Chiral monoterpenes reveal forest emission mechanisms and drought responses

Monoterpenes exist in mirror image forms called enantiomers, but their individual formation pathways in plants and ecological functions are poorly understood, as enantiomers are usually measured and modelled together. Here we present enantiomerically separated atmospheric monoterpene and isoprene data from an enclosed tropical rainforest ecosystem without photo-chemistry during a four-month controlled drought and rewetting experiment. Surprisingly, the enantiomers showed distinct diel emission peaks, which responded differently to progressive drying. Isotopic labelling established that vegetation emitted (-)-α-pinene mainly de novo while (+)-α-pinene was emitted from storage pools. As drought stress increased, (-)-α-pinene emis-sions shifted to storage pools, which are released later in the day, favouring cloud formation. The α-pinene enantiomers each correlated better with other monoterpenes than with each other, indicating different enzymatic controls. These results show that enantiomeric distribution is key to understanding the processes driving monoterpene emission from ecosystems and to predict-ing atmospheric feedbacks in response to climate change.

UV-photochemistry of the biologically relevant thiol group and the disulfide bond: Evolution of early photoproducts from picosecond X-ray absorption spectroscopy at the sulfur K-Edge

We report on the UV-induced photochemistry of the biologically relevant sulfur-containing thiol group and the disulfide bond in solution using picosecond X-ray absorption spectroscopy at the sulfur K-edge. This study provides element-specific insight into the 267-nm induced photo-chemistry of two model compounds, an aromatic thiol and an aliphatic disulfide. Our transient spectra point to two primary and several secondary photoproducts, and our analysis may aid in understanding UV damage in proteins.

The (photo)chemistry of Stenhouse photoswitches: guiding principles and system design

Stenhouse switches are a novel class of photoswitches with great potential for visible-light-controlled applications.