Studying the first order hyperpolarizability spectra in chalcone-based derivatives and the relation with one- and two-photon absorption transitions.

The first-order molecular hyperpolarizability (ß) dispersion was measured in seven chalcone-based molecules utilizing the tunable femtosecond hyper-Rayleigh scattering (tHRS) technique. Additionally, a theoretical model based on photophysical parameters was employed to better understand ß dispersion. Due to the distinct substitution patterns of the aryl/heteroaryl rings within the chalcone structure, varying profiles of one- and two-photon absorption spectra and ß dispersion were observed. The applied model highlighted two important factors contributing to achieving high ß values: (i) the presence of red-shifted one-photon and two-photon absorption bands; and (ii) the number of discernible absorption bands. To contextualize these results with other molecular structures, we employed the HRS figure of merit (FOM). Remarkably, it was revealed that chemically engineered small chalcone molecules exhibit a FOM comparable to larger quadrupolar and octupolar ones. This underscores the significance of tHRS scattering measurements and their correlation with absorptive parameters in the design and characterization of nonlinear optical materials.

Modeling the First-Order Molecular Hyperpolarizability Dispersion from Experimentally Obtained One- and Two-Photon Absorption.

The search for optical materials, particularly organic compounds, is still an attractive and essential field for developing several photonic devices and applications. For example, some applications are based on light scattering with twice the energy of the incoming photon for selected compounds, that is, the nonlinear optical effect related to the second-order susceptibility term from the electronic polarization expression. The microscopic interpretation of this phenomenon is called the first-order molecular hyperpolarizability or incoherent second harmonic generation of light. Understanding such phenomena as a function of the incoming wavelength is crucial to improving the optical response of future materials. Still, the experimental apparatus, hyper-Rayleigh scattering, apparently simple, is indeed a challenging task. Therefore, we proposed a proper alternative to obtain the dispersion of the first-order hyperpolarizability using the well-known one- and two-photon absorption techniques. By the spectral analysis of both the spectra, we gathered spectroscopic parameters and applied them for predicting the first-order hyperpolarizability dispersion. This prediction is based on an n-level energy system, taking into account the position and magnitude of transition dipole moments and the difference between the permanent dipole moment of the n-excited states. Moreover, using the presented method, we can avoid underestimating the first-order hyperpolarizability by not suppressing higher-energy transitions. Quantum chemical calculations and the hyper-Rayleigh scattering technique were used to validate the proposed method.

Synthesis and application of a highly fluorescent styryl-benzothiadiazole derivative as a chemosensor for ethanol in hydroalcoholic solutions.

Two fluorescent D-A-D styryl-benzothiadiazole fluorophores possessing either styryl-BTD-styryl (2) or aryl-BTD-styryl (4) architectures have been synthesized using Heck reactions as key step. Compounds presented absorption in blue region and emission ranging from 531 to 560 nm with positive solvatochromism. Lippert Mattaga plots indicated a substantial effect of solvent polarity over the emission profile. As the fluorescence of the compound 4 was more sensitive to changes in the environment, this compound was evaluated as a probe to chemosensing etanol/water percentage in hydroalcoholic solutions. Good linearity was observed between fluorescence intensity and ethanol content in the range from 40% to 90%. Analyses of commercial solutions of sanitizers and cleaning products (% ethanol = 46%, 70% and 92%) indicate that reference values are within the confidence interval of experimental results produced by the proposed method.

Synthesis of limonene beta-amino alcohol derivatives in support of new antileishmanial therapies.

A series of seven limonene beta-amino alcohol derivatives has been regioselectively synthesised in moderate to good yields. Two of these compounds were found to be significantly effective against in vitro cultures of the Leishmania (Viannia) braziliensis promastigote form in the micromolar range. The activities found for 3b and 3f were about 100-fold more potent than the standard drug, Pentamidine, in the same test, while limonene did not display any activity. This is the first report of antileishmanial activity by limonene beta-amino alcohol derivatives.

Charge-tagged ligands: useful tools for immobilising complexes and detecting reaction species during catalysis.

In recent years, charge-tagged ligands (CTLs) have become valuable tools in organometallic catalysis. Insertion of an ionic side chain into the molecular skeleton of a known ligand has become a useful protocol for anchoring ligands, and consequently catalysts, in polar and ionic liquid phases. In addition, the insertion of a cationic moiety into a ligand is a powerful tool that can be used to detect reaction intermediates in organometallic catalysis through electrospray ionisation mass spectrometry (ESI-MS) experiments. The insertion of an ionic tag ensures the charge in the intermediates independently of the ESI-MS. For this reason, these ligands have been used as ionic probes in mechanistic studies for several catalytic reactions. Here, we summarise selected examples on the use of CTLs as immobilising agents in organometallic catalysis and as probes for studying mechanisms through ESI-MS.

Synthesis of limonene β-amino alcohol derivatives in support of new antileishmanial therapies

A series of seven limonene β-amino alcohol derivatives has been regioselectively synthesised in moderate to good yields. Two of these compounds were found to be significantly effective against in vitro cultures of the Leishmania (Viannia) braziliensis promastigote form in the micromolar range. The activities found for 3b and 3f were about 100-fold more potent than the standard drug, Pentamidine, in the same test, while limonene did not display any activity. This is the first report of antileishmanial activity by limonene β-amino alcohol derivatives.