Water heavily fractionated as it ascends on Mars as revealed by ExoMars/NOMAD.

Isotopic ratios and, in particular, the water D/H ratio are powerful tracers of the evolution and transport of water on Mars. From measurements performed with ExoMars/NOMAD, we observe marked and rapid variability of the D/H along altitude on Mars and across the whole planet. The observations (from April 2018 to April 2019) sample a broad range of events on Mars, including a global dust storm, the evolution of water released from the southern polar cap during southern summer, the equinox phases, and a short but intense regional dust storm. In three instances, we observe water at very high altitudes (>80 km), the prime region where water is photodissociated and starts its escape to space. Rayleigh distillation appears the be the driving force affecting the D/H in many cases, yet in some instances, the exchange of water reservoirs with distinctive D/H could be responsible.

Transient HCl in the atmosphere of Mars.

A major quest in Mars' exploration has been the hunt for atmospheric gases, potentially unveiling ongoing activity of geophysical or biological origin. Here, we report the first detection of a halogen gas, HCl, which could, in theory, originate from contemporary volcanic degassing or chlorine released from gas-solid reactions. Our detections made at ~3.2 to 3.8 µm with the Atmospheric Chemistry Suite and confirmed with Nadir and Occultation for Mars Discovery instruments onboard the ExoMars Trace Gas Orbiter, reveal widely distributed HCl in the 1- to 4-ppbv range, 20 times greater than previously reported upper limits. HCl increased during the 2018 global dust storm and declined soon after its end, pointing to the exchange between the dust and the atmosphere. Understanding the origin and variability of HCl shall constitute a major advance in our appraisal of martian geo- and photochemistry.

Discovery and SAR Studies of Orally Active Somatostatin Receptor Subtype-2 (SSTR2) Agonists for the Treatment of Acromegaly.

Acromegaly is a disease caused by the oversecretion of growth hormone. It is currently treated by intravenous injection with cyclic peptide drugs that activate somatostatin receptor subtype 2 (SSTR2). Here, novel nonpeptidic, small-molecule, and orally active SSTR2 agonists were identified from a hit compound (13). Pharmacophore studies enabled scaffold hopping to obtain a unique 3,4,5-trisubstituted pyridine motif. Further optimization conferred potent SSTR2 agonistic activity and metabolic stability. Several compounds were evaluated and these showed good oral pharmacokinetic profiles in rats, and one representative compound (25) showed highly potent inhibition of growth hormone secretion induced by growth hormone-releasing hormone in rats. Based on these results, 25 was identified as a promising lead for further optimization. A structure-activity relationship (SAR) study and the metabolic stability data for this compound are also described.

Catalyst-controlled regiodivergent ring-opening C(sp3)-Si bond-forming reactions of 2-arylaziridines with silylborane enabled by synergistic palladium/copper dual catalysis.

A catalyst-controlled regiodivergent and stereospecific ring-opening C(sp3)-Si cross-coupling of 2-arylaziridines with silylborane enabled by synergistic Pd/Cu dual catalysis has been developed. Just by selecting a suitable combination of catalysts, the regioselectivity of the coupling is completely switched to efficiently provide two regioisomers of ß-silylamines (i.e., ß-silyl-α-phenethylamines and ß-silyl-ß-phenethylamines) in good to high yields. Furthermore, a slight modification of the reaction conditions caused a drastic change in reaction pathways, leading to a tandem reaction to produce another regioisomer of silylamine (i.e., α-silyl-ß-phenethylamines) in an efficient and selective manner.

No detection of methane on Mars from early ExoMars Trace Gas Orbiter observations.

The detection of methane on Mars has been interpreted as indicating that geochemical or biotic activities could persist on Mars today1. A number of different measurements of methane show evidence of transient, locally elevated methane concentrations and seasonal variations in background methane concentrations2-5. These measurements, however, are difficult to reconcile with our current understanding of the chemistry and physics of the Martian atmosphere6,7, which-given methane's lifetime of several centuries-predicts an even, well mixed distribution of methane1,6,8. Here we report highly sensitive measurements of the atmosphere of Mars in an attempt to detect methane, using the ACS and NOMAD instruments onboard the ESA-Roscosmos ExoMars Trace Gas Orbiter from April to August 2018. We did not detect any methane over a range of latitudes in both hemispheres, obtaining an upper limit for methane of about 0.05 parts per billion by volume, which is 10 to 100 times lower than previously reported positive detections2,4. We suggest that reconciliation between the present findings and the background methane concentrations found in the Gale crater4 would require an unknown process that can rapidly remove or sequester methane from the lower atmosphere before it spreads globally.

Martian dust storm impact on atmospheric H2O and D/H observed by ExoMars Trace Gas Orbiter.

Global dust storms on Mars are rare1,2 but can affect the Martian atmosphere for several months. They can cause changes in atmospheric dynamics and inflation of the atmosphere3, primarily owing to solar heating of the dust3. In turn, changes in atmospheric dynamics can affect the distribution of atmospheric water vapour, with potential implications for the atmospheric photochemistry and climate on Mars4. Recent observations of the water vapour abundance in the Martian atmosphere during dust storm conditions revealed a high-altitude increase in atmospheric water vapour that was more pronounced at high northern latitudes5,6, as well as a decrease in the water column at low latitudes7,8. Here we present concurrent, high-resolution measurements of dust, water and semiheavy water (HDO) at the onset of a global dust storm, obtained by the NOMAD and ACS instruments onboard the ExoMars Trace Gas Orbiter. We report the vertical distribution of the HDO/H2O ratio (D/H) from the planetary boundary layer up to an altitude of 80 kilometres. Our findings suggest that before the onset of the dust storm, HDO abundances were reduced to levels below detectability at altitudes above 40 kilometres. This decrease in HDO coincided with the presence of water-ice clouds. During the storm, an increase in the abundance of H2O and HDO was observed at altitudes between 40 and 80 kilometres. We propose that these increased abundances may be the result of warmer temperatures during the dust storm causing stronger atmospheric circulation and preventing ice cloud formation, which may confine water vapour to lower altitudes through gravitational fall and subsequent sublimation of ice crystals3. The observed changes in H2O and HDO abundance occurred within a few days during the development of the dust storm, suggesting a fast impact of dust storms on the Martian atmosphere.

Publisher Correction: No detection of methane on Mars from early ExoMars Trace Gas Orbiter observations.

The surname of author Cathy Quantin-Nataf was misspelled 'Quantin-Nata', authors Ehouarn Millour and Roland Young were missing from the ACS and NOMAD Science Teams list, and minor changes have been made to the author and affiliation lists; see accompanying Amendment. These errors have been corrected online.

Publisher Correction: Martian dust storm impact on atmospheric H2O and D/H observed by ExoMars Trace Gas Orbiter.

The surname of author Cathy Quantin-Nataf was misspelled 'Quantin-Nata' , authors Ehouarn Millour and Roland Young were missing from the ACS Science Team list, and minor changes have been made to the author and affiliation lists; see accompanying Amendment. These errors have been corrected online.

Phosphine oxide-catalyzed enantioselective intramolecular aldol reaction via regioselective enolization of unsymmetrical diketones with tetrachlorosilane.

The phosphine oxide-catalyzed asymmetric intramolecular aldol reactions of diketones were investigated. The combination of tetrachlorosilane and a chiral phosphine oxide catalyst promoted the acetyl-selective enolization of diketones, and the subsequent intramolecular aldol reaction occurred in an enantioselective manner. The introduction of two trimethylsilyl groups at the 4- and 4'-positions in BINAP dioxide catalyst improved the enantioselectivity. This reaction provides an effective synthetic method to access ß-tertiary-hydroxy cyclohexanones in high yields and with high enantioselectivity.

Trichlorosilyl triflate-mediated enantioselective directed cross-aldol reaction between ketones using a chiral phosphine oxide as an organocatalyst.

Trichlorosilyl triflate-promoted directed cross-aldol reaction between ketones in the presence of a chiral phosphine oxide as an organocatalyst is described. This is the first enantioselective cross-aldol reaction between simple ketones with good enantioselectivity.