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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Mechanistic Studies on the Insertion of Carbonyl Substrates into Cu‐H: Different Rate‐Limiting Steps as a Function of Electrophilicity

Abstract We report mechanistic studies on the insertion reactions of [(NHC)Cu(μ‐H)] 2 complexes with carbonyl substrates by UV‐vis and 1 H NMR spectroscopic kinetic studies, H/D isotopic labelling, and X‐ray crystallography. The results of these comprehensive studies show that the insertion of Cu‐H with an aldehyde, ketone, activated ester/amide, and unactivated amide consist of two different rate limiting steps: the formation of Cu‐H monomer from Cu‐H dimer for more electrophilic substrates, and hydride transfer from a transient Cu‐H monomer for less electrophilic substrates. We also report spectroscopic and crystallographic characterization of rare Cu‐hemiacetalate and Cu‐hemiaminalate moieties from the insertion of an ester or amide into the Cu−H bond.

Tran, Ba L.↗
DOE OSTI2019

An Aqueous Dual-Ion Battery Cathode of Mn 3 O 4 via Reversible Insertion of Nitrate

We report reversible electrochemical insertion of NO3- into manganese(II, III) oxide (Mn3O4) as a cathode for aqueous dual-ion batteries. Characterization by TGA, FTIR, EDX, XANES, EXAFS, and EQCM collectively provides unequivocal evidence that reversible oxidative NO 3 - insertion takes place inside Mn 3 O 4 . Ex situ HRTEM and corresponding EDX mapping results suggest that NO 3 - insertion de-crystallizes the structure of Mn 3 O 4 Kinetic studies reveal fast migration of NO 3 - in the Mn 3 O 4 structure. This finding may open a new direction for novel low-cost aqueous dual-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

Mechanistic Studies on the Insertion of Carbonyl Substrates into Cu-H: Different Rate-Limiting Steps as a Function of Electrophilicity

In this paper, we report mechanistic studies on the insertion reactions of [(NHC)Cu(H)] 2 complexes with carbonyl substrates by UV-vis and 1 H NMR spectroscopic kinetic studies, H/D isotopic labelling, and X-ray crystallography. The results of these comprehensive studies show that the insertion of Cu-H with an aldehyde, ketone, activated ester/amide, and unactivated amide consist of two different rate limiting steps: the formation of Cu-H monomer from Cu-H dimer for more electrophilic substrates and hydride transfer from a transient Cu-H monomer for less electrophilic substrates. We also report spectroscopic and crystallographic characterization of rare Cu-hemiacetalate and Cu-hemiaminalate moieties from the insertion of an ester and amide into the Cu-H bond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Placement of a peripherally inserted central catheter into the azygous vein

Peripherally inserted central catheters (PICC) are used for a variety of infusion therapies. They are indicated in patients requiring long-term venous access. Incorrect positioning of the insertion of a PICC line is one of the known complications when inserting the device in clinical practice. Radiographers once performing imaging will commonly check if the tip of a PICC has entered the superior vena cava. This case study will report on a lesser known incorrect placement of a PICC line into the azygous vein and how this can be detected on radiographic imaging. This outcome for the patient can be detrimental as it has an increased risk of perforation, thrombus, and fistula formation.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2018

A Deep-Learning System for Fully-Automated Peripherally Inserted Central Catheter (PICC) Tip Detection

A peripherally inserted central catheter (PICC) is a thin catheter that is inserted via arm veins and threaded near the heart, providing intravenous access. The final catheter tip position is always confirmed on a chest radiograph (CXR) immediately after insertion since malpositioned PICCs can cause potentially life-threatening complications. Although radiologists interpret PICC tip location with high accuracy, delays in interpretation can be significant. In this study, we proposed a fully-automated, deep-learning system with a cascading segmentation AI system containing two fully convolutional neural networks for detecting a PICC line and its tip location. A preprocessing module performed image quality and dimension normalization, and a post-processing module found the PICC tip accurately by pruning false positives. Our best model, trained on 400 training cases and selectively tuned on 50 validation cases, obtained absolute distances from ground truth with a mean of 3.10 mm, a standard deviation of 2.03 mm, and a root mean squares error (RMSE) of 3.71 mm on 150 held-out test cases. This system could help speed confirmation of PICC position and further be generalized to include other types of vascular access and therapeutic support devices.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2019

Effects of insertion loss, laser profile and inhomogeneity of dots distribution on properties of all-optical modulator based on GaN/AlN quantum dots

This paper reports the effects of insertion loss, laser profile and inhomogeneity of dots distribution on properties of an all-optical modulator based on spherical quantum dot. The aim of this paper is to give a quantitative description for the variation of main properties of an all-optical quantum dot modulator such as, absorption, transmission and modulation depth regard to insertion loss, laser profile and inhomogeneity of dots. To realize these points, first, we extract the field distribution in optical fiber and channel waveguide (modulator) which are defined by their structure characteristics and boundary conditions. Using the electric field equations, input coupling efficiency and insertion loss and also role of laser profile are observable. Finally we investigate the effect of size distribution and inhomogeneity of quantum dots on the modulator performance. In this structure we used electromagnetically induced transparency (EIT) in GaN/AlN structure, associated with inter-sublevel transitions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Generation of ubiquitin-based binder with an inserted active peptide

Highlights: • We aimed to develop a grafting method using ubiquitin as a scaffold protein. • We generated ubiquitin derivatives, into which the active peptide was inserted. • The derivatives maintained a similar structure to that of ubiquitin. • The affinity of the peptide was almost 300 times greater than that of free peptide. The grafting of active peptides onto structurally stable scaffold proteins is effective for the generation of functional proteins. In this study, we aimed to develop a grafting method using ubiquitin as a scaffold protein. Ubiquitin is a small protein consisting of 76 amino acid residues that is highly stable against heat and pH stress, which are desirable characteristics for a scaffold protein. Moreover, its structure is maintained even if it is split or additional residues are inserted. Therefore, we assumed that grafting of an active peptide into ubiquitin would result in a functional protein. As a proof of concept, we developed the ubiquitin-based binder (UbB), into which the p53 (17–28) peptide was inserted between Ile36 and Pro37. The p53 (17–28) peptide, utilized as a model active peptide in this work, is known to bind to mouse double minute 2 homolog (Mdm2). Size exclusion chromatography and circular dichroism indicated that UbB maintained a similar structure to that of ubiquitin. The affinity for Mdm2 measured by surface plasmon resonance was 292 times greater than that of the p53 (17–28) peptide. These observations indicate that ubiquitin is a robust scaffold for peptide grafting. We hope that this study will aid further development of ubiquitin-based protein engineering.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2017

Mitigation of tin whisker growth by inserting Ni nanocones

Highlights: • Tin whisker growth is mitigated effectively by inserting Ni nanocones. • Ni nanocones impede Sn dynamic recrystallization by blocking dislocation motions. • The inhibition method and mechanism are important to the study of tin whisker. - Abstract: An innovative controllable way has been proposed to mitigate tin whisker growth by inserting Ni nanocones prepared by electrodeposition. The results reveal that, after inserting Ni nanocones, tin whisker formation is mitigated effectively for 1.6 μm Sn coating but there is no inhibition effect for 4.5 μm Sn coating. The coatings are characterized by X-ray diffraction, scanning electron microscopy, energy dispersive spectrometer and electron backscatter diffraction (EBSD). The EBSD results show that Sn grain size without Ni nanocones increases significantly after indentation test compared with Sn grains with Ni nanocones. The inhibition effect of Ni nanocones on whisker growth can be ascribed to its specific structure which prevents dynamic recrystallization and produces horizontal grain boundaries of Sn grains. The structural inhibition method and mechanism proposed are of great importance to the research of tin whisker.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2016

Complete replication-competent adenovirus 11p vectors with E1 or E3 insertions show improved heat stability

Conventional adenovirus vectors harboring E1 or E3 deletions followed by the insertion of an exogenous gene show considerably reduced virion stability. Here, we report strategies to generate complete replication-competent Ad11p(RCAd11p) vectors that overcome the above disadvantage. A GFP cassette was successfully introduced either upstream of E1A or in the E3A region. The resulting vectors showed high expression levels of the hexon and E1genes and also strongly induced the cytopathic effect in targeted cells. When harboring oversized genomes, the RCAd11pE1 and RCAd11pE3 vectors showed significantly improved heat stability in comparison to Ad11pwt;of the three, RCAd11pE3 was the most tolerant to heat treatment. Electron microscopy showed that RCAd11pE3, RCAd11pE1, Ad11pwt, and Ad11pE1 Delmanifested dominant, moderate, minimum, or no full virus particles after heat treatment at 47 °C for 5 h. Our results demonstrated that both genome size and the insertion site in the viral genome affect virion stability. -- Highlights: •Replicating adenovirus 11p GFP vectors at the E1 or E3 region were generated. •RCAd11pE3 and RCAd11pE1 vectors manifested significantly improved heat stability. •RCAd11pE3 and RCAd11pE1 showed more full viral particles than Ad11pwt after heating. •We demonstrated that both genome size and the insertion site affect virion stability.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Structural Evolution of Layered Manganese Oxysulfides during Reversible Electrochemical Lithium Insertion and Copper Extrusion

The electrochemical lithiation and delithiation of the layered oxysulfide Sr 2 MnO 2 Cu 4-δ S 3 has been investigated by using a combination of in situ powder X-ray diffraction and ex situ neutron powder diffraction, X-ray absorption and 7 Li NMR spectroscopy, together with a range of electrochemical experiments. Sr 2 MnO 2 Cu 4-δ S 3 consists of [Sr 2 MnO 2 ] perovskite-type cationic layers alternating with highly defective antifluorite-type [Cu 4-δ S 3 ] (δ ≈ 0.5) anionic layers. It undergoes a combined displacement/intercalation (CDI) mechanism on reaction with Li, where the inserted Li replaces Cu, forming Li 4 S 3 slabs and Cu + is reduced and extruded as metallic particles. For the initial 2-3% of the first discharge process, the vacant sites in the sulfide layer are filled by Li; Cu extrusion then accompanies further insertion of Li. Mn 2.5+ is reduced to Mn 2+ during the first half of the discharge. The overall charging process involves the removal of Li and re-insertion of Cu into the sulfide layers with re-oxidation of Mn 2+ to Mn 2.5+ . However, due to the different diffusivities of Li and Cu, the processes operating on charge are quite different from those operating during the first discharge: charging to 2.75 V results in the removal of most of the Li, little reinsertion of Cu, and good capacity retention. A charge to 3.75 V is required to fully reinsert Cu, which results in significant changes to the sulfide sublattice during the following discharge and poor capacity retention. This detailed structure-property investigation will promote the design of new functional electrodes with improved device performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Pressure-Driven Helium Insertion for Structural Stability of CH 3 NH 3 PbBr 3 Hybrid Perovskites

Organic−inorganic metal halide perovskites (MHPs) have garnered significant attention due to their outstanding performance in optoelectronic devices, but they are prone to degradation through a variety of pathways. High-pressure studies are being used to understand the mechanical and structural stability of MHPs and investigate new methods for improving these. In this study, we map the high-pressure, low-temperature structural phase diagram of CH 3 NH 3 PbBr 3 (MAPbBr 3 ) between 15−300 K and up to 1.5 GPa. We first compare the temperature and pressure effects on the global and local structures of MAPbBr 3 using synchrotron X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS), respectively, and find evidence of PbBr 6 octahedral distortion. Our results also suggest that He inserts into the MAPbBr 3 structure. The thermodynamics of He insertion into MAPBHe x are calculated to be plausible at room temperature for x ≤ 1 and P = 1−3 GPa and shown to stabilize higher-symmetry phases. This phenomenon increases the fitted bulk modulus of MAPbBr 3 . Structural stabilization by inert atom insertion is proposed as a method to improve the mechanical robustness of MHPs and other soft hybrid materials.

Diffraction↗
DOE OSTI2025

Following CO and H Insertion into Ru–C Bonds with X-ray Photoelectron and Absorption Spectroscopies

Insertion reactions play a central role in the catalytic synthesis of ethanol and higher alcohols. X-ray photoelectron and absorption spectroscopies have been used to follow migratory CO insertion and C─C coupling in a cis-[Ru(2,2′-bipyridine) 2 (CO)(CH 3 )] + complex heated in a vacuum or exposed to CO. Heating of the Ru complex in a vacuum to temperatures above 50 °C induced spontaneous migration of CO into the Ru─CH 3 bond to yield a ─COCH 3 ligand. In conclusion, after adding CO to the background gas, the CO insertion reaction was seen at room temperature, opening the door for the synthesis of ethanol and more energy dense liquids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Investigating the Mechanism of Reversible Lithium Insertion into Anti-NASICON Fe 2 (WO 4 ) 3

The gram-scale preparation of Fe 2 (WO 4 ) 3 by a new solution-based route and detailed characterization of the material are presented. The resulting Fe 2 (WO 4 ) 3 undergoes a reversible electrochemical reaction against lithium centered around 3.0 V with capacities near 93% of the theoretical maximum. Evolution of the Fe 2 (WO 4 ) 3 structure upon lithium insertion and deinsertion is probed using a battery of characterization techniques, including in situ X-ray diffraction, neutron total scattering, and X-ray absorption spectroscopy (XAS). A structural transformation from monoclinic to orthorhombic phases is confirmed during lithium intercalation. XAS and neutron total scattering measurements verify that Fe 2 (WO 4 ) 3 consists of trivalent iron and hexavalent tungsten ions. As lithium ions are inserted into the framework, iron ions are reduced to the divalent state, while the tungsten ions are electrochemically inactive and remain in the hexavalent state. Lastly, lithium insertion occurs via a concerted rotation of the rigid polyhedra in the host lattice driven by electrostatic interactions with the Li + ions; the magnitude of these polyhedral rotations was found to be slightly larger for Fe 2 (WO 4 ) 3 than for the Fe 2 (MoO 4 ) 3 analog.

25 ENERGY STORAGE↗
DOE OSTI2021

Revealing the Fast and Durable Na + Insertion Reactions in a Layered Na 3 Fe 3 (PO 4 ) 4 Anode for Aqueous Na-Ion Batteries

Aqueous sodium-ion batteries represent a promising approach for stationary energy storage; however, the lack of appropriate anode materials has substantially retarded their development. Herein, we demonstrated an iron-based phosphate material of Na 3 Fe 3 (PO 4 ) 4 as an inexpensive and efficacious anode alternative. While the Fe 3+ /Fe 2+ redox couple renders a two-Na-insertion reaction with desirable potentials, its unique layered structure further facilitates the Na-insertion kinetics and reversibility. Consequently, this electrode exhibits an appealing Na-insertion performance, with a reversible capacity of ~83 mAh g –1 , suitable anode potential of -0.4 V vs Ag/AgCl, excellent rate capability of 200 C, and outstanding cycling of 6000 cycles. Utilizing operando synchrotron X-ray diffraction and X-ray absorption spectroscopy, we revealed the structural evolution of the Na 3 Fe 3 (PO 4 ) 4 anode during the two-electron reaction, where the extremely small volume expansion (~3%) enables its fast-charging and long-cycling capability. Our work suggests new considerations of developing versatile iron phosphate compounds as appealing anode materials for energy storage in aqueous electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2024

Cascade CO 2 Insertion in Carbanion Ionic Liquids Driven by Structure Rearrangement

The CO 2 chemisorption in state-of-the-art sorbents based on oxide/hydroxide/amine moieties is driven by strong chemical bonding formation in the carbonate/bicarbonate/carbamate products, which in turn leads to high energy input in sorbent regeneration. In addition, the CO 2 uptake capacity was limited by the active sites’ utilization efficiency, with each active site incorporating one CO 2 molecule or less. In this work, a new concept and generation of sorbent was developed to achieve cascade insertion of multiple CO 2 molecules by leveraging structure rearrangement as the driving force, leading to in situ generation of extra CO 2 -binding sites and significantly reduced energy input for CO 2 release. The designed ionic liquids (ILs) containing carbanions with conjugated and asymmetric structure, deprotonated (methylsulfonyl)acetonitrile ([MSA]) anion, allowed the cascade insertion of two CO 2 molecules via consecutive C–C and O–C bond formations. The proton transfer and structure rearrangement of the carboxylic acid intermediates played critical roles in stabilizing the first integrated CO 2 and generating extra electron-rich oxygen sites for the insertion of the second CO 2 . The structure variation and reaction pathway were confirmed by operando spectroscopy, magnetic resonance spectroscopy (NMR), mass spectroscopy, and computational chemistry. The energy input in sorbent regeneration could be further reduced by harnessing the phase-changing behavior of the carbanion salts in ether solutions upon reacting with CO 2 , avoiding the energy consumption in heating the solvent. In conclusion, the fundamental insights obtained herein provide a promising approach to greatly improve the CO 2 sorption performance via sophisticated molecular-scale structural engineering of the sorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Reversible magnesium and aluminium ions insertion in cation-deficient anatase TiO 2

In contrast to monovalent lithium or sodium ions, the reversible insertion of multivalent ions such as Mg 2+ and Al 3+ into electrode materials remains an elusive goal. In this work, we demonstrate a new strategy to achieve reversible Mg 2+ and Al 3+ insertion in anatase TiO 2 , achieved through aliovalent doping, to introduce a large number of titanium vacancies that act as intercalation sites. We present a broad range of experimental and theoretical characterizations that show a preferential insertion of multivalent ions into titanium vacancies, allowing a much greater capacity to be obtained compared to pure TiO 2 . In conclusion, this result highlights the possibility to use the chemistry of defects to unlock the electrochemical activity of known materials providing a new strategy for the chemical design of materials for practical multivalent batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Structural basis for proficient oxidized ribonucleotide insertion in double strand break repair

Reactive oxygen species (ROS) oxidize cellular nucleotide pools and cause double strand breaks (DSBs). Non-homologous end-joining (NHEJ) attaches broken chromosomal ends together in mammalian cells. Ribonucleotide insertion by DNA polymerase (pol) μ prepares breaks for end-joining and this is required for successful NHEJ in vivo. We previously showed that pol μ lacks discrimination against oxidized dGTP (8-oxo-dGTP), that can lead to mutagenesis, cancer, aging and human disease. Here we reveal the structural basis for proficient oxidized ribonucleotide (8-oxo-rGTP) incorporation during DSB repair by pol μ. Time-lapse crystallography snapshots of structural intermediates during nucleotide insertion along with computational simulations reveal substrate, metal and side chain dynamics, that allow oxidized ribonucleotides to escape polymerase discrimination checkpoints. Abundant nucleotide pools, combined with inefficient sanitization and repair, implicate pol μ mediated oxidized ribonucleotide insertion as an emerging source of widespread persistent mutagenesis and genomic instability.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2020

A robust benchmark for detection of germline large deletions and insertions

New technologies and analysis methods are enabling genomic structural variants (SVs) to be detected with ever-increasing accuracy, resolution and comprehensiveness. To help translate these methods to routine research and clinical practice, we developed a sequence-resolved benchmark set for identification of both false-negative and false-positive germline large insertions and deletions. To create this benchmark for a broadly consented son in a Personal Genome Project trio with broadly available cells and DNA, the Genome in a Bottle Consortium integrated 19 sequence-resolved variant calling methods from diverse technologies. The final benchmark set contains 12,745 isolated, sequence-resolved insertion (7,281) and deletion (5,464) calls ≥50 base pairs (bp). The Tier 1 benchmark regions, for which any extra calls are putative false positives, cover 2.51 Gbp and 5,262 insertions and 4,095 deletions supported by ≥1 diploid assembly. We demonstrate that the benchmark set reliably identifies false negatives and false positives in high-quality SV callsets from short-, linked- and long-read sequencing and optical mapping.

59 BASIC BIOLOGICAL SCIENCES↗