Cycloadditions, such as the 4+2 Diels-Alder reaction to form six-membered rings, are among the most powerful and widely used methods in synthetic chemistry. The analogous 2+2 alkene cycloaddition to ...synthesize cyclobutanes is kinetically accessible by photochemical methods, but the substrate scope and functional group tolerance are limited. Here, we report iron-catalyzed intermolecular 2+2 cycloaddition of unactivated alkenes and cross cycloaddition of alkenes and dienes as regio- and stereoselective routes to cyclobutanes. Through rational ligand design, development of this base metal–catalyzed method expands the chemical space accessible from abundant hydrocarbon feedstocks.
We assess evidence relevant to Earth's equilibrium climate sensitivity per doubling of atmospheric CO2, characterized by an effective sensitivity S . This evidence includes feedback process ...understanding, the historical climate record, and the paleoclimate record. An S value lower than 2 K is difficult to reconcile with any of the three lines of evidence. The amount of cooling during the Last Glacial Maximum provides strong evidence against values of S greater than 4.5 K. Other lines of evidence in combination also show that this is relatively unlikely. We use a Bayesian approach to produce a probability density (PDF) for S given all the evidence, including tests of robustness to difficult‐to‐quantify uncertainties and different priors. The 66% range is 2.6‐3.9 K for our Baseline calculation, and remains within 2.3‐4.5 K under the robustness tests; corresponding 5‐95% ranges are 2.3‐4.7 K, bounded by 2.0‐5.7 K (although such high‐confidence ranges should be regarded more cautiously). This indicates a stronger constraint on S than reported in past assessments, by lifting the low end of the range. This narrowing occurs because the three lines of evidence agree and are judged to be largely independent, and because of greater confidence in understanding feedback processes and in combining evidence. We identify promising avenues for further narrowing the range in S , in particular using comprehensive models and process understanding to address limitations in the traditional forcing‐feedback paradigm for interpreting past changes.
Hyaluronic acid (HA), lubricin, and phospholipid species (PLs) contribute independently or together to the boundary lubrication of articular joints that is provided by synovial fluid (SF). Our study ...is the first reporting quantitative data about the molecular weight (MW) forms of HA, lubricin, and PLs in SF from cohorts of healthy donors, patients with early (eOA)- or late (lOA)-stage osteoarthritis (OA), and patients with active rheumatoid arthritis (RA).
We used human SF from unaffected controls, eOA, lOA, and RA. HA and lubricin levels were measured by enzyme-linked immunosorbent assay. PLs was quantified by electrospray ionization tandem mass spectrometry. Fatty acids (FAs) were analyzed by gas chromatography, coupled with mass spectrometry. The MW distribution of HA was determined by agarose gel electrophoresis.
Compared with control SF, the concentrations of HA and lubricin were lower in OA and RA SF, whereas those of PLs were higher in OA and RA SF. Moreover, the MW distribution of HA shifted toward the lower ranges in OA and RA SF. We noted distinct alterations between cohorts in the relative distribution of PLs and the degree of FA saturation and chain lengths of FAs.
The levels, composition, and MW distribution of all currently known lubricants in SF--HA, lubricin, PLs--vary with joint disease and stage of OA. Our study is the first delivering a comprehensive view about all joint lubricants during health and widespread joint diseases. Thus, we provide the framework to develop new optimal compounded lubricants to reduce joint destruction.
The discovery of optical solitons being understood as temporally and spectrally stationary optical states has enabled numerous innovations among which, most notably, supercontinuum light sources have ...become widely used in both fundamental and applied sciences. Here, we report on experimental evidence for dynamics of hybrid solitons-a new type of solitary wave, which emerges as a result of a strong non-instantaneous nonlinear response in CS
-filled liquid-core optical fibres. Octave-spanning supercontinua in the mid-infrared region are observed when pumping the hybrid waveguide with a 460 fs laser (1.95 μm) in the anomalous dispersion regime at nanojoule-level pulse energies. A detailed numerical analysis well correlated with the experiment uncovers clear indicators of emerging hybrid solitons, revealing their impact on the bandwidth, onset energy and noise characteristics of the supercontinua. Our study highlights liquid-core fibres as a promising platform for fundamental optics and applications towards novel coherent and reconfigurable light sources.Here, Chemnitz et al. report experimental evidence for hybrid solitons - a type of solitary wave, which emerges as a result of a strong non-instantaneous nonlinear response in CS
-filled liquid-core optical fibres, demonstrating efficient soliton-driven supercontinuum generation.
Improvements in the GISTEMP Uncertainty Model Lenssen, Nathan J. L.; Schmidt, Gavin A.; Hansen, James E. ...
Journal of geophysical research. Atmospheres,
27 June 2019, Volume:
124, Issue:
12
Journal Article
Peer reviewed
Open access
We outline a new and improved uncertainty analysis for the Goddard Institute for Space Studies Surface Temperature product version 4 (GISTEMP v4). Historical spatial variations in surface temperature ...anomalies are derived from historical weather station data and ocean data from ships, buoys, and other sensors. Uncertainties arise from measurement uncertainty, changes in spatial coverage of the station record, and systematic biases due to technology shifts and land cover changes. Previously published uncertainty estimates for GISTEMP included only the effect of incomplete station coverage. Here, we update this term using currently available spatial distributions of source data, state‐of‐the‐art reanalyses, and incorporate independently derived estimates for ocean data processing, station homogenization, and other structural biases. The resulting 95% uncertainties are near 0.05 °C in the global annual mean for the last 50 years and increase going back further in time reaching 0.15 °C in 1880. In addition, we quantify the benefits and inherent uncertainty due to the GISTEMP interpolation and averaging method. We use the total uncertainties to estimate the probability for each record year in the GISTEMP to actually be the true record year (to that date) and conclude with 86% likelihood that 2016 was indeed the hottest year of the instrumental period (so far).
Key Points
A total uncertainty analysis for GISTEMP is presented for the first time
Uncertainty in global mean surface temperature is roughly 0.05 degrees Celsius in recent decades increasing to 0.15 degrees Celsius in the nineteenth century
Annual mean uncertainties are small relative to the long‐term trend
We investigated auditory, dorsal attention, and default mode networks in adults with tinnitus and hearing loss in a resting state functional connectivity study. Data were obtained using continuous ...functional magnetic resonance imaging (fMRI) while the participants were at "rest" and were not performing any task. Participants belonged to one of three groups: middle-aged adults with tinnitus and mild-to-moderate high frequency hearing loss (TIN), age-matched controls with normal hearing and no tinnitus (NH), and a second control group with mild-to-moderate high frequency hearing loss without tinnitus (HL). After standard preprocessing, (a) a group independent component analysis (ICA) using 30 components and (b) a seeding-based connectivity analysis were conducted. In the group ICA, the default mode network was the only network to display visual differences between subject groups. In the seeding analysis, we found increased connectivity between the left parahippocampus and the auditory resting state network in the TIN group when compared to NH controls. Similarly, there was also an increased correlation between the right parahippocampus and the dorsal attention network when compared to HL controls. Other group differences in this attention network included decreased correlations between the seed regions and the right supramarginal gyrus in TIN patients when compared to HL controls. In the default mode network, there was a strong decrease in correlation between the seed regions and the precuneus when compared to both control groups. The findings of this study identify specific alterations in the connectivity of the default mode, dorsal attention, and auditory resting state networks due to tinnitus. The results suggest that therapies for tinnitus that mitigate the increased connectivity of limbic regions with auditory and attention resting state networks and the decreased coherence of the default mode network could be effective at reducing tinnitus-related distress.
We aimed to investigate the differences in plasma concentrations and in intakes of amino acids between male meat-eaters, fish-eaters, vegetarians and vegans in the Oxford arm of the European ...Prospective Investigation into Cancer and Nutrition.
This cross-sectional analysis included 392 men, aged 30-49 years. Plasma amino acid concentrations were measured with a targeted metabolomic approach using mass spectrometry, and dietary intake was assessed using a food frequency questionnaire. Differences between diet groups in mean plasma concentrations and intakes of amino acids were examined using analysis of variance, controlling for potential confounding factors and multiple testing.
In plasma, concentrations of 6 out of 21 amino acids varied significantly by diet group, with differences of -13% to +16% between meat-eaters and vegans. Concentrations of methionine, tryptophan and tyrosine were highest in fish-eaters and vegetarians, followed by meat-eaters, and lowest in vegans. A broadly similar pattern was seen for lysine, whereas alanine concentration was highest in fish-eaters and lowest in meat-eaters. For glycine, vegans had the highest concentration and meat-eaters the lowest. Intakes of all 18 dietary amino acids differed by diet group; for the majority of these, intake was highest in meat-eaters followed by fish-eaters, then vegetarians and lowest in vegans (up to 47% lower than in meat-eaters).
Men belonging to different habitual diet groups have significantly different plasma concentrations of lysine, methionine, tryptophan, alanine, glycine and tyrosine. However, the differences in plasma concentrations were less marked than and did not necessarily mirror those seen for amino acid intakes.
We present a new 3‐dimensional 1° × 1° gridded data set for the annual mean seawater oxygen isotope ratio (δ18O) to use in oceanographic and paleoceanographic applications. It is constructed from a ...large set of observations made over the last 50 years combined with estimates from regional δ18O to salinity relationships in areas of sparse data. We use ocean fronts and water mass tracer concentrations to help define distinct water masses over which consistent local relationships are valid. The resulting data set compares well to the GEOSECS data (where available); however, in certain regions, particularly where sea ice is present, significant seasonality may bias the results. As an example application of this data set, we use the resulting surface δ18O as a boundary condition for isotope‐enabled GISS ModelE to yield a more realistic comparison to the isotopic composition of precipitation data, thus quantifying the ‘source effect’ of δ18O on the isotopic composition of precipitation.
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