New oxacalix[4]arene carboxylate detects viologen in protic media

ABSTRACT

We demonstrate that Ullman fragment-coupling can be used to synthesise an oxacalix[4]arene monocarboxylic acid, which provides easy access to its water-soluble carboxylato derivatives. Crystallographic and computational data suggest that the new carboxyl-substituted oxacalix[4]arene adopts a 1,3-alternate conformation both in the solid-state and in methanol solution. Its water-soluble tetrabutylammonium derivate can detect the herbicide paraquat at neutral pH in aqueous media (K _a = 111 ± 3 M^–1) and in methanol (K _a = 2020 ± 70 M^–1).     

Size,Charge, and Stability of Fully Serine‐Based Catanionic Vesicles: Towards Versatile Biocompatible Nanocarriers

Vesicles based on mixed cationic and anionic surfactants (catanionic vesicles) offer a number of advantageous colloidal features over conventional lipid‐based vesicles, namely spontaneity in formation, long‐term stability, and easy modulation of size and charge. If biocompatibility is added through rational design of the chemical components, the potential for biorelated applications further emerges. Here, we report for the first time on two catanionic vesicle systems in which both ionic amphiphiles are derivatized from the same amino acid—serine—with the goal of enhancing aggregate biocompatibility. Phase behavior maps for a mixture with chain length symmetry, 12Ser/12‐12Ser, and another with asymmetry, 16Ser/8‐8Ser, are presented, for which regions of vesicles, micelles, and coexisting aggregates are identified. For the asymmetric mixture, detailed phase behavior and microstructure characterization have been carried out based on surface tension, light microscopy, cryo‐SEM, cryo‐TEM, and dynamic light scattering analysis. Vesicles are found with tunable mean size, pH, and zeta potential. Changes in aggregate shape with varying composition and the effect of preparation methods and aging on vesicle features and stability have been investigated in detail. The results are discussed in the light of self‐assembly models and related catanionic systems reported before. A versatile system of robust vesicles is thus presented for potential applications.     

The Plasticity of the Carbohydrate Recognition Domain Dictates the Exquisite Mechanism of Binding of Human Macrophage Galactose-Type Lectin

The human macrophage galactose-type lectin (MGL), expressed on macrophages and dendritic cells (DCs), modulates distinct immune cell responses by recognizing N-acetylgalactosamine (GalNAc) containing structures present on pathogens, self-glycoproteins, and tumor cells. Herein, NMR spectroscopy and molecular dynamics (MD) simulations were used to investigate the structural preferences of MGL against different GalNAc-containing structures derived from the blood group A antigen, the Forssman antigen, and the GM2 glycolipid. NMR spectroscopic analysis of the MGL carbohydrate recognition domain (MGL-CRD, C181-H316) in the absence and presence of methyl α-GalNAc (α-MeGalNAc), a simple monosaccharide, shows that the MGL-CRD is highly dynamic and its structure is strongly altered upon ligand binding. This plasticity of the MGL-CRD structure explains the ability of MGL to accommodate different GalNAc-containing molecules. However, key differences are observed in the recognition process depending on whether the GalNAc is part of the blood group A antigen, the Forssman antigen, or GM2-derived structures. These results are in accordance with molecular dynamics simulations that suggest the existence of a distinct MGL binding mechanism depending on the context of GalNAc moiety presentation. These results afford new perspectives for the rational design of GalNAc modifications that fine tune MGL immune responses in distinct biological contexts, especially in malignancy.     

Unravelling the Time Scale of Conformational Plasticity and Allostery in Glycan Recognition by Human Galectin-1

The interaction of human galectin-1 with a variety of oligosaccharides, from di-(N-acetyllactosamine) to tetra-saccharides (blood B type-II antigen) has been scrutinized by using a combined approach of different NMR experiments, molecular dynamics (MD) simulations, and isothermal titration calorimetry. Ligand- and receptor-based NMR experiments assisted by computational methods allowed proposing three-dimensional structures for the different complexes, which explained the lack of enthalpy gain when increasing the chemical complexity of the glycan. Interestingly, and independently of the glycan ligand, the entropy term does not oppose the binding event, a rather unusual feature for protein-sugar interactions. CLEANEX-PM and relaxation dispersion experiments revealed that sugar binding affected residues far from the binding site and described significant changes in the dynamics of the protein. In particular, motions in the microsecond-millisecond timescale in residues at the protein dimer interface were identified in the presence of high affinity ligands. The dynamic process was further explored by extensive MD simulations, which provided additional support for the existence of allostery in glycan recognition by human galectin-1.     

Photodynamic Therapy and Immunity: An Update

Dr. Thomas Dougherty and his Oncology Foundation of Buffalo were the first to support my (S.O.G.) research into the effects of photodynamic therapy (PDT) on the host immune system. The small grant I was awarded in 2002 launched my career as an independent researcher; at the time, there were few studies on the importance of the immune response on the efficacy of PDT and no studies demonstrating the ability of PDT to enhance antitumor immunity. Over the last decades, the interest in PDT as an enhancer of antitumor immunity and our understanding of the mechanisms by which PDT enhances antitumor immunity have dramatically increased. In this review article, we look back on the studies that laid the foundation for our understanding and provide an update on current advances and therapies that take advantage of PDT enhancement of immunity.     

Enantioselective comprehensive two‐dimensional gas chromatography. A route to elucidate the authenticity and origin of Rosa damascena Miller essential oils

The analysis of Bulgarian and Turkish Rosa damascena Miller essential oils was performed by flow‐modulated comprehensive two‐dimensional gas chromatography using simultaneous detection of the second column effluent by flame ionization and quadrupole mass spectrometric detection. Enantioselective separations were obtained by running the samples on 2,3‐di‐O‐ethyl‐6‐O‐tert‐butyldimethylsilyl‐β‐cyclodextrin column as the first column and on polyethylene glycol as the second column. The determination of enantiomeric or diastereomeric excess of some terpenoic solutes is a possible route for quality or authenticity control as well as for the elucidation of the country of origin.