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New opportunities for molecular photoswitches as wearable ultraviolet radiation dosimeters

Australians have the highest incidence of melanoma globally, despite increasing awareness of the risks of excessive sun exposure. Although excess ultraviolet radiation (UVR) can cause irreparable cell damage and lead to cancer, some exposure is vital to maintain bodily processes such as vitamin D production. For an individual, finding the balance between healthy exposure and skin damage is largely guesswork. The ability to provide a simple, individualised indicator of cumulative UVR dosage could be transformative in preventing skin cancer. This review will provide a brief overview of the variety of UVR sensor technologies and explain the important role of colourimetric dosimeters. The chemistry behind some recent examples of colourimetric dosimeters will be discussed, identifying that molecular photoswitches are ideal candidates to enable this technology. We discuss the chemical mechanisms of photoswitches and how to modify their chemical structure to optimise their properties for use as dosimeters. Through this lens, diarylethenes have been identified as prime dosimeter candidates, owing to their sensitivity, stability, adaptability and the variety of visually striking colours possible. Finally, some specific challenges are identified in the design and fabrication of personalised colourimetric dosimeters that can equitably meet the requirements of all users in our community.

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Synthesis and stability studies of constrained peptide–antimony bicycles

Peptide therapeutics play an increasingly important role in modern drug discovery. Improving the pharmacokinetic profile of bioactive peptides has been effectively achieved with chemical modifications, especially macrocyclisation reactions. Consequently, there is a great demand for highly constrained compounds such as bicyclic peptides. In our previous research, we introduced peptide–bismuth bicycles and peptide–arsenic bicycles as new classes of constrained peptides. In this work, we extend our peptide bicyclisation strategy towards antimony. Similar to arsenic and bismuth, antimony(III) selectively binds to three cysteine residues in peptides, enabling the in situ formation of stable bicycles. The bicyclisation reaction occurs instantaneously under biocompatible conditions at physiological pH. Antimony–peptide bicycles remain largely intact in the presence of the common metal chelator ethylenediaminetetraacetic acid (EDTA) and the main endogenous thiol competitor glutathione (GSH). Furthermore, when challenged with bismuth(III) from water-soluble gastrodenol (bismuth tripotassium dicitrate), antimony–peptide bicycles convert into the corresponding bismuth–peptide bicycle, highlighting the superior thiophilicity of bismuth over other pnictogens. Our study further expands the toolbox of peptide multicyclisation with main group elements previously underexplored in chemical biology.

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