Artificial Control of Cell Signaling Using a Photocleavable Cobalt(III)–Nitrosyl Complex

Abstract

Cells use gaseous molecules such as nitric oxide (NO) to transmit both intracellular and intercellular signals.In principle,the endogenous small molecules regulate physiological changes,b ut it is unclear howr andomly diffusive molecules trigger and discriminate signaling programs. Herein, it is shown that gasotransmitters use time-dependent dynamics to discriminate the endogenous and exogenous inputs.F or ar eal-time stimulation of cell signaling, we synthesized ap hoto-cleavable metal-nitrosyl complex, [Co III -(MDAP)(NO)(CH 3 CN)] 2+ (MDAP = N,N'-dimethyl-2,11diaza[3,3](2,6)pyridinophane), which can stably deliver and selectively release NO with fine temporal resolution in the cytosol, and used this to study the extracellular signal-regulated kinases (ERKs), revealing howc ells use both exogenous and endogenous NO to disentangle cellular responses.T his technique can be to understand how diverse cellular signaling networks are dynamically interconnected and also to control drug delivery systems.

Visible-to-NIR-Light Activated Release: From Small Molecules to Nanomaterials

“…Cho and co-workers recently synthesized a Co III -nitrosyl complex 356 ( Figure 56 ) that efficiently released NO upon white-light irradiation (λ irr = 385–740 nm; Φ r = 0.78) 1304 and was used in a real-time simulation of cell signaling to study extracellular signal-regulated kinases.…”