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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 523 records · Page 29

Pushing the limits of size selectivity in nanoscale solute separations

Transport of a spherical solute through a cylindrical pore has been modelled for decades using well-established hindered transport theory, predicting solutes with a size smaller than the pore to be rejected nonetheless because of convective and diffusive hindrance; this rejection mechanism prevents extremely sharp solute separations by a membrane. Whereas the model has been historically verified, solute transport through near-perfect isoporous membranes may finally overcome this limitation. Here, in this study, encouraging solute rejections are achieved using nanofabricated, defect-free silicon nitride isoporous membranes. The membrane is challenged by a recirculated feed to increase the opportunity for interactions between solutes and the pore array. Results show the membrane completely reject solutes with greater size than the pore size while effectively allowing smaller solutes to permeate through. With effectively increasing the number of interactions, we propose that a steeper size-selective rejection curve may be achieved. With this traditional hurdle overcome, there is new promise for unprecedented membrane separations through judicious process design and extremely tight pore-size distributions.

Gao, Feng↗

Structural basis for Clostridium perfringens enterotoxin targeting of claudins at tight junctions in mammalian gut

The bacterium Clostridium perfringens causes severe, sometimes lethal gastrointestinal disorders in humans, including enteritis and enterotoxemia. Type F strains produce an enterotoxin (CpE) that causes the third most common foodborne illness in the United States. CpE induces gut breakdown by disrupting barriers at cell–cell contacts called tight junctions (TJs), which are formed and maintained by claudins. Targeted binding of CpE to specific claudins, encoded by its C-terminal domain (cCpE), loosens TJ barriers to trigger molecular leaks between cells. Cytotoxicity results from claudin-bound CpE complexes forming pores in cell membranes. In mammalian tissues, ~24 claudins govern TJ barriers—but the basis for CpE’s selective targeting of claudins in the gut was undetermined. We report the structure of human claudin-4 in complex with cCpE, which reveals that enterotoxin targets a motif conserved in receptive claudins and how the motif imparts high-affinity CpE binding to these but not other subtypes. The structural basis of CpE targeting is supported by binding affinities, kinetics, and half-lives of claudin–enterotoxin complexes and by the cytotoxic effects of CpE on claudin-expressing cells. By correlating the binding residence times of claudin–CpE complexes we determined to claudin expression patterns in the gut, we uncover that the primary CpE receptors differ in mice and humans due to sequence changes in the target motif. These findings provide the molecular and structural element CpE employs for subtype-specific targeting of claudins during pathogenicity of C. perfringens in the gut and a framework for new strategies to treat CpE-based illnesses in domesticated mammals and humans.

59 BASIC BIOLOGICAL SCIENCES↗

Developing Enzyme Immobilization with Fibrous Membranes: Longevity and Characterization Considerations

Fibrous membranes offer broad opportunities to deploy immobilized enzymes in new reactor and application designs, including multiphase continuous flow-through reactions. Enzyme immobilization is a technology strategy that simplifies the separation of otherwise soluble catalytic proteins from liquid reaction media and imparts stabilization and performance enhancement. Flexible immobilization matrices made from fibers have versatile physical attributes, such as high surface area, light weight, and controllable porosity, which give them membrane-like characteristics, while simultaneously providing good mechanical properties for creating functional filters, sensors, scaffolds, and other interface-active biocatalytic materials. This review examines immobilization strategies for enzymes on fibrous membrane-like polymeric supports involving all three fundamental mechanisms of post-immobilization, incorporation, and coating. Post-immobilization offers an infinite selection of matrix materials, but may encounter loading and durability issues, while incorporation offers longevity but has more limited material options and may present mass transfer obstacles. Coating techniques on fibrous materials at different geometric scales are a growing trend in making membranes that integrate biocatalytic functionality with versatile physical supports. Biocatalytic performance parameters and characterization techniques for immobilized enzymes are described, including several emerging techniques of special relevance for fibrous immobilized enzymes. Diverse application examples from the literature, focusing on fibrous matrices, are summarized, and biocatalyst longevity is emphasized as a critical performance parameter that needs increased attention to advance concepts from lab scale to broader utilization. This consolidation of fabrication, performance measurement, and characterization techniques, with guiding examples highlighted, is intended to inspire future innovations in enzyme immobilization with fibrous membranes and expand their uses in novel reactors and processes.

59 BASIC BIOLOGICAL SCIENCES↗

Structures of a synthetic antibody selected against and bound to the C‐terminal domain of Clostridium perfringens enterotoxin

Abstract Clostridium perfringensenterotoxin (CpE) causes cytotoxic gastrointestinal disease in mammalian epithelium by binding membrane protein receptors called claudins. Claudins direct the formation of cell/cell tight junctions through oligomerization and govern the transport of molecules between individual cells. CpE binds claudins through its C‐terminal domain (cCpE) and induces cytotoxicity through its N‐terminal domain. The non‐toxic cCpE is a useful tool to study claudins, tight junctions, and for translational applications, such as increasing the permeability of restrictive tissues like the blood–brain barrier or selective targeting of claudin overexpressing cancers. Conversely, there are no specialized molecular tools to study CpE or cCpE, or to modulate or inhibit their functions. We previously reported the development of synthetic antigen‐binding fragments (sFabs) that bind cCpE, and low‐resolution structures of them bound to claudin/cCpE complexes. Here, we determine high‐resolution structures of sFab COP‐2 bound to cCpE using X‐ray crystallography and cryogenic electron microscopy. The structures and biophysical findings provide the mechanism of COP‐2 binding to cCpE and the molecular determinants driving their interactions. These insights can advance the design of new antibody‐based tools from our COP‐2 scaffold to study or alter cCpE function and give rise to a “Trojan horse” strategy that exploits cCpE's tight junction barrier disrupting function to selectively deliver conjugated therapeutics through normally impermeable tissues.

Biochemistry & Molecular Biology↗

Gas Separations using Nanoporous Atomically Thin Membranes: Recent Theoretical, Simulation, and Experimental Advances

Abstract Porous graphene and other atomically thin 2D materials are regarded as highly promising membrane materials for high‐performance gas separations due to their atomic thickness, large‐scale synthesizability, excellent mechanical strength, and chemical stability. When these atomically thin materials contain a high areal density of gas‐sieving nanoscale pores, they can exhibit both high gas permeances and high selectivities, which is beneficial for reducing the cost of gas‐separation processes. Here, recent modeling and experimental advances in nanoporous atomically thin membranes for gas separations is discussed. The major challenges involved, including controlling pore size distributions, scaling up the membrane area, and matching theory with experimental results, are also highlighted. Finally, important future directions are proposed for real gas‐separation applications of nanoporous atomically thin membranes.

2D materials↗

Proton exchange membrane fuel cells

Disclosed embodiments concern a membrane electrode assembly or a proton exchange membrane fuel cell comprising a phosphoric acid-doped polymeric membrane comprising a cationic functional group, such as an assembly or fuel cell having an ion exchange capacity of 0.8 to 3 mmol/gram and an operating temperature range of from 80° C. to 220° C. The cationic functional group can be any suitable functional group, such as ammonium, imidazolium, guanidinium, phosphazenium, sulfonium, oxonium, and phosphonium, with working embodiments typically using quaternary ammonium cationic functional groups tethered to the polymeric core. The polymeric material may be any suitable polymeric material, such as a material selected from polyaryl polymers, polyarylamides, polyimides, polystyrenes, polysulfones, polyethers, polyether sulfones, polyketones, polyetherketones, polyarylethers, polyolefins, and polynitriles. The membrane electrode assembly or a proton exchange membrane fuel cell can be used in any application now known or hereafter developed, such as a vehicle or a stationary power device.

30 DIRECT ENERGY CONVERSION↗

Rapid Quantification of 237 U Specific Activity for Nuclear Forensics

In the event of an unattributed nuclear explosion, rapid assessment of the short-lived uranium isotope activity and mass can provide valuable information for subsequent forensic analysis. Rapid analysis in the field is enabled by using microfluidic chemistry and deployable instrumentation. Here, this work presents a flow chemistry system, controlled in LabVIEW, that integrates three functionalities: (1) selective extraction of uranium from the sample matrix via a 3D-printed supported liquid membrane module; (2) UV–visible absorbance spectrophotometry to measure the total uranium concentration in the strip flow; and (3) a portable CdTe γ-ray spectrometer coupled to a 3D-printed flow cell to measure 237 U activity concentration in the strip solution. The system was calibrated using standard solutions, and its functionality was demonstrated using a solution of depleted uranium spiked with 237 U. Uranium concentrations of 40–5000 μg/mL were directly quantified online using a 100 mm optical flow cell, while concentrations of 0.5–10 μg/mL were quantified online using a colorimetric reagent. The mass concentration measurement takes approximately 60 min while the activity concentration via γ-ray spectrometry varies depending on the activity of 237 U, with 1 kBq/mL requiring about 30 min of acquisition time to obtain <10% uncertainty at 1σ. This platform provides a fieldable approach for quantifying uranium mass and radioactivity relevant to postdetonation nuclear debris.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthetic antibodies against BRIL as universal fiducial marks for single-particle cryoEM structure determination of membrane proteins

We propose the concept of universal fiducials based on a set of pre-made semi-synthetic antibodies (sABs) generated by customized phage display selections against the fusion protein BRIL, an engineered variant of apocytochrome b562a. These sABs can bind to BRIL fused either into the loops or termini of different GPCRs, ion channels, receptors and transporters without disrupting their structure. A crystal structure of BRIL in complex with an affinity-matured sAB (BAG2) that bound to all systems tested delineates the footprint of interaction. Negative stain and cryoEM data of several examples of BRIL-membrane protein chimera highlight the effectiveness of the sABs as universal fiducial marks. Taken together with a cryoEM structure of sAB bound human nicotinic acetylcholine receptor, this work demonstrates that these anti-BRIL sABs can greatly enhance the particle properties leading to improved cryoEM outcomes, especially for challenging membrane proteins.

59 BASIC BIOLOGICAL SCIENCES↗

Disentangling the gap between pure and mixed-gas performance of thin film composite membranes through improved cell design and testing methods

Testing thin film composite (TFC) membrane coupons at low stage-cuts (≤5%) in a sweep-gas permeation system is a common practice to obtain mixed-gas separation properties for benchmarking performance and making scale-up decisions. However, even under these idealized conditions, mixed-gas permeance and selectivity can be more than 30% lower than their pure-gas values, partially due to concentration polarization, an effect that typically intensifies with increased membrane permeance. This study investigates the effect of cell design on mixed-gas testing using PolyActive TM TFC membranes with pure-gas CO 2 permeance of 1700 – 3100 gas permeance unit (GPU), covering the permeance range of most state-of-the-art CO 2 /N 2 separation membranes. Here, we designed and 3D-printed a counter-current permeation cell with enhanced feed and sweep flow efficiency, resulting in a 33 – 41% increase in mixed-gas CO 2 permeance compared to traditional permeation cells. Furthermore, we compared sweep-gas and vacuum permeation methods using traditional permeation cells, revealing that the latter delivers 41% higher mixed-gas CO 2 permeance, because vacuuming effectively minimizes the downstream concentration polarization. These findings highlight the importance of cell design and permeation apparatus selection in lab-scale mixed-gas testing, with strong implications for module design and process optimization at the industrial scale.

mixed gas performance↗

Effect of Viscosity of a Deep Eutectic Solvent on CO 2 Capture Performance in an Energy-Efficient Membrane Contactor-Based Process

Greenhouse gas contributions to climate change have driven intense interest in the separation of CO 2 from wet flue gas streams. Deep eutectic solvents (DESs) are an emerging class of highly selective CO 2 absorbents. A prototypical DES, reline, is a mixture of choline chloride and urea. Reline is a thermally stable, nontoxic, and biodegradable solvent with negligible volatility and is inexpensive. We demonstrate a scalable and energy-efficient hollow fiber membrane contactor (HFMC)-based process using a green solvent for CO 2 capture. This process uses reline in HFMC to provide close interfacial interactions and contact between DES and CO 2 . This approach overcomes the disadvantages associated with direct absorption in DES and could potentially be applied to a variety of solvent-based CO 2 capture methods. Commercial, low-cost polymer hollow fiber membranes were evaluated for the capture of CO 2 with reline. From a mixed gas containing N 2 and CO 2 , the DES-based HFMC separated CO 2 with a purity of 97 mol %. The effect of the viscosity of reline on the CO 2 capture performance was investigated by adding water to the reline. The addition of water to reline significantly reduced its viscosity, which led to a permeate flux of 170 mmol/(m 2 ·h) at 35 °C, 4 bar, and 60 wt % water in solvent, which was approximately 8 times higher than that of the pure reline in the membrane contactor system. In situ Fourier transform infrared spectroscopy and nuclear magnetic resonance (NMR) revealed that reline absorbs CO 2 by physical absorption without forming new chemical compounds and that CO 2 separation by reline occurs via the pressure swing mechanism. This research provides fundamental insights about green physical solvent-based separation processes and a pathway toward industrial deployment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluating the impact of functional groups on membrane‐mediated CO 2 / N 2 gas separations using a common polymer backbone

Abstract Polymeric membranes have shown tremendous promise for the separation of CO 2 from flue gas streams. However, few systematic studies have been conducted to better understand the impact that chemical functionalities have on membrane‐based gas separation performance. To address this gap, we herein describe the synthesis and gas separation performance of a series of vinyl‐addition polynorbornenes bearing various CO 2 ‐philic functional groups. To facilitate direct comparison between functional groups, each material was designed to maintain a common polymer backbone. Though the incorporation of CO 2 ‐philic moieties within a dense polymeric membrane is frequently hypothesized to enhance CO 2 solubility, and thereby increase CO 2 /N 2 selectivity, our results demonstrate that the incorporation of CO 2 ‐philic groups onto a common polymer backbone do not necessarily result in increased gas separation performance. Experimental and computational results demonstrate that the incorporation of amidoxime groups onto a polynorbornene backbone increase CO 2 /N 2 selectivity, whereas commonly employed ethereal side chains only increased permeability.

Higgins, Morgan A.↗

Cell specific photoswitchable agonist for reversible control of endogenous dopamine receptors

Dopamine controls diverse behaviors and their dysregulation contributes to many disorders. Our ability to understand and manipulate the function of dopamine is limited by the heterogenous nature of dopaminergic projections, the diversity of neurons that are regulated by dopamine, the varying distribution of the five dopamine receptors (DARs), and the complex dynamics of dopamine release. In order to improve our ability to specifically modulate distinct DARs, here we develop a photo-pharmacological strategy using a Membrane anchored Photoswitchable orthogonal remotely tethered agonist for the Dopamine receptor (MP-D). Our design selectively targets D1R/D5R receptor subtypes, most potently D1R (MP-D1 ago ), as shown in HEK293T cells. In vivo, we targeted dorsal striatal medium spiny neurons where the photo-activation of MP-D1 ago increased movement initiation, although further work is required to assess the effects of MP-D1 ago on neuronal function. Our method combines ligand and cell type-specificity with temporally precise and reversible activation of D1R to control specific aspects of movement. Our results provide a template for analyzing dopamine receptors.

59 BASIC BIOLOGICAL SCIENCES↗

Structural basis for enzymatic terminal C–H bond functionalization of alkanes

Alkane monooxygenase (AlkB) is a widely occurring integral membrane metalloenzyme that catalyzes the initial step in the functionalization of recalcitrant alkanes with high terminal selectivity. AlkB enables diverse microorganisms to use alkanes as their sole carbon and energy source. Here we present the 48.6-kDa cryo-electron microscopy structure of a natural fusion from Fontimonas thermophila between AlkB and its electron donor AlkG at 2.76 Å resolution. The AlkB portion contains six transmembrane helices with an alkane entry tunnel within its transmembrane domain. A dodecane substrate is oriented by hydrophobic tunnel-lining residues to present a terminal C–H bond toward a diiron active site. AlkG, an [Fe–4S] rubredoxin, docks via electrostatic interactions and sequentially transfers electrons to the diiron center. The archetypal structural complex presented reveals the basis for terminal C–H selectivity and functionalization within this broadly distributed evolutionary class of enzymes.

59 BASIC BIOLOGICAL SCIENCES↗

In vivo human T cell engineering with enveloped delivery vehicles

Viruses and virally derived particles have the intrinsic capacity to deliver molecules to cells, but the difficulty of readily altering cell-type selectivity has hindered their use for therapeutic delivery. Here, we show that cell surface marker recognition by antibody fragments displayed on membrane-derived particles encapsulating CRISPR–Cas9 protein and guide RNA can deliver genome editing tools to specific cells. Compared to conventional vectors like adeno-associated virus that rely on evolved capsid tropisms to deliver virally encoded cargo, these Cas9-packaging enveloped delivery vehicles (Cas9-EDVs) leverage predictable antibody–antigen interactions to transiently deliver genome editing machinery selectively to cells of interest. Antibody-targeted Cas9-EDVs preferentially confer genome editing in cognate target cells over bystander cells in mixed populations, both ex vivo and in vivo. By using multiplexed targeting molecules to direct delivery to human T cells, Cas9-EDVs enable the generation of genome-edited chimeric antigen receptor T cells in humanized mice, establishing a programmable delivery modality with the potential for widespread therapeutic utility.

42 ENGINEERING↗

Long-Term Statistical Process Monitoring of an Ultrafiltration Water Treatment Process

As water treatment technology has improved, the amount of available process data has substantially increased, making real-time, data-driven fault detection a reality. One shortcoming of the fault detection literature is that methods are usually evaluated by comparing their performance on hand-picked, short-term case studies, which yields no insight into long-term performance. In this work, we first evaluate multiple statistical and machine learning approaches for detrending process data. Then, we evaluate the performance of a PCA-based fault detection approach, applied to the detrended data, to monitor influent water quality, filtrate quality, and membrane fouling of an ultrafiltration membrane system for indirect potable reuse. Based on two short case studies, the adaptive lasso detrending method is selected, and the performance of the multivariate approach is evaluated over more than a year. The method is tested for different sets of three critical tuning parameters, and we find that for long-term, autonomous monitoring to be successful, these parameters should be carefully evaluated. However, in comparison with industry standards of simpler, univariate monitoring or daily pressure decay tests, multivariate monitoring produces substantial benefits in long-term testing.

ammonia↗

In Situ Tracking of Nonthermal Plasma Etching of ZIF-8 Films

Surface characterization is critical for understanding the processes used for preparing catalysts, sorbents, and membranes. Nonthermal plasma (NTP) is a process that achieves high reactivity at low temperatures and is used to tailor the surface properties of materials. In this work, we combine the capabilities of infrared reflection absorption spectroscopy (IRRAS) with NTP for the in situ interrogation of zeolitic imidazolate framework-8 (ZIF-8) thin films to probe modifications in the material induced by oxygen and nitrogen plasmas. The IRRAS measurements in oxygen plasma reveal etching of organic ligands with sequential removal of the methyl group and imidazole ring and with the formation of carbonyl moieties (C═O). In contrast, nitrogen plasma induces mild etching and grafting of nitrile groups (−C≡N). Scanning electron microscopy imaging shows that oxygen plasma, at prolonged times, significantly degrades the ZIF-8 film at the grain boundaries. Treatment of ZIF-8 membranes using mild plasma conditions yields a fivefold enhancement for H 2 /N 2 and CO 2 /CH 4 ideal selectivities and an eightfold enhancement for CO 2 /N 2 ideal selectivity. Additionally, the new tools described here can be used for spectroscopic in situ tracking of plasma-induced chemistry on thin films in general.

IRRAS↗