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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 109 records · Page 6

Selective Biosorption of Valuable Rare Earth Elements Among Co-Occurring Lanthanides

To meet the increasing demand for rare earth elements (REEs) essential for low carbon-intensity energy technologies, new methods are needed for selective REE extraction from unconventional resources. Only a few REEs have significant economic value, but isolation of target rare earths from co-occurring lanthanides is challenging due to their similar chemical behavior. We present a novel approach to enhance separation of specific REEs from lanthanide mixtures. Escherichia coli cells engineered with lanthanide binding tags (LBTs) were immobilized in nonadsorbing, permeable polyethylene glycol diacrylate beads and packed into continuous flow, fixed-bed columns. Breakthrough of 15 rare earths in the +3 oxidation state resulted in notable differences in adsorption selectivity, with greatest separation between europium (Eu) and lanthanum (La) due to competitive displacement. REE adsorption onto fixed-bed columns was predicted by coupling a surface complexation model to a calibrated one-dimensional dual porosity transport model that accounts for interbead advective and intrabead diffusive transport. A tradeoff between high-abundance, low-affinity native carboxyl sites and low-abundance, high-affinity engineered LBT sites dictates process recovery efficiency and selectivity. Key chemical and operational parameters are identified to maximize selective extraction of high-value lanthanides, achieving a threefold enhancement of Eu recovery relative to La in a mixed REE solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Steric regulation of tandem calponin homology domain actin-binding affinity

Tandem calponin homology (CH1–CH2) domains are common actin-binding domains in proteins that interact with and organize the actin cytoskeleton. Despite regions of high sequence similarity, CH1–CH2 domains can have remarkably different actin-binding properties, with disease-associated point mutants known to increase as well as decrease affinity for F-actin. To investigate features that affect CH1–CH2 affinity for F-actin in cells and in vitro, we perturbed the utrophin actin-binding domain by making point mutations at the CH1–CH2 interface, replacing the linker domain, and adding a polyethylene glycol (PEG) polymer to CH2. Consistent with a previous model describing CH2 as a steric negative regulator of actin binding, we find that utrophin CH1–CH2 affinity is both increased and decreased by modifications that change the effective “openness” of CH1 and CH2 in solution. We also identified interface mutations that caused a large increase in affinity without changing solution “openness,” suggesting additional influences on affinity. Interestingly, we also observe nonuniform subcellular localization of utrophin CH1–CH2 that depends on the N-terminal flanking region but not on bulk affinity. Finally, these observations provide new insights into how small sequence changes, such as those found in diseases, can affect CH1–CH2 binding properties.

59 BASIC BIOLOGICAL SCIENCES↗

Osmosensing by WNK Kinases

With No Lysine (K) WNK kinases regulate electro-neutral cotransporters that are controlled by osmotic stress and chloride. We showed previously that autophosphorylation of WNK1 is inhibited by chloride, raising the possibility that WNKs are activated by osmotic stress. Here we demonstrate that unphosphorylated WNK isoforms 3 and 1 autophosphorylate in response to osmotic pressure in vitro, applied with the crowding agent polyethylene glycol (PEG)400 or osmolyte ethylene glycol (EG), and that this activation is opposed by chloride. Small angle x-ray scattering of WNK3 in the presence and absence of PEG400, static light scattering in EG, and crystallography of WNK1 were used to understand the mechanism. Osmosensing in WNK3 and WNK1 appears to occur through a conformational equilibrium between an inactive, unphosphorylated, chloride-binding dimer and an autophosphorylation-competent monomer. An improved structure of the inactive kinase domain of WNK1, and a comparison with the structure of a monophosphorylated form of WNK1, suggests that large cavities, greater hydration, and specific bound water may participate in the osmosensing mechanism. Our prior work showed that osmolytes have effects on the structure of phosphorylated WNK1, suggestive of multiple stages of osmotic regulation in WNKs.

59 BASIC BIOLOGICAL SCIENCES↗

Novel Functional Thermal Energy Storage Materials for Buildings Applications

The leakage of solid-liquid phase change materials (PCMs) tremendously limits their long-term application in thermal energy storage (TES). In this work, we present durable and form-stable shape-stabilized PCMs (ss-PCMs) for TES in building envelopes. These ss-PCMs are fabricated by encapsulating polyethylene glycol (PEG) consisting of different molecular weights within mesoporous magnesium oxide and silica dioxide. For the first time, the phase transition temperature (Tt) of ss-PCMs has been fine-tuned synthetically to be comfortable to building occupants by utilizing PEG blends with molecular weights of 600 and 800 g/mol. Several parameters, including surface hydrophilicity/hydrophobicity, surface area, and PCM loading percentage, have been studied to maximize the latent heat enthalpy for high energy efficiency and maintain form stability. The best ss-PCM candidate with suitable Tt and appreciable latent heat enthalpy exhibits a repeatable phase change behavior for up to 1,000 thermal cycles without leakage, which provides a promising solution for durable TES in buildings. The Tt tunability extends its application over a wider temperature range beyond buildings.

building envelope↗

Space-tiled colloidal crystals from DNA-forced shape-complementary polyhedra pairing

Generating space-filling arrangements of most discrete polyhedra nanostructures of the same shape is not possible. However, if the appropriate individual building blocks are selected (e.g., cubes), or multiple shapes of the appropriate dimensions are matched (e.g., octahedra and tetrahedra) and their pairing interactions are subsequently forced, space-filled architectures may be possible. With flexible molecular ligands (polyethylene glycol–modified DNA), the shape of a polyhedral nanoparticle can be deliberately altered and used to realize geometries that favor space tessellation. In this work, 10 new colloidal crystals were synthesized from DNA-modified nanocrystal building blocks that differed in shapes and sizes, designed to form space-filling architectures with micron-scale dimensions. The insights and capabilities provided by this new strategy substantially expand the scope of colloidal crystals possible and provide an expanded tool kit for researchers interested in designing metamaterials.

Science & Technology - Other Topics↗

Antibacterial activity of iron oxide, iron nitride, and tobramycin conjugated nanoparticles against Pseudomonas aeruginosa biofilms

Novel methods are necessary to reduce morbidity and mortality of patients suffering from infections with Pseudomonas aeruginosa. Being the most common infectious species of the Pseudomonas genus, P. aeruginosa is the primary Gram-negative etiology responsible for nosocomial infections. Due to the ubiquity and high adaptability of this species, an effective universal treatment method for P. aeruginosa infection still eludes investigators, despite the extensive research in this area. Results We report bacterial inhibition by iron-oxide (nominally magnetite) nanoparticles (NPs) alone, having a mean hydrodynamic diameter of ~ 16 nm, as well as alginate-capped iron-oxide NPs. Alginate capping increased the average hydrodynamic diameter to ~ 230 nm. We also investigated alginate-capped iron-oxide NP-drug conjugates, with a practically unchanged hydrodynamic diameter of ~ 232 nm. Susceptibility and minimum inhibitory concentration (MIC) of the NPs, NP-tobramycin conjugates, and tobramycin alone were determined in the PAO1 bacterial colonies. Investigations into susceptibility using the disk diffusion method were done after 3 days of biofilm growth and after 60 days of growth. MIC of all compounds of interest was determined after 60-days of growth, to ensure thorough establishment of biofilm colonies. Conclusions Positive inhibition is reported for uncapped and alginate-capped iron-oxide NPs, and the corresponding MICs are presented. We report zero susceptibility to iron-oxide NPs capped with polyethylene glycol, suggesting that the capping agent plays a major role in enabling bactericidal ability in of the nanocomposite. Our findings suggest that the alginate-coated nanocomposites investigated in this study have the potential to overcome the bacterial biofilm barrier. Magnetic field application increases the action, likely via enhanced diffusion of the iron-oxide NPs and NP-drug conjugates through mucin and alginate barriers, which are characteristic of cystic-fibrosis respiratory infections. We demonstrate that iron-oxide NPs coated with alginate, as well as alginate-coated magnetite–tobramycin conjugates inhibit P. aeruginosa growth and biofilm formation in established colonies. We have also determined that susceptibility to tobramycin decreases for longer culture times. However, susceptibility to the iron-oxide NP compounds did not demonstrate any comparable decrease with increasing culture time. These findings imply that iron-oxide NPs are promising lower-cost alternatives to silver NPs in antibacterial coatings, solutions, and drugs, as well as other applications in which microbial abolition or infestation prevention is sought.

Biotechnology & Applied Microbiology↗

Molecular Imaging of Matrix Metalloproteinase-2 in Atherosclerosis Using a Smart Multifunctional PET/MRI Nanoparticle

Matrix metalloproteinases from macrophages are important intraplaque components that play pivotal roles in plaque progression and regression. This study sought to develop a novel multifunctional positron emission tomography (PET) and magnetic resonance imaging (MRI) contrast agents based on MMP-2 cleavable nanoparticles to noninvasive assessment of MMP-2 activity in mouse carotid atherosclerotic plaques. Macrophage-rich vascular lesions were induced by carotid ligation plus high-fat diet and streptozotocin-induced diabetes in CL57/BL6 mice. To render iron oxide nanoparticles (IONP) specific for the extracellular MMP-2, the magnetic nanoparticle base material has been derivatized with 1,4,7-triazacyclononane-1,4,7-triacetic acid (NOTA) for the nuclear tracer 64 Cu labeling and the MMP-2-cleavable peptide modified with polyethylene glycol 2000, yielding a multi-modality reporter ( 64 Cu-NOTA-IONP@MMP2c-PEG2K, MMP2cNPs) for PET/MR imaging. Small animal PET imaging and biodistribution data revealed that MMP2cNPs exhibited remarkable plaque uptake (3.06 ± 0.87% ID/g and 1.83 ± 0.28% ID/g at 4 and 12 h, respectively). And MMP2cNPs were rapidly cleared from the contralateral normal carotid artery, resulting in excellent plaque-to-normal carotid artery contrasts. Furthermore, in vivo MRI showed a preferential accumulation of MMP2cNPs in atherosclerotic lesions compared with the non-cleavable reference compound, MMP2ncNPs. In addition, histological analyses revealed iron accumulations in the carotid atherosclerotic plaque, in colocalization with MMP-2 expression and macrophages. Using a combination of innovative imaging modalities, in this study, we demonstrate the feasibility of applying the novel smart MMP2cNPs as a PET/MR hybrid imaging contrast agent for detection of MMP-2 in atherosclerotic plaque in vivo.

60 APPLIED LIFE SCIENCES↗

Development of 3D Printing Techniques for Solid-State Lithium Batteries: Energy Storage Internship (Final Report)

The goal of this internship was to develop a solid polymer electrolyte with a suitable ionic conductivity and mechanical properties and integrate it with 3D printed cathode for solid state lithium batteries. While liquid electrolytes will have much higher conductivities and therefore higher power densities than solid electrolytes, batteries with such electrolytes suffer from extreme dendritic growth, short-circuiting, and general failure. Typically, batteries prevent this by including a solid yet porous separator somewhere between the anode and cathode to suppress dendritic growth. Solid polymer electrolyte acts as the conductive medium between electrodes as well as the separator that prevents failure from short-circuiting. The specific system explored is a vinyl ethylene carbonate (VEC) and polyethylene glycol diacrylate (PEGDA) mixed polymer solution using both 2,2’-azobis(2-methylpropionitrile) (AIBN) and Irgacure 819, respectively as thermal and photo- initiators. Electrochemical and rheological techniques were used to determine the optimal polymer solution and curing conditions. Through this research, multiple new pathways of exploration have been determined to create a usable solid polymer electrolyte through a combination of varying cure intensities and initiator concentrations.

25 ENERGY STORAGE↗

Synthesis of Hydrophilic Derivative Surfactants From Algae-Derived Unsaponifiable Lipids

In the context of decarbonizing the economy, the utilization of biologically sourced feedstocks to produce replacements for petroleum-derived materials is becoming more urgent. Improving renewable biomass production and utilization is imperative for commercializing future biorefineries. Algae-derived biomass is a particularly promising feedstock thanks to its attractive oil content and composition; specifically, the high-value products in the unsaponifiable lipids have not been included in a conversion process. Here we demonstrate surfactant synthesis from a complex oil fraction as the hydrophobic donor moieties, yielding products that are similar to commercially available surfactants such as the linear alkyl benzene sulfonates. Unsaponifiable lipids extracted from algae were derivatized to non-ionic surfactants using a green chemical synthesis route based on a double esterification with succinic acid and polyethylene glycol. The in-depth molecular and structural surfactant characterization is included and indicates that the resulting properties fall between those of pure cholesterol and phytol used as surrogates for the reaction synthesis demonstration. This is the first demonstration of an effective and potentially high-value synthesis of functional surfactants with properties that can be tailored based on the relative composition of the resulting hydrocarbon alcohol components in the mixture. This novel green chemistry synthesis approach provides a route to high-value product synthesis from algae.

09 BIOMASS FUELS↗

Solvent-Induced Selectivity of Isoprene From Bio-Derived Prenol

In this work we demonstrate the selective catalytic conversion of prenol, which is an allylic alcohol that can be prepared from renewable resources to isoprene. The catalyst is an inexpensive molybdenum complex (Molyvan L) designed and used as an additive for lubricants. Isoprene is generated under relatively mild reaction parameters at 130–150°C, for 2 h, under vapor pressure conditions that do not exceed 50 psi. Two cases were studied: one in which Molyvan L was dissolved in a base oil at 1% concentration (weight/weight) and then mixed with a solvent and prenol and the other in which neat Molyvan L was introduced in the reaction and the base oil was replaced with the solvent and prenol. We investigated the selectivity of the reaction using the following solvents in both cases: dodecane, dodecanol, isododecane, octane, blendstock for oxygenate blending (BOB3), a fuel surrogate, a polyalphaolefin (PAO4), and methoxy polyethylene glycol (methoxy PEG350). Although conversion of prenol was above 94% in all experiments, isoprene was formed with various degrees of efficiency alongside a prenol isomeric alcohol, diprenyl ether and mixed ether via intramolecular and intermolecular dehydration reactions. Dodecane appeared to have the highest level of selectivity initially in base oil so we studied the effect of various dodecane-like solvents on isoprene yield and product profile. Surprisingly, octane (similar to dodecane) and isododecane (branched alkane) generated insignificant amounts of byproducts, essentially providing the highly desired isoprene with a very high selectivity. Branching of the solvent does not appear to have an effect on selectivity. Another advantage of this catalyst is the low loadings required to effect the transformation; that is, 0.25% (weight/volume) in the cases using neat Molyvan L and 0.5% (weight/volume) in the cases using Molyvan L dissolved in the base oil. Provided that prenol can be produced in large scale from bioresources, this work would enable the sustainable production of isoprene, in good yield, and with very high selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tuning gold-based surface functionalization for streptavidin detection: A combined simulative and experimental study

A rationally designed gold-functionalized surface capable of capturing a target protein is presented using the biotin–streptavidin pair as a proof-of-concept. We carried out multiscale simulations to shed light on the binding mechanism of streptavidin on four differently biotinylated surfaces. Brownian Dynamics simulations were used to reveal the preferred initial orientation of streptavidin over the surfaces, whereas classical molecular dynamics was used to refine the binding poses and to investigate the fundamental forces involved in binding, and the binding kinetics. We assessed the binding events and the stability of the streptavidin attachment through a quartz crystal microbalance with dissipation monitoring (QCM-D). The sensing element comprises of biotinylated polyethylene glycol chains grafted on the sensor’s gold surface via thiol-Au chemistry. Finally, we compared the results from experiments and simulations. We found that the confined biotin moieties can specifically capture streptavidin from the liquid phase and provide guidelines on how to exploit the microscopic parameters obtained from simulations to guide the design of further biosensors with enhanced sensitivity.

59 BASIC BIOLOGICAL SCIENCES↗

Effect of Polyphenylsulfone and Polysulfone Incompatibility on the Structure and Performance of Blend Membranes for Ultrafiltration

This study deals with the modification of polyphenylsulfone ultrafiltration membranes by introduction of an incompatible polymer polysulfone to the polyphenylsulfone casting solution to improve the permeability. The correlation between properties of the blend polyphenylsulfone/polysulfone solutions and porous anisotropic membranes for ultrafiltration prepared from these solutions was revealed. The blend polyphenylsulfone/polysulfone solutions were investigated using a turbidity spectrum method, optical microscopy and measurements of dynamic viscosity and turbidity. The structure of the prepared blend flat sheet membranes was studied using scanning electron microscopy. Membrane separation performance was investigated in the process of ultrafiltration of human serum albumin buffered solutions. It was found that with the introduction of polysulfone to the polyphenylsulfone casting solution in N-methyl-2-pyrrolidone the size of supramolecular particles significantly increases with the maximum at (40–60):(60:40) polyphenylsulfone:polysulfone blend ratio from 76 nm to 196–354 nm. It was shown that polyphenylsulfone/polysulfone blend solutions, unlike the solutions of pristine polymers, are two-phase systems (emulsions) with the maximum droplet size and highest degree of polydispersity at polyphenylsulfone/polysulfone blend ratios (30–60):(70–40). Pure water flux of the blend membranes passes through a maximum in the region of the most heterogeneous structure of the casting solution, which is associated with the imposition of a polymer-polymer phase separation on the non-solvent induced phase separation upon membrane preparation. The application of polyphenylsulfone/polysulfone blends as membrane-forming polymers and polyethylene glycol (Mn = 400 g·mol -1 ) as a pore-forming agent to the casting solutions yields the formation of ultrafiltration membranes with high membrane pure water flux (270 L·m -2 ·h -1 at 0.1MPa) and human serum albumin rejection of 85%.

36 MATERIALS SCIENCE↗

Viscoelastic Particle Focusing and Separation in a Spiral Channel

As one type of non-Newtonian fluid, viscoelastic fluids exhibit unique properties that contribute to particle lateral migration in confined microfluidic channels, leading to opportunities for particle manipulation and separation. In this paper, particle focusing in viscoelastic flow is studied in a wide range of polyethylene glycol (PEO) concentrations in aqueous solutions. Polystyrene beads with diameters from 3 to 20 μm are tested, and the variation of particle focusing position is explained by the coeffects of inertial flow, viscoelastic flow, and Dean flow. We showed that particle focusing position can be predicted by analyzing the force balance in the microchannel, and that particle separation resolution can be improved in viscoelastic flows.

42 ENGINEERING↗

Magnetic-Core/Gold-Shell Nanoparticles for the Detection of Hydrophobic Chemical Contaminants

Magnetic-core/gold-shell nanoparticles (MAuNPs) are of interest for enabling rapid and portable detection of trace adulterants in complex media. Gold coating provides biocompatibility and facile functionalization, and a magnetic core affords analyte concentration and controlled deposition onto substrates for surface-enhanced Raman spectroscopy. Iron oxide cores were synthesized and coated with gold by reduction of HAuCl4 by NH2OH. MAuNPs were grafted with polyethylene glycol (PEG) and/or functionalized with 4-mercaptobenzoic acid (4-MBA) and examined using a variety of microscopic, spectroscopic, magnetometric, and scattering techniques. For MAuNPs grafted with both PEG and 4-MBA, the order in which they were grafted impacted not only the graft density of the individual ligands, but also the overall graft density. Significant Raman signal enhancement of the model analyte, 4-MBA, was observed. This enhancement demonstrates the functionality of MAuNPs in direct detection of trace contaminants. The magnetic deposition rate of MAuNPs in chloroform and water was explored. The presence of 4-MBA slowed the mass deposition rate, and it was postulated that the rate disparity originated from differing NP-substrate surface interactions. These findings emphasize the importance of ligand choice in reference to the medium, target analyte, and substrate material, as well as functionalization procedure in the design of similar sensing platforms.

36 MATERIALS SCIENCE↗

Electrospun PVA Fibers for Drug Delivery: A Review

Innovation in biomedical science is always a field of interest for researchers. Drug delivery, being one of the key areas of biomedical science, has gained considerable significance. The utilization of simple yet effective techniques such as electrospinning has undergone significant development in the field of drug delivery. Various polymers such as PEG (polyethylene glycol), PLGA (Poly(lactic-co-glycolic acid)), PLA(Polylactic acid), and PCA (poly(methacrylate citric acid)) have been utilized to prepare electrospinning-based drug delivery systems (DDSs). Polyvinyl alcohol (PVA) has recently gained attention because of its biocompatibility, biodegradability, non-toxicity, and ideal mechanical properties as these are the key factors in developing DDSs. Moreover, it has shown promising results in developing DDSs individually and when combined with natural and synthetic polymers such as chitosan and polycaprolactone (PCL). Considering the outstanding properties of PVA, the aim of this review paper was therefore to summarize these recent advances by highlighting the potential of electrospun PVA for drug delivery systems.

59 BASIC BIOLOGICAL SCIENCES↗

Monolithic Polyepoxide Membranes for Nanofiltration Applications and Sustainable Membrane Manufacture

The present work details the development of carbon fiber-reinforced epoxy membranes with excellent rejection of small-molecule dyes. It is a proof-of-concept for a more sustainable membrane design incorporating carbon fibers, and their recycling and reuse. 4,4′-methylenebis(cyclohexylamine) (MBCHA) polymerized with either bisphenol-A-diglycidyl ether (BADGE) or tetraphenolethane tetraglycidylether (EPON Resin 1031) in polyethylene glycol (PEG) were used to make monolithic membranes reinforced by nonwoven carbon fibers. Membrane pore sizes were tuned by adjusting the molecular weight of the PEG used in the initial polymerization. Membranes made of BADGE-MBCHA showed rejection of Rose Bengal approaching 100%, while tuning the pore sizes substantially increased the rejection of Methylene Blue from ~65% to nearly 100%. The membrane with the best permselectivity was made of EPON-MBCHA polymerized in PEG 300. It has an average DI flux of 4.48 LMH/bar and an average rejection of 99.6% and 99.8% for Rose Bengal and Methylene Blue dyes, respectively. Degradation in 1.1 M sodium hypochlorite enabled the retrieval of the carbon fiber from the epoxy matrix, suggesting that the monolithic membranes could be recycled to retrieve high-value products rather than downcycled for incineration or used as a lower selectivity membrane. The mechanism for epoxy degradation is hypothesized to be part chemical and part physical due to intense swelling stress leading to erosion that leaves behind undamaged carbon fibers. The retrieved fibers were successfully used to make another membrane exhibiting similar performance to those made with pristine fibers.

Polymer Science↗

New polymers for phase partitioning

The synthesizing of several polyethylene glycols having crown ethers attached is reported. This work led to the identification of three new polymer types which promise to be more effective at selectively binding specific cell types. Work was completed on identification of chemical properties of the new polymer crowns and on development of new techniques for determination of polymer-phase composition.

Harris, J. M.↗

A theory of electrophoresis of emulsion drops in aqueous two-phase polymer systems

An electrophoresis study has been carried out in an emulsion formed from an electrically neutral aqueous mixture of dextran and polyethylene glycol equilibrated at sufficient concentrations in the presence of electrolytes. Electrophoresis of a drop of one phase suspended in the other is observed, and the direction of the drop's motion is reversed when the disperse phase and the continuous phase are interchanged. In the presence of sulfate, phosphate, or citrate ions, an electrostatic potential difference of the order of a few mV exists between the two phases. The potential implied by the direction of the electrophoretic motion is opposite to the Donnan potential observed between the two phases. The mobility of an emulsion drop increases with the drop radius and depends on ion concentration. These results are explained in terms of a model postulating an electric dipole layer associated with a mixture of oriented polymer molecules at the surface of a drop, with a potential difference between the interiors of the two phases resulting from the unequal ion distribution.

Levine, S.↗