A green and efficient method for the synthesis of homodimeric (β-dicarbonyl) arylmethanes and dihydropyridine from dimedone in water

A direct method has been developed for the synthesis of the dihydropyridine ring system by means of Michael reaction. The reaction of dimedone with 1 .0 equiv. of amines in water provides intermediate product, which allowed dihydropyridine derivatives by intramolecular cyclization in various yields. Of particular interest is the use of the water as solvent of reaction and in absence of catalyst. Also these operating conditions protect the environment and economic points of view.Keywords: aqueous synthesis; bioactivity; dihydropyridine; dimedone; green method; selective condition

Measurement and modeling of ablation of the bottom of supraglacial lakes in western Greenland

We report measurements of ablation rates of the bottom of two supraglacial lakes and of temperatures at different depths collected during the summers of 2010 and 2011 in west Greenland. To our knowledge, this is the first time that such data sets are reported and discussed in the literature. The measured ablation rates at the bottom of the two lakes are of the order of ∼6 cm/day, versus a rate of ∼2.5–3 cm/day in the case of bare ice of surrounding areas. Though our measurements suggest the presence of a vertical temperature gradient, it is not possible to draw final conclusions as the measured gradient is smaller than the accuracy of our temperature sensors. In-situ measurements are compared with the results of a thermodynamic model forced with the outputs of a regional climate model. In general, the model is able to satisfactorily reproduce the measured quantities with RMSE of the order of 3–4 cm for the ablation and ∼1.5°C in the case of water temperature. Our results confirm that the ablation at the bottom of supraglacial lakes plays an important role on the overall lake volume with the ablation in the case of ice covered by a lake being 110–135% of that over bare ice at nearby locations. Beside ice sheet hydrological implications, melting at the bottom of a supraglacial lake might affect estimates of lake volume from spaceborne visible and near-infrared measurements

What controls the isotopic composition of Greenland surface snow?

International audienceWater stable isotopes in Greenland ice core data provide key paleoclimatic information, and have been compared with precipitation isotopic composition simulated by isotopically enabled atmospheric models. However, post-depositional processes linked with snow metamorphism remain poorly documented. For this purpose, monitoring of the isotopic composition (d18O, dD) of near-surface water vapor, precipitation and samples of the top (0.5 cm) snow surface has been conducted during two summers (2011-2012) at NEEM, NW Greenland. The samples also include a subset of 17O-excess measurements over 4 days, and the measurements span the 2012 Greenland heat wave. Our observations are consistent with calculations assuming isotopic equilibrium between surface snow and water vapor. We observe a strong correlation between near-surface vapor d18O and air temperature (0.85 ± 0.11‰ °C-1 (R = 0.76) for 2012). The correlation with air temperature is not observed in precipitation data or surface snow data. Deuterium excess (d-excess) is strongly anti-correlated with d18O with a stronger slope for vapor than for precipitation and snow surface data. During nine 1-5-day periods between precipitation events, our data demonstrate parallel changes of d18O and d-excess in surface snow and near-surface vapor. The changes in d18O of the vapor are similar or larger than those of the snow d18O. It is estimated using the CROCUS snow model that 6 to 20% of the surface snow mass is exchanged with the atmosphere. In our data, the sign of surface snow isotopic changes is not related to the sign or magnitude of sublimation or deposition. Comparisons with atmospheric models show that day-to-day variations in near-surface vapor isotopic composition are driven by synoptic variations and changes in air mass trajectories and distillation histories. We suggest that, in between precipitation events, changes in the surface snow isotopic composition are driven by these changes in near-surface vapor isotopic composition. This is consistent with an estimated 60% mass turnover of surface snow per day driven by snow recrystallization processes under NEEM summer surface snow temperature gradients. Our findings have implications for ice core data interpretation and model-data comparisons, and call for further process studies. © Author(s) 2014

A plan for play - An Eye View Series report

There is a simple, inexpensive and joyful way to address many of the major challenges facing society and its children; addressing the alarming mental health crisis and obesity epidemic and helping to prepare children for an ever-changing work force. The solution that is all too often overlooked and neglected is - play. The right to play is so important that it is enshrined in the UN Convention on the Rights of the Child. Research documents its importance to every aspect of child health, development and wellbeing. Yet many children have little or no access to high quality play opportunities. Play provision should be considered in relation to every aspect of children’s lives – the design of their neighbourhoods, as well as within the services they access, such as child care centres, schools, hospitals, recreation facilities, parks and adventure playgrounds. Play cannot be relegated to the places and context that adults decide are appropriate It should be woven into the fabric of every aspect of children’s lives and the communities they are part of. Equitable access to play means reducing the insidious gradient of inequity that impacts children’s lives even before they are born and continues across their lifespan. Schools are one important venue to ensure equitable access to play. For some children, it will be the only opportunity they have for this nourishing and necessary activity. Play comprises a quarter of the school year, yet teachers and support staff receive no proper training or support to ensure that children in their care – our society’s future – have fulfilling play time. We know that early life experiences set the stage for the future, and that early intervention saves unquantifiable and unnecessary suffering and costs later on – for children, families and society as a whole. We owe it to children and ourselves both now and tomorrow, to make a plan for play that sees every child in every place playing every day. This report makes that case

Interfacial Profile and Propagation of Frontal Photopolymerization Waves

We investigate the frontal photopolymerization of a thiol–ene system with a combination of experiments and modeling, focusing on the interfacial conversion profile and its planar wave propagation. We spatially resolve the solid-to-liquid front by FT-IR and AFM mechanical measurements, supplemented by differential scanning calorimetry. A simple coarse-grained model is found to describe remarkably well the frontal kinetics and the sigmoidal interface, capturing the effects of UV light exposure time (or dose) and temperature, as well as the front position and resulting patterned dimensions after development. Analytical solutions for the conversion profile enable the description of all conditions with a single master curve in the moving frame of the front position. Building on this understanding, we demonstrate the design and fabrication of gradient polymer materials, with tunable properties <i>along</i> the direction of illumination, which can be coupled with lateral patterning by modulated illumination or grayscale lithography

Using continuous measurements of near-surface atmospheric water vapour isotopes to document snow-air interactions

Water stable isotope data from Greenland ice cores provide key paleoclimatic information. However, postdepositional processes linked with snow metamorphism remain poorly documented. For this purpose, a monitoring of the isotopic composition δ18O and δD at several height levels (up to 13 meter) of near-surface water vapor, precipitation and snow in the first 0.5 cm from the surface has been conducted during three summers (2010-2012) at NEEM, NW Greenland. We observe a clear diurnal cycle in both the value and gradient of the isotopic composition of the water vapor above the snow surface. The diurnal amplitude in δD is found to be ~15‰. The diurnal isotopic composition follows the absolute humidity cycle. This indicates a large flux of vapor from the snow surface to the atmosphere during the daily warming and reverse flux during the daily cooling. The isotopic measurements of the flux of water vapor above the snow give new insights into the post depositional processes of the isotopic composition of the snow. During nine 1-5 days periods between precipitation events, our data demonstrate parallel changes of δ18O and d-excess in surface snow and near-surface vapor. The changes in δ18O of the vapor are similar or larger than those of the snow δ18O. It is estimated using the CROCUS snow model that 6 to 20% of the surface snow mass is exchanged with the atmosphere. In our data, the sign of surface snow isotopic changes is not related to the sign or magnitude of sublimation or deposition. Comparisons with atmospheric models show that day-to-day variations in near-surface vapor isotopic composition are driven by synoptic variations and changes in air mass trajectories and distillation histories. We suggest that, in-between precipitation events, changes in the surface snow isotopic composition are driven by these changes in near-surface vapor isotopic composition. This is consistent with an estimated 60% mass turnover of surface snow per day driven by snow recrystallization processes associated with temperature gradients near the snow surface. Our findings have implications for ice core data interpretation and model-data comparisons, and call for further process studies

Infantile Convulsions with Paroxysmal Dyskinesia (ICCA Syndrome) and Copy Number Variation at Human Chromosome 16p11

BACKGROUND: Benign infantile convulsions and paroxysmal dyskinesia are episodic cerebral disorders that can share common genetic bases. They can be co-inherited as one single autosomal dominant trait (ICCA syndrome); the disease ICCA gene maps at chromosome 16p12-q12. Despite intensive and conventional mutation screening, the ICCA gene remains unknown to date. The critical area displays highly complicated genomic architecture and is the site of deletions and duplications associated with various diseases. The possibility that the ICCA syndrome is related to the existence of large-scale genomic alterations was addressed in the present study. METHODOLOGY/PRINCIPAL FINDINGS: A combination of whole genome and dedicated oligonucleotide array comparative genomic hybridization coupled with quantitative polymerase chain reaction was used. Low copy number of a region corresponding to a genomic variant (Variation_7105) located at 16p11 nearby the centromere was detected with statistical significance at much higher frequency in patients from ICCA families than in ethnically matched controls. The genomic variant showed no apparent difference in size and copy number between patients and controls, making it very unlikely that the genomic alteration detected here is ICCA-specific. Furthermore, no other genomic alteration that would directly cause the ICCA syndrome in those nine families was detected in the ICCA critical area. CONCLUSIONS/SIGNIFICANCE: Our data excluded that inherited genomic deletion or duplication events directly cause the ICCA syndrome; rather, they help narrowing down the critical ICCA region dramatically and indicate that the disease ICCA genetic defect lies very close to or within Variation_7105 and hence should now be searched in the corresponding genomic area and its surrounding regions

The historical Greenland Climate Network (GC-Net) curated and augmented level-1 dataset

The Greenland Climate Network (GC-Net) consists of 31 automatic weather stations (AWSs) at 30 sites across the Greenland Ice Sheet. The first site was initiated in 1990, and the project has operated almost continuously since 1995 under the leadership of the late Konrad Steffen. The GC-Net AWS measured air temperature, relative humidity, wind speed, atmospheric pressure, downward and reflected shortwave irradiance, net radiation, and ice and firn temperatures. The majority of the GC-Net sites were located in the ice sheet accumulation area (17 AWSs), while 11 AWSs were located in the ablation area, and two sites (three AWSs) were located close to the equilibrium line altitude. Additionally, three AWSs of similar design to the GC-Net AWS were installed by Konrad Steffen's team on the Larsen C ice shelf, Antarctica. After more than 3 decades of operation, the GC-Net AWSs are being decommissioned and replaced by new AWSs operated by the Geological Survey of Denmark and Greenland (GEUS). Therefore, making a reassessment of the historical GC-Net AWS data is necessary. We present a full reprocessing of the historical GC-Net AWS dataset with increased attention to the filtering of erroneous measurements, data correction and derivation of additional variables: continuous surface height, instrument heights, surface albedo, turbulent heat fluxes, and 10 m ice and firn temperatures. This new augmented GC-Net level-1 (L1) AWS dataset is now available at https://doi.org/10.22008/FK2/VVXGUT (Steffen et al., 2023) and will continue to be refined. The processing scripts, latest data and a data user forum are available at https://github.com/GEUS-Glaciology-and-Climate/GC-Net-level-1-data-processing (last access: 30 November 2023). In addition to the AWS data, a comprehensive compilation of valuable metadata is provided: maintenance reports, yearly pictures of the stations and the station positions through time. This unique dataset provides more than 320 station years of high-quality atmospheric data and is available following FAIR (findable, accessible, interoperable, reusable) data and code practices.</p