Doubly and Triply Charged Species Formed from Chlorobenzene Reveal Unusual C-Cl Multiple Bonding
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Authors: Fantuzzi, Felipe; Rudek, Benedikt; Wolff, Wania; Chaer Nascimento, Marco Antonio
Abstract
In free-radical halogenation of aromatics, singly charged ions are usually formed as intermediates. These stable species can be easily observed by time-of-flight mass spectrometry (TOF-MS). Here we used electron and proton beams to ionize chlorobenzene (C6H5Cl) and investigate the ions stability by TOF-MS. Additionally to the singly charged parent ion and its fragments, we find a significant yield of doubly and triply charged parent ions not previously reported. In order to characterize these species, we used high-level theoretical methods based on density functional theory (DFT), coupled-cluster (CC), and generalized valence bond (GVB) to calculate the structure, relative stabilities, and bonding of these dications and trications. The most stable isomers exhibit unusual carbon-chlorine multiple bonding: a terminal C=Cl double bond in a formyl-like CHCl moiety (1, r(C-Cl) = 1.621 angstrom) and a ketene-like C=C=Cl cumulated species (2, r(C-Cl) = 1.542 angstrom). The calculations suggest that an excited state of 2 has a nitrile-like CEF Cl triple bond structure.
Stimulation of cyclic electron flow around photosystem I upon a sudden transition from low to high light in two angiosperms Arabidopsis thaliana and Bletilla striata
PLANT SCIENCE
Authors: Yang, Ying-Jie; Ding, Xiao-Xi; Huang, Wei
Abstract
In angiosperms, cyclic electron flow (CEF) around photosystem I (PSI) is more important for photoprotection under fluctuating light than under constant light. However, the underlying mechanism is not well known. In the present study, we measured the CEF activity, P700 redox state and electrochromic shift signal upon a sudden transition from low to high light in wild-type plants of Arabidopsis thaliana and Bletilla striata (Orchidaceae). Within the first 20 s after transition from low to high light, P700 was highly reduced in both species, which was accompanied with a sufficient proton gradient (Delta pH) across the thylakoid membranes. Meanwhile, the level of CEF activation was elevated. After transition from low to high light for 60 s, the plants generated an optimal Delta pH. Under such condition, PSI was highly oxidized and the level of CEF activation decreased to the steady state. Furthermore, the CEF activation was positively correlated to the P700 reduction ratio. These results indicated that upon a sudden transition from low to high light, the insufficient Delta pH led to the over-reduction of PSI electron carriers, which in turn stimulated the CEF around PSI. This transient stimulation of CEF not only favored the rapid Delta pH formation but also accepted electrons from PSI, thus protecting PSI at donor and acceptor sides. These findings provide new insights into the important role of CEF in regulation of photosynthesis under fluctuating light.