Silver Dendritic Gels with Luminescence and Aggregation-Induced Emission Effect.

This work reports on a novel family of silver metallogels based on discrete coordination complexes. Structurally, they consist of dendrimers containing a trinuclear silver metallacycle at the core, with the general formula [M(µ-pz)]3, and poly(benzyl)ether branched structures with different numbers or terminal alkoxy chains at the periphery. These silver metallodendrimers are able to gel low-polarity solvents such as dodecane or cyclohexane, giving rise to luminescent organogels at room temperature with the property of aggregation-induced emission (AIE). This property means that in solution or the sol state, they are weak emitters, but in the gel state, luminescence is considerably increased. In this particular case, they exhibit blue luminescence. Two different dendritic scaffolds have been studied, finding significant differences in solubility, gel formation and dependence of luminescence on temperature. The results show that properly tailored silver gelators can show luminescence in the gel state.

L-Thyroxine and L-thyroxine-based antimicrobials against Streptococcus pneumoniae and other Gram-positive bacteria.

Objectives: The rise of antibiotic-resistant Streptococcus pneumoniae (Sp) poses a significant global health threat, urging the quest for novel antimicrobial solutions. We have discovered that the human hormone l-thyroxine has antibacterial properties. In order to explore its drugability we perform here the characterization of a series of l-thyroxine analogues and describe the structural determinants influencing their antibacterial efficacy. Method: We performed a high-throughput screening of a library of compounds approved for use in humans, complemented with ITC assays on purified Sp-flavodoxin, to pinpoint molecules binding to this protein. Antimicrobial in vitro susceptibility assays of the hit compound (l-thyroxine) as well as of 13 l-thyroxine analogues were done against a panel of Gram-positive and Gram-negative bacteria. Toxicity of compounds on HepG2 cells was also assessed. A combined structure-activity and computational docking analysis was carried out to uncover functional groups crucial for the antimicrobial potency of these compounds. Results: Human l-thyroxine binds to Sp-flavodoxin, forming a 1:1 complex of low micromolar Kd. While l-thyroxine specifically inhibited Sp growth, some derivatives displayed activity against other Gram-positive bacteria like Staphylococcus aureus and Enterococcus faecalis, while remaining inactive against Gram-negative pathogens. Neither l-thyroxine nor some selected derivatives exhibited toxicity to HepG2 cells. Conclusions: l-thyroxine derivatives targeting bacterial flavodoxins represent a new and promising class of antimicrobials.

Making Coaxial Wires Out of Janus Dendrimers for Efficient Charge Transport.

Highly conductive coaxial supramolecular wires are prepared by using a new family of Janus dendrimers that combines two rigid aromatic parts and two flexible aliphatic parts. The two external regions consist of a promesogenic block based on a third generation Percec-type dendron with four terminal dodecyloxy alkyl chains, whereas the two internal regions are formed by one, two, or three carbazole units bearing flexible spacers. These functional Janus dendrimers self-organize in columnar liquid crystal phases with a strong coaxial segregation within each column. Interestingly, the charge mobility studies revealed that these Janus dendrimers display semiconductor properties with hole mobility values up to 0.5 cm2 V-1 s-1, depending on the packing within the columns which can be tuned by the number of carbazole functional units. The high hole mobility values measured in these materials are among the highest values reported for columnar liquid crystals.

Supramolecular Columnar Liquid Crystals with Tapered-Shape Simple Pyrazoles Obtained by Efficient Henry/Michael Reactions.

A straightforward synthesis of mesogenic pyrazoles starting from benzaldehydes by a combination of efficient Henry and Michael reactions led to novel supramolecular liquid crystals. The mesogens are fluorescent 3,5-dimethyl-4-(di or trialkoxyphenyl)pyrazoles and, in spite of the tapered shape of these molecules and their structural simplicity (only one phenyl ring), columnar liquid-crystal phases were formed that are stable at room temperature. The self-assembled structure was studied by XRD and the columnar cross section contains two molecules on average with an antiparallel arrangement of pyrazoles interacting through hydrogen bonds. In contrast, the single-crystal structure of a trimethoxy analog did not show hydrogen-bonded pyrazoles but chains of head-to-tail arranged molecules.