Raman spectra of acetonitrile in imidazolium ionic liquids

Raman spectra of dilute solutions of acetonitrile in ionic liquids reveal the characteristic features of ionic liquids` polarity. This is accomplished by investigating the Raman bandshape of the nu (CN) band, corresponding to the CN stretching mode of CH(3)CN, which is a very sensitive probe of the local environment. The amphiphilic nature of the CH(3)CN molecule allows us to observe the effect of electron pair acceptor and electron pair donor characteristics on ionic liquids. It has been found that the overall polarity of nine different ionic liquids based on 1-alkyl-3-methylimidazolium cations is more dependent on the anion than cation. The observed wavenumber shift of the nu (CN) band of CH(3)CN in ionic liquids containing alkylsulfate anions agrees with the significant different values previously measured for the dielectric constant of these ionic liquids. The conclusions obtained from the analysis of the nu (CN) band were corroborated by the analysis of the symmetric nu(1) (CD(3)) stretching mode of deuterated acetonitrile in different ionic liquids. Copyright (C) 2010 John Wiley & Sons, Ltd.

Surface-enhanced Raman scattering study of alizarin red S

This paper presents the application of surface-enhanced resonance Raman spectroscopy (SERRS) for the structural study of alizarin red S (ARS) and the nature of its interaction with silver nanoparticles. SERRS data for ARS over nanostructured silver electrodes suggest a surface-induced reaction of the adsorbed dye and the formation of an ion stabilized by the dye and alkali ions adsorbed at the metal surface. We found that precoating the SERS active substrate with 1-propanethiol inhibits the surface-induced modification of ARS. In addition to preventing structural modifications of ARS, the coating also concentrates the hydrophobic dye close enough to the SERS active interface enabling the observation of excellent Raman spectra of ARS in aqueous environment at ppm levels. The influence of resonance Raman effect and of the pH on the SERS spectra of ARS was also investigated. (C) 2010 Elsevier B.V. All rights reserved.

Raman spectra of polymer electrolytes based on poly(ethylene glycol) dimethyl ether, lithium perchlorate, and the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate

Raman spectra of polymer electrolytes based on poly(ethylene glycol) dimethyl ether (PEGdME) with LiClO(4), PEGdME/LiClO(4), and the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate, PEGdME/[bmim]PF(6), are compared. Raman spectroscopy suggests stronger interactions in PEGdME/LiClO(4) than PEGdmE/[bmim]PF(6), thus corroborating previous results obtained by molecular dynamics simulations. Quantum Chemistry methods have been used to calculate vibrational frequencies and the equilibrium structure of segments of the polymer chain around the cation. A consistent picture has been obtained from Raman spectroscopy, density functional theory (DFT) calculations, and molecular dynamics simulations for these polymer electrolytes. (C) 2010 Elsevier B.V. All rights reserved.

Spectroscopic and theoretical studies of some 2-ethylsulfinyl-(4 `-substituted)-phenylthioacetates

The analysis of the IR nu(co) bands of the 2-ethylsulfinyl-(4`-substituted)-phenylthioacetates 4`-Y-C(6)H(4)SC(O)CH(2)S(O)Et (Y = NO(2) 1, Cl 2, Br 3, H 4, Me 5, OMe 6) supported by B3LY/6-31G(d,p) calculations along with the NBO analysis for 1.4 and 6 and X-ray analysis for 3, indicated the existence of four gauche (q-g-syn, g(3)-syn. g(1)-atin and q-g(2)-syn) conformers for 1-6 The calculations reproduce quite well the experimental results, i e the computed q-g-syn and g3-syn conformers correspond in the IR spectrum (in solution), to the nu(co) doublet higher frequency component of larger intensity, while the computed grant, conformer correspond to the nu(co) doublet lower frequency component (in solution) NBO analysis showed that the n(s) -> pi(center dot)(c1=o2), no(co) -> sigma(c1-s3), no(co) -> sigma(c1-c4) orbital interactions are the main factors which stabilize the q-g-syn, g(3)-syn, g(1)-anti and q-g(2)-syn conformers for 1, 4 and 6 The no(co) -> sigma(c1-s3) interaction which stabilizes the q-g-syn, g(3)-syn and q-g(2)-syn conformers into a larger extent than the granti conformer, is responsible for the larger tto frequencies of the former conformers relative to the latter one. The q-g-syn, g(3)-syn and q-g(2)-syn conformers are further stabilized sigma(c4-s5) -> pi(co)center dot (strong). pi(co)/sigma(c1-c4,) no(co) -> sigma(c6-H17[Et]) (weak) and pi(co)/sigma(c4-c5) pi(co) (strong) orbital interactions. The q-g-syn conformer is also stabilized by sigma(c4-s5) -> pi(center dot)(co) (strong), pi(co)/sigma(c4-c5).no(co) -> sigma(c6-H17[Et]), pi(C9=C11[ph]) -> sigma(c4-H6x-CH2]) (weak). no((SO)) -> sigma(C11-H23[ph]) (medium) pi(co)/sigma(c4-c5)(strong) orbital interactions. The q-g-syn conformei is further stabilized by the n(S5) O((C))(8-) S((SO))(8+) attractive Coulornbic interaction while the q-g(2)-syn conformer is destabilized by the n55 0,8c-0) repulsive Coulombic interaction. This analysis indicates the following conformer stabilization order. q-g-syn, g(3)-syn > g(1)-anti >> q-g(2)-syn X-ray single crystal analysis of 3 indicates that it assumes in the solid a distorted q-g(2)-syn geometry which is stabilized through almost the same orbital and Coulombic interaction which takes place for the q-g(2)-syn conformer, in the gas, along with dipole moment coupling and a series intermolecular C-HO0 interactions. (C) 2010 Elsevier B V All rights reserved

FT-Raman, FTIR and density functional theory studies of a hydrogen-bonded formamide: pyridine complex

Raman and IR experiments have been carried out on formamide (FA) and pyridine (Py) mixtures at different compositions. The appearance of a new Raman band at 996 cm(-1) (nu(1) region of Py), whose intensity depends on the FA concentration, is assigned to an FA: Py adduct and this result is in excellent agreement with those of other authors who employed noisy light-based coherent Raman scattering spectroscopy (I((2)) CARS). Another band at 1587 cm(-1) (nu(8) region of Py) has been observed for the first time by using Raman and IR spectroscopies. Its intensity shows the same dependence on the FA concentration and this fact allows us to also attribute it to an FA: Py adduct. The good relationship between the Raman and IR data demonstrates the potential of the vibrational spectroscopy for this kind of study. Owing to higher absolute Raman scattering cross section, the nu(1) region of Py has been chosen for the quantitative analysis and a stoichiometry of 1 : 1 FA: Py is reported. The experimental data are very well supported by the density functional theory (OFT) calculation, which was employed for the first time to the present system. Furthermore, the actual investigation shows an excellent agreement with those reported from computational calculations for similar systems. A comparison with our previous studies confirms that: the solvent dielectric constant determines the stoichiometry of a given Lewis acid-base adduct in the infinite dilution limit. Copyright (C) 2009 John Wiley & Sons, Ltd.

Crystal and molecular structures of three 2-sulphur-substituted cyclohexanones studied by X-ray crystallography and by ab initio molecular orbital calculations

The conformational features of three 2-sulphur-substituted cyclohexanone derivatives, which differ in the number of sulphur-bound oxygen atoms, i.e. zero (I), one (II) and two (III), were investigated by single crystal X-ray crystallography and geometry optimized structures determined using Hartree-Fock method. In each of (I)-(III) an intramolecular S center dot center dot center dot O(carbonyl) interaction is found with the magnitude correlated with the oxidation state of the sulphur atom, i.e. 2.838(3) angstrom in (I) to 2.924(2) angstrom in (II) to 3.0973(18) angstrom in (III). There is an inverse relationship between the strength of this interaction and the magnitude of the carbonyl bond. The supramolecular aggregation patterns are primarily determined by C-H center dot center dot center dot O contacts and are similarly influenced by the number of oxygen atoms in the molecular structures. Thus, a supramolecular chain is found in the crystal structure of (I). With an additional oxygen atom available to participate in C-H center dot center dot center dot O interactions, as in (II), a two-dimensional array is found. Finally, a three-dimensional network is found for (III). Despite there being differences in conformations between the experimental structures and those calculated in the gas-phase, the S center dot center dot center dot O interactions persist. The presence of intermolecular C-H center dot center dot center dot O interactions involving the cyclohexanone-carbonyl group in the solid-state, disrupts the stabilising intramolecular C-H center dot center dot center dot O interaction in the energetically-favoured conformation. (I): C(12)H(13)NO(3)S, triclinic space group P (1) over bar with a = 5.392(3) angstrom b = 10.731(6) angstrom, c = 11.075(6) angstrom, alpha = 113.424(4)degrees, beta = 94.167(9)degrees, gamma = 98.444(6)degrees, V = 575.5(6) angstrom(3), Z = 2, R(1) = 0.052; (II): C(12)H(13)NO(4)S, monoclinic P2(1)/n, a = 7.3506(15) angstrom, b = 6.7814(14) angstrom, c = 23.479(5) angstrom, beta = 92.94(3)degrees, V = 1168.8(4) angstrom(3), Z = 4, R(1) = 0.046; (III): C(12)H(13)NO(5)S, monoclinic P2(1)/c, a = 5.5491(11) angstrom, b = 24.146(3) angstrom, c = 11.124(3) angstrom, beta = 114.590(10)degrees, V = 1355.3(5) angstrom(3), Z = 4, R(1) = 0.051.

Stereochemical and electronic interaction studies of some N-methoxy-N-methyl-2-[(4 `-substituted)phenylsulfinyl]propanamides

The (1)H NMR spectra of N-methoxy-N-methyl-2-[(4`-substituted)phenylsulfinyl]-propanamides [Y-Ph-S(O)CH(Me)C(O)N(OMe)Me; Y = OMe 1, Me 2, H 3. Cl 4, NO(2) 5] along with the X-ray diffraction analysis of the nitro-derivative (5). have shown the existence of two pairs of diastereomers (racemic mixture) [C(R)S(S)/C(S)S(R) (diast(1)) and C(R)S(R)/C(S)S(S) (diast(2))] in the ratio of ca. 7:3. respectively. The v(CO) IR analysis of the title compounds supported by HF and B3LYP/6-31G** calculations of 3 and of the parent N-methoxy-N-methyl-propanamide (6) by HF, have shown that diast(1) exists in an equilibrium between the two more polar and more stable quasi-cis (q-c(1) and q-c(2)) conformers and the gauche(g) conformer. The population of the g conformer in the equilibrium increases with the increase in the solvent polarity, which is attributed to a larger solvation effect on the carbonyl and sulfinyl groups. Diast(2) of compound 3 occurs in the gas phase as an equilibrium between the most stable quasi-gauche (q-g) conformer and the quasi-cis (q-c) conformer, both presenting very similar dipole moments. The former is stabilized by electrostatic and charge transfer interactions, which results in a less solvated spatial arrangement. Moreover, all conformers of both diastereomers are stabilized by several intramolecular hydrogen bonds. X-ray single crystal analysis performed for diast(1) and for diast(2) of 5 indicates that both stereoisomers assume, in the solid state, the anti-clinal (gauche) conformation. For the crystal packing, diast(1) of 5 is made up of three molecules joined through two centro-symmetric H center dot center dot center dot O hydrogen bonds. (C) 2008 Elsevier B.V. All rights reserved.

The influence of acetic acid on the ethanol electrooxidation on a platinum electrode

In the presented work, the evaluation of the influence of acetic acid in the electrochemical environment on the ethanol electro-oxidation reaction on a polycrystalline platinum electrode is presented for the first time. Using cyclic voltammetry. chronoamperometry and in situ Fourier Transformed IR spectroscopy (FTIR) it was demonstrated that an inhibition of the ethanol oxidation reaction occurs for bulk acetic acid concentrations of the order 0.1 mu mol L(-1) -5 mmol L(-1). This inhibition effect is related to the decrease of CO(2) and acetaldehyde production as confirmed by spectroscopic results. (C) 2011 Elsevier B.V. All rights reserved.

Activation Energies of the Electrooxidation of Formic Acid on Pt(100)

The electrooxidation of small organic molecules on platinum surfaces usually involves different structure-dependent steps that include adsorption and desorption of various species and multiple reaction pathways. Because temperature plays a decisive role on each individual step, understanding its global influence on the reaction mechanism is often a difficult task, especially when the system is studied under far from equilibrium conditions in the presence of kinetic instabilities. Aiming at contributing to unravel this problem, herein, we report an experimental study of the role played by temperature on the electrooxidation of formic acid on a Pt(100) electrode. The system was investigated under both close and far from equilibrium conditions, and apparent activation energies were estimated using different strategies. Overall, comparable activation energies were estimated under oscillatory and quasi-stationary conditions, at high potentials. At low potentials, the poisoning process associated with the formic acid dehydration step presented a negligible dependence with temperature and, therefore, zero activation energy. On the basis of our experimental findings, we suggest that formic acid dehydration is the main, but maybe not the unique, step that differentiates the temperature dependence of the oscillatory electrooxidation of formic acid on Pt(100) with that on polycrystalline platinum.

A three-dimensional network constructed from the assembly of 1,3-diaminopropane-copper(II) and tetracyanopalladate(II) moieties

The coordination polymer [Cu(Pd(CN)(4))(pn)](n) (pn = 1,3-diaminopropane) has been synthesized and characterized by elemental analysis, infrared spectroscopy and single-crystal X-ray diffraction. The crystal structure showed that three cyano groups of each [Pd(CN)(4)] unit bridge Cu(II) centers leading to the formation of a three-dimensional network. A series of bifurcated hydrogen bonds between the amino groups of the diamine and the nonbridging cyano groups of the cyanometallate result in the organization of suprarnolecular chains and rings along the polymer. (c) 2008 Elsevier B.V. All rights reserved.

A surface-enhanced infrared absorption spectroscopic (SEIRAS) study of the oscillatory electro-oxidation of methanol on platinum

The oscillatory electro-oxidation of methanol was studied by means of in situ infrared (IR) spectroscopy in the attenuated total reflection (ATR) configuration using a platinum film on a Si prism as working electrode. The surface-enhanced infrared absorption (SEIRA) effect considerably improves the spectroscopic resolution, allowing at following the coverage of some adsorbing species during the galvanostatic oscillations. Carbon monoxide was the main adsorbed specie observed in the induction period and within the oscillatory regime. The system was investigated at two distinct time-scales and its dynamics characterized accordingly. During the induction period the main transformation observed as the system move through the phase space towards the oscillatory region was the decrease of the coverage of adsorbed carbon, coupled to the increase of the electrode potential. Similar transition characterizes the evolution within the oscillatory region, but at a considerably slower rate. Experiments with higher time resolution revealed that the electrode potential oscillates in-phase with the frequency of the linearly adsorbed CO vibration and that the amount of adsorbed CO oscillates with small amplitude. Adsorbed formate was found to play, if any, a very small role. Results are discussed and compared with other systems. (C) 2010 Elsevier B.V. All rights reserved.

Using azahetercyclic electrophiles to synthesize novel Bicyclooxacalixarenes and Oxacalix[2]N-hexylnaphthalimide[2]naphthyridines

Various bicyclooxacalixarenes, tricyclooxacalixarenes and oxacalix[2]N-hexylnapthalimide[2]naphthyridines are synthesized via SnAr condensation. This research has involved synthesis optimization. The oxacalix[2]N-hexylnaphthalimide[2]naphthyridines have exhibited host-guest binding in fluorescence experiments. These compounds have been characterized by NMR spectroscopy as well as single crystal X-ray diffraction.

Surface-enhanced Raman scattering and micro-Raman imaging of Langmuir-Blodgett films of rhodium phthalocyanine

Rhodium phthalocyanine (RhPc) was synthesized and ultra thin Langmuir-Blodgett (LB) films of RhPc were successfully fabricated. The LB film characterization was carried out using both UV-vis absorption spectra and Raman scattering. The Raman spectroscopy was carried out using 633 and 780 nm laser lines. LB films were deposited onto Ag nanoparticles to achieve the surface-enhanced pre-resonance Raman scattering (pre-SERRS) and surface-enhanced Raman scattering (SERS) for both laser lines, respectively, which allowed the characterization of the RhPc ultra thin films. The morphology of the LB RhPc neat film is extracted from micro-Raman imaging. (C) 2003 Elsevier B.V. All rights reserved.

Vibrational spectroscopy applied to the study of archeological ceramic artifacts from Guarani culture in Brazil

An archeological artifact can be seen as a chronological element, which helps to determine the age of certain society and to understand the thinking, values and the way of life of this society. Thus, the classification of archeological artifacts is one of the approaches used to study the cultural system of antique societies trying to reconstruct their history. The "Centro de Museologia, Antropologia e Argueologia (CEMAARQ)" of the "Unesp Univ Estadual Paulista" in Presidente Prudente, São Paulo state, Brazil, develops projects within this context (identification and preservation). This is the case of the archeological site named "Lagoa São Paulo-02" discovered in 1993 at the margins of the Parana river in the region of Presidente Epitacio city, São Paulo state, Brazil. This site has ceramic fragments of different shapes and sizes that have a strong influence of traces of the Guarani culture, which is one of the Brazilian native populations. These samples were basically characterized via micro-Raman scattering and Fourier transform infrared absorption (FTIR) spectroscopies. The main objective was to identify the pigments used in the manufacture of the ceramic artifacts and to analyze the composition of the ceramic body to understand how the artifacts were made. Three pigments were found: red, black and white. For the red pigment were identified characteristic bands of hematite, an iron oxide found in the red rocks of the river banks that were eroded by water. The black pigment, probably, is due to the use of vegetal charcoal, which is found in nature as the product of burning organic material such as wood. For the white pigment, the FTIR spectra suggested the use of kaolin, either in the ceramic body or in the proper white pigment, due to the presence of the characteristic bands of the kaolinite. Complementary, the additives applied as anti-plastics were identified as charcoal and quartz, being the latter found in the rocks present in the archeological site. (C) 2010 Elsevier B.V. All rights reserved.

Incorporation of Ag nanoparticles into membrane mimetic systems composed by phospholipid layer-by-layer (LbL) films to achieve surface-enhanced Raman scattering as a tool in drug interaction studies

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)