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.     

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.     

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.     

Effect of amino acid modifications on the molecular structure of adsorbed and nonadsorbed bombesin 6–14 fragments on an electrochemically roughened silver surface

This work used infrared absorption and Raman spectroscopy to determine the structure of seven modified fragments (residues 6–14 of the polypeptide chain) of bombesin (BN^6–14). The peptides studied are cyclo[D ‐Phe⁶, His⁷, Leu¹⁴]BN^6–14, [D ‐Phe⁶, Leu‐NHEt¹³, des‐Met¹⁴]BN^6–14, [D ‐Phe⁶, Leu¹³‐®‐p‐chloro‐Phe¹⁴]BN^6–14, [D ‐Phe⁶, β‐Ala¹¹, Phe¹³, Nle¹⁴]BN^6–14, [D ‐Tyr⁶, β‐Ala¹¹, Phe¹³, Nle¹⁴]BN^6–14, [D ‐Tyr⁶, β‐Phe¹¹, Phe¹³, Nle¹⁴OH]BN^6–14 and [D ‐Cys⁶, Asn⁷, D ‐Ala¹¹, Cys¹⁴]BN^6–14. These peptides are potent bombesin agonists useful in the treatment of tumors. Surface‐enhanced Raman scattering (SERS) spectroscopy was also used to examine the behavior of these molecules on an electrochemically roughened silver surface. The SERS spectra reveal that substituting native amino acids in these molecules with synthetic ones changes their adsorption state slightly on an electrochemically roughened surface of silver. The peptides [D ‐Tyr⁶, β‐Ala¹¹, Phe¹³, Nle¹⁴]BN^6–14 and [D ‐Tyr⁶, β‐Phe¹¹, Phe¹³, Nle¹⁴OH]BN^6–14 tend to adsorb strongly on this surface via C fragment (∼1400 cm⁻¹). The observed medium enhancement of the Trp⁸ residue and amide bond Raman signals indicate further interactions between these fragments and the surface. [D ‐Phe⁶, Leu‐NHEt¹³, des‐Met¹⁴]BN^6–14 and [D ‐Cys⁶, Asn⁷, D ‐Ala¹¹, Cys¹⁴]BN^6–14 are shown to be coordinated to the silver through  CONH , CO, and the indole ring. The strongest SERS bands (∼1506, ∼1275, ∼1149, and ∼1007 cm⁻¹) of [D ‐Phe⁶, Leu¹³‐®‐p‐chloro‐Phe¹⁴]BN^6–14 and [D ‐Phe⁶, β‐Ala¹¹, Phe¹³, Nle¹⁴]BN^6–14 suggest that these two peptides bind to the silver via Trp⁸ and  CONH . In the case of cyclo[D ‐Phe⁶, His⁷, Leu¹⁴]BN^6–14, the formation of a peptide/Ag complex is confirmed by the strong SERS bands involving Trp⁸ and  CONH vibrations, which are accompanied by a SERS signal due to the CO vibrations. For these analogs, the relative potency for inhibition of binding of ¹²⁵I‐[Tyr⁴]BN to rat pancreas acini cells was correlated with the behavior of the amide bond on the silver surface, while the contribution of the structural components to the ability to interact with the rGRP‐R was correlated with the SERS patterns. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman and surface‐enhanced Raman studies of α‐aminophosphinic inhibitors of metalloenzymes

Here, we report the nature of new di‐α‐amino (L¹–L³) and α‐amino‐α‐hydroxyphosphinic (L⁴–L⁶) acids, which are considered potential inhibitors of the aminopeptidase N, adsorbed on a colloidal silver surface by means of surface‐enhanced Raman scattering (SERS) spectroscopy. In order to reveal the adsorption mechanism of these species from their SERS spectra, Fourier‐transform Raman (FT‐RS) spectra of these nonadsorbed molecules were measured. By examining the enhancement, shift in wavenumbers, and changes in breadth of the SERS bands due to the adsorption process, we revealed that the tilted compounds interact with the colloidal silver substrate mainly through the benzene ring, amino group, and phosphinic moiety in the following way. The benzene ring of L² and L³ is ‘standing up’ on the colloidal silver surface, and the C N bond is almost vertical to it, while the tilt angle between the O PO bond and this surface is greater than 45°. On the other hand, for L¹, L⁴, and L⁵, the aromatic ring and C N bond are arranged more or less tilted, and the tilt angle between the O PO bond and the silver substrate is smaller than 45°. The elongation of the bond to the benzene ring, the L⁶ case, produces an almost horizontal orientation of the benzene ring and the O PO bond on the silver nanoparticles. For these ligands, the complement inhibition IC₅₀ tested in vitro using porcine kidney leucine aminopeptidase was correlated mainly with the behavior of the O PO and C CH N fragments on the silver surface. Copyright © 2009 John Wiley & Sons, Ltd.     

Theoretical and vibrational spectral investigation of sodium salt of acenocoumarol

The FT‐IR and FT‐Raman spectra of sodium salt of 4‐hydroxy‐3[1‐(4‐nitrophenyl)‐3‐oxobutyl]‐2H‐1‐benzopyran‐2‐one (acenocoumarol sodium salt) in solid phase have been recorded and analyzed. The optimization geometry, intramolecular hydrogen bonding, and harmonic vibrational wavenumbers of acenocoumarol sodium salt have been investigated with the help of B3LYP density functional theory (DFT) methods. The infrared and Raman spectra were predicted theoretically from the calculated intensities. Natural bond orbital (NBO) analysis indicates the presence of C H···O hydrogen bonding in the molecule. The first static hyperpolarizability of the molecule has been computed. Copyright © 2009 John Wiley & Sons, Ltd.     

Vibrational spectroscopy and DFT calculations of di‐amino acid cyclic peptides. Part I: cyclo(Gly‐Gly), cyclo(L‐Ala‐L‐Ala) and cyclo(L‐Ala‐Gly) in the solid state and in aqueous solution

Investigations of the vibrational spectra of cyclo(Gly‐Gly), cyclo(L‐Ala‐L ‐Ala) and cyclo(L ‐Ala‐Gly) are reported. Raman scattering and Fourier transform infrared (FTIR) spectra of solid‐state and aqueous protonated samples, as well as their corresponding N‐deuterated isotopomers, have been examined. In addition, density functional theory (DFT) (B3‐LYP/cc‐pVDZ) calculations of molecular structures and their associated vibrational modes were carried out. In each case, the calculated structures of lowest energy for the isolated gas‐phase molecules have boat conformations. Assignments have been made for the observed Raman and FTIR vibrational bands of the cyclic di‐amino acid peptides (CDAPs) examined. Raman polarization studies of aqueous phase samples are consistent with C₂ and C₁ symmetries for the six‐membered rings of cyclo(L‐Ala‐L‐Ala) and cyclo(L‐Ala‐Gly), respectively. There is a good correlation between experimental and calculated vibrational bands for the three CDAPs. These data are in keeping with boat conformations for cyclo(L‐Ala‐L‐Ala) and cyclo(L‐Ala‐Gly) molecules, predicted by the ab initio calculations, in both the solid and aqueous solution states. However, Raman spectroscopic results might infer that cyclo(L‐Ala‐Gly) deviates only slightly from planarity in the solid state. The potential energy distributions of the amide I and II modes of a cis‐peptide linkage are shown to be significantly different from those of the trans‐peptides. For example, deuterium shifts have shown that the cis‐amide I vibrations found in cyclo(Gly‐Gly), cyclo(L‐Ala‐L‐Ala), and cyclo(L‐Ala‐Gly) have larger N‐H contributions compared to their trans‐amide counterparts. Compared to trans‐amide II vibrations, cis‐amide II vibrations show a considerable decrease in N H character. Copyright © 2009 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.     

Raman analysis of synthetic eritadenine

Eritadenine, 2(R),3(R)‐dihydroxy‐4‐(9‐adenyl)‐butyric acid, is a cholesterol‐reducing compound naturally occurring in the shitake mushroom (Lentinus edodes). To identify the unknown Raman spectrum of this compound, pure synthetic eritadenine was examined and the vibrational modes were assigned by following the synthesis pathway. This was accomplished by comparing the known spectra of the starting compounds adenine and D ‐ribose with the spectra of a synthesis intermediate, methyl 5‐(6‐Aminopurin‐9H‐9‐yl)‐2,3‐O‐isopropylidene‐5‐deoxy‐β‐D ‐ribofuranoside (MAIR) and eritadenine. In the Raman spectrum of eritadenine, a distinctive vibrational mode at 773 cm⁻¹ was detected and ascribed to vibrations in the carbon chain, ν(C C). A Raman line that arose at 1212 cm⁻¹, both in the Raman spectrum of MAIR and eritadenine, was also assigned to ν(C C). Additional Raman lines detected at 1526 and at 1583 cm⁻¹ in the Raman spectrum of MAIR and eritadenine were assigned to ν(N C) and a deformation of the purine ring structure. In these cases the vibrational modes are due to the linkage between adenine and the ribofuranoside moiety for MAIR, and between adenine and the carbon chain for eritadenine. This link is also the cause for the disappearance of adenine specific Raman lines in the spectrum of both MAIR and eritadenine. Several vibrations observed in the spectrum of D ‐ribose were not observed in the Raman spectrum of eritadenine due to the absence of the ribose ring structure. In the Raman spectrum of MAIR some of the D ‐ribose specific Raman lines disappeared due to the introduction of methyl and isopropylidene moieties to the ribose unit. With the approach presented in this study the so far unknown Raman spectrum of eritadenine could be successfully identified and is presented here for the first time. Copyright © 2008 John Wiley & Sons, Ltd.     

FT‐IR,FT‐Raman and DFT calculations of the salicylanilide derivate 4‐chloro‐2‐(4‐bromophenylcarbamoyl)phenyl acetate

FT‐IR and FT‐Raman spectra of 4‐chloro‐2‐(4‐bromophenylcarbamoyl)phenyl acetate were recorded and analyzed. The vibrational wavenumbers and corresponding vibrational assignments were examined theoretically using the Gaussian03 set of quantum chemistry codes. The red shift of the NH stretching wavenumber in the infrared (IR) spectrum from the computed wavenumber indicates the weakening of the NH bond resulting in proton transfer to the neighbouring oxygen atom. The simultaneous IR and Raman activations of the CO stretching mode give the charge transfer interaction through a π‐conjugated path. Optimized geometrical parameters of the title compound are in agreement with similar reported structures. From the optimized structure, it is clear that the hydrogen bonding decreases the double bond character of CO bond and increases the double bond character of the C N bonds. The first hyperpolarizability, predicted infrared intensities and Raman activities are reported. The calculated first hyperpolarizability is comparable with the reported values of similar derivatives and is an attractive object for future studies of non‐linear optics. The assignments of the normal modes are done by potential energy distribution (PED) calculations. Copyright © 2009 John Wiley & Sons, Ltd.     

First order molecular hyperpolarizabilities and intramolecular charge transfer from the vibrational spectra of NLO material: ethyl‐3‐(3, 4‐dihydroxyphenyl)‐2‐propenoate

As part of the efforts for the design of new organic nonlinear optical(NLO) materials with high efficiency for present day technological requirements, a comprehensive investigation on the intramolecular charge transfer(CT) of an efficient π‐conjugated potential push–pull NLO chromophore, ethyl‐3‐(3,4‐dihydroxyphenyl)‐2‐propenoate(EDP) to a strong electron‐acceptor group through the π‐conjugated bridge has been carried out from their vibrational spectra. The first hyperpolarizabilities of caffeic derivatives are investigated by ab initio method. The NLO efficiency is experimentally measured by powder efficiency experiment. The strongest vibrational modes contributing to the electro‐optic effect from the simultaneous infrared(IR) and Raman activities of the ring CC stretching modes, in‐plane deformation modes, and the umbrella mode of the methyl groups have been identified and analyzed unambiguously. The influence of electronic effects, hyperconjugation and backdonation, on the C H stretching vibrations of both methyl and methylene groups causing the decrease of stretching wavenumbers and IR intensities has been extensively investigated. Copyright © 2009 John Wiley & Sons, Ltd.     

Structural conformations and electronic interactions of the natural product,oroxylin: a vibrational spectroscopic study

The oroxylin, 5,7‐dihydroxy 6‐methoxy flavone is a potent natural product extracted from ‘Vitex peduncularis’. Density functional theory (DFT) at B3LYP/6‐311G(d,p) level has been used to compute energies of different conformers of oroxylin to find out their stability, the optimized geometry of the most stable conformer and its vibrational spectrum. The conformer ORLN‐1 with torsion angles 0, 180, 180 and 0 degrees, respectively, for H₁₃ O₁₂ C₆ C₅, H₁₄ O₁₀ C₄ C₅, H₁₃ O₁₂ C₆ C₅ and H₁₄ O₁₀ C₄ C₅ is found to be most stable. The optimized geometry reveals that the dihedral angle φ between phenyl ring B and the chrome part of the molecule in − 19.21° is due to the repulsive force due to steric interaction between the ortho‐hydrogen atom H₂₉ of the B ring and H₁₈ of the ring C (H₂₉·H₁₈ = 2.198 Å). A vibrational analysis based on the near‐infrared Fourier transform(NIR‐FT) Raman, Fourier transform‐infrared (FT‐IR) and the computed spectrum reveals that the methoxy group is influenced by the oxygen lone pair‐aryl p_z orbital by back donation. Hence the stretching and bending vibrational modes of the methoxy group possess the lowest wavenumber from the normal values of methyl group. The carbonyl stretching vibrations have been lowered due to conjugation and hydrogen bonding in the molecules. The intramolecular H‐bonding and nonbonded intramolecular interactions shift the band position of O₁₀ H₁₄ and O₁₂ H₁₃ stretching modes, which is justified by DFT results. Copyright © 2008 John Wiley & Sons, Ltd.     

Reference database of Raman spectra of biological molecules

Raman spectra of biological materials are very complex, because they consist of signals from all molecules present in cells. In order to obtain chemical information from these spectra, it is necessary to know the Raman patterns of the possible components of a cell. In this paper, we present a collection of Raman spectra of biomolecules that can serve as references for the interpretation of Raman spectra of biological materials. We included the most important components present in a cell: (1) DNA and RNA bases (adenine, cytosine, guanine, thymine and uracil), (2) amino acids (glycine, L ‐alanine, L ‐valine, L ‐serine, L ‐glutamic acid, L ‐arginine, L ‐phenylalanine, L ‐tyrosine, L ‐tryptophan, L ‐histidine, L ‐proline), (3) fatty acids and fats (lauric acid, myristic acid, palmitic acid, stearic acid, 12‐methyltetradecanoic acid, 13‐methylmyristic acid, 14‐methylpentadecanoic acid, 14‐methylhexadecanoic acid, 15‐methylpalmitic acid, oleic acid, vaccenic acid, glycerol, triolein, trilinolein, trilinolenin), (4) saccharides (β‐D ‐glucose, lactose, cellulose, D ‐(+)‐dextrose, D ‐(+)‐trehalose, amylose, amylopectine, D ‐(+)‐mannose, D ‐(+)‐fucose, D ‐(−)‐arabinose, D ‐(+)‐xylose, D ‐(−)‐fructose, D ‐(+)‐galactosamine, N‐acetyl‐D ‐glucosamine, chitin), (5) primary metabolites (citric acid, succinic acid, fumarate, malic acid, pyruvate, phosphoenolpyruvate, coenzyme A, acetyl coenzyme A, acetoacetate, D ‐fructose‐6‐phosphate) and (6) others (β‐carotene, ascorbic acid, riboflavin, glutathione). Examples of Raman spectra of bacteria and fungal spores are shown, together with band assignments to the reference products. Copyright © 2007 John Wiley & Sons, Ltd.     

Effect of an aliphatic spacer group on the adsorption mechanism of phosphonodipeptides containing N-terminal glycine on the colloidal silver surface

This study presents the complete solid-state vibrational assignments for a series of five zwitterionic phosphonodipeptides containing an N-terminal glycine: L -Gly-L -CH(Me)-PO₃H₂ (G1), L -Gly-C(Me,Me)-PO₃H₂ (G2), L -Gly-L -CH(Et)-PO₃H₂ (G3), L -Gly-C(Me,Et)-PO₃H₂ (G4), and L -Gly-L -CH(iBu)-PO₃H₂ (G5). The assignments are based primarily on Fourier-transform Raman spectra (FT-RS) and Fourier-transform infrared spectra (FT-IR) spectra, as well as density functional theory (DFT) calculations at the B3LYP; 6-31 + + G** level of theory. Existing literature data are also taken into consideration. The surface geometry of these molecules on a colloidal silver surface was also determined by observing the wavenumber, width, and relative intensity changes of enhanced bands in their surface-enhanced Raman scattering spectra. It is proposed that G1 mainly adsorbs onto the colloidal silver particles through the phosphonate terminus, whereas the PO bond in G3 and G5 assists in the interaction of these molecules with the silver surface. G3 interacts with Ag mainly via α-methlyalanine and the amide bond. It is also shown that the amide bond and glycine backbone are involved in the adsorption of G3 on the silver nanoparticles. In addition, the differences recorded for G4 and G5 SERS spectra are mainly due to interactions between the silver surface and the amine group and N- and P-terminus, respectively, and are manifestations of the characteristic vibrations of these groups. Copyright © 2008 John Wiley & Sons, Ltd.     

Characterization of adsorption mode of new B2 bradykinin receptor antagonists onto colloidal Ag substrate

In this paper, the surface‐enhanced Raman scattering (SERS) spectra of the potent B₂ bradykinin receptor antagonists, [D‐Arg⁰,Hyp³,Thi^5,8,L‐Pip⁷]BK, Aaa[D‐Arg⁰,Hyp³,Thi^5,8,L‐Pip⁷]BK, [D‐Arg⁰,Hyp³,Thi⁵,D‐Phe⁷,L‐Pip⁸]BK, and Aaa[D‐Arg⁰,Hyp³,Thi⁵,D‐Phe⁷,L‐Pip⁸]BK, were measured when immobilized onto a colloidal assembly of apparently randomly adhering Ag spheres with diameters of approximately 20 – 25 nm. The observed SERS bands corresponding to different vibrational modes of the molecule, attached to or near Ag, and the variations in these bands resulting from competitive interactions of the functional groups of the peptides with the SERS‐active Ag surfaces were analyzed in this study. Briefly, it was shown that Pip, in generally in vertical orientation, and Thi, in the edge‐on position, relative to the colloidal Ag surface interacted with this surface through their lone electron pairs on the nitrogen and sulfur atoms, respectively. The imide bond of the X‐Pro peptide linkage and the guanidine group of Arg were involved in the adsorption process. In addition, it was demonstrated that the specific differences in the amino acid sequences slightly influenced the mode of adsorption. For example, Aaa in Aaa[D‐Arg⁰,Hyp³,Thi^5,8,L‐Pip⁷]BK and Aaa[D‐Arg⁰,Hyp³,Thi⁵,D‐Phe⁷,L‐Pip⁸]BK and D‐Phe (vertical with respect to the colloidal Ag surface) in [D‐Arg⁰,Hyp³,Thi⁵,D‐Phe⁷,L‐Pip⁸]BK, and Aaa[D‐Arg⁰,Hyp³,Thi⁵,D‐Phe⁷,L‐Pip⁸]BK assisted in the adsorption of these peptides onto the colloidal Ag particles. To discuss these spectral alterations due to the different surface adsorption mechanisms of these peptides, the spectral changes were analyzed according to the adsorption process and Fourier‐transform‐Raman spectra. Copyright © 2013 John Wiley & Sons, Ltd.     

FT‐IR,FT‐Raman,and computational calculations of 4‐chloro‐2‐(3‐chlorophenyl carbamoyl)phenyl acetate

FT‐IR and FT‐Raman spectra of 4‐chloro‐2‐(3‐chlorophenylcarbamoyl) phenyl acetate were studied. Vibrational wavenumbers and corresponding vibrational assignments were examined theoretically using the Gaussian03 set of quantum chemistry codes and the normal modes are assigned by potential energy distribution (PED) calculations. Simultaneous IR and Raman activation of the CO stretching mode shows the charge transfer interaction through a π‐conjugated path. Optimized geometrical parameters of the title compound are in agreement with the reported values. Analysis of the phenyl ring modes shows that C C stretching mode is equally active as strong bands in both IR and Raman, which can be interpreted as the evidence of intramolecular charge transfer via conjugated ring path and is responsible for hyperpolarizability enhancement leading to nonlinear optical activity. The red‐shift of the NH‐stretching wavenumber in the infrared spectrum from the computed wavenumber indicates the weakening of the NH bond resulting in proton transfer to the neighboring oxygen atom. Copyright © 2009 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.     

Molecular structure,spectroscopic (FTIR,FTIR gas phase,FT‐Raman) first‐order hyperpolarizability and HOMO–LUMO analysis of 4‐methoxy‐2‐methyl benzoic acid

Vibrational spectral analysis was carried out for 4‐methoxy‐2‐methyl benzoic acid (4M2MBA) by using Fourier transform infrared (FT‐IR) (solid, gas phase) and FT‐Raman spectroscopy in the range of 400–4000 and 10–3500 cm⁻¹ respectively. The effects of molecular association through O H···O hydrogen bonding have been described by the single dimer structure. The theoretical computational density functional theory (DFT) and Hatree‐Fock (HF) method were performed at 6–311++G(d,p) levels to derive the equilibrium geometry, vibrational wavenumbers, infrared intensities and Raman scattering activities. The scaled theoretical wavenumbers were also shown to be in good agreement with experimental data. The first‐order hyperpolarizability (β₀) of this novel molecular system and related properties (β, α₀ and Δα) of 4M2MBA are calculated using the B3LYP/cc‐pvdz basis set, based on the finite‐field approach. A detailed interpretation of the infrared and Raman spectra of 4M2MBA is reported. The theoretical spectrograms for FT‐IR and FT‐Raman spectra of the title molecule were also constructed and compared with the experimental one. Copyright © 2010 John Wiley & Sons, Ltd.     

Raman light scattering,infrared absorption and DSC studies of the phase transition and vibrational and reorientational dynamics of H2O ligands and ClO4– anions in [Ba(H2O)3](ClO4)2

[Ba(H₂O)₃](ClO₄)₂ between 90 and 300 K possesses two solid phases. One phase transition of the first‐order type at: = 211.3 K (on heating) and = 204.6 K (on cooling) was determined by differential scanning calorimetry. The entropy change value (ΔS ≈ 15 Jmol^–1 K^–1), associated with the observed phase transition, indicates a moderate degree of molecular dynamical disorder. Both, vibrational and reorientational motions of H₂O ligands and ClO₄^– anions, in the high‐temperature and low‐temperature phases, were investigated by Fourier transform far‐infrared and middle‐infrared and Raman light scattering spectroscopies. The temperature dependences of the full‐width at half‐maximum values of the bands associated with ρ_w(H₂O) mode, in both infrared (~570 cm^–1) and Raman light scattering (~535 cm^–1) spectra, suggest that the observed phase transition is not associated with a sudden change of a speed of the H₂O reorientational motions. Ligands reorient fast, with correlation time of the order of several picoseconds, with a mean activation energy value E_a = 5.1 kJ mol^–1 in both high and low temperature phases. On the other hand, measurements of temperature dependences of full‐width at half‐maximum values of the infrared band at ~460 cm^–1, associated with δ_d(OClO)E mode, and Raman band at ~1105 cm^–1, associated with ν_as(ClO)F₂ mode, revealed the existence of a fast ClO₄^– reorientation in phase I and in phase II, with the E_a(I) and E_a(II) values equal to 8.0 and 6.5 kJ mol^–1, respectively. These reorientational motions of ClO₄^– are slightly distorted at the T_C. Fourier transform far‐infrared and middle‐infrared spectra with decreasing of temperature indicated characteristic changes at the vicinity of PT at T_C, which suggested lowering of the crystal structure symmetry. All these experimental facts suggest that the discovered phase transition is associated with small change of H₂O ligands and somewhat major change of ClO₄^– anions reorientational dynamics, and with insignificant change of the crystal structure, too. Copyright © 2012 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.