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At least 235 records · Page 13

Demonstration of a MOT in a sub-millimeter membrane hole

Abstract We demonstrate the generation of a cold-atom ensemble within a sub-millimeter diameter hole in a transparent membrane, a so-called “membrane MOT”. With a sub-Doppler cooling process, the atoms trapped by the membrane MOT are cooled down to 10 $$\upmu$$ μ K. The atom number inside the unbridged/bridged membrane hole is about $$10^4$$ 10 4 to $$10^5$$ 10 5 , and the $$1/e^2$$ 1 / e 2 -diameter of the MOT cloud is about 180 $$\upmu$$ μ m for a 400 $$\upmu$$ μ m-diameter membrane hole. Such a membrane device can, in principle, efficiently load cold atoms into the evanescent-field optical trap generated by the suspended membrane waveguide for strong atom-light interaction and provide the capability of sufficient heat dissipation at the waveguide. This represents a key step toward the photonic atom trap integrated platform (ATIP).

74 ATOMIC AND MOLECULAR PHYSICS↗

Impact of Fatty-Acid Labeling of Bacillus subtilis Membranes on the Cellular Lipidome and Proteome

Developing cultivation methods that yield chemically and isotopically defined fatty acid (FA) compositions within bacterial cytoplasmic membranes establishes an in vivo experimental platform to study membrane biophysics and cell membrane regulation using novel approaches. Yet before fully realizing the potential of this method, it is prudent to understand the systemic changes in cells induced by the labeling procedure itself. In this work, analysis of cellular membrane compositions was paired with proteomics to assess how the proteome changes in response to the directed incorporation of exogenous FAs into the membrane of Bacillus subtilis. Key findings from this analysis include an alteration in lipid headgroup distribution, with an increase in phosphatidylglycerol lipids and decrease in phosphatidylethanolamine lipids, possibly providing a fluidizing effect on the cell membrane in response to the induced change in membrane composition. Changes in the abundance of enzymes involved in FA biosynthesis and degradation are observed; along with changes in abundance of cell wall enzymes and isoprenoid lipid production. The observed changes may influence membrane organization, and indeed the well-known lipid raft-associated protein flotillin was found to be substantially down-regulated in the labeled cells – as was the actin-like protein MreB. Taken as a whole, this study provides a greater depth of understanding for this important cell membrane experimental platform and presents a number of new connections to be explored in regard to modulating cell membrane FA composition and its effects on lipid headgroup and raft/cytoskeletal associated proteins.

59 BASIC BIOLOGICAL SCIENCES↗

Direct Chemical Vapor Deposition Synthesis of Porous Single-Layer Graphene Membranes with High Gas Permeances and Selectivities

Single-layer graphene containing molecular-sized in-plane pores is regarded as a promising membrane material for high-performance gas separations due to its atomic thickness and low gas transport resistance. However, typical etching-based pore generation methods cannot decouple pore nucleation and pore growth, resulting in a trade-off between high areal pore density and high selectivity. In contrast, intrinsic pores in graphene formed during chemical vapor deposition are not created by etching. Therefore, intrinsically porous graphene can exhibit high pore density while maintaining its gas selectivity. Here in this work, the density of intrinsic graphene pores is systematically controlled for the first time, while appropriate pore sizes for gas sieving are precisely maintained. As a result, single-layer graphene membranes with the highest H 2 /CH 4 separation performances recorded to date (H 2 permeance > 4000 GPU and H 2 /CH 4 selectivity > 2000) are fabricated by manipulating growth temperature, precursor concentration, and non-covalent decoration of the graphene surface. Moreover, it is identified that nanoscale molecular fouling of the graphene surface during gas separation where graphene pores are partially blocked by hydrocarbon contaminants under experimental conditions, controls both selectivity and temperature dependent permeance. Overall, the direct synthesis of porous single-layer graphene exploits its tremendous potential as high-performance gas-sieving membranes.

chemical vapor deposition↗

Molecular Modeling of Surfactant Interaction on Phospholipid Bilayers Mimicking Corneal Epithelium

Surfactants found in consumer products can compromise eye corneal membrane integrity upon accidental exposure. Traditional in vitro and in vivo approaches to evaluate membrane–surfactant interaction pose experimental limitations such as species variability, reproducibility, and most often do not provide the overall picture. These limitations motivate the use of in silico models to study phenomena like cellular disruption assays caused by surfactants at the molecular scale. In this work, coarse-grained molecular dynamics simulations have been employed to investigate how nonionic alcohol ethoxylate (AE) and anionic surfactant alcohol ethoxy sulfate (AES) interact with lipid bilayer liposomes that mimic corneal epithelial cell membranes. The spherical liposome is composed of 1,2-dihexadecanoyl-sn-glycero-3-phosphocholine (DPPC), 1,2-di(9Z-octadecenoyl)-sn-glycero-3-phosphoethanolamine (DOPE), 1,2-di(9Z-octadecenoyl)-sn-glycero-3-phospho-l-serine (DOPS), and cholesterol, resembling the composition of the corneal epithelial cells’ membrane bilayer. The simulation consisted of varying degrees of representative surfactant compositions and two initial types of surfactant configurations within or outside the liposome. Our results reveal that both surfactants induce outer leaflet bulging, agreeing with membrane solubilization models. The more highly ethoxylated surfactant, AE, caused more consistent inner leaflet disruption than AES, resulting in significantly more water permeation and membrane thinning. In addition, both surfactants increase the lateral diffusion of lipids within the membrane layers, with higher ethoxylated AE showing a stronger effect than AES. This study demonstrates how surfactant structure and localization influence bilayer membrane integrity, offering mechanistic insights into the irritation potential, thus guiding the rational design of effective surfactant-based formulations.

Lipids↗

The C‐Terminal Domain of α‐Synuclein Confers Steric Stabilization on Synaptic Vesicle‐Like Surfaces

Abstract While α‐synuclein, an intrinsically disordered protein linked to Parkinson's disease, has been shown to associate with membrane organelles, its overall cellular function remains nebulous. α‐Synuclein binds to membranes through its amino‐terminal domain (first ≈100 residues), but there is no consensus on the biophysical function of the carboxyl‐terminal domain (last ≈40 residues) due, in part, to its lack of strong interaction partners and persisting intrinsic disorder even when membrane bound. Here, by directly applying force on α‐synuclein bound to spherical nanoparticle‐supported lipid bilayers (SSLBs) and tracking higher‐order structural changes through small‐angle X‐ray scattering, strong evidence is presented that α‐synuclein sterically stabilizes membrane surfaces through its carboxyl‐terminal domain. Full‐length α‐synuclein dramatically increases the critical osmotic pressure at which SSLBs cluster ( P C ≈ 1.3 × 10 5 Pa) compared to α‐synuclein without the carboxyl‐terminal domain ( P C ≈ 1.9 × 10 4 Pa) at physiological salt and temperature conditions. This clustering of α‐synuclein‐bound SSLBs is shown to be reversible and sensitive to monovalent/divalent salt, both features of grafted polyelectrolyte‐mediated steric stabilization. In elucidating the biophysical function of α‐synuclein in the framework of polymer science, it is demonstrated that the carboxyl‐terminal domain can potentially utilize its persisting intrinsic disorder to functionalize membrane surfaces.

Chung, Peter J.↗

Hyperthin Membranes for Gas Separations (Final Technical Report)

This final technical report summarizes DOE-supported research that we have carried out over the past 18 years; i.e., 09/01/2005-08/31/2023. Two hyperthin types of membranes that were reported most recently, which have practical potential for the separation of CO 2 from N 2 in flue are highlighted in this final technical report.

36 MATERIALS SCIENCE↗

Proton Conducting Silicon Oxide Membranes as a Fluorine Free Alternative to Nafion for Low Temperature Water Electrolysis

Driven by environmental and health concerns related to per- and polyfluoroalkyl substances (PFAS), there has been growing interest in developing fluorine-free proton (H + ) exchange membrane (PEM) materials for fuel cells and water electrolyzers. In this study, we present a side-by-side comparison of the key transport properties of submicron thick, PFAS-free amorphous silicon dioxide (SiO 2 ) membranes to Nafion, a fluorinated polymer electrolyte membrane that represents the industry standard for PEM fuel cells and electrolyzers. Here, measurements of proton (H + ) conductivity (σ H + ), hydrogen (H 2 ) permeability (P H 2 ), and electrical resistivity (ρ e – ) were conducted using model thin films comprised of SiO 2 membranes deposited by atomic layer deposition (ALD). Although the H + conductivity of the SiO 2 membranes is 2–3 orders of magnitude lower than Nafion, the addition of phosphorus dopants (PO x ) improves H + conductivity such that the area specific membrane resistance of thin (<50 nm) PO x -doped SiO 2 membranes is more than an order of magnitude lower than Nafion-117. Importantly, the safe operation of such nanoscale membranes within a PEM electrolyzer is feasible thanks to the low H 2 permeability of dense SiO 2 -based membranes, which are predicted to limit H 2 crossover rates to acceptable levels for pressures up to ≈ 100 bar. As a proof-of-principle demonstration, a chip-scale water electrolyzer based on 100 nm thick PO x -SiO 2 membrane is shown to achieve a current density of 2 A cm –2 at a potential of 2.5 V. If this technology can be successfully scaled up, H + conducting oxide membranes offer an attractive PFAS-free alternative to Nafion for efficient and durable water electrolysis and fuel cell technologies.

Nafion↗

Studying Corrosion Using Miniaturized Particle Attached Working Electrodes and the Nafion Membrane

We developed a new approach to attach particles onto a conductive layer as a working electrode (WE) in a microfluidic electrochemical cell with three electrodes. Nafion, an efficient proton transfer molecule, is used to form a thin protection layer to secure particle electrodes. Spin coating is used to develop a thin and even layer of Nafion membrane. The effects of Nafion (5 wt% 20 wt%) and spinning rates were evaluated using multiple sets of replicates. The electrochemical performance of various devices was demonstrated. Additionally, the electrochemical performance of the devices is used to select and optimize fabrication conditions. The results show that a higher spinning rate and a lower Nafion concentration (5 wt%) induce a better performance, using cerium oxide (CeO2) particles as a testing model. The WE surfaces were characterized using atomic force microscopy (AFM), scanning electron microscopy-focused ion beam (SEM-FIB), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and X-ray photoelectron spectroscopy (XPS). The comparison between the pristine and corroded WE surfaces shows that Nafion is redistributed after potential is applied. Our results verify that Nafion membrane offers a reliable means to secure particles onto electrodes. Furthermore, the electrochemical performance is reliable and reproducible. Thus, this approach provides a new way to study more complex and challenging particles, such as uranium oxide, in the future.

42 ENGINEERING↗

Design of PGM-free cathodic catalyst layers for advanced PEM fuel cells

Here, the design of cathodic catalysts layer (CCL) consisted of Platinum Group Metal-free (PGM-free) electrocatalysts was done by catalyst coated membrane approach. Three different Fe-Mn-N-C compounds were synthesized with Fe:Mn ratio of 1:1, 2:1 and 2:1 with modified heat treatment profile. The catalysts were characterized by X-ray photoelectron spectroscopy, X-ray powder diffraction, pore and particle size distribution, zeta potential and transmission electron microscopy. Electrocatalysts were integrated into membrane electrode assembly and evaluated by electrochemical methods. Electrochemical impedance spectroscopy in combination with modeling were used for estimation of proton conductivity of CCL and its oxygen diffusivity. It was found that all CCLs possess extremely high proton conductivity, which was demonstrated for the first time for these types of PGM-free catalysts. The observed ORR mechanism was predominantly 4e- due to peroxide/radicals scavenging effect of Mn.

impedance↗

Atomic Force Microscopy to Characterize Antimicrobial Peptide-Induced Defects in Model Supported Lipid Bilayers

Antimicrobial peptides (AMPs) interact with bacterial cell membranes through a variety of mechanisms, causing changes extending from nanopore formation to microscale membrane lysis, eventually leading to cell death. Several AMPs also disrupt mammalian cell membranes, despite their significantly different lipid composition and such collateral hemolytic damage hinders the potential therapeutic applicability of the AMP as an anti-microbial. Elucidating the mechanisms underlying the AMP–membrane interactions is challenging due to the variations in the chemical and structural features of the AMPs, the complex compositional variations of cell membranes and the inadequacy of any single experimental technique to comprehensively probe them. (1) Background: Atomic Force Microscopy (AFM) imaging can be used in combination with other techniques to help understand how AMPs alter the orientation and structural organization of the molecules within cell membranes exposed to AMPs. The structure, size, net charge, hydrophobicity and amphipathicity of the AMPs affect how they interact with cell membranes of differing lipid compositions. (2) Methods: Our study examined two different types of AMPs, a 20-amino acid, neutral, α-helical (amphipathic) peptide, alamethicin, and a 13-amino acid, non-α-helical cationic peptide, indolicidin (which intramolecularly folds, creating a hydrophobic core), for their interactions with supported lipid bilayers (SLBs). Robust SLB model membranes on quartz supports, incorporating predominantly anionic lipids representative of bacterial cells, are currently not available and remain to be developed. Therefore, the SLBs of zwitterionic egg phosphatidylcholine (PC), which represents the composition of a mammalian cell membrane, was utilized as the model membrane. This also allows for a comparison with the results obtained from the Quartz Crystal Microbalance with Dissipation (QCM-D) experiments conducted for these peptides interacting with the same zwitterionic SLBs. Further, in the case of alamethicin, because of its neutrality, the lipid charge may be less relevant for understanding its membrane interactions. (3) Results: Using AFM imaging and roughness analysis, we found that alamethicin produced large, unstable defects in the membrane at 5 µM concentrations, and completely removed the bilayer at 10 µM. Indolicidin produced smaller holes in the bilayer at 5 and 10 µM, although they were able to fill in over time. The root-mean-square (RMS) roughness values for the images showed that the surface roughness caused by visible defects peaked after peptide injection and gradually decreased over time. (4) Conclusions: AFM is useful for helping to uncover the dynamic interactions between different AMPs and cell membranes, which can facilitate the selection and design of more efficient AMPs for use in therapeutics and antimicrobial applications.

Swana, Kathleen W.↗

High-Performance AEM LTE with Advanced Membranes, Ionomers and PGM-Free Electrodes

Alkaline low temperature electrolysis (LTE) systems enjoy several potential advantages over acid-based LTE systems including facile oxygen evolution reaction (OER) kinetics and electrodes that can use little to no platinum group metals (PGM). The polymer membranes and membrane electrode assembly (MEA) structures going into alkaline electrochemical systems have seen significant advances in recent years. The objective of this project is to combine state-of-the-art alkaline polymer electrolyzer components into one optimized membrane electrode assembly (MEA) system to achieve DOE low temperature electrolysis (LTE) goals. The benefit of individual component advances cannot be fully appreciated until all aspects and components of the MEA are working at an equally high level of performance. New electrode fabrication methods were developed where solvent cast catalyst/ionomer solutions were used in place of insoluble ionomers to significantly improve adhesion. The membranes were improved in terms of durability and mechanical properties. The OER and HER catalysts were improved and made more durable.

08 HYDROGEN↗

Field Validation of a Pilot-scale Black Liquor Membrane for Water Removal at Ahlstrom-Munksjö Paper Mill in Mosinee, WI

Project Background: The Industrial Technology Validation (ITV) program aims to identify and demonstrate the performance of new, emerging, and underutilized technologies in the industrial sector to help inform decisions towards accelerating commercialization and deployment. Pulp and paper is considered one of the most energy-intensive industries in the manufacturing sector. There are several methodologies for converting wood into pulp in the paper-making industry. The kraft process is a chemical method for producing wood pulp. The kraft process generates black liquor as a byproduct of pulp production. Traditionally, water is evaporated from the liquor by a set of multi-effect evaporators (MEEs), which concentrate weak black liquor (WBL) into strong black liquor (SBL) to support efficient combustion in a recovery boiler. Concentrating black liquor is an energy-intensive step in recovering pulping chemicals and generating high-pressure steam from dissolved wood solids. About 7% of pulp and paper energy usage, or nearly 164 trillion Btu, is used to remove water from black liquor in U.S. kraft pulp mills per year. The U.S. DOE’s IEDO is interested in the black liquor membrane technology evaluated in this report because it offers the potential for a more energy-efficient and less carbon-intensive kraft pulping process across 99 kraft pulp mills in 24 states (Agenda 2020 Technology Alliance 2016). This ITV project validates an innovative black liquor membrane technology for kraft pulp mills to understand its impact and benefits. Via Separations is a technology vendor that developed a graphene oxide membrane system to remove water from WBL before entering the evaporator set. High-pressure positive displacement (HPR) pumps move the black liquor through membranes that separate water and create a more concentrated black liquor. The vendor claims their pre-commercial technology reduces evaporator steam consumption by dewatering WBL before entering the evaporators. They also claim their technology has non-energy benefits such as enhanced soap collection and improved pulp throughput. This evaluation focuses on validating the energy and carbon dioxide (CO 2 e) emissions benefits associated with the membrane system.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Interferometric measurements of graphene-based membranes for micromechanical applications

Recent studies on piezoelectricity in 2D materials, such as graphene, have revealed their potential in multiple applications including microelectromechanical systems. Herein, we reveal piezoelectricity in few-layer graphene sheets deposited on amorphous Si 3 N 4 membranes. The response in the center of square membrane of 6.7 × 6.7 mm 2 size reaches about 14 nm at resonance and could be further enhanced by adjusting the composite structure. Resonance piezoelectric phenomena are fully consistent with the earlier piezoresponse force microscopy observations on free-standing piezoelectric graphene and open up a possibility of using 2D materials in micromechanical applications.

36 MATERIALS SCIENCE↗

Tunable Ion Transport with Freestanding Vermiculite Membranes

Membranes integrating two-dimensional (2D) materials have emerged as a category with unusual ion transport and potentially useful separation applications in both aqueous and nonaqueous systems. The interlayer galleries in these membranes drive separation and selectivity, with specific transport properties determined by the chemical and structural modifications within the inherently different interlayers. Here, in this work, we report an approach to tuning interlayer spacing with a single source material–exfoliated and restacked vermiculite with alkanediamine cross-linkers–to both control the gallery height and enhance the membrane stability. The as-prepared cross-linked 2D vermiculite membranes exhibit ion diffusivities tuned by the length of the selected diamine molecule. The 2D nanochannels in these stabilized vermiculite membranes enable a systematic study of confined ionic transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Biomimetic Rebuilding of Multifunctional Red Blood Cells: Modular Design Using Functional Components

The design and synthesis of artificial materials that mimic the structures, mechanical properties, and ultimately functionalities of biological cells remains a current holy grail of materials science. Here based on a silica cell bio-replication approach, we report the design and construction of synthetic rebuilt red blood cells (RRBCs) that fully mimic the broad properties of native RBCs: size, biconcave shape, deformability, oxygen carrying capacity, long circulation time. Four successive nano-scale processing steps: RBC bioreplication, layer-by-layer polymer deposition, and precision silica etching, followed by RBC ghost membrane vesicles fusion are employed for RRBC construction. A panel of physicochemical analyses including zeta potential measurement, fluorescence microscopy, and antibody-mediated agglutination assay proved the recapitulation of RBC shape, size, and membrane structure. Flow-based deformation studies carried out in a microfluidic blood capillary model confirrned the ability of RRBCs to deform and pass through small slits and reconstitute themselves in a manner comparable to native RBCs. Circulation studies of RRBCs conducted ex-ovo in a chick embryo and in vivo in a mouse model demonstrated the requirement of both deformability and native cell membrane surface to achieve long-term circulation. To confer additional non-native functionalities to RRBCs, we developed modular procedures in which to load functional cargos such as hemoglobin, drugs, magnetic nanoparticles, and ATP biosensors within the RRBC interior to enable various functions, including oxygen delivery, therapeutic drug delivery, magnetic manipulation, and toxin biosensing and detection. Taken together, RRBCs represent a class of long circulating RBC-inspired artificial hybrid materials with a broad range of potential applications.

59 BASIC BIOLOGICAL SCIENCES↗

Cost optimization of low-salt-rejection reverse osmosis

Low-salt-rejection reverse osmosis (LSRRO) is an emerging membrane-based desalination technology for concentrating brines with potentially lower energy consumption and cost than thermally driven processes. We assess the technoeconomic performance of LSRRO by using an optimization model that minimizes the levelized cost of water (LCOW). We develop detailed models for the RO module and other equipment using WaterTAP (Water treatment Technoeconomic Assessment Platform), an open-source simulation and optimization software for water treatment. We improve upon previous LSRRO cost optimization studies by optimizing the salt permeability for each stage, which has significant implications for technoeconomic performance. We present the cost-optimal design, operation, and performance for three cases: 35 g/L TDS feed at 70% recovery, 70 g/L at 55%, and 125 g/L at 35%. The cost-optimal LCOW and specific energy consumption (SEC) for these cases are 0.70, 1.89, and 7.41 $/m 3 and 3.9, 8.4, and 30.4 kWh/m 3 , respectively. For each case, we use sensitivity analyses to provide guidance on key factors that impact economic viability. We also present the cost-optimal LCOW and SEC for feed concentrations between 5 and 220 g/L TDS and recoveries between 30 and 90%. So, we compare LSRRO to other high-salinity desalination technologies and find that it may be cost-competitive below feed concentrations of 125 g/L.

54 ENVIRONMENTAL SCIENCES↗

Microporous pentiptycene-based polybenzimidazole membranes for high temperature H 2 /CO 2 separation

Separating H 2 from syngas at elevated temperatures (100–250 °C) have attracted significant attention in recent years as a means to reduce energy consumption and capital costs in precombustion carbon capture processes, such as those following steam reforming of natural gas or coal gasification. Polybenzimidazole (PBI), particularly m-PBI, has been reported as a leading membrane material for high-temperature H 2 /CO 2 separation. However, m-PBI exhibits extremely low H 2 permeability, even at high temperatures, which limits its productivity in H 2 /CO 2 separation applications. Here, to address this limitation, this work introduces a new pentiptycene-based polybenzimidazole (PPBI) featuring significantly enhanced H 2 permeability and attractive high-temperature H 2 /CO 2 separation performance, which stems from the unique configurational free volume elements introduced by pentiptycene moieties. Further tuning of the free volume architecture of PPBI films is achieved via acid doping with phosphoric acid (PA) or trans-aconitic acid (TaA), which introduces crosslinking among PPBI chains. Under mixed-gas environment (50/50 mol% H 2 /CO 2 ) at 180 °C, the acid-doped PPBI films exhibit a ∼230 % increase in H 2 /CO 2 selectivity compared to pristine PPBI film while maintaining high H 2 permeability that is nearly 500 % of m-PBI. These properties approach the predicted upper bound for membrane operating at 180 °C, highlighting its great potential for high-temperature H 2 /CO 2 separation.

Liu, Mengdi [University of Notre Dame, IN (United ↗