Sol-gel synthesis of Eu3+ doped silica-gold nanorod composites with tunable optical properties.

Gold nanorods (AuNRs) suspension at various concentrations was added into the sol-gel process to engineer nanostructured europium-doped silica host matrices as light-emitting composites. For this purpose, the samples were prepared following two different routes depending on the chemicals used as dopant and catalyst: (a) Eu(NO3)3·5H2O and HNO3, and (b) EuCl·6H2O and HCl. In any case, samples adding various concentrations of AuNRs suspension were prepared. The structural characterization of the samples was through STEM, backscattered electrons (BSE), and EDS analysis. Additionally, their optical properties were evaluated by PL spectroscopy and CIE colorimetry. The results confirmed that (a) methodology produced samples with AuNRs embedded and randomly distributed in the samples. However, these features were not observed in the samples obtained through (b) due to AuNRs dissolution in HCl media. Regarding the optical properties, the analysis of the relative intensity ratio 5D0 → 7F2/5D0 → 7F1 suggested that Eu3+ ions occupy non-centrosymmetric sites in (a) host matrices and centrosymmetric sites in (b). Hence, the increase of AuNRs suspension when fabricating (a) host matrices produced remarkable color changes in the luminescence of the samples towards the reddish-orange region. Meanwhile, the dissolution of AuNRs in (b) minimized the localized surface plasmon resonance (LSPR) effects on the Eu3+ luminescence. These findings revealed that the evaluation and selection of chemicals are critical factors when engineering these materials for more efficient coupling between the LSPR and Eu3+ luminescence.

Insights into ligand binding to a glutathione S-transferase from mango: Structure, thermodynamics and kinetics.

We studied a mango glutathione S-transferase (GST) (Mangifera indica) bound to glutathione (GSH) and S-hexyl glutathione (GSX). This GST Tau class (MiGSTU) had a molecular mass of 25.5 kDa. MiGSTU Michaelis-Menten kinetic constants were determined for their substrates obtaining a Km, Vmax and kcat for CDNB of 0.792 mM, 80.58 mM min-1 and 68.49 s-1 respectively and 0.693 mM, 105.32 mM min-1 and 89.57 s-1, for reduced GSH respectively. MiGSTU had a micromolar affinity towards GSH (5.2 µM) or GSX (7.8 µM). The crystal structure of the MiGSTU in apo or bound to GSH or GSX generated a model that explains the thermodynamic signatures of binding and showed the importance of enthalpic-entropic compensation in ligand binding to Tau-class GST enzymes.

Experimental and theoretical investigation on the molecular structure, spectroscopic and electric properties of 2,4-dinitrodiphenylamine, 2-nitro-4-(trifluoromethyl)aniline and 4-bromo-2-nitroaniline.

2,4-Dinitrodiphenylamine (I), 2-nitro-4-(trifluoromethyl)aniline (II) and 4-bromo-2-nitroaniline (III) have been investigated by DFT and experimental FTIR, Raman and UV-Vis spectroscopies. The gas-phase molecular geometries were consistent with similar compounds already reported in the literature. From the vibrational analysis, the main functional groups were identified and their absorption bands were assigned. Some differences were found between the calculated and the experimental UV-Vis spectra. These differences were analyzed and explained in terms of the TD-DFT/B3LYP limitations, which were mainly attributed to charge-transfer (CT) effects. These findings were in agreement with previous works, which reported that TD-DFT/B3LYP calculations diverge from experimental results when the electronic transitions involve CT. Despite this, TD-DFT/B3LYP calculations provided satisfactory results and a detailed description of the electronic transitions involved in the absorption bands of the UV-Vis spectra. In terms of the NLO properties, it was found that compound (I) is a good candidate for NLO applications and deserves further study due to its good ß values. However, the ß values for compounds (II) and (III) were negatively affected compared to those found on o-nitroaniline.

N-containing boronic esters as self-complementary building blocks for the assembly of 2D and 3D molecular networks.

The combination of two heteroaromatic boronic acids with pentaerythritol gave self-complementary tectons which were suitable for the generation of 2D and 3D molecular networks.

Solvent-solvent and solvent-solute interactions in a 3D chloroform clathrate with diorganotin macrocycles in the nano-sized pores.

A 3D clathrate of deuterochloroform molecules was formed in the presence of nano-sized macrocyclic molecules.