OctTES/TEOS system for hybrid coatings: real‐time monitoring of the hydrolysis and condensation by Raman spectroscopy

The hybrid organic–inorganic system Tetra‐ethyl‐ortho‐silicate functionalized with Octyl‐triethoxy‐silane, studied as protective coating for the preservation of historical glasses from the environmental weathering agents, has been characterized by Raman spectroscopy by monitoring the sol‐gel reactions over time through characteristic features in the spectrum. In particular, for the hydrolysis reaction the disappearance of the 653 cm⁻¹ (Si‐O symmetric breathing) and 810 cm⁻¹ (CH₂ rocking in Si‐alkoxides) peaks and the growth of the 710 cm⁻¹ band, because of hydrolyzed alkyl‐silane, and of the 881 cm⁻¹ peak (ethanol C–C symmetric stretching) have been checked. Moreover, the condensation reaction can be tracked by the disappearance of the two main peaks of the alcohols at 816 and 881 cm⁻¹, going along with the growth of the broad band between 250 and 500 cm⁻¹ (Si–O–Si symmetric bending) and of the feature at 840 cm⁻¹ (Si–O–Si stretching). At the end of the condensation process the Raman spectrum still displays spectral bands unique to the alkyl chain in Octyl‐triethoxy‐silane, in the 1330–1450 cm⁻¹ and 2725–3000 cm⁻¹ ranges. Copyright © 2016 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the magnesium‐carbonate minerals—artinite and dypingite

Magnesium minerals are important in the understanding of the concept of geosequestration. The two hydrated hydroxy magnesium‐carbonate minerals artinite and dypingite were studied by Raman spectroscopy. Intense bands are observed at 1092 cm⁻¹ for artinite and at 1120 cm⁻¹ for dypingite, attributed ν₁ symmetric stretching mode of CO₃²⁻. The ν₃ antisymmetric stretching vibrations of CO₃²⁻ are extremely weak and are observed at 1412 and 1465 cm⁻¹ for artinite and at 1366, 1447 and 1524 cm⁻¹ for dypingite. Very weak Raman bands at 790 cm⁻¹ for artinite and 800 cm⁻¹ for dypingite are assigned to the CO₃²⁻ν₂ out‐of‐plane bend. The Raman band at 700 cm⁻¹ of artinite and at 725 and 760 cm⁻¹ of dypingite are ascribed to CO₃²⁻ν₂ in‐plane bending mode. The Raman spectrum of artinite in the OH stretching region is characterised by two sets of bands: (1) an intense band at 3593 cm⁻¹ assigned to the MgOH stretching vibrations and (2) the broad profile of overlapping bands at 3030 and 3229 cm⁻¹ attributed to water stretching vibrations. X‐ray diffraction studies show that the minerals are disordered. This is reflected in the difficulty of obtaining Raman spectra of reasonable quality, and explains why the Raman spectra of these minerals have not been previously or sufficiently described. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman and mid‐IR spectroscopic study of the magnesium carbonate minerals—brugnatellite and coalingite

Two hydrated hydroxy magnesium carbonate minerals brugnatellite and coalingite with a hydrotalcite‐like structure were studied by Raman spectroscopy. Intense bands are observed at 1094 cm⁻¹ for brugnatellite and at 1093 cm⁻¹ for coalingite attributed to the CO₃²⁻ν₁ symmetric stretching mode. Additional low intensity bands are observed at 1064 cm⁻¹. The existence of two symmetric stretching modes is accounted for in terms of different anion structural arrangements. Very low intensity bands at 1377 and 1451 cm⁻¹ are observed for brugnatellite, and the Raman spectrum of coalingite displays two bands at 1420 and 1465 cm⁻¹ attributed to the (CO₃)²⁻ν₃ antisymmetric stretching modes. Very low intensity bands at 792 cm⁻¹ for brugnatellite and 797 cm⁻¹ for coalingite are assigned to the CO₃²⁻ out‐of‐plane bend (ν₂). X‐ray diffraction studies by other researchers have shown that these minerals are disordered. This is reflected in the difficulty of obtaining Raman spectra of reasonable quality and explains why the Raman spectra of these minerals have not been previously or sufficiently described. A comparison is made with the Raman spectra of other hydrated magnesium carbonate minerals. Copyright © 2008 John Wiley & Sons, Ltd.     

FT‐Raman spectroscopic spectra on 3‐phenylpropylamine inclusion compounds

Some new Hofmann‐3‐phenylpropylamine‐type clathrates with chemical formulae of M(3‐phenylpropylamine)₂ Ni(CN)₄. 2G (MNi or Co, G = 1,2‐dichlorobenzene or 1,3‐dichlorobenzene) have been prepared and their Fourier transform infrared(FT‐IR; 4000–400 cm⁻¹), far‐infrared (600–100 cm⁻¹) and FT‐Raman (4000–60 cm⁻¹) spectra are reported. The ligand molecule, guest molecules, polymeric sheet and metal‐ligand bands of the clathrates are assigned in detail. The compounds are also characterized by thermal gravimetric analysis (TGA), differential thermal analysis (DTA), elemental analysis and magnetic susceptibility measurements. From the results, the monodentate 3‐phenylpropylamine ligand molecule bonds to the metal atom of |M‐Ni(CN)₄ | _∞ polymeric layers in the trans‐gauche‐gauche (TGG) form, and 1,2‐dichlorobenzene or 1,3‐dichlorobenzene molecules are guested by this structure revealing the inclusion ability of the host complexes. Copyright © 2010 John Wiley & Sons, Ltd.     

(13)C CPMAS NMR and DFT calculations of anthocyanidins

Anthocyanidins, red dyes from flower petals and fruits, are beneficial to human health. They attract considerable attention owing to their strong antioxidant and radical scavenging properties, however they are unstable in solution and available in small amounts only. (13)C CP MAS NMR spectra were recorded to characterize solid-state conformation of nine anthocyanidins: apigenidin, pelargonidin, cyanidin, delphinidin, peonidin, malvidin robinetidin, luteolinidin and diosmetinidin chlorides. For some carbons, the solid-state chemical shifts were different from those obtained for solutions, indicating differences in conformation and intermolecular interactions. The principal elements of the (13)C chemical shift tensor were measured for pelargonidin, cyanidin, delphinidin and malvidin chlorides using PASS-2D NMR technique. DFT GIAO calculations of shielding constants were performed for apigenidin and several geometric isomers of pelargonidin. Comparison of experimental (13)C delta(ii) with the theoretical shielding parameters was helpful in predicting the most reliable geometry in the solid state. The cross-polarization parameters were obtained from variable-contact time experiments; T(CH) are longer and the values of T(1)(rho)(H) are shorter in the order: pelargonidin相似文献   

Raman spectroscopic study of the hydrogen‐arsenate mineral pharmacolite Ca(AsO3OH)·2H2O—implications for aquifer and sediment remediation

The removal of arsenate anions from aqueous media, sediments and wasted soils is of environmental significance. The reaction of gypsum with the arsenate anion results in pharmacolite mineral formation, together with related minerals. Raman and infrared (IR) spectroscopy have been used to study the mineral pharmacolite Ca(AsO₃OH)· 2H₂O. The mineral is characterised by an intense Raman band at 865 cm⁻¹ assigned to the ν₁ (AsO₃)²⁻ symmetric stretching mode. The equivalent IR band is found at 864 cm⁻¹. The low‐intensity Raman bands in the range from 844 to 886 cm⁻¹ provide evidence for ν₃ (AsO₃) antisymmetric stretching vibrations. A series of overlapping bands in the 300‐450 cm⁻¹ region are attributed to ν₂ and ν₄ (AsO₃) bending modes. Prominent Raman bands at around 3187 cm⁻¹ are assigned to the OH stretching vibrations of hydrogen‐bonded water molecules and the two sharp bands at 3425 and 3526 cm⁻¹ to the OH stretching vibrations of only weakly hydrogen‐bonded hydroxyls in (AsO₃OH)²⁻ units. Copyright © 2009 John Wiley & Sons, Ltd.     

Micro‐Raman study of orbiton–phonon coupling in YbVO3

First‐order and multiphonon Raman active excitations are studied in YbVO₃ as a function of temperature in the orthorhombic and monoclinic phases. Below T ≃ 170 K, a G‐type orbital ordering with a concomitant monoclinic transition occurs. They enhance the phonon polarizabilities, allowing the resolution of room‐temperature bands, and activate new excitations around 700 cm⁻¹. Below T ∼ 65 K, the 700 cm⁻¹ excitations disappear, indicating a C‐type orbital ordering and a return to the orthorhombic structure. The observed phonon combinations around 1400 cm⁻¹ with a dominant Jahn‐Teller vibration at ∼690 cm⁻¹ reflect a possible orbiton‐phonon coupling. Copyright © 2011 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the magnesium carbonate mineral hydromagnesite (Mg5[(CO3)4(OH)2]· 4H2O)

Magnesium minerals are important for understanding the concept of geosequestration. One method of studying the hydrated hydroxy magnesium carbonate minerals is through vibrational spectroscopy. A combination of Raman and infrared spectroscopy has been used to study the mineral hydromagnesite. An intense band is observed at 1121 cm⁻¹, attributed to the CO₃²⁻ν₁ symmetric stretching mode. A series of infrared bands at 1387, 1413 and 1474 cm⁻¹ are assigned to the CO₃²⁻ν₃ antisymmetric stretching modes. The CO₃²⁻ν₃ antisymmetric stretching vibrations are extremely weak in the Raman spectrum and are observed at 1404, 1451, 1490 and 1520 cm⁻¹. A series of Raman bands at 708, 716, 728 and 758 cm⁻¹ are assigned to the CO₃²⁻ν₂ in‐plane bending mode. The Raman spectrum in the OH stretching region is characterized by bands at 3416, 3516 and 3447 cm⁻¹. In the infrared spectrum, a broad band is found at 2940 cm⁻¹, which is assigned to water stretching vibrations. Infrared bands at 3430, 3446, 3511, 2648 and 3685 cm⁻¹ are attributed to MgOH stretching modes. Copyright © 2011 John Wiley & Sons, Ltd.     

Micro Raman spectroscopy for monitoring alterations between human skin keratinocytes HaCaT and their tumorigenic derivatives A5RT3—toward a Raman characterization of a skin carcinoma model

Raman scattering provides molecular information about biochemical differences between healthy and cancerous cells in a non‐invasive and non‐destructive fashion. We have monitored such changes for the human skin keratinocyte cell line HaCaT and its cancerogenic counterpart A5RT3 at 514.5 and 647 nm excitations, with either fixed‐cell droplets or adherent fixed and living cells for repeated preparations over time in order to discriminate intrinsic characteristic changes. Cell droplets yielded average but rather reproducible information and helped to rapidly determine such changes. The Raman spectra show differences in the relative intensity ratios of the protein amide I band at 1656 cm⁻¹ and amide III bands around 1250 cm⁻¹ and of the phenylalanine ring mode at 1003.6 cm⁻¹ to the CH₂ deformation band at 1448 cm⁻¹, which are considerably greater for HaCaT cells than A5RT3 cells. Interestingly, these observations were accompanied by severe and consistent changes in the amide III region and in the collagen marker region around 936 cm⁻¹, therefore providing an unambiguous evidence of protein degradation and changes in the essential amino acid phenylalanine and in the lipid components in tumorigenic A5RT3 cells. Ultimately, in light of these intrinsic changes, the present findings are consistent with the passage number of the non‐tumorigenic HaCaT cells, because low pass HaCaT showed less pronounced alterations than high pass HaCaT, suggesting a correlation of tumorigenic transformation with primarily genetic instabilities in HaCaT cells. This work represents the first Raman spectroscopy discrimination of the skin carcinoma model cell lines, the non‐tumorigenic HaCaT and the cancerous A5RT3 cells, addressing the importance of delineating nonspecific variations from intrinsic characteristic changes and giving a spectroscopic indication for the influence of the passage number of HaCaT cells on the tumorigenic development. 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.     

Raman spectroscopic study of the antimonate mineral brandholzite Mg[Sb2(OH)12]·6H2O

Raman spectra of brandholzite Mg[Sb₂(OH)₁₂]·6H₂O were studied, complemented with infrared spectra, and related to the structure of the mineral. An intense Raman sharp band at 618 cm⁻¹ is attributed to the SbO symmetric stretching mode. The low‐intensity band at 730 cm⁻¹ is ascribed to the SbO antisymmetric stretching vibration. Low‐intensity Raman bands were found at 503, 526 and 578 cm⁻¹. Corresponding infrared bands were observed at 527, 600, 637, 693, 741 and 788 cm⁻¹. Four Raman bands observed at 1043, 1092, 1160 and 1189 cm⁻¹ and eight infrared bands at 963, 1027, 1055, 1075, 1108, 1128, 1156 and 1196 cm⁻¹ are assigned to δ SbOH deformation modes. A complex pattern resulting from the overlapping band of the water and hydroxyl units is observed. Raman bands are observed at 3240, 3383, 3466, 3483 and 3552 cm⁻¹; infrared bands at 3248, 3434 and 3565 cm⁻¹. The Raman bands at 3240 and 3383 cm⁻¹ and the infrared band at 3248 cm⁻¹ are assigned to water‐stretching vibrations. The two higher wavenumber Raman bands observed at 3466 and 3552 cm⁻¹ and two infrared bands at 3434 and 3565 cm⁻¹ are assigned to the stretching vibrations of the hydroxyl units. Observed Raman and infrared bands in the OH stretching region are associated with O‐H···O hydrogen bonds and their lengths 2.72, 2.79, 2.86, 2.88 and 3.0 Å (Raman) and 2.73, 2.83 and 3.07 Å (infrared). Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of an aliphatic spacer group on the adsorption mechanism on the colloidal silver surface of L‐proline phosphonodipeptides

A comparative study of molecular structures of five L ‐proline (L ‐Pro) phosphonodipeptides: L ‐Pro‐NH‐C(Me,Me)‐PO₃H₂ (P1), L ‐Pro‐NH‐C(Me,iPr)‐PO₃H₂ (P2), L ‐Pro‐L ‐NH‐CH(iBu)‐PO₃H₂ (P3), L ‐Pro‐L ‐NH‐CH(PA)‐PO₃H₂ (P4) and L ‐Pro‐L ‐NH‐CH(BA)‐PO₃H₂ (P5) has been carried out using Raman and absorption infrared techniques of molecular spectroscopy. The interpretation of the obtained spectra has been supported by density functional theory calculations (DFT) at the B3LYP; 6–31 + + G** level using Gaussian 2003 software. The surface‐enhanced Raman scattering (SERS) on Ag‐sol in aqueous solutions of these phosphonopeptides has also been investigated. The surface geometry of these molecules on a silver colloidal surface has been determined by observing the position and relative intensity changes of the Pro ring, amide, phosphonate and so‐called spacer (−R) groups vibrations of the enhanced bands in their SERS spectra. Results show that P4 and P5 adsorb onto the silver as anionic molecules mainly via the amide bond (∼1630, ∼1533, ∼1248, ∼800 and ∼565 cm⁻¹), Pro ring (∼956, ∼907 and ∼876 cm⁻¹) and carboxylate group (∼1395 and ∼909 cm⁻¹). Coadsorption of the imine nitrogen atom and PO group with the silver surface, possibly by formation of a weaker interaction with the metal, is also suggested by the enhancement of the bands at 1158 and 1248 cm⁻¹. P1, P2 and P3 show two orientations of their main chain on the silver surface resulting from different interactions of the  C CH₃,  NH and  CONH fragments with this surface. Bonding to the Ag surface occurs mainly through the imino atom (1166 cm⁻¹) for P2, while for P1 and P3 it occurs via the methyl group(s) (1194–1208 cm⁻¹). The amide group functionality (CONH) is practically not involved in the adsorption process for P1 and P2, whereas the C_s P bonds do assist in the adsorption. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis and Raman spectroscopic characterisation of the oxalate mineral wheatleyite Na2Cu2+(C2O4)2·2H2O

The mineral wheatleyite has been synthesised and characterised by Raman spectroscopy complimented with infrared spectroscopy. Two Raman bands at 1434 and 1470 cm⁻¹ are assigned to the ν_{(C O)} stretching mode and implies two independent oxalate anions. Two intense Raman bands observed at 904 and 860 cm⁻¹ are assigned to the ν(C C) stretching mode and support the concept of two non‐equivalent oxalate units in the wheatleyite structure. Two strong bands observed at 565 and 585 cm⁻¹ are assigned to the symmetric CCO in plane bending modes. The Raman band at 387 cm⁻¹ is attributed to the CuO stretching vibration and the bands at 127 and 173 cm⁻¹ to OCuO bending vibrations. A comparison is made with Raman spectra of selected natural oxalate bearing minerals. Oxalates are markers or indicators of environmental events. Oxalates are readily determined by Raman spectroscopy. Thus, deterioration of works of art, biogeochemical cycles, plant metal complexation, the presence of pigments and minerals formed in caves can be analysed. Copyright © 2008 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.     

Raman spectroscopic study of the antimonate mineral bahianite Al5Sb35+O14(OH)2

Raman spectroscopy has been used to characterize the antimonate mineral bahianite Al₅Sb₃⁵⁺O₁₄(OH)₂, a semi‐precious gemstone. The mineral is characterized by an intense Raman band at 818 cm⁻¹ assigned to Sb₃O₁₄¹³⁻ stretching vibrations. Other lower intensity bands at 843 and 856 cm⁻¹ are also assigned to this vibration, and this concept suggests the non‐equivalence of SbO units in the structure. Low‐intensity Raman bands at 669 and 682 cm⁻¹ are probably assignable to the OSbO antisymmetric stretching vibrations. Raman bands at 1756, 1808 and 1929 cm⁻¹ may be assigned to δ SbOH deformation modes, while the bands at 3462 and 3495 cm⁻¹ are assigned to AlOH stretching vibrations. The complexity in the low wave number region is attributed to the composition of the mineral. Copyright © 2009 John Wiley & Sons, Ltd.     

Studies on the resonance Raman spectra of polyaniline obtained with near‐IR excitation

The effects of near‐IR (NIR) laser power over the Raman spectra of poly(aniline) emeraldine salt (PANI‐ES) and base (PANI‐EB) were investigated. The reasons for the existence of several bands from 1324 to 1500 cm⁻¹ in the Raman spectra of poly(aniline) obtained at NIR region were also studied. The bands from 1324 to 1375 cm⁻¹ were associated to νC N of polarons with different conjugation lengths and the bands from 1450 to 1500 cm⁻¹ in Raman spectra of PANI emeraldine and pernigraniline base forms were correlated to νCN modes associated with quinoid units having different conjugation lengths. The increase of laser power at 1064.0 nm causes the deprotonation of PANI‐ES and the formation of cross‐linking segments having phenazine and/or oxazine rings. For PANI‐EB only a small spectral change is observed when the laser power is increased, owing to the low absorption of this form in the NIR region. Copyright © 2007 John Wiley & Sons, Ltd.     

Transition of synthetic chromium oxide gel to crystalline chromium oxide: a hot‐stage Raman spectroscopic study

Chromium oxide gel material was synthesised and appeared to be amorphous in X‐ray diffraction study. The changes in the structure of the synthetic chromium oxide gel were investigated using hot‐stage Raman spectroscopy based upon the results of thermogravimetric analysis. The thermally decomposed product of the synthetic chromium oxide gel in nitrogen atmosphere was confirmed to be crystalline Cr₂O₃ as determined by the hot‐stage Raman spectra. Two bands were observed at 849 and 735 cm⁻¹ in the Raman spectrum at 25 °C, which were attributed to the symmetric stretching modes of O Cr^III OH and O Cr^III O. With temperature increase, the intensity of the band at 849 cm⁻¹ decreased, while that of the band at 735 cm⁻¹ increased. These changes in intensity are attributed to the loss of OH groups and formation of O Cr^III O units in the structure. A strongly hydrogen‐bonded water H O H bending band was found at 1704 cm⁻¹ in the Raman spectrum of the chromium oxide gel; however, this band shifted to around 1590 cm⁻¹ due to destruction of the hydrogen bonds upon thermal treatment. Six new Raman bands were observed at 578, 540, 513, 390, 342 and 303 cm⁻¹ attributed to the thermal decomposed product Cr₂O₃. The use of the hot‐stage Raman spectroscopy enabled low‐temperature phase changes brought about through dehydration and dehydroxylation to be studied. Copyright © 2010 John Wiley & Sons, Ltd.     

Raman spectroscopy of the borosilicate mineral ferroaxinite

Raman spectroscopy, complemented by infrared spectroscopy, has been used to characterise the ferroaxinite minerals of the theoretical formula Ca₂Fe²⁺Al₂BSi₄O₁₅(OH), a ferrous aluminium borosilicate. The Raman spectra are complex but are subdivided into sections on the basis of the vibrating units. The Raman spectra are interpreted in terms of the addition of borate and silicate spectra. Three characteristic bands of ferroaxinite are observed at 1082, 1056 and 1025 cm⁻¹ and are attributed to BO₄ stretching vibrations. Bands at 1003, 991, 980 and 963 cm⁻¹ are assigned to SiO₄ stretching vibrations. Bands are found in these positions for each of the ferroaxinites studied. No Raman bands were found above 1100 cm⁻¹ showing that ferroaxinites contain only tetrahedral boron. The hydroxyl stretching region of ferroaxinites is characterised by a single Raman band between 3368 and 3376 cm⁻¹, the position of which is sample‐dependent. Bands for ferroaxinite at 678, 643, 618, 609, 588, 572, 546 cm⁻¹ may be attributed to the ν₄ bending modes and the three bands at 484, 444 and 428 cm⁻¹ may be attributed to the ν₂ bending modes of the (SiO₄)²⁻. Copyright © 2006 John Wiley & Sons, Ltd.     

Why the ΔνCH blue shift is larger in chloral than in dichloroacetyl chloride dimers?

Raman spectra of the Cl₃CCHO/CCl₄ and Cl₃CCHO/C₆D₁₂ binary systems were recorded as a function of the mole fraction. Features originating from self‐aggregates of chloral (trichloroethanal, trichloroacetaldehyde—TCAA) molecules were detected in different spectral regions. The most pronounced changes were observed in the vicinity of the ν(CO) and ν(C H) stretching vibration bands. Using two‐dimensional correlation spectroscopy (2D‐COS), evolving‐factor analysis (EFA) and multivariate curve resolution (MCR), dimer bands were identified, and their positions were determined. The ν(C H) stretching vibration band in dimers was blue‐shifted by nearly 18 cm⁻¹, whereas the ν(CO) dimer band was red‐shifted by more than 5 cm⁻¹. For these bands, the observed shifts were accompanied by an almost twofold change in the bandwidth, from approximately 19 and 6 cm⁻¹ for dilute solutions (x = 0.05) to 36.6 and 11.5 cm⁻¹, respectively, in pure TCAA. The formation of dimers was confirmed by multivariate analysis of the Raman spectra of chloral recorded as a function of temperature. Analogous analysis of dichloroacetyl chloride (DCAC) spectra gave an 8.9 cm⁻¹ blue shift for the ν(C H) vibration band and − 5.5/− 10.1 cm⁻¹ shifts for the ν(CO) stretching vibrations of the two conformers present. To facilitate the interpretation of experimental findings, the optimized geometries and vibrational wavenumbers of the Cl₃CCHO/HCl₂CCClO molecules and (Cl₃CCHO)₂/(HCl₂CCClO)₂ dimers were calculated at the B3LYP/6‐311 + + G(3df,3pd) level. Copyright © 2010 John Wiley & Sons, Ltd.     

A vibrational spectroscopic investigation of rhodanine and its derivatives in the solid state

Raman and infrared spectra are reported for rhodanine, 3‐aminorhodanine and 3‐methylrhodanine in the solid state. Comparisons of the spectra of non‐deuterated/deuterated species facilitate discrimination of the bands associated with N H, NH₂, CH₂ and CH₃ vibrations. DFT calculations of structures and vibrational spectra of isolated gas‐phase molecules, at the B3‐LYP/cc‐pVTZ and B3‐PW91/cc‐pVTZ level, enable normal coordinate analyses in terms of potential energy distributions for each vibrational normal mode. The cis amide I mode of rhodanine is associated with bands at ∼1713 and 1779 cm⁻¹, whereas a Raman and IR band at ∼1457 cm⁻¹ is assigned to the amide II mode. The thioamide II and III modes of rhodanine, 3‐aminorhodanine and 3‐methylrhodanine are observed at 1176 and 1066/1078; 1158 and 1044; 1107 and 984 cm⁻¹ in the Raman and at 1187 and 1083; 1179 and 1074; 1116 and 983 cm⁻¹ in the IR spectra, respectively. Copyright © 2010 John Wiley & Sons, Ltd.