| Autor: |
Fosnacht KG; Department of Chemistry and Biochemistry, Materials Science Institute, Knight Campus for Accelerating Scientific Impact, Institute of Molecular Biology, University of Oregon, Eugene, Oregon 97403, United States., Cerda MM; Department of Chemistry and Biochemistry, Materials Science Institute, Knight Campus for Accelerating Scientific Impact, Institute of Molecular Biology, University of Oregon, Eugene, Oregon 97403, United States., Mullen EJ; Department of Chemistry and Biochemistry, Materials Science Institute, Knight Campus for Accelerating Scientific Impact, Institute of Molecular Biology, University of Oregon, Eugene, Oregon 97403, United States., Pigg HC; Department of Chemistry and Biochemistry, Materials Science Institute, Knight Campus for Accelerating Scientific Impact, Institute of Molecular Biology, University of Oregon, Eugene, Oregon 97403, United States., Pluth MD; Department of Chemistry and Biochemistry, Materials Science Institute, Knight Campus for Accelerating Scientific Impact, Institute of Molecular Biology, University of Oregon, Eugene, Oregon 97403, United States. |
| Abstrakt: |
Persulfides (RSSH) are important reactive sulfur species (RSS) that are intertwined with the biological functions of hydrogen sulfide (H 2 S). The direct study of persulfides is difficult, however, due to their both nucleophilic and electrophilic character, which leads to the generation of an equilibrium of different RSS. To investigate the effects of persulfides directly, especially in biological systems, persulfide donors are needed to generate persulfides in situ . Here, we report the synthesis of esterase-activated perthiocarbonate persulfide donors and investigate the effects of structural modifications on persulfide release. Although steric bulk of the ester did not significantly alter persulfide release kinetics, increased steric bulk of the thiol increased the persulfide release rate. In addition, we found that the steric bulk and identity of the thiol significantly impact persulfide persistence. Further mechanistic investigations into different competing reaction pathways from perthiocarbonates revealed that multiple RSS can be delivered ( i.e. , H 2 S, COS, or RSSH) depending on the persulfide donor structure and activator identity. |
