Influence of constitution and charge on radical pairing interactions in tris-radical tricationic complexes

The results of a systematic investigation of trisradical tricationic complexes formed between cyclobis(paraquat-p-phenylene) bisradical dicationic (CBPQT2(•+)) rings and a series of 18 dumbbells, containing centrally located 4,4′-bipyridinium radical cationic (BIPY•+) units within oligomethylene chains terminated for the most part by charged 3,5-dimethylpyridinium (PY+) and/or neutral 3,5-dimethylphenyl (PH) groups, are reported. The complexes were obtained by treating equimolar amounts of the CBPQT4+ ring and the dumbbells containing BIPY2+ units with zinc dust in acetonitrile solutions. Whereas UV–Vis–NIR spectra revealed absorption bands centered on ca. 1100 nm with quite different intensities for the 1:1 complexes depending on the constitutions and charges on the dumbbells, titration experiments showed that the association constants (Ka) for complex formation vary over a wide range, from 800 M–1 for the weakest to 180 000 M–1 for the strongest. While Coulombic repulsions emanating from PY+ groups located at the ends of some of the dumbbells undoubtedly contribute to the destabilization of the trisradical tricationic complexes, solid-state superstructures support the contention that those dumbbells with neutral PH groups at the ends of flexible and appropriately constituted links to the BIPY•+ units stand to gain some additional stabilization from C–H···π interactions between the CBPQT2(•+) rings and the PH termini on the dumbbells. The findings reported in this Article demonstrate how structural changes implemented remotely from the BIPY•+ units influence their non-covalent bonding interactions with CBPQT2(•+) rings. Different secondary effects (Coulombic repulsions versus C–H···π interactions) are uncovered, and their contributions to both binding strengths associated with trisradical interactions and the kinetics of associations and dissociations are discussed at some length, supported by extensive DFT calculations at the M06-D3 level. A fundamental understanding of molecular recognition in radical complexes has relevance when it comes to the design and synthesis of non-equilibrium systems

Life Beyond the Solar System: Space Weather and Its Impact on Habitable Worlds

The search of life in the Universe is a fundamental problem of astrobiology and a major priority for NASA. A key area of major progress since the NASA Astrobiology Strategy 2015 (NAS15) has been a shift from the exoplanet discovery phase to a phase of characterization and modeling of the physics and chemistry of exoplanetary atmospheres, and the development of observational strategies for the search for life in the Universe by combining expertise from four NASA science disciplines including heliophysics, astrophysics, planetary science and Earth science. The NASA Nexus for Exoplanetary System Science (NExSS) has provided an efficient environment for such interdisciplinary studies. Solar flares, coronal mass ejections and solar energetic particles produce disturbances in interplanetary space collectively referred to as space weather, which interacts with the Earth upper atmosphere and causes dramatic impact on space and ground-based technological systems. Exoplanets within close in habitable zones around M dwarfs and other active stars are exposed to extreme ionizing radiation fluxes, thus making exoplanetary space weather (ESW) effects a crucial factor of habitability. In this paper, we describe the recent developments and provide recommendations in this interdisciplinary effort with the focus on the impacts of ESW on habitability, and the prospects for future progress in searching for signs of life in the Universe as the outcome of the NExSS workshop held in Nov 29 - Dec 2, 2016, New Orleans, LA. This is one of five Life Beyond the Solar System white papers submitted by NExSS to the National Academy of Sciences in support of the Astrobiology Science Strategy for the Search for Life in the Universe.Comment: 5 pages, the white paper was submitted to the National Academy of Sciences in support of the Astrobiology Science Strategy for the Search for Life in the Univers

Controls on gut phosphatisation : the trilobites from the Weeks Formation Lagerstätte (Cambrian; Utah)

Despite being internal organs, digestive structures are frequently preserved in Cambrian Lagerstätten. However, the reasons for their fossilisation and their biological implications remain to be thoroughly explored. This is particularly true with arthropods--typically the most diverse fossilised organisms in Cambrian ecosystems--where digestive structures represent an as-yet underexploited alternative to appendage morphology for inferences on their biology. Here we describe the phosphatised digestive structures of three trilobite species from the Cambrian Weeks Formation Lagerstätte (Utah). Their exquisite, three-dimensional preservation reveals unique details on trilobite internal anatomy, such as the position of the mouth and the absence of a differentiated crop. In addition, the presence of paired pygidial organs of an unknown function is reported for the first time. This exceptional material enables exploration of the relationships between gut phosphatisation and the biology of organisms. Indeed, soft-tissue preservation is unusual in these fossils as it is restricted to the digestive structures, which indicates that the gut played a central role in its own phosphatisation. We hypothesize that the gut provided a microenvironment where special conditions could develop and harboured a source of phosphorus. The fact that gut phosphatization has almost exclusively been observed in arthropods could be explained by their uncommon ability to store ions (including phosphorous) in their digestive tissues. However, in some specimens from the Weeks Formation, the phosphatisation extends to the entire digestive system, suggesting that trilobites might have had some biological particularities not observed in modern arthropods. We speculate that one of them might have been an increased capacity for ion storage in the gut tissues, related to the moulting of their heavily-mineralised carapace