Fano resonance in heavily doped porous silicon

Unexpectedly, the Fano resonance caused by the interference of continuum electron excitations with the longitudinal optical (LO) phonons was observed in random porous Si by Raman scattering. The analysis of the experimental data shows that the electron states trapped at the Si-SiO(2) interface dominate in the observed Raman scattering. The gap energy associated with the interface states was determined. Copyright (C) 2011 John Wiley & Sons, Ltd.

Detailed analysis of the charge transfer complex N,N-dimethylaniline-SO(2) by Raman spectroscopy and density functional theory calculations

Although the amine sulfur dioxide chemistry was well characterized in the past both experimentally and theoretically, no systematic Raman spectroscopic study describes the interaction between N,N-dimethylaniline (DMA) and sulfur dioxide (SO(2)). The formation of a deep red oil by the reaction of SO(2) with DMA is an evidence of the charge transfer (CT) nature of the DMA-SO(2) interaction. The DMA -SO(2) normal Raman spectrum shows the appearance of two intense bands at 1110 and 1151 cm(-1), which are enhanced when resonance is approached. These bands are assigned to nu(s)(SO(2)) and nu(phi-N) vibrational modes, respectively, confirming the interaction between SO(2) and the amine via the nitrogen atom. The dimethyl group steric effect favors the interaction of SO(2) with the ring pi electrons, which gives rise to a pi-pi* low-energy CT electronic transition, as confirmed by time-dependent density functional theory (TDDFT) calculations. In addition, the calculated Raman DMA-SO(2) spectrum at the B3LYP/6-311++g(3df,3pd) level shows good agreement with the experimental results (vibrational wavenumbers and relative intensities), allowing a complete assignment of the vibrational modes. A better understanding of the intermolecular interactions in this model system can be extremely useful in designing new materials to absorb, detect, or even quantify SO(2). Copyright (C) 2009 John Wiley & Sons, Ltd.

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

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

Reaction of a model siderophore with Ni(II), Co(II) and Zn(II) in aqueous solution: Kinetics and spectroscopy

A spectroscopic study was performed showing that the [Fe(III)(L(2-))(2)](1-) (L(2-) = dopacatecholate) complex reacts with Ni(II), Co(II) and Zn(II) in an aqueous solution containing S(2)O(3)(2-) resulting in the soluble [M(L(1-))(3)](1-) (L(1-) = dopasemiquinone; M = Ni(II), Co(II) or Zn(II) complex species. The Raman and IR spectra of the [CTA][M(L(1-))(3)] complexes, CTA hexadecyltrimethylammonium cation, in the solid state were obtained. The kinetic constants for the metal substitution reactions were determined at four different temperatures, providing values for Delta W(not equal) Delta S(not equal) and Delta G(not equal). The reactions were slow (k = 10(-1)1 M s(-1)) and endothermic. The system investigated can be considered as a simplified model to explain some aspects of siderophore chemistry. (c) 2007 Elsevier Inc. All rights reserved.

Fluctuations of the Stokes and anti-Stokes surface-enhanced resonance Raman scattering intensities in an electrochemical environment

Stokes and anti-Stokes SERRS intensity fluctuations were observed from a roughened silver electrode immersed in diluted solutions of Brilliant Green (BG), a behaviour linked to single-molecule events. The distributions of the anti-Stokes to Stokes ratios were obtained and their shape showed a strong dependence on the applied potential.

(1)H NMR spectroscopy as a tool to determine accurate photoisomerization quantum yields of stilbene-like ligands coordinated to rhenium(I) polypyridyl complexes

In this work, the use of proton nuclear magnetic resonance, (1)H NMR, was fully described as a powerful tool to follow a photoreaction and to determine accurate quantum yields, so called true quantum yields (Phi(true)), when a reactant and photoproduct absorption overlap. For this, Phi(true) for the trans-cis photoisomerization process were determined for rhenium(I) polypyridyl complexes, fac-[Re(CO)(3)(NN)(trans-L)](+) (NN = 1,10-phenanthroline, phen, or 4,7-diphenyl-1,10-phenanthroline, ph(2)phen, and L = 1,2-bis(4-pyridyl) ethylene, bpe, or 4-styrylpyridine, stpy). The true values determined at 365 nm irradiation (e. g. Phi(NMR) = 0.80 for fac-[Re(CO)(3)(phen)(trans-bpe)](+)) were much higher than those determined by absorption spectral changes (Phi(UV-Vis) = 0.39 for fac-[Re(CO)(3)(phen)(trans-bpe)](+)). Phi(NMR) are more accurate in these cases due to the distinct proton signals of trans and cis-isomers, which allow the actual determination of each component concentration under given irradiation time. Nevertheless when the photoproduct or reactant contribution at the probe wavelength is negligible, one can determine Phi(true) by regular absorption spectral changes. For instance, Phi(313) nm for free ligand photoisomerization determined both by absorption and (1)H NMR variation are equal within the experimental error (bpe: Phi(UV-Vis) = 0.27, Phi(NMR) = 0.26; stpy: Phi(UV-Vis) = 0.49, Phi(NMR) = 0.49). Moreover, (1)H NMR data combined with electronic spectra allowed molar absorptivity determination of difficult to isolate cis-complexes. (C) 2009 Elsevier B. V. All rights reserved.

Reactivity of Beer Bitter Acids Toward the 1-Hydroxyethyl Radical as Probed by Spin-Trapping Electron Paramagnetic Resonance (EPR) and Electrospray Ionization-Tandem Mass Spectrometry (ESI-MS/MS)

The iso-alpha-acids or isohumulones are the major contributors to the bitter taste of beer, and it is well-recognized that they are degraded during beer aging. In particular, the trans-isohumulones seem to be less stable than the cis-isohumulones. The major radical identified in beer is the 1-hydroxyethyl radical; however, the reactivity between this radical and the isohumulones has not been reported until now. Therefore, we studied the reactivity of isohumulones toward the 1-hydroxyethyl radical through a competitive kinetic approach. It was observed that both cis- and trans-isohumulones and dihydroisohumulones are decomposed in the presence of 1-hydroxyethyl radicals, while the reactivities are comparable. On the other hand, the tetrahydroisohumulones did not react with 1-hydroxyethyl radicals. The apparent second-order rate constants for the reactions between the 1-hydroxyethyl radical and these compounds were determined by electron paramagnetic resonance (EPR) spectroscopy and electrospray ionization-tandem mass spectrometry [ESI(+)-MS/MS]. It follows that degradation of beer bitter acids is highly influenced by the presence of 1-hydroxyethyl radicals. The reaction products were detected by liquid chromatography electrospray ionization-ion trap-tandem mass spectrometry (LC-ESI-IT-MS/MS), and the formation of oxidized derivatives of the isohumulones was confirmed. These data help to understand the mechanism of beer degradation upon aging.

Nuclear magnetic resonance characterization of metabolite disorder in orange trees caused by citrus sudden death disease

Citrus sudden death (CSD) is a new disease of sweet orange and mandarin trees grafted on Rangpur lime and Citrus volkameriana rootstocks. It was first seen in Brazil in 1999, and has since been detected in more than four million trees. The CSD causal agent is unknown and the current hypothesis involves a virus similar to Citrus tristeza virus or a new virus named Citrus sudden death-associated virus. CSD symptoms include generalized foliar discoloration, defoliation and root death, and, in most cases, it can cause tree death. One of the unique characteristics of CSD disease is the presence of a yellow stain in the rootstock bark near the bud union. This region also undergoes profound anatomical changes. In this study, we analyse the metabolic disorder caused by CSD in the bark of sweet orange grafted on Rangpur lime by nuclear magnetic resonance (NMR) spectroscopy and imaging. The imaging results show the presence of a large amount of non-functional phloem in the rootstock bark of affected plants. The spectroscopic analysis shows a high content of triacylglyceride and sucrose, which may be related to phloem blockage close to the bud union. We also propose that, without knowing the causal CSD agent, the determination of oil content in rootstock bark by low-resolution NMR can be used as a complementary method for CSD diagnosis, screening about 300 samples per hour.

Surface-enhanced resonance Raman scattering: Single-molecule detection in a Langmuir-Blodgett monolayer

Surface-enhanced resonance Raman scattering (SERRS) is used for single-molecule detection from spatially resolved 1-mum(2) sections of a Langmuir-Blodgett (LB) monolayer deposited onto a Ag film. The target molecule, his (benzimidazo) thioperylene (BZP), is dispersed in an arachidic acid monomolecular layer containing one BZP molecule per mum(2) which is also the probing area of the Raman microscope. For concentrated samples (attomole quantities in the field of view), average SERRS, surface-enhanced fluorescence (SEF), and Raman imaging, including line mapping and global images at different temperatures, were recorded. Single-molecule SERRS spectra, obtained using an LB monolayer, present changes in bandwidth and relative intensities, highlighting the properties of single-molecule SERRS that are lost in average SERRS measurements of mixed LB monolayers obtained at the same temperatures. Also, the dilute system phenomenon of blinking is discussed with regard to results obtained from LB monolayers. The dilution process used in the single-molecule LB SERRS work is independently supported by fluorescence results obtained from very dilute solutions with monomer concentrations down to 10(-12) M.

Coupling Surface-Enhanced Resonance Raman Scattering and Electronic Tongue as Characterization Tools to Investigate Biological Membrane Mimetic Systems

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

Vibrational spectra and surface-enhanced resonance Raman scattering of palladium phthalocyanine evaporated films

The vibrational spectra of palladium phthalocyanine (PdPc) evaporated thin solid films are reported, including the resonance Raman scattering, surface-enhanced resonance Raman scattering (SERRS) and SERRS mapping of the film surface using micro-Raman spectroscopy with 633 nm laser radiation. SERRS of PdPc was obtained by evaporating an overlayer of Ag nanoparticles on to the PdPc film on glass. The SERRS enhancement factor is estimated as similar to10(4) with reference to PdPc evaporated films on glass. The molecular organization of the PdPc evaporated films was probed using transmission and reflection-absorption infrared spectra. It was established that a random molecular distribution found in PdPc evaporated films is independent of temperature. No evidence of thermal degradation due to thermal annealing was found in the films. Electronic absorption and emission spectra are also discussed. Copyright (C) 2002 John Wiley Sons, Ltd.

Characterization of humic acids from a Brazilian Oxisol under different tillage systems by EPR, C-13 NMR, FTIR and fluorescence spectroscopy

The importance of soil organic matter functions is well known, but structural information, chemical composition and changes induced by anthropogenic factors such as tillage practices are still being researched. In the present paper were characterized Brazilian humic acids (HAs) from an Oxisol under different treatments: conventional tillage/maize-bare fallow (CT1); conventional tillage/maize rotation with soybean-bare fallow (CT2)-, no-till/maize-bare fallow (NT1); no-till/maize rotation with soybean-bare fallow (NT2); no-till/maize-cajanus (NT3) and no cultivated soil under natural vegetation (NC). Soil HA samples were analyzed by electron paramagnetic resonance (EPR), solid-state C-13 nuclear magnetic resonance (C-13 NMR), Fourier transform intra-red (FTIR) and UV-Vis fluorescence spectroscopies and elemental analysis (CHNS). The FTIR spectra of the HAs were similar for all treatments. The level of semiquinone-type free radical determined from the EPR spectra was lower for treatments no-till/maize-cajanus (NT3) and noncultivated soil (1.74 X 10(17) and 1.02 x 10(17) spins g(-1) HA, respectively), compared with 2.3 X 10(17) spins g(-1) HA for other soils under cultivation. The percentage of aromatic carbons determined by C-13 NMR also decreases for noncultivated soil to 24%, being around 30% for samples of the other treatments. The solid-state C-13 NMR and EPR spectroscopies showed small differences in chemical composition of the HA from soils where incorporation of vegetal residues was higher, showing that organic matter (OM) formed in this cases is less aromatic. The fluorescence intensities were in agreement with the percentage of aromatic carbons, determined by NMR (r = 0.97 P < 0.01) and with semiquinone content, determined by EPR (r = 0.97 P < 0.01). No important effect due to tillage system was observed in these areas after 5 years of cultivation. Probably, the studied Oxisol has a high clay content that offers protection to the clay-Fe-OM complex against strong structural alterations. (C) 2003 Elsevier B.V. All rights reserved.

Structural studies of NaPO3-WO3 glasses by solid state NMR and Raman spectroscopy

Vitreous samples were prepared in the (100 2 x) NaPO3-x WO3 (0 <= x <= 70) glass forming system using conventional melting-quenching methods. The structural evolution of the vitreous network was monitored as a function of composition by thermal analysis, Raman spectroscopy and high resolution one- and two-dimensional P-31 solid state NMR. Addition of WO3 to the NaPO3 glass melt leads to a pronounced increase in the glass transition temperatures, suggesting a significant increase in network connectivity. At the same time Raman spectra indicate that up to about 30 mol% WO3 the tungsten atoms are linked to some non-bridging oxygen atoms (W-O- or W=O bonded species), suggesting that the network modifier sodium oxide is shared to some extent between both network formers. W-O- W bond formation occurs only at WO3 contents exceeding 30 mol%. P-31 magic angle spinning (MAS)-NMR spectra, supported by two-dimensional J-resolved spectroscopy, allow a clear distinction between species having two, one, and zero P-O-P linkages. The possible formation of some anionic tungsten sites suggested from the Raman data implies an average increase in the degree of polymerization for the phosphorus species, which would result in diminished P-31/Na-23 interactions. This prediction is indeed confirmed by P-31{Na-23} and Na-23{P-31} rotational echo double resonance (REDOR) NMR results, which indicate that successive addition of WO3 to NaPO3 glass significantly diminishes the strength of phosphorus-sodium dipole-dipole couplings.

Determination of site-site distance and site concentration within polymer beads: A combined swelling-electron paramagnetic resonance study

[GRAPHICS]This work proposes a combined swelling-electron paramagnetic resonance (EPR) approach aiming at determining some unusual polymer solvation parameters relevant for chemical processes occurring inside beads. Batches of benzhydrylamine-resin (BHAR), a copolymer of styrene-1% divinylbenzene containing phenylmethylamine groups were, labeled with the paramagnetic amino acid 2,2,6,6-tetramethylpiperidine-1-oxyl-4-amine-4-carboxylic acid (TOAC), and their swelling properties and EPR spectra were examined in DCM and DMF. By taking into account the BHARs labeling degrees, the corresponding swelling values, and some polymer structural characteristics, it was possible to calculate polymer swelling parameters, among them, the volume and the number of sites per bead, site-site distances and site concentration. The latter values ranged from 17 to 170 angstrom and from 0.4 to 550 mM, respectively. EPR spectroscopy was applied to validate the multistep calculation strategy of these swelling parameters. Spin-spin interaction was detected in the labeled resins at site-site distances less than approximately 60 A or probe concentrations higher than approximately 1 x 10(-2) M, in close agreement with the values obtained for the spin probe free in solution. Complementarily, the yield of coupling reactions in different resins indicated that the greater the inter-site distance or the lower the site concentration, the faster the reaction. The results suggested that the model and the experimental measurements developed for the determination of solvation parameters represent a relevant step forward for the deeper understanding and improvement of polymer-related processes.

Analysis of the ethidium bromide bound to DNA by photoacoustic and FTIR spectroscopy

Under physiological conditions B-form DNA is an exceedingly stable structure. However, experimental evidences obtained through nuclear magnetic resonance and fluorescence anisotropy suggest that the structure of the double helix fluctuates substantially. We describe photoacoustic phase modulation frequency measurements of ethidium bromide (Eb) with calf thymus, DNA. As in fluorescence phase modulation measurements, we used an intercalating dye as a probe; however, we monitored the triplet excited state lifetime at different ionic strengths. The triplet lifetime of Eb varied from about 0.30 ms, with no DNA present, to 20 ms, (at a DNA:Eb molar ratio of 5). With salt titration, this value falls, to about 2.0 ms. This result suggests, a strong coupling between the phenantridinium ring of the ethidium and the base pairs because of the stacking movement of the DNA molecule under salt effect. This, effect may be understood considering DNA as a polyelectrolyte. The counterions, in the solution shield the phosphate groups, reducing the electrostatic repulsion force between them, hence compacting the DNA molecule. The results from Fourier transform infrared demonstrated two important bands: 3187 cm(-1) corresponding to the symmetric stretching of the NH group of the bases, and 1225 cm(-1) corresponding to the asymmetric stretching of phosphate groups shifted toward higher wavenumbers, suggesting a proximity between the intercalant and base pairs and a modification of the DNA backbone state, both induced by salt accretion.