Microsolvation effects on the pi*<--pi electronic transitions in simple aromatic chromophores: the role of the Slater-type Gaussian orbitals in the complete active space self-consistent field approach

One of the most studied feature of aromatic molecular clusters in the gas phase is the shift of the pi*<--pi electronic transitions between the bare aromatic chromophore and its clusters. In the present ab initio complete active space self-consistent field study the coupling of the basis set superposition error and counterpoise procedure and a combination of Pople- and Slater-type Gaussian basis sets has been proven to reproduce quantitatively the gas-phase experimental shifts. The quantal results are here analyzed with respect to the electrostatic and polarization forces and electron density differences, and connected with the sign of the shifts of the electronic transitions.     

Peptide-Functionalized Silk Fibers as a Platform to Stabilize Gelatin for Use in Ingestible Devices

The combination of pharmacologic and endoscopic therapies is the gold standard for treating intestinal failures. The possibility of chemical solubility in water is mandatory for intelligent capsules. Functionalised silk fibroin with peptides and covalently linking different molecular entities to its structure make this protein a platform for preparing gels dissolving in the small and large intestine for drug delivery. In the present study, we linked a peptide containing the cell-adhesive motif Arginine–Glycine–Aspartic acid (RGD) to degummed silk fibres (DSF). Regenerated silk fibroin (RS) films obtained by dissolving functionalised DSF in formic acid were used to prepare composite gelatin. We show that such composite gelatin remains stable and elastic in the simulated gastric fluid (SGF) but can dissolve in the small and large intestines’ neutral-pH simulated intestine fluid (SIF). These findings open up the possibility of designing microfabricated and physically programmable scaffolds that locally promote tissue regeneration, thanks to bio-enabled materials based on functionalised regenerated silk.     

How Computations Can Assist the Rational Design of Drugs for Photodynamic Therapy: Photosensitizing Activity Assessment of a Ru(II)-BODIPY Assembly

Ruthenium-based complexes represent a new frontier in light-mediated therapeutic strategies against cancer. Here, a density functional-theory-based computational investigation, of the photophysical properties of a conjugate BODIPY-Ru(II) complex, is presented. Such a complex was reported to be a good photosensitizer for photodynamic therapy (PDT), successfully integrating the qualities of a NIR-absorbing distyryl-BODIPY dye and a PDT-active [Ru(bpy)₃]²⁺ moiety. Therefore, the behaviour of the conjugate BODIPY-Ru(II) complex was compared with those of the metal-free BODIPY chromophore and the Ru(II) complex. Absorptions spectra, excitation energies of both singlet and triplet states as well as spin–orbit-matrix elements (SOCs) were used to rationalise the experimentally observed different activities of the three potential chromophores. The outcomes evidence a limited participation of the Ru moiety in the ISC processes that justifies the small SOCs obtained for the conjugate. A plausible explanation was provided combining the computational results with the experimental evidences.     

Classification of Unifloral Honeys from SARDINIA (Italy) by ATR-FTIR Spectroscopy and Random Forest

Nowadays, the mislabeling of honey floral origin is a very common fraudulent practice. The scientific community is intensifying its efforts to provide the bodies responsible for controlling the authenticity of honey with fast and reliable analytical protocols. In this study, the classification of various monofloral honeys from Sardinia, Italy, was attempted by means of ATR-FTIR spectroscopy and random forest. Four different floral origins were considered: strawberry-tree (Arbutus Unedo L.), asphodel (Asphodelus microcarpus), thistle (Galactites tormentosa), and eucalyptus (Eucalyptus calmadulensis). Training a random forest on the infrared spectra allowed achieving an average accuracy of 87% in a cross-validation setting. The identification of the significant wavenumbers revealed the important role played by the region 1540–1175 cm⁻¹ and, to a lesser extent, the region 1700–1600 cm⁻¹. The contribution of the phenolic fraction was identified as the main responsible for this observation.     

Correlative Cellular Mass Spectrometry Imaging and Amperometry Show Dose Dependent Changes in Lipid Composition and Exocytosis

Aberrant functioning of the proteasome has been associated with crucial pathologic conditions including neurodegeneration. Yet, the complex underlying causes at the cellular level remain unclear and there are conflicting reports of neuroprotective to neurodegenerative effects of proteasomal inhibitors such as lactacystin that are utilised as models for neurodegenerative diseases. The conflicting results may be associated with different dose regimes of lactacystin and hence we have performed a dose dependent study of the effects of lactacystin to identify concurrent changes in the cell membrane lipid profile and the dynamics of exocytosis using a combination of surface sensitive mass spectrometry and single cell amperometry. Significant changes of negatively charged lipids were associated with different lactacystin doses that showed a weak correlation with exocytosis while changes in PE and PE−O lipids showed dose dependent changes correlated with initial pore formation and total release of vesicle content respectively.