181 research outputs found

    The use of QBO, ENSO, and NAO perturbations in the evaluation of GOME-2 MetOp A total ozone measurements

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    In this work we present evidence that quasi-cyclical perturbations in total ozone (quasi-biennial oscillation – QBO, El Niño–Southern Oscillation – ENSO, and North Atlantic Oscillation – NAO) can be used as independent proxies in evaluating Global Ozone Monitoring Experiment (GOME) 2 aboard MetOp A (GOME-2A) satellite total ozone data, using ground-based (GB) measurements, other satellite data, and chemical transport model calculations. The analysis is performed in the frame of the validation strategy on longer time scales within the European Organisation for the Exploitation of Meteorological Satellites (EUMETSAT) Satellite Application Facility on Atmospheric Composition Monitoring (AC SAF) project, covering the period 2007–2016. Comparison of GOME-2A total ozone with ground observations shows mean differences of about -0.7±1.4&thinsp;% in the tropics (0–30∘), about +0.1±2.1&thinsp;% in the mid-latitudes (30–60∘), and about +2.5±3.2&thinsp;% and 0.0±4.3&thinsp;% over the northern and southern high latitudes (60–80∘), respectively. In general, we find that GOME-2A total ozone data depict the QBO–ENSO–NAO natural fluctuations in concurrence with the co-located solar backscatter ultraviolet radiometer (SBUV), GOME-type Total Ozone Essential Climate Variable (GTO-ECV; composed of total ozone observations from GOME, SCIAMACHY – SCanning Imaging Absorption SpectroMeter for Atmospheric CHartographY, GOME-2A, and OMI – ozone monitoring instrument, combined into one homogeneous time series), and ground-based observations. Total ozone from GOME-2A is well correlated with the QBO (highest correlation in the tropics of +0.8) in agreement with SBUV, GTO-ECV, and GB data which also give the highest correlation in the tropics. The differences between deseazonalized GOME-2A and GB total ozone in the tropics are within ±1&thinsp;%. These differences were tested further as to their correlations with the QBO. The differences had practically no QBO signal, providing an independent test of the stability of the long-term variability of the satellite data. Correlations between GOME-2A total ozone and the Southern Oscillation Index (SOI) were studied over the tropical Pacific Ocean after removing seasonal, QBO, and solar-cycle-related variability. Correlations between ozone and the SOI are on the order of +0.5, consistent with SBUV and GB observations. Differences between GOME-2A and GB measurements at the station of Samoa (American Samoa; 14.25∘&thinsp;S, 170.6∘&thinsp;W) are within ±1.9&thinsp;%. We also studied the impact of the NAO on total ozone in the northern mid-latitudes in winter. We find very good agreement between GOME-2A and GB observations over Canada and Europe as to their NAO-related variability, with mean differences reaching the ±1&thinsp;% levels. The agreement and small differences which were found between the independently produced total ozone datasets as to the influence of the QBO, ENSO, and NAO show the importance of these climatological proxies as additional tool for monitoring the long-term stability of satellite–ground-truth biases.</p

    Surface Doping Quantum Dots with Chemically Active Native Ligands: Controlling Valence without Ligand Exchange

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    One remaining challenge in the field of colloidal semiconductor nanocrystal quantum dots is learning to control the degree of functionalization or valence per nanocrystal. Current quantum dot surface modification strategies rely heavily on ligand exchange, which consists of replacing the nanocrystal\u27s native ligands with carboxylate- or amine-terminated thiols, usually added in excess. Removing the nanocrystal\u27s native ligands can cause etching and introduce surface defects, thus affecting the nanocrystal\u27s optical properties. More importantly, ligand exchange methods fail to control the extent of surface modification or number of functional groups introduced per nanocrystal. Here, we report a fundamentally new surface ligand modification or doping approach aimed at controlling the degree of functionalization or valence per nanocrystal while retaining the nanocrystal\u27s original colloidal and photostability. We show that surface-doped quantum dots capped with chemically active native ligands can be prepared directly from a mixture of ligands with similar chain lengths. Specifically, vinyl and azide-terminated carboxylic acid ligands survive the high temperatures needed for nanocrystal synthesis. The ratio between chemically active and inactive-terminated ligands is maintained on the nanocrystal surface, allowing to control the extent of surface modification by straightforward organic reactions. Using a combination of optical and structural characterization tools, including IR and 2D NMR, we show that carboxylates bind in a bidentate chelate fashion, forming a single monolayer of ligands that are perpendicular to the nanocrystal surface. Moreover, we show that mixtures of ligands with similar chain lengths homogeneously distribute themselves on the nanocrystal surface. We expect this new surface doping approach will be widely applicable to other nanocrystal compositions and morphologies, as well as to many specific applications in biology and materials science

    Molecular Chemistry to the Fore: New Insights into the Fascinating World of Photoactive Colloidal Semiconductor Nanocrystals

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    Colloidal semiconductor nanocrystals possess unique properties that are unmatched by other chromophores such as organic dyes or transition-metal complexes. These versatile building blocks have generated much scientific interest and found applications in bioimaging, tracking, lighting, lasing, photovoltaics, photocatalysis, thermoelectrics, and spintronics. Despite these advances, important challenges remain, notably how to produce semiconductor nanostructures with predetermined architecture, how to produce metastable semiconductor nanostructures that are hard to isolate by conventional syntheses, and how to control the degree of surface loading or valence per nanocrystal. Molecular chemists are very familiar with these issues and can use their expertise to help solve these challenges. In this Perspective, we present our group\u27s recent work on bottom-up molecular control of nanoscale composition and morphology, low-temperature photochemical routes to semiconductor heterostructures and metastable phases, solar-to-chemical energy conversion with semiconductor-based photocatalysts, and controlled surface modification of colloidal semiconductors that bypasses ligand exchange

    The genetics of blood pressure regulation and its target organs from association studies in 342,415 individuals

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    To dissect the genetic architecture of blood pressure and assess effects on target-organ damage, we analyzed 128,272 SNPs from targeted and genome-wide arrays in 201,529 individuals of European ancestry and genotypes from an additional 140,886 individuals were used for validation. We identified 66 blood pressure loci, of which 17 were novel and 15 harbored multiple distinct association signals. The 66 index SNPs were enriched for cis-regulatory elements, particularly in vascular endothelial cells, consistent with a primary role in blood pressure control through modulation of vascular tone across multiple tissues. The 66 index SNPs combined in a risk score showed comparable effects in 64,421 individuals of non-European descent. The 66-SNP blood pressure risk score was significantly associated with target-organ damage in multiple tissues, with minor effects in the kidney. Our findings expand current knowledge of blood pressure pathways and highlight tissues beyond the classic renal system in blood pressure regulation
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