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At least 145 records · Page 8

Electron transport across the cell envelope via multiheme c -type cytochromes in Geobacter sulfurreducens

Extracellular electron transfer (EET) enables certain microorganisms to respire using soluble and insoluble extracellular electron acceptors by transporting electrons across the cell envelope. Among these, G. sulfurreducens serves as a model organism for understanding direct EET pathways, where multiheme c-type cytochromes mediate electron transport from intracellular redox carriers to extracellular acceptors such as Fe(III) oxides and electrodes. This review focuses on heme-dependent electron transfer in Geobacter sulfurreducens, detailing the roles of inner membrane cytochromes, periplasmic carriers, outer membrane conduits, and recently characterized extracellular nanowires formed by polymerized multiheme c-type cytochromes, including OmcS, OmcE, and OmcZ. We examine the state of understanding of their physiological function, their structural features, expression patterns, and essentiality under various respiratory conditions. These insights advance our understanding of microbial anaerobic respiration and have implications for biogeochemical cycling, bioenergy generation, and bioremediation. The molecular architecture, assembly mechanisms, and secretion pathways of multiheme c-type cytochrome nanowires remain active areas of investigation, offering promising directions for future research and biotechnological innovation in engineered microbial systems.

Chemistry↗

Characterization of Polyamide Thin Films by Atomic Force Microscopy

This study directly compares the mechanical behavior of novel molecular layer deposition (MLD) and analogous interfacial polymerization (IP) polyamide thin films in environments relevant to reverse osmosis (RO) membrane operation. The elastic modulus of the films was determined using atomic force microscopy (AFM) in dry, hydrated, and chlorinated states. Surface roughness characteristics were also obtained given their potential influence on AFM modulus measurements. The much smoother MLD films demonstrated a statistically higher modulus in all states as compared to their IP counterparts. The MLD films maintained a modulus ~3X and ~5X greater than that of IP films after hydration and chlorination, respectively. Such differences in behavior may be due to the higher density and correspondingly lower void content of the MLD films. Results from this study provide a rationale for future development of MLD for fabrication of polyamide films for incorporation in RO membranes.

atomic force microscopy↗

Empirical evidence that glucan-interacting amino acid side chains within the transmembrane channel collectively facilitate cellulose synthase function

The fundamental mechanism of cellulose synthesis is widely conserved across Kingdoms and depends on cellulose synthases, which are processive, dual-function, family 2 glycosyltransferases (GT-2). These enzymes polymerize glucose on the cytoplasmic side of the plasma membrane and export the glucan chain to the cell surface through an integral transmembrane (TM) channel. Structural studies of active plant cellulose synthases (CESAs) have revealed interactions between the nascent glucan chain and the side chains of polar, charged, and aromatic amino acid residues that line the TM channel. However, the functional consequences of modifying these side chains have not been tested in vivo in CESAs or other processive GT-2s. To test this, we used an established in vivo assay based on genetic complementation of CESA5 in the moss, Physcomitrium patens. For accurate prediction of glucan-interacting amino acid residues, we generated a complete homotrimeric molecular model of PpCESA5 using a combination of homology and de novo modeling. All-atom molecular dynamics-based analyses of contact metrics and interaction energy identified 23 amino acid residues with high propensity to interact with the nascent glucan chain within the TM channel or on the apoplastic surface of PpCESA5. Mutating any one of 18 of these amino acid residues to alanine, thereby removing their side chains, abolished or impaired CESA function, with the strongest effects observed upon the loss of charged amino acid side chains. This provides direct evidence to support the hypothesis that multiple amino acid residues collectively maintain a smooth energy landscape within the TM channel to facilitate glucan translocation.

59 BASIC BIOLOGICAL SCIENCES↗

Discovery of multi-functional polyimides through high-throughput screening using explainable machine learning

Polyimides have been widely used in modern industries because of their excellent mechanical and thermal properties, e.g., high-temperature fuel cells, displays, and aerospace composites. However, it usually takes decades of experimental efforts to develop a successful product. Aiming to expedite the discovery of high-performance polyimides, we utilize computational methods of machine learning (ML) and molecular dynamics (MD) simulations. Our study provides compelling evidence for the effectiveness of a data-driven approach in discovering novel polyimides. We first build a comprehensive library of more than 8 million hypothetical polyimides based on the polycondensation of existing dianhydride and diamine/diisocyanate molecules. Then we establish multiple ML models for the thermal and mechanical properties of polyimides based on their experimentally reported values, including glass transition temperature, Young’s modulus, and tensile yield strength. The obtained ML models demonstrate excellent predictive performance in identifying the key chemical substructures influencing the thermal and mechanical properties of polyimides. The use of explainable machine learning describes the effect of chemical substructures on individual properties, from which human experts can understand the cause of the ML model decision. Applying the well-trained ML models, we obtain property predictions of the 8 million hypothetical polyimides. Then, we screen the whole hypothetical dataset and identify three (3) best-performing novel polyimides that have better-combined properties than existing ones through Pareto frontier analysis. For an easy query of the discovered high-performing polyimides, we also create an online platform https://polyimide-explorer.herokuapp.com/ that embeds the developed ML model with interactive visualization. Furthermore, we validate the ML predictions through all-atom MD simulations and examine their synthesizability. The MD simulations are in good agreement with the ML predictions and the three novel polyimides are predicted to be easy to synthesize via Schuffenhauer’s synthetic accessibility score. Following the proposed ML guidance, we successfully synthesized a novel polyimide and the experimentally obtained high glass transition/thermal decomposition temperature demonstrated its excellent thermal stability. Here our study demonstrates an efficient way to expedite the discovery of novel polymers using ML prediction and MD validation. The high-throughput screening of a large computational dataset can serve as a general approach for new material discovery in other polymeric material exploration problems, such as organic photovoltaics, polymer membranes, and dielectrics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhancing membrane performance for CO 2 capture from flue gas with ultrahigh MW polyvinylamine

Membranes for post-combustion CO 2 capture are required to have a high CO 2 permeance due to the limited driving force. For facilitated transport membranes synthesized with polyvinylamine (PVAm), a defect-free selective layer of <200 nm is usually required to render sufficient permeance with high CO 2 /N 2 selectivity. In order to meet such a demand through the knife-coating process, the coating solution needs to have a high viscosity at a relatively low concentration to minimize its penetration into the substrate. The demand was met by synthesizing PVAm with an ultrahigh molecular weight (MW) via inverse emulsion polymerization (IEP) in this study. Compared to solution polymerization, IEP isolates the reaction in inverse micelles suspended in a continuous organic phase, which allows excellent dissipation of the heat generated by the reaction and reduces gel formation drastically. The polymerization parameters, including monomer concentration, initiator concentration, and reaction temperature, were investigated to obtain the optimal MW of PVAm for membrane performance. As compared to solution polymerization, IEP enhanced the MW of PVAm from 1.2 to 12.7 MDa, which minimized the penetration of the coating solution into the substrate and hence the extra mass transfer resistance. The effect of MW and degree of hydrolysis of PVAm on the membrane transport properties were studied. Furthermore, by employing PVAm with a MW of 12.7 MDa to strengthen the polymer matrix, the loading of piperazine glycinate in the membrane was increased up to 85 wt.%. In conclusion, the resultant membrane achieved a CO 2 permeance of 839 GPU and a CO 2 /N 2 selectivity of 161 at the typical flue gas temperature of 57°C.

20 FOSSIL-FUELED POWER PLANTS↗

Binder Effects on Processing, Mechanical Properties, and Performance of Thin Sulfide Solid‐State Electrolytes

All‐solid‐state batteries (ASSBs) offer enhanced safety and energy density compared to conventional lithium‐ion batteries by replacing flammable liquid electrolytes with solid‐state electrolytes (SSEs). Among SSEs, sulfide‐based electrolytes exhibit high ionic conductivity and mechanical deformability, making them promising candidates for next‐generation energy storage. However, their practical implementation is hindered by interfacial instability, mechanical brittleness, and challenges in fabricating ultrathin electrolyte membranes (<30 μm) with robust mechanical integrity. Here, this study systematically examines the influence of polymeric binders—polyisobutylene, hydrogenated nitrile butadiene rubber, and styrene–ethylene–butylene–styrene (SEBS)—on the structural, mechanical, and electrochemical performance of thin sulfide SSE membranes. Key findings reveal that SEBS enables the fabrication of ultrathin, uniform membranes, while binder elasticity significantly affects structural stability during cycling. Operando stack pressure measurements indicate that binder properties directly influence adhesion force for LPSCl particles, influencing their stabilizing cycling period. These results underscore the critical role of polymer binders beyond mechanical reinforcement, positioning them as essential design variables in sulfide SSE engineering. By linking binder chemistry to processability and electrochemical performance, this study provides insights into optimizing sulfide SSEs, advancing their commercial viability in ASSBs.

argyrodite sulfide electrolyte↗

Design strategies for ion-sieving charge mosaic membranes toward sustainable lithium extraction

Membrane-based technologies are essential for realizing sustainable ion-sieving processes such as lithium extraction. Much effort was devoted to designing new membrane materials, whereas the effect of charge distribution has been largely overlooked. Here, we filled this knowledge gap by providing a quantitative transport model for selective ion diffusion through a charge mosaic membrane (CMM). Composed of alternating regions of Li-selective ceramic and anion-selective polymeric materials, CMMs offered the unique advantage of promoting the transport of both Li + and anions while blocking other cations. As a result, the membrane achieved a high Li/Mg selectivity of 62 and a high permeation rate of 59 mmol·m −2 ·h −1 at a low feeding concentration of 30 mM, without any external driving force. Systematical experiments revealed the influence of brine Mg/Li ratio and membrane ceramic/polymer ratio on the overall extraction rate, which was consistent with the prediction of our transport model. In conclusion, the model developed in this work not only presented the design strategies of CMMs for Li extraction but also provided guidance for the development of other ion-sieving processes in general.

25 ENERGY STORAGE↗

Molecular Design of Functional Polymers for Silica Scale Inhibition

Silica polymerization, which involves the condensation reaction of silicic acid, is a fundamental process with wide-ranging implications in biological systems, material synthesis, and scale formation. The formation of a silica-based scale poses significant technological challenges to energy-efficient operations in various industrial processes, including heat exchangers and water treatment membranes. Despite the common strategy of applying functional polymers for inhibiting silica polymerization, the underlying mechanisms of inhibition remain elusive. In this study, we synthesized a series of nitrogen-containing polymers as silica inhibitors and elucidated the role of their molecular structures in stabilizing silicic acids. Polymers with both charged amine and uncharged amide groups in their backbones exhibit superior inhibition performance, retaining up to 430 ppm of reactive silica intact for 8 h under neutral pH conditions. In contrast, monomers of these amine/amide-containing polymers as well as polymers containing only amine or amide functionalities present insignificant inhibition. Molecular dynamics simulations reveal strong binding between the deprotonated silicic acid and a polymer when the amine groups in the polymer are protonated. Notably, an extended chain conformation of the polymer is crucial to prevent proximity between the interacting monomeric silica species, thereby facilitating effective silica inhibition. Furthermore, the hydrophobic nature of alkyl segments in polymer chains disrupts the hydration shell around the polymer, resulting in enhanced binding with ionized silicic acid precursors compared to monomers. Finally, our findings provide novel mechanistic insights into the stabilization of silicic acids with functional polymers, highlighting the molecular design principles of effective inhibitors for silica polymerization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Graphene membrane microfluidic system

A microfluidic assembly can include a first microchannel substrate defining one or more first microchannels, a second microchannel substrate defining one or more second microchannels. The assembly can further include a membrane positioned between the first and second microchannel substrates and comprising a first polymeric layer, a second polymeric layer, and one or more graphene layers disposed between the first and second polymeric layers. At least a portion of the first microchannels can overlap at least a portion of the second microchannels such that, when a first fluid is present in the first microchannels and a second fluid is present in the second microchannels, the first fluid and the second fluid contact opposite sides of the membrane.

Dervishi, Enkeleda↗

Combinatorial Membrane Synthesis: Fundamentals of Hybrid Metal-Organic Brush (MOB) Membranes for Organic Solvent Nanofiltration (Renewal)

(a) Goals: The goals of our current 3-year research project are (i) expansion of the novel modification technique Single Electron Transfer- Living Radical Polymerization (SET-LRP) to graft polymer brushes on a polyimide stable support followed by characterization and testing of the ensuing membrane (ii) stiffen brush network utilizing (a) metal organic frameworks and (b) covalent bonds formed as a result of crosslinking the grafted brush network. (b) Approach: The approach taken for this research was: (i) to graft branches terminated with a carboxyl group on each bristle (or bristle branch) allowing (a) metal immobilization to form MOF-like structures between branches or (b) crosslink bristles using aliphatic or aromatic diamines; (ii) to test the performance of the membranes using organic dyes, pure solvents (alcohols) and industrially relevant organic solvent separations; and (iii) to characterize these modified brush membranes. (c) Findings: The significant findings from the past one year are summarized below (papers resulting from this work are listed below and in D. PUBLICATIONS and relevant references are found in E. REFERENCES.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Scaling dynamics in low-salt-rejection reverse osmosis for high-salinity produced water desalination: Mechanistic modeling and membrane autopsy

Membrane scaling remains a critical barrier to the reliable operation of desalination systems, particularly for hypersaline produced water (PW) treatment. This study fills the knowledge gap of autopsy-based model validation for PW desalination by elucidating scaling mechanisms in a Low-Salt-Rejection Reverse Osmosis (LSRRO) system through the integration of pilot-scale experimentation and complementary modeling approaches. A semi-empirical modeling framework was developed and applied to a multistage pilot LSRRO system equipped with nanofiltration and RO membranes treating high-salinity PW from the Permian Basin. Water quality analysis showed that total dissolved solids decreased from ~130,000 mg/L to ~1900 mg/L in the permeate, then further reduced to ~300 mg/L by a second-pass RO. Two different thermodynamic modeling approaches were evaluated: the first extends the LSRRO framework by incorporating system complexity and scaling phenomena, whereas the second method explicitly captures concentration polarization in localized supersaturation. Both methods illustrate the tendency for carbonate and sulfate scaling throughout the stages. Membrane autopsies revealed a silica-dominated deposit matrix, localized CaSO 4 at Stage 2, and minor barite/celestite despite their prominence in model predictions. Quantum-chemical calculations indicated silica scaling can be rationalized by favorable adsorption of H 4 SiO 4 on Fe-oxide surfaces (ΔG ≈ −44 kJ/mol), providing a kinetic pathway for interfacial inorganic polymerization even when bulk equilibrium predictions are conservative. Overall, the thermodynamic scaling modeling and membrane autopsy revealed heterogeneous, localized deposits with limited impact on LSRRO performance, while quantum analysis rationalized the thermodynamically unfavorable precipitation formation under bulk equilibrium, reconciling model–autopsy discrepancies. These insights support targeted pretreatment and silica-specific antiscalants to extend membrane lifetime and increase recovery, providing a transferable framework for hypersaline water desalination systems. The combined experimental–computational approach provides new mechanistic insight into scaling in hypersaline membrane systems and establishes a transferable framework for predicting and mitigating scaling in next-generation desalination technologies.

Low-salt-rejection reverse osmosis↗

Toward Thermally Stimuli-Responsive Polymeric Vesicles Fabricated by Block Copolymer Blends for Nanocarriers

Polymeric vesicles, characterized by enhanced colloidal stability, excellent mechanical properties, controllable surface functionality, and adjustable membrane thickness, are extremely useful in nano- and bio-technology for potential applications as nanosized carriers for drugs and enzymes. However, a few preparative steps are necessary to achieve a unilamellar vesicle with a narrow size distribution. Herein, we report the spontaneous formation of unilamellar polymeric vesicles with nanometer sizes (<50 nm), fabricated by simply mixing diblock copolymers (P(EO-AGE)(2K-2K) and P(EO-AGE)(0.75K-2K)) with differing hydrophilic mass fractions in aqueous solutions. Depending on the mixing ratio of block copolymers and the temperature, the block copolymer mixtures self-assemble into various nanostructures, such as spherical and cylindrical micelles, or vesicles. The self-assembled structures of the block copolymer mixtures were characterized by small-angle neutron scattering, resulting in a phase diagram drawn as a function of temperature and the mixing condition. Notably, the critical temperature for the micelle-to-vesicle phase transition can be easily controlled by altering the mixing conditions; it decreases with an increase in the concentration of one of the block copolymers.

block copolymers↗

Investigation of competitive sorption and plasticization of hyperaged CANAL ladder polymers for acid gas purification

Identifying membrane materials that have exceptional separation performance and stability to complex CO 2 -containing mixtures is a pressing topic in separation science. In this work, the membrane separation performance for a recently discovered class of contorted polymers synthesized via catalytic arene-norbornene annulation (CANAL) polymerization is presented. These CANAL polymers achieve high CO 2 /CH 4 selectivity of 68 after physical aging (up to ∼1 year), which significantly augments the size-sieving capabilities of the membranes. Binary CO 2 /CH 4 and ternary H 2 S/CO 2 /CH 4 testing result in a 41 % and 50 % enhancement in selectivities, respectively, for hyperaged (∼1 year) contorted CANAL polymers, highlighting their size-sieving capabilities. The remarkably high CO 2 /CH 4 mixed-gas and combined acid gas (CAG, (CO 2 +H 2 S)/CH 4 ) selectivities of 88 and 95, respectively, for CANAL-Me-S 5 F in particular surpass both the 2018 CO 2 /CH 4 mixed-gas and CAG upper bounds. Performance stability was also investigated for high concentrations of CO 2 , revealing a reduction in CO 2 /CH 4 mixed-gas selectivity without compromising CO 2 permeability, suggesting strong sorption of CO 2 but minimal plasticization effects for short testing periods. In addition, time-dependent plasticization shows negligible effects on CO 2 /CH 4 mixed-gas selectivity despite an increase in CO 2 permeability when exposed to high concentrations of plasticizing CO 2 over an extended period of 170 h. This study provides valuable insights into hyperaged CANAL polymers and their performance in practical industrial processes.

03 NATURAL GAS↗

Polybenzimidazole-Based Polymer Electrolyte Membranes for High-Temperature Fuel Cells: Current Status and Prospects

Polymer electrolyte membrane fuel cells (PEMFCs) expect a promising future in addressing the major problems associated with production and consumption of renewable energies and meeting the future societal and environmental needs. Design and fabrication of new proton exchange membranes (PEMs) with high proton conductivity and durability is crucial to overcome the drawbacks of the present PEMs. Acid-doped polybenzimidazoles (PBIs) carry high proton conductivity and long-term thermal, chemical, and structural stabilities are recognized as the suited polymeric materials for next-generation PEMs of high-temperature fuel cells in place of Nafion® membranes. This paper aims to review the recent developments in acid-doped PBI-based PEMs for use in PEMFCs. The structures and proton conductivity of a variety of acid-doped PBI-based PEMs are discussed. More recent development in PBI-based electrospun nanofiber PEMs is also considered. The electrochemical performance of PBI-based PEMs in PEMFCs and new trends in the optimization of acid-doped PBIs are explored.

25 ENERGY STORAGE↗

Quantum effects on the dynamics and properties of soft materials

The quantum effects of nuclear and electronic motion play an important role in the structure, dynamics, and function of soft materials, yet they are difficult to capture with conventional classical simulations or static electronic–structure methods. In this work several complementary approaches for treating quantum effects in polymeric and soft–matter systems are demonstrated, with a focus being on the hydrogen-bonded networks, ion and charge transport, and photoactive chromophores. The proton transfer, tunneling, and isotope effects are captured within the reduced-dimensionality models by implementing grid-based nuclear quantum dynamics in terms of the discrete variable and Fourier bases. The nuclear quantum dynamics is extended to larger systems by employing the quantum trajectories and quantum–thermal bath schemes combined with on-the-fly electronic structure, enabling the description of high-dimensional polymeric environments at feasible cost. The dynamics in the electronic degrees of freedom, simulating the optical response in large chromophores such as chlorophylls, is performed using the real-time time-dependent density functional theory implemented in the real-space multigrid (RMG) code. These approaches are demonstrated on case studies of the proton and hydroxide transport in hydrated polymer membranes, charge transfer in conjugated polymers, and the optical spectra of chlorophyll chromophores relevant to polymerized chlorophyll materials and chlorophyll–polymer hybrids. The reviewed methods and applications highlight practical routes of including quantum effects in simulations of soft functional materials.

Garashchuk, Sophya [Univ. of South Carolina, Colum↗

Comprehensive analysis of the human ESCRT-III-MIT domain interactome reveals new cofactors for cytokinetic abscission

The 12 related human ESCRT-III proteins form filaments that constrict membranes and mediate fission, including during cytokinetic abscission. The C-terminal tails of polymerized ESCRT-III subunits also bind proteins that contain Microtubule-Interacting and Trafficking (MIT) domains. MIT domains can interact with ESCRT-III tails in many different ways to create a complex binding code that is used to recruit essential cofactors to sites of ESCRT activity. Here, we have comprehensively and quantitatively mapped the interactions between all known ESCRT-III tails and 19 recombinant human MIT domains. We measured 228 pairwise interactions, quantified 60 positive interactions, and discovered 18 previously unreported interactions. We also report the crystal structure of the SPASTIN MIT domain in complex with the IST1 C-terminal tail. Three MIT enzymes were studied in detail and shown to: (1) localize to cytokinetic midbody membrane bridges through interactions with their specific ESCRT-III binding partners (SPASTIN-IST1, KATNA1-CHMP3, and CAPN7-IST1), (2) function in abscission (SPASTIN, KATNA1, and CAPN7), and (3) function in the ‘NoCut’ abscission checkpoint (SPASTIN and CAPN7). Our studies define the human MIT-ESCRT-III interactome, identify new factors and activities required for cytokinetic abscission and its regulation, and provide a platform for analyzing ESCRT-III and MIT cofactor interactions in all ESCRT-mediated processes.

59 BASIC BIOLOGICAL SCIENCES↗

Thin-film composite membranes based on hyperbranched poly(ethylene oxide) for CO 2 /N 2 separation

Cross-linked amorphous poly(ethylene oxide) (XLPEO) is one of the leading membrane materials for post-combustion CO 2 capture. For example, XLPEO prepared from poly(ethylene glycol) methyl ether acrylate (PEGMEA) exhibited CO 2 permeability of 570 Barrer and CO 2 /N 2 selectivity of 41 at 35 °C. However, these XLPEOs cannot be dissolved in coating solutions, making it impossible to be fabricated into thin-film composite (TFC) membranes using state-of-the-art manufacturing processes. In this study, we synthesized high molecular weight yet soluble HPEO via atom transfer radical polymerization (ATRP). These polymers were thoroughly characterized and compared with XLPEO, including thermal transitions, free volumes, and pure-gas sorption and permeation properties. A polymer with the best combination of CO 2 permeability (540 Barrer) and CO 2 /N 2 selectivity (43) was fabricated into defect-free TFC membranes with a thickness as thin as 506 ± 44 nm. When challenged with simulated flue gas containing water vapor at 35 °C for over 100 h, the membrane shows stable CO 2 permeance of 850 GPU and CO 2 /N 2 selectivity of 37, comparable to the leading commercial membranes for carbon capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Anion exchange membrane and methods of making and using the same

Anion exchange membrane and methods of making and using the same. In one embodiment, the anion exchange membrane may be made by a method that includes a two-step polymerization. In the first step, an α-olefin monomer containing a pendant halide, such as 8-bromo-1-octene, may be polymerized by Ziegler-Natta polymerization to form a first polymer portion, the first polymer portion being a homopolymer. In the second step, the polymerization is charged with a non-functionalized α-olefin monomer, such as ethylene, thereby forming a second polymer portion, the second polymer being a copolymer made up predominantly of the non-functionalized olefin monomer. If desired, a small amount of an α-olefin monomer containing a crosslinking functionality may be included in the first and/or second steps. Following the two-step polymerization, the polymer is fabricated into a thin film. Thereafter, the thin film may be functionalized by replacing the pendant halides with pendant cations.

Strasser, Derek J.↗