Preparação e caracterização óptica de filmes híbridos dopados com o azocorante Disperse Red 1

The Sol-gel process has facilitated the processing of Organic-Inorganic Hybrid Materials with several scientific applications and technologies. The hybrid combine the advantages of the Sol-gel process with specific characteristics of organic polymers, allowing processing of thin films without fractures or fissures. The incorporation of azo dyes in polymer matrices has been widely used in the investigation of optical properties. The azo dye Disperse Red (DR1) presents optical alterations when exposed to visible or ultraviolet light. The alterations occur due to transitions of their isomers, trans and cis, caused by photoisomerization, due to electronic transitions of azo group (-N=N-), presenting photochromic and/or photorefractive effects. The hybrid system used in this work is the precursor 3- Glycidoxypropyl-Trimethoxi-silane (GPTS), the Tetraethylorthosilicate (TEOS) and DR1 as a dopant. The characterizations were performed using absorption spectroscopy UV-Vis which allowed the identification of the absorption bands and its variations when the samples were treated thermally and/or illuminated by ultraviolet light

Performance characteristics of UV and visible spectrophotometry methods for quantitative determination norfloxacin in tablets

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

Thermal analysis and validation of UV and visible spectrophotometric methods for the determination of new antibiotic tigecycline in pharmaceutical product

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

Propriedades estruturais e espectroscópicas de WO3 e WO3:Eu3+

Used as catalysts even in organic and inorganic molecules, as additives on catalysts, electrochromic films on smart windows the tungsten trioxide have been largely studied on the lasts decades, but there is just a few about it's luminescence. Using as precursors nitric acid and sodium tungstate the tungsten trioxide were been prepared thru wet process then treating on thermic and hydrothermal treatments. Where been evaluated the effects of methodology, nitric acid concentration, duration and temperature of treatments. The samples were characterized by X-ray diffraction (XRD), Raman scattering spectroscopy (RSS), Fourier transformed infrared spectroscopy, photoluminescence spectroscopy (PLS) and X-ray excited optical luminescence (XEOL). Hydrated phases of tungsten trioxide were obtained through hydrothermal treatments and the non-hydrated phases occur with thermic treatments. The acid concentration has the ability to determine the major phase formed as well the temperature determine the hydratation of the product. With lower temperatures dihydrate phase were preferable formed and with the rise of temperature, the water molecules were lost up to the fractionary hydratation and then the non-hydrated phase with higher temperatures depending on the atmosphere used on the thermal treatment. Doping the system with europium ions even substituting tungsten or in the interstices of the matrix were not been successful, as well the XEOL spectroscopy intensity were null and quite low for ultraviolet and visible excitation photoluminescence because of oxygen defect levels localized into the prohibited band.

Propriedades estruturais e espectroscópicas de WO3 e WO3:Eu3+

Used as catalysts even in organic and inorganic molecules, as additives on catalysts, electrochromic films on smart windows the tungsten trioxide have been largely studied on the lasts decades, but there is just a few about it's luminescence. Using as precursors nitric acid and sodium tungstate the tungsten trioxide were been prepared thru wet process then treating on thermic and hydrothermal treatments. Where been evaluated the effects of methodology, nitric acid concentration, duration and temperature of treatments. The samples were characterized by X-ray diffraction (XRD), Raman scattering spectroscopy (RSS), Fourier transformed infrared spectroscopy, photoluminescence spectroscopy (PLS) and X-ray excited optical luminescence (XEOL). Hydrated phases of tungsten trioxide were obtained through hydrothermal treatments and the non-hydrated phases occur with thermic treatments. The acid concentration has the ability to determine the major phase formed as well the temperature determine the hydratation of the product. With lower temperatures dihydrate phase were preferable formed and with the rise of temperature, the water molecules were lost up to the fractionary hydratation and then the non-hydrated phase with higher temperatures depending on the atmosphere used on the thermal treatment. Doping the system with europium ions even substituting tungsten or in the interstices of the matrix were not been successful, as well the XEOL spectroscopy intensity were null and quite low for ultraviolet and visible excitation photoluminescence because of oxygen defect levels localized into the prohibited band.

Near-infrared quantum cutting through a three-step energy transfer process in Nd3+-Yb3+ co-doped fluoroindogallate glasses

The Nd3+-Yb3+ couple was investigated in fluoroindogallate glasses using optical spectroscopy to elucidate the energy transfer mechanisms involved in the downconversion (DC) process. Upon excitation of a Nd3+ ion by an ultraviolet photon, DC through a three-step energy transfer process occurs, in which the energy of the ultraviolet photon absorbed by the Nd3+ ion is converted into three infrared photons emitted by Yb3+ ions, i.e. quantum cutting (QC). In addition, with excitation in the visible, our results confirm that the DC process occurs through a one-step energy transfer process, in which the energy of a visible photon absorbed by the Nd3+ ion is converted into only one infrared photon emitted by an Yb3+ ion. Time-resolved measurements enabled the estimation of the efficiencies of the cross-relaxation processes between Nd3+ and Yb3+ ions.

Structure and peroxidase activity of ferric Streptomyces clavuligerus orf10-encoded protein P450CLA: UV-visible, CD, MCD and EPR spectroscopic characterization

The present study reports the spectroscopic characterization by UV-visible absorption spectroscopy, magnetic circular dichroism (MCD) and electron paramagnetic resonance (EPR) of the recombinant orf10-encoded P450-camphor like protein (P450CLA)of Streptomyces clavuligerus expressed in Escherichia coli Rosetta in the native form and associated to external ligands containing the β-lactam, oxazole and alkylamine-derived (alcohol) moieties of the clavulamic acid. Considering the diversity of potential applications for the enzyme, the reactivity with tert-butylhydroperoxide (tert-BuOOH) was also characterized. P450CLA presents a covalently bound heme group and exhibited the UV-visible, CD and MCD spectral features of P450CAM including the fingerprint Soret band at 450 nm generated by the ferrous CO-complex. P450CLA was converted to high valence species by tert-BuOOH and promoted homolytic scission of the O-O bond. The radical profile of the reaction was tert-butyloxyl as primary and methyl and butylperoxyl as secondary radicals. The secondary methyl and butylperoxyl radicals resulted respectively from the β-scission of the alkoxyl radical and from the reaction of methyl radical with molecular oxygen.

Determination of degree of ionization of poly(allylamine hydrochloride) (PAH) and poly[1-[4-(3-carboxy‑4 hydroxyphenylazo)benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO) in layer-by-layer films using vacuum photoabsorption spectroscopy

Electrostatic and hydrophobic interactions govern most of the properties of supramolecular systems, which is the reason determining the degree of ionization of macromolecules has become crucial for many applications. In this paper, we show that highresolution ultraviolet spectroscopy (VUV) can be used to determine the degree of ionization and its effect on the electronic excitation energies of layer-by-layer (LbL) films of poly(allylamine hydrochloride) (PAH) and poly[1-[4-(3-carboxy-4 hydroxyphenylazo)- benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO). A full assignment of the VUV peaks of these polyelectrolytes in solution and in cast or LbL films could be made, with their pH dependence allowing us to determine the p'K IND. a' using the Henderson-Hasselbach equation. The p'K IND. a' for PAZO increased from ca. 6 in solution to ca. 7.3 in LbL films owing to the charge transfer from PAH. Significantly, even using solutions at a fixed pH for PAH, the amount adsorbed on the LbL films still varied with the pH of the PAZO solutions due to these molecular-level interactions. Therefore, the procedure based on a comparison of VUV spectra from solutions and films obtained under distinct conditions is useful to determine the degree of dissociation of macromolecules, in addition to permitting interrogation of interface effects in multilayer films.

Reaction intermediates of ethanol electro-oxidation on platinum investigated by SFG spectroscopy

Although electrochemical oxidation of simple organic molecules on metal catalysts is the basic ingredient of fuel cells, which have great technological potential as a renewable source of electrical energy, the detailed reaction mechanisms are in most cases not completely understood. Here, we investigate the ethanol-platinum interface in acidic aqueous solution using infrared-visible sum frequency generation (SFG) spectroscopy and theoretical calculations of vibrational spectra in order to identify the intermediates present during the electro-oxidation of ethanol. The complex vibrational spectrum in the fingerprint region imply on the coexistence of several adsorbates. Based on spectra in ultra-high-vacuum (UHV) and electrochemical environment from the literature and our density functional theory (DFT) calculations of vibrational spectra, new adsorbed intermediates, never before observed with conventional infrared (IR) spectroscopy, are proposed here: g2-acetaldehyde, g2-acetyl, ethylidyne, monodentate acetate, methoxy, tertiary methanol derivative, COH residue, g2-formaldehyde, mono and bidentate formate, CH3 and CH2 residues. In addition, we present new evidences for an ethoxy intermediate, a secondary ethanol derivative and an acetyl species, and we confirm the presence of previously observed adsorbates: a tertiary ethanol derivative, bidentate acetate, and COad. These results indicate that the platinum surface is much more reactive, and the reaction mechanism for ethanol electro-oxidation is considerably more complex than previously considered. This might be also true for many other molecule-catalyst systems.

Multiple stellar populations in globular clusters with photometry and low resolution spectroscopy

Our view of Globular Clusters has deeply changed in the last decade. Modern spectroscopic and photometric data have conclusively established that globulars are neither coeval nor monometallic, reopening the issue of the formation of such systems. Their formation is now schematized as a two-step process, during which the polluted matter from the more massive stars of a first generation gives birth, in the cluster innermost regions, to a second generation of stars with the characteristic signature of fully CNO-processed matter. To date, star-to-star variations in abundances of the light elements (C, N, O, Na) have been observed in stars of all evolutionary phases in all properly studied Galactic globular clusters. Multiple or broad evolutionary sequences have also been observed in nearly all the clusters that have been observed with good signal-to-noise in the appropriate photometric bands. The body of evidence suggests that spreads in light-element abundances can be fairly well traced by photometric indices including near ultraviolet passbands, as CNO abundance variations affect mainly wavelengths shorter than ~400 nm owing to the rise of some NH and CN molecular absorption bands. Here, we exploit this property of near ultraviolet photometry to trace internal chemical variations and combined it with low resolution spectroscopy aimed to derive carbon and nitrogen abundances in order to maximize the information on the multiple populations. This approach has been proven to be very effective in (i) detecting multiple population, (ii) characterizing their global properties (i.e., relative fraction of stars, location in the color-magnitude diagram, spatial distribution, and trends with cluster parameters) and (iii) precisely tagging their chemical properties (i.e., extension of the C-N anticorrelation, bimodalities in the N content).

Unraveling efficiency-limiting processes in organic solar cells by ultrafast spectroscopy - impact of chemical structure and morphology on photophysics and efficiency

Diese Arbeit widmet sich der Untersuchung der photophysikalischen Prozesse, die in Mischungen von Elektronendonoren mit Elektronenakzeptoren zur Anwendung in organischen Solarzellen auftreten. Als Elektronendonoren werden das Copolymer PBDTTT-C, das aus Benzodithiophen- und Thienothiophene-Einheiten besteht, und das kleine Molekül p-DTS(FBTTh2)2, welches Silizium-überbrücktes Dithiophen, sowie fluoriertes Benzothiadiazol und Dithiophen beinhaltet, verwendet. Als Elektronenakzeptor finden ein planares 3,4:9,10-Perylentetracarbonsäurediimid-(PDI)-Derivat und verschiedene Fullerenderivate Anwendung. PDI-Derivate gelten als vielversprechende Alternativen zu Fullerenen aufgrund der durch chemische Synthese abstimmbaren strukturellen, optischen und elektronischen Eigenschaften. Das gewichtigste Argument für PDI-Derivate ist deren Absorption im sichtbaren Bereich des Sonnenspektrums was den Photostrom verbessern kann. Fulleren-basierte Mischungen übertreffen jedoch für gewöhnlich die Effizienz von Donor-PDI-Mischungen.rnUm den Nachteil der PDI-basierten Mischungen im Vergleich zu den entsprechenden Fulleren-basierten Mischungen zu identifizieren, werden die verschiedenen Donor-Akzeptor-Kombinationen auf ihre optischen, elektronischen und strukturellen Eigenschaften untersucht. Zeitaufgelöste Spektroskopie, vor allem transiente Absorptionsspektroskopie (TA), wird zur Analyse der Ladungsgeneration angewendet und der Vergleich der Donor-PDI Mischfilme mit den Donor-Fulleren Mischfilmen zeigt, dass die Bildung von Ladungstransferzuständen einen der Hauptverlustkanäle darstellt.rnWeiterhin werden Mischungen aus PBDTTT-C und [6,6]-Phenyl-C61-buttersäuremethylesther (PC61BM) mittels TA-Spektroskopie auf einer Zeitskala von ps bis µs untersucht und es kann gezeigt werden, dass der Triplettzustand des Polymers über die nicht-geminale Rekombination freier Ladungen auf einer sub-ns Zeitskala bevölkert wird. Hochentwickelte Methoden zur Datenanalyse, wie multivariate curve resolution (MCR), werden angewendet um überlagernde Datensignale zu trennen. Zusätzlich kann die Regeneration von Ladungsträgern durch Triplett-Triplett-Annihilation auf einer ns-µs Zeitskala gezeigt werden. Darüber hinaus wird der Einfluss des Lösungsmitteladditivs 1,8-Diiodooctan (DIO) auf die Leistungsfähigkeit von p-DTS(FBTTh2)2:PDI Solarzellen untersucht. Die Erkenntnisse von morphologischen und photophysikalischen Experimenten werden kombiniert, um die strukturellen Eigenschaften und die Photophysik mit den relevanten Kenngrößen des Bauteils in Verbindung zu setzen. Zeitaufgelöste Photolumineszenzmessungen (time-resolved photoluminescence, TRPL) zeigen, dass der Einsatz von DIO zu einer geringeren Reduzierung der Photolumineszenz führt, was auf eine größere Phasentrennung zurückgeführt werden kann. Außerdem kann mittels TA Spektroskopie gezeigt werden, dass die Verwendung von DIO zu einer verbesserten Kristallinität der aktiven Schicht führt und die Generation freier Ladungen fördert. Zur genauen Analyse des Signalzerfalls wird ein Modell angewendet, das den gleichzeitigen Zerfall gebundener CT-Zustände und freier Ladungen berücksichtigt und optimierte Donor-Akzeptor-Mischungen zeigen einen größeren Anteil an nicht-geminaler Rekombination freier Ladungsträger.rnIn einer weiteren Fallstudie wird der Einfluss des Fullerenderivats, namentlich IC60BA und PC71BM, auf die Leistungsfähigkeit und Photophysik der Solarzellen untersucht. Eine Kombination aus einer Untersuchung der Struktur des Dünnfilms sowie zeitaufgelöster Spektroskopie ergibt, dass Mischungen, die ICBA als Elektronenakzeptor verwenden, eine schlechtere Trennung von Ladungstransferzuständen zeigen und unter einer stärkeren geminalen Rekombination im Vergleich zu PCBM-basierten Mischungen leiden. Dies kann auf die kleinere Triebkraft zur Ladungstrennung sowie auf die höhere Unordnung der ICBA-basierten Mischungen, die die Ladungstrennung hemmen, zurückgeführt werden. Außerdem wird der Einfluss reiner Fullerendomänen auf die Funktionsfähigkeit organischer Solarzellen, die aus Mischungen des Thienothienophen-basierenden Polymers pBTTT-C14 und PC61BM bestehen, untersucht. Aus diesem Grund wird die Photophysik von Filmen mit einem Donor-Akzeptor-Mischungsverhältnis von 1:1 sowie 1:4 verglichen. Während 1:1-Mischungen lediglich eine co-kristalline Phase, in der Fullerene zwischen den Seitenketten von pBTTT interkalieren, zeigen, resultiert der Überschuss an Fulleren in den 1:4-Proben in der Ausbildung reiner Fullerendomänen zusätzlich zu der co kristallinen Phase. Transiente Absorptionsspektroskopie verdeutlicht, dass Ladungstransferzustände in 1:1-Mischungen hauptsächlich über geminale Rekombination zerfallen, während in 1:4 Mischungen ein beträchtlicher Anteil an Ladungen ihre wechselseitige Coulombanziehung überwinden und freie Ladungsträger bilden kann, die schließlich nicht-geminal rekombinieren.

Visibility of vascular phenylalanine in dynamic uptake studies in humans using magnetic resonance spectroscopy

In general, vascular contributions to the in vivo magnetic resonance (MR) brain spectrum are too small to be relevant. In cerebral uptake studies, however, vascular contributions may constitute a major confounder. MR visibility of vascular Phe was investigated by recording localized spectra from fully oxygenated and well-mixed whole blood. Blood Phe levels determined by MR spectroscopy (MRS) and ion-exchange chromatography showed excellent correlation. In addition, effects of blood flow were shown to have a small effect on signal amplitude with the MRS methodology used. Hence, blood Phe is almost completely MR visible at 1.5 T, even though it is severely broadened at higher fields. Without appropriate correction, cerebral Phe influx in studies of brain Phe uptake in phenylketonuria patients or healthy subjects would appear to be faster and lead to higher levels. Similar effects are envisaged for studies of ethanol or glucose uptake across the blood-brain barrier.

Proton diffusion tensor spectroscopy of metabolites in human muscle in vivo

PURPOSE To study the apparent diffusivity and its directionality for metabolites of skeletal muscle in humans in vivo by (1) H magnetic resonance spectroscopy. METHODS The diffusion tensors were determined on a 3 Tesla MR system using optimized acquisition and processing methods including an adapted STEAM sequence with orientation-dependent diffusion weighting, pulse-triggering with individually adapted delays, eddy-current correction schemes, median filtering, and simultaneous prior-knowledge fitting of all related spectra. RESULTS The average apparent diffusivities, as well as the fractional anisotropies of taurine (ADCav  = 0.74 × 10(-3) s/mm(2) , FA = 0.46), creatine (ADCav  = 0.41 × 10(-3)  s/mm(2) , FA = 0.33), trimethylammonium compounds (ADCav  = 0.48 × 10(-3)  s/mm(2) , FA = 0.34), carnosine (ADCav  = 0.46 × 10(-3)  s/mm(2) , FA = 0.47), and water (ADCav  = 1.5 × 10(-3)  s/mm(2) , FA = 0.36) were estimated. The diffusivities of most metabolites and water were significantly different from each other. Diffusion was found to be anisotropic and the diffusion tensors showed tensor correlation coefficients close to 1 and were hence found to be essentially coaligned. The magnitudes of apparent metabolite diffusivities were largely ordered according to molecular weight, with taurine as the smallest molecule diffusing fastest, both along and across the fiber direction. CONCLUSION Diffusivities, directional dependence of diffusion and fractional anisotropies of (1) H MRS-visible muscle metabolites were presented. It was shown that metabolites share diffusion directionality with water and have similar fractional anisotropies, hinting at similar diffusion barriers. Magn Reson Med, 2014. © 2014 Wiley Periodicals, Inc.

Visible and Infrared Spectroscopical Applications

Spectra in the visible (VIS) and infrared (IR) region contain a wide variety of information about inorganic and organic substances in sediments. The information from the spectra enables a wide array of applications that allow quantitative, semiquantitative, and qualitative characterization of sediment. Due to the fact that instrument/experimental setups are simple, rapid, and cost-saving and that only small sample quantities are required, the technique has become valuable in paleolimnological and Quaternary science. This article summarizes the theoretical background of VIS and IR spectroscopy, explains the analytical process, introduces statistical tools used for interpretation of spectra, and provides examples of applications in Quaternary science.

Real-time observation of the charge-transfer-to-solvent dynamics

Intermolecular electron-transfer reactions have a crucial role in biology, solution chemistry and electrochemistry. The first step of such reactions is the expulsion of the electron to the solvent, whose mechanism is determined by the structure and dynamical response of the latter. Here we visualize the electron transfer to water using ultrafast fluorescence spectroscopy with polychromatic detection from the ultraviolet to the visible region, upon photo-excitation of the so-called charge transfer to solvent states of aqueous iodide. The initial emission is short lived (~60 fs) and it relaxes to a broad distribution of lower-energy charge transfer to solvent states upon rearrangement of the solvent cage. This distribution reflects the inhomogeneous character of the solvent cage around iodide. Electron ejection occurs from the relaxed charge transfer to solvent states with lifetimes of 100–400 fs that increase with decreasing emission energy.