51343-11-4Relevant articles and documents
Reversible Photoswitchable Inhibitors Generate Ultrasensitivity in Out-of-Equilibrium Enzymatic Reactions
Teders, Michael,Pogodaev, Aleksandr A.,Bojanov, Glenn,Huck, Wilhelm T. S.
supporting information, p. 5709 - 5716 (2021/05/07)
Ultrasensitivity is a ubiquitous emergent property of biochemical reaction networks. The design and construction of synthetic reaction networks exhibiting ultrasensitivity has been challenging, but would greatly expand the potential properties of life-like materials. Herein, we exploit a general and modular strategy to reversibly regulate the activity of enzymes using light and show how ultrasensitivity arises in simple out-of-equilibrium enzymatic systems upon incorporation of reversible photoswitchable inhibitors (PIs). Utilizing a chromophore/warhead strategy, PIs of the protease α-chymotrypsin were synthesized, which led to the discovery of inhibitors with large differences in inhibition constants (Ki) for the different photoisomers. A microfluidic flow setup was used to study enzymatic reactions under out-of-equilibrium conditions by continuous addition and removal of reagents. Upon irradiation of the continuously stirred tank reactor with different light pulse sequences, i.e., varying the pulse duration or frequency of UV and blue light irradiation, reversible switching between photoisomers resulted in ultrasensitive responses in enzymatic activity as well as frequency filtering of input signals. This general and modular strategy enables reversible and tunable control over the kinetic rates of individual enzyme-catalyzed reactions and makes a programmable linkage of enzymes to a wide range of network topologies feasible.
Rh(iii)-Catalyzed regioselective mono- and di-iodination of azobenzenes using alkyl iodide
Li, Jixing,Cong, Wenxia,Gao, Zeng,Zhang, Jinlong,Yang, Huameng,Jiang, Gaoxi
, p. 3479 - 3486 (2018/05/23)
A new approach for highly regioselective iodination of azobenzenes with alkyl iodide as the iodinating reagent enabled by Rh-catalyzed oxidative C-H activation has been developed. By changing the oxidant, various mono- and di-iodinated azobenzenes were smoothly obtained in moderate to excellent yields, respectively. The preliminary mechanistic study reveals that the reaction process might undergo electrophilic substitution of the directed ortho metalated five-membered rhodacycle compound by an iodine cationic species generated in situ from alkyl iodide and oxidant.
Cu/Pd cooperatively catalyzed tandem C-N and C-P bond formation: Access to phosphorated 2: H -indazoles
Wei, Weiwei,Li, Xuanyi,Gu, Meng,Yao, Hequan,Lin, Aijun
supporting information, p. 8458 - 8462 (2017/10/19)
A novel Cu/Pd cooperatively catalyzed tandem C-N and C-P bond formation reaction between 2-alkynyl azobenzenes and P(O)H compounds has been developed. This reaction provides a convenient approach for the synthesis of various phosphorated 2H-indazoles in m
