOO, rapeseed and corn oil) and 44 quaternary mixtures (EVOO, rapeseed, corn and soybean oil). Partial least squares (PLS) calibration models with 10-fold cross validation were constructed for binary, ternary and quaternary oil mixtures to determine the purity of spiked EVOO. The PLS model on the complex dataset (binary + ternary + quaternary) where the spectra obtained with different measurement parameters and sample conditions can able to determine the purity of spiked EVOO inspite of being blended with one or more cheaper oils. As a proof of concept, in this study, we used single batch of commercial oil bottles for estimating the purity of EVOO. The developed method is not only limited to EVOO, but can be applied to clean EVOO obtained from the production site and other types of food. Full article
(This article belongs to the Special Issue Novel Insights to Raman Spectroscopy: Advances and Prospects)
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23 pages, 32441 KiB  
Article
In Situ Hyperspectral Raman Imaging: A New Method to Investigate Sintering Processes of Ceramic Material at High-temperature
by Kerstin Hauke, Johannes Kehren, Nadine Böhme, Sinje Zimmer and Thorsten Geisler
Appl. Sci. 2019, 9(7), 1310; https://doi.org/10.3390/app9071310 - 29 Mar 2019
Cited by 21 | Viewed by 4415
Abstract
In the last decades, Raman spectroscopy has become an important tool to identify and investigate minerals, gases, glasses, and organic material at room temperature. In combination with high-temperature and high-pressure devices, however, the in situ investigation of mineral transformation reactions and their kinetics [...] Read more.
In the last decades, Raman spectroscopy has become an important tool to identify and investigate minerals, gases, glasses, and organic material at room temperature. In combination with high-temperature and high-pressure devices, however, the in situ investigation of mineral transformation reactions and their kinetics is nowadays also possible. Here, we present a novel approach to in situ studies for the sintering process of silicate ceramics by hyperspectral Raman imaging. This imaging technique allows studying high-temperature solid-solid and/or solid-melt reactions spatially and temporally resolved, and opens up new avenues to study and visualize high-temperature sintering processes in multi-component systems. After describing in detail the methodology, the results of three application examples are presented and discussed. These experiments demonstrate the power of hyperspectral Raman imaging for in situ studies of the mechanism(s) of solid-solid or solid-melt reactions at high-temperature with a micrometer-scale resolution as well as to gain kinetic information from the temperature- and time-dependent growth and breakdown of minerals during isothermal or isochronal sintering. Full article
(This article belongs to the Special Issue Novel Insights to Raman Spectroscopy: Advances and Prospects)
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10 pages, 1775 KiB  
Article
Study of Implantation Defects in CVD Graphene by Optical and Electrical Methods
by Grzegorz Gawlik, Paweł Ciepielewski and Jacek M. Baranowski
Appl. Sci. 2019, 9(3), 544; https://doi.org/10.3390/app9030544 - 06 Feb 2019
Cited by 17 | Viewed by 2783
Abstract
A Chemical Vapor Deposition graphene monolayer grown on 6H–SiC (0001) substrates was used for implantation experiments. The graphene samples were irradiated by He+ and N+ ions. The Raman spectra and electrical transport parameters were measured as a function of increasing implantation [...] Read more.
A Chemical Vapor Deposition graphene monolayer grown on 6H–SiC (0001) substrates was used for implantation experiments. The graphene samples were irradiated by He+ and N+ ions. The Raman spectra and electrical transport parameters were measured as a function of increasing implantation fluence. The defect concentration was determined from intensity ratio of the Raman D and G peaks, while the carrier’s concentration was determined from the relations between G and 2D Raman modes energies. It was found that the number of defects generated by one ion is 0.0025 and 0.045 and the mean defect radius about 1.5 and 1.34 nm for He+ and N+, respectively. Hole concentration and mobility were determined from van der Pauw measurements. It was found that mobility decreases nearly by three orders of magnitude with increase of defect concentration. The inverse of mobility versus defect concentration is a linear function, which indicates that the main scattering mechanism is related to defects generated by ion implantation. The slope of inverse mobility versus defect concentration provides the value of defect radius responsible for scattering carriers at about 0.75 nm. This estimated defect radius indicates that the scattering centres most likely consist of reconstructed divacancies or larger vacancy complexes. Full article
(This article belongs to the Special Issue Novel Insights to Raman Spectroscopy: Advances and Prospects)
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Review

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11 pages, 2374 KiB  
Review
Micro-Raman Mapping of the Strain Field in GaAsN/GaAsN:H Planar Heterostructures: A Brief Review and Recent Evolution
by Enrico Giulotto and Mario Geddo
Appl. Sci. 2019, 9(22), 4864; https://doi.org/10.3390/app9224864 - 13 Nov 2019
Cited by 1 | Viewed by 2011
Abstract
Raman scattering is an effective tool for the investigation of the strain state of crystalline solids. In this brief review, we show how the analysis of the GaAs-like longitudinal optical phonon frequency allowed to map the strain behavior across interfaces in planar heterostructures [...] Read more.
Raman scattering is an effective tool for the investigation of the strain state of crystalline solids. In this brief review, we show how the analysis of the GaAs-like longitudinal optical phonon frequency allowed to map the strain behavior across interfaces in planar heterostructures consisting of GaAsN wires embedded in GaAsN:H matrices. Moreover, we recently showed how the evolution of the longitudinal optical frequency with increasing H dose strongly depends on polarization geometry. In a specific geometry, we observed a relaxation of the GaAs selection rules. We also present new results which demonstrate how laser irradiation intensity–even at low levels–may affect the line shape of the GaAs-like spectral features in GaAsN hydrogenated materials. Full article
(This article belongs to the Special Issue Novel Insights to Raman Spectroscopy: Advances and Prospects)
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12 pages, 3509 KiB  
Review
Micro-Raman Spectroscopy, a Powerful Technique Allowing Sure Identification and Complete Characterization of Asbestiform Minerals
by Caterina Rinaudo and Alessandro Croce
Appl. Sci. 2019, 9(15), 3092; https://doi.org/10.3390/app9153092 - 31 Jul 2019
Cited by 8 | Viewed by 3174
Abstract
Micro-Raman spectroscopy has been applied to fibrous minerals regulated as “asbestos”—anthophyllite, actinolite, amosite, crocidolite, tremolite, and chrysotile—responsible of severe diseases affecting mainly, but not only, the respiratory system. The technique proved to be powerful in the identification of the mineral phase and in [...] Read more.
Micro-Raman spectroscopy has been applied to fibrous minerals regulated as “asbestos”—anthophyllite, actinolite, amosite, crocidolite, tremolite, and chrysotile—responsible of severe diseases affecting mainly, but not only, the respiratory system. The technique proved to be powerful in the identification of the mineral phase and in the recognition of particles of carbonaceous materials (CMs) lying on the “asbestos” fibers surface. Also, erionite, a zeolite mineral, from different outcrops has been analyzed. To erionite has been ascribed the peak of mesothelioma noticed in Cappadocia (Turkey) during the 1970s. On the fibers, micro-Raman spectroscopy allowed to recognize many grains, micrometric in size, of iron oxy-hydroxides or potassium iron sulphate, in erionite from Oregon, or particles of CMs, in erionite from North Dakota, lying on the crystal surface. Raman spectroscopy appears therefore to be the technique allowing, without preparation of the sample, a complete characterization of the minerals and of the associated phases. Full article
(This article belongs to the Special Issue Novel Insights to Raman Spectroscopy: Advances and Prospects)
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