Pressure‐induced phase transitions in L‐leucine crystal

Raman spectra of a crystal of L ‐leucine, an essential amino acid, were obtained for pressures between 0 and 6 GPa. The results show anomalies at three pressure values, one between 0 and 0.46 GPa, another between 0.8 and 1.46 GPa, and a third at P ∼ 3.6 GPa. The first two anomalies are characterized by the disappearance of lattice modes (which can indicate occurrence of phase transitions), the appearance of several internal modes, or the splitting of modes of high wavenumbers. The changes of internal modes are related to CH and CH₃ unit motions as well as hydrogen bonds, as can be inferred from the behavior of bands associated with CO₂⁻ moieties. The third anomaly is a discrete change of the slopes of the wavenumber versus pressure plots for most modes observed. Further, decompression to ambient pressure generates the original Raman spectrum, showing that the pressure‐induced anomalies undergone by L ‐leucine crystals are reversible. Copyright © 2008 John Wiley & Sons, Ltd.     

Low‐temperature Raman spectra of racemate DL‐Alanine crystals

Raman spectra of DL ‐Alanine crystals were investigated in the 50–3200 cm⁻¹ spectral region for temperatures ranging from 15 to 295 K. The crystalline structure of DL ‐Alanine represents a rare example of an amino acid racemate crystallizing in a non‐centrosymmetric space group. From this study, we have observed changes in the wavenumber of modes associated with both rocking of CO₂⁻ and skeletal vibrations. On the other hand, neither changes in the modes associated to CH or CH₃ vibrations nor substantial modifications of the lattice modes of the crystal were observed. Such result indicates slight changes of the CO₂ group orientation without observation of a solid–solid phase transition in the DL ‐Alanine crystal. 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.     

High‐pressure Raman spectra of deuterated L‐alanine crystal

Raman spectra of deuterated L ‐alanine have been obtained at high‐pressure conditions. A phase transition at ∼1.5 GPa associated with the splitting of some internal modes and increase of the wavenumber of the external modes was observed. Similarly to the hydrogenated L ‐alanine crystal, this first transition was related to a symmetry change. Moreover, further modifications of the Raman spectra were observed at 4.4 GPa, which may be associated to conformational changes of the molecule. To give further support to such a hypothesis, neutron powder diffraction measurements were performed. Information about the cell parameter at atmospheric pressure gave valuable information about the N D distances, shedding light on the behavior of the torsional vibration of ND₃⁺. Copyright © 2009 John Wiley & Sons, Ltd.     

IR/Raman spectroscopy and DFT calculations of cyclic di‐amino acid peptides. Part III: comparison of solid state and solution structures of cyclo(L‐Ser‐L‐Ser)

B3‐LYP/cc‐pVDZ calculations of the gas‐phase structure and vibrational spectra of the isolated molecule cyclo(L ‐Ser‐L ‐Ser), a cyclic di‐amino acid peptide (CDAP), were carried out by assuming C₂ symmetry. It is predicted that the minimum‐energy structure is a boat conformation for the diketopiperazine (DKP) ring with both L ‐seryl side chains being folded slightly above the ring. An additional structure of higher energy (15.16 kJ mol⁻¹) has been calculated for a DKP ring with a planar geometry, although in this case two fundamental vibrations have been calculated with imaginary wavenumbers. The reported X‐ray crystallographic structure of cyclo(L ‐Ser‐L ‐Ser), shows that the DKP ring displays a near‐planar conformation, with both the two L ‐seryl side chains being folded above the ring. It is hypothesized that the crystal packing forces constrain the DKP ring in a planar conformation and it is probable that the lower energy boat conformation may prevail in the aqueous environment. Raman scattering and Fourier‐transform infrared (FT‐IR) spectra of solid state and aqueous solution samples of cyclo(L ‐Ser‐L ‐Ser) are reported and discussed. Vibrational band assignments have been made on the basis of comparisons with the calculated vibrational spectra and band wavenumber shifts upon deuteration of labile protons. The experimental Raman and IR results for solid‐state samples show characteristic amide I vibrations which are split (Raman: 1661 and 1687 cm⁻¹, IR: 1666 and 1680 cm⁻¹), possibly due to interactions between molecules in a crystallographic unit cell. The cis amide I band is differentiated by its deuterium shift of ∼30 cm⁻¹, which is larger than that previously reported for trans amide I deuterium shifts. A cis amide II mode has been assigned to a Raman band located at 1520 cm⁻¹. The occurrence of this cis amide II mode at a wavenumber above 1500 cm⁻¹ concurs with results of previously examined CDAP molecules with low molecular weight substituents on the C^α atoms, and is also indicative of a relatively unstrained DKP ring. Copyright © 2009 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.     

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.     

Vibrational spectra and crystal structure of the di‐amino acid peptide cyclo(L‐Met‐L‐Met): comparison of experimental data and DFT calculations

Experimental Raman and FT‐IR spectra of solid‐state non‐deuterated and N‐deuterated samples of cyclo(L ‐Met‐L ‐Met) are reported and discussed. The Raman and FT‐IR results show characteristic amide I vibrations (Raman: 1649 cm⁻¹, infrared: 1675 cm⁻¹) for molecules exhibiting a cis amide conformation. A Raman band, assigned to the cis amide II vibrational mode, is observed at ∼1493 cm⁻¹ but no IR band is observed in this region. Cyclo(L ‐Met‐L ‐Met) crystallises in the triclinic space group P1 with one molecule per unit cell. The overall shape of the diketopiperazine (DKP) ring displays a (slightly distorted) boat conformation. The crystal packing employs two strong hydrogen bonds, which traverse the entire crystal via translational repeats. B3‐LYP/cc‐pVDZ calculations of the structure of the molecule predict a boat conformation for the DKP ring, in agreement with the experimentally determined X‐ray structure. Copyright © 2009 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.     

Raman spectroscopic study of the multi‐anion uranyl mineral schroeckingerite

Raman spectroscopy complemented with infrared (IR) spectroscopy has been used to study the mineral schroeckingerite. The mineral is a multi‐anion mineral and has (UO₂)²⁺, (SO₄)²⁻ and (CO₃)²⁻ units in its structure, and bands attributed to these vibrating units are readily identified in the Raman spectra. Symmetric stretching modes at 815, 983 and 1092 cm⁻¹ are assigned to (UO₂)²⁺, (SO₄)²⁻ and (CO₃)²⁻ units, respectively. The antisymmetric stretching modes of (UO₂)²⁺, (SO₄)²⁻ are not observed in the Raman spectra but may be readily observed in the IR spectrum at 898 and 1180 cm⁻¹. The antisymmetric stretching mode of (CO₃)²⁻ is observed in the Raman spectrum at 1374 cm⁻¹, as is also the ν₄ (CO₃)²⁻ bending modes at 742 and 707 cm⁻¹. No ν₂ (CO₃)²⁻ bending modes are observed in the Raman spectrum of schroeckingerite. All the spectroscopic evidence points to a highly ordered structure of this mineral. Copyright © 2007 John Wiley & Sons, Ltd.     

Raman spectrum of decrespignyite [(Y,REE)4Cu(CO3)4Cl(OH)5·2H2O] and its relation with those of other halogenated carbonates including bastnasite,hydroxybastnasite, parisite and northupite

Raman spectroscopy complemented with infrared spectroscopy has been used to study the rare‐earth‐based mineral decrespignyite [(Y,REE)₄Cu(CO₃)₄Cl(OH)₅· 2H₂O] and the spectrum compared with the Raman spectra of a series of selected natural halogenated carbonates from different origins including bastnasite, parisite and northupite. The Raman spectrum of decrespignyite displays three bands at 1056, 1070 and 1088 cm⁻¹ attributed to the CO₃²⁻ symmetric stretching vibration. The observation of three symmetric stretching vibrations is very unusual. The position of the CO₃²⁻ symmetric stretching vibration varies with the mineral composition. The Raman spectrum of decrespignyite shows bands at 1391, 1414, 1489 and 1547 cm⁻¹, whereas the Raman spectra of bastnasite, parisite and northupite show a single band at 1433, 1420 and 1554 cm⁻¹, respectively, assigned to the ν₃ (CO₃)²⁻ antisymmetric stretching mode. The observation of additional Raman bands for the ν₃ modes for some halogenated carbonates is significant in that it shows distortion of the carbonate anion in the mineral structure. Four Raman bands are observed at 791, 815, 837 and 849 cm⁻¹, which are assigned to the (CO₃)²⁻ν₂ bending modes. Raman bands are observed for decrespignyite at 694, 718 and 746 cm⁻¹ and are assigned to the (CO₃)²⁻ν₄ bending modes. Raman bands are observed for the carbonate ν₄ in‐phase bending modes at 722 cm⁻¹ for bastnasite, 736 and 684 cm⁻¹ for parisite and 714 cm⁻¹ for northupite. Multiple bands are observed in the OH stretching region for decrespignyite, bastnasite and parisite, indicating the presence of water and OH units in the mineral structure. Copyright © 2011 John Wiley & Sons, Ltd.     

Vibrational characterization of L‐valine phosphonate dipeptides: FT‐IR,FT‐RS,and SERS spectroscopy studies and DFT calculations

Four L ‐valine (L ‐Val) phosphonate dipeptides that are potent inhibitors of zinc metalloproteases, namely, L ‐Val‐C(Me)₂‐PO₃H₂ (V1), L ‐Val‐CH(iP)‐PO₃H₂ (V2), L ‐Val‐CH(iB)‐PO₃H₂ (V3), and L ‐Val‐C(Me)(iP)‐PO₃H₂ (V4), are studied by Fourier‐transform infrared (FT‐IR) spectroscopy, Fourier‐transform Raman spectroscopy (FT‐RS), and surface‐enhanced Raman scattering (SERS). The band assignment (wavenumbers and intensities) is made based on (B3LYP/6‐311 + + G**) calculations. Comparison of theoretical FT‐IR and FT‐RS spectra with those of SERS allows to obtain information on the orientation of these dipeptides as well as specific‐competitive interactions of their functionalities with the silver substrate. More specifically, V1 and V4 appear to interact with the silver substrate mainly via a  C_sgCH₃ moiety localized at the  N_amideC_sg(CH₃)P molecular fragment. In addition, the  POH and isopropyl units of V4 assist in the adsorption process of this molecule. In contrast, the  C_αNH₂ and  PO₃H⁻ groups of V2 and V3 interact with the silver nanoparticles, whereas their isopropyl and isobutyl fragments seem to be repelled by the silver substrate (except for the  CH₂  of V3), similar to the  C_β(CH₃)₂ fragment of L ‐Val for all L ‐Val phosphonate dipeptides investigated in this work. The adsorption mechanism of these molecules onto the colloidal silver surface is also affected by amide bond behavior. Copyright © 2010 John Wiley & Sons, Ltd.     

Local structural order in carbonic acid polymorphs: Raman and FT‐IR spectroscopy

Two different polymorphs of carbonic acid, α‐ and β‐H₂CO₃, were identified and characterized using infrared spectroscopy (FT‐IR) previously. Our attempts to determine the crystal structures of these two polymorphs using powder and thin‐film X‐ray diffraction techniques have failed so far. Here, we report the Raman spectrum of the α‐polymorph, compare it with its FT‐IR spectrum and present band assignments in line with our work on the β‐polymorph [Angew. Chem. Int. Ed. 48 (2009) 2690–2694]. The Raman spectra also contain information in the wavenumber range ∼90–400 cm⁻¹, which was not accessible by FT‐IR spectroscopy in the previous work. While the α‐polymorph shows Raman and IR bands at similar positions over the whole accessible range, the rule of mutual exclusion is obeyed for the β‐polymorph. This suggests that there is a center of inversion in the basic building block of β‐H₂CO₃ whereas there is none in α‐H₂CO₃. Thus, as the basic motif in the crystal structure we suggest the cyclic carbonic acid dimer containing a center of inversion in case of β‐H₂CO₃ and a catemer chain or a sheet‐like structure based on carbonic acid dimers not containing a center of inversion in case of α‐H₂CO₃. This hypothesis is strengthened when comparing Raman active lattice modes at < 400 cm⁻¹ with the calculated Raman spectra for different dimers. In particular, the intense band at 192 cm⁻¹ in β‐H₂CO₃ can be explained by the inter‐dimer stretching mode of the centrosymmetric RC(OHO)₂ CR entity with ROH. The same entity can be found in gas‐phase formic acid (RH) and in β‐oxalic acid (RCOOH) and produces an intense Raman active band at a very similar wavenumber. The absence of this band in α‐H₂CO₃ confirms that the difference to β‐H₂CO₃ is found in the local coordination environment and/or monomer conformation rather than on the long range. Copyright © 2011 John Wiley & Sons, Ltd.     

Self‐association and hydrogen bonding of propionaldehyde in binary mixtures with water and methanol investigated by concentration‐dependent polarized Raman study and DFT calculations

The Raman spectra of neat propionaldehyde [CH₃CH₂CHO or propanal (Pr)] and its binary mixtures with hydrogen‐donor solvents, water (W) and methanol (M), [CH₃CH₂CHO + H₂O] and CH₃CH₂CHO + CH₃OH] with different mole fractions of the reference system, Pr varying from 0.1 to 0.9 at a regular interval of 0.1, were recorded in the ν(CO) stretching region, 1600–1800 cm⁻¹. The isotropic parts of the Raman spectra were analyzed for both the cases. The wavenumber positions and line widths of the component bands were determined by a rigorous line‐shape analysis, and the peaks corresponding to self‐associated and hydrogen‐bonded species were identified. Raman peak at ∼1721 cm⁻¹ in neat Pr, which has been attributed to the self‐associated species, downshifts slightly (∼1 cm⁻¹) in going from mole fraction 0.9 to 0.6 in (Pr + W) binary mixture, but on further dilution it shows a sudden downshift of ∼7 cm⁻¹. This has been attributed to the low solubility of Pr in W (∼30%), which does not permit a hydrogen‐bonded network to form at higher concentrations of Pr. A significant decrease in the intensity of this peak in the Raman spectra of Pr in a nonpolar solvent, n‐heptane, at high dilution (C = 0.05) further confirms that this peak corresponds to the self‐associated species. In case of the (Pr + M) binary mixture, however, the spectral changes with concentration show a rather regular trend and no special features were observed. Copyright © 2010 John Wiley & Sons, Ltd.     

A Raman spectroscopic study of the uranyl mineral rutherfordine—revisited

The molecular structure of the uranyl mineral rutherfordine has been investigated by the measurement of the near‐infrared (NIR) and Raman spectra and complemented with infrared spectra including their interpretation. The spectra of rutherfordine show the presence of both water and hydroxyl units in the structure as evidenced by IR bands at 3562 and 3465 cm⁻¹ (OH) and 3343, 3185 and 2980 cm⁻¹ (H₂O). Raman spectra show the presence of four sharp bands at 3511, 3460, 3329 and 3151 cm⁻¹. Corresponding molecular water bending vibrations were only observed in both Raman and infrared spectra of one of two studied rutherfordine samples. The second rutherfordine sample studied contained only hydroxyl ions in the equatorial uranyl plane and did not contain any molecular water. The infrared spectra of the (CO₃)²⁻ units in the antisymmetric stretching region show complexity with three sets of carbonate bands observed. This combined with the observation of multiple bands in the (CO₃)²⁻ bending region in both the Raman and IR spectra suggests that both monodentate and bidentate (CO₃)²⁻ units may be present in the structure. This cannot be exactly proved and inferred from the spectra; however, it is in accordance with the X‐ray crystallographic studies. Complexity is also observed in the IR spectra of (UO₂)²⁺ antisymmetric stretching region and is attributed to non‐identical UO bonds. U O bond lengths were calculated using wavenumbers of the ν₃ and ν₁ (UO₂)²⁺ and compared with data from X‐ray single crystal structure analysis of rutherfordine. Existence of solid solution having a general formula (UO₂)(CO₃)_1−x(OH)_2x.yH₂O (x, y ≥ 0) is supported in the crystal structure of rutherfordine samples studied. Copyright © 2009 John Wiley & Sons, Ltd.     

A Raman spectroscopic study of the uranyl carbonate rutherfordine

The molecular structure of the uranyl mineral rutherfordine has been investigated by the measurement of its Raman spectra at 298 and 77 K and complemented with infrared spectra. The infrared spectra of the (CO₃)²⁻ units in the anti‐symmetric stretching region show complexity with three sets of carbonate bands observed. This, combined with the observation of multiple bands in the (CO₃)²⁻ bending region in both Raman and IR spectra, suggests that both monodentate and bidentate (CO₃)²⁻ units are present in the structure in accordance with the X‐ray crystallographic studies. Complexity is also observed in the IR spectra of (UO₂)²⁺ anti‐symmetric stretching region and is attributed to non‐identical UO bonds. Both Raman and infrared spectra of the rutherfordine show the presence of both water and hydroxyl units in the structure, as evidenced by IR bands at 3562 and 3465 cm⁻¹ (OH) and 3343, 3185 and 2980 cm⁻¹ (H₂O). Raman spectra show the presence of four sharp bands at 3511, 3460, 3329 and 3151 cm⁻¹. Copyright © 2007 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.     

Raman spectroscopic study of the uranyl carbonate mineral zellerite

Raman and infrared spectra of the uranyl mineral zellerite, Ca[(UO₂)(CO₃)₂(H₂O)₂]·3H₂O, were measured and tentatively interpreted. U O bond in uranyl and O H···O hydrogen bonds were calculated from the vibrational spectra. The presence of structurally nonequivalent water molecules in the crystal structure of zellerite was inferred. A proposed chemical formula of zellerite is supported. Raman bands at 3514, 3375 and 2945 cm⁻¹and broad infrared bands at 3513, 3396 and 3326 cm⁻¹ are related to the ν OH stretching vibrations of hydrogen‐bonded water molecules. Observed wavenumbers of these vibrations prove that in fact hydrogen bonds participate in the crystal structure of zellerite. The presence of two bands at 1618 and 1681 cm⁻¹ proves structurally distinct and nonequivalent water molecules in the crystal structure of zellerite. Copyright © 2008 John Wiley & Sons, Ltd.     

Identification of epidermal L‐tryptophan and its oxidation products by in vivo FT‐Raman Spectroscopy further supports oxidative stress in patients with vitiligo

In the past, non‐invasive in vivo FT‐Raman spectroscopy has been used to detect H₂O₂‐mediated oxidation of methionine to methionine sulfoxide and methionine sulfone, as well as cysteine to cysteic acid, in the sequence of proteins in the epidermis of patients with vitiligo. L ‐tryptophan (Trp) is another potential target for this oxidation. Owing to the presence of 10⁻³M epidermal albumin which contains one Trp residue, it was tempting to follow the oxidation of this amino acid. Using in vivo and in vitro FT‐Raman spectroscopy, we show for the first time that epidermal Trp is oxidised in patients with vitiligo, yielding 5‐OH‐Trp at 930 cm⁻¹ and other oxidation products (i.e. N‐formyl kynurenine and kynurenine) from indole ring oxidation peaking at 1050 cm⁻¹. On the basis of detailed in vitro results, we could conclude that 5‐OH‐Trp as well as formyl kynurenine and kynurenine are formed via H₂O₂‐mediated Fenton chemistry. These results once again bring out the strength of non‐invasive in vivo FT‐Raman Spectroscopy in dermatology to follow the effect of oxidative stress in the skin of patients with vitiligo. Copyright © 2008 John Wiley & Sons, Ltd.