RESUMEN
Aerosol particles found in the atmosphere affect the climate and worsen air quality. To mitigate these adverse impacts, aerosol particle formation and aerosol chemistry in the atmosphere need to be better mapped out and understood. Currently, mass spectrometry is the single most important analytical technique in atmospheric chemistry and is used to track and identify compounds and processes. Large amounts of data are collected in each measurement of current time-of-flight and orbitrap mass spectrometers using modern rapid data acquisition practices. However, compound identification remains a major bottleneck during data analysis due to lacking reference libraries and analysis tools. Data-driven compound identification approaches could alleviate the problem, yet remain rare to non-existent in atmospheric science. In this perspective, the authors review the current state of data-driven compound identification with mass spectrometry in atmospheric science and discuss current challenges and possible future steps toward a digital era for atmospheric mass spectrometry.
RESUMEN
Products of hydrogen cyanide (HCN) reactivity are suspected to play important roles in astrochemistry and, possibly, the origin of life. The composition, chemical structure, and mechanistic details for formation of products from HCN's self-reactions have, however, proven elusive for decades. Here, we elucidate base-catalyzed reaction mechanisms for the formation of diaminomaleonitrile and polyimine in liquid HCN using ab initio molecular dynamics simulations. Both materials are proposed as key intermediates for driving further chemical evolution. The formation of these materials is predicted to proceed at similar rates, thereby offering an explanation of how HCN's self-reactions can diversify quickly under kinetic control. Knowledge of these reaction routes provides a basis for rationalizing subsequent reactivity in astrochemical environments such as on Saturn's moon Titan, in the subsurface of comets, in exoplanet atmospheres, and on the early Earth.
RESUMEN
Hydrogen cyanide (HCN) is known to react with complex organic materials and is a key reagent in the formation of various prebiotic building blocks, including amino acids and nucleobases. Here, we explore the possible first step in several such processes, the dimerization of HCN into iminoacetonitrile. Our study combines steered ab initio molecular dynamics and quantum chemistry to evaluate the kinetics and thermodynamics of base-catalyzed dimerization of HCN in the liquid state. Simulations predict a formation mechanism of iminoacetonitrile that is consistent with experimentally observed time scales for HCN polymerization, suggesting that HCN dimerization may be the rate-determining step in the assembly of more complex reaction products. The predicted kinetics permits for iminoacetonitrile formation in a host of astrochemical environments, including on the early Earth, on periodically heated subsurfaces of comets, and following heating events on colder bodies, such as Saturn's moon Titan.
RESUMEN
From a cohort of 1836 Swedish patients infected with ESBL-producing Enterobacteriaceae (EPE) during 2004-2014, 513 patients with recurrent EPE infection were identified. Only in 14 of the 513 patients was a change of species (ESBL-E. coli to ESBL-K. pneumoniae or vice versa) found between the index and subsequent infection. Eleven sequential urine isolates from 5 of the 14 patients were available for further analysis of possible transfer of ESBL-carrying plasmids. The plasmid content was studied using optical DNA mapping (ODM), PCR-based replicon typing, and ESBL gene sequencing. ODM allowed us to directly compare whole plasmids between isolates and found similar ESBL-carrying plasmids in 3 out of the 5 patients. The ODM results and the rarity in shift of species between ESBL-E. coli and ESBL-K. pneumoniae imply that in recurrent EPE infections interspecies plasmid transfer is uncommon.
