Circular spectropolarimetric sensing of chiral photosystems in decaying leaves

Circular polarization spectroscopy has proven to be an indispensable tool in photosynthesis research and (bio)-molecular research in general. Oxygenic photosystems typically display an asymmetric Cotton effect around the chlorophyll absorbance maximum with a signal $\leq 1 \%$. In vegetation, these signals are the direct result of the chirality of the supramolecular aggregates. The circular polarization is thus directly influenced by the composition and architecture of the photosynthetic macrodomains, and is thereby linked to photosynthetic functioning. Although ordinarily measured only on a molecular level, we have developed a new spectropolarimetric instrument, TreePol, that allows for both laboratory and in-the-field measurements. Through spectral multiplexing, TreePol is capable of fast measurements with a sensitivity of $\sim 1*10^{-4}$ and is therefore suitable of non-destructively probing the molecular architecture of whole plant leaves. We have measured the chiroptical evolution of \textit{Hedera helix} leaves for a period of 22 days. Spectrally resolved circular polarization measurements (450-900 nm) on whole leaves in transmission exhibit a strong decrease in the polarization signal over time after plucking, which we accredit to the deterioration of chiral macro-aggregates. Chlorophyll \textit{a} levels measured over the same period by means of UV-Vis absorption and fluorescence spectroscopy showed a much smaller decrease. With these results we are able to distinguish healthy from deteriorating leaves. Hereby we indicate the potency of circular polarization spectroscopy on whole and intact leaves as a nondestructive tool for structural and plant stress assessment. Additionally, we underline the establishment of circular polarization signals as remotely accessible means of detecting the presence of extraterrestrial life.Comment: 29 pages, 6 figure

Variability of protistan and bacterial communities in two Arctic fjords (Spitsbergen)

Krossfjorden and Kongsfjorden are Arctic fjords on the western side of Spitsbergen. These fjords share a common mouth to the open sea, and both are influenced by the input of sediment-rich glacial meltwater leading to decreased surface salinity, increased turbidity and decreased light penetration during summer. Earlier classical taxonomic studies had described the pelagic protistan composition of the Kongsfjorden during summer, revealing the dominance of flagellates of often unresolved taxonomic origin. Only little information existed on microbial eukaryote composition of the Krossfjorden as well as the bacterial composition of both fjords. The aim of the present study was to analyze and compare surface summertime protistan and bacterial communities in both fjords, using molecular approaches (16S and 18S rRNA DGGE, sequencing). Samples were collected three times a week from the central Kongsfjorden over a 1-month period. Additionally, 10 marine and 2 freshwater sites were sampled within a 1-week period in both Kongsfjorden and Krossfjorden. The central Kongsfjorden revealed a relatively stable protistan community over time with dinoflagellates, chlorophytes and small heterotrophs dominating. In contrast, the bacterial community varied over time and appeared to be correlated with the inflow of glacial meltwater. The Kongsfjorden and Krossfjorden were found to harbor distinctive bacterial and eukaryotic communities. We speculate that differences in glacial meltwater composition and fjord bathymetry affect the surface water properties and therefore the observed spatial variability in the community fingerprints.</p

Establishing PQ-ERA photoclick reactions with unprecedented efficiency by engineering of the nature of the phenanthraquinone triplet state

The light-induced photocycloaddition of 9,10-phenanthrenequinone (PQ) with electron-rich alkenes (ERA), known as the PQ-ERA reaction, is a highly attractive photoclick reaction characterized by high selectivity, external non-invasive control with light and biocompatibility. The conventionally used PQ compounds show limited reactivity, which hinders the overall efficiency of the PQ-ERA reaction. To address this issue, we present in this study a simple strategy to boost the reactivity of the PQ triplet state to further enhance the efficiency of the PQ-ERA reaction, enabled by thiophene substitution at the 3-position of the PQ scaffold. Our investigations show that this substitution pattern significantly increases the population of the reactive triplet state (3ππ*) during excitation of 3-thiophene PQs. This results in a superb photoreaction quantum yield (ΦP, up to 98%), high second order rate constants (k2, up to 1974 M−1 s−1), and notable oxygen tolerance for the PQ-ERA reaction system. These results have been supported by both experimental transient absorption data and theoretical calculations, providing further evidence for the effectiveness of this strategy, and offering fine prospects for fast and efficient photoclick transformations.</p

Excited-state electronic asymmetry prevents photoswitching in terthiophene compounds

The diarylethene moiety is one of the most extensively used switches in the field of molecular electronics. Here we report on spectroscopic and quantum chemical studies of two diarylethene-based compounds with a non-C3-symmetric triethynyl terthiophene core symmetrically substituted with RuCp*(dppe) or trimethylsilyl termini. The ethynyl linkers are strong IR markers that we use in time-resolved vibrational spectroscopic studies to get insight into the character and dynamics of the electronically excited states of these compounds on the picosecond to nanosecond time scale. In combination with electronic transient absorption studies and DFT calculations, our studies show that the conjugation of the non-C3-symmetric triethynyl terthiophene system in the excited state strongly affects one of the thiophene rings involved in the ring closure. As a result, cyclization of the otherwise photochromic 3,3″-dimethyl-2,2′:3′,2″-terthiophene core is inhibited. Instead, the photoexcited compounds undergo intersystem crossing to a long-lived triplet excited state from which they convert back to the ground state

A visible-light-driven molecular motor based on barbituric acid

We present a class of visible-light-driven molecular motors based on barbituric acid. Due to a serendipitous reactivity we observed during their synthesis, these motors possess a tertiary stereogenic centre on the upper half, characterised by a hydroxy group. Using a combination of femto- and nanosecond transient absorption spectroscopy, molecular dynamics simulations and low-temperature 1H NMR experiments we found that these motors operate similarly to push-pull second-generation overcrowded alkene-based molecular motors. Interestingly, the hydroxy group at the stereocentre enables a hydrogen bond with the carbonyl groups of the barbituric acid lower half, which drives a sub-picosecond excited-state isomerisation, as observed spectroscopically. Computational simulations predict an excited state “lasso” mechanism where the intramolecular hydrogen bond pulls the molecule towards the formation of the metastable state, with a high predicted quantum yield of isomerisation (68%) in gas phase.</p

How Landscape Ecology Informs Global Land-Change Science and Policy

Landscape ecology is a discipline that explicitly considers the influence of time and space on the environmental patterns we observe and the processes that create them. Although many of the topics studied in landscape ecology have public policy implications, three are of particular concern: climate change; land use–land cover change (LULCC); and a particular type of LULCC, urbanization. These processes are interrelated, because LULCC is driven by both human activities (e.g., agricultural expansion and urban sprawl) and climate change (e.g., desertification). Climate change, in turn, will affect the way humans use landscapes. Interactions among these drivers of ecosystem change can have destabilizing and accelerating feedback, with consequences for human societies from local to global scales. These challenges require landscape ecologists to engage policymakers and practitioners in seeking long-term solutions, informed by an understanding of opportunities to mitigate the impacts of anthropogenic drivers on ecosystems and adapt to new ecological realities

Phenylimino Indolinone:A Green-Light-Responsive T-Type Photoswitch Exhibiting Negative Photochromism

Imines are photoaddressable motifs useful in the development of new generations of molecular switches, but their operation with low-energy photons and control over isomer stability remain challenging. Based on a computational design, we developed phenylimino indolinone (PIO), a green-light-addressable T-type photoswitch showing negative photochromism. The isomerization behavior of this photoactuator of the iminothioindoxyl (ITI) class was studied using time-resolved spectroscopies on time scales from femtoseconds to the steady state and by quantum-chemical analyses. The understanding of the isomerization properties and substituent effects governing these photoswitches opens new avenues for the development of novel T-type visible-light-addressable photoactuators based on C=N bonds