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DOE OSTI2021

Functionalized Embedded Monometallic Nickel Catalysts for Enhanced Hydrogen Evolution: Performance and Stability

Viable anionic exchange membrane (AEM) electrolysis for H 2 production requires highly active hydrogen evolution reaction (HER) catalysts that are also robust and cost-effective. Traditionally juxtaposition of two transition metals with one being more oxophilic is necessary for easier access to water in the inner Helmholtz plane as a source of protons in the crucial Volmer step for enhanced HER activity. However, they are prone to passivation at anodic potentials or deactivation via the formation of sub-surface metal hydrides at high cathodic overpotentials. Here we report a method of enabling close juxtaposition of Ni-Ni-oxide surfaces by functionalizing Ni-based catalysts via the careful thermal treatment of carbon-supported Ni nano-particles chelated with a select organic chelating compound referred to as cupferron. This functionalization results in an embedded Ni surface with a clear graphitic coating engendering long-term stability for passivation and subsurface hydride formation. The stability and activity of the functionalized Ni catalyst are demonstrated in half-cell RDE and full-cell AEM membrane-based hydrogen pump experiments. In the case of the latter, the functionalized Ni outperforms carbon-supported Pt.

25 ENERGY STORAGE↗

NASA NTRS2004

Centrifugal Adsorption Cartridge System

The centrifugal adsorption cartridge system (CACS) is an apparatus that recovers one or more bioproduct(s) from a dilute aqueous solution or suspension flowing from a bioreactor. The CACS can be used both on Earth in unit gravity and in space in low gravity. The CACS can be connected downstream from the bioreactor; alternatively, it can be connected into a flow loop that includes the bioreactor so that the liquid can be recycled. A centrifugal adsorption cartridge in the CACS (see figure) includes two concentric cylinders with a spiral ramp between them. The volume between the inner and outer cylinders, and between the turns of the spiral ramp is packed with an adsorbent material. The inner cylinder is a sieve tube covered with a gas-permeable, hydrophobic membrane. During operation, the liquid effluent from the bioreactor is introduced at one end of the spiral ramp, which then constrains the liquid to flow along the spiral path through the adsorbent material. The spiral ramp also makes the flow more nearly uniform than it would otherwise be, and it minimizes any channeling other than that of the spiral flow itself. The adsorbent material is formulated to selectively capture the bioproduct(s) of interest. The bioproduct(s) can then be stored in bound form in the cartridge or else eluted from the cartridge. The centrifugal effect of the spiral flow is utilized to remove gas bubbles from the liquid. The centrifugal effect forces the bubbles radially inward, toward and through the membrane of the inner cylinder. The gas-permeable, hydrophobic membrane allows the bubbles to enter the inner cylinder while keeping the liquid out. The bubbles that thus enter the cylinder are vented to the atmosphere. The spacing between the ramps determines rate of flow along the spiral, and thereby affects the air-bubble-removal efficiency. The spacing between the ramps also determines the length of the fluid path through the cartridge adsorbent, and thus affects the bioproduct-capture efficiency of the cartridge. Depending on the application, several cartridges could be connected in a serial or parallel flow arrangement. A parallel arrangement can be used to increase product-capturing and flow capacities while maintaining a low pressure drop. A serial arrangement can be used to obtain high product-capturing capacity; alternatively, series-connected cartridges can be packed with different adsorbents to capture different bioproducts simultaneously.

Gonda, Steve R.↗

DOE OSTI2024

“Off‐Label Use” of the Siderophore Enterobactin Enables Targeted Imaging of Cancer with Radioactive Ti (IV)

Abstract The development of inert, biocompatible chelation methods is required to harness the emerging positron emitting radionuclide 45 Ti for radiopharmaceutical applications. Herein, we evaluate the Ti (IV) ‐coordination chemistry of four catechol‐based, hexacoordinate chelators using synthetic, structural, computational, and radiochemical approaches. The siderophore enterobactin (Ent) and its synthetic mimic TREN‐CAM readily form mononuclear Ti (IV) species in aqueous solution at neutral pH. Radiolabeling studies reveal that Ent and TREN‐CAM form mononuclear complexes with the short‐lived, positron‐emitting radionuclide 45 Ti (IV) , and do not transchelate to plasma proteins in vitro and exhibit rapid renal clearance in naïve mice. These features guide efforts to target the 45 Ti isotope to prostate cancer tissue through the design, synthesis, and evaluation of Ent‐DUPA, a small molecule conjugate composed of a prostate specific membrane antigen (PSMA) targeting peptide and a monofunctionalized Ent scaffold. The [ 45 Ti][Ti(Ent‐DUPA)] 2− complex forms readily at room temperature. In a tumor xenograft model in mice, selective tumor tissue accumulation (8±5 %, n =5), and low off‐target uptake in other organs is observed. Overall, this work demonstrates targeted imaging with 45 Ti (IV) , provides a foundation for advancing the application of 45 Ti in nuclear medicine, and reveals that Ent can be repurposed as a 45 Ti‐complexing cargo for targeted nuclear imaging applications.

Koller, Angus J.↗

DOE OSTI2025

Unique Structural Features Relate to Evolutionary Adaptation of Cytochrome P450 in the Abyssal Zone

Cytochromes P450 (CYPs) form one of the largest enzyme superfamilies, with similar structural folds yet biological functions varying from synthesis of physiologically essential compounds to metabolism of myriad xenobiotics. Sterol 14α-demethylases (CYP51s) represent a very special P450 family, regarded as a possible evolutionary progenitor for all currently existing P450s. In metazoans CYP51 is critical for the biosynthesis of sterols including cholesterol. Here we determined the crystal structures of ligand-free CYP51s from the abyssal fish Coryphaenoides armatus and human-. Comparative sequence–structure–function analysis revealed specific structural elements that imply elevated conformational flexibility, uncovering a molecular basis for faster catalytic rates, lower substrate selectivity, and intrinsic resistance to inhibition. In addition, the C. armatus structure displayed a large-scale repositioning of structural segments that, in vivo, are immersed in the endoplasmic reticulum membrane and border the substrate entrance (the FG arm, >20 Å, and the β4 hairpin, >15 Å). The structural distinction of C. armatus CYP51, which is the first structurally characterized deep sea P450, suggests stronger involvement of the membrane environment in regulation of the enzyme function. We interpret this as a co-adaptation of the membrane protein structure with membrane lipid composition during evolutionary incursion to life in the deep sea.

Biochemistry & Molecular Biology↗

NASA NTRS2002

Peptides at Membrane Surfaces and their Role in the Origin of Life

All ancestors of contemporary cells (protocells) had to transport ions and organic matter across membranous walls, capture and utilize energy and transduce environmental signals. In modern organisms, all these functions are preformed by membrane proteins. We make the parsimonious assumption that in the protobiological milieu the same functions were carried out by their simple analogs - peptides. This, however, required that simple peptides could self-organize into ordered, functional structures. In a series of detailed, molecular-level computer simulations we demonstrated how this is possible. One example is the peptide (LSLLLSL)3 which forms a trameric bundle capable of transporting protons across membranes. Another example is the transmembrane pore of the influenza M2 protein. This aggregate of four identical alpha-helices, each built of 25 amino acids, forms an efficient and selective voltage-gated proton channel. Our simulations explain the gating mechanism in this channel. The channel can be re-engineered into a simple proton pump.

Pohorille, Andrew↗

DOE OSTI2022

Tailoring sub-3.3 Å ultramicropores in advanced carbon molecular sieve membranes for blue hydrogen production

Carbon molecular sieve (CMS) membranes prepared by carbonization of polymers containing strongly size-sieving ultramicropores are attractive for high-temperature gas separations. However, polymers need to be carbonized at extremely high temperatures (900° to 1200°C) to achieve sub-3.3 Å ultramicroporous channels for H 2 /CO 2 separation, which makes them brittle and impractical for industrial applications. Here, we demonstrate that polymers can be first doped with thermolabile cross-linkers before low-temperature carbonization to retain the polymer processability and achieve superior H 2 /CO 2 separation properties. Specifically, polybenzimidazole (PBI) is cross-linked with pyrophosphoric acid (PPA) via H bonding and proton transfer before carbonization at ≤600°C. The synergistic PPA doping and subsequent carbonization of PBI increase H 2 permeability from 27 to 140 Barrer and H 2 /CO 2 selectivity from 15 to 58 at 150°C, superior to state-of-the-art polymeric materials and surpassing Robeson’s upper bound. This study provides a facile and effective way to tailor subnanopore size and porosity in CMS membranes with desirable molecular sieving ability.

42 ENGINEERING↗

DOE OSTI2020

Synthesis of imidazolium-mediated Poly(benzoxazole) Ionene and composites with ionic liquids as advanced gas separation membranes

We report thermally rearranged (TR) polymers and ionic polymers are two material classes which have been employed in leading gas separation membranes. This work introduces a novel approach of combining the benzoxazole functionality associated with TR polymers with tailorable cationic groups, yielding a new type of imidazolium-mediated poly(benzoxazole) ionene polymer, “Im-PBO-Ionene” with the aim of enhanced CO 2 separation performance. The structural changes exhibited from the Coulombic interactions between the ionene backbone and the “free” ionic liquid (IL) resulted in enhanced gas separation performance, shown in fundamental characterizations, observed through increased diffusivities and more notably, retained high selectivities and 3x or 5x respective increases in CO 2 permeability upon the addition of 1 or 2 equivalents of IL per polymer repeat unit. These new high-performance ionenes demonstrate the versatility of ionene design and potential of the ionene + IL material platform for gas separation membranes with versatile incorporation of sophisticated functional and structural features.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Influence of Coating Method on the Performance of Roll-to-Roll Coated PEM Fuel Cell Catalyst Layers

As production of fuel cell vehicles and power systems increases there is a need to understand the process science of fuel cell manufacturing. Industrial production of polymer electrolyte membrane fuel cell (PEMFC) electrodes will rely on continuous roll-to-roll (R2R) coating methods to meet the rates needed for mass production. There are a variety of coating methods that could be used to coat catalyst layers. The different physics of each method may result in different morphologies and performance. Here we present the results of a study comparing fuel cell catalyst layers coated using two R2R coating methods: slot-die and gravure. These two methods were selected because the physics of applying the liquid to the substrate is very different between the two cases. Pt/C catalysts layers were coated directly onto carbon-fiber gas diffusion media to create gas diffusion electrodes (GDEs), without the use of a decal transfer process. These GDEs were assembled into membrane electrode assemblies (MEAs) by hot pressing to Nafion membranes. In situ performance and other electrochemical diagnostics were used to determine the influence of coating method on catalyst layer electrochemical properties. Electron microscopy was utilized to understand the influence of coating method on electrode morphology and its influence on electrochemical properties. We also explored the influence of solvent ratio to understand the potential coupling between ink formulation and coating methodology.

DIRECT ENERGY CONVERSION,MATERIALS SCIENCE↗

DOE OSTI2020

A reactive separation process for pre-combustion CO 2 capture employing oxygen-blown coal gasifier off-gas

In this paper, we present an experimental study of a reactive separation system, consisting of a membrane reactor (MR) and an adsorptive reactor (AR) operating in tandem, with the MR’s reject stream serving as the AR’s feed. We investigates the feasibility of applying this MR-AR system for high-purity H 2 production and simultaneous CO 2 capture via the water gas shift (WGS) reaction in the context of Integrated Gas Combined Cycle (IGCC) power generation employing oxygen-blown gasifier syngas from biomass and coal. We previously studied this MR-AR system for the IGCC process employing air-blown gasifier syngas, for which it demonstrated good performance, attaining high conversion exceeding equilibrium, producing ultra-pure H 2 for power generation, and a CO 2 stream ready for sequestration. In this study, we focus on oxygen-blown gasifier off-gas that contains no N 2 , with composition distinctly different from the air-blown gasifier syngas which has a large N 2 content. We employ a carbon molecular sieve membrane (CMSM), a commercial sour-shift WGS catalyst, and a hydrotalcite (HTC) adsorbent. We carried out experiments to determine membrane performance and to identify promising operating conditions in an IGCC-relevant environment. The CMSM proved robust during a long-term (~344 hr run) experimental run under high temperature and pressure maintaining a high He/N 2 selectivity (~170). Multi-cycle runs were carried out during which the MR-AR system displayed superior performance to that of a PBR, by producing a high purity H 2 product directly usable in power generation. Therefore, the findings from this study demonstrate the ability of the MR-AR system to operate stably for a broad range of gasifier off-gas compositions, and indicate its potential for integration into IGCC plants for power generation with CO 2 capture.

01 COAL, LIGNITE, AND PEAT↗

DOE OSTI2022

Effect of Commercial Gas Diffusion Layers on Catalyst Durability of Polymer Electrolyte Fuel Cells in Varied Cathode Gas Environment

Gas diffusion layers (GDLs) play a crucial role in heat transfer and water management of cathode catalyst layers in polymer electrolyte fuel cells (PEFCs). Thermal and water gradients can accelerate electrocatalyst degradation and therefore the selection of GDLs can have a major influence on PEFC durability. Currently, the role of GDLs in electrocatalyst degradation is poorly studied. Here, we perform electrocatalyst accelerated stress test studies on membrane electrode assemblies (MEAs) prepared using three most commonly used GDLs. The effect of GDLs on electrocatalyst degradation is evaluated in both nitrogen (non-reactive) and air (reactive) gas environments at 100% relative humidity. In situ electrochemical characterization and extensive physical characterization is performed to understand the subtle differences in electrocatalyst degradation and correlated to the use of different GDLs. Overall, no difference is observed in the electrocatalyst degradation due to GDLs based on polarization curves at the end of life. But interestingly, MEA with a cracked microporous layer (MPL) in the GDL exhibited a higher electrocatalyst loading loss, which resulted in a lower and more heterogeneous increase in the average electrocatalyst nanoparticle size.

25 ENERGY STORAGE↗

NASA NTRS2007

Triamcinolone Acetonide Selectively Inhibits Angiogenesis in Small Blood Vessels and Decreases Vessel Diameter within the Vascular Tree

The steroid triamcinolone acetonide (TA) is a potent anti-angiogenesis drug used to treat retinal vascular diseases that include diabetic retinopathy, vascular occlusions and choroidal neovascularization. To quantify the effects of TA on branching morphology within the angiogenic microvascular tree of the chorioallantoic membrane (CAM) of quail embryos. Increasing concentrations of TA (0-16 ng/ml) were applied topically on embryonic day 7 (E7) to the chorioallantoic membrane (CAM) of quail embryos cultured in Petri dishes, and incubated for an additional 24 or 48 hours until fixation. Binary (black/white) microscopic images of arterial end points were quantified by VESGEN software (for Generational Analysis of Vessel Branching) to obtain major vascular parameters that include vessel diameter (Dv), fractal dimension (Df), tortuosity (Tv) and densities of vessel area, length, number and branch point (Av, Lv, Nv and Brv). For assessment of specific changes in vascular morphology induced by TA, the VESGEN software automatically segmented the vascular tree into branching generations (G1...G10) according to changes in vessel diameter and branching. Vessel density decreased significantly up to 34% as the function of increasing concentration of TA according to Av, Lv, Brv, Nv and Df. TA selectively inhibited the growth of new, small vessels, because Lv decreased from 13.14plus or minus 0.61 cm/cm2 for controls to 8.012 plus or minus 0.82 cm/cm2 at 16 ng TA/ml in smaller branching generations (G7-G10), and for Nv from 473.83 plus or minus 29.85 cm(-)2 to 302.32 plus or minus 33.09 cm-()2. In contrast, vessel diameter (Dv) decreased throughout the vascular tree (G1-G10).

McKay, Terri L.↗

DOE OSTI2023

High-Performance Hemofiltration via Molecular Sieving and Ultra-Low Friction in Carbon Nanotube Capillary Membranes

Conventional dialyzer membranes typically comprise of unevenly distributed polydisperse, tortuous, rough pores, embedded in relatively thick ≈20–50 µm polymer layers wherein separation occurs via size exclusion as well as differences in diffusivity of the permeating species. However, transport in such polymeric pores is increasingly hindered as the molecule size approaches the pore dimension, resulting in significant retention of undesirable middle molecules (≥15–60 kDa) and uremic toxins. Enhanced removal of middle molecules is usually accompanied by high albumin loss (≈66 kDa) causing hypoalbuminemia. Here, the scalable bottom-up fabrication of wafer-scale carbon nanotube (CNT) membranes with highly aligned, low-friction, straight-channels/capillaries and narrow pore-diameter distributions (≈0.5–4.5 nm) is demonstrated, to overcome persistent challenges in hemofiltration/hemodialysis. Using fluorescein isothiocyanate (FITC)-Ficoll 70 and albumin in phosphate buffered saline (PBS) as well as in bovine blood plasma, it is shown that CNT membranes can allow for significantly higher hydraulic permeability (more than an order of magnitude when normalized to pore area) than commercial high-flux hemofiltration/hemodialysis membranes (HF 400), as well as greatly enhance removal of middle molecules while maintaining comparable albumin retention. These findings are rationalized via an N-pore transport model that highlights the critical role of molecular flexing and deformation during size-selective transport within nanoscale confinements of the CNTs. In conclusion, the unique transport characteristics of CNTs coupled with size-exclusion and wafer-scale fabrication offer transformative advances for hemofiltration, and the obtained insight into molecular transport can aid advancements in several other bio-systems/applications beyond hemofiltration/hemodialysis.

36 MATERIALS SCIENCE↗

DOE OSTI2024

“Off‐Label Use” of the Siderophore Enterobactin Enables Targeted Imaging of Cancer with Radioactive Ti (IV)

The development of inert, biocompatible chelation methods is required to harness the emerging positron emitting radionuclide 45 Ti for radiopharmaceutical applications. Herein, we evaluate the Ti (IV) -coordination chemistry of four catechol-based, hexacoordinate chelators using synthetic, structural, computational, and radiochemical approaches. The siderophore enterobactin (Ent) and its synthetic mimic TREN-CAM readily form mononuclear Ti (IV) species in aqueous solution at neutral pH. Radiolabeling studies reveal that Ent and TREN-CAM form mononuclear complexes with the short-lived, positron-emitting radionuclide 45 Ti (IV) , and do not transchelate to plasma proteins in vitro and exhibit rapid renal clearance in naïve mice. These features guide efforts to target the 45 Ti isotope to prostate cancer tissue through the design, synthesis, and evaluation of Ent-DUPA, a small molecule conjugate composed of a prostate specific membrane antigen (PSMA) targeting peptide and a monofunctionalized Ent scaffold. Additionally, the [ 45 Ti][Ti(Ent-DUPA)] 2− complex forms readily at room temperature. In a tumor xenograft model in mice, selective tumor tissue accumulation (8±5 %, n=5), and low off-target uptake in other organs is observed. Overall, this work demonstrates targeted imaging with 45 Ti (IV) , provides a foundation for advancing the application of 45 Ti in nuclear medicine, and reveals that Ent can be repurposed as a 45 Ti-complexing cargo for targeted nuclear imaging applications.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

NASA NTRS2008

Elastic Distribution of Microshutters, Measurements Obtainable on James Web Space Telescope

Spectrographic astronomy measurements in the near-infrared region will be done by functional two-dimensional microshutter arrays that are being fabricated at the NASA Goddard Space Flight Center for the James Webb Space Telescope (JWST). These micro-shutter arrays will represent the first mission-critical MEMS devices to be flown in space. JWST will use microshutter arrays to select focal plane object. 2-D programmable aperture masks of more than 200,000 elements select such space object. The use of silicon wafer material promises high efficiency and high contrast. Microshutter operation temperature is around 35K. Microshutter arrays are fabricated as close-packed silicon nitride membranes with a unit cell size of 105 x 204 micrometers. A layer of magnetic material is deposited onto each shutter. Individual shutters are equipped with a torsion flexure. Reactive ion etching (RIE) releases the shutters so they can open up to 90 degrees using the torsion flexure. Shutter rotation is initiated into a silicon support structure via an external magnetic field. Two electrically independent aluminum electrodes are deposited, one onto each shutter and another onto the support structure side-wall, permitting electrostatic latching and 2-D addressing to hold specific shutters open via external electronics.

Kletetschka, Gunther↗

DOE OSTI2021

Polypeptide and yeast cell compositions and methods of using the same

Polypeptides comprising maltose/maltotriose transporters are provided. Additionally, polynucleotides, DNA constructs, and vectors encoding a maltose/maltotriose transporter, or yeast cells harboring such polynucleotides are provided. The yeast cell may be a Saccharomyces eubayanus cell modified to increase the expression or transport activity of a maltose/maltotriose transporter at the plasma membrane of the cell. Further, methods are provided for making a fermentation product by culturing any one of the yeast cells described herein with a fermentable substrate. Finally, methods are provided to select for and isolate maltotriose-utilizing strains of Saccharomyces eubayanus.

Hittinger, Chris Todd↗

DOE OSTI2023

Polypeptide and yeast cell compositions and methods of using the same

Hittinger, Chris Todd↗

DOE OSTI2024

A Rapid Microfluidic Neptunium Extraction Using a Supported Liquid Membrane Module

Extraction of neptunium from acidic matrices is important for its quantification, but its complex redox chemistry can cause variable yields. This study develops a microfluidic redox extraction for rapidly separating neptunium from submilliliter samples, achieving up to 90% process yield in less than 10 min for samples as small as 100 μL, with over 97% steady-state yield achieved after 20 min. It uses a supported liquid membrane module loaded with 30 vol % tributyl phosphate in n-dodecane, which performs forward- and back-extractions in a single, continuous step. Neptunium is first oxidized to +6 for extraction and then reduced during stripping. Bromate was selected as an oxidant over permanganate for its greater compatibility with the organic phase, achieving complete oxidation in under 30 s. Ascorbic acid and hydrogen peroxide were both effective reductants. Finally, the system’s high yield and rapid kinetics make it promising for future separations from complex mixtures.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2025

Nonpigmented PsbR is involved in the integrity of excitation landscape in higher plant photosystem II, a case study in Arabidopsis thaliana and a mutant

PsbR is a nonpigmented 10 kDa protein in Photosystem II (PSII) in algae and plants. A recent structural study clarified its enigmatic structural location in a Photosystem II megacomplex that has baffled the community for more than four decades. Our current study interrogates whether absence of PsbR affects the overall dynamics of excitation energy migration within light harvesting complexes (LHC) and PSII super assemblies using highly-active PSII membrane particles, so-called BBY particles, isolated from a PsbR deletion mutant (ΔPsbR) of Arabidopsis thaliana. A femto-second (fs)-time-resolved transient absorption experimentation recorded at 77 K with selective excitation of Chl b which is exclusively present in LHCs enabled us to resolve the temporal differences in LHC→LHC and LHC→PSII excitation energy transfer steps. By applying specific target spectro-kinetic models to the transient absorption datasets, we demonstrated that the time constants of Chl a LHC → Chl a LHC excitation transfer significantly elongates in the ΔPsbR LHC-PSII particles, suggestive of the decreased aggregation level of photosynthetic proteins in the mutant. These findings highlight excitation energy transfer integrity in LHC-PSII assembly is not only determined by the pigmented light-harvesting complexes, but also synergistically by the nonpigmented PSII components. Furthermore, the disturbed integrity in dynamics of excitation energy transfer pathway within LHC-PSII supercomplex is discussed in the context of the altered LHC-PSII megacomplexes type I and II architectures which result from the absence of the PsbR protein in higher plant PSII.

Chlorophyll↗