Using a non-precious metal catalyst for long-term enhancement of methane production in a zero-gap microbial electrosynthesis cell.

Microbial electrosynthesis (MES) cells exploit the ability of microbes to convert CO2 into valuable chemical products such as methane and acetate, but high rates of chemical production may need to be mediated by hydrogen and thus require a catalyst for the hydrogen evolution reaction (HER). To avoid the usage of precious metal catalysts and examine the impact of the catalyst on the rate of methane generation by microbes on the electrode, we used a carbon felt cathode coated with NiMo/C and compared performance to a bare carbon felt or a Pt/C-deposited cathode. A zero-gap configuration containing a cation exchange membrane was developed to produce a low internal resistance, limit pH changes, and enhance direct transport of H2 to microorganisms on the biocathode. At a fixed cathode potential of -1 V vs Ag/AgCl, the NiMo/C biocathode enabled a current density of 23 ± 4 A/m2 and a high methane production rate of 4.7 ± 1.0 L/L-d. This performance was comparable to that using a precious metal catalyst (Pt/C, 23 ± 6 A/m2, 5.4 ± 2.8 L/L-d), and 3-5 times higher than plain carbon cathodes (8 ± 3 A/m2, 1.0 ± 0.4 L/L-d). The NiMo/C biocathode was operated for over 120 days without observable decay or severe cathode catalyst leaching, reaching an average columbic efficiency of 53 ± 9 % based on methane production under steady state conditions. Analysis of microbial community on the biocathode revealed the dominance of the hydrogenotrophic genus Methanobacterium (∼40 %), with no significant difference found for biocathodes with different materials. These results demonstrated that HER catalysts improved rates of methane generation through facilitating hydrogen gas evolution to an attached biofilm, and that the long-term enhancement of methane production in MES was feasible using a non-precious metal catalyst and a zero-gap cell design.

Lactate-mediated medium-chain fatty acid production from expired dairy and beverage waste.

Fruits, vegetables, and dairy products are typically the primary sources of household food waste. Currently, anaerobic digestion is the most used bioprocess for the treatment of food waste with concomitant generation of biogas. However, to achieve a circular carbon economy, the organics in food waste should be converted to new chemicals with higher value than energy. Here we demonstrate the feasibility of medium-chain carboxylic acid (MCCA) production from expired dairy and beverage waste via a chain elongation platform mediated by lactate. In a two-stage fermentation process, the first stage with optimized operational conditions, including varying temperatures and organic loading rates, transformed expired dairy and beverage waste into lactate at a concentration higher than 900 mM C at 43 °C. This lactate was then used to produce >500 mM C caproate and >300 mM C butyrate via microbial chain elongation. Predominantly, lactate-producing microbes such as Lactobacillus and Lacticaseibacillus were regulated by temperature and could be highly enriched under mesophilic conditions in the first-stage reactor. In the second-stage chain elongation reactor, the dominating microbes were primarily from the genera Megasphaera and Caproiciproducens, shaped by varying feed and inoculum sources. Co-occurrence network analysis revealed positive correlations among species from the genera Caproiciproducens, Ruminococcus, and CAG-352, as well as Megasphaera, Bacteroides, and Solobacterium, indicating strong microbial interactions that enhance caproate production. These findings suggest that producing MCCAs from expired dairy and beverage waste via lactate-mediated chain elongation is a viable method for sustainable waste management and could serve as a chemical production platform in the context of building a circular bioeconomy.

Impacts of monosaccharide composition on immunomodulation by cello-pentaose, manno-pentaose, and xylo-pentaose: Unraveling the underlying molecular mechanisms.

Different types of functional oligosaccharides exhibit varying degrees of immune-enhancing effects, which might be attributable to differences in their glycosyl structures. The differences in the immunomodulatory action of three functional oligosaccharides with distinct glycosyl compositions: cello-oligosaccharides (COS), manno-oligosaccharides (MOS), and xylo-oligosaccharides (XOS), were investigated in mouse-derived macrophage RAW264.7. Moreover, the immune enhancement mechanism of oligosaccharides with diverse glycosyl compositions was investigated from a molecular interaction perspective. The TLR4-dependent immunoregulatory effect of functional oligosaccharides was shown by measuring the levels of tumor necrosis factor (TNF)-α and interleukin (IL)-6 in RAW264.7 cells treated with different functional oligosaccharides, both with and without Resatorvid [TAK-242] (a Toll-like receptor 4 [TLR4] inhibitor). Western blot analysis showed that binding of the three oligosaccharides to TLR4 activated the downstream signaling pathway and consequently enhanced the immune response. The fluorescence spectra and molecular docking results revealed that the main mechanisms by which these oligosaccharides attach to the TLR4 active pocket are hydrogen bonds and van der Waals forces. Functional oligosaccharides were ranked according to their affinity for TLR4, as follows: MOS > COS > XOS, indicating that oligosaccharides or polysaccharides containing mannose units may confer significant advantages for immune enhancement.

Thin-Film Composite Membranes for Hydrogen Evolution with a Saline Catholyte Water Feed.

Hydrogen gas evolution using an impure or saline water feed is a promising strategy to reduce overall energy consumption and investment costs for on-site, large-scale production using renewable energy sources. The chlorine evolution reaction is one of the biggest concerns in hydrogen evolution with impure water feeds. The "alkaline design criterion" in impure water electrolysis was examined here because water oxidation catalysts can exhibit a larger kinetic overpotential without interfering chlorine chemistry under alkaline conditions. Here, we demonstrated that relatively inexpensive thin-film composite (TFC) membranes, currently used for high-pressure reverse osmosis (RO) desalination applications, can have much higher rejection of Cl- (total crossover of 2.9 ± 0.9 mmol) than an anion-exchange membrane (AEM) (51.8 ± 2.3 mmol) with electrolytes of 0.5 M KOH for the anolyte and 0.5 M NaCl for the catholyte with a constant current (100 mA/cm2 for 20 h). The membrane resistances, which were similar for the TFC membrane and the AEM based on electrochemical impedance spectroscopy (EIS) and Ohm's law methods, could be further reduced by increasing the electrolyte concentration or removal of the structural polyester supporting layer (TFC-no PET). TFC membranes could enable pressurized gas production, as this membrane was demonstrated to be mechanically stable with no change in permeate flux at 35 bar. These results show that TFC membranes provide a novel pathway for producing green hydrogen with a saline water feed at elevated pressures compared to systems using AEMs or porous diaphragms.

Reducing Chloride Ion Permeation during Seawater Electrolysis Using Double-Polyamide Thin-Film Composite Membranes.

Low-cost polyamide thin-film composite membranes are being explored as alternatives to expensive cation exchange membranes for seawater electrolysis. However, transport of chloride from seawater to the anode chamber must be reduced to minimize the production of chlorine gas. A double-polyamide composite structure was created that reduced the level of chloride transport. Adding five polyamide layers on the back of a conventional polyamide composite membrane reduced the chloride ion transport by 53% and did not increase the applied voltage. Decreased chloride permeation was attributed to enhanced electrostatic and steric repulsion created by the new polyamide layers. Charge was balanced through increased sodium ion transport (52%) from the anolyte to the catholyte rather than through a change in the transport of protons and hydroxides. As a result, the Nernstian loss arising from the pH difference between the anolyte and catholyte remained relatively constant during electrolysis despite membrane modifications. This lack of a change in pH showed that transport of protons and hydroxides during electrolysis was independent of salt ion transport. Therefore, only sodium ion transport could compensate for the reduction of chloride flux to maintain the set current. Overall, these results prove the feasibility of using a double-polyamide structure to control chloride permeation during seawater electrolysis without sacrificing energy consumption.

Alleviation effect of GR24, a strigolactone analogue, on low-nitrogen stress in Malus baccata seedlings.

To investigate the efficacy of foliar application of GR24, a strigolactone analogue, in alleviating low-nitrogen stress in Malus baccata, we applied GR24 with different concentrations (0, 1, 5, 10, and 20 µmol·L-1) to leaves of plants under low nitrogen stress. We evaluated the changes in photosynthetic characteristics of leaves, reactive oxygen metabolism, and nitrogen assimilation in roots. The results showed that shoot biomass of seedling significantly decreased and root-shoot ratio increased under low-nitrogen stress. The chlorophyll contents decreased, the carotenoid content increased, and the photosynthetic activity decreased. The activities of superoxide dismutase and catalase enzymes in roots changed little, while the activities of peroxidase and ascorbic acid peroxidase enzymes, along with the levels of soluble sugar, free proline, and reactive oxygen species showed a significant increase, and the soluble protein content decreased. The NO3- content in roots decreased, the NH4+ content increased, while activities of nitrate reductase and glutamine synthase decreased. Compared to the control group without GR24 application, foliar sprays of 10 and 20 µmol·L-1 GR24 under both normal and low-nitrogen increased biomass and root-shoot ratio to varying degrees. Additionally, GR24 application increased chlorophyll content, photosynthesis indices (net photosynthetic rate, transpiration rate and stomatal conductance), and fluorescence (maximum photochemical efficiency of PSⅡ and quantum yield of electron transfer per unit area) performance parameters, as well as the contents of osmotic regulation substances (soluble protein, soluble sugar, and free proline) and glutamine synthase activity. Application of 10 and 20 µmol·L-1 GR24 under low-nitrogen stress decreased carotenoid, reactive oxygen species, and NH4+ contents, while increased the activities of antioxidases and key enzymes in nitrogen metabolism (nitrate reductase and glutamine synthase) and NO3- content. The 10 µmol·L-1 GR24 treatment was the most effective in alleviating low nitrogen stress, which has potential for application in apple orchards with low nitrogen soil.

Relative Insignificance of Polyamide Layer Selectivity for Seawater Electrolysis Applications.

Low-cost polyamide thin-film composite (TFC) membranes are being explored as alternatives to cation exchange membranes for seawater electrolysis. An optimal membrane should have a low electrical resistance to minimize applied potentials needed for water electrolysis and be able to block chloride ions present in a seawater catholyte from reaching the anode. The largest energy loss associated with a TFC membrane was the Nernstian overpotential of 0.74 V (equivalent to 37 Ω cm2 at 20 mA cm-2), derived from the pH difference between the anolyte and catholyte and not the membrane ohmic overpotential. Based on analysis using electrochemical impedance spectroscopy, the pristine TFC membrane contributed only 5.00 Ω cm2 to the ohmic resistance. Removing the polyester support layer reduced the resistance by 79% to only 1.04 Ω cm2, without altering the salt ion transport between the electrolytes. Enlarging the pore size (∼5 times) in the polyamide active layer minimally impacted counterion transport across the membrane during electrolysis, but it increased the total concentration of chloride transported by 60%. Overall, this study suggests that TFC membranes with thinner but mechanically strong supporting layers and size-selective active layers should reduce energy consumption and the potential for chlorine generation for seawater electrolyzers.

A structure-activity understanding of the interaction between lignin and various cellulase domains.

To elucidate the structure-activity relationship between lignin and various cellulase domains, four lignin fractions with specific structures and molecular weight were prepared from bamboo kraft lignin (BKL) and used to investigate the adsorption mechanism between different cellulase domains by fluorescence spectroscopy and SDS-PAGE. Endo-cellulase 6B exhibited a higher affinity to BKL fractions than the carbohydrate-binding module (CBM4A) of cellulase, which is positively correlated to molecular weight. The thermodynamic mechanism showed that the adsorption between BKL fractions and endo-cellulase 6B was dominated by van der Waals and electrostatic forces, while hydrophobic force is the driver for BKL fractions to adsorb CBM4A. Structure-activity relationship between lignin fractions and cellulase domain revealed that thermodynamics and interaction forces were more easily affected by the structure of BKL, including S/G ratio, molecular weight and hydrophobicity. The aforementioned results demonstrated that lignin's structure plays a critical role in its adsorption with various cellulase domains.

Identification of exosomal mRNA, lncRNA and circRNA signatures in an osteoarthritis synovial fluid-exosomal study.

AIMS: Osteoarthritis (OA) is a common degenerative disease that is pathologically characterized by destruction of the joint matrix and reduction of articular chondrocytes, resulting in joint deformity and motor dysfunction. However, the molecular mechanisms governing this pathology have not been elucidated to date. METHODS: In this study, we determined the expression levels of lncRNAs, circRNAs, and mRNAs extracted from synovial exosomes of OA and control patients. A network of circRNA/lncRNA-miRNA-mRNA interactions was established using MiRanda and TargetScan software to explore OA pathogenesis. The exosomal lncRNA, circRNA and mRNA expression profiles of the OA and control groups were analysed using LC human competing endogenous RNA (ceRNA) microarrays. The differentially expressed genes were analysed to determine their potential roles in the pathogenesis of OA by bioinformatic analysis. RESULTS: There were 52 mRNAs, 196 lncRNAs and 98 circRNAs differentially expressed in synovial exosomes between osteoarthritis synovial and the control group. The final ceRNA network of lncRNAs and circRNAs exhibited a complex interaction between ncRNA and mRNA related to OA pathological mechanisms. An intersection analysis of the ceRNA network showed that 22 miRNAs, 45 lncRNAs, and 34 circRNAs enriched in the PI3K/Akt and autophagy pathways correlated with 7 mRNAs and may play important roles in OA pathological mechanisms. CONCLUSION: Our work analysed mRNA/lncRNA/circRNA expression and displayed the ceRNA network of lncRNAs and circRNAs to profile the pathogenesis of OA in synovial exosomes. The results of this study may help to elucidate the pathogenesis of OA and may provide important references for further research attempting to identify more effective targets for the diagnosis and therapy of OA.

Long-Term Continuous Extraction of Medium-Chain Carboxylates by Pertraction With Submerged Hollow-Fiber Membranes.

Medium-chain carboxylic acids (MCCAs), which can be generated from organic waste and agro-industrial side streams through microbial chain elongation, are valuable chemicals with numerous industrial applications. Membrane-based liquid-liquid extraction (pertraction) as a downstream separation process to extract MCCAs has been applied successfully. Here, a novel pertraction system with submerged hollow-fiber membranes in the fermentation bioreactor was applied to increase the MCCA extraction rate and reduce the footprint. The highest average surface-corrected MCCA extraction rate of 655.2 ± 86.4 mmol C m-2 d-1 was obtained, which was higher than any other previous reports, albeit the relatively small surface area removed only 11.6% of the introduced carbon via pertraction. This submerged extraction system was able to continuously extract MCCAs with a high extraction rate for more than 8 months. The average extraction rate of MCCA by internal membrane was 3.0- to 4.7-fold higher than the external pertraction (traditional pertraction) in the same bioreactor. A broth upflow velocity of 7.6 m h-1 was more efficient to extract MCCAs when compared to periodic biogas recirculation operation as a means to prevent membrane fouling. An even higher broth upflow velocity of 40.5 m h-1 resulted in a significant increase in methane production, losing more than 30% of carbon conversion to methane due to a loss of H2, and a subsequent drop in the H2 partial pressure. This resulted in the shift from a microbial community with chain elongators as the key functional group to methanogens, because the drop in H2 partial pressure led to thermodynamic conditions that oxidizes ethanol and carboxylic acids to acetate and H2 with methanogens as the syntrophic partner. Thus, operators of chain elongating systems should monitor the H2 partial pressure when changes in operating conditions are made.

Resistance assessment of microbial electrosynthesis for biochemical production to changes in delivery methods and CO2 flow rates.

Microbial electrosynthesis (MES) for CO2 valorization could be influenced by fluctuations in CO2 mass transfer and flow rates. In this study, we developed an efficient method for CO2 delivery to cathodic biofilm by directly sparging CO2 through the pores of ceramic hollow fiber wrapped with Ni-foam/carbon nanotube electrode, and obtained 45% and 77% higher acetate and methane production, respectively. This was followed by the MES stability test in response to fluctuations in CO2 flow rates varying from 0.3 ml/min to 10 ml/min. The biochemical production exhibited an increasing trend with CO2 flow rates, achieving higher acetate (47.0 ± 18.4 mmol/m2/day) and methane (240.0 ± 32.2 mmol/m2/day) generation at 10 ml/min with over 90% coulombic efficiency. The biofilm and suspended biomass, however, showed high resistance to CO2 flow fluctuations with Methanobacterium and Acetobacterium accounting for 80% of the total microbial community, which suggests the robustness of MES for onsite carbon conversion.

Microbial electrosynthesis from CO2: Challenges, opportunities and perspectives in the context of circular bioeconomy.

Recycling CO2 into organic products through microbial electrosynthesis (MES) is attractive from the perspective of circular bioeconomy. However, several challenges need to be addressed before scaling-up MES systems. In this review, recent advances in electrode materials, microbe-catalyzed CO2 reduction and MES energy consumption are discussed in detail. Anode materials are briefly reviewed first, with several strategies proposed to reduce the energy input for electron generation and enhance MES bioeconomy. This was followed by discussions on MES cathode materials and configurations for enhanced chemolithoautotroph growth and CO2 reduction. Various chemolithoautotrophs, effective for CO2 reduction and diverse bioproduct formation, on MES cathode were also discussed. Finally, research efforts on developing cost-effective process for bioproduct extraction from MES are presented. Future perspectives to improve product formation and reduce energy cost are discussed to realize the application of the MES as a chemical production platform in the context of building a circular economy.

Enhancement in Power Conversion Efficiency of GaAs Solar Cells by Utilizing Gold Nanostar Film for Light-Trapping.

Light trapping, caused by the introduction of metallic nanoparticles, has been demonstrated to enhance photo-absorption in GaAs solar cells. In this study, we successfully synthesized gold nanostar thin film with hot spots and obtained a notable improvement of power conversion efficiency (PCE) in single-junction and three-junction high-performance GaAs solar cells by incorporating the poly (3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) layer, which enables a much stronger light trapping capability and scattering enhancement than conventional metal nanostructures. Increases of 5.2% and 3.94% in short circuit current density (Isc) were achieved for single-junction cells and three-junction cells while the enhancement in cell PCE was 3.85 and 2.50%, respectively. The relationship between the optical characteristics, the distribution density of the gold NSs and the performance of GaAs solar cells was systemically investigated.

Dual-Function Conductive Copper Hollow Fibers for Microfiltration and Anti-biofouling in Electrochemical Membrane Bioreactors.

Membrane bioreactors (MBRs) with polymeric/ceramic microfiltration (MF) membranes have been commonly used for wastewater treatment today. However, membrane biofouling often results in a dramatically-reduced service life of MF membranes, which limits the application of this technology. In this study, Cu hollow fiber membranes (Cu-HFMs) with low resistivity (104.8-309.8 nΩ·m) and anti-biofouling properties were successfully synthesized. Further analysis demonstrated that Cu-HFMs reduced at 625°C achieved the bimodal pore size distribution of ~1 µm and a porosity of 46%, which enable high N2 permeance (1.56 × 10-5 mol/m2 s pa) and pure water flux (5812 LMH/bar). The Cu-HFMs were further applied as the conductive cathodes, as well as MF membranes, in the electrochemical membrane bioreactor (EMBR) system that was enriched with domestic wastewater at an applied voltage of 0.9 V. Excellent permeate quality (Total suspended solids (TSS) = 11 mg/L) was achieved at a flux of 9.47 LMH after Cu-HFM filtration, with relatively stable transmembrane pressure (TMP) and low Cu2+ dissolvability (<25 µg/L). The anti-biofouling over time was demonstrated by SEM characterization of the rare biofilm formation on the Cu-HFM cathode surface. By using Cu-HFMs in EMBR systems, an effective strategy to control the membrane biofouling is developed in this study.

Dual-Function Electrocatalytic and Macroporous Hollow-Fiber Cathode for Converting Waste Streams to Valuable Resources Using Microbial Electrochemical Systems.

Dual-function electrocatalytic and macroporous hollow-fiber cathodes are recently proposed as promising advanced material for maximizing the conversion of waste streams such as wastewater and waste CO2 to valuable resources (e.g., clean freshwater, energy, value-added chemicals) in microbial electrochemical systems. The first part of this progress report reviews recent developments in this type of cathode architecture for the simultaneous recovery of clean freshwater and energy from wastewater. Critical insights are provided on suitable materials for fabricating these cathodes, as well as addressing some challenges in the fabrication process with proposed strategies to overcome them. The second and complementary part of the progress report highlights how the unique features of this cathode architecture can solve one of the intrinsic bottlenecks (gas-liquid mass transfer limitation) in the application of microbial electrochemical systems for CO2 reduction to value-added products. Strategies to further improve the availability of CO2 to microbial catalysts on the cathode are proposed. The importance of understanding microbe-cathode interactions, as well as electron transfer mechanisms at the cathode-cell and cell-cell interface to better design dual-function macroporous hollow-fiber cathodes, is critically discussed with insights on how the choice of material is important in facilitating direct electron transfer versus mediated electron transfer.

Direct Pen Writing of Adhesive Particle-Free Ultrahigh Silver Salt-Loaded Composite Ink for Stretchable Circuits.

In this article, we describe a writable particle-free ink for fast fabrication of highly conductive stretchable circuits. The composite ink mainly consists of soluble silver salt and adhesive rubber. Low toxic ketone was employed as the main solvent. Attributed to ultrahigh solubility of silver salt in short-chain ketone and salt-assisted dissolution of rubber, the ink can be prepared into particle-free transparent solution. As-prepared ink has a good chemical stability and can be directly filled into ballpoint pens and use to write on different substrates to form well adhesive silver salt-based composite written traces as needed. As a result of high silver salt loading, the trace can be converted into highly conductive silver nanoparticle-based composites after in situ reduction. Because of the introduction of adhesive elastomeric rubber, the as-formed conductive composite written trace can not only maintain good adhesion to various substrates but also show good conductivity under various deformations. The conductivity of written traces can be enhanced by repeated writing-reduction cycles. Different patterns can be fabricated by either direct handwriting or hand-copying. As proof-of-concept demonstrations, a typical handwriting heart-like circuit was fabricated to show its capability to work under different deformations, and a pressure-sensitive switch was also manufactured to present pressure-dependent change of resistance.