Light-Mediated Sulfenic Acid Generation from Photocaged Cysteine Sulfoxide

Abstract

S-Sulfenylation is a post-translational modification with crucial role in regulating protein function. However, its analysis has remained challenging due to the lack of facile sulfenic acid models. We report the first photocaged cysteine sulfenic acid with efficient photodeprotection, and demonstrate its utility by generating sulfenic acid in a thiol peroxidase after illumination in vitro. These caged sulfoxides should be promising for site-specific incorporation of Cys sulfenic acid in living cells via genetic code expansion.

Bottom‐Up Construction of Porous Organic Frameworks with Built‐In TEMPO as a Cathode for Lithium–Sulfur Batteries

“…[24] After loading of sulfur,t he characteristic FT-IR vibrationo ft he nitroxyl radicals at 1363 cm À1 disappeared in both POF-S composites. [25] These results suggest that covalent bonds are formed between the TEMPO radicals and elemental sulfur. [25] These results suggest that covalent bonds are formed between the TEMPO radicals and elemental sulfur.…”

“…Meanwhile, new bands, assigned to the NÀSb ond, appeared at around7 64 and 1155 cm À1 for both polymers (Figure S2 d, f). [25] These results suggest that covalent bonds are formed between the TEMPO radicals and elemental sulfur.…”

A Fuel-Driven Chemical Reaction Network Based on Conjugate Addition and Elimination Chemistry

“…Sulfenic acids are inherently unstable and are prone to disproportionate to thiols and sulfinic acids (Figure 3b). [25][26][27] Although the final reaction did not yield the starting point maleimide and thiol, it does afford the adduct of maleimide 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 and thiol. This result suggests that in principle it is possible to achieve the proposed chemical reaction network.…”

A Fuel‐Driven Chemical Reaction Network Based on Conjugate Addition and Elimination Chemistry

“…The latter may have formed from the disproportionation of sulfenic acid 6 as the another product of elimination (Figure a and 3b). Sulfenic acids are inherently unstable and are prone to disproportionate to thiols and sulfinic acids (Figure b) . Although the final reaction did not yield the starting point maleimide and thiol, it does afford the adduct of maleimide and thiol.…”

“…Sulfenic acids are inherently unstable and are prone to disproportionate to thiols and sulfinic acids (Figure 3b). [25][26][27] Although the final reaction did not yield the starting point maleimide and thiol, it does afford the adduct of maleimide…”