Transient receptor potential canonical (TRPC) channels TRPC3, TRPC6 and TRPC7 are able to sense the lipid messenger diacylglycerol (DAG). The DAG-sensing and lipid-gating processes in these ion channels are still unknown. To gain insights into the lipid-sensing principle, we generated a DAG photoswitch, OptoDArG, that enabled efficient control of TRPC3 by light. A structure-guided mutagenesis screen of the TRPC3 pore domain unveiled a single glycine residue behind the selectivity filter (G652) that is exposed to lipid through a subunit-joining fenestration. Exchange of G652 with larger residues altered the ability of TRPC3 to discriminate between different DAG molecules. Light-controlled activation-deactivation cycling of TRPC3 channels by an OptoDArG-mediated optical 'lipid clamp' identified pore domain fenestrations as pivotal elements of the channel´s lipid-sensing machinery. We provide evidence for a novel concept of lipid sensing by TRPC channels based on a lateral fenestration in the pore domain that accommodates lipid mediators to control gating.

A new photochromic ligand enables high precision control over native TRPC channels.

Natural and synthetic coumarin derivatives have gained increased attention in the design of functional polymers and polymer networks due to their unique optical, biological, and photochemical properties. This review provides a comprehensive overview over recent developments in macromolecular architecture and mainly covers examples from the literature published from 2004 to 2020. Along with a discussion on coumarin and its photochemical properties, we focus on polymers containing coumarin as a nonreactive moiety as well as polymer systems exploiting the dimerization and/or reversible nature of the [2πs + 2πs] cycloaddition reaction. Coumarin moieties undergo a reversible [2πs + 2πs] cycloaddition reaction upon irradiation with specific wavelengths in the UV region, which is applied to impart intrinsic healability, shape-memory, and reversible properties into polymers. In addition, coumarin chromophores are able to dimerize under the exposure to direct sunlight, which is a promising route for the synthesis and cross-linking of polymer systems under “green” and environment-friendly conditions. Along with the chemistry and design of coumarin functional polymers, we highlight various future application fields of coumarin containing polymers involving tissue engineering, drug delivery systems, soft robotics, or 4D printing applications.

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While latent catalysts are a well-established strategy for initiating and controlling the rate of polymerization reactions, their use in dynamic polymer networks is still in its infancy. The ideal latent catalyst should be thermally stable and release a highly active species in response to an external trigger. Here, we have synthesized a temperature resistant (> 200 °C) organic phosphate with a photolabile o-nitrobenzyl protecting group that can be cleaved by UV light. Introduced in a visible light curable thiol-click photopolymer, the sequence-dependent λ-orthogonality of the curing and cleavage enables an efficient network formation at 451 nm, without premature release of the catalyst. Once cured, irradiation at 372 nm spatiotemporally activates the phosphate, which catalyzes transesterifications at elevated temperature. The formed catalyst has no effect on the thermal stability of the polymeric network and allows the activation of bond exchange reactions in selected domains of printed 3D objects.