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Elucidating details of biology’s selective uptake and trafficking of rare earth elements, particularly the lanthanides, has the potential to inspire sustainable biomolecular separations of these essential metals for myriad modern technologies. Here, we biochemically and structurally characterizeMethylobacterium(Methylorubrum)extorquensLanD, a periplasmic protein from a bacterial gene cluster for lanthanide uptake. This protein provides only four ligands at its surface-exposed lanthanide-binding site, allowing for metal-centered protein dimerization that favors the largest lanthanide, LaIII. However, the monomer prefers NdIIIand SmIII, which are disfavored lanthanides for cellular utilization. Structure-guided mutagenesis of a metal-ligand and an outer-sphere residue weakens metal binding to the LanD monomer and enhances dimerization for PrIIIand NdIIIby 100-fold. Selective dimerization enriches high-value PrIIIand NdIIIrelative to low-value LaIIIand CeIIIin an all-aqueous process, achieving higher separation factors than lanmodulins and comparable or better separation factors than common industrial extractants. Finally, we show that LanD interacts with lanmodulin (LanM), a previously characterized periplasmic protein that shares LanD’s preference for NdIIIand SmIII. Our results suggest that LanD’s unusual metal-binding site transfers less-desirable lanthanides to LanM to siphon them away from the pathway for cytosolic import. The properties of LanD show how relatively weak chelators can achieve high selectivity, and they form the basis for the design of protein dimers for separation of adjacent lanthanide pairs and other metal ions.more » « less
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Low Earth orbit (LEO) radio occultation|radio occultations (RO) constellations can provide global electron density profiles (EDPs) to better specify and forecast the ionosphere‐thermosphere (I‐T) system. To inform future RO constellation design, this study uses comprehensive Observing System Simulation Experiments (OSSEs) to assess the ionospheric specification impact of assimilating synthetic EDPs into a coupled I‐T model. These OSSEs use 10 different sets of RO constellation configurations containing 6 or 12 LEO satellites with base orbit parameter combinations of 520 or 800 km altitude, and 24° or 72° inclination. The OSSEs are performed using the Ensemble Adjustment Kalman Filter implemented in the data assimilation (DA) Research Testbed and the Thermosphere‐Ionosphere‐Electrodynamics General Circulation Model (TIEGCM). A different I‐T model is used for the nature run, the Whole Atmosphere Model‐Ionosphere Plasmasphere Electrodynamics (WAM‐IPE), to simulate the period of interest is the St. Patrick's Day storm on March 13–18, 2015. Errors from models and EDP retrieval are realistically accounted for in this study through distinct I‐T models and by retrieving synthetic EDPs through an extension Abel inversion algorithm. OSSE assessment, using multiple metrics, finds that greater EDP spatial coverage leading to improved specification at altitudes 300 km and above, with the 520 km altitude constellations performing best due to yielding the highest observation counts. A potential performance limit is suggested with two 6‐satellite constellations. Lastly, close examination of Abel inversion error impacts highlights major EDP limitations at altitudes below 200 km and dayside equatorial regions with large horizontal gradients and low electron density magnitudes.more » « less
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Ravikumar, Pradeep (Ed.)Data augmentation (DA) is a powerful workhorse for bolstering performance in modern machine learning. Specific augmentations like translations and scaling in computer vision are traditionally believed to improve generalization by generating new (artificial) data from the same distribution. However, this traditional viewpoint does not explain the success of prevalent augmentations in modern machine learning (e.g. randomized masking, cutout, mixup), that greatly alter the training data distribution. In this work, we develop a new theoretical framework to characterize the impact of a general class of DA on underparameterized and overparameterized linear model generalization. Our framework reveals that DA induces implicit spectral regularization through a combination of two distinct effects: a) manipulating the relative proportion of eigenvalues of the data covariance matrix in a training-data-dependent manner, and b) uniformly boosting the entire spectrum of the data covariance matrix through ridge regression. These effects, when applied to popular augmentations, give rise to a wide variety of phenomena, including discrepancies in generalization between over-parameterized and under-parameterized regimes and differences between regression and classification tasks. Our framework highlights the nuanced and sometimes surprising impacts of DA on generalization, and serves as a testbed for novel augmentation design.more » « less
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Abstract The electron/ion density/temperature and ion velocities observed by the ROCSAT-1 and DEMETER satellites are used to examine the daytime wavenumber-4 (WN4) feature in the equatorial/low latitude ionosphere during various months and solar activity levels of 1999–2010. A moving median process has been employed to isolate WN4 features and calculate their amplitudes, while the upward ion drift is used to estimate electric fields. The ROCSAT-1 and DEMETER ion density, ion temperature, and ion velocity generally yield prominent WN4 features over the center of Pacific Ocean, the west side of South America, the center of the Atlantic Ocean, and Southern India. The correlation coefficient between the deviation of ion density and upward ion drift is significant during high solar activity of 1999–2004, while it approaches to zero during low solar activity of 2004–2010. This confirms that the longitudinal variation of the upward ion drift is essential during high solar activity, and the associated amplitude of dynamo eastward electric field is in the range of 0.10–0.14 mV/m, which is 15–19% of daily dynamo electric field. By contrast, the deviation of the ion density and the northward field-aligned ion flow show a clear anti-correlation which yields a maximum coefficient in August during low solar activity but no correlation during high solar activity. These indicate that the longitudinal variation of the meridional field-aligned ion flow could play an important role during low solar activity, and its amplitude is in the range of 10.44–13.91 m/s, which is 10–13% of the ambient ion flows.more » « less
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Abstract Technologically critical rare-earth elements are notoriously difficult to separate, owing to their subtle differences in ionic radius and coordination number1–3. The natural lanthanide-binding protein lanmodulin (LanM)4,5is a sustainable alternative to conventional solvent-extraction-based separation6. Here we characterize a new LanM, fromHansschlegelia quercus(Hans-LanM), with an oligomeric state sensitive to rare-earth ionic radius, the lanthanum(III)-induced dimer being >100-fold tighter than the dysprosium(III)-induced dimer. X-ray crystal structures illustrate how picometre-scale differences in radius between lanthanum(III) and dysprosium(III) are propagated toHans-LanM’s quaternary structure through a carboxylate shift that rearranges a second-sphere hydrogen-bonding network. Comparison to the prototypal LanM fromMethylorubrum extorquensreveals distinct metal coordination strategies, rationalizingHans-LanM’s greater selectivity within the rare-earth elements. Finally, structure-guided mutagenesis of a key residue at theHans-LanM dimer interface modulates dimerization in solution and enables single-stage, column-based separation of a neodymium(III)/dysprosium(III) mixture to >98% individual element purities. This work showcases the natural diversity of selective lanthanide recognition motifs, and it reveals rare-earth-sensitive dimerization as a biological principle by which to tune the performance of biomolecule-based separation processes.more » « less
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Retrospect and prospect of ionospheric weather observed by FORMOSAT-3/COSMIC and FORMOSAT-7/COSMIC-2Abstract FORMOSAT-3/COSMIC (F3/C) constellation of six micro-satellites was launched into the circular low-earth orbit at 800 km altitude with a 72-degree inclination angle on 15 April 2006, uniformly monitoring the ionosphere by the GPS (Global Positioning System) Radio Occultation (RO). Each F3/C satellite is equipped with a TIP (Tiny Ionospheric Photometer) observing 135.6 nm emissions and a TBB (Tri-Band Beacon) for conducting ionospheric tomography. More than 2000 RO profiles per day for the first time allows us globally studying three-dimensional ionospheric electron density structures and formation mechanisms of the equatorial ionization anomaly, middle-latitude trough, Weddell/Okhotsk Sea anomaly, etc. In addition, several new findings, such as plasma caves, plasma depletion bays, etc., have been reported. F3/C electron density profiles together with ground-based GPS total electron contents can be used to monitor, nowcast, and forecast ionospheric space weather. The S4 index of GPS signal scintillations recorded by F3/C is useful for ionospheric irregularities monitoring as well as for positioning, navigation, and communication applications. F3/C was officially decommissioned on 1 May 2020 and replaced by FORMOSAT-7/COSMIC-2 (F7/C2). F7/C2 constellation of six small satellites was launched into the circular low-Earth orbit at 550 km altitude with a 24-degree inclination angle on 25 June 2019. F7/C2 carries an advanced TGRS (Tri Gnss (global navigation satellite system) Radio occultation System) instrument, which tracks more than 4000 RO profiles per day. Each F7/C2 satellite also has a RFB (Radio Reference Beacon) on board for ionospheric tomography and an IVM (Ion Velocity Meter) for measuring ion temperature, velocity, and density. F7/C2 TGRS, IVM, and RFB shall continue to expand the F3/C success in the ionospheric space weather forecasting.more » « less
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