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3 pages, 151 KiB

Open AccessEditorial

Special Issue “Raman Spectroscopy: A Spectroscopic ‘Swiss-Army Knife’”

by Keith C. Gordon

Molecules 2019, 24(15), 2852; https://doi.org/10.3390/molecules24152852 - 6 Aug 2019

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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

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18 pages, 1985 KiB

Open AccessArticle

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 16 | Viewed by 4684

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, k_Ln–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 (C_T > 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

Open AccessArticle

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 23 | Viewed by 4786

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

Open AccessEditor’s ChoiceArticle

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 92 | Viewed by 9689

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

Open AccessArticle

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 - 2 Feb 2019

Cited by 16 | Viewed by 3689

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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SEM images of the ordered Ag-FeS arrays, which were prepared by cosputtering Ag with a constant sputtering power (5 W) and FeS with varied sputtering powers for 300 s on the PSCP templates. The sputtering powers of FeS were (a) 50 W, (b) 60 W, (c) 70 W, (d) 80 W and (e) 90 W; sputtered pure FeS (f); and pure Ag (g) for 300 s. Full article ">Figure 2
UV-Vis absorbance spectra of cosputtered Ag and FeS; Ag was deposited with a constant sputtering power (5 W) and FeS was deposited with varied sputtering powers (50 W, 60 W, 70 W, 80 W and 90 W) for 300 s on PSCP templates. Full article ">Figure 3
The XPS spectra of cosputtered Ag (5 W sputtering power) and FeS (50 W, 60 W, 70 W, 80 W and 90 W sputtering power) deposited for 300 s on the PSCP templates: Fe 2p (a), S 2p (b), Ag 3d (c) and survey (d) spectra. Full article ">Figure 4
Raman spectrum of MB in ethanol. Full article ">Figure 5
(a) SERS spectra of MB (10−3 mol/L) adsorbed on PSCP@Ag-FeS arrays with different FeS sputtering powers, the triangle-marked peaks were attributed to Si Wafer; (b) the ratios of the sputtering power of FeS to the Raman intensity of MB (taking 1627 cm−1 as an example). Full article ">Scheme 1
A large, hydrophilic silicon wafer with the ethanol/PSCP mixture was immersed in water at a tilt angle of 45° and the arrays on the Si wafer were transferred onto the surface of the water. Then, the arrays were removed by washing the 2.0 × 2.0 cm Si wafer and they were completely dried in air by static natural evaporation. The FeS and Ag targets were simultaneously deposited onto the 200-nm PSCP templates by a magnetron sputtering system. The SERS spectrum of the PSCP@Ag-FeS-MB assemblies was collected using an excitation wavelength of 514 nm. Full article ">

12 pages, 2098 KiB

Open AccessArticle

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 4093

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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(a) The steady-state near-IR inverse Raman spectrum of a pristine P3HT film; (b) the steady-state near-IR inverse Raman spectrum of an FeCl3-doped P3HT film; (c) the steady-state stimulated Raman spectrum of an FeCl3-doped P3HT film. Broad bands between 1000 and 1300 cm−1 in (c) are artifacts originating from vibrational overtone absorption of water vapor in the air. Full article ">Figure 2
(a) Femtosecond time-resolved near-IR inverse Raman spectra of a pristine P3HT film; (b) femtosecond time-resolved near-IR inverse Raman spectra of a P3HT:PCBM blend film. The samples were photoexcited with energy density of 60 μJ cm−2 for the actinic pump pulse. Wavelengths of the actinic and Raman pump pulses was 480 and 1190 nm, respectively. Full article ">Figure 3
(a) Pulse energy density dependence of transient inverse Raman spectra of a pristine P3HT film at 0.20 ps; (b) a pristine P3HT film at 50 ps; (c) a P3HT:PCBM blend film at 0.20 ps; (d) a P3HT:PCBM blend film at 50 ps. Full article ">Figure 4
The difference inverse Raman spectrum of a pristine P3HT film at 50 ps between the spectra with energy density of 4.4 × 102 and 0 μJ cm−2. The 0 μJ cm−2 spectrum was multiplied by 0.325 on the calculation of the difference spectrum. Full article ">Figure 5
Time dependence of Raman loss for P3HT in the ground state, singlet exciton states, and positive polaron states in a P3HT:PCBM blend film. Energy density of the actinic pump pulse was 60 μJ cm−2. Filled circles represent the amplitude of the transients obtained by the least-squares fitting analysis of the time-resolved inverse Raman spectra with linear combinations of the spectra of the transients. Solid traces are the best fitted curves obtained by the least-squares fitting analysis with an error function, an exponential function and an offset, two exponential functions for the ground state, the singlet exciton states, and the positive polaron states, respectively. Full article ">

11 pages, 1956 KiB

Open AccessArticle

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 31 | Viewed by 5240

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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Schematic structures of DMT (a) and OMT (b). Full article ">Figure 2
Raman spectrum of solid DMT (a), SERS spectra of 10−4 M DMT measured immediately after sample preparation (b) or 15 min later(c), and OMT SERS spectrum (d) (adapted from Guerrini et al. [<a href="#B11-molecules-24-00292" class="html-bibr">11</a>]). Experimental details: (a) measured on microRaman Renishaw RM2000 spectrometer with 10s accumulation time and 3 averages; (b) and (c) measured on BWTek portable spectrometer with 50s accumulation time and 4 averages. Spectra are baseline corrected. The wavenumbers of the characteristic Raman bands of DMT and OMT discussed in the text are indicated. Full article ">Figure 3
SERS spectra (785 nm excitation, BWTek portable Raman spectrometer) for different nominal DMT concentration: 0.0 (only AgNPs in water) (a), 1 × 10−6 (b), 5 × 10−6 (c), 1 × 10−5 M (d). Spectra are vertically shifted to improve data readability. The arrow points to the 406 cm−1 band used for DMT quantification. Full article ">Figure 4
SERS signal (785 nm excitation, BWTek portable Raman spectrometer) of the band at 406 cm−1 as a function of DMT nominal concentration, measured on three sets of samples. The standard deviation for each data point is reported. Full article ">Figure 5
Comparison between the SERS spectra measured on olive leavesDMT spikedand SERS spectra of the standard materials in solution. (a) SERS spectrum measured with laboratory equipment on the olive leaf spiked with 10−4 M DMT. (b) SERS spectrum measured with portable equipment on the olive leaf spiked with 10−2 M DMT. (c) SERS spectrum of 10−4 M DMT measured immediately after sample preparation. (d) SERS spectrum of 10−4 M DMT measured 15 min after sample preparation. (e) OMT SERS spectrum (adapted from Guerrini et al. [<a href="#B11-molecules-24-00292" class="html-bibr">11</a>]). Experimental conditions: 785 nm laser excitation; (a) measured with Renishaw RM2000 microRaman spectrometers; (b,c,d) measured with a BWTek portable Raman spectrometer; (a) 2 mW at the sample, 20x objective, 10 s integration time, 20 averages; (b) 2.5 mW at the sample, 40x microscope objective, 10 s integration time, 10 averages; (c,d) 20 mW at the sample, macro Raman fiber probe, 50s integration time, 4 averages. All spectra are baseline corrected. Full article ">Figure 6
Plot of the 406 cm−1 peak area in a 5 mm line-scan (20 μm step) passing across a 3 mm diameter area treated with the AgNPs solution, either DMT treated or not. The flat, blue line refers to the DMT-free leaf surface; the red line refers to the DMT-treated leaf surface. The inset show a picture of the leaf and the two measured areas (DMT treated and not), possibly identified as grey circles due to the presence of AgNPs. We placed the tip of a 2 mm hex key in between the two spots to set the scale of the image. Data obtained with the Renishaw RM2000 Raman microscope. Full article ">Figure 7
DMT determination with the BWTek portable microRaman spectrometer on olive leaves. Logarithmic plot of the SERS signal (406 cm−1 band area) vs. DMT concentration. Conditions: 40× objective, 785 nm excitation wavelength, 2.5 mW laser power on the sample, 10 s integration time and 10 averages. Full article ">

9 pages, 1905 KiB

Open AccessArticle

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 29 | Viewed by 5299

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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(A) Charging and discharging profiles during the first and second cycles of a LiFePO4/Li cell. (B) In situ Raman spectra of LiFePO4 cathode in the 930–1800 cm−1 region measured during the charging-discharging processes of the first and second cycles of LiFePO4/Li cell. Full article ">Figure 2
In situ Raman spectra in the PO43− stretching region (930–980 cm−1) of OCV, a–f: the first cycle (a: 1 h, b: 7 h, c: 10 h 30 min (end of charge), d: 11 h, e: 18 h, f: 20 h (end of discharge)) and g–i: the second cycle (g: 1 h, h: 7 h, i: 9 h 8 min (end of charge), j: 10 h, k: 15 h, l: 18 h (end of discharge)). Full article ">Figure 3
(A,C) Synchronous and (B,D) asynchronous 2D correlation spectra of in situ Raman spectra during the (A,B) charging and (C,D) discharging processes in the first cycle obtained <a href="#molecules-24-00291-f001" class="html-fig">Figure 1</a>. Full article ">Figure 4
(A,C) Synchronous and (B,D) asynchronous 2D correlation spectra of in situ Raman spectra during the (A,B) charging and (C,D) discharging processes in the second cycle obtained <a href="#molecules-24-00291-f001" class="html-fig">Figure 1</a>. Full article ">

14 pages, 1668 KiB

Open AccessArticle

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 4276

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 [Ru^II(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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In situ (A) UV-vis-NIR absorption and (B) difference spectra of [Ru(tbtpy)2](PF6)2 collected during the first (red) and the second (blue) reduction wave. Insets in A: Molecular structure and CV of [Ru(tbtpy)2](PF6)2 in ACN containing the 0.1 M TBABF4 electrolyte, recorded in the spectro-electrochemistry (SEC) cell. The electrode potential for acquisition of the absorption spectra is marked in the CV (scan rate 5 mV/s, Pt-gauze working, Pt-counter, and Ag/AgCl-pseudo-reference electrodes). Full article ">Figure 2
Experimental (dashed line) and theoretical absorption spectra of [Ru(tbtpy)2](PF6)2 (solid line and bars), obtained at the time-depended density functional (TDDFT) level of theory with the B3LYP functional and the 6-31G(d) basis set and applying a PCM model to consider effects of solvation (ACN) of the (A) non-reduced specie (Eocp), (B) singly reduced specie, and (C) doubly reduced species of singlet and (D) triplet multiplicity, respectively. The vertical gray line indicates the excitation wavelength for the resonance Raman spectro-electrochemistry (RR-SEC) measurements. The experimental spectra for the singly and doubly reduced [Ru(tbtpy)2](PF6)2 (0.55 M in ACN containing 0.1 M TBABF4) are collected after polarizing the electrode for 300 s at −1.45 and −1.70 V, respectively. Full article ">Figure 3
Dependence of the normalized absorbance intensity (normalized to the first reduction) at selected wavelengths on the applied electrode potential for the (A) first and the (B) second reduction wave. Full article ">Figure 4
Experimental and calculated RR spectra of non-reduced [Ru(tbtpy)2](PF6)2 collected at (A) ocp and non-reduced singlet, at (B) −1.45 V and spectrum of the singly reduced doublet species, (C) spectrum collected at EWE = −1.80 V and spectrum of doubly reduced singlet species, and (D) spectrum collected at EWE = −1.80 V and spectrum of doubly reduced triplet species, excited at 514 nm. Full article ">Figure 5
(A) Schematic representation and (B) a photograph of the measuring setup including an Argon ion Laser (1), laser line bandpass filter (2), a microscope objective (3), the SEC cell (4), a potentiostate (5), UV-vis achromatic optics (6,8), longpass filter (7), spectrometer (9), and a computer (10). (C) Photograph of the thin-layer SEC-cell within the custom-made holder, RE: Ag/AgCl reference electrode, CE: Platinum counter electrode, WE: Platinum networking electrode. (D) The principle of a SEC measurement starts with recording a CV (D, left) either directly in the thin-layer SEC cell or in a conventional electrochemistry cell to determine the redox potential of the analyte. The applied potential for the acquisition of UV-vis and Raman spectra are marked with a blue or a red point in the CV. Subsequently the analyte is investigated by UV-Vis- (D, middle) and resonance Raman (D, right) spectro-electrochemistry (the blue spectra are recorded at open circuit potential, the red spectra are recorded at a certain redox potential). RR excitation wavelengths are displayed as vertical lines in the UV-vis spectra (D, middle). Full article ">

14 pages, 3612 KiB

Open AccessArticle

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 27 | Viewed by 6567

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

Open AccessArticle

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 8 | Viewed by 3952

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

Open AccessArticle

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 - 7 Dec 2018

Cited by 12 | Viewed by 4999

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−nCl_n]⁺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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Full article ">Figure 1
Left: Structure of the octaaqua Lu3+- ion (symmetry S8) as a gas phase cluster and imbedded in a polarizable dielectric continuum simulating the bulk water. At the right: The LuO8 skeleton (H2O as point masses) with its D4d symmetry. Full article ">Figure 2
Raman spectrum in R-format (polarized, depolarized and isotropic scattering) of a 0.186 mol·L−1 Lu(ClO4)3 solution (Rw = 289.0). The isotropic band at 396 cm−1 is the symmetric stretching mode of the LuO8 skeleton of [Lu(OH2)8]3+. The ClO4− (aq) deformation bands at 462 and 628 cm−1 are depolarized and do therefore not appear in the isotropic scattering. The broad band at 179 cm−1 is the restricted translation mode of water. Full article ">Figure 3
Anisotropic scattering profile in R-format of a 2.233 mol·L−1 Lu(ClO4)3 (aq) solution. Given are the measured curve, the sum curve and the 5 component bands of the band fit. Full article ">Figure 4
(A). Raman scattering profiles in R-format (from top to bottom: polarized, depolarized and isotropic scattering) of a 3.199 mol·L−1 LuCl3 solution. Note, the downshift of the Lu-O mode to 390 cm−1 compared to the one in Lu(ClO4)3 (aq) (compare <a href="#molecules-23-03237-f002" class="html-fig">Figure 2</a>) is due to the substitution of Cl− for a water molecule in the first hydration sphere, forming [Lu(OH2)7Cln]2+. The extremely broad mode at 672 cm−1 is due to the librational water band influenced by the solute. The mode at 192 cm−1 is due to the restricted O-H···O band of H2O and the broad feature at ~251 cm−1 is assigned to [Lu(OH2)7Cl]2+. (B). Raman scattering profiles in R-format (from top to bottom: Polarized, depolarized and isotropic scattering) of a 0.478 mol·L−1 LuCl3 solution. Note, the ν1 Lu-O mode at 396 cm−1 for [Lu(OH2)8]3+. The extremely broad mode at 807 cm−1 in Riso (Rpol: 706 cm−1) is due to the librational water band influenced by the solute. The mode at 175 cm−1 (Riso) is due to the restricted translation O-H···O band of H2O. Full article ">Figure 4 Cont.
(A). Raman scattering profiles in R-format (from top to bottom: polarized, depolarized and isotropic scattering) of a 3.199 mol·L−1 LuCl3 solution. Note, the downshift of the Lu-O mode to 390 cm−1 compared to the one in Lu(ClO4)3 (aq) (compare <a href="#molecules-23-03237-f002" class="html-fig">Figure 2</a>) is due to the substitution of Cl− for a water molecule in the first hydration sphere, forming [Lu(OH2)7Cln]2+. The extremely broad mode at 672 cm−1 is due to the librational water band influenced by the solute. The mode at 192 cm−1 is due to the restricted O-H···O band of H2O and the broad feature at ~251 cm−1 is assigned to [Lu(OH2)7Cl]2+. (B). Raman scattering profiles in R-format (from top to bottom: Polarized, depolarized and isotropic scattering) of a 0.478 mol·L−1 LuCl3 solution. Note, the ν1 Lu-O mode at 396 cm−1 for [Lu(OH2)8]3+. The extremely broad mode at 807 cm−1 in Riso (Rpol: 706 cm−1) is due to the librational water band influenced by the solute. The mode at 175 cm−1 (Riso) is due to the restricted translation O-H···O band of H2O. Full article ">Figure 5
Isotropic Raman scattering profiles of aqueous LuCl3 solutions: from top to bottom: 3.199 mol·L−1 (Rw = 15.68), 1.890 mol·L−1 (Rw = 28.51), 0.935 mol·L−1 (Rw = 98), 0.478 mol·L−1 (Rw = 116) and 0.241 mol·L−1 (Rw = 229.86). The Lu-O mode in the most concentrated solution (3.199 mol·L−1) at 390 cm−1 compares to the one at 396 cm−1 in a 0.241 mol·L−1 LuCl3 (aq). This slight frequency shift is due to the substitution of Cl− into the first hydration sphere, forming [Lu(OH2)7Cl]2+. The broad feature at ~254 cm−1 is assigned to [Lu(OH2)7Cl]2+. See also <a href="#molecules-23-03237-f004" class="html-fig">Figure 4</a>A,B. Full article ">Figure 6
Fraction of species detected by quantitative Raman spectroscopy. The filled circles denote the [Lu(OH2)8]3+, the fully hydrated Lu3+ and the filled squares the 1:1 chloro-complex species. Full article ">Figure 7
Isotropic Raman spectrum of a ternary LuCl3/HCl composed of 1.589 mol·L−1 LuCl3 plus 6.047 mol·L−1 HCl from which the isotropic scattering profile of a 6.02 mol·L−1 HCl solution was subtracted. The difference spectrum shows clearly that Cl− must have substituted water molecules of the first hydration sphere of Lu3+. Lu-O mode of the complex, [Lu(OH2)8−nCln]+3−n (n = 1, 2) and the broad mode at 230 cm−1 with a shoulder at 263 cm−1 and at 110 cm−1 are due to the chloro-complex species. Full article ">

14 pages, 2591 KiB

Open AccessArticle

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 - 1 Dec 2018

Cited by 14 | Viewed by 3934

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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Figure 1
Temperature dependence of the real part of the complex permittivity and its inverse shown on the left and right ordinate, respectively, which was measured at the probe frequency of 500 kHz upon cooling. The solid line is the best-fitted result for the inverse dielectric constant in the paraelectric phase obtained by using the Curie–Weiss law (see the text). Full article ">Figure 2
Temperature dependence of the Brillouin spectrum of BaTiO3 measured at the backward scattering geometry upon (a) cooling and (b) heating. The phonon propagation direction was <100>. The LA and the TA mode indicate the longitudinal and the transverse acoustic mode, respectively. The ferroelectric phase transition temperature TC is indicated by a horizontal arrow. Full article ">Figure 3
Temperature dependence of (a) the Brillouin shift of the LA mode, (b) the full width at half maximum (FWHM) of the LA mode, (c) the Brillouin shift of the TA mode, and (d) the Brillouin shift of the LA mode around the tetragonal–orthorhombic transition point. The two insets in (a,c) are the extended views of the data in the vicinity of TC. The temperature ranges given in numbers denote the phase transition temperatures. Full article ">Figure 4
Temperature dependence of (a) the depolarized (VH) spectrum and (b) the FWHM of BaTiO3 measured in a wider frequency range of ±540 GHz (±18 cm−1). The inset shows the extended view of the FWHM near TC. The solid line denotes the fitting result in terms of Equation (1). Full article ">Figure 5
Maps of (a) the transmitted light intensity of 570 nm wavelength, (b) the |sinδ|, and (c) the angle φ measured for BaTiO3 single crystal at 250 °C, far above TC. The meaning of each symbol is described in the text. The rectangle visible in Figure (c) is the area of 160 × 100 µm2 for which the data shown in <a href="#molecules-23-03171-f006" class="html-fig">Figure 6</a>a were calculated. Black points in Figure (a) are the air pores visible on the crystal surface. Full article ">Figure 6
(a) Temperature dependence of the birefringence of both BaTiO3 single crystals above TC. The data of the TSSG-grown BaTiO3 was taken from Reference [<a href="#B17-molecules-23-03171" class="html-bibr">17</a>]. (b) Local minimum of the phase shift of the admittance accompanying piezoelectric resonances measured in the paraelectric phase for the virgin crystal by means of dynamic method and presented at several temperatures. Full article ">Figure 7
The left and the right single crystals were grown in terms of TSSG and SSCG method, respectively. The TSSG-grown BaTiO3 single crystal was investigated in Reference [<a href="#B17-molecules-23-03171" class="html-bibr">17</a>]. Full article ">

12 pages, 4247 KiB

Open AccessArticle

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 3230

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

Open AccessArticle

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 38 | Viewed by 8447

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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The average Raman spectra obtained from neurectomized (NX group) mice and Sham operation mice (Sham group). Previous studies can be used to assign apparent peaks in Raman spectra originating from the bone mineral and matrix components (<a href="#molecules-23-03081-t001" class="html-table">Table 1</a>). Raman peaks originating from the mineral components are as follows: ν2 PO43−, 430–450 cm−1; ν4 PO43−, 584–610 cm−1; ν1 PO43−, 960 cm−1; and ν1 CO32− ν3 PO43−, 1035–1076 cm−1. Those originating from the matrix components are as follows: Proline, 855 cm−1 and 922 cm−1; hydroxyproline, 876 cm−1; phenylalanine, 1002 cm−1; amide III, 1243–1320 cm−1; CH2, 1448 cm−1; and amide I, 1664 cm−1. Full article ">Figure 2
Raman peak intensity ratios in the NX and Sham groups. (a) Carbonate/phosphate ratio (1069 cm-1/960 cm−1), (b) mineral/phenylalanine ratio (960 cm−1/1002 cm−1), and (c) mineral/proline+hydroxyproline ratio (960 cm−1/922 cm−1 + 855 cm−1 + 876 cm-1) were significantly higher in the NX group than in the Sham group. (d) Mineral/CH2 ratio (960 cm−1/1448 cm−1) and (e) mineral/amide I ratio (960 cm−1/1664 cm−1) were also higher in the NX group, and (f) amide I/CH2 ratio (1664 cm−1/1448 cm−1) was lower in the NX group, although there were no significant differences. ** p < 0.01. Full article ">Figure 3
Score plots of the Principal Component Analysis (PCA) analysis of Raman spectra. The X and Y axes include any principal components (PCs) that differed between the NX and Sham groups, with the distance on the axis indicating the degree of difference. PCA plots were built with (a) all spectral regions, (b) a partially extracted spectral region for the mineral component, and (c) a partially extracted spectral region for the matrix component. Full article ">Figure 4
Mean bone mineral density (BMD) of the (a) femurs and (b) tibiae. The BMD of both the femurs and tibiae was significantly decreased in the NX group compared to the Sham group. * p < 0.05, ** p < 0.01. Full article ">Figure 5
Volume rendering images constructed from X-ray micro-CT data of the proximal tibiae of (a) Sham and (b) NX mice. In the NX mouse, the thickness of the cortical bone is obviously decreased, and the microstructure of the cancellous bone is altered. Full article ">Figure 6
Micro-CT parameters. Relative to the Sham group, the NX group demonstrated an altered (a) bone volume (BV/TV), (b) connectivity density, (c) structural model index (SMI), (d) trabecular number, (e) trabecular thickness, (f) trabecular separation, (g) cancellous BMD, (h) cortical thickness, and (i) cortical BMD. * p < 0.05, ** p < 0.01. Full article ">

14 pages, 3129 KiB

Open AccessArticle

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 - 7 Nov 2018

Cited by 21 | Viewed by 5082

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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Full article ">Figure 1
The bright field images of BGC823 cells under conditions of different concentrations of PTX treatment for 48 h. (a) Control group without PTX treatment; (b–i) The morphological change in BGC823 cells with increasing PTX concentrations. The cellular volume obviously increased with the drug concentration. Full article ">Figure 2
Dose–response relationships for different cancer cell lines with different anti-cancer drug treatments (expressed as drug(s): cell). (a–e), BGC823, SGC7901, MGC803, AGS, or MGC803 cells treated with concentration gradients of the drugs PTX, DDP, PTX, and combinations of DDP and 5 Fu, or PTX and 5 Fu, respectively; (a1–e1), the averaged RS from different drug concentrations; (a2–e2), the averaged RS area; (a3–e3), the 1001 cm−1 band; the averaged RSs and bar graphs present mean ± s.d., n ≥ 30 cells per condition. p < 0.001 for all groups (a one-way ANOVA). Full article ">Figure 3
Drug response and heterogeneity changes for different cancer cell lines treated with anti-cancer drugs for multiple culture durations. (a,b), BGC 823 cells treated with 140 ng/mL PTX (~IC50). (d,e), AGS cells treated with 30 µg/mL PTX (~2 × IC50). Bars represent the mean ± s.d. (c,f), the heterogeneity ratio changes with drug treatment time for BGC 823 and AGS cells. The curve is a result of quadratic function fitting. Cell number was n ≥ 30 in each group. Data were collected every 6 h for 48 h. Full article ">Figure 4
The RSI method to measure molecularly targeted anti-cancer drug effects. Trastuzumab (250 nM) and everolimus (20 nM, referring to the plasma concentration) were used singly or together. Bars represent mean ± s.d. of drug treated cells to control cells, n ≥ 30 cells per group. Data were collected at 24, 48, and 72 h. p value: two-tailed Student’s t-test. Full article ">Figure 5
The long-term inhibitory effect and changes in heterogeneous characteristics due to everolimus treatment of NCI-N87. (a) Exponential fittings of proliferation rates of NCI-N87 cells. The rate constant for the control group was 0.2904 and the doubling-time was 2.387 days, with R2 = 0.9785. The rate constant for the everolimus group was 0.2684, with a doubling-time of 2.853 days and R2 = 0.9622; (b) Changes in the heterogeneous characteristics of NCI-N87 cells with the everolimus treatment time. The s.d. of the heterogeneity obtained from control groups over 7 days; (c) The drug response of NCI-N87 cells with everolimus treatment (RSI-AUC); (d) The drug response of NCI-N87 cells with everolimus treatment (RSI-1001 cm−1). Bars represent the mean ± s.d. of drug treated cells to control cells, n ≥ 30. Full article ">

10 pages, 1872 KiB

Open AccessArticle

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 - 8 Sep 2018

Cited by 3 | Viewed by 3619

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

Open AccessArticle

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 23 | Viewed by 5249

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 ?g, 4 ?g, 4 ?g, 6 ?g, 6 ?g, and 4 ?g, 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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Jump to: Editorial, Research

16 pages, 2714 KiB

Open AccessReview

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 126 | Viewed by 16732

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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Figure 1
Comparison of Raman spectra of cellulose I, cellulose II, and cellulose III in various spectral regions; (A) 50–750 cm−1, (B) 850–1550 cm−1, (C) 2600–3600 cm−1. Reproduced from Ref. [<a href="#B13-molecules-24-01659" class="html-bibr">13</a>]. Full article ">Figure 2
Calibration set Raman spectra after subtracting amorphous spectrum in the region 250–700 cm−1; (a) control, cotton microcrystalline cellulose, and plots (b) to (h) are spectra of mixture 1, mixture 2, mixture 3, mixture 4, mixture 5, mixture 6, and 120-min ball milled cellulose, respectively. Note that in the case of 120-min spectrum the intensities below 700 cm−1 are all zero because of the subtraction. Spectra were offset on the intensity scale for display purposes. Reproduced with permission from Ref. [<a href="#B23-molecules-24-01659" class="html-bibr">23</a>]. Copyright Springer Nature 2010. Full article ">Figure 3
Low frequency Raman spectra of calibration set samples, calculated crystallinities of the samples are listed on the left hand side in the Figure. Reproduced with permission from Ref. [<a href="#B24-molecules-24-01659" class="html-bibr">24</a>]. Copyright Springer Nature 2010. Full article ">Figure 4
Raman spectra of molecularly thin (single digit angstrom thickness) cellulose nanoparticles that were obtained by intensive sonication of TEMPO-oxidized cellulose fibers. Spectra of TEMPO treated (WT) and control wood pulp (WP) are also shown. Reproduced with permission from Ref. [<a href="#B30-molecules-24-01659" class="html-bibr">30</a>]. Copyright American Chemical Society 2011. Full article ">Figure 5
Raman images of xylem for poplar wood calculated by integrating from 2800 to 3030 cm−1 (a, b overall morphology), from 2800 to 2918 cm−1 (c, d carbohydrates), from 1540 to 1700 cm−1 (e, f, lignin), from 1255 to 1290 cm−1 (g, h G units), and from 1320 to 1338 cm−1 (i, j, S units). Images a, c, e, g, i: xylem near the cambium and images b, d, f, h, j xylem near the annual ring (AR). Reproduced with permission from Ref. [<a href="#B59-molecules-24-01659" class="html-bibr">59</a>]. Copyright SPRINGER NATURE 2018. Full article ">Figure 6
Raman spectrum and SRS imaging of corn stover. (a) Raman spectrum of raw corn stover. The peak at 1600 cm−1 (red arrow) corresponds to the lignin distribution, and the peak at 1100 cm−1 (green arrow) corresponds to cellulose. (b) SRS image of the vascular bundle including the edge of the stem in raw corn stover at 1600 cm−1, showing the lignin distribution. Labeled structures are discussed in the text: parenchyma (PC), phloem (PH), vessel (VE), tracheid (TR), fiber (FI). Reproduced with permission from Ref. [<a href="#B61-molecules-24-01659" class="html-bibr">61</a>]. Copyright JOHN WILEY AND SONS 2010. Full article ">

25 pages, 4965 KiB

Open AccessReview

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 23 | Viewed by 11881

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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