Surface enhanced Raman spectroscopic (SERS) behavior of substituted propenoic acids used in heterogeneous catalytic asymmetric hydrogenation

The strength and geometry of adsorption of substituted propenoic acids on silver surface were studied by means of surface enhanced Raman spectroscopy (SERS) using silver sol. Based on their SERS behavior, two classes of phenylpropenoic acids studied were distinguished. The first class of propenoic acids (atropic acid, (E)‐2,3‐diphenylpropenoic acid, (E)‐2‐(2‐methoxyphenyl)‐3‐phenylpropenoic acid, (E)‐2,3‐di‐(4‐methoxyphenyl)phenylpropenoic acid and (E)‐2‐(2‐methoxyphenyl)‐3‐(4‐fluorophenyl)propenoic acid) has shown strong charge transfer (CT) effect. We suggest bidentate carboxyl bonded species based on the SERS enhanced bands of νCOO⁻ around 1394 cm⁻¹ and νC―C of the ―C―COO⁻ moiety at 951 cm⁻¹. In these series the plane of the α‐phenyl group (γCH out‐of‐plane vibrations at 850–700 cm⁻¹) is almost parallel to the silver surface, while the β‐phenyl group is in tilted position depending on the type and the position of substituent(s) showing strong SERS enhanced bands of νCC + βCH (in‐plane mode) at 1075 cm⁻¹, νCC (ring breathing mode, in‐plane) at 1000 cm⁻¹ and γCCC (out‐of‐plane mode) around 401 cm⁻¹. The other class of propenoic acids (cinnamic acid, (E)‐2‐phenyl‐3‐(4‐methoxyphenyl)propenoic acid) has shown weak electromagnetic (EM) enhancement (CC bands is enhanced in cinnamic acid). In this case no significant carboxyl enhancement was observed, so we suggest that adsorbed species lie parallel to the surface. The two types of adsorption can be related to the dissociation ability of the carboxylic group. In the first case the carboxylic H dissociates, while in the second case it does not, as indicated also by the characteristic νCO band at 1686 cm⁻¹ in the FT‐Raman spectra of methanolic solutions. Copyright © 2015 John Wiley & Sons, Ltd.     

Raman spectroscopy of the transition of α‐gallium oxyhydroxide to β‐gallium oxide nanorods

The thermo‐Raman spectra of synthesised α‐gallium oxyhydroxide nanorod prove that the transition of α‐gallium oxyhydroxide to β‐gallium oxide nanorods occurs above 350 °C but below 400 °C. Scanning electron microscopy proves that the morphology of the α‐gallium oxyhydroxide nanorods is retained upon calcination to β‐gallium oxide. X‐ray diffraction patterns show that the nanorods are α‐gallium oxyhydroxide converting upon calcination to β‐gallium oxide. Intense Raman bands are observed at 190, 262, 275, 430, 520, 605, and 695 cm⁻¹, which undergo a red shift of ∼5 cm⁻¹ upon heating to 350 °C. Upon thermal treatment above 350 °C, the Raman spectrum shows a significantly different pattern. Raman bands are observed at 155, 212, 280, 430, 570, and 685 cm⁻¹. The thermo‐Raman spectra are in harmony with the TG and DTG patterns, which show that the reaction of α‐gallium oxyhydroxide to β‐gallium oxide occurs at 365 °C. Copyright © 2008 John Wiley & Sons, Ltd.     

Vibrational spectroscopy and density functional theory calculations of poly‐D‐mannuronate and heteropolymeric fractions from sodium alginate

The tetrasaccharide of 1 → 4β‐D‐mannopyranuronate (MM) and the alternating tetrasaccharide of 1 → 4 b‐D‐mannopyranuronate and 1 → 4α‐L‐gulopyranuronate (MG) were analyzed based on density functional theory (DFT) by employing the Gaussian 03 W package. The molecular geometries were fully optimized by using the Becke's three‐parameter hybrid exchange functional combined with Lee–Yang–Parr correlation functional (B3LYP) and using a 6‐31G(d,p) basis set. The calculated IR spectrum of MM presents a band at 1093 cm⁻¹ for C C stretching vibration, which is in good agreement with the experimental observation (1096 cm⁻¹) for the polymannuronate fraction obtained by partial hydrolysis of sodium alginate extracted from the hybrid brown seaweed Lessonia–Macrocystis. The calculated value at 826 cm⁻¹for MM is in close agreement with the experimental value and confirms that this band is characteristic of polymannuronate blocks. Most of the bands in the IR spectrum are also present in the observed Raman spectrum of the polymannuronate fraction. The experimental IR spectrum of heteropolymeric fraction obtained by partial hydrolysis of sodium alginate shows absorbances similar to those calculated for the model tetrasaccharide (MG). Surface‐enhanced Raman scattering (SERS) allows differentiation between the homopolymeric and heteropolymeric fractions of sodium alginate. The SERS spectrum of the heteropolymeric fraction shows an enhanced signal at 731 cm⁻¹which is present in the calculated Raman spectrum of the tetrasaccharide MG at 729 cm⁻¹. This band is assigned to the ring‐breathing deformation of the β‐D‐mannopyranuronate and α‐L‐gulopyranuronate residues. Copyright © 2010 John Wiley & Sons, Ltd.     

Characterization of sodium alginate and its block fractions by surface‐enhanced Raman spectroscopy

The surface‐enhanced Raman scattering (SERS) of sodium alginates and their hetero‐ and homopolymeric fractions obtained from four seaweeds of the Chilean coast was studied. Alginic acid is a copolymer of β‐D ‐mannuronic acid (M) and α‐L guluronic acid (G), linked 1 → 4, forming two homopolymeric fractions (MM and GG) and a heteropolymeric fraction (MG). The SERS spectra were registered on silver colloid with the 632.8 nm line of a He Ne laser. The SERS spectra of sodium alginate and the polyguluronate fraction present various carboxylate bands which are probably due to the coexistence of different molecular conformations. SERS allows to differentiate the hetero‐ and homopolymeric fractions of alginic acid by characteristic bands. In the fingerprint region, all the poly‐D ‐mannuronate samples present a band around 946 cm⁻¹ assigned to C O stretching, and C C H and C O H deformation vibrations, a band at 863 cm⁻¹ assigned to deformation vibration of β‐C₁ H group, and one at 799–788 cm⁻¹ due to the contributions of various vibration modes. Poly‐L ‐guluronate spectra show three characteristic bands, at 928–913 cm⁻¹ assigned to symmetric stretching vibration of C O C group, at 890–889 cm⁻¹ due to C C H, skeletal C C, and C O vibrations, and at 797 cm⁻¹ assigned to α C₁ H deformation vibration. The heteropolymeric fractions present two characteristic bands in the region with the more important one being an intense band at 730 cm⁻¹ due to ring breathing vibration mode. Copyright © 2009 John Wiley & Sons, Ltd.     

Food additives characterization by infrared,Raman, and surface‐enhanced Raman spectroscopies

Fourier‐transform infrared (FT‐IR), Raman (RS), and surface‐enhanced Raman scattering (SERS) spectra of β‐hydroxy‐β‐methylobutanoic acid (HMB), L ‐carnitine, and N‐methylglycocyamine (creatine) have been measured. The SERS spectra have been taken from species adsorbed on a colloidal silver surface. The respective FT‐IR and RS band assignments (solid‐state samples) based on the literature data have been proposed. The strongest absorptions in the FT‐IR spectrum of creatine are observed at 1398, 1615, and 1699 cm⁻¹, which are due to ν_s(COOH) + ν(CN) + δ(CN), ρ_s(NH₂), and ν(C O) modes, respectively, whereas those of L ‐carnitine (at 1396/1586 cm⁻¹ and 1480 cm⁻¹) and HMB (at 1405/1555/1585 cm⁻¹ and 1437–1473 cm⁻¹) are associated with carboxyl and methyl/methylene group vibrations, respectively. On the other hand, the strongest bands in the RS spectrum of HMB observed at 748/1442/1462 cm⁻¹ and 1408 cm⁻¹ are due to methyl/methylene deformations and carboxyl group vibrations, respectively. The strongest Raman band of creatine at 831 cm⁻¹ (ρ_w(R NH₂)) is accompanied by two weaker bands at 1054 and 1397 cm⁻¹ due to ν(CN) + ν(R NH₂) and ν_s(COOH) + ν(CN) + δ(CN) modes, respectively. In the case of L ‐carnitine, its RS spectrum is dominated by bands at 772 and 1461 cm⁻¹ assigned to ρ_r(CH₂) and δ(CH₃), respectively. The analysis of the SERS spectra shows that HMB interacts with the silver surface mainly through the  COO⁻, hydroxyl, and  CH₂ groups, whereas L ‐carnitine binds to the surface via  COO⁻ and  N⁺(CH₃)₃ which is rarely enhanced at pH = 8.3. On the other hand, it seems that creatine binds weakly to the silver surface mainly by  NH₂, and C O from the  COO⁻ group. Copyright © 2006 John Wiley & Sons, Ltd.     

DFT study and quantitative detection by surface‐enhanced Raman scattering (SERS) of ethyl carbamate

Ethyl carbamate (EC), a potentially toxic compound, is found in alcoholic beverages and fermented foodstuff. A combined experimental and theoretical study of Raman on EC is reported in this work for the first time. The Raman bands observed for EC in solid phase are characteristic for the carbonyl group, C―C, C―H and N―H stretching and deformation vibrations. These spectral features coupled with a pKa study allowed establishing the neutral species of EC present in the aqueous solutions experimentally tested at different concentrations. In addition, by performing a density functional theory study in the gas phase, the calculated geometry, the harmonic vibrational modes, and the Raman scattering activities of EC were found to be in good agreement with our experimental data and helped establish the surface‐enhanced Raman scattering (SERS) behavior and EC adsorption geometry on the silver surfaces. The Raman peak at 1006 cm⁻¹, assigned to the υ_s(CC) + ω(CH) modes, the strongest and best reproducible peak in the SERS spectra, was used for a quantitative evaluation of EC. The limit of detection, which corresponds to a signal‐to‐noise ratio equal to 3, was found to be 2 × 10⁻⁷ M (17.8 µg l⁻¹). SERS spectra obtained by using hydroxylamine hydrochloride‐reduced silver nanoparticles provide a fast and reproducible qualitative and quantitative determination of EC in aqueous solution. Copyright © 2013 John Wiley & Sons, Ltd.     

Some aspects of SERS temporal fluctuations: analysis of the most intense spectra of hydrogenated amorphous carbon deposited on silver

Surface‐enhanced Raman scattering (SERS) spectra of hydrogenated amorphous carbon (a C:H) deposited on silver substrates have been recorded with a confocal Raman microscope. When scattered radiation is collected during a short time from an area of a few square micrometres, the subsequently measured SERS spectra often exhibit strong temporal changes (fluctuations). In this paper we present examples of spectra for which the intensity maxima of the fluctuating narrow Raman bands are significantly higher than that of the background (the background is usually dominated by two broad Raman bands centred at about 1350 and 1590 cm⁻¹). In a series of successively measured spectra, one can find spectra with noticeably different total integral intensity. This suggests that the results of averaging the spectra revealing strong and weak fluctuations may be different (at least in intensity). The influence of some electrolytes on the SERS spectral fluctuations is also analysed. Our experiments revealed that the efficiencies of quenching of the SERS spectral fluctuations by various electrolytes are significantly different. We suggest that only anions directly interacting with the metal surface quench strong SERS fluctuations, and that the large differences between chloride and perchloride solutions are caused by differences in the strength of interaction of Cl⁻ and ClO₄⁻ anions with the silver surface. Copyright © 2007 John Wiley & Sons, Ltd.     

Raman scattering of L‐tryptophan enhanced by surface plasmon of silver nanoparticles: vibrational assignment and structural determination

Vibrational bands of L ‐tryptophan which was adsorbed on Ag nanoparticles (∼10 nm in diameter) have been investigated in the spectral range of 200–1700 cm⁻¹ using surface‐enhanced Raman scattering (SERS) spectroscopy. Compared with the normal Raman scattering (NRS) of L ‐tryptophan in either 0.5 M aqueous solution (NRS‐AS) or solid powder (NRS‐SP), the intensified signals by SERS have made the SERS investigation at a lower molecular concentration (5 × 10⁻⁴ M ) possible. Ab initio calculations at the B3LYP/6‐311G level have been carried out to predict the optimal structure and vibrational wavenumbers for the zwitterionic form of L ‐tryptophan. Facilitated with the theoretical prediction, the observed vibrational modes of L ‐tryptophan in the NRS‐AS, NRS‐SP, and SERS spectra have been analyzed. In the spectroscopic observations, there are no significant changes for the vibrational bands of the indole ring in either NRS‐AS, NRS‐SP, or SERS. In contrast, spectral intensities involving the vibrations of carboxylate and amino groups are weak in NRS‐AS and NRS‐SP, but strong in SERS. The intensity enhancement in the SERS spectrum can reach 10³–10⁴‐fold magnification. On the basis of spectroscopic analysis, the carboxylate and amino groups of L ‐tryptophan are determined to be the preferential terminal groups to attach onto the surfaces of Ag nanoparticles in the SERS measurement. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman spectroscopy and characterisation of α‐gallium oxyhydroxide and β‐gallium oxide nanorods

Raman spectroscopy complemented by infrared spectroscopy was used to characterise both gallium oxyhydroxide (α‐GaO(OH)) and gallium oxide (β‐Ga₂O₃) nanorods synthesised with and without the surfactants using a soft chemical methodology at low temperatures. Nano‐ to micro‐sized gallium oxyhydroxide and gallium oxide materials were characterised and analysed by both X‐ray diffraction and Raman spectroscopy. Rod‐like GaO(OH) crystals with average length of ∼2.5 µm and width of 1.5 µm were obtained. Upon thermally treating gallium oxyhydroxide GaO(OH) to 900 °C, β‐Ga₂O₃ was synthesised retaining the initial GaO(OH) morphology. Raman spectroscopy has been used to study the structure of nanorods of GaO(OH) and Ga₂O₃ crystals. Raman spectroscopy shows bands characteristic of GaO(OH) at 950 and ∼1000 cm⁻¹ attributed to Ga OH deformation modes. Bands at 261, 275, 433 and 522 cm⁻¹ are assigned to vibrational modes involving Ga OH units. Bands observed at 320, 346, 418 and 472 cm⁻¹ are assigned to the deformation modes of Ga₂O₆ octahedra. Two sharp infrared bands at 2948 and 2916 cm⁻¹ are attributed to the GaO(OH) symmetric stretching vibrations. Raman spectroscopy of Ga₂O₃ provides bands at 630, 656 and 767 cm⁻¹ which are assigned to the bending and stretching of GaO₄ units. Raman bands at 417 and 475 cm⁻¹ are attributed to the symmetric stretching modes of GaO₂ units. The Raman bands at 319 and 347 cm⁻¹ are assigned to the bending modes of GaO₂ units. Copyright © 2008 John Wiley & Sons, Ltd.     

Silver‐decorated carbon nanotube networks as SERS substrates

We report on investigations upon a surface‐enhanced Raman scattering (SERS) substrate produced from a two‐dimensional single‐walled carbon nanotube (SWNT) network decorated with Ag nanoparticles. Using the strong and unique Raman spectrum of SWNTs as a reference, the SWNT/Ag nanostructure can be considered to provide two regions: one with an ultrasensitive SERS response for single‐molecule SERS (SMSERS) study; and another with uniform SERS enhancement over an area of several square millimeters for general SERS measurements. We report the appearance of an anomalous Raman feature at around 2180 cm⁻¹ in the high‐sensitivity region which exhibits the characteristics of SMSERS. The SERS performance of the uniform area was characterized using pyridine vapor adsorbed onto the substrate. The presence of the SWNT/Ag nanostructure enhanced the Raman intensity by over seven orders of magnitude, a factor comparable to or exceeding that obtained on SERS substrates reported by other groups. The results indicate great potential to produce highly sensitive, uniform SERS substrates via further fine‐tuning of the nanostructure. Copyright © 2011 John Wiley & Sons, Ltd.     

Effect of the structural order of all‐trans‐β‐carotene on the Raman scattering cross section at low concentrations

Using the technique of liquid‐core optical fiber (LCOF), we measured the Raman scattering cross sections (RSCSs) of the carbon–carbon (C C) stretching vibrational modes of all‐trans‐β‐carotene in carbon disulfide (CS₂) at concentrations ranging from 10⁻⁶ to 10⁻¹¹ M . It was found that the RSCSs of all‐trans‐β‐carotene were extremely high with decreasing concentration, and the absolute RSCS of C stretching modes of all‐trans‐β‐carotene reached the value of 2.6 × 10⁻²⁰ cm² molecule⁻¹ Sr⁻¹ at 8 × 10⁻¹¹ M , which is larger than at 8 × 10⁻⁶ Mby 4 orders of magnitude. A theoretical interpretation of the anomalous experimental results is given, which introduces a qualitative nonlinear model of coherent weakly damped electron‐lattice vibrations in structural order of all‐trans‐β‐carotene. Copyright © 2010 John Wiley & Sons, Ltd.     

Stimulated Raman scattering influenced by concentration,fluorescence profile and bandwidth of β‐carotene in liquid‐core optical fiber

We demonstrated stimulated Raman scattering (SRS) of carbon disulfide (CS₂) influenced by β‐carotene in a liquid‐core optical fiber (LCOF). Owing to the double fluorescence characteristics and large third‐order optical nonlinearity of β‐carotene, the high‐order Stokes lines, such as the seventh‐order Stokes line of CS₂, can be observed at a relatively low input‐laser power. The thresholds of Stokes lines lowered with the addition of the carotenoid when the concentration of solution was within 10⁻¹² and 10⁻⁷ mol/L; the threshold increments and intensities of Stokes lines were correlative with the fluorescence profile of β‐carotene: when the fluorescence intensity of the wavenumber region on the spectrum was high, the Stokes line intensity was also high and its threshold increment was small, and vice versa. These results are expected to be worthy of the applications on the tunable laser and the seeding laser. Copyright © 2009 John Wiley & Sons, Ltd.     

Vibrational spectroscopic studies and computational study of methyl(2‐methyl‐4,6–dinitrophenylsulfanyl)ethanoate

FT‐IR and FT‐Raman spectra of methyl(2‐methyl‐4,6–dinitrophenylsulfanyl)ethanoate (MDIE) were recorded and analyzed. Surface‐enhanced Raman scattering (SERS) spectra were recorded in silver colloid and silver electrode. The vibrational wavenumbers were computed using HF/6‐31G* and B3LYP/6‐31G* basis. The data obtained from vibrational wavenumber calculations are used to assign vibrational bands obtained in infrared and Raman spectroscopies as well as in SERS of the studied molecule. The first hyperpolarizability and infrared intensities are reported. The geometrical parameters of the title compound are in agreement with the reported similar derivatives. The presence of new bands at 1045 and 948 cm⁻¹ in the SERS spectrum in silver electrode is related to the change in orientation of the molecule with respect to the metal surface. In silver colloid SERS spectrum, the methyl group attached to the methoxy carbonyl group is close to the metal surface, whereas on silver electrode the methyl group attached to the phenyl ring is close to the metal surface. Copyright © 2009 John Wiley & Sons, Ltd.     

Nature of some features in Raman spectra of hydroxyapatite‐containing materials

A very broad vibrational band ranging from 1000 up to 4000 cm⁻¹ and two relatively sharp bands at 5000 and 5027 cm⁻¹ are found in the Raman scattering spectrum of hydroxyapatite‐containing films obtained by gas detonation spray method. We developed a theoretical model that interprets the broad band as a result of strong interaction between the high‐frequency hydrogen bond vibrations and lattice phonons. Both sharp bands around 5000 cm⁻¹ are assigned to the overtones of v‐OH vibrations. Copyright © 2016 John Wiley & Sons, Ltd.     

Dussertite BaFe3+3(AsO4)2(OH)5—a Raman spectroscopic study of a hydroxy‐arsenate mineral

The mineral dussertite, a hydroxy‐arsenate mineral with formula BaFe³⁺₃(AsO₄)₂(OH)₅, has been studied by Raman spectroscopy complemented with infrared spectroscopy. The spectra of three minerals from different origins were investigated and proved to be quite similar, although some minor differences were observed. In the Raman spectra of the Czech dussertite, four bands are observed in the 800–950 cm⁻¹ region. The bands are assigned as follows: the band at 902 cm⁻¹ is assigned to the (AsO₄)³⁻ν₃ antisymmetric stretching mode, the one at 870 cm⁻¹ to the (AsO₄)³⁻ν₁ symmetric stretching mode, and those at 859 and 825 cm⁻¹ to the As‐OM^{2 + /3+} stretching modes and/or hydroxyl bending modes. Raman bands at 372 and 409 cm⁻¹ are attributed to the ν₂ (AsO₄)³⁻ bending mode and the two bands at 429 and 474 cm⁻¹ are assigned to the ν₄ (AsO₄)³⁻ bending mode. An intense band at 3446 cm⁻¹ in the infrared spectrum and a complex set of bands centred upon 3453 cm⁻¹ in the Raman spectrum are attributed to the stretching vibrations of the hydrogen‐bonded (OH)⁻ units and/or water units in the mineral structure. The broad infrared band at 3223 cm⁻¹ is assigned to the vibrations of hydrogen‐bonded water molecules. Raman spectroscopy identified Raman bands attributable to (AsO₄)³⁻ and (AsO₃OH)²⁻ units. Copyright © 2010 John Wiley & Sons, Ltd.     

pH‐sensing nanostar probe using surface‐enhanced Raman scattering (SERS): theoretical and experimental studies

Local pH environment has been considered to be a potential biomarker for tumor diagnosis because solid tumors contain highly acidic environments. A pH‐sensing nanoprobe based on surface‐enhanced Raman scattering (SERS) using nanostars under near‐infrared excitation has been developed for potential biomedical applications. To theoretically investigate the effect of protonation state on SERS spectra of p‐mercaptobenzoic acid (pMBA), we used the density functional theory (DFT) with the B3LYP functional to calculate Raman vibrational spectra of pMBA‐Au/Ag complex in both protonated and deprotonated states. Vibrational spectral bands were assigned with DFT calculation and used to investigate SERS spectral changes observed from experiment when varying pH value between five and nine. The SERS peak position of pMBA at ~1580 cm⁻¹ was identified to be a novel pH‐sensing index, which has small but noticeable downshift with pH increase. This phenomenon is confirmed and well‐explained with theoretical simulation. The study demonstrates that SERS is a sensitive tool to monitor minor structural changes due to local pH environment, and DFT calculations can be used to investigate Raman spectra changes associated with minor differences in molecular structure. Copyright © 2013 John Wiley & Sons, Ltd.     

Vibrational spectroscopic studies of the structure of di‐amino acid peptides. Part II: cyclo(L‐Asp‐L‐Asp) in the solid state and in aqueous solution

Solid‐state protonated and N,O‐deuterated Fourier transform infrared (IR) and Raman scattering spectra together with the protonated and deuterated Raman spectra in aqueous solution of the cyclic di‐amino acid peptide cyclo(L ‐Asp‐L ‐Asp) are reported. Vibrational band assignments have been made on the basis of comparisons with previously cited literature values for diketopiperazine (DKP) derivatives and normal coordinate analyses for both the protonated and deuterated species based upon DFT calculations at the B3‐LYP/cc‐pVDZ level of the isolated molecule in the gas phase. The calculated minimum energy structure for cyclo(L ‐Asp‐L ‐Asp), assuming C₂ symmetry, predicts a boat conformation for the DKP ring with both the two L ‐aspartyl side chains being folded slightly above the ring. The CO stretching vibrations have been assigned for the side‐chain carboxylic acid group (e.g. at 1693 and 1670 cm⁻¹ in the Raman spectrum) and the cis amide I bands (e.g. at 1660 cm⁻¹ in the Raman spectrum). The presence of two bands for the carboxylic acid CO stretching modes in the solid‐state Raman spectrum can be accounted for by factor group splitting of the two nonequivalent molecules in a crystallographic unit cell. The cis amide II band is observed at 1489 cm⁻¹ in the solid‐state Raman spectrum, which is in agreement with results for cyclic di‐amino acid peptide molecules examined previously in the solid state, where the DKP ring adopts a boat conformation. Additionally, it also appears that as the molecular mass of the substituent on the C^α atom is increased, the amide II band wavenumber decreases to below 1500 cm⁻¹; this may be a consequence of increased strain on the DKP ring. The cis amide II Raman band is characterized by its relatively small deuterium shift (29 cm⁻¹), which indicates that this band has a smaller N H bending contribution than the trans amide II vibrational band observed for linear peptides. Copyright © 2009 John Wiley & Sons, Ltd.     

Pump power dependence in resonance femtosecond stimulated Raman spectroscopy

Femtosecond stimulated Raman spectroscopy (FSRS) has emerged as a powerful new technique that is capable of obtaining resonance Raman spectra of fluorescent species and transient photochemical intermediates. Unlike related transient infrared absorption techniques, the FSRS signal is quite sensitive to the laser power utilized in the vibrational probing event. In particular, FSRS spectra are highly sensitive to the intensity of the picosecond Raman‐pump pulse. We have measured the power dependence of the FSRS signal using pulse energies from ~10⁻⁹ to ~10⁻⁵ J and molecules with a range of molar absorptivities at the Raman‐pump wavelength of 400 nm, including β‐carotene (ε₄₀₀ = 58 300 M⁻¹ cm⁻¹), para‐nitroaniline (17 800 M⁻¹ cm⁻¹), nitronaphthalene (247 M⁻¹ cm⁻¹) and ferrocene (57 M⁻¹ cm⁻¹). We show that for strongly absorbing molecular systems, such as β‐carotene and para‐nitroaniline, the ground‐state (GS) FSRS signal actually decreases with increasing pump power at pump fluences above ~10⁻² J cm⁻², due to depletion of the GS population. However, for weakly absorbing species like nitronaphthalene and ferrocene, the signal increases linearly with increasing pump fluence until ~0.5 J cm⁻², at which point two‐photon absorption by the solute induces nonlinear absorption of the pump pulse and attenuation of the FSRS signal. The data are quantitatively simulated with a photophysical kinetic model, and the results are analyzed to provide simple guidelines for acceptable Raman‐pump powers in resonance FSRS experiments. The acceptable Raman‐pump power is proportional to the focused beam area and depends inversely on the sample's molar absorptivity. Copyright © 2013 John Wiley & Sons, Ltd.     

Thermo‐Raman spectroscopy of synthetic nesquehonite — implication for the geosequestration of greenhouse gases

Pure nesquehonite (MgCO₃·3H₂O)/Mg(HCO₃)(OH)·2H₂O was synthesised and characterised by a combination of thermo‐Raman spectroscopy and thermogravimetry with evolved gas analysis. Thermo‐Raman spectroscopy shows an intense band at 1098 cm⁻¹, which shifts to 1105 cm⁻¹ at 450 °C, assigned to the ν₁CO₃²⁻ symmetric stretching mode. Two bands at 1419 and 1509 cm⁻¹ assigned to the ν₃ antisymmetric stretching mode shift to 1434 and 1504 cm⁻¹ at 175 °C. Two new peaks at 1385 and 1405 cm⁻¹ observed at temperatures higher than 175 °C are assigned to the antisymmetric stretching modes of the (HCO₃)⁻ units. Throughout all the thermo‐Raman spectra, a band at 3550 cm⁻¹ is attributed to the stretching vibration of OH units. Raman bands at 3124, 3295 and 3423 cm⁻¹ are assigned to water stretching vibrations. The intensity of these bands is lost by 175 °C. The Raman spectra were in harmony with the thermal analysis data. This research has defined the thermal stability of one of the hydrous carbonates, namely nesquehonite. Thermo‐Raman spectroscopy enables the thermal stability of the mineral nesquehonite to be defined, and, further, the changes in the formula of nesquehonite with temperature change can be defined. Indeed, Raman spectroscopy enables the formula of nesquehonite to be better defined as Mg(OH)(HCO₃)·2H₂O. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman spectroscopy as a tool to the in situ study of three lichens species from Antarctica and Brazil

In this investigation the chemistry of the lichens Gondwania regalis, Teloschistes exilis and Xanthoria candelaria (Teloschistaceae) have been recorded by means of Raman spectroscopy. The non‐destructive analysis provided the recognition of parietin and conjugated polyenes, probably belonging to the carotenoid family for all the investigated specimens. Bands at ca. 1370 and 1600 cm⁻¹, respectively, assigned to the ν(C―O) and ν(CO) modes of the phenyl group of the anthraquinone compound, as well the bands at ca. 1005, 1158 and 1527 cm⁻¹, possibly assigned to the β‐carotene in the FT‐Raman spectra, have provided valuable spectroscopy data for the identification of the biomarkers for these lichen pigments. Thus, this is the first report of parietin and carotenoid in T. exilis and X. candelaria tissues even as the parietin anthraquinone for G. regalis tissues, which are effective pigments against free radicals from UV radiation. Copyright © 2014 John Wiley & Sons, Ltd.