UV solar irradiance in observations and the NRLSSI and SATIRE-S models

Total solar irradiance and UV spectral solar irradiance have been monitored since 1978 through a succession of space missions. This is accompanied by the development of models aimed at replicating solar irradiance by relating the variability to solar magnetic activity. The NRLSSI and SATIRE-S models provide the most comprehensive reconstructions of total and spectral solar irradiance over the period of satellite observation currently available. There is persistent controversy between the various measurements and models in terms of the wavelength dependence of the variation over the solar cycle, with repercussions on our understanding of the influence of UV solar irradiance variability on the stratosphere. We review the measurement and modelling of UV solar irradiance variability over the period of satellite observation. The SATIRE-S reconstruction is consistent with spectral solar irradiance observations where they are reliable. It is also supported by an independent, empirical reconstruction of UV spectral solar irradiance based on UARS/SUSIM measurements from an earlier study. The weaker solar cycle variability produced by NRLSSI between 300 and 400 nm is not evident in any available record. We show that although the method employed to construct NRLSSI is principally sound, reconstructed solar cycle variability is detrimentally affected by the uncertainty in the SSI observations it draws upon in the derivation. Based on our findings, we recommend, when choosing between the two models, the use of SATIRE-S for climate studies

Magnesiate addition/ring-expansion strategy to access the 6-7-6 tricyclic core of hetisine-type C20-diterpenoid alkaloids

A synthetic strategy to access the fused 6–7–6 tricyclic core of hetisine-type C20-diterpenoid alkaloids is reported. This strategy employs a Diels–Alder cycloaddition to assemble a fused bicyclic anhydride intermediate, which is elaborated to a vinyl lactone-acetal bearing an aromatic ring in five steps. Aromatic iodination is followed by magnesium–halogen exchange with a trialkyl magnesiate species, which undergoes intramolecular cyclization. Subsequent oxidation provides the desired 6–7–6 tricyclic diketoaldehyde, with carbonyl groups at all three positions for eventual C–N bond formation and subsequent elaboration

Bicyclic Boronate β-Lactamase Inhibitors: The Present Hope against Deadly Bacterial Pathogens

The use of β-lactamase inhibitors in combination with β-lactam antibiotics is an emerging area in drug discovery. This strategy allows the restoration of the therapeutic efficacy of these antibiotics in clinical use against multiresistant bacteria. These pathogens are drug resistant because they express β-lactamase enzymes, which prevent the antibiotic therapeutic action by catalyzing the hydrolysis of the β-lactam ring. These enzymes are quite diverse in both their structural architecture and hydrolytic capability, as well as in the mechanism of action. The ever-increasing emergence of pathogens that are capable of coproducing different types of β-lactamases has triggered the search for ultrabroad-spectrum inhibitors capable of deactivating both serine- and metallo-β-lactamases. A recent breakthrough in this long-pursued and unmet need is the discovery of bicyclic boronate inhibitors, specifically taniborbactam, VNRX-7145, and QPX7728, which are currently under clinical development in combination with cefepime, ceftibuten, and QPX2014, respectively. The present article highlights the therapeutic potential of these inhibitors and their spectrum of efficacy is compared with those of other β-lactam/β-lactamase inhibitor combinations recently approved by the food and drug administration. The molecular basis of the ultrabroad-spectrum of activity of boron-based inhibitors is also discussed, on the basis of the available crystal structures and the results of computational studiesinancial support from the Spanish Ministry of Economy and Competiveness (SAF2016-75638-R, PID2019-105512RB-I00), the Xunta de Galicia [ED431B 2018/04 and Centro singular de investigación de Galicia accreditation 2019–2022 (ED431G 2019/03)], and the European Regional Development Fund (ERDF) is gratefully acknowledgedS

Conversion of Aniline to Azobenzene at Functionalized Carbon Nanotubes: A Possible Case of a Nanodimensional Reaction

Aniline is oxidized to nitrosobenzene as the initial product, which undergoes further oxidation to nitrobenzene. The nitrosobenzene formation is catalyzed by functionalized multiwalled carbon nanotubes (CNT) followed by a coupling reaction between nitrosobenzene and aniline to produce azobenzene. This coupling requires close proximity of the reactants. It proceeds rapidly resulting in the UV-VIS absorption spectrum showing maxima at 327 nm and 425 nm. The nitrosobenzene yield in the presence of CNTs is controlled by the amount present in the medium. As the reaction is not catalyzed by unfunctionalized CNTs or graphitic particles, the uniqueness of the functionalized multiwalled CNTs in this catalysis suggests a nanodimensional reaction pathway

N-Heterocyclic carbene acyl anion organocatalysis by ball-milling

The ability to conduct N‐heterocyclic carbene‐catalysed acyl anion chemistry under ball‐milling conditions is reported for the first time. This process has been exemplified through applications to intermolecular‐benzoin, intramolecular‐benzoin, intermolecular‐Stetter and intramolecular‐Stetter reactions including asymmetric examples and demonstrates that this mode of mechanistically complex organocatalytic reaction can operate under solvent‐minimised conditions

One-pot synthesis of styrene derivatives from allyl silanes via b(c6f5)3-catalyzed isomerization-Hiyama coupling

Herein, we report a one-pot synthesis of styrene derivatives via a novel B(C6F5)3-catalyzed E-selective isomerization of readily accessible allyl silanes and subsequent Hiyama coupling of the versatile alkenyl silane intermediates. This one-pot, two-step approach enables access to a broad range of styrene derivatives, including those containing Lewis basic functional groups, that cannot be accessed via the previously developed B(C6F5)3-catalyzed isomerization of allyl benzenes

Lacustrine leaf wax hydrogen isotopes indicate strong regional climate feedbacks in Beringia since the last ice age

The Late-Quaternary climate of Beringia remains unresolved despite the region\u27s role in modulating glacial-interglacial climate and as the likely conduit for human dispersal into the Americas. Here, we investigate Beringian temperature change using an ~32,000-year lacustrine record of leaf wax hydrogen isotope ratios (δ2Hwax) from Arctic Alaska. Based on Monte Carlo iterations accounting for multiple sources of uncertainty, the reconstructed summertime temperatures were ~3 oC colder (range: -8 to +3 oC) during the Last Glacial Maximum (LGM; 21-25 ka) than the pre-industrial era (PI; 2-0.1 ka). This ice-age summer cooling is substantially smaller than in other parts of the Arctic, reflecting altered atmospheric circulation and increased continentality which weakened glacial cooling in the region. Deglacial warming was punctuated by abrupt events that are largely synchronous with events seen in Greenland ice cores that originate in the North Atlantic but which are also controlled locally, such as by the opening of the Bering Strait between 13.4 and 11 ka. Our reconstruction, together with climate modeling experiments, indicates that Beringia responds more strongly to North Atlantic freshwater forcing under modern-day, open-Bering Strait conditions than under glacial conditions. Furthermore, a 2 oC increase (Monte Carlo range: -1 to +5 oC) over the anthropogenic era reverses a 6 oC decline (Monte Carlo range: -10 to 0 oC) through the Holocene, indicating that recent warming in Arctic Alaska has not surpassed peak Holocene summer warmth

Bostonia: The Boston University Alumni Magazine. Volume 32

Founded in 1900, Bostonia magazine is Boston University's main alumni publication, which covers alumni and student life, as well as university activities, events, and programs

Electrochemical deconstructive functionalization of arylcycloalkanes via fragmentation of anodically generated aromatic radical cations

This highlight summarises electrochemical approaches for the deconstructive functionalization of arylcycloalkanes via the fragmentation of anodically generated aromatic radical cations. A diverse range of deconstructive functionalization processes is described, including discussion on the electrochemical reaction conditions employed, scope and limitations, and reaction mechanisms, in addition to highlighting future opportunities in this burgeoning area of sustainable synthesis

Electrochemical generation and utilization of alkoxy radicals

This highlight summarises electrochemical approaches for the generation and utilization of alkoxy radicals, predominantly focusing on recent advances (2012–present). The application of electrochemically generated alkoxy radicals in a diverse range of transformations is described, including discussion on reaction mechanisms, scope and limitations, in addition to highlighting future challenges in this burgeoning area of sustainable synthesis