Study of the spectroscopic properties and first hyperpolarizabilities of disperse azo dyes derived from 2-amino-5-nitrothiazole

The solvatochromism and other spectroscopic and photophysical characteristics of four azo disperse dyes, derived from 2-amino-5-nitrothiazole, were evaluated and interpreted with the aid of experimental data and quantum mechanical calculations. For the non-substituted compound two conformers, E and Z, were proposed for the isolated molecules, being the second one considerably less stable. The optimization of these structures in combination with a SCRF methodology (IEFPCM, Simulating the molecules in a continuum dielectric with characteristics of methanol), suggests that the Z form is not stable in solution. This same behaviour is expected for the substituted compounds, which is corroborated by experimental data presented in previous investigations [A.E.H. Machado, L.M. Rodrigues, S. Gupta, A.M.F. Oliveira-Campos, A.M.S. Silva, J. Mol. Struct. 738 (2005) 239-245]. For the substituted compounds, two forms derived from E conformer (A and R) are possible. Quantum mechanical data suggest for the isolated molecules, that the low energy absorption hand of the E conformers involve at least two close electronic states. having the low-lying excited state a (1)(n,pi*) nature, and being the S-2 state attributed to a (1)(pi,pi*) transition. The data also suggest a small energy gap between the absorption peaks of A and B, related to the easy conversion between these forms. For the structures optimized in combination with the applied SCRF methodology, an states inversion is observed for the Substituted compounds, with a considerable diminish of the energy gap between A and B absorption peaks. The electronic spectra of these compounds are quite sensitive to changes in the solvent polarity. The positive solvatochromism is more evident in aprotic solvents, probably due to the polarization induced by the solute. These compounds do not fluoresce at 298 K, but present a small but perceptible fluorescence at 77 K, which seems to be favoured by the nature of the group in the 2 `-position of the phenyl ring. Moreover, such compounds present expressive values for first hyperpolarizability, which implies in good non-linear optics (NLO) responses and photoswitching capability. (C) 2008 Elsevier B.V. All rights reserved.

Calorimetric investigations of luminescent films polycarbonate (PC) doped with europium complex [Eu(TTA)(3)(H(2)O)(2)]

Polymers doped with rare earth complexes are advantaged in film production for many applications in the luminescent field. In this luminescent polycarbonate (PC) films doped with diaquatris(thenoyltrifluoroacetonate)europium(III) complex [Eu(TTA)(3)(H(2)O)(2)] were prepared and their calorimetric and luminescent properties in the solid state are reported. The thermal behavior was investigated by utilization of differential scanning calorimetry (DSC) and thermogravimetry (TG). Due of the addition of rare earth [Eu(TTA)(3)(H(2)O)(2)] into PC matrix, changes were observed in the thermal behavior concerning the glass transition and thermal stability. Characteristic broadened narrow bands arising from the (5)D(0) -> (7)F(J) transitions (J = 4-0) of Eu(3+) ion indicate the incorporation of the Eu(3+) ions in the polymer. The luminescent films show enhancement emission intensity with an increase of rare earth concentration in polymeric matrix accompanied by decrease in thermal stability.

Size-selective investigations of spectral and emission properties of small particles and nanotubes

In dieser Arbeit wurde die Elektronenemission von Nanopartikeln auf Oberflächen mittels spektroskopischen Photoelektronenmikroskopie untersucht. Speziell wurden metallische Nanocluster untersucht, als selbstorganisierte Ensembles auf Silizium oder Glassubstraten, sowie ferner ein Metall-Chalcogenid (MoS2) Nanoröhren-Prototyp auf Silizium. Der Hauptteil der Untersuchungen war auf die Wechselwirkung von fs-Laserstrahlung mit den Nanopartikeln konzentriert. Die Energie der Lichtquanten war kleiner als die Austrittsarbeit der untersuchten Proben, so dass Ein-Photonen-Photoemission ausgeschlossen werden konnte. Unsere Untersuchungen zeigten, dass ausgehend von einem kontinuierlichen Metallfilm bis hin zu Clusterfilmen ein anderer Emissionsmechanismus konkurrierend zur Multiphotonen-Photoemission auftritt und für kleine Cluster zu dominieren beginnt. Die Natur dieses neuen Mechanismus` wurde durch verschiedenartige Experimente untersucht. Der Übergang von einem kontinuierlichen zu einem Nanopartikelfilm ist begleitet von einer Zunahme des Emissionsstroms von mehr als eine Größenordnung. Die Photoemissions-Intensität wächst mit abnehmender zeitlicher Breite des Laserpulses, aber diese Abhängigkeit wird weniger steil mit sinkender Partikelgröße. Die experimentellen Resultate wurden durch verschiedene Elektronenemissions-Mechanismen erklärt, z.B. Multiphotonen-Photoemission (nPPE), thermionische Emission und thermisch unterstützte nPPE sowie optische Feldemission. Der erste Mechanismus überwiegt für kontinuierliche Filme und Partikel mit Größen oberhalb von mehreren zehn Nanometern, der zweite und dritte für Filme von Nanopartikeln von einer Größe von wenigen Nanometern. Die mikrospektroskopischen Messungen bestätigten den 2PPE-Emissionsmechanismus von dünnen Silberfilmen bei „blauer“ Laseranregung (hν=375-425nm). Das Einsetzen des Ferminiveaus ist relativ scharf und verschiebt sich um 2hν, wenn die Quantenenergie erhöht wird, wogegen es bei „roter“ Laseranregung (hν=750-850nm) deutlich verbreitert ist. Es zeigte sich, dass mit zunehmender Laserleistung die Ausbeute von niederenergetischen Elektronen schwächer zunimmt als die Ausbeute von höherenergetischen Elektronen nahe der Fermikante in einem Spektrum. Das ist ein klarer Hinweis auf eine Koexistenz verschiedener Emissionsmechanismen in einem Spektrum. Um die Größenabhängigkeit des Emissionsverhaltens theoretisch zu verstehen, wurde ein statistischer Zugang zur Lichtabsorption kleiner Metallpartikel abgeleitet und diskutiert. Die Elektronenemissionseigenschaften bei Laseranregung wurden in zusätzlichen Untersuchungen mit einer anderen Anregungsart verglichen, der Passage eines Tunnelstroms durch einen Metall-Clusterfilm nahe der Perkolationsschwelle. Die elektrischen und Emissionseigenschaften von stromtragenden Silberclusterfilmen, welche in einer schmalen Lücke (5-25 µm Breite) zwischen Silberkontakten auf einem Isolator hergestellt wurden, wurden zum ersten Mal mit einem Emissions-Elektronenmikroskop (EEM) untersucht. Die Elektronenemission beginnt im nicht-Ohmschen Bereich der Leitungsstrom-Spannungskurve des Clusterfilms. Wir untersuchten das Verhalten eines einzigen Emissionszentrums im EEM. Es zeigte sich, dass die Emissionszentren in einem stromleitenden Silberclusterfilm Punktquellen für Elektronen sind, welche hohe Emissions-Stromdichten (mehr als 100 A/cm2) tragen können. Die Breite der Energieverteilung der Elektronen von einem einzelnen Emissionszentrum wurde auf etwa 0.5-0.6 eV abgeschätzt. Als Emissionsmechanismus wird die thermionische Emission von dem „steady-state“ heißen Elektronengas in stromdurchflossenen metallischen Partikeln vorgeschlagen. Größenselektierte, einzelne auf Si-Substraten deponierte MoS2-Nanoröhren wurden mit einer Flugzeit-basierten Zweiphotonen-Photoemissions-Spektromikroskopie untersucht. Die Nanoröhren-Spektren wiesen bei fs-Laser Anregung eine erstaunlich hohe Emissionsintensität auf, deutlich höher als die SiOx Substratoberfläche. Dagegen waren die Röhren unsichtbar bei VUV-Anregung bei hν=21.2 eV. Eine ab-initio-Rechnung für einen MoS2-Slab erklärt die hohe Intensität durch eine hohe Dichte freier intermediärer Zustände beim Zweiphotonen-Übergang bei hν=3.1 eV.

Magnetic resonance spectroscopy investigations of functionally defined language areas in schizophrenia patients with and without auditory hallucinations

Background: Cerebral dysfunction occurring in mental disorders can show metabolic disturbances which are limited to circumscribed brain areas. Auditory hallucinations have been shown to be related to defined cortical areas linked to specific language functions. Here, we investigated if the study of metabolic changes in auditory hallucinations requires a functional rather than an anatomical definition of their location and size to allow a reliable investigation by magnetic resonance spectroscopy (MRS). Methods: Schizophrenia patients with (AH; n = 12) and without hallucinations (NH; n = 8) and healthy controls (HC; n = 11) underwent a verbal fluency task in functional MRI (fMRI) to functionally define Broca's and Wernicke's areas. Left and right Heschl's gyri were defined anatomically. Results: The mean distances in native space between the fMRI-defined regions and a corresponding anatomically defined area were 12.4 ± 6.1 mm (range: 2.7–36.1 mm) for Broca's area and 16.8 ± 6.2 mm (range: 4.5–26.4 mm) for Wernicke's area, respectively. Hence, the spatial variance was of similar extent as the size of the investigated regions. Splitting the investigations into a single voxel examination in the frontal brain and a spectroscopic imaging part for the more homogeneous field areas led to good spectral quality for almost all spectra. In Broca's area, there was a significant group effect (p = 0.03) with lower levels of N-acetyl-aspartate (NAA) in NH compared to HC (p = 0.02). There were positive associations of NAA levels in the left Heschl's gyrus with total (p = 0.03) and negative (p = 0.006) PANSS scores. In Broca's area, there was a negative association of myo-inositol levels with total PANSS scores (p = 0.008). Conclusion: This study supports the neurodegenerative hypothesis of schizophrenia only in a frontal region whereas the results obtained from temporal regions are in contrast to the majority of previous studies. Future research should test the hypothesis raised by this study that a functional definition of language regions is needed if neurochemical imbalances are expected to be restricted to functional foci.

Investigations on selected chalcogenide glasses towards the realization of photonic devices

Among various optical sensing schemes, infrared spectroscopy is a powerful tool for detecting and determining the composition of complex organic samples since vibrational finger prints of all biomolecules and organic species are located in this window. This spectroscopic technique is simple, reliable, fast, non-destructive, cost-effective while having low sensitivity. Use of metallic nanoparticles in association with a good IR transparent sensing substrate, is one of the promising solutions to enhance the sensitivity. Chalcogenide glasses are promising substrate material because of their extended optical transmission window starting from the visible to the far infrared range up to 20 μm, high refractive index usually between 2 and 3 and high optical nonlinearity, which make them good candidates as IR sensors and optical ultrafast nonlinear devices. These glasses are favorable sensor materials for the infrared spectral range because of their high IR transparency to allow for low optical loss at wavelengths corresponding to the characteristic optical absorption bands of organic molecules, high refractive index for tight confinement of optical energy within the resonator structure, processibility into thin film form, chemical compatibility for adhesion of silver nano particles and thin films and resistance to the chemical environment to be sensed. Molecules adsorbed to silver island structures shows enhanced IR absorption spectra and the extent of enhancement is determined by many factors such as the size, density and morphology of silver structures, optical and dielectric properties of the substrate material etc.

The'cave' mineral oxammite: a high resolution thermogravimetry and Raman spectroscopic study

The thermal decomposition of natural ammonium oxalate known as oxammite has been studied using a combination of high resolution thermogravimetry coupled to an evolved gas mass spectrometer and Raman spectroscopy coupled to a thermal stage. Three mass loss steps were found at 57, 175 and 188°C attributed to dehydration, ammonia evolution and carbon dioxide evolution respectively. Raman spectroscopy shows two bands at 3235 and 3030 cm-1 attributed to the OH stretching vibrations and three bands at 2995, 2900 and 2879 cm-1, attributed to the NH vibrational modes. The thermal degradation of oxammite may be followed by the loss of intensity of these bands. No intensity remains in the OH stretching bands at 100°C and the NH stretching bands show no intensity at 200°C. Multiple CO symmetric stretching bands are observed at 1473, 1454, 1447 and 1431cm-1, suggesting that the mineral oxammite is composed of a mixture of chemicals including ammonium oxalate dihydrate, ammonium oxalate monohydrate and anhydrous ammonium oxalate.

Near-infrared spectroscopic study of basic aluminum sulfate and nitrate

The tridecameric Al-polymer [AlO4Al12(OH)24(H2O)12]7+ was prepared by forced hydrolysis of Al3+ up to an OH/Al molar ratio of 2.2. Under slow evaporation crystals were formed of Al13-nitrate. Upon addition of sulfate the tridecamer crystallised as the monoclinic Al13-sulfate. These crystals have been studied using near-infrared spectroscopy and compared to Al2(SO4)3.16H2O. Although the near-infrared spectra of the Al13-sulfate and nitrate are very similar indicating similar crystal structures, there are minor differences related to the strength with which the crystal water molecules are bonded to the salt groups. The interaction between crystal water and nitrate is stronger than with the sulfate as reflected by the shift of the crystal water band positions from 6213, 4874 and 4553 cm–1 for the Al13 sulfate towards 5925, 4848 and 4532 cm–1 for the nitrate. A reversed shift from 5079 and 5037 cm–1 for the sulfate towards 5238 and 5040 cm–1 for the nitrate for the water molecules in the Al13 indicate that the nitrate-Al13 bond is weakened due to the influence of the crystal water on the nitrate. The Al-OH bond in the Al13 complex is not influenced by changing the salt group due to the shielding by the water molecules of the Al13 complex.

New dimeric supramolecular structure of mixed (phthalocyaninato)(porphyrinato)-europium(III) sandwiches : preparation and spectroscopic characteristics

The mixed double-decker Eu\[Pc(15C5)4](TPP) (1) was obtained by base-catalysed tetramerisation of 4,5-dicyanobenzo-15-crown-5 using the half-sandwich complex Eu(TPP)(acac) (acac = acetylacetonate), generated in situ, as the template. For comparative studies, the mixed triple-decker complexes Eu2\[Pc(15C5)4](TPP)2 (2) and Eu2\[Pc(15C5)4]2(TPP) (3) were also synthesised by the raise-by-one-story method. These mixed ring sandwich complexes were characterised by various spectroscopic methods. Up to four one-electron oxidations and two one-electron reductions were revealed by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). As shown by electronic absorption and infrared spectroscopy, supramolecular dimers (SM1 and SM3) were formed from the corresponding double-decker 1 and triple-decker 3 in the presence of potassium ions in MeOH/CHCl3.

An infrared spectroscopic study of the some Autunite minerals

A series of selected autunites with phosphate as the anion have been studied using infrared spectroscopy. Each autunite mineral has its own characteristic spectrum. The spectra for different autunites with the same composition are different. It is proposed that this difference is due to the structure of water and hydrated cations in the interlayer region between the uranyl phosphate sheets. This structure is different for different autunites. The position of the water hydroxyl stretching bands is related to the strength of the hydrogen bonds as determined by hydrogen bond distance. The highly ordered structure of water is also observed in the water HOH bending modes where a high wavenumber bands are observed. The phosphate and uranyl stretching vibrations overlap and are obtained by curve resolution.