Experimental vibrational study of imidazolium-based ionic liquids: Raman and infrared spectra of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and 1-ethyl-3-methylimidazolium ethylsulfate

The vibrational structure of two room-temperature ionic liquids with the cation 1-ethyl-3-methylimidazolium [EMIM] and the respective anions bis(trifluoromethylsulfonyl)imide [TFSI] and ethylsulfate [EtOSO(3)] is investigated. In particular, attenuated total reflection (ATR) infrared (IR) as well as Raman spectra in the spectral range from 500 to 3500 cm(-1) have been recorded and analyzed. Moreover, the depolarization ratios of the Raman lines are determined. The individual peaks are assigned to the corresponding vibrational modes of the molecules. While the CH stretching region around 3000 cm(-1) is dominating in Raman spectra, it is remarkably weak in IR spectra. Finally, the results for 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide are compared to previous studies of single ions available in the literature. This comparison shows good agreement.     

The importance of protonation in the investigation of protein phosphorylation using Raman spectroscopy and Raman optical activity

The effect of protonation on amino acid monomers and protein phosphorylation was studied by means of a combination of Raman scattering and Raman optical activity (ROA). In the past, identifying spectral variations in phosphorylated proteins arising from either the phosphate stretch or amide vibrational modes has proven to be challenging mainly due to the loss of amide and P═O band intensity in the presence of phosphate. By contrast, we have developed a novel strategy based on the careful monitoring of the sample pH and thereby modified the protonation state, such that these difficulties can be overcome and phosphate-derived vibrations are readily visualized with both Raman and ROA. Variations in pH-dependent spectral sets of phosphorylated amino acid monomers serine and threonine demonstrated that the protonation state could be determined by the intensity of the monobasic (-OPO(3)H(-)) phosphate stretch band occurring at ~1080 cm(-1) versus the dibasic (-OPO(3)(2-)) band measured at ~980 cm(-1) in both Raman and ROA. Furthermore, by adjustment of the pH of aqueous samples of the phosphoprotein α-casein and comparing this result with dephosphorylated α-casein, spectral variations in phosphate stretch bands and amide bands could be easily determined. Consequently, structural variations due to both protonation and dephosphorylation could be distinguished, demonstrating the potential of Raman and ROA for future investigations of phosphoprotein structure and interactions.     

Revealing covariance structures in fourier transform infrared and Raman microspectroscopy spectra: a study on pork muscle fiber tissue subjected to different processing parameters

The aim of this study was to investigate the correlation patterns between Fourier transform infrared (FT-IR) and Raman microspectroscopic data obtained from pork muscle tissue, which helped to improve the interpretation and band assignment of the observed spectral features. The pork muscle tissue was subjected to different processing factors, including aging, salting, and heat treatment, in order to induce the necessary degree of variation of the spectra. For comparing the information gained from the two spectroscopic techniques with respect to the experimental design, multiblock principal component analysis (MPCA) was utilized for data analysis. The results showed that both FT-IR and Raman spectra were mostly affected by heat treatment, followed by the variation in salt content. Furthermore, it could be observed that IR amide I, II, and III band components appear to be effected to a different degree by brine-salting and heating. FT-IR bands assigned to specific protein secondary structures could be related to different Raman C-C stretching bands. The Raman C-C skeletal stretching bands at 1,031, 1,061, and 1,081 cm(-1) are related to the IR bands indicative of aggregated beta-structures, while the Raman bands at 901 cm(-1) and 934 cm(-1) showed a strong correlation with IR bands assigned to a alpha-helical structures. At the same time, the IR band at 1,610 cm(-1), which formerly was assigned to tyrosine in spectra originating from pork muscle, did not show a correlation to the strong tyrosine doublet at 827 and 852 cm(-1) found in Raman spectra, leading to the conclusion that the IR band at 1,610 cm(-1) found in pork muscle tissue is not originating from tyrosine.     

Determination of the structure and orientation of organic molecules tethered to flat graphitic carbon by ATR-FT-IR and Raman spectroscopy

Mono- and multilayers of nitroazobenzene (NAB), azobenzene (AB), nitrobiphenyl (NBP), biphenyl (BP), and fluorene (FL) were covalently bonded to flat pyrolyzed photoresist films (PPF) by electrochemical reduction of their diazonium derivatives. The structure and orientation of the molecular layers were probed with ATR-FT-IR and Raman spectroscopy. A hemispherical germanium ATR element used with p-polarized light at 65 degrees incidence angle yielded high signal/noise IR spectra for monolayer coverage of molecules on PPF. The IR spectra are dominated by in-plane vibrational modes in the 1000-2000-cm(-1) spectral range but also exhibit weaker out-of-plane deformations in the 650-1000-cm(-1) region. The average tilt angle with respect to the surface normal for the various molecules varied from 31.0 +/- 4.5 degrees for NAB to 44.2 +/- 5.4 degrees for FL with AB, NBP, and BP exhibiting intermediate adsorption geometries. Raman intensity ratios of NAB and AB for p- and s-polarized incident light support the conclusion that the chemisorbed molecules are in a predominantly upright orientation. The results unequivocally indicate that molecules electroreduced from their diazonium precursors are not chemisorbed flat on the PPF surface, but rather at an angle, similar to the behavior of Au/thiol self-assembled monolayers, Langmuir-Blodgett films, and porphyrin molecules chemisorbed thermally on silicon and PPF from alkyne and alkene precursors.     

Broadly Tunable, Mode-Hop-Tuned cw Optical Parametric Oscillator Based on Periodically Poled Lithium Niobate

We describe a broadly tunable, cw optical parametric oscillator (OPO) based on periodically poled lithium niobate. The OPO can be tuned over a broad region in the mid IR (2900-3100 cm(-1)) covering the important C-H stretch region while a high spectral resolution (<0.1 cm(-1)) is maintained. The OPO is the light source for a field-portable photoacoustic spectrometer for gas-phase monitoring of volatile organic compounds.     

Prediction of mutagenic activity of nitronaphthalene isomers by infrared and Raman spectroscopy

IR and Raman spectra of 1- and 2-nitronaphthalene isomers (1-NN and 2-NN) have been investigated to obtain more insight into the effect of the structure on mutagenic properties. To this purpose we have performed density functional theory calculations using B3LYP functional with cc-pVDZ basis set. The results have shown that IR and Raman spectra of nitronaphthalene isomers are somewhat similar to each other. A notable exception regards the symmetrical NO bonds stretching +CN bond stretching vibration (nusNO2+nuCN), which appears as very intense peak near 1350 cm(-1) in IR and Raman spectra of both isomers. Present calculations predict that for 2-NN isomer IR and Raman absorptions of this vibration are more intense by ca. 50 and 60%, respectively, than those of 1-NN isomer. The noticeably higher IR and Raman intensity values of the nusNO2+nuCN mode for 2-NN originate, respectively, from large dipole moment and polarizability changes with respect to the normal mode, suggesting that intermolecular interactions are especially favoured along this coordinate. These results are consistent with higher mutagenic activities of 2-NN in comparison to 1-NN isomer, supporting the binding to enzyme mechanism as a determining step in mutagenic pathways for this series of nitroaromatic compounds.     

Molecular structure and infrared spectra of guanidinium cation: A combined theoretical and spectroscopic study

The guanidinium cations seem to be very interesting chemical species which can be used in design of molecular complexes with exactly planed chemical and physical properties suitable for nonlinear optics (NLO).The molecular structure of guanidinium cation C(NH₂)⁺ has been calculated with the aim of density functional (B3LYP) method with the extended 6-311 + G(df,dp) basis set. The calculated geometrical parameters of guanidinium cation in gas phase were compared with experimental data of other guanidinium compounds. The harmonic frequencies and IR and Raman intensities of C(NH₂)⁺ were calculated with the B3LYP method using 6-311 + G(df,dp) basis set. The calculated frequencies were compared with the experimental ones observed in vibrational spectra measured for three newly obtained compounds in which guanidinium cation is common component. The assignment of the experimental spectra has been made on the basis of the calculated potential energy distribution (PED).     

In situ infrared microspectroscopy of approximately 850 million-year-old prokaryotic fossils

In situ infrared (IR) and Raman microspectroscopy have been conducted on Neoproterozoic, organic-walled microfossils (prokaryotic fossils) in doubly polished, petrographic thin sections in order to detect their spectral signatures. The microfossils are very well preserved and occur in black chert from the approximately 850 million-year-old Bitter Springs Formation, Northern Territory, Australia. Raman microspectroscopy on two species of microfossils, one a filament and the other a coccoid, shows disordered peaks (D peak, 1340 cm(-1)) and graphite peaks (G peak, 1600 cm(-1)), indicating that they consist of disordered carbonaceous materials. IR micro-mapping results of the filament reveal that the distributions of peak heights at 2920 cm(-1) (aliphatic CH(2)), 1585 cm(-1) (aromatic C-C), and 1370 cm(-1) (aliphatic CH(3)) match the shape of the filamentous microfossil. These results suggest that IR microspectroscopy can be used for in situ characterization of organic polar signatures that morphologically indicate microfossils embedded in chert by using doubly-polished rock (petrographic) thin section samples. Further, these methods can be applied to controversial microfossil-like structures to test their biogenic nature.     

Plasmon‐Driven Selective Reductions Revealed by Tip‐Enhanced Raman Spectroscopy

We successfully realized in‐situ monitoring plasmon‐driven selective reduction of 2,4‐dinitrobenzenethiol to 2,2′‐diamino‐dimercaptoazobenzene, revealed by high vacuum tip‐enhanced Raman spectroscopy (HV‐TERS). The HV‐TER spectra revealed that the 2‐nitro and the 4‐nitro of 2,4‐DNBT were selectively reduced to the 2‐amine and the –N = N– bond of 2,2′‐diamino‐dimercaptoazobenzene (2,2′DA‐DMAB). Raman‐active and IR‐active modes as well as Fermi resonance were simultaneously observed in HV‐TERS, which demonstrated the advantages of HV‐TERS over SERS, since only Raman‐active modes were observed in SERS. The intensities of molecular IR‐active modes can be manipulated by the distance between tip and substrate in the near field, due to different dependences of the plasmon gradient and plasmon intensity over the distance of nano gap. Our results in HV‐TERS are in‐situ “complete‐vibration modes” spectral analysis, which significantly extend the application of HV‐TERS in the field of ultrasensitive spectral analysis on the nano scale.     

Estimation of crystallinity in isotropic isotactic polypropylene with Raman spectroscopy

The Raman spectrum of isotactic polypropylene (iPP) has been found to exhibit vibrational peaks in the region of 750 to 880 cm(-1) that are sensitive to the degree of crystallinity. These features are broadly assigned to various modes of methyl group rocking, rho(CH2), and there have been various attempts to assess crystallinity based on the integrated intensities of these bands. Various vibrational analyses performed in the past in combination with experimental studies have concluded that the presence of crystalline order with trans-gauche conformation gives rise to a peak at 809 cm(-1), which is assigned to a rho(CH2) mode coupled with the skeletal stretching mode. However, the presence of additional peaks at 830 cm(-1), 841 cm(-1), and 854 cm(-1), within the same envelope, have been the subject of controversy. In this work isotropic films of iPP derived from the same precursor of identical tacticity have been subjected to various degrees of annealing and the integrated intensities of the Raman bands were measured. The results showed that true 3d crystallinity in isotropic iPP can only be expressed by the 809 cm(-1) band whereas the band at 841 cm(-1) corresponds to an uncoupled rho(CH2) fundamental mode and thus is a measure of the amorphous content. The less intense satellite bands at 830 cm(-1) and 854 cm(-1) of solid iPP cannot be distinguished from the 841 cm(-1) band in the melt and are generally considered as intermediate phases possibly related to non-crystalline components with 3(1)-helical conformations. Independent differential scanning calorimetry (DSC) crystallinity measurements were in broad agreement with the Raman measurements based on the normalized intensity of the 809 cm(-1) Raman band. By comparing the Raman with the DSC data a new value for the theoretical heat of fusion for the 100% crystalline iPP has been proposed.     

Vibrational behavior of the -NO2 group in energetic compounds

The vibrational modes of the -NO2 group in more than fifty energetic compounds containing the C-nitro and N-nitro functionalities were observed and then calculated in optimized structures using density functional theory (B3LYP/6-31+G*). The trends in the symmetric and asymmetric stretches and scissor and out-of-plane deformations were explained by these calculations. A previously unreported correlation was found between the nitro group internal bonding angle and its asymmetric stretching frequency. The concept of meta and ortho/para directing groups was applicable to the trends in coupled motions in the nitroaromatic compounds. Both the scissor motion of C-NO2 groups and the out-of-plane deformation of N-NO2 groups were found to be virtually insensitive to the remainder of the molecule. These findings may be useful in analytical methods of explosive detection based on their infrared (IR) spectra.     

Molecular orientation evolution and solvent evaporation during electrospinning of atactic polystyrene using real-time Raman spectroscopy

Real-time Raman spectroscopy was successfully utilized to monitor solvent evaporation and molecular orientation during electrospinning of atactic polystyrene (a-PS). The use of a binary solvent system of N,N-dimethyl formamide (DMF) and tetrahydrofuran (THF) provided a stable, straight jet during the experiment. The prominent Raman bands centered at 866 cm(-1), 914 cm(-1), and 1004 cm(-1), unique to DMF, THF, and a-PS, respectively, were used to monitor solvent concentration changes along the electrospinning jet for two different a-PS solutions. In addition, the changes in relative intensity for the radial skeletal ring vibration of the aromatic group of a-PS at 623 cm(-1) in two different polarization geometries, ZZ and YY, were monitored for orientation information. This study reports the first quantitative vibrational spectroscopic measurement during the electrospinning process. A significant change in concentration and orientation was observed during the process. The changes are explained in relation to the electrospinning process.     

Vibrational and surface-enhanced Raman spectra of 1,6-diphenyl-1,3,5-hexatriene

The vibrational spectra and surface-enhanced Raman scattering (SERS) of 1,6-diphenyl-1,3,5-hexatriene (DPH) are discussed. The fundamental vibrational frequencies, overtones, and combinations observed in the infrared and Raman spectra of DPH are reported. The interpretation of the observed vibrational spectra was supported by a complete geometry optimization, followed by vibrational frequency and intensity computations for the cis- and trans- isomers of the DPH using density functional theory at the B3LYP/6-31G(d,p) level of theory. Because the molecule is photo-chemically active on Ag metal surfaces, the best SERS results for silver islands were obtained at low temperature and low energy density of the exciting laser line. DPH SERS on Au films was obtained at room temperature.     

Raman spectra of proteinaceous materials used in paintings: a multivariate analytical approach for classification and identification

This work presents Raman spectra obtained from thin films of protein materials which are commonly used as binding media in painted works of art. Spectra were recorded over the spectral range of 3250-250 cm(-1), using an excitation wavelength of 785 nm, and several bands have been identified in the fingerprint region that correspond to the various proteins examined. Differences in the C-H vibrations located between 3200 and 2700 cm(-1) can be accounted for with reference to the amino acid composition of the protein-based binding media as well as the presence of fatty acid esters, in the case of egg yolk. In addition, the discrimination of different proteins on the basis of variations in spectra between 3200 and 2700 cm(-1) can be achieved following multivariate analysis of a large data set of spectra, providing a novel and nondestructive alternative based on Raman spectroscopy to other methods commonly used for the analysis of proteins.     

Extension of fourier transform vibrational circular dichroism into the near-infrared region: continuous spectral coverage from 800 to 10 000 cm(-1)

We report the first vibrational circular dichroism (VCD) spectra with continuous coverage from 800 cm(-1) in the mid-infrared (MIR) region to 10 000 cm(-1) in the near-infrared (NIR) region. This coverage is illustrated with MIR and NIR absorbance and VCD spectra of 2,2-dimethyl-dioxolane-4-methanol (DDM), alpha-pinene, and camphor that serve as calibration samples over this entire region. Commercially available, dual-source Fourier transform (FT) MIR and NIR VCD spectrometers were equipped with appropriate light sources, optics, and detectors, and were modified for dual-polarization-modulation (DPM) operation. The combination of liquid-nitrogen- and thermoelectric-cooled HgCdTe (MCT) detectors, as well as InGaAs and Germanium (Ge) detectors operating at room temperature, permitted collection of the desired absorbance and VCD spectra across the range of vibrational fundamental, combination band, and overtone frequencies. The spectra of DDM and alpha-pinene were measured as neat liquids and recorded for both enantiomers in the various spectral regions. Spectra for camphor were all measured in CCl(4) solution at a concentration of 0.6 M, except for the carbonyl-stretching region, where a more dilute concentration was used. The typical anisotropy ratios (g) of the three molecules were estimated with respect to their strongest VCD bands in each spectral region. It was found that for all three molecules in the spectral regions above 2000 cm(-1), anisotropy ratios are approximately the same order (10(-5)) of magnitude. However, in the MIR region, the typical anisotropy ratios are significantly different for the three molecules. This study demonstrates that with modern FT-VCD spectrometers modified for DPM operation, VCD spectra can be measured continuously across a wide spectral range from the MIR to nearly the visible region with an unsurpassed combination of signal-to-noise ratio and spectral resolution.     

Magnetic Properties of a Nitronyl Nitroxide Triradical as a Model for Single-Component Molecule-Based Ferrimagnets

IR and Raman spectra of neutral iodine substituted electron donors DIET, DIEDO and DIETS were measured. Their fundamental vibrational modes were calculated and compared with the experimental data. Additionally, we studied IR and Raman spectra of 2:1 charge-transfer salts formed by these donors with paramagnetic [Fe(bpca)(CN)₃] anions. Polarized IR reflectance spectra of DIET and DIEDO salts were also recorded.     

Dynamic infrared linear dichroism study of the temperature-dependent, viscoelastic behavior of a poly(ester urethane)

In the study reported here, of the poly(ester urethane), Estane 5703, simultaneous dynamic mechanical analysis (DMA) and dynamic infrared linear dichroism (DIRLD) measurements have been carried out at continuously variable temperatures from -50 to +30 degrees C. Multivariate curve resolution-alternating least squares (MCR-ALS) analysis of the spectral data has been correlated with the thermo-mechanical properties. Spectral changes, analyzed as a function of temperature, are compared with the storage and loss moduli to provide insight into viscoelastic behavior at the molecular level. In addition, the data for pure Estane have been compared to those for plasticized Estane samples, which contain 10 and 30% plasticizer by weight. These comparisons show a strong and consistent correlation between the macroscopic rheological properties and the microscopic (molecular, inter-molecular, and sub-molecular) responses of this block co-polymer.     

Interferometric Raman spectrometry with fiber waveguides

We present the design and expected performance of a Fourier-transform fiber-optic Raman spectrometer that should be capable of rapidly diagnosing environmental contamination to levels approaching a few parts per thousand. The system design is predicated on fiber arms that are unequal in length initially. A voltage applied to the piezoceramic substrate hosting the shorter fiber strains it through zero path difference to a new length that exceeds the reference arm by its initial length deficiency. This approach permits one to resolve spectral features separated by 0.5 cm(-1) over an electromagnetic bandwidth that exceeds 2000 cm(-1) without using a moving mirror or introducing a second laser to provide the sampling reference. Specific expressions are given for computing the spectral resolution, modulation bandwidth, and modulated signal-to-noise ratio of the device as a function of the system's design parameters.     

Vibrational spectra and surface-enhanced vibrational spectra of 1-nitropyrene

The present report on the vibrational spectra of 1-nitropyrene (1NP) describes the infrared and Raman spectra; their interpretation is aided by local density functional theory (DFT) calculations at the B3LYP/6-311G(d, p) level of theory and by the surface-enhanced vibrational spectra (SEVS) with the final objective of trace organic analytical applications. The surface-enhanced Raman scattering (SERS) on silver island films and mixed silver/gold island films was investigated with several laser lines in the visible region. Surface-enhanced infrared absorption (SEIRA) was attempted on silver and gold island films. The interface of the organic 1-NP with smooth metal surfaces of silver and copper was also probed using reflection-absorption infrared (RAIRS) spectra that, in conjunction with the transmission spectra, allow one to extract the molecular orientation in vacuum evaporated thin solid films. Chemical adsorption of 1-NP on silver and further photochemical decomposition of the 1-NP-metal adsorbates was detected with all visible laser lines. Resonance Raman scattering (RRS) using UV-laser excitation at 325 nm was also recorded.