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.     

Quantization of an electromagnetic field in two-dimensional photonic structures based on the scattering matrix formalism (<Emphasis Type="Italic">S</Emphasis>-quantization)

We have analyzed the parameters of the Franck–Condon and Herzberg–Teller interactions, which form the fine-structure spectra of diphenylbutadiene substituted derivatives with the general formula X–Ph–(C=C)2–Ph–Y (where X, Y = H, NO₂, N(CH₃)₂, and NH₂ are the substituents in different combinations) in solutions of n-paraffins at 4.2 K. The influence of substituents on the vibronic parameters of characteristic bands that describe the states (vibrations, types of deformations upon excitation) of the phenyl rings and diphenylbutadiene polyene bridge has been considered. Data on the influence of the H, NO₂, N(CH₃)₂, or NH₂ terminal fragment on the parameters of the intra- and intermolecular interactions of diphenylbutadiene substituted derivatives have been presented.     

Anisotropic hyperfine interactions and spin relaxation in neptunyl salts

Mössbauer spectra of hexavalent neptunyls X₂(NpO₂)Cl₄ and X₄(NpO₂)(CO₃)₃ with X=Na, K, Cs, (NH₄) and [C₂H₅)₄N] are discussed and compared to EPR data. In cases where reliable values of hyperfine parameters can be extracted, the Mössbauer spectra give fine details of bonding structure. It is found that the O–Np–O bond is not linear and that exchanging the cation results in small but definite changes.Work supported by the Bundesministerium für Forschung und Technologie and the U.S. Department of Energydeceased     

A photoelectron and energy-loss spectroscopy study of Ti and its interaction with H2, O2, N2 and NH3

A unified electron spectroscopic study of polycrystalline Ti and its interaction with H₂, O₂, N₂, and NH₃ are described. Auger electron spectroscopy (AES), electron energy-loss spectroscopy (ELS), ultraviolet and X-ray photoelectron spectroscopy (UPS and XPS) are combined to provide detailed information about the electronic structure of the titanium surface and its interaction with these adsorbates. X-ray and ultraviolet photoelectron spectra and electron energy-loss spectra are presented for the clean titanium surface, and following exposure to H₂, O₂, N₂ and NH₃. Spectral assignments are provided in each case. The electron spectra of oxygen exposed Ti and nitrogen sputtered Ti are quite similar, and are interpreted with reference to band structure calculations for TiO and TiN. Electron spectroscopy indicates essentially complete dissociative adsorption of NH₃ on the clean titanium surface.     

Band Assignments in the Infrared Spectra of Some Metal(II) Complexes of Pyrazine

The IR spectra of [Co(pz)₂X₂]_n (pz = pyrazine; X = C1, Br, I), [Cu(pz)X₂]_n (X = C1, Br), [Cu(pz)₂](C10₄)₂ and [Cu(py)₄] (C10₄)₂ (py = pyridine) derived from deuterated pz and py, and their unlabelled analogues are discussed. Assignments of the metal-ligand vibrations are based on the effects of the isotopic substitutions.     

Anilinium Ions: Relations Between pK, σ and Intensity of the UV Transition

Spectroscopists have often assumed, based only on the UV spectrum of the anilinium ion (φNH₃ ⁺), that ammonium groups cannot bring a “mesomeric” effect upon π systems. This assumption^(1–3) which could be justified for the anilinium ion itself, whose OO band of the secondary transition (towards 260 nm) is very weak, has been unduly extended to all the ammonium groups. Actually, the interaction between a π system and (NX_aX_bX_c)⁺ groups has been studied by several authors^(4–8) and we have shown that contrary to what had been assumed by spectroscopists, such an interaction induces strong effects on the UV spectrum of the benzene chromophore^(9–11). Using the MNDO and the CNDO methods, we have studied the quantum factors which play a part in the long range interaction, between: an ω group X on the one hand, N on the other hand, and then φ, in φNH₂ ⁺CH₂X, φNH⁺ (CH₂X_a) CH₂X_b and φNH⁺ (C₂H₄)₂X.     

Magnetism of single-walled silicon carbide nanotubes doped by boron,nitrogen and oxygen

We calculated, using spin polarized density functional theory, the electronic properties of zigzag (10,0) and armchair (6,6) semiconductor silicon carbide nanotubes (SiCNTs) doped once at the time with boron, nitrogen, and oxygen. We have looked at the two possible scenarios where the guest atom X (B, N, O), replaces the silicon X_Si, or the carbon atom X_C, in the unit cell. We found that in the case of one atom B @ SiCNT replacing a carbon atom position annotated by B_C exhibits a magnetic moment of 1 μ_B/cell in both zigzag and armchair nanotubes. Also, B replacing Si, (B_Si), induce a magnetic moment of 0.46 μ_B/cell in the zigzag (10,0) but no magnetic moment in armchair (6,6). For N substitution; (N_C) and (N_Si) each case induce a magnetic moment of 1 μ_B/cell in armchair (6,6), while N_Si give rise to 0.75 μ_B/cell in zigzag (10,0) and no magnetic moment for N_C. In contrast the case of O_C and O_Si did not produce any net magnetic moment in both zigzag and armchair geometries.     

EPR study on star-shaped copolymers containing C60 core

A series of novel star-shaped copolymers containing C₆₀ core [C₆₀(PPMS)_X(CH₃)_X, C₆₀(PMS)_X(CH₃)_X, C₆₀(PVK)_XH_X and C₆₀(PAN)_X(CH₃)_X] were prepared by reaction of C₆₀ with the livingn-butyl-terminated vinyl polymer which was synthesized via anionic polymerization reaction of a vinyl compound in the presence ofn-butyllithium. The results of the electron paramagnetic resonance (EPR) experiment indicated that the spectroscopic properties of the copolymers are different from their parent polymers and pure C₆₀. The star-shaped copolymers exhibited two kinds of paramagnetic species. The temperature dependence of the EPR spectra of the C₆₀(PAN)_X(CH₃)_X copolymer has also been investigated, and a pyrolytic mechanism of the formation of a new conjugated system for this copolymer is suggested.     

Self,nitrogen and oxygen broadening of the 115-GHz line of carbon monoxide

Self nitrogen, oxygen and air-broadened half-widths of the 115-GHz line of CO have been measured at various temperatures between 293 K (room temperature) and 220 K. The temperature dependence of the broadening parameter CCO-XW is described by a power law CCO-XW (T) = CCO-XW(293 K)(T/293)-n co-x. The values of CCOW (293 K) and nCO-X are presented for each broadening gas X, X - CO, N2 and O2. The usual relation CCO-airW (T) = 0.78CCO−N2W(T) + 0.21CCO−O2 W(T) is found to be valid in the temperature and pressure ranges of the present experiments.     

Kinetics and mechanism of the reaction of alkoxymethylidene malonate and malononitrile with hydrazines and anilines

The kinetics and mechanism of the nucleophilic vinylic substitution of dialkyl (alkoxymethylidene)malonates (alkyl: methyl, ethyl) and (ethoxymethylidene)malononitrile with substituted hydrazines and anilines R¹–NH₂ (R¹: (CH₃)₂N, CH₃NH, NH₂, C₆H₅NH, CH₃CONH, 4‐CH₃C₆H₄SO₂NH, 3‐ and 4‐X‐C₆H₄; X: H, 4‐Br, 4‐CH₃, 4‐CH₃O, 3‐Cl) were studied at 25 °C in methanol. It was found that the reactions with all hydrazines (the only exception was the reaction of (ethoxymethylidene)malononitrile with N,N‐dimethylhydrazine) showed overall second‐order kinetics and k_obs were linearly dependent on the hydrazine concentration which is consistent with the rate‐limiting attack of the hydrazine on the double bond of the substrate. Corresponding Brønsted plots are linear (without deviating N‐methyl and N,N‐dimethylhydrazine), and their slopes (β_Nuc) gradually increase from 0.59 to 0.71 which reflects gradually increasing order of the C–N bond formed in the transition state. The deviation of both methylated hydrazines is probably caused by the different site of nucleophilicity/basicity in these compounds (tertiary/secondary vs. primary nitrogen). A somewhat different situation was observed with the anilines (and once with N,N‐dimethylhydrazine) where parabolic dependences of the kinetics gradually changing to linear dependences as the concentration of nucleophile/base increases. The second‐order term in the nucleophile indicates the presence of a steady‐state intermediate ‐ most probably T^±. Brønsted and Hammett plots gave β_Nuc = 1.08 and ρ = ?3.7 which is consistent with a late transition state whose structure resembles T^±. Copyright © 2013 John Wiley & Sons, Ltd.     

Electronic structure of binary zirconium compounds: Cluster calculations using different molecular orbital methods

Cluster calculations of the electronic structure and charge distribution in the refractory compounds ZrX(X = C, N, O) and ZrO₂ have been performed using different molecular orbital methods; a semiempirical LCAO model based on the Mulliken-Wolfsberg-Helmholz approximation, and the Hartree-Fock-Slater model in both the Discrete Variational X_α and Multiple Scattering X_α versions. The main features of chemical bonding are discussed and illustrated by contour level diagrams of some bonding molecular orbitais of the valence band. Finally, the results are compared with X-ray emission and X-ray photoelectron spectra, and also with band structure calculations.     

Electronic structure and the infrared absorption and Raman spectra of the semiconductor clusters C24, B12N12, Si12C12, Zn12O12, and Ga12N12

The optimized configurations, electronic structures, charge transfers, band gaps, total energies, cohesive energies, electron density maps, infrared absorption spectra, Raman spectra, and relevant modes of natural acoustic vibrations for the semiconductor clusters C₂₄, B₁₂N₁₂, Si₁₂C₁₂, Zn₁₂O₁₂, and Ga₁₂N₁₂ are calculated using the ab initio Hartree-Fock method in the 6–31G basis set. Original Russian Text ? V.V. Pokropivny, L.I. Ovsyannikova, 2007, published in Fizika Tverdogo Tela, 2007, Vol. 49, No. 3, pp. 535–542.     

The structure and the analytical potential energy function of NH2 （X^2B1）

This paper reports that the equilibrium structure of NH2 has been optimized at the QCISD/6-311＋＋G （3df, 3pd） level. The ground-state NH2 has a bent （C2v, X^2B1） structure with an angle of 103.0582°. The geometrical structure is in good agreement with the other calculational and experimental results. The harmonic frequencies and the force constants have also been calculated. Based on the group theory and the principle of microscopic reversibility, the dissociation limits of NH2（C2v, X^2B1） have been derived. The potential energy surface of NH2（X^2B1） is reasonable. The contour lines are constructed, the structure and energy of NH2 reappear on the potential energy surface.     

Vibrational spectroscopy of alkaline tungsten oxyfluoride crystals: structure,lattice dynamics,ordering processes,and phase transitions

Raman scattering (RS) and infrared absorption (IR) of ammonium oxyfluoride crystals (NH₄)₃WO₃F₃, (NH₄)₂KWO₃F₃, and Cs₂(NH₄)WO₃F₃are compared. Conformation of the WO₃F₃ octahedral groups has been established; anomalies have been found close to the transition temperatures in the internal vibrational regions of ammonium and WO₃F₃ groups. The phase transition in (NH₄)₃WO₃F₃ is associated mostly with the ordering of octahedral groups and formation of W O···H N hydrogen bonds. In (NH₄)₂KWO₃F₃ crystal, the transition is not related to the ordering processes; Cs₂(NH₄)WO₃F₃ retains its disordered structure down to 10 K. Copyright © 2010 John Wiley & Sons, Ltd.     

Effects of buried high-Z layers on fast electron propagation

Density functional study is performed on the stabilities, aromaticity, infrared spectra, and optical properties of exohedral fullerene derivatives C₇₆X₁₈(X = H, F, Cl, and Br). The bond dissociation energy and energy gap between HOMO and LUMO of C₇₆H₁₈ are larger than those of the isolated C₇₆F₁₈ and C₇₆Cl₁₈, indicating the possibility for synthesising C₇₆H₁₈ from the viewpoint of thermodynamics and kinetics. C₇₆X₁₈(X = H, F, Cl, and Br) show strong aromaticity, suggesting their stabilities are correlative with the conjugation. The tensors of static linear polarisabilities, mean static linear polarisabilities, polarisability anisotropy, and first-order hyperpolarisabilities of C₇₆X₁₈(X = F, Cl, and Br) increase as X goes from F to Br. We rationalise the nonlinear properties by studying the low-energy optical absorption band obtained by employing time-dependent density functional theory.     

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.     

DFT investigation on the structures and stabilities of exohedral derivatives for D<Subscript>3</Subscript> C<Subscript>32</Subscript> fullerene: C<Subscript>32</Subscript>X<Subscript>n</Subscript> (X = H and Cl)

A systematic investigation of D₃ C₃₂ fullerene and its derivatives C₃₂X_n (X = H and Cl) has been performed using B3LYP/6-31G(d) method based on the density functional theory. The geometry structures, reaction energies, relative stabilities, and electronic properties have been studied. By investigating the possible C₃₂X_n (X = H and Cl) molecules, C₃₂H₂ and C₃₂Cl₂ behave more thermodynamically accessible with respect to other derivatives. The frontier molecular orbitals and electronic density of states calculations of C₃₂X₂ system indicate that H and Cl passivation have less contribution to the electronic structures, but significantly improve the stability of D₃ C₃₂ fullerene. Finally, the ¹³C NMR chemical shifts of C₃₂H₂ and C₃₂Cl₂ have been simulated to provide helpful information for further experiment identification.     

Kinetic ion-acoustic solitary waves in collisional plasmas

In this study, a bipolar high-voltage pulse with 20 ns rising time is employed to generate diffuse dielectric barrier discharge plasma using wire-plate electrode configuration in nitrogen at atmospheric pressure. The gas temperature of the plasma is determined by comparing the experimental and the best fitted optical emission spectra of the second positive bands of N₂(C³Π_u → B³ Π_g, 0-2) and the first negative bands of N₂ ⁺ (B² Σ_u ⁺ → X² Σ_g ⁺, 0-0). The effects of the concentration of argon and oxygen on the emission intensities of N₂ (C³Π_u → B³Π_g, 0-0, 337.1 nm), OH?(A ²Σ → X²Π, 0-0) and N₂ ⁺ (B² Σ_u ⁺ → X² Σ_g ⁺, 0-0, 391.4 nm) are investigated. It is shown that the plasma gas temperature keeps almost constant with the pulse repetition rate and pulse peak voltage increasing. The emission intensities of N₂ (C³Π_u → B³Π_g, 0-0, 337.1 nm), OH(A²Σ → X²Π, 0-0) and N₂ ⁺ (B² Σ_u ⁺ → X² Σ_g ⁺, 0-0, 391.4 nm) rise with increasing the concentration of argon, but decrease with increasing the concentration of oxygen, and the influences of oxygen concentration on the emission intensities of N₂(C³Π_u → B³Π_g, 0-0, 337.1 nm) and OH (A²Σ → X²Π, 0-0) are more greater than that on the emission intensity of N₂ ⁺ (B² Σ_u ⁺ → X² Σ_g ⁺, 0-0, 391.4 nm).     

Vibrational analysis of ethylamines: Trans and gauche forms

Starting from force constant values calculated by an ab initio MO method ($\text{4-31G(N}{}^1\text{)}$), and by adjusting the diagonal elements, a practical force constant matrix (F) has been reached which could explain the observed infrared and Raman spectra (in the frequency range lower than 2000 cm^?1) of the gauche form of the ethylamine CH₃CH₂NH₂ molecule and five isotopic species CH₃¹³CH₂NH₂, CH₃CH₂¹⁵NH₂, CH₃CD₂NH₂, CH₃CH₂ND₂, and CD₃CD₂NH₂. The F matrix for the trans form of ethylamine was constructed by transferring ab initio $\text{4-31G(N}{}^1\text{)}$ values and by revising diagonal elements with conversion factors whose values are equal to the corresponding values of gauche form. A nearly complete set of assignments was achieved of the vibrational bands of ethylamines, observed so far in the spectral range 2000–100 cm^?1. In matrix isolation spectroscopy, two bands assignable to the NH₂ wagging vibrations of gauche and trans forms have been found at 775 and 782 cm^?1, respectively, for CH₃CH₂NH₂. They are at 768 and 774 cm^?1, respectively, for CD₃CD₂NH₂. From the intensity changes of these bands observed on changing the nozzle temperature in the matrix formation, the energy difference ΔE (gauche-trans) of these two conformers has been estimated to be 100 ± 10 cm^?1.     

Molecular Structures of H2X and D2X(X=0, S,Se, Te)

There are two possible configurations for H₂O, linear(D_∞h) or bent(C_2v). For a C_2v′, the three bands ν_1′ ν₂ and ν₃ should appear in both Raman and infrared. For a D_∞h. however, the ν₁, band should appear in only Raman and the ν₂ and ν₃ bands, in only infrared, that is, a principle of mutual exclusion of Raman and infrared should hold. The present author concludes that H₂X and D₂X(X=O, S, Se, Te) have a linear D_∞h. structure, since the obtained spectra show mutual exclusion of Raman and infrared.