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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 451 records · Page 25

Structural analysis of extracellular ATP-independent chaperones of streptococcal species and protein substrate interactions

ABSTRACT During infection, bacterial pathogens rely on secreted virulence factors to manipulate the host cell. However, in gram-positive bacteria, the molecular mechanisms underlying the folding and activity of these virulence factors after membrane translocation are not clear. Here, we solved the protein structures of two secreted parvulin and two secreted cyclophilin-like peptidyl-prolyl isomerase (PPIase) ATP-independent chaperones found in gram-positive streptococcal species. The extracellular parvulin-type PPIase, PrsA inStreptococcus pneumoniaeandStreptococcus mutansmaintain dimeric crystal structures reminiscent of folding catalysts that consist of two domains, a PPIase and foldase domain. Structural comparison of the two cyclophilin-like extracellular chaperones fromS. pneumoniaeandStreptococcus pyogeneswith other cyclophilins demonstrates that this group of cyclophilin-like chaperones has novel structural appendages formed by 9- and 24-residue insertions. Furthermore, we demonstrate that deletion ofprsAandslrAgenes impairs the secretion of the cholesterol-dependent pore-forming toxin, pneumolysin inS. pneumoniae. Using protein pull-down and biophysical assays, we demonstrate a direct interaction between PrsA and SlrA with Ply. Then, we developed chaperone-assisted folding assays that show that theS. pneumoniaePrsA and SlrA extracellular chaperones accelerate pneumolysin folding. In addition, we demonstrate that SlrA and, for the first time,S. pyogenes PpiA exhibit PPIase activity and can bind the immunosuppressive drug, cyclosporine A. Altogether, these findings suggest a mechanistic role for streptococcal PPIase chaperones in the activity and folding of secreted virulence factors such as pneumolysin. IMPORTANCE Streptococcal species are a leading cause of lower respiratory infections that annually affect millions of people worldwide. During infection, streptococcal species secrete a medley of virulence factors that allow the bacteria to colonize and translocate to deeper tissues. In many gram-positive bacteria, virulence factors are secreted from the cytosol across the bacterial membrane in an unfolded state. The bacterial membrane-cell wall interface is exposed to the potentially harsh extracellular environment, making it difficult for native virulence factors to fold before being released into the host. ATP-independent PPIase-type chaperones, PrsA and SlrA, are thought to facilitate folding and stabilization of several unfolded proteins to promote the colonization and spread of streptococci. Here, we present crystal structures of the molecular chaperones of PrsA and SlrA homologs from streptococcal species. We provide evidence that theStreptococcus pyogenesSlrA homolog, PpiA, has PPIase activity and binds to cyclosporine A. In addition, we show thatStreptococcus pneumoniaePrsA and SlrA directly interact and fold the cholesterol-dependent pore-forming toxin and critical virulence determinant, pneumolysin.

Microbiology↗

Structurally ordered nanoparticles, methods and applications

Embodiments provide a nanoparticle and a method for preparing the nanoparticle, as well as a membrane that includes the nanoparticle and a fuel cell that includes the membrane. The method comprises a thermal treatment method that provides from a nanoparticle comprising a structurally disordered material the nanoparticle comprising: (1) a structurally ordered core comprising a first material; and (2) a shell surrounding and further structurally aligned with the structurally ordered core and comprising a second material different from the first material. Particularly desirable is a nanoparticle comprising a Pt3Co@Pt/C structurally ordered core-shell composition supported upon a carbon support.

Abruna, Hector D.↗

Elucidating the impact of the ionomer equivalent weight on a platinum group metal-free PEMFC cathode via oxygen limiting current

Leveraging the interactions between ionomer and catalyst can increase the performance of proton exchange membrane fuel cells. The impacts of the equivalent weight (EW) of perfluorosulfonic acid–based ionomers on the platinum group metal-free electrode structure and fuel cell performance have not been fully explored. Four membrane electrode assemblies (MEAs) were prepared by using a commercial Fe–N–C catalyst, two perfluorosulfonic acid ionomers with different EWs, that is, Aquivion 720 (A720) and Nafion 1100 (N1100), and two ionomer-to-catalyst (I/C) ratios. The four MEAs were characterized to understand the impact of the ionomer EW and content on the capacitance, proton conductivity, and mass transport on the cathode. The mass transport resistance was measured for the first time using a new oxygen reduction reaction limiting current method enabling to couple the effects of oxygen diffusion with liquid water generation. Low EW ionomer combined with a moderate I/C results in improved performance due to its enhanced proton conductivity. However, when used at high I/C, it can cause severe water flooding at high current density due to the enhanced liquid water uptake, especially at high relative humidity, resulting in lower catalyst utilization and higher mass transport resistance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Substituted polynorbornene membranes: a modular template for targeted gas separations

Polynorbornenes are ideal materials for systematic structure–property investigations designed to correlate gas-transport properties to polymer structure. The modular nature of norbornene-based systems provides a facile route towards the synthesis of diverse polymeric materials. Though many valuable correlations between gas-permeability and polynorbornene structure have been summarized in a prior review (2017), many of these efforts focused heavily on the design of materials with high permeabilities. More recently, the design of next-generation polynorbornene membranes has shifted toward the development of materials that are highly selective for multiple targeted gas separations. Since 2017, tremendous progress has been realized in the preparation of stable and highly selective polynorbornenes for membrane-based gas separations. Examples include polynorbornene derivatives that exhibit very high selectivity for CO 2 /N 2 and light hydrocarbon (e.g., C 3 +/C 1 ) separations, some of which exhibit gas separation performances that approach or exceed the 2008 upper bound. In this work, we summarize prior findings, present recent developments in the field of advanced polynorbornene membrane materials for targeted gas separations, and provide an outlook for the future of this field of research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spiroligomer‐Based Macrocycles for Atomically Precise Membranes

Abstract Here, we report a new class of peptidomimetic macrocycles with well‐defined three‐dimensional structures and low conformational flexibility. They are assembled from fused‐ring spiro‐ladder oligomers (spiroligomers) by modular solid‐phase synthesis. Two‐dimensional nuclear magnetic resonance confirms their shape persistency. Triangular macrocycles of tunable sizes assemble into membranes with atomically precise pores, which exhibit size and shape‐dependent molecular sieving towards a series of structurally similar compounds. The exceptional structural diversity and stability of spiroligomer‐based macrocycles will be explored for more applications.

Xie, Yihui↗

Assembly of respiratory syncytial virus matrix protein lattice and its coordination with fusion glycoprotein trimers

Respiratory syncytial virus (RSV) is an enveloped, filamentous, negative-strand RNA virus that causes significant respiratory illness worldwide. RSV vaccines are available, however there is still significant need for research to support the development of vaccines and therapeutics against RSV and related Mononegavirales viruses. Individual virions vary in size, with an average diameter of ~130 nm and ranging from ~500 nm to over 10 µm in length. Though the general arrangement of structural proteins in virions is known, we use cryo-electron tomography and sub-tomogram averaging to determine the molecular organization of RSV structural proteins. We show that the peripheral membrane-associated RSV matrix (M) protein is arranged in a packed helical-like lattice of M-dimers. We report that RSV F glycoprotein is frequently observed as pairs of trimers oriented in an anti-parallel conformation to support potential interactions between trimers. Our sub-tomogram averages indicate the positioning of F-trimer pairs is correlated with the underlying M lattice. These results provide insight into RSV virion organization and may aid in the development of RSV vaccines and anti-viral targets.

59 BASIC BIOLOGICAL SCIENCES↗

Potential-induced wetting and dewetting in pH-responsive block copolymer membranes for mass transport control

Wetting and dewetting behavior in channel-confined hydrophobic volumes is used in biological membranes to effect selective ion/molecular transport. Artificial biomimetic hydrophobic nanopores have been devised utilizing wetting and dewetting, however, tunable mass transport control utilizing multiple transport modes is required for applications such as controllable release/transport, water separation/purification and energy conversion. Here, we investigate the potential-induced wetting and dewetting behavior in a pH-responsive membrane composed of a polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) block copolymer (BCP) when fabricated as a hierarchically-organized sandwich structure on a nanopore electrode array (NEA), i.e. BCP@NEA. At pH < pK a (P4VP) (pK a ~ 4.8), the BCP acts as an anion-exchange membrane due to the hydrophilic, protonated P4VP cylindrical nanodomains, but at pH > pK a (P4VP), the P4VP domains exhibit charge-neutral, hydrophobic and collapsed structures, blocking mass transport via the hydrophobic membrane. However, when originally prepared in a dewetted condition, mass transport in the BCP membrane may be switched on if sufficiently negative potentials are applied to the BCP@NEA architecture. When the hydrophobic BCP membrane is introduced on top of 2-electrode-embedded nanopore arrays, electrolyte solution in the nanopores is introduced, then isolated, by exploiting the potential-induced wetting and dewetting transitions in the BCP membrane. The potential-induced wetting/dewetting transition and the effect on cyclic voltammetry in the BCP@NEA structures is characterized as a function of the potential, pH and ionic strength. Additionally chronoamperometry and redox cycling experiments are used to further characterize the potential response. The multi-modal mass transport system proposed in this work will be useful for ultrasensitive sensing and single-molecule studies, which require long-time monitoring to explore reaction dynamics as well as molecular heterogeneity in nanoconfined volumes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural basis of cell-surface signaling by a conserved sigma regulator in Gram-negative bacteria

Cell-surface signaling (CSS) in Gram-negative bacteria involves highly conserved regulatory pathways that optimize gene expression by transducing extracellular environmental signals to the cytoplasm via inner-membrane sigma regulators. The molecular details of ferric siderophore-mediated activation of the iron import machinery through a sigma regulator are unclear. Here, we present the 1.56 Å resolution structure of the periplasmic complex of the C-terminal CSS domain (CCSSD) of PupR, the sigma regulator in the Pseudomonas capeferrum pseudobactin BN7/8 transport system, and the N-terminal signaling domain (NTSD) of PupB, an outer-membrane TonB-dependent transducer. The structure revealed that the CCSSD consists of two subdomains: a juxta-membrane subdomain, which has a novel all-β-fold, followed by a secretin/TonB, short N-terminal subdomain at the C terminus of the CCSSD, a previously unobserved topological arrangement of this domain. Using affinity pulldown assays, isothermal titration calorimetry, and thermal denaturation CD spectroscopy, we show that both subdomains are required for binding the NTSD with micromolar affinity and that NTSD binding improves CCSSD stability. Our findings prompt us to present a revised model of CSS wherein the CCSSD:NTSD complex forms prior to ferric-siderophore binding. Upon siderophore binding, conformational changes in the CCSSD enable regulated intramembrane proteolysis of the sigma regulator, ultimately resulting in transcriptional regulation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polybenzimidazole (PBI) membranes for redox flow batteries

Disclosed are redox flow battery membranes, redox flow batteries incorporating the membranes, and methods of forming the membranes. The membranes include a polybenzimidazole gel membrane that is capable of incorporating a high liquid content without loss of structure that is formed according to a process that includes in situ hydrolysis of a polyphosphoric acid solvent. The membranes are imbibed with a redox flow battery supporting electrolyte such as sulfuric acid and can operate at very high ionic conductivities of about 100 mS/cm or greater. Redox flow batteries incorporating the PBI-based membranes can operate at high current densities of about 100 mA/cm2 or greater.

Benicewicz, Brian C.↗

Polybenzimidazole (PBI) membranes for redox flow batteries

Disclosed are redox flow battery membranes, redox flow batteries incorporating the membranes, and methods of forming the membranes. The membranes include a polybenzimidazole gel membrane that is capable of incorporating a high liquid content without loss of structure that is formed according to a process that includes in situ hydrolysis of a polyphosphoric acid solvent. The membranes are imbibed with a redox flow battery supporting electrolyte such as sulfuric acid and can operate at very high ionic conductivities of about 100 mS/cm or greater. Redox flow batteries incorporating the PBI-based membranes can operate at high current densities of about 100 mA/cm 2 or greater.

Benicewicz, Brian C.↗

Three-Dimensional Polymeric-Scaffold-Based Current Collector for a Lithium Metal Anode toward High-Energy-Density Batteries

Here, the practical applications of high-energy-density rechargeable lithium (Li) metal batteries (LMBs) have been impeded by the intrinsic issues of the Li metal anode (LMA) including high reactivity with electrolyte and dendritic formation. Conventional LMAs, which have the "hostless" feature consisting of a Li layer on a two-dimensional copper (Cu) foil as a current collector, led to additional loss in specific energy density, since Cu is a nonfaradaic heavy metal, bringing formidable areal capacity loss. To address these problems, a heat-treated three-dimensional-structured Cu-coated polyimide (HT-Cu@PI) membrane is designed and fabricated as a current collector. Benefiting from this unique material/structure, it enables not only better electrochemically deposited Li by a uniform/continuous Li-ion transport pathway but also a significant increase in the gravimetric/volumetric energy densities of LMBs by allowing more Li deposition in a fixed weight/volume. Therefore, this new LMA structure will accelerate the practical application of high-energy-density LMBs.

25 ENERGY STORAGE↗

Anionic Lipids Regulate the Light-Harvesting Complex 1-Reaction Center Photocycle in Purple Bacteria

Photosynthetic purple bacteria can capture and convert sunlight with a remarkable, nearly 100% quantum efficiency. The light-harvesting complex 1-reaction center (LH1-RC) core complex is the membrane complex fundamentally responsible for solar energy conversion. LH1-RC has a highly conserved surrounding lipid composition known to favor anionic lipids for an unknown function. Here, in this work, we compared experimentally the rate of LH1-to-RC energy transfer in detergent, membrane nanodiscs with varying lipid compositions, purified membrane fragments, and live cells. The energy transfer rate indicated that RC turnover decreased in neutral lipids, yet was partially restored in anionic lipids, revealing an unexpected lipid dependence. In complementary molecular dynamics simulations, the anionic lipid cardiolipin showed electrostatic interactions with LH1-RC that may mediate quinone exchange, providing a mechanism for the observed lipid dependence. Overall, these results revealed that anionic lipids facilitate LH1-RC redox cycling, identifying a functional role for membrane composition in photosynthetic solar energy conversion.

bacteria↗

What are grana in chloroplasts of vascular plants good for?

All plants and green algae contain stacked grana thylakoid membranes in their chloroplasts, underscoring an evolutionary pressure to maintain this unique structural feature. In addition, numerous studies have demonstrated that particular lateral and vertical dimensions of grana facilitate the function, regulation and repair of the photosynthetic machinery responsible for energy conversion. In this review, we present an updated overview of our understanding concerning the structure of grana thylakoids, the forces that contribute to their formation and their architectural dynamics. After establishing the structural foundation, we continue by reviewing the implications of grana formation on light harvesting, electron transport and protein maintenance in the thylakoid membranes of vascular plants. Regarding light harvesting, we discuss the implications of grana formation on energy spillover, macromolecular crowding, lateral versus vertical excitation energy transfer, and state transition. With respect to electron transport, we summarize recent findings regarding the functional connectivity of spatially separated photosystems facilitated by grana formation through small mobile electron carriers. We also explore how the dynamic responses of grana architecture regulate electron transport. Finally, we address how grana formation contributes to the organization of protein repair and biogenesis within thylakoid membranes.

59 BASIC BIOLOGICAL SCIENCES↗

Modelling Hyperglycaemia in an Epithelial Membrane Model: Biophysical Characterisation

Biomimetic models are valuable platforms to improve our knowledge on the molecular mechanisms governing membrane-driven processes in (patho)physiological conditions, including membrane permeability, transport, and fusion. However, current membrane models are over simplistic and do not include the membrane’s lipid remodelling in response to extracellular stimuli. Our study describes the synthesis of glycated dimyristoyl-phosphatidylethanolamine (DMPE-glyc), which was structurally characterised by mass spectrometry (ESI-MS) and quantified by NMR spectroscopy to be further incorporated in a complex phospholipid (PL) membrane model enriched in cholesterol (Chol) and (glyco)sphingolipids (GSL) designed to mimic epithelial membranes (PL/Chol/GSL) under hyperglycaemia conditions. Characterisation of synthesised DMPE-glyc adducts by tandem mass spectrometry (ESI-MS/MS) show that synthetic DMPE-glyc adducts correspond to Amadori products and quantification by 1H NMR spectroscopy show that the yield of glycation reaction was 8%. The biophysical characterisation of the epithelial membrane model shows that excess glucose alters the thermotropic behaviour and fluidity of epithelial membrane models likely to impact permeability of solutes. The epithelial membrane models developed to mimic normo- and hyperglycaemic scenarios are the basis to investigate (poly)phenol-lipid and drug–membrane interactions crucial in nutrition, pharmaceutics, structural biochemistry, and medicinal chemistry.

Reis, Ana (ORCID:0000000245379902)↗

Calcium-organic matter fouling in nanofiltration: Synchrotron-based X-ray fluorescence and absorption near-edge structure spectroscopy for speciation

Calcium (Ca)-enhanced organic matter (OM) fouling of nanofiltration (NF) membranes leads to reduced flux during desalination and requires frequent cleaning. Fouling mechanisms are not fully understood, which limits the development of targeted fouling control methods. This study employed synchrotron-based X-ray fluorescence (XRF) and X-ray absorption near-edge structure (XANES) spectroscopy to quantify the spatial distribution and mass of Ca deposition as well as changes in the Ca coordination environment characteristic of specific fouling mechanisms, respectively. Bench-scale filtration experiments were performed using feed solutions containing Ca and ten different types of organic matter (OM), as well as the common scalants, calcium carbonate (CaCO 3 ) and calcium sulfate (CaSO 4 ). Osmotic backwash (OB) was performed at regular intervals for fouling control. Ca-OM aggregation resulted in greater flux decline and lower flux recovery during OB than Ca conditioning of membranes followed by filtration of feed solution with OM. Linear combination fitting (LCF) of XANES absorption spectra from fouled membranes indicated that Ca-OM aggregation preferentially occurred for OM types that exhibited both high carboxylic group and negative charge density. Consequently, these OM types exhibited greater deposition of Ca and TOC on the membrane surface when compared to other OM types. For the coexistence of scalants and OM, Ca speciation within the fouling layer was characteristic of both Ca bound to the membrane (i.e. potential bridging, charge screening) as well as Ca-OM aggregation and deposition mechanisms, while a range of crystal polymorphs were observed to occur simultaneously. XRF and XANES represent powerful tools for the elucidation of NF fouling mechanisms by quantification of Ca deposition as well as Ca speciation. Fouling control methods should target OM types with high carboxyl group density and negative charge to neutralize or eliminate interactions with Ca.

42 ENGINEERING↗

Structure-Driven Liquid Microjunction Surface-Sampling Probe Mass Spectrometry

The rhizosphere is the narrow region of soil surrounding the roots of plants that is influenced by root exudates, root secretions, and associated microbial communities. This region is crucial to plant growth and development and plays a critical role in nutrient uptake, disease resistance, and soil transformation. Understanding the function of exogenous compounds in the rhizosphere starts with determining the spatiotemporal distribution of these molecular components. Using liquid microjunction surface-sampling probe mass spectrometry (LMJ-SSP-MS) and microfluidic devices with attached microporous membranes enables in situ, nondisruptive, and nondestructive spatiotemporal measurement of exogenous compounds from plant roots. However, long imaging times (>2 h) can negatively affect plant heath and limit temporal studies. Here, we present a novel strategy to optimize the number and location of sampling sites on these microporous membrane-covered microfluidic devices. In conclusion, this novel, “structure-driven” sampling workflow takes into consideration the channel structure of the microfluidic device to maximize sampling from the channels and minimize acquisition time (~4× less time in some cases while providing similar chemical image accuracy), thus reducing stress on plants during in situ LMJ-SSP-MS analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rapid and robust antibody Fab fragment crystallization utilizing edge-to-edge beta-sheet packing

Antibody therapeutics are one of the most important classes of drugs. Antibody structures have become an integral part of predicting the behavior of potential therapeutics, either directly or as the basis of modeling. Structures of Fab:antigen complexes have even greater value. While the crystallization and structure determination of Fabs is easy relative to many other protein classes, especially membrane proteins, broad screening and optimization of crystalline hits is still necessary. Through a comprehensive review of rabbit Fab crystal contacts and their incompatibility with human Fabs, we identified a small secondary structural element from the rabbit light chain constant domain potentially responsible for hindering the crystallization of human Fabs. Upon replacing the human kappa constant domain FG loop (HQGLSSP) with the two residue shorter rabbit loop (QGTTS), we dramatically improved the crystallization of human Fabs and Fab:antigen complexes. Our design, which we call “Crystal Kappa”, enables rapid crystallization of human fabs and fab complexes in a broad range of conditions, with less material in smaller screens or from dilute solutions.

59 BASIC BIOLOGICAL SCIENCES↗