ChemSpaX: Exploration of chemical space by automated functionalization of molecular scaffold

Exploration of the local chemical space of molecular scaffolds by post-functionalization (PF) is a promising route to discover novel molecules with desired structure and function. PF with rationally chosen substituents...

Dually Reactive Multilayer Coatings Enable Orthogonal Manipulation of Underwater Superoleophobicity and Oil Adhesion via Post-Functionalization

Fish scale-inspired underwater superoleophobic coatings with low oil adhesion can be achieved through the creation of hierarchical surface topography on water-compatible materials (including polymeric hydrogels, metal oxides, and electrostatic multilayers)....

Bioinspired and Post-Functionalized 3D-Printed Surfaces with Parahydrophobic Properties

Desertification is a growing risk for humanity. Studies show that water access will be the leading cause of massive migration in the future. For this reason, significant research efforts are devoted to identifying new sources of water. Among this work, one of the more interesting strategies takes advantage of atmospheric non-liquid water using water harvesting. Various strategies exist to harvest water, but many suffer from low yield. In this work, we take inspiration from a Mexican plant (Echeveria pulvinate) to prepare a material suitable for future water harvesting applications. Observation of E. pulvinate reveals that parahydrophobic properties are favorable for water harvesting. To mimic these properties, we leveraged a combination of 3D printing and post-functionalization to control surface wettability and obtain parahydrophobic properties. The prepared surfaces were investigated using IR and SEM. The surface roughness and wettability were also investigated to completely describe the elaborated surfaces and strongly hydrophobic surfaces with parahydrophobic properties are reported. This new approach offers a powerful platform to develop parahydrophobic features with desired three-dimensional shape.

Reactant-Induced Photoactivation of a Gold-Catalyzed Csp2-Csp Cross-Coupling Leading to Indoles

A novel access to 2,3-disubstituted indoles from o-alkynyl aniline and iodoalkyne derivatives via a gold-catalyzed sequence under visible-light irradiation and in the absence of an exogenous photocatalyst was uncovered. A wide scope of the process was observed. Of note, 2-iodo-ynamides that have never been used in any organometallic cross-coupling reaction could be used as electrophiles. The resulting N-alkynyl indoles lend themselves to post-functionalization affording valuable scaffolds, notably benzo[a]carbazoles. Mechanistic studies converged on the fact that a potassium sulfonyl amide generates emissive aggregates in the reaction medium. Static quenching of these aggregates by a vinylgold(I) intermediate yields to an excited state of the latter, which can react with an electrophile via oxidative addition and reductive elimination to forge the key C-C bond. This reactant-induced photoactivation of an organogold intermediate opens rich perspectives in the field of cross-coupling reactions.

Preparation of Nanofibers Mats Derived from Task-Specific Polymeric Ionic Liquid for Sensing and Catalytic Applications

Nanofibers mats derived from the task-specific functionalized polymeric ionic liquids based on homocysteine thiolactone are obtained by electrospinning them as blends with polyvinylpyrrolidone. The presence of this functional moiety allowed the post-functionalization of these mats through the aminolysis of the thiolactone ring in the presence of an amine by a thiol–alkene “click” reaction. Under controlled experimental conditions the modification can be performed introducing different functionalization and crosslinking of the electrospun fibers, while maintaining the nanostructure obtained by the electrospinning. Initial studies suggest that the nanofibers based on these functionalized polymeric ionic liquids can be used in both sensing and catalytic applications.

Reactant-Induced Photoactivation of a Gold-Catalyzed Csp2-Csp Cross-Coupling Leading to Indoles

A novel access to 2,3-disubstituted indoles from o-alkynyl aniline and iodoalkyne derivatives via a gold-catalyzed sequence under visible-light irradiation and in the absence of an exogenous photocatalyst was uncovered. A wide scope of the process was observed. Of note, 2-iodo-ynamides that have never been used in any organometallic cross-coupling reaction could be used as electrophiles. The resulting N-alkynyl indoles lend themselves to post-functionalization affording valuable scaffolds, notably benzo[a]carbazoles. Mechanistic studies converged on the fact that a potassium sulfonyl amide generates emissive aggregates in the reaction medium. Static quenching of these aggregates by a vinylgold(I) intermediate yields to an excited state of the latter, which can react with an electrophile via oxidative addition and reductive elimination to forge the key C-C bond. This reactant-induced photoactivation of an organogold intermediate opens rich perspectives in the field of cross-coupling reactions.

Post-functionalization of drug-loaded nanoparticles prepared by polymerization-induced self-assembly (PISA) with mitochondria targeting ligands

Herein, the postfunctionalization of different non-fouling PISA particles, prepared from either poly(oligo ethylene glycol methyl ether methacrylate) (pPEGMA) and the anticancer drug PENAO (4-(N-(S-penicillaminylacetyl)amino)phenylarsenonous acid) or zwitterionic 2-methacryloyloxyethyl phosphorylcholine (MPC) and PENAO were reported. Both PISA particles were reacted with triphenylphosphonium (TPP) as mitochondria targeting units in order to evaluate the changes in cellular uptake or the toxicity of the conjugated arsenic drug. Attachment of TPP onto the PISA particles however was found not to enhance the mitochondrial accumulation, but it did influence overall the biological activity of pMPC-based particles in 2D and 3D cultured sarcoma SW982 cells. When TPP was conjugated to the pMPC PISA particles more cellular uptake as well as better spheroid penetration were observed, while TPP on PEG-based PISA had only little effect. It was hypothesized that TPP on the micelle surface may not be accessible enough to allow mitochondria targeting, but more structural investigations are required to elucidate this.