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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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Copper induces hepatocyte injury due to the endoplasmic reticulum stress in cultured cells and patients with Wilson disease

Copper is an essential trace element, however, excess copper is harmful to human health. Excess copper-derived oxidants contribute to the progression of Wilson disease, and oxidative stress induces accumulation of abnormal proteins. It is known that the endoplasmic reticulum (ER) plays an important role in proper protein folding, and that accumulation of misfolded proteins disturbs ER homeostasis resulting in ER stress. However, copper-induced ER homeostasis disturbance has not been fully clarified. We treated human hepatoma cell line (Huh7) and immortalized-human hepatocyte cell line (OUMS29) with copper and chemical chaperones, including 4-phenylbutyrate and ursodeoxycholic acid. We examined copper-induced oxidative stress, ER stress and apoptosis by immunofluorescence microscopy and immunoblot analyses. Furthermore, we examined the effects of copper on carcinogenesis. Excess copper induced not only oxidative stress but also ER stress. Furthermore, excess copper induced DNA damage and reduced cell proliferation. Chemical chaperones reduced this copper-induced hepatotoxicity. Excess copper induced hepatotoxicity via ER stress. We also confirmed the abnormality of ultra-structure of the ER of hepatocytes in patients with Wilson disease. These findings show that ER stress plays a pivotal role in Wilson disease, and suggests that chemical chaperones may have beneficial effects in the treatment of Wilson disease.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2018

Widespread Distribution and Functional Specificity of the Copper Importer CcoA: Distinct Cu Uptake Routes for Bacterial Cytochrome c Oxidases

ABSTRACT Cytochrome c oxidases are members of the heme-copper oxidase superfamily. These enzymes have different subunits, cofactors, and primary electron acceptors, yet they all contain identical heme-copper (Cu B ) binuclear centers within their catalytic subunits. The uptake and delivery pathways of the Cu B atom incorporated into this active site, where oxygen is reduced to water, are not well understood. Our previous work with the facultative phototrophic bacterium Rhodobacter capsulatus indicated that the copper atom needed for the Cu B site of cbb 3 -type cytochrome c oxidase ( cbb 3 -Cox) is imported to the cytoplasm by a major facilitator superfamily-type transporter, CcoA. In this study, a comparative genomic analysis of CcoA orthologs in alphaproteobacterial genomes showed that CcoA is widespread among organisms and frequently co-occurs with cytochrome c oxidases. To define the specificity of CcoA activity, we investigated its function in Rhodobacter sphaeroides , a close relative of R. capsulatus that contains both cbb 3 - and aa 3 -Cox. Phenotypic, genetic, and biochemical characterization of mutants lacking CcoA showed that in its absence, or even in the presence of its bypass suppressors, only the production of cbb 3 -Cox and not that of aa 3 -Cox was affected. We therefore concluded that CcoA is dedicated solely to cbb 3 -Cox biogenesis, establishing that distinct copper uptake systems provide the Cu B atoms to the catalytic sites of these two similar cytochrome c oxidases. These findings illustrate the large variety of strategies that organisms employ to ensure homeostasis and fine control of copper trafficking and delivery to the target cuproproteins under different physiological conditions. IMPORTANCE The cbb 3 - and aa 3 -type cytochrome c oxidases belong to the widespread heme-copper oxidase superfamily. They are membrane-integral cuproproteins that catalyze oxygen reduction to water under hypoxic and normoxic growth conditions. These enzymes diverge in terms of subunit and cofactor composition, yet they all share a conserved heme-copper binuclear site within their catalytic subunit. In this study, we show that the copper atoms of the catalytic center of two similar cytochrome c oxidases from this superfamily are provided by different copper uptake systems during their biogenesis. This finding illustrates different strategies by which organisms fine-tune the trafficking of copper, which is an essential but toxic micronutrient.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2014

Intracytoplasmic Copper Homeostasis Controls Cytochrome c Oxidase Production

Copper is an essential micronutrient used as a metal cofactor by a variety of enzymes, including cytochrome c oxidase (Cox). In all organisms from bacteria to humans, cellular availability and insertion of copper into target proteins are tightly controlled due to its toxicity. The major subunit of Cox contains a copper atom that is required for its catalytic activity. Previously, we identified CcoA (a member of major facilitator superfamily transporters) as a component required for cbb 3 -type Cox production in the Gram-negative, facultative phototroph Rhodobacter capsulatus. Here, first we demonstrate that CcoA is a cytoplasmic copper importer. Second, we show that bypass suppressors of a ccoA deletion mutant suppress cbb 3 -Cox deficiency by increasing cellular copper content and sensitivity. Third, we establish that these suppressors are single-base-pair insertion/deletions located in copA, encoding the major P1B-type ATP-dependent copper exporter (CopA) responsible for copper detoxification. A copA deletion alone has no effect on cbb 3 -Cox biogenesis in an otherwise wild-type background, even though it rescues the cbb 3 -Cox defect in the absence of CcoA and renders cells sensitive to copper. We conclude that a hitherto unknown functional interplay between the copper importer CcoA and the copper exporter CopA controls intracellular copper homeostasis required for cbb 3 -Cox production in bacteria like R. capsulatus.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Design and Characterization of High Thermal Conductivity Pipes from Roll-to- Roll Processed Hybrid Copper-Polymer Strips for Waste Heat Recovery

Metal based heat exchangers targeting low temperature (<150°C) waste heat recovery (WHR) face high maintenance and material costs [1] that result in long payback periods (>1 year). Low-cost polymer pipes suffer from poor thermal conductivity (~0.2 W/m.K), and thus a low overall heat transfer coefficient. Previous reports demonstrated thermal conductivity enhancement in polymers through systematic molecular alignment [2, 3, 4], or by metal micro-particle inclusions [5]. However, these approaches suffer from scalability issues for WHR heat exchangers in terms of cost [1, 3], and thermomechanical considerations [6, 7]. In this work, we propose hybrid metal-polymer strips that are strategically designed to enhance thermal conductivity by cladding copper around polymer strips. The polymer strips with copper-clad edges are wound helically to form the pipes for a heat exchanger. Through numerical simulations, we optimize the copper-polymer strip layouts to achieve high wall thermal conductivity (k > 1 W/m.K) and also have low volume fraction of copper (<70%) for the composite pipes. In copper-polymer composite heat exchangers, the bottlenecks for heat transfer are the thermal interfacial resistances of copper-copper and copper-polymer joints. We experimentally measured interfacial resistances to be ~1x10 -5 K.m 2 /W and ~4x10 -5 K.m 2 /W for copper-copper and copper-polymer joints, respectively. Using the measured interfacial resistances, we further optimized the design of the hybrid pipes to find high thermal conductivity (> 1 W/m.K) designs. We predict up to ~20 % enhancement in overall heat transfer relative to an all polymer (k = 0.2 W/m.K) heat exchanger system. Using a cohesive zone modelling (CZM) for predicting delamination at the weld joints, we find that our hybrid pipes can have operating internal pressures > 200 psi. The optimized designs of hybrid metal-polymer pipes provide a scalable and cost- effective means for harvesting waste heat from low temperature sources. Thekdi, A., and Nimbalkar, S. Oak Ridge National Lab (2014). Shen, Sheng, et al. Nature nanotechnology 5.4 (2010). Xu, Yanfei, et al. Science advances 4.3 (2018). Smith et al. ACS nano, 9(2), (2015). Sofian, N.M., et al., Journal of Thermoplastic Composite Materials (2001). Aymonier et al. Chemistry of Materials, 15(25), (2003). Tavman, I.H., Journal of Applied Polymer Science, 62(12), (1996).

C Rajagopal, Manjunath↗
NASA NTRS1973

High temperature, low-cycle fatigue of copper-base alloys in argon. Part 1: Preliminary results for 12 alloys at 1000 F (538 C)

Short-term tensile evaluations at room temperature and 538 C and low-cycle fatigue evaluations at 538 C are presented for the following materials: Zirconium copper-annealed, Zirconium copper-1/4 hard, Zirconium copper-1/2 hard, Tellurium copper-1/2 hard, Chromium copper-SA and aged, OFHC copper-hard, OFHC copper-1/4 hard, OFHC copper-annealed, Silver-as drawn, Zr-Cr-Mg copper-SA, CW and aged, Electroformed copper-30-35 ksi, and Co-Be-Zr- copper-SA, aged. A total of 50 tensile tests and 76 low-cycle fatigue tests were performed using a strain rate of 0.2 percent per second.

Conway, J. B.↗
NASA NTRS1990

Corrosion Prevention in Copper Combustion Chamber Liners of Liquid Oxygen/Methane Booster Engines

Prior research conducted by United Technologies Research Center and Rockwell International Rocketdyne Division encountered severe copper corrosion while flowing hydrocarbon fuels through copper cooling tubes. These experimental results have very important implications for the development of low-cost, regeneratively cooled, oxygen/hydrocarbon bipropellant booster engines. Aerojet TechSystems undertook a program sponsored by NASA/Lewis Research Center in 1986 with two objectives: (1) to define the corrosive interaction process that occurs between hydrocarbon fuels and copper combustion chamber liner materials, using both static and dynamic test methods, and (2) to identify and demonstrate protective measures against this corrosive process. The results of the first program task demonstrated that the most damaging corrosive process was caused by trace amounts of sulfur-containing impurities in the hydrocarbon fuel which react with the copper chamber liner material to form cuprous sulfide (Cu2S), as reported in Paper No. AlAA 88-3215. Experiments were conducted which demonstrated this corrosive process with Mil-Spec RP-1, propane, and methane fuels in contact with OFHC, NASA-Z, and ZrCu coppers. The preliminary results of the second program task demonstrated that electrodeposited gold and platinum coatings held promise of preventing corrosion of copper chamber liners by methane contaminated with sulfur-containing impurities, as reported in Paper No. AIAA 89-2738. Experiments were conducted which demonstrated greatly reduced corrosion of copper by hydrogen sulfide (H2S) and methyl mercaptan (CH3SH) as measured impurities in methane. This paper presents the concluding, confirmatory results from the second program task. The efficacy of a protective gold coating on NASA-Z copper cooling channel walls was conclusively demonstrated. Tests were conducted in the Aerojet Carbothermal Test Facility which provide realistic simulations of booster engine cooling channel conditions such as temperature, pressure, flow velocity, and heat flux. Dynamic test series were performed with methane containing 5 and 10 ppm (by volume) hydrogen sulfide. Gold-plated and unplated copper alloy specimens were evaluated. The tests demonstrated that gold coatings were effective in preventing corrosion of the copper. Posttest metallographic examinations of the unplated specimens showed severe corrosion as a result of reaction with the sulfur containing contaminant in the fuel. In contrast, posttest metallographic examination of the gold-coated specimens showed no corrosion under similar operating conditions. The findings from metallurgical and chemical analyses of the copper specimens, chemical analysis of the methane, and description of all test conditions are provided. Conclusions are reached as to the efficacy of the plating methods and the effectiveness of the metal coatings in the prevention of corrosion in hydrocarbon-fueled booster engine combustion chamber liners.

S D Rosenberg↗
DOE OSTI2015

Copper substrate as a catalyst for the oxidation of chemical vapor deposition-grown graphene

We report the catalytic effect of copper substrate on graphene–oxygen reaction at high temperature. Previous studies showed that graphene grown on copper are mostly defect-free with strong oxidation resistance. We found that a freshly prepared copper-supported graphene sample can be completely oxidized in trace amount of oxygen (<3 ppm) at 600 °C within 2 h. Both X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) suggest that upon ambient air exposure, oxygen molecules diffuse into the space between graphene and copper, resulting in the formation of copper oxide which acts as catalytic sites for the graphene-oxygen reaction. This result has important implications for the characterization, processing, and storage of copper-supported graphene samples. - Graphical abstract: The copper substrate enhances the thermel oxidation of single-layer graphene. - Highlights: • A copper-supported graphene can be oxidized in Ar (O{sub 2}<3 ppm, 600 °C, 2 h). • O{sub 2} intercalates between graphene and copper upon exposure to air. • The copper foil should not be considered as an inert substrate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Unfolding pathway of CotA-laccase and the role of copper on the prevention of refolding through aggregation of the unfolded state

Highlights: Black-Right-Pointing-Pointer CotA-laccase unfolds with an intermediate state. Black-Right-Pointing-Pointer Copper stabilizes the native and the intermediate state. Black-Right-Pointing-Pointer Copper binding to the unfolded state prevents refolding through protein aggregation. Black-Right-Pointing-Pointer Copper incorporation in CotA-laccase occurs as a later step during folding. -- Abstract: Copper is a redox-active metal and the main player in electron transfer reactions occurring in multicopper oxidases. The role of copper in the unfolding pathway and refolding of the multicopper oxidase CotA laccase in vitro was solved using double-jump stopped-flow experiments. Unfolding of apo- and holo-CotA was described as a three-state process with accumulation of an intermediate in between the native and unfolded state. Copper stabilizes the native holo-CotA but also the intermediate state showing that copper is still bound to this state. Also, copper binds to unfolded holo-CotA in a non-native coordination promoting CotA aggregation and preventing refolding to the native structure. These results gather information on unfolding/folding pathways of multicopper oxidases and show that copper incorporation in vivo should be a tight controlled process as copper binding to the unfolded state under native conditions promotes protein aggregation.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2020

The direct and indirect effects of copper on vector-borne disease dynamics

Metal pollution is a growing concern that affects the health of humans and animals globally. Copper is an essential insect micronutrient required for respiration, pigmentation and oxidative stress protection but can also act as a potentially toxic trace element. While several studies have focused on the negative fitness effects of copper on the aquatic larvae of mosquitoes, the effects of larval copper exposure on adult mosquito fitness (i.e., survival and fecundity) and their ability to transmit parasites (i.e., vector competence) remains unclear. Here, using a well-studied model vector-parasite system, the mosquito Aedes aegypti and parasite Dirofilaria immitis, we show that sublethal copper exposure in larval mosquitoes alters adult female fecundity and vector competence. Specifically, mosquitoes exposed to copper had a hormetic fecundity response and mosquitoes exposed to 600 μg/L of copper had significantly fewer infective parasite larvae than control mosquitoes not exposed to copper. Therefore, exposure of mosquito larvae to copper levels far below EPA-mandated safe drinking water limits (1300 μg/L) can impact vector-borne disease dynamics not only by reducing mosquito abundance (through increased larval mortality), but also by reducing parasite transmission risk. Our results also demonstrated that larval copper is retained through metamorphosis to adulthood in mosquitoes, indicating that these insects could transfer copper from aquatic to terrestrial foodwebs, especially in urban areas where they are abundant. To our knowledge this is the first study to directly link metal exposure with vector competence (i.e., ability to transmit parasites) in any vector-parasite system. Additionally, it also demonstrates unequivocally that mosquitoes can transfer contaminants from aquatic to terrestrial ecosystems. These results have broad implications for public health because they directly linking contaminants and vector-borne disease dynamics, as well as linking mosquitoes and contaminant dynamics.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2015

Interfacial microstructure and properties of copper clad steel produced using friction stir welding versus gas metal arc welding

A preliminary study compares the feasibility and microstructures of pure copper claddings produced on a pressure vessel A516 Gr. 70 steel plate, using friction stir welding versus gas metal arc welding. A combination of optical and scanning electron microscopy is used to characterize the grain structures in both the copper cladding and heat affected zone in the steel near the fusion line. The friction stir welding technique produces copper cladding with a grain size of around 25 μm, and no evidence of liquid copper penetration into the steel. The gas metal arc welding of copper cladding exhibits grain sizes over 1 mm, and with surface microcracks as well as penetration of liquid copper up to 50 μm into the steel substrate. Transmission electron microscopy reveals that metallurgical bonding is produced in both processes. Increased diffusion of Mn and Si into the copper cladding occurs when using gas metal arc welding, although some nano-pores were detected in the FSW joint interface. - Highlights: • Cladding of steel with pure copper is possible using either FSW or GMAW. • The FSW yielded a finer grain structure in the copper, with no evidence of cracking. • The FSW joint contains some evidence of nano-pores at the interface of the steel/copper. • Copper cladding by GMAW contained surface cracks attributed to high thermal stresses. • The steel adjacent to the fusion line maintained a hardness value below 248 HV.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Subneurotoxic copper(II)-induced NF-κB-dependent microglial activation is associated with mitochondrial ROS

Microglia-mediated neuroinflammation and the associated neuronal damage play critical roles in the pathogenesis of neurodegenerative disorders. Evidence shows an elevated concentration of extracellular copper(II) in the brains of these disorders, which may contribute to neuronal death through direct neurotoxicity. Here we explored whether extracellular copper(II) triggers microglial activation. Primary rat microglia and murine microglial cell line BV-2 cells were cultured and treated with copper(II). The content of tumor necrosis factor-α (TNF-α) and nitric oxide in the medium was determined. Extracellular hydrogen peroxide was quantified by a fluorometric assay with Amplex Red. Mitochondrial superoxide was measured by MitoSOX oxidation. At subneurotoxic concentrations, copper(II) treatment induced a dose- and time-dependent release of TNF-α and nitric oxide from microglial cells, and caused an indirect, microglia-mediated neurotoxicity that was blocked by inhibition of TNF-α and nitric oxide production. Copper(II)-initiated microglial activation was accompanied with reduced IkB-α expression as well as phosphorylation and translocation of nuclear factor-κB (NF-κB) p65 and was blocked by NF-κB inhibitors (BAY11-7082 and SC-514). Moreover, copper(II) treatment evoked a rapid release of hydrogen peroxide from microglial cells, an effect that was not affected by NADPH oxidase inhibitors. N-acetyl-cysteine, a scavenger of reactive oxygen species (ROS), abrogated copper(II)-elicited microglial release of TNF-α and nitric oxide and subsequent neurotoxicity. Importantly, mitochondrial production of superoxide, paralleled to extracellular release of hydrogen peroxide, was induced after copper(II) stimulation. Our findings suggest that extracellular copper(II) at subneurotoxic concentrations could trigger NF-κB-dependent microglial activation and subsequent neurotoxicity. NADPH oxidase-independent, mitochondria-derived ROS may be involved in this activation. - Highlights: • Subneurotoxic copper(II) triggers NF-κB-dependent microglial activation. • This activation leads to hippocampal neuronal death. • This activation may involve mitochondria-derived reactive oxygen species.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2015

Eco-friendly copper recovery process from waste printed circuit boards using Fe{sup 3+}/Fe{sup 2+} redox system

Highlights: • We developed an ecofriendly mediated electrochemical process for copper recovery. • The recovery of copper was achieved without mechanical pretreatment of the samples. • We identified the optimal flow rate for the leaching and electrowinning of copper. • The copper content of the obtained cathodic deposits was over 99.9%. - Abstract: The present study aimed at developing an original and environmentally friendly process for the recovery of copper from waste printed circuit boards (WPCBs) by chemical dissolution with Fe{sup 3+} combined with the simultaneous electrowinning of copper and oxidant regeneration. The recovery of copper was achieved in an original set-up consisting of a three chamber electrochemical reactor (ER) connected in series with a chemical reactor (CR) equipped with a perforated rotating drum. Several experiments were performed in order to identify the optimal flow rate for the dissolution of copper in the CR and to ensure the lowest energy consumption for copper electrodeposition in the ER. The optimal hydrodynamic conditions were provided at 400 mL/min, leading to the 75% dissolution of metals and to a low specific energy consumption of 1.59 kW h/kg Cu for the electrodeposition process. In most experiments, the copper content of the obtained cathodic deposits was over 99.9%.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2018

Evidence for Copper Dimers in Low-Loaded CuO x /SiO 2 Catalysts for Cyclohexane Oxidative Dehydrogenation

Copper oxide catalysts supported on KIT-6 silica were evaluated for cyclohexane oxidative dehydrogenation (ODH) to determine the effects of copper oxide domain size on ODH activity and selectivity. The catalysts were prepared by incipient wetness impregnation of KIT-6 at copper surface densities spanning 0.01–0.7 Cu/nm 2 with carefully controlled drying and calcination conditions to systematically vary the average local copper oxide domain size. A distinct copper oxide active site exhibiting an order of magnitude higher activity than large copper oxide domains was identified by model cyclohexane ODH studies coupled with in situ X-ray absorption and UV–visible spectroscopies during reduction in H 2 . The structure of this site is experimentally identified by a combination of extended X-ray absorption fine structure analysis, resonant Raman studies, and modeling by density functional theory. All constraints imposed by these techniques indicate the active site is a mono(μ-oxo)dicopper(II) structure with copper sited in 4-member rings formed by copper insertion into highly strained 3-member siloxane ring defects which form on dehydrated silica. Given the ubiquity of copper oxide sites in selective oxidation catalysis, the understanding of such structures may prove relevant for other oxidation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Manufacturing of low-background copper electrical components for rare-event detection. Final report

This SBIR Phase I project developed the manufacturing capability for the production of ultra-low-background copper and lead for use in electronic interconnects and support architecture. Copper is an attractive electronic and support material because of its favorable conductivity and mechanical properties. Fortuitously, the material can also be electroplated with high radiopurity, particularly if the electroforming is performed in shielded, buried facilities within which the cosmogenic background is minimized. The machining of the electroformed copper into wires, feedthroughs, and support hardware can potentially introduce impurities through the shop environment or through the dies used in wire-drawing and part formation. During Phase I, we demonstrated an alternative low-cost solution-based approach in which copper nanoparticles are colloidally-grown and self-assembled into solids that can serve as thermal structures- such as cold-fingers, mechanical structures- such as the inner shielding lining, and electronic devices. We demonstrated ultrastrong, high-conductivity free-standing copper conductors during Phase I suitable for battery electrodes, interconnects, and cabling, all components that enable next-generation flexible electronics. In nanoparticle form, copper forms in a crystalline lattice with very low impurity content, but its self-assembly is facilitated by organic capping ligands that can serve as impurity sources. Upon the formation of a colloidal solid, the copper particles can be fused and the organic components evaporated through vacuum annealing. The study of ultra-pure copper was expanded during Phase I to include nanostructured lead, which is an important radiation-shielding material. By growing lead particles in a water-based solution the resulting solution can be poured into the desired form-factor mold, within which it will self-assemble and harden upon evaporation of the water and any organics. The effort during Phase II is designed to complete the development of the manufacturing process and to use that process to deliver high radio-purity copper and lead components to the rare-event detection community so that the noise-floor contribution from the surrounding materials is substantially eliminated.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Influence of fuel ash on the recoverability of copper from the spent material of chemical looping combustion

Chemical looping combustion (CLC) is an advanced energy production technology that inherently separates the CO 2 generated. The oxygen needed for fuel conversion is supplied by the oxygen carrier. When using copper-based oxygen carriers, oxygen carrier attrition is a challenge to the process economics, unless the attrited copper that is mixed with fuel ash in the spent material can be recovered by, for instance, acid leaching. However, fuel ash may transform the attrited copper into certain complexes of low leachability (e.g., CuAl 2 O 4 ), hindering the copper recovery. In this study, the copper content in the spent material was first evaluated. The effects of ash composition and copper content on the occurrence mode of copper in spent material were predicted by thermodynamic modeling. Redox cycles of simulated spent materials based on various coal ashes were performed to reveal the characteristics of CuAl 2 O 4 /CuFe 2 O 4 formation. The CuO-Al 2 O 3 reaction was investigated under the temperatures and solid residence times experienced in CLC. The materials were analyzed by X-ray diffraction. The results suggest that the fuel ash with a high Al/Ca ratio may lower the recoverability of copper when the temperature is above 925 °C. The slow formation of CuFe 2 O 4 is not expected to affect the copper recovery.

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

Rapid assessment of human amylin aggregation and its inhibition by copper(II) ions by laser ablation electrospray ionization mass spectrometry with ion mobility separation

Native electrospray ionization (ESI) mass spectrometry (MS) is often used to monitor noncovalent complex formation between peptides and ligands. The relatively low throughput of this technique, however, is not compatible with extensive screening. Laser ablation electrospray ionization (LAESI) MS combined with ion mobility separation (IMS) can analyze complex formation and provide conformation information within a matter of seconds. Islet amyloid polypeptide (IAPP) or amylin, a 37-amino acid residue peptide, is produced in pancreatic beta-cells through proteolytic cleavage of its prohormone. Both amylin and its precursor can aggregate and produce toxic oligomers and fibrils leading to cell death in the pancreas that can eventually contribute to the development of type 2 diabetes mellitus. The inhibitory effect of the copper(II) ion on amylin aggregation has been recently discovered, but details of the interaction remain unknown. Finding other more physiologically tolerated approaches requires large scale screening of potential inhibitors. In this paper, we demonstrate that LAESI-IMS-MS can reveal the binding stoichiometry, copper oxidation state, and the dissociation constant of human amylin–copper(II) complex. The conformations of hIAPP in the presence of copper(II) ions were also analyzed by IMS, and preferential association between the β-hairpin amylin monomer and the metal ion was found. The copper(II) ion exhibited strong association with the —HSSNN– residues of the amylin. In the absence of copper(II), amylin dimers were detected with collision cross sections consistent with monomers of β-hairpin conformation. When copper(II) was present in the solution, no dimers were detected. Thus, the copper(II) ions disrupt the association pathway to the formation of β-sheet rich amylin fibrils. Using LAESI-IMS-MS for the assessment of amylin–copper(II) interactions demonstrates the utility of this technique for the high-throughput screening of potential inhibitors of amylin oligomerization and fibril formation. Finally and more generally, this rapid technique opens the door for high-throughput screening of potential inhibitors of amyloid protein aggregation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Evaluating Effects of Shear Processing on 2D Crystalline Materials in 3D Metal Matrices: Atomistic Understanding of High Shear Deformation of Copper Graphene Composites

Composites made of copper and graphene demonstrate high strength, lubricity and enhanced electrical and thermal conductivity compared pure copper. However, manufacturing these composites at bulk volumes for industrial applications has been a big challenge. Shear deformation assisted processing is an effective method for manufacturing materials such as copper-graphene composites demonstrating ultra-fine grain structures and compositional homogeneity. Nevertheless, microstructural evolution of the composites and their property development under such conditions is not clearly understood currently. To rectify this gap in literature, high strain shear deformation of copper coated graphene foils was performed using a tribometer pin in this study. Changes in microstructure of the composite as well as the constituent components under shear deformation was correlated to process conditions. A sharp increase in the coefficient of friction attributed to rupture and smearing of graphene layer into copper substrate was observed during the shear processing. The coefficient of friction of the sheared copper/graphene composite was lower than that of pure copper, suggesting that partially worn graphene is effectively lubricious at the macroscale. A multimodal characterization of the processed region further revealed a shear deformation-induced ultrafine two-phase grain-structure consisting of copper and graphitic domains. Shear deformation reduced the copper grain size from around 50 – 100 µm to ~200 nm on an average and ~2 – 5 nm in some locations. The semicrystalline graphene films were observed to fracture into 10 – 50 µm size flakes. Oxygen enrichment was observed in the processed region. Finally, graphitic domain were identified for the first time in the copper matrix and not just at the grain boundaries providing evidence for a metastable composite microstructure as a result of solid phase processing at room temperature.

36 MATERIALS SCIENCE↗
NASA NTRS1983

Kinetics of copper ion absorption by cross-linked calcium polyacrylate membranes

The absorption of copper ions from aqueous copper acetate solutions by cross-linked calcium acrylate membranes was found to obey parabolic kinetics similar to that found for oxidation of metals that form protective oxide layers. For pure calcium polyacrylate membranes the rate constant was essentially independent of copper acetate concentration and film thickness. For a cross-linked copolymer film of polyvinyl alcohol and calcium polyacrylate, the rate constant was much greater and dependent on the concentration of copper acetate. The proposed mechanism in each case involves the formation of a copper polyacrylate phase on the surface of the membrane. The diffusion of the copper ion through this phase appears to be the rate controlling step for the copolymer film. The diffusion of the calcium ion is apparently the rate controlling step for the calcium polyacrylate. At low pH, the copper polyacrylate phase consists of the normal copper salt; at higher pH, the phase appears to be the basic copper salt.

Philipp, W. H.↗