Electron-transfer cross-reactions between neutral molecules and their radical cations spanning a wide range of structural type and intrinsic reactivity have been analyzed using classical Marcus theory. The principal factor found to govern intrinsic reactivity is the inner-shell bond reorganization energy. The HOMO-LUMO overlap of alkyl groups on reacting molecules is generally sufficient to pro...

The radical anions of β-lactams, photogenerated in the presence of DABCO as an electron donor, undergo cycloreversion via N-C4 bond cleavage, back electron transfer and final C2-C3 bond cleavage, leading to olefins. The involved intermediates are 1,4-radical anions and 1,4-biradicals. The experimental observations are consistent with the results of DFT calculations.

Cellular energy metabolism is altered in sepsis as a consequence of dysfunction of mitochondrial electron transport and glycolytic pathways. The purpose of the present study was to determine whether sepsis is associated with compensatory increases in gene expression of electron transport chain and glycolytic pathway proteins or, alternatively, whether gene expression decreases in sepsis, contri...

Usually the rates for electron transfer (kET) decrease with increasing donor-acceptor distance, but Marcus theory predicts a regime in which kET is expected to increase when the transfer distance gets longer. Until recently, experimental evidence for such counter-intuitive behavior had been very limited, and consequently this effect is much less well-known than the Gaussian free energy dependen...

Condensed phase electron transfer problems are often simplified by making the Condon approximation: the approximation that the coupling connecting two charge-transfer diabatic states is a constant. Unfortunately, the Condon approximation does not predict the existence of conical intersections, which are ubiquitous in both gas-phase and condensed-phase photochemical dynamics. In this paper, we d...

Protonmotive force produced by the electron transport chain is harnessed by the rotary molecular nanomotor ATP synthase to generate ATP. In this issue of Cell, Adachi et al. (2007), in a dazzling display of technical sophistication, now disentangle the coupling between the mechanical force generated by rotation of the ATP synthase subunits and the chemical reactions that occur simultaneously at...

A novel method for the step-growth polymerization of diphenyldithienothiophene in the presence of diphenyliodonium salt by photoinduced electron transfer is described.

A carbon dot-based fluorescence turn-on sensor for hydrogen peroxide (H2O2) with a photo-induced electron transfer mechanism was developed. The sensor exhibits good selectivity, sensitivity, and rapid response to H2O2 with a detection limit of 84 nM. The sensor maintains excellent sensing performance over a wide pH range.

Ultrafast photoinduced electron transfer preceding energy equilibration still poses many experimental and conceptual challenges to the optimization of photoconversion since an atomic-scale description has so far been beyond reach. Here we combine femtosecond transient optical absorption spectroscopy with ultrafast X-ray emission spectroscopy and diffuse X-ray scattering at the SACLA facility to...