RESUMO
Two different qualities of riboflavin (RF) i.e., synthetic (RFs) and biosynthetic riboflavin (RFbs) have been investigated with respect to photoinduced color change in the solid state. Several methods (XRD, FT-IR, VIS-, NIR- and fluorescence spectroscopy) were employed to elucidate the properties of the crystalline structure of RFs and RFbs and the influence of irradiation on the color and structural changes of the samples in the solid state. It was shown that RFs an RFbs represent two different crystal modifications of riboflavin and that RFbs can easily be transformed into a dihydrate upon exposure to humidity. Based on the observed irreversible color change and reduction in fluorescence intensity upon irradiation, an irreversible photoreduction of the molecule was assumed in case of RFs. A more pronounced, reversible color change and reversible reduction in fluorescence intensity indicated a reversible photoreduction process in the case of RFbs. The mechanism of these processes was further investigated by means of NIR and FT-IR spectrophotometry. It is apparent from the current study that the crystal modification of RF can strongly influence the solid state photochemistry of this molecule.
Assuntos
Fármacos Fotossensibilizantes/química , Riboflavina/química , Aminoácidos/análise , Cromatografia Líquida de Alta Pressão , Cromatografia em Camada Fina , Cor , Cristalização , Umidade , Luz , Microscopia Eletrônica de Varredura , Fotoquímica , Fármacos Fotossensibilizantes/síntese química , Fármacos Fotossensibilizantes/efeitos da radiação , Riboflavina/síntese química , Riboflavina/efeitos da radiação , Espectrometria de Fluorescência , Espectrofotometria Ultravioleta , Espectroscopia de Infravermelho com Transformada de Fourier , Espectroscopia de Luz Próxima ao Infravermelho , Difração de Raios XRESUMO
An experimental technique that allows faster assessment of out-of-plane strain dynamics of thin film heterostructures via x-ray diffraction is presented. In contrast to conventional high-speed reciprocal space-mapping setups, our approach reduces the measurement time drastically due to a fixed measurement geometry with a position-sensitive detector. This means that neither the incident (ω) nor the exit ( 2 θ ) diffraction angle is scanned during the strain assessment via x-ray diffraction. Shifts of diffraction peaks on the fixed x-ray area detector originate from an out-of-plane strain within the sample. Quantitative strain assessment requires the determination of a factor relating the observed shift to the change in the reciprocal lattice vector. The factor depends only on the widths of the peak along certain directions in reciprocal space, the diffraction angle of the studied reflection, and the resolution of the instrumental setup. We provide a full theoretical explanation and exemplify the concept with picosecond strain dynamics of a thin layer of NbO2.
RESUMO
In this study we report on the investigation of epitaxially grown Sb2Te3 by employing Fourier-Transform transmission Spectroscopy (FTS) with laser-induced Coherent Synchrotron Radiation (CSR) in the Terahertz (THz) spectral range. Static spectra in the range between 20 and 120 cm-1 highlight a peculiar softening of an in-plane IR-active phonon mode upon temperature decrease, as opposed to all Raman active modes which instead show a hardening upon temperature decrease in the same energy range. The phonon mode softening is found to be accompanied by an increase of free carrier concentration. A strong coupling of the two systems (free carriers and phonons) is observed and further evidenced by exciting the same phonon mode at 62 cm-1 within an ultrafast pump-probe scheme employing a femtosecond laser as pump and a CSR single cycle THz pulse as probe. Separation of the free carrier contribution and the phonon resonance in the investigated THz range reveals that, both damping of the phonon mode and relaxation of hot carriers in the time domain happen on the same time scale of 5 ps. This relaxation is about a factor of 10 slower than expected from the Lorentz time-bandwidth limit. The results are discussed in the framework of phonon scattering at thermal and laser induced transient free carriers.
RESUMO
A combination of far-infrared and Raman spectroscopy is employed to investigate vibrational modes and the carrier behavior in amorphous and crystalline ordered GeTe-Sb2Te3 alloys (GST) epitaxially grown on Si(111). The infrared active GST mode is not observed in the Raman spectra and vice versa, indication of the fact that inversion symmetry is preserved in the metastable cubic phase in accordance with the Fm3 space group. For the trigonal phase, instead, a partial symmetry break due to Ge/Sb mixed anion layers is observed. By studying the crystallization process upon annealing with both the techniques, we identify temperature regions corresponding to the occurrence of different phases as well as the transition from one phase to the next. Activation energies of 0.43 eV and 0.08 eV for the electron conduction are obtained for both cubic and trigonal phases, respectively. In addition a metal-insulator transition is clearly identified to occur at the onset of the transition between the disordered and the ordered cubic phase.