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At least 667 records · Page 37

Pertechnetate/perrhenate–capped Zr/Hf–Dihydroxide Dimers: Elucidating Zr–TcO 4 Co–Mobility in the Nuclear Fuel Cycle

Spent nuclear fuel contains heavy element fission products that must be separated for effective reprocessing for a safe and sustainable nuclear fuel cycle. 93 Zr and 99 Tc are high-yield fission products that co-transport in liquid-liquid extraction processes. Here we seek atomic-level information of this co-extraction process, as well as fundamental knowledge about Zr IV (and Hf IV ) aqueous speciation in the presence of topology-directing ligands such as pertechnetate (TcO 4 – ) and non-radioactive surrogate perrhenate (ReO 4 – ). In this context, we show that the flat tetrameric oxyhydroxyl-cluster [M IV 4 (OH) 8 (H 2 O) 16 ] 8+ (and related polymers) is dissociated by perrhenate/pertechnetate to yield isostructural dimers, M 2 (OH) 2 (XO 4 – ) 6 (H 2 O) 6 • 3H 2 O (M=Zr/Hf IV ; X=Re/Tc VII ), elucidated by single-crystal X-ray diffraction. We used these model compounds to understand the pervasive 93 Zr- 99 Tc coextraction with further speciation studies in water, nitric acid, and tetrabutylphosphate (TBP) -kerosene; where the latter two media are relevant to nuclear fuel reprocessing. SAXS (small angle X-ray scattering), compositional evaluation, and where experimentally feasible, ESI-MS (electrospray ionization mass spectrometry) showed that perrhenate/pertechnetate influence Zr/Hf IV -speciation in water. Here, in Zr-XO 4 solvent extraction studies to simulate fuel reprocessing, we provide evidence that TcO 4 – enhances extraction of Zr IV , and compositional analysis of the extracted metal-complexes (Zr-ReO 4 study) is consistent with the crystallized Zr IV 2 (OH) 2 (Re VII O 4 – ) 6 (H 2 O) 6 •dimer.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Modeling of the effectiveness of novel edge seal designs for fast, low‐Cap‐Ex manufacturing

Abstract In the manufacturing of photovoltaic (PV) modules, the lamination process can take up to 20 min to complete. In this work, new lamination processes are being developed, and have been prototyped, which hope to be able to cut this time down to as little as 30 s. This could provide significant savings in the cost of lamination equipment, floor space, and energy. PV modules are expected to have a lifespan exceeding 20 to 30 years. For moisture‐sensitive PV technologies, the edge seal between the two layers of glass can be the weakest point of its reliability. There is an inherent challenge when evaluating edge seal materials due to their low permeation rates. As part of Colorado State University's Photovoltaic Research and Development 2, work at the National Renewable Energy Laboratory has developed models to evaluate edge seal configurations in glass‐glass PV modules. Here, this new manufacturing process is evaluated for long‐term moisture durability. Different edge seal design options within glass–glass PV modules are explored. Most of these designs are targeting a superstrate on glass configuration, e.g CdTe, but some designs could be used on conventional crystalline Si cells. Using COMSOL finite element simulation software, we investigated the edge seal and interlayer design configurations containing silicone perimeter edge adhesive, desiccated polyisobutylene‐based edge seal, air, and polyolefin while integrating climate conditions equivalent to a hot and humid environment such as Miami, Florida. We found optimized configurations that will allow the module to prevent moisture ingress over 50 years minimizing the amount of time and material used while utilizing polymers that are easily dispensed.

14 SOLAR ENERGY↗

Hydrogenation Mechanisms of Poly-Si/SiO x Passivating Contacts by Different Capping Layers

Herein, posttreatment techniques of phosphorus-doped poly-Si/SiO x passivating contacts, including forming gas annealing (FGA), atomic layer deposition (ALD) of hydrogenated aluminum oxide (AlO x :H), and plasma-enhanced chemical vapor deposition (PECVD) of hydrogenated silicon nitride (SiN x :H), are investigated and compared in terms of their application to silicon solar cells. A simple FGA posttreatment produces a significant increase in the implied open circuit voltage (iV oc ) and the effective minority-carrier lifetime (teff) of high-resistivity crystalline Si (c-Si) samples, whereas low-resistivity samples show a minimal change. Treatment by means of AlO x :H and/or SiN x :H followed by postdeposition FGA results in a universal increase in t eff and iV oc for all substrate resistivities (as high as 12.5 ms and 728 mV for 100 Ω cm and 5.4 ms and 727 mV for 2 Ω cm n-type c-Si substrates). In addition, both the FGA and AlO x :H + FGA techniques can inject sufficient hydrogen into the samples to passivate defects at the SiO x /c-Si and poly-Si/SiO x interfaces. However, this hydrogen concentration is insufficient to neutralize both the nonradiative defects inside the poly-Si films and dangling bonds associated with the amorphous Si phase present in them. The hydrogen injected by the SiN x :H + FGA technique can passivate both the interfaces and the defects and dangling bonds within the poly-Si film. These results are confirmed by low-temperature photoluminescence spectroscopy, Fourier transform infrared spectroscopy, and dynamic secondary-ion mass spectrometry measurements.

14 SOLAR ENERGY↗

Citric Acid Capped Iron Oxide Nanoparticles as an Effective MALDI Matrix for Polymers

A new matrix-assisted laser desorption ionization (MALDI) mass spectrometry matrix is proposed for molecular mass determination of polymers. This matrix contains an iron oxide nanoparticle (NP) core with citric acid (CA) molecules covalently bound to the surface. With the assistance of additives, the particulate nature of NPs allows the matrix to mix uniformly with polar or nonpolar polymer layers and promotes ionization, which may simplify matrix selection and sample preparation procedures. Several distinctively different polymer classes (polyethyleneglycol (PEG), polywax/polyethylene, perfluoropolyether, and polydimethylsiloxane) are effectively detected by the water or methanol dispersed NPCA matrix with NaCl, NaOH, LiOH, or AgNO{sub 3} as additives. Furtheremore, successful quantitative measurements of PEG1000 using polypropylene glycol 1000 as an internal standard are demonstrated. .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural Basis for the Species-Selective Binding of N,C-Capped Dipeptides to the Mycobacterium tuberculosis Proteasome

The Mycobacterium tuberculosis (Mtb) 20S proteasome is vital for the pathogen to survive under nitrosative stress in vitro and to persist in mice. To qualify for drug development, inhibitors targeting Mtb 20S must spare both the human constitutive proteasome (c-20S) and immunoproteasome (i-20S). We recently reported members of a family of noncovalently binding dipeptide proteasome inhibitors that are highly potent and selective for Mtb 20S over human c-20S and i-20S. To understand the structural basis of their potency and selectivity, we have studied the structure–activity relationship of six derivatives and solved their cocrystal structures with Mtb 20S. The dipeptide inhibitors form an antiparallel β-strand with the active site β-strands. Selectivity is conferred by several features of Mtb 20S relative to its mouse counterparts, including a larger S1 pocket, additional hydrogen bonds in the S3 pocket, and hydrophobic interactions in the S4 pocket. Serine-20 and glutamine-22 of Mtb 20S interact with the dipeptides and confer Mtb-specific inhibition over c-20S and i-20S. The Mtb 20S and mammalian i-20S have a serine-27 that interacts strongly with the dipeptides, potentially explaining the higher inhibitory activity of the dipeptides toward i-20S over c-20S. This detailed structural knowledge will aid in optimizing the dipeptides as anti-tuberculosis drugs.

59 BASIC BIOLOGICAL SCIENCES↗