Unlocking the Potential of Push-Pull Pyridinic Photobases: Aggregation-Induced Excited-State Proton Transfer.

The pH effect on the photophysics of three push-pull compounds bearing dimethoxytriphenylamine (TPA-OMe) as electron donor and pyridine as electron acceptor, with different ortho-functionalization (-H, -Br, and -TPA-OMe), is assessed through steady-state and time-resolved spectroscopic techniques in DMSO/water mixed solutions and in water dispersions over a wide pH range. The enhanced intramolecular charge transfer upon protonation of the pyridinic ring leads to the acidochromic (from colorless to yellow) and acido(fluoro)chromic (from cyan to pink) behaviours of the investigated compounds. In dilute DMSO/buffer mixtures these molecules exhibited low pK values (≤3.

Amino-OPE glycosides and blue light: a powerful synergy in photodynamic therapy.

Herein we report the synthesis and biological properties of sugar-conjugated oligophenylene ethynylene (OPE) dyes, used as novel photosensitizers (PSs) for photodynamic treatment (PDT) under blue light. The OPE-bearing glycosides at both ends are successfully prepared by a Pd-catalyzed Sonogashira cross-coupling reaction. The live-cell imaging studies have shown that these OPE glycosides (including glucose, mannose and maltose derivatives) efficiently penetrate the cytoplasm of cultured HeLa cancer cells.

Carbohydrates and Charges on Oligo(phenylenethynylenes): Towards the Design of Cancer Bullets.

Two new tetralkylammonium-OPEs, bearing one or two positively charged groups directly linked to the aromatic residues and two β-d-glucopyranose terminations, were synthesized. Their peculiar structural features, joining the biologically relevant sugar moieties, flat aromatic cores and positive charges, make these luminescent dyes soluble in aqueous media and able to strongly interact with DNA. As a result of UV/Vis spectral variations, DNA melting temperature measures, viscometric titrations and induced CD, we propose a partial insertion of the OPEs aromatic core into the helix, stabilized by glucose H-bonding with the groups accessible from the grooves.

Transient Sulfenic Acids in the Synthesis of Biologically Relevant Products.

Sulfenic acids as small molecules are too unstable to be isolated and their transient nature offers the possibility to involve them in concerted processes that lead to the obtainment of functional groups such as sulfoxides, sulfones, and disulfides. All these functions are present in a number of natural and synthetic drugs and can represent structural motives inducing biologically relevant properties. In this small review the generation and reactions of sulfenic acid bearing naturally occurring residues are described.