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Raman Spectroscopy: A Spectroscopic 'Swiss-Army Knife'
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Raman Spectroscopy: A Spectroscopic 'Swiss-Army Knife'

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

Deadline for manuscript submissions: closed (15 December 2018) | Viewed by 102896

Special Issue Editor

Prof. Dr. Keith C. Gordon

E-Mail Website
Guest Editor
Department of Chemistry, University of Otago, Dunedin, New Zealand
Interests: vibrational spectroscopy; chemometrics; Raman microscopy; low frequency Raman spectroscopy; resonance Raman spectroscopy; food analysis; electronic materials analysis

Special Issue Information

Dear Colleagues,

Since its first report by Raman and Krishnan in 1928, Raman spectroscopy has become an important form of vibrational spectroscopy in the physical and biological sciences. This Special Issue aims to encompass a number of diverse studies which exemplify the usefulness of this technique in these areas. This will include the use of Raman spectroscopy as an analytical tool in biological and materials sciences, as well as its use as a structural tool in molecular electronic materials and in dynamic systems—such as in photocatalysis.

In the effort to celebrate Raman spectroscopy, experts working with this technique are cordially invited to submit manuscripts. Particular interest is given to new innovations in the field that have enhanced the capability of Raman spectroscopy—on any type of sample.

Prof. Keith C. Gordon
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Raman spectroscopy
  • Raman microscopy
  • Imaging
  • Chemometrics
  • Surface-Enhance Raman
  • Spatially-Offset Raman
  • Two-Dimensional correlation

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Editorial

Jump to: Research, Review

3 pages, 151 KiB  
Editorial
Special Issue “Raman Spectroscopy: A Spectroscopic ‘Swiss-Army Knife’”
by Keith C. Gordon
Molecules 2019, 24(15), 2852; https://doi.org/10.3390/molecules24152852 - 06 Aug 2019
Viewed by 2455
Abstract
This special issue highlights the astonishingly wide range of scientific studies that use Raman spectroscopy to provide insight [...] Full article
(This article belongs to the Special Issue Raman Spectroscopy: A Spectroscopic 'Swiss-Army Knife')

Research

Jump to: Editorial, Review

18 pages, 1985 KiB  
Article
On the Hydration of Heavy Rare Earth Ions: Ho3+, Er3+, Tm3+, Yb3+ and Lu3+—A Raman Study
by Wolfram Rudolph and Gert Irmer
Molecules 2019, 24(10), 1953; https://doi.org/10.3390/molecules24101953 - 21 May 2019
Cited by 12 | Viewed by 3886
Abstract
Raman spectra of aqueous Ho3+, Er3+, Tm3+, Yb3+, and Lu3+-perchlorate solutions were measured over a large wavenumber range from 50–4180 cm−1. In the low wavenumber range (terahertz region), strongly polarized Raman [...] Read more.
Raman spectra of aqueous Ho3+, Er3+, Tm3+, Yb3+, and Lu3+-perchlorate solutions were measured over a large wavenumber range from 50–4180 cm−1. In the low wavenumber range (terahertz region), strongly polarized Raman bands were detected at 387 cm−1, 389 cm−1, 391 cm−1, 394 cm−1, and 396 cm−1, respectively, which are fairly broad (full widths at half height at ~52 cm−1). These isotropic Raman bands were assigned to the breathing modes, ν1 Ln–O of the heavy rare earth (HRE) octaaqua ions, [Ln(H2O)8]3+. The strong polarization of these bands (depolarization degree ~0) reveals their totally symmetric character. The vibrational isotope effect was measured in Yb(ClO4)3 solutions in H2O and D2O and the shift of the ν1 mode in changing from H2O to D2O further supports the character of the band. The Ln–O bond distances of these HRE ions (Ho3+, Er3+, Tm3+, Yb3+, and Lu3+) follow the order of Ho–O > Er–O > Tm–O > Yb–O > Lu–O which correlates inversely with the band positions of the breathing modes of their corresponding octaaqua ions [Ln(OH2)8]3+. Furthermore, the force constants, kLn–O, were calculated for these symmetric stretching modes. Ytterbium perchlorate solutions were measured over a broad concentration range, from 0.240 mol·L−1 to 2.423 mol·L−1, and it was shown that with increasing solute concentration outer-sphere ion pairs and contact ion pairs were formed. At the dilute solution state (~0.3 mol·L−1), the fully hydrated ions [Yb(H2O)8]3+ exist, while at higher concentrations (CT > 2 mol·L−1), ion pairs are formed. The concentration behavior of Yb(ClO4)3 (aq) shows similar behavior to the one observed for La(ClO4)3(aq), Ce(ClO4)3(aq) and Lu(ClO4)3(aq) solutions. In ytterbium chloride solutions in water and heavy water, representative for the behavior of the other HRE ions, 1:1 chloro-complex formation was detected over the concentration range from 0.422–3.224 mol·L−1. The 1:1 chloro-complex in YbCl3(aq) is very weak, diminishing rapidly with dilution and vanishing at a concentration < 0.4 mol·L−1. Full article
(This article belongs to the Special Issue Raman Spectroscopy: A Spectroscopic 'Swiss-Army Knife')
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14 pages, 6932 KiB  
Article
On-Line Raman Spectroscopic Study of Cytochromes’ Redox State of Biofilms in Microbial Fuel Cells
by Adolf Krige, Magnus Sjöblom, Kerstin Ramser, Paul Christakopoulos and Ulrika Rova
Molecules 2019, 24(3), 646; https://doi.org/10.3390/molecules24030646 - 12 Feb 2019
Cited by 21 | Viewed by 4121
Abstract
Bio-electrochemical systems such as microbial fuel cells and microbial electrosynthesis cells depend on efficient electron transfer between the microorganisms and the electrodes. Understanding the mechanisms and dynamics of the electron transfer is important in order to design more efficient reactors, as well as [...] Read more.
Bio-electrochemical systems such as microbial fuel cells and microbial electrosynthesis cells depend on efficient electron transfer between the microorganisms and the electrodes. Understanding the mechanisms and dynamics of the electron transfer is important in order to design more efficient reactors, as well as modifying microorganisms for enhanced electricity production. Geobacter are well known for their ability to form thick biofilms and transfer electrons to the surfaces of electrodes. Currently, there are not many “on-line” systems for monitoring the activity of the biofilm and the electron transfer process without harming the biofilm. Raman microscopy was shown to be capable of providing biochemical information, i.e., the redox state of C-type cytochromes, which is integral to external electron transfer, without harming the biofilm. In the current study, a custom 3D printed flow-through cuvette was used in order to analyze the oxidation state of the C-type cytochromes of suspended cultures of three Geobacter sulfurreducens strains (PCA, KN400 and ΔpilA). It was found that the oxidation state is a good indicator of the metabolic state of the cells. Furthermore, an anaerobic fluidic system enabling in situ Raman measurements was designed and applied successfully to monitor and characterize G. sulfurreducens biofilms during electricity generation, for both a wild strain, PCA, and a mutant, ΔS. The cytochrome redox state, monitored by the Raman peak areas, could be modulated by applying different poise voltages to the electrodes. This also correlated with the modulation of current transferred from the cytochromes to the electrode. The Raman peak area changed in a predictable and reversible manner, indicating that the system could be used for analyzing the oxidation state of the proteins responsible for the electron transfer process and the kinetics thereof in-situ. Full article
(This article belongs to the Special Issue Raman Spectroscopy: A Spectroscopic 'Swiss-Army Knife')
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10 pages, 2076 KiB  
Article
Temperature-Dependent Evolution of Raman Spectra of Methylammonium Lead Halide Perovskites, CH3NH3PbX3 (X = I, Br)
by Kousuke Nakada, Yuki Matsumoto, Yukihiro Shimoi, Koji Yamada and Yukio Furukawa
Molecules 2019, 24(3), 626; https://doi.org/10.3390/molecules24030626 - 11 Feb 2019
Cited by 75 | Viewed by 8591
Abstract
We present a Raman study on the phase transitions of organic/inorganic hybrid perovskite materials, CH3NH3PbX3 (X = I, Br), which are used as solar cells with high power conversion efficiency. The temperature dependence of the Raman bands of [...] Read more.
We present a Raman study on the phase transitions of organic/inorganic hybrid perovskite materials, CH3NH3PbX3 (X = I, Br), which are used as solar cells with high power conversion efficiency. The temperature dependence of the Raman bands of CH3NH3PbX3 (X = I, Br) was measured in the temperature ranges of 290 to 100 K for CH3NH3PbBr3 and 340 to 110 K for CH3NH3PbI3. Broad ν1 bands at ~326 cm−1 for MAPbBr3 and at ~240 cm−1 for MAPbI3 were assigned to the MA–PbX3 cage vibrations. These bands exhibited anomalous temperature dependence, which was attributable to motional narrowing originating from fast changes between the orientational states of CH3NH3+ in the cage. Phase transitions were characterized by changes in the bandwidths and peak positions of the MA–cage vibration and some bands associated with the NH3+ group. Full article
(This article belongs to the Special Issue Raman Spectroscopy: A Spectroscopic 'Swiss-Army Knife')
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12 pages, 3720 KiB  
Article
Controllable Preparation of SERS-Active Ag-FeS Substrates by a Cosputtering Technique
by Ning Ma, Xin-Yuan Zhang, Wenyue Fan, Bingbing Han, Sila Jin, Yeonju Park, Lei Chen, Yongjun Zhang, Yang Liu, Jinghai Yang and Young Mee Jung
Molecules 2019, 24(3), 551; https://doi.org/10.3390/molecules24030551 - 02 Feb 2019
Cited by 15 | Viewed by 3081
Abstract
In this work, we introduced an ordered metal-semiconductor molecular system and studied the resulting surface-enhanced Raman scattering (SERS) effect. Ag-FeS nanocaps with sputtered films of different thicknesses were obtained by changing the sputtering power of FeS while the sputtering power of Ag and [...] Read more.
In this work, we introduced an ordered metal-semiconductor molecular system and studied the resulting surface-enhanced Raman scattering (SERS) effect. Ag-FeS nanocaps with sputtered films of different thicknesses were obtained by changing the sputtering power of FeS while the sputtering power of Ag and the deposition time remained constant. When metallic Ag and the semiconductor FeS are cosputtered, the Ag film separates into Ag islands partially covered by FeS and strong coupling occurs among the Ag islands isolated by FeS, which contributes to the SERS phenomenon. We also investigated the SERS enhancement mechanism by decorating the nanocap arrays produced with different FeS sputtering powers with methylene blue (MB) probe molecules. As the FeS sputtering power increased, the SERS signal first increased and then decreased. The experimental results show that the SERS enhancement can mainly be attributed to the surface plasmon resonance (SPR) of the Ag nanoparticles. The coupling between FeS and Ag and the SPR displacement of Ag vary with different sputtering powers, resulting in changes in the intensity of the SERS spectra. These results demonstrate the high sensitivity of SERS substrates consisting of Ag-FeS nanocap arrays. Full article
(This article belongs to the Special Issue Raman Spectroscopy: A Spectroscopic 'Swiss-Army Knife')
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12 pages, 2098 KiB  
Article
Direct Observation of Structure and Dynamics of Photogenerated Charge Carriers in Poly(3-hexylthiophene) Films by Femtosecond Time-Resolved Near-IR Inverse Raman Spectroscopy
by Tomohisa Takaya, Ippei Enokida, Yukio Furukawa and Koichi Iwata
Molecules 2019, 24(3), 431; https://doi.org/10.3390/molecules24030431 - 25 Jan 2019
Cited by 15 | Viewed by 3633
Abstract
The initial charge separation process of conjugated polymers is one of the key factors for understanding their conductivity. The structure of photogenerated transients in conjugated polymers can be observed by resonance Raman spectroscopy in the near-IR region because they exhibit characteristic low-energy transitions. [...] Read more.
The initial charge separation process of conjugated polymers is one of the key factors for understanding their conductivity. The structure of photogenerated transients in conjugated polymers can be observed by resonance Raman spectroscopy in the near-IR region because they exhibit characteristic low-energy transitions. Here, we investigate the structure and dynamics of photogenerated transients in a regioregular poly(3-hexylthiophene) (P3HT):[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) blend film, as well as in a pristine P3HT film, using femtosecond time-resolved resonance inverse Raman spectroscopy in the near-IR region. The transient inverse Raman spectrum of the pristine P3HT film at 50 ps suggests coexistence of neutral and charged excitations, whereas that of the P3HT:PCBM blend film at 50 ps suggests formation of positive polarons with a different structure from those in an FeCl3-doped P3HT film. Time-resolved near-IR inverse Raman spectra of the blend film clearly show the absence of charge separation between P3HT and PCBM within the instrument response time of our spectrometer, while they indicate two independent pathways of the polaron formation with time constants of 0.3 and 10 ps. Full article
(This article belongs to the Special Issue Raman Spectroscopy: A Spectroscopic 'Swiss-Army Knife')
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11 pages, 1956 KiB  
Article
Surface Enhanced Raman Spectroscopy for In-Field Detection of Pesticides: A Test on Dimethoate Residues in Water and on Olive Leaves
by Lorenzo Tognaccini, Marilena Ricci, Cristina Gellini, Alessandro Feis, Giulietta Smulevich and Maurizio Becucci
Molecules 2019, 24(2), 292; https://doi.org/10.3390/molecules24020292 - 15 Jan 2019
Cited by 26 | Viewed by 4486
Abstract
Dimethoate (DMT) is an organophosphate insecticide commonly used to protect fruit trees and in particular olive trees. Since it is highly water-soluble, its use on olive trees is considered quite safe, because it flows away in the residual water during the oil extraction [...] Read more.
Dimethoate (DMT) is an organophosphate insecticide commonly used to protect fruit trees and in particular olive trees. Since it is highly water-soluble, its use on olive trees is considered quite safe, because it flows away in the residual water during the oil extraction process. However, its use is strictly regulated, specially on organic cultures. The organic production chain certification is not trivial, since DMT rapidly degrades to omethoate (OMT) and both disappear in about two months. Therefore, simple, sensitive, cost-effective and accurate methods for the determination of dimethoate, possibly suitable for in-field application, can be of great interest. In this work, a quick screening method, possibly useful for organic cultures certification will be presented. DMT and OMT in water and on olive leaves have been detected by surface enhanced Raman spectroscopy (SERS) using portable instrumentations. On leaves, the SERS signals were measured with a reasonably good S/N ratio, allowing us to detect DMT at a concentration up to two orders of magnitude lower than the one usually recommended for in-field treatments. Moreover, detailed information on the DMT distribution on the leaves has been obtained by Raman line- (or area-) scanning experiments. Full article
(This article belongs to the Special Issue Raman Spectroscopy: A Spectroscopic 'Swiss-Army Knife')
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9 pages, 1905 KiB  
Article
Investigation of the Phase Transition Mechanism in LiFePO4 Cathode Using In Situ Raman Spectroscopy and 2D Correlation Spectroscopy during Initial Cycle
by Yeonju Park, Soo Min Kim, Sila Jin, Sung Man Lee, Isao Noda and Young Mee Jung
Molecules 2019, 24(2), 291; https://doi.org/10.3390/molecules24020291 - 14 Jan 2019
Cited by 23 | Viewed by 4308
Abstract
The phase transition of the LiFePO4 and FePO4 in Li-ion cell during charging-discharging processes in the first and second cycles is elucidated by Raman spectroscopy in real time. In situ Raman spectroscopy showed the sudden phase transition between LiFePO4 and [...] Read more.
The phase transition of the LiFePO4 and FePO4 in Li-ion cell during charging-discharging processes in the first and second cycles is elucidated by Raman spectroscopy in real time. In situ Raman spectroscopy showed the sudden phase transition between LiFePO4 and FePO4. Principal component analysis (PCA) results also indicated that the structural changes and electrochemical performance (charge-discharge curve) are correlated with each other. Phase transition between LiFePO4 and FePO4 principally appeared in the second charging process compared with that in the first charging process. 2D correlation spectra provided the phase transition mechanism of LiFePO4 cathode which occurred during the charging-discharging processes in the first and second cycles. PCA and 2D correlation spectroscopy are very helpful methods to understand in situ Raman spectra for the Li-ion battery. Full article
(This article belongs to the Special Issue Raman Spectroscopy: A Spectroscopic 'Swiss-Army Knife')
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14 pages, 1668 KiB  
Article
Resonance Raman Spectro-Electrochemistry to Illuminate Photo-Induced Molecular Reaction Pathways
by Linda Zedler, Sven Krieck, Stephan Kupfer and Benjamin Dietzek
Molecules 2019, 24(2), 245; https://doi.org/10.3390/molecules24020245 - 10 Jan 2019
Cited by 8 | Viewed by 3631
Abstract
Electron transfer reactions play a key role for artificial solar energy conversion, however, the underlying reaction mechanisms and the interplay with the molecular structure are still poorly understood due to the complexity of the reaction pathways and ultrafast timescales. In order to investigate [...] Read more.
Electron transfer reactions play a key role for artificial solar energy conversion, however, the underlying reaction mechanisms and the interplay with the molecular structure are still poorly understood due to the complexity of the reaction pathways and ultrafast timescales. In order to investigate such light-induced reaction pathways, a new spectroscopic tool has been applied, which combines UV-vis and resonance Raman spectroscopy at multiple excitation wavelengths with electrochemistry in a thin-layer electrochemical cell to study [RuII(tbtpy)2]2+ (tbtpy = tri-tert-butyl-2,2′:6′,2′′-terpyridine) as a model compound for the photo-activated electron donor in structurally related molecular and supramolecular assemblies. The new spectroscopic method substantiates previous suggestions regarding the reduction mechanism of this complex by localizing photo-electrons and identifying structural changes of metastable intermediates along the reaction cascade. This has been realized by monitoring selective enhancement of Raman-active vibrations associated with structural changes upon electronic absorption when tuning the excitation wavelength into new UV-vis absorption bands of intermediate structures. Additional interpretation of shifts in Raman band positions upon reduction with the help of quantum chemical calculations provides a consistent picture of the sequential reduction of the individual terpyridine ligands, i.e., the first reduction results in the monocation [(tbtpy)Ru(tbtpy•)]+, while the second reduction generates [(tbtpy•)Ru(tbtpy•)]0 of triplet multiplicity. Therefore, the combination of this versatile spectro-electrochemical tool allows us to deepen the fundamental understanding of light-induced charge transfer processes in more relevant and complex systems. Full article
(This article belongs to the Special Issue Raman Spectroscopy: A Spectroscopic 'Swiss-Army Knife')
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14 pages, 3612 KiB  
Article
Diagnosis of Bacterial Pathogens in the Urine of Urinary-Tract-Infection Patients Using Surface-Enhanced Raman Spectroscopy
by Ni Tien, Tzu-Hsien Lin, Zen-Chao Hung, Hsiu-Shen Lin, I-Kuan Wang, Hung-Chih Chen and Chiz-Tzung Chang
Molecules 2018, 23(12), 3374; https://doi.org/10.3390/molecules23123374 - 19 Dec 2018
Cited by 24 | Viewed by 5815
Abstract
(1) Background: surface-enhanced Raman spectroscopy (SERS) is a novel method for bacteria identification. However, reported applications of SERS in clinical diagnosis are limited. In this study, we used cylindrical SERS chips to detect urine pathogens in urinary tract infection (UTI) patients. (2) Methods: [...] Read more.
(1) Background: surface-enhanced Raman spectroscopy (SERS) is a novel method for bacteria identification. However, reported applications of SERS in clinical diagnosis are limited. In this study, we used cylindrical SERS chips to detect urine pathogens in urinary tract infection (UTI) patients. (2) Methods: Urine samples were retrieved from 108 UTI patients. A 10 mL urine sample was sent to conventional bacterial culture as a reference. Another 10 mL urine sample was loaded on a SERS chip for bacteria identification and antibiotic susceptibility. We concentrated the urine specimen if the intensity of the Raman spectrum required enhancement. The resulting Raman spectrum was analyzed by a recognition software to compare with spectrum-form reference bacteria and was further confirmed by principal component analysis (PCA). (3) Results: There were 97 samples with single bacteria species identified by conventional urine culture and, among them, 93 can be successfully identified by using SERS without sample concentration. There were four samples that needed concentration for bacteria identification. Antibiotic susceptibility can also be found by SERS. There were seven mixed flora infections found by conventional culture, which can only be identified by the PCA method. (4) Conclusions: SERS can be used in the diagnosis of urinary tract infection with the aid of the recognition software and PCA. Full article
(This article belongs to the Special Issue Raman Spectroscopy: A Spectroscopic 'Swiss-Army Knife')
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15 pages, 8591 KiB  
Article
Continuous Gradient Temperature Raman Spectroscopy of Fish Oils Provides Detailed Vibrational Analysis and Rapid, Nondestructive Graphical Product Authentication
by C. Leigh Broadhurst, Walter F. Schmidt, Jianwei Qin, Kuanglin Chao and Moon S. Kim
Molecules 2018, 23(12), 3293; https://doi.org/10.3390/molecules23123293 - 12 Dec 2018
Cited by 7 | Viewed by 3441
Abstract
Background: Gradient temperature Raman spectroscopy (GTRS) applies the continuous temperature gradients utilized in differential scanning calorimetry (DSC) to Raman spectroscopy, providing a new means for rapid high throughput material identification and quality control. Methods: Using 20 Mb three-dimensional data arrays with [...] Read more.
Background: Gradient temperature Raman spectroscopy (GTRS) applies the continuous temperature gradients utilized in differential scanning calorimetry (DSC) to Raman spectroscopy, providing a new means for rapid high throughput material identification and quality control. Methods: Using 20 Mb three-dimensional data arrays with 0.2 °C increments and first/second derivatives allows complete assignment of solid, liquid and transition state vibrational modes. The entire set or any subset of the any of the contour plots, first derivatives or second derivatives can be utilized to create a graphical standard to quickly authenticate a given source. In addition, a temperature range can be specified that maximizes information content. Results: We compared GTRS and DSC data for five commercial fish oils that are excellent sources of docosahexaenoic acid (DHA; 22:6n-3) and eicosapentaenoic acid (EPA; 20:5n-3). Each product has a unique, distinctive response to the thermal gradient, which graphically and spectroscopically differentiates them. We also present detailed Raman data and full vibrational mode assignments for EPA and DHA. Conclusion: Complex lipids with a variety of fatty acids and isomers have three dimensional structures based mainly on how structurally similar sites pack. Any localized non-uniformity in packing results in discrete “fingerprint” molecular sites due to increased elasticity and decreased torsion. Full article
(This article belongs to the Special Issue Raman Spectroscopy: A Spectroscopic 'Swiss-Army Knife')
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20 pages, 2153 KiB  
Article
Hydration and Ion Pair Formation in Aqueous Lu3+- Solution
by Wolfram Rudolph and Gert Irmer
Molecules 2018, 23(12), 3237; https://doi.org/10.3390/molecules23123237 - 07 Dec 2018
Cited by 11 | Viewed by 4217
Abstract
Aqueous solutions of Lu3+- perchlorate, triflate and chloride were measured by Raman spectroscopy. A weak, isotropic mode at 396 cm−1 (full width at half height (fwhh) at 50 cm−1) was observed in perchlorate and triflate solutions. This mode [...] Read more.
Aqueous solutions of Lu3+- perchlorate, triflate and chloride were measured by Raman spectroscopy. A weak, isotropic mode at 396 cm−1 (full width at half height (fwhh) at 50 cm−1) was observed in perchlorate and triflate solutions. This mode was assigned to the totally symmetric stretching mode of [Lu(OH2)8]3+, ν1LuO8. In Lu(ClO4)3 solutions in heavy water, the ν1LuO8 symmetric stretch of [Lu(OD2)8]3+ appears at 376.5 cm−1. The shift confirms the theoretical isotopic effect of this mode. In the anisotropic scattering of aqueous Lu(ClO4)3, five bands of very low intensity were observed at 113 cm−1, 161.6 cm−1, 231 cm−1, 261.3 cm−1 and 344 cm−1. In LuCl3 (aq) solutions measured over a concentration range from 0.105–3.199 mol·L−1 a 1:1 chloro-complex was detected. Its equilibrium concentration, however, disappeared rapidly with dilution and vanished at a concentration < 0.5 mol·L−1. Quantitative Raman spectroscopy allowed the detection of the fractions of [Lu(OH2)8]3+, the fully hydrated species and the mono-chloro complex, [Lu(OH2)7Cl]2+. In a ternary LuCl3/HCl solution, a mixtrure of chloro-complex species of the type [Lu(OH2)8−nCln]+3−n (n = 1 and 2) were detected. DFT geometry optimization and frequency calculations are reported for Lu3+- water cluster in vacuo and with a polarizable dielectric continuum (PC) model including the bulk solvent implicitly. The bond distance and angle for [Lu(OH2)8]3+ within the PC are in good agreement with data from structural experiments. The DFT frequencies for the Lu-O modes of [Lu(OH2)8]3+ and its deuterated analog [Lu(OD2)8]3+ in a PC are in fair agreement with the experimental ones. The calculated hydration enthalpy of Lu3+ (aq) is slightly lower than the experimental value. Full article
(This article belongs to the Special Issue Raman Spectroscopy: A Spectroscopic 'Swiss-Army Knife')
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14 pages, 2591 KiB  
Article
Precursor Phenomena of Barium Titanate Single Crystals Grown Using a Solid-State Single Crystal Growth Method Studied with Inelastic Brillouin Light Scattering and Birefringence Measurements
by Soo Han Oh, Jae-Hyeon Ko, Ho-Yong Lee, Iwona Lazar and Krystian Roleder
Molecules 2018, 23(12), 3171; https://doi.org/10.3390/molecules23123171 - 01 Dec 2018
Cited by 12 | Viewed by 3211
Abstract
The nature of precursor phenomena in the paraelectric phase of ferroelectrics is one of the main questions to be resolved from a fundamental point of view. Barium titanate (BaTiO3) is one of the most representative perovskite-structured ferroelectrics intensively studied until now. [...] Read more.
The nature of precursor phenomena in the paraelectric phase of ferroelectrics is one of the main questions to be resolved from a fundamental point of view. Barium titanate (BaTiO3) is one of the most representative perovskite-structured ferroelectrics intensively studied until now. The pretransitional behavior of BaTiO3 single crystal grown using a solid-state crystal growth (SSCG) method was investigated for the first time and compared to previous results. There is no melting process in the SSCG method, thus the crystal grown using a SSCG method have inherent higher levels of impurity and defect concentrations, which is a good candidate for investigating the effect of crystal quality on the precursor phenomena. The acoustic, dielectric, and piezoelectric properties, as well as birefringence, of the SSCG-grown BaTiO3 were examined over a wide temperature range. Especially, the acoustic phonon behavior was investigated in terms of Brillouin spectroscopy, which is a complementary technique to Raman spectroscopy. The obtained precursor anomalies of the SSCG-grown BaTiO3 in the cubic phase were similar to those of other single crystals, in particular, of high-quality single crystal grown by top-seeded solution growth method. These results clearly indicate that the observed precursor phenomena are common and intrinsic effect irrespective of the crystal quality. Full article
(This article belongs to the Special Issue Raman Spectroscopy: A Spectroscopic 'Swiss-Army Knife')
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12 pages, 4247 KiB  
Article
Time-Resolved Spectroscopic and Density Functional Theory Investigation of the Photogeneration of a Bifunctional Quinone Methide in Neutral and Basic Aqueous Solutions
by Zhiping Yan, Lili Du, Xin Lan, Yuanchun Li, Wenchao Wang and David Lee Phillips
Molecules 2018, 23(12), 3102; https://doi.org/10.3390/molecules23123102 - 27 Nov 2018
Cited by 1 | Viewed by 2755
Abstract
Binol quinone methides (BQMs) can be generated from 1,1′-(2,2′-dihydroxy-1,1′-binaphthyl-6,6′-diyl)bis(N,N,N-trimethylmethanamiuium) bromide (BQMP-b) in a 1:1 MeCN:H2O mixed solution via a ground state intramolecular proton transfer (GSIPT), as mentioned in our previously reported studies. Here, the photoreaction [...] Read more.
Binol quinone methides (BQMs) can be generated from 1,1′-(2,2′-dihydroxy-1,1′-binaphthyl-6,6′-diyl)bis(N,N,N-trimethylmethanamiuium) bromide (BQMP-b) in a 1:1 MeCN:H2O mixed solution via a ground state intramolecular proton transfer (GSIPT), as mentioned in our previously reported studies. Here, the photoreaction of BQMP-b in neutral and basic aqueous solution (pH = 7, 10, 12) was investigated to explore the possible mechanisms and the key intermediates produced in the process of the photoreaction and to examine whether they are different from those in a neutral mild-mixed MeCN:H2O solution. The studies were conducted using femtosecond transient absorption (fs-TA), nanosecond transient absorption (ns-TA), and nanosecond time-resolved resonance Raman spectroscopy (ns-TR3) in conjunction with results from density functional theory (DFT) computations. The results showed that BQMP-b was deprotonated initially and produced BQMs species more effectively through an E1bc elimination reaction in a strong basic aqueous condition (pH = 12), which differed from the reaction pathway that took place in the solution with pH = 7 or 10. A related single naphthol ring molecule 1-(6-hydroxynaphthalen-2-yl)-N,N,N-trimethylmethanaminium bromide (QMP-b) that did not contain a second naphthol ring was also investigated. The related reaction mechanisms are elucidated in this work, and it is briefly discussed how the mechanisms vary as a function of aqueous solution pH conditions. Full article
(This article belongs to the Special Issue Raman Spectroscopy: A Spectroscopic 'Swiss-Army Knife')
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14 pages, 2649 KiB  
Article
Raman Spectroscopic Analysis to Detect Reduced Bone Quality after Sciatic Neurectomy in Mice
by Yasumitsu Ishimaru, Yusuke Oshima, Yuuki Imai, Tadahiro Iimura, Sota Takanezawa, Kazunori Hino and Hiromasa Miura
Molecules 2018, 23(12), 3081; https://doi.org/10.3390/molecules23123081 - 25 Nov 2018
Cited by 32 | Viewed by 7461
Abstract
Bone mineral density (BMD) is a commonly used diagnostic indicator for bone fracture risk in osteoporosis. Along with low BMD, bone fragility accounts for reduced bone quality in addition to low BMD, but there is no diagnostic method to directly assess the bone [...] Read more.
Bone mineral density (BMD) is a commonly used diagnostic indicator for bone fracture risk in osteoporosis. Along with low BMD, bone fragility accounts for reduced bone quality in addition to low BMD, but there is no diagnostic method to directly assess the bone quality. In this study, we investigated changes in bone quality using the Raman spectroscopic technique. Sciatic neurectomy (NX) was performed in male C57/BL6J mice (NX group) as a model of disuse osteoporosis, and sham surgery was used as an experimental control (Sham group). Eight months after surgery, we acquired Raman spectral data from the anterior cortical surface of the proximal tibia. We also performed a BMD measurement and micro-CT measurement to investigate the pathogenesis of osteoporosis. Quantitative analysis based on the Raman peak intensities showed that the carbonate/phosphate ratio and the mineral/matrix ratio were significantly higher in the NX group than in the Sham group. There was direct evidence of alterations in the mineral content associated with mechanical properties of bone. To fully understand the spectral changes, we performed principal component analysis of the spectral dataset, focusing on the matrix content. In conclusion, Raman spectroscopy provides reliable information on chemical changes in both mineral and matrix contents, and it also identifies possible mechanisms of disuse osteoporosis. Full article
(This article belongs to the Special Issue Raman Spectroscopy: A Spectroscopic 'Swiss-Army Knife')
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14 pages, 3129 KiB  
Article
Anti-Cancer Drug Sensitivity Assay with Quantitative Heterogeneity Testing Using Single-Cell Raman Spectroscopy
by Yong Zhang, Jingjing Xu, Yuezhou Yu, Wenhao Shang and Anpei Ye
Molecules 2018, 23(11), 2903; https://doi.org/10.3390/molecules23112903 - 07 Nov 2018
Cited by 20 | Viewed by 4422
Abstract
A novel anti-cancer drug sensitivity testing (DST) approach was developed based on in vitro single-cell Raman spectrum intensity (RSI). Generally, the intensity of Raman spectra (RS) for a single living cell treated with drugs positively relates to the sensitivity of the cells to [...] Read more.
A novel anti-cancer drug sensitivity testing (DST) approach was developed based on in vitro single-cell Raman spectrum intensity (RSI). Generally, the intensity of Raman spectra (RS) for a single living cell treated with drugs positively relates to the sensitivity of the cells to the drugs. In this study, five cancer cell lines (BGC 823, SGC 7901, MGC 803, AGS, and NCI-N87) were exposed to three cytotoxic compounds or to combinations of these compounds, and then they were evaluated for their responses with RSI. The results of RSI were consistent with conventional DST methods. The parametric correlation coefficient for the RSI and Methylthiazolyl tetrazolium assay (MTT) was 0.8558 ± 0.0850, and the coefficient of determination was calculated as R2 = 0.9529 ± 0.0355 for fitting the dose–response curve. Moreover, RSI data for NCI-N87 cells treated by trastuzumab, everolimus (cytostatic), and these drugs in combination demonstrated that the RSI method was suitable for testing the sensitivity of cytostatic drugs. Furthermore, a heterogeneity coefficient H was introduced for quantitative characterization of the heterogeneity of cancer cells treated by drugs. The largest possible variance between RSs of cancer cells were quantitatively obtained using eigenvalues of principal component analysis (PCA). The ratio of H between resistant cells and sensitive cells was greater than 1.5, which suggested the H-value was effective to describe the heterogeneity of cancer cells. Briefly, the RSI method might be a powerful tool for simple and rapid detection of the sensitivity of tumor cells to anti-cancer drugs and the heterogeneity of their responses to these drugs. Full article
(This article belongs to the Special Issue Raman Spectroscopy: A Spectroscopic 'Swiss-Army Knife')
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10 pages, 1872 KiB  
Article
Strong Coupling of Folded Phonons with Plasmons in 6H-SiC Micro/Nanocrystals
by Yao Huang, Run Yang, Shijie Xiong, Jian Chen and Xinglong Wu
Molecules 2018, 23(9), 2296; https://doi.org/10.3390/molecules23092296 - 08 Sep 2018
Cited by 3 | Viewed by 3093
Abstract
Silicon carbide (SiC) has a large number of polytypes of which 3C-, 4H-, 6H-SiC are most common. Since different polytypes have different energy gaps and electrical properties, it is important to identify and characterize various SiC polytypes. Here, Raman scattering is performed on [...] Read more.
Silicon carbide (SiC) has a large number of polytypes of which 3C-, 4H-, 6H-SiC are most common. Since different polytypes have different energy gaps and electrical properties, it is important to identify and characterize various SiC polytypes. Here, Raman scattering is performed on 6H-SiC micro/nanocrystal (MNC) films to investigate all four folded transverse optic (TO) and longitudinal optic (LO) modes. With increasing film thickness, the four folded TO modes exhibit the same frequency downshift, whereas the four folded LO modes show a gradually-reduced downshift. For the same film thickness, all the folded modes show larger frequency downshifts with decreasing MNC size. Based on plasmons on MNCs, these folded modes can be attributed to strong coupling of the folded phonons with plasmons which show different strengths for the different folded modes while changing the film thickness and MNC size. This work provides a useful technique to identify SiC polytypes from Raman scattering. Full article
(This article belongs to the Special Issue Raman Spectroscopy: A Spectroscopic 'Swiss-Army Knife')
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13 pages, 4438 KiB  
Article
Rapid Detection of Six Glucocorticoids Added Illegally to Dietary Supplements by Combining TLC with Spot-Concentrated Raman Scattering
by Li Li, Xin Liang, Tao Xu, Feng Xu and Wei Dong
Molecules 2018, 23(7), 1504; https://doi.org/10.3390/molecules23071504 - 21 Jun 2018
Cited by 17 | Viewed by 4528
Abstract
The objective of this study was to establish a novel method for rapid detection of six glucocorticoids (prednisone, prednisone acetate, prednisolone, hydrocortisone, hydrocortisone acetate, and dexamethasone) added illegally in dietary supplements simultaneously by combining thin layer chromatography (TLC) with spot-concentrated Raman scattering (SCRS). [...] Read more.
The objective of this study was to establish a novel method for rapid detection of six glucocorticoids (prednisone, prednisone acetate, prednisolone, hydrocortisone, hydrocortisone acetate, and dexamethasone) added illegally in dietary supplements simultaneously by combining thin layer chromatography (TLC) with spot-concentrated Raman scattering (SCRS). The doping ingredients were separated by TLC, and viewed and located with UV light (254 nm), enriched by chromatography, then Raman spectra were directly detected by a Raman Imagine microscope with 780 nm laser source. This method had complementary advantages of TLC and Raman spectroscopy, which enhanced the specificity of the test results. The limit of detection (LOD) of the reference substances were 4 μg, 4 μg, 4 μg, 6 μg, 6 μg, and 4 μg, respectively. The method was used to study the six glucocorticoids added illegally in five dietary supplements. Fake drugs had been detected. The study showed that the TLC-SCRS method is simple, rapid, specific, sensitive, and reliable. The method could be used for effective separation and detection of six chemical components used in dietary supplement products, and would have good prospects for on-site qualitative screening of dietary supplement products for adulterants. Full article
(This article belongs to the Special Issue Raman Spectroscopy: A Spectroscopic 'Swiss-Army Knife')
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Review

Jump to: Editorial, Research

16 pages, 2714 KiB  
Review
Analysis of Cellulose and Lignocellulose Materials by Raman Spectroscopy: A Review of the Current Status
by Umesh P. Agarwal
Molecules 2019, 24(9), 1659; https://doi.org/10.3390/molecules24091659 - 27 Apr 2019
Cited by 100 | Viewed by 13221
Abstract
This review is a summary of the Raman spectroscopy applications made over the last 10 years in the field of cellulose and lignocellulose materials. This paper functions as a status report on the kinds of information that can be generated by applying Raman [...] Read more.
This review is a summary of the Raman spectroscopy applications made over the last 10 years in the field of cellulose and lignocellulose materials. This paper functions as a status report on the kinds of information that can be generated by applying Raman spectroscopy. The information in the review is taken from the published papers and author’s own research—most of which is in print. Although, at the molecular level, focus of the investigations has been on cellulose and lignin, hemicelluloses have also received some attention. The progress over the last decade in applying Raman spectroscopy is a direct consequence of the technical advances in the field of Raman spectroscopy, in particular, the application of new Raman techniques (e.g., Raman imaging and coherent anti-Stokes Raman or CARS), novel ways of spectral analysis, and quantum chemical calculations. On the basis of this analysis, it is clear that Raman spectroscopy continues to play an important role in the field of cellulose and lignocellulose research across a wide range of areas and applications, and thereby provides useful information at the molecular level. Full article
(This article belongs to the Special Issue Raman Spectroscopy: A Spectroscopic 'Swiss-Army Knife')
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25 pages, 4965 KiB  
Review
Raman Characterization on Two-Dimensional Materials-Based Thermoelectricity
by Zuoyuan Dong, Hejun Xu, Fang Liang, Chen Luo, Chaolun Wang, Zi-Yu Cao, Xiao-Jia Chen, Jian Zhang and Xing Wu
Molecules 2019, 24(1), 88; https://doi.org/10.3390/molecules24010088 - 27 Dec 2018
Cited by 17 | Viewed by 10094
Abstract
The emergence and development of two-dimensional (2D) materials has provided a new direction for enhancing the thermoelectric (TE) performance due to their unique structural, physical and chemical properties. However, the TE performance measurement of 2D materials is a long-standing challenge owing to the [...] Read more.
The emergence and development of two-dimensional (2D) materials has provided a new direction for enhancing the thermoelectric (TE) performance due to their unique structural, physical and chemical properties. However, the TE performance measurement of 2D materials is a long-standing challenge owing to the experimental difficulties of precise control in samples and high demand in apparatus. Until now, there is no universal methodology for measuring the dimensionless TE figure of merit (ZT) (the core parameter for evaluating TE performance) of 2D materials systematically in experiments. Raman spectroscopy, with its rapid and nondestructive properties for probing samples, is undoubtedly a powerful tool for characterizing 2D materials as it is known as a spectroscopic ‘Swiss-Army Knife’. Raman spectroscopy can be employed to measure the thermal conductivity of 2D materials and expected to be a systematic method in evaluating TE performance, boosting the development of thermoelectricity. In this review, thermoelectricity, 2D materials, and Raman techniques, as well as thermal conductivity measurements of 2D materials by Raman spectroscopy are introduced. The prospects of obtaining ZT and testing the TE performance of 2D materials by Raman spectroscopy in the future are also discussed. Full article
(This article belongs to the Special Issue Raman Spectroscopy: A Spectroscopic 'Swiss-Army Knife')
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