Photochemical Nitric Oxide Release from S‐Nitrosothiol‐Functionalized Chitosan

Abstract

AbstractS‐nitrosothiols (RSNOs) are nitric oxide (NO) donor molecules with potential biomedical applications since they mimic NO biological functions, such as vasodilation and inflammatory process regulation. In this work, chitosan (CS), a natural biopolymer widely used as a biomaterial, is functionalized with thioglycolic acid (TGA) or mercaptosuccinic acid (MSA) in reactions mediated by a carbodiimide, yielding CS with thiol contents of 88 µmol g–1 (CS‐TGA) and 126 µmol g–1 (CS‐MSA). The subsequent S‐nitrosation of CS‐TGA and CS‐MSA generates the corresponding S‐nitroso derivatives, CS‐TGA(SNO) and CS‐MSA(SNO). The UV–Vis spectral changes associated with the S‐NO bond cleavage of CS‐TGA(SNO) and CS‐MSA(SNO), monitored in solution over 18 days of storage in a common refrigerator, reveal that these S‐nitroso CS derivatives display enhanced thermal stability in the dark, with half‐life values of 36.1 for CS‐TGA(SNO) and 16.1 days for CS‐MSA(SNO). Conversely, CS‐TGA(SNO) and CS‐MSA(SNO) can release NO photochemically on‐demand under visible light irradiation in a first‐order process triggered by photon absorption that leads to a half‐life of 33 min for both S‐nitroso CS. These results show that CS‐TGA(SNO) and CS‐MSA(SNO) may emerge as new CS‐based biomaterials for providing light‐triggered local NO release in biomedical applications.