Vibrational Spectroscopy and Phonon-Related Properties of the L-Aspartic Acid Anhydrous Monoclinic Crystal.

The infrared absorption and Raman scattering spectra of the monoclinic P21 l-aspartic acid anhydrous crystal were recorded and interpreted with the help of density functional theory (DFT) calculations. The effect of dispersive forces was taken into account, and the optimized unit cells allowed us to obtain the vibrational normal modes. The computed data exhibits good agreement with the measurements for low wavenumbers, allowing for a very good assignment of the infrared and Raman spectral features. The vibrational spectra of the two lowest energy conformers of the l-aspartic molecule were also evaluated using the hybrid B3LYP functional for the sake of comparison, showing that the molecular calculations give a limited description of the measured IR and Raman spectra of the l-aspartic acid crystal for wavenumbers below 1000 cm(-1). The results obtained reinforce the need to use solid-state calculations to describe the vibrational properties of molecular crystals instead of calculations for a single isolated molecule picture even for wavenumbers beyond the range usually associated with lattice modes (200 cm(-1) < ω < 1000 cm(-1)).

Photophysics and visible light photodissociation of supramolecular meso-tetra(4-pyridyl) porphyrin/RuCl2(CO)(PPh3)2 structures.

In the last decades, supramolecular structures have been explored in many technological efforts. One example of such supramolecules is attained when ruthenium complexes are attached in the outer sites of a porphyrin. Ruthenium complexes act as modulators of the photophysical processes of macrocyclic molecules. Besides the investigation of the main changes introduced by the ruthenium complexes in the electronic and vibronic properties, and in the excited state deactivation processes of porphyrins, discussions concerning the photostability of these supramolecules are much needed. Here, we investigate the supramolecular free-base meso-tetra(4-pyridyl) porphyrin decorated with "RuCl2(CO)(PPh3)2" ruthenium species linked at each of its (4-pyridyl) moieties. The modifications in the photophysical processes introduced by the metallic outlying species are discussed and our results suggest an energy transfer process from the porphyrin B-band to the ruthenium complex MLCT-band. The demonstration of visible light photodissociation of the supramolecule, via both pulsed and continuous laser, is also addressed.

Rose Bengal incorporated to α-cyclodextrin microparticles for photodynamic therapy against the cariogenic microorganism Streptococcus mutans.

Rose Bengal@α-cyclodextrin (RB@α-CD) microparticles (µPs) were prepared and the RB inclusion in α-CD was experimentally demonstrated through infrared, UV-VIS absorption spectroscopy and cyclic voltammetry. The RB inclusion in α-CD was theoretically investigated using classical molecular mechanics calculations, the simulation results showing that RB can be included in both the narrow and wide apertures of the α-cyclodextrin ring with configurations exhibiting average binding energies of about 27 kcal mol-1. The prepared RB@α-CD microparticles were characterized through Scanning Electron Microscopy (SEM) and it was demonstrated that they are highly efficient in the photodynamic therapy against a Streptococcus mutans (the main bacteria of cariogenic dental plaque) suspension, as a concentration of RB@α-CD µPs 10 times smaller than the usual concentration of pure RB is still capable to produce significant antibacterial activity.