Functionalized hyperbranched polymers via olefin metathesis

Hyperbranched polymers are highly branched, three-dimensional macromolecules which are closely related to dendrimers and are typically prepared via a one-pot polycondensation of AB_(n≥2) monomers.^1 Although hyperbranched macromolecules lack the uniformity of monodisperse dendrimers, they still possess many attractive dendritic features such as good solubility, low solution viscosity, globular structure, and multiple end groups.^1-3 Furthermore, the usually inexpensive, one-pot synthesis of these polymers makes them particularly desirable candidates for bulk-material and specialty applications. Toward this end, hyperbranched polymers have been investigated as both rheology-modifying additives to conventional polymers and as substrate-carrying supports or multifunctional macroinitiators, where a large number of functional sites within a compact space becomes beneficial

Linking Sub-Tropical Evaporation and Extreme Precipitation Over East Antarctica: An Atmospheric River Case Study

We investigate an intense snowfall event between 15 and 18 February 2011 over the East Antarctic coastal region which contributed to roughly 24% of the annual snow accumulation. The event was previously associated with an atmospheric river, and here we use both Eulerian and Lagrangian analysis to gain an understanding of the processes contributing to the atmospheric river signature. The planetary-scale configuration during the event consisted of a persistent blocking situation resulting in a sustained meridional flow from the sub-tropics to the Antarctic ice sheet between 20 and 50°E. Within this configuration, synoptic-scale cyclogenesis contributed to slantwise ascent of moisture loaded air parcels toward Antarctica. Landfall of this cyclone’s warm sector coincided with the onset of Antarctic precipitation. Subsequently, a secondary cyclone developed along a pre-existing baroclinic zone. The rapid intensification and propagation speed of this mesoscale cyclone alongside the warm, moist air mass resulted in strong moisture flux convergence ahead of the cyclone, providing additional poleward moisture transport. The poleward progression of warm moist air and a corresponding decrease of sea-surface temperatures implied downward surface sensible and latent heat fluxes throughout the region of intense poleward moisture, roughly between 40 and 60°S. Hence, moisture uptake via surface evaporation was suppressed between the sub-tropics and the polar continent, favoring long-range transport. Identification of the surface moisture uptake region by tracing changes in moisture in air parcels confirmed the limited uptake of moisture during the poleward transport in this case study, with the primary moisture source for Antarctic precipitation located in the sub-tropics.publishedVersio

Cyclic Ruthenium-Alkylidene Catalysts for Ring-Expansion Metathesis Polymerization

A series of cyclic Ru-alkylidene catalysts have been prepared and evaluated for their efficiency in ring-expansion metathesis polymerization (REMP). The catalyst structures feature chelating tethers extending from one N-atom of an N-heterocyclic carbene (NHC) ligand to the Ru metal center. The catalyst design is modular in nature, which provided access to Ru complexes having varying tether lengths, as well as electronically different NHC ligands. Structural impacts of the tether length were unveiled through 1H NMR spectroscopy as well as single-crystal X-ray analyses. Catalyst activities were evaluated via polymerization of cyclooctene, and key data are provided regarding propagation rates, intramolecular chain transfer, and catalyst stabilities, three areas necessary for the efficient synthesis of cyclic poly(olefin)s via REMP. From these studies, it was determined that while increasing the tether length of the catalyst leads to enhanced rates of polymerization, shorter tethers were found to facilitate intramolecular chain transfer and release of catalyst from the polymer. Electronic modification of the NHC via backbone saturation was found to enhance polymerization rates to a greater extent than did homologation of the tether. Overall, cyclic Ru complexes bearing 5- or 6-carbon tethers and saturated NHC ligands were found to be readily synthesized, bench-stable, and highly active catalysts for REMP

Ring-Expansion Metathesis Polymerization: Catalyst-Dependent Polymerization Profiles

Ring-expansion metathesis polymerization (REMP) mediated by recently developed cyclic Ru catalysts has been studied in detail with a focus on the polymer products obtained under varied reaction conditions and catalyst architectures. Depending upon the nature of the catalyst structure, two distinct molecular weight evolutions were observed. Polymerization conducted with catalysts bearing six-carbon tethers displayed rapid polymer molecular weight growth which reached a maximum value at ca. 70% monomer conversion, resembling a chain-growth polymerization mechanism. In contrast, five-carbon-tethered catalysts led to molecular weight growth that resembled a step-growth mechanism with a steep increase occurring only after 95% monomer conversion. The underlying reason for these mechanistic differences appeared to be ready release of five-carbon-tethered catalysts from growing polymer rings, which competed significantly with propagation. Owing to reversible chain transfer and the lack of end groups in REMP, the final molecular weights of cyclic polymers was controlled by thermodynamic equilibria. Large ring sizes in the range of 60−120 kDa were observed at equilibrium for polycyclooctene and polycyclododecatriene, which were found to be independent of catalyst structure and initial monomer/catalyst ratio. While six-carbon-tethered catalysts were slowly incorporated into the formed cyclic polymer, the incorporation of five-carbon-tethered catalysts was minimal, as revealed by ICP-MS. Further polymer analysis was conducted using melt-state magic-angle spinning ^(13)C NMR spectroscopy of both linear and cyclic polymers, which revealed little or no chain ends for the latter topology

Atmospheric Rivers over the Arctic with the ICON model

The Arctic climate changes faster than the ones of other regions, but the relative role of the individual feedback mechanisms contributing to Arctic amplification is still unclear. Atmospheric Rivers (ARs) are narrow and transient river-style moisture flows arriving from the sub-polar regions. The integrated water vapour transport associated with ARs can explain up to 70% of the precipitation variance north of 70N. However, there are still uncertainties regarding the specific role and the impact of ARs on the Arctic climate variability. For the first time, the high-resolution ICON modelling framework is used over the Arctic region (from 13 km down to ca. 2 km) to investigate processes related with anomalous moisture transport into the Arctic. Based on a case study for Svalbard, the representation of the atmospheric circulation and the spatio-temporal structure of water vapour, temperature, and precipitation and snowfall within the limited-area mode (LAM) of the ICON model is assessed. The impact on the surface energy budget will be calculated

Atmospheric rivers and associated precipitation patterns during the ACLOUD/PASCAL campaigns near Svalbard (May-June 2017): case studies using observations, reanalyses, and a regional climate model

Recently, a significant increase in the atmospheric moisture content has been documented over the Arctic, where both local contributions and poleward moisture transport from lower latitudes can play a role. This study focuses on the anomalous moisture transport events confined to long and narrow corridors, known as atmospheric rivers (ARs), which are expected to have a strong influence on Arctic moisture amounts, precipitation, and the energy budget. During two concerted intensive measurement campaigns – Arctic CLoud Observations Using airborne measurements during polar Day (ACLOUD) and the Physical feedbacks of Arctic planetary boundary layer, Sea ice, Cloud and AerosoL (PASCAL) – that took place at and near Svalbard, three high-water-vapour-transport events were identified as ARs, based on two tracking algorithms: the 30 May event, the 6 June event, and the 9 June 2017 event. We explore the temporal and spatial evolution of the events identified as ARs and the associated precipitation patterns in detail using measurements from the French (Polar Institute Paul Emile Victor) and German (Alfred Wegener Institute for Polar and Marine Research) Arctic Research Base (AWIPEV) in Ny-Ålesund, satellite-borne measurements, several reanalysis products (the European Centre for Medium-Range Weather Forecasts (ECMWF) Re-Analysis (ERA) Interim (ERA-Interim); the ERA5 reanalysis; the Modern-Era Retrospective analysis for Research and Applications, version 2 (MERRA-2); the Climate Forecast System version 2 (CFSv2); and the Japanese 55-Year Reanalysis (JRA-55)), and the HIRHAM regional climate model version 5 (HIRHAM5). Results show that the tracking algorithms detected the events differently, which is partly due to differences in the spatial and temporal resolution as well as differences in the criteria used in the tracking algorithms. The first event extended from western Siberia to Svalbard, caused mixed-phase precipitation, and was associated with a retreat of the sea-ice edge. The second event, 1 week later, had a similar trajectory, and most precipitation occurred as rain, although mixed-phase precipitation or only snowfall occurred in some areas, mainly over the coast of north-eastern Greenland and the north-east of Iceland, and no differences were noted in the sea-ice edge. The third event showed a different pathway extending from the north-eastern Atlantic towards Greenland before turning south-eastward and reaching Svalbard. This last AR caused high precipitation amounts on the east coast of Greenland in the form of rain and snow and showed no precipitation in the Svalbard region. The vertical profiles of specific humidity show layers of enhanced moisture that were concurrent with dry layers during the first two events and that were not captured by all of the reanalysis datasets, whereas the HIRHAM5 model misrepresented humidity at all vertical levels. There was an increase in wind speed with height during the first and last events, whereas there were no major changes in the wind speed during the second event. The accuracy of the representation of wind speed by the reanalyses and the model depended on the event. The objective of this paper was to build knowledge from detailed AR case studies, with the purpose of performing long-term analysis. Thus, we adapted a regional AR detection algorithm to the Arctic and analysed how well it identified ARs, we used different datasets (observational, reanalyses, and model) and identified the most suitable dataset, and we analysed the evolution of the ARs and their impacts in terms of precipitation. This study shows the importance of the Atlantic and Siberian pathways of ARs during spring and beginning of summer in the Arctic; the significance of the AR-associated strong heat increase, moisture increase, and precipitation phase transition; and the requirement for high-spatio-temporal-resolution datasets when studying these intense short-duration events

Extreme precipitation records in Antarctica

Monitoring extreme precipitation records (EPRs), that is, the most extreme precipitation events, is a challenge in Antarctica due to the reduced number of stations available in the continent and the limitations of the instrumentation for measuring solid precipitation. Still, extreme precipitation events may contribute substantially to the variability of ice sheet snow accumulation and even may cause important ecological impacts. This article presents the Antarctic EPRs at different temporal scales, studying the relationship between precipitation amount and temporal duration through a power scaling law, ranging from 1 day to 2 years. This is achieved using precipitation datasets from the ERA5 reanalysis and the RACMO2 regional climate model. Moreover, we present a selection of EPRs case studies examining the synoptic mechanisms that produce such events in Antarctica. Despite ERA5 EPRs are usually lower than those found in RACMO2, they present similar scaling exponents. EPRs are found in Loubet and south Graham Coasts, in the central section of the Antarctic Peninsula, and in the north of Alexander Island, where orographic enhancement increases precipitation amounts. As expected, Antarctic EPRs are much lower than world-wide EPRs, ranging from 6 to 10% at short temporal scales (from 1 to 10 days) and from 10 to 20% at long temporal scales (from 90 days to 2 years) in ERA5. Regional variability of extreme precipitation scaling exponents show similar spatial patterns than previously calculated precipitation concentration.Agencia Estatal de Investigación; European Regional Development Fund, Grant/Award Numbers: CGL2015-65627-C3-1-R, CGL2015-65627-C3-2-R, RTI2018-098693-B-C32, PID2020-116520RB-I00; Generalitat de Catalunya; Ministério da Ciência, Tecnologia e Inovação; Fundação para a Ciência e a Tecnologia, Grant/Award Numbers: CIRCNA/CAC/0273/2019, UIDP/04423/2020, UIDB/04423/2020, LA/P/0094/2020, UIDB/50017/2020, UIDP/50017/2020