Synthesis of Enantioenriched Sulfoxides by an Oxidation-Reduction Enzymatic Cascade.

Chiral sulfoxides are versatile synthons and have gained a particular interest in asymmetric synthesis of active pharmaceutical and agrochemical ingredients. Herein, a linear oxidation-reduction bienzymatic cascade to synthesize chiral sulfoxides is reported. The extraordinarily stable and active vanadium-dependent chloroperoxidase from Curvularia inaequalis (CiVCPO) was used to oxidize sulfides into racemic sulfoxides, which were then converted to chiral sulfoxides by highly enantioselective methionine sulfoxide reductase A (MsrA) and B (MsrB) by kinetic resolution, respectively. The combinatorial cascade gave a broad range of structurally diverse sulfoxides with excellent optical purity (>99 %  ee) with complementary chirality. The enzymatic cascade requires no NAD(P)H recycling, representing a facile method for chiral sulfoxide synthesis. Particularly, the envisioned enzymatic cascade not only allows CiVCPO to gain relevance in chiral sulfoxide synthesis, but also provides a powerful approach for (S)-sulfoxide synthesis; the latter case is significantly unexplored for heme-dependent peroxidases and peroxygenases.

A comparison of digestate management options at a large anaerobic digestion plant.

Increased biogas production from increasing numbers of anaerobic digestion (AD) facilities has increased the mass of digestate applied to agricultural land close to AD plants and has led to an oversupply in some regions. This necessitates long distance digestate transportation accompanied by economic, environmental, and social drawbacks. This work assesses the performance of three different digestate management options (MOs); land application of whole digestate (MO1), digestate separation (MO2), and digestate separation and evaporation (MO3), combined with centralised or decentralised digestate storage. All MOs required the same landbank area, whilst MO2 and MO3 reduced digestate management costs by 9% and 37% (if recovered heat is used) respectively. GHG emissions from MO2 were 41% lower than MO1 if renewable electricity was used. MO3 reduced GHG emissions by 63% compared to MO1, if renewable electricity and recovered heat were used. MO2 required the same centralised digestate storage volume as MO1 while MO3 required 44% of the centralised storage volume. Centralised digestate storage required a maximum of 79 days for digestate transportation (33 trucks/day, 20 m3 capacity) to land for MO1 and MO2, and 35 days for MO3. Decentralised digestate storage required 63 storage tanks and 15 trucks/day for MO1, 69 tanks and 15 trucks/day for MO2, and 68 tanks and 7 trucks/day for MO3. Tank size ranged from 500 m3 to 20,000 m3. MO3 combined with decentralised storage could reduce the cost and GHG emissions (if recovered energy is used), vehicle movements, and the number of storage tanks required for digestate management.

Biochar confers significant microbial resistance to ammonia toxicity in n-caproic acid production.

Microbial chain elongation integrating innovative bioconversion technologies with organic waste utilization can transition current energy-intensive n-caproic acid production to sustainable circular bioeconomy systems. However, ammonia-rich waste streams, despite their suitability, pose inhibitory challenges to these bioconversion processes. Herein, biochar was employed as an additive to enhance the activity of chain elongating microbes under ammonia inhibition conditions, with an objective to detail underlying mechanisms of improvements. Biochar addition significantly improved chain elongation performance even under severe ammonia stress (exceeding 8 g N/L), increasing n-caproic acid yields by 40 % to 158 % and reducing lag times by 51 % to 90 %, compared with the best-performing group without biochar addition. The material contribution to n-caproic production reached up to 94.3 % (at 4 g N/L). These enhancements were mainly attributed to the new electron syntrophy induced by biochar, which improved electron transfer system activity and electrical conductivity of the fermentation system. This is further substantiated by increased relative abundances of the genus Sporanaerobacter, electroactive bacteria, and up-regulated direct electron transfer-related genes including conductive pili and c-type cytochrome. This study demonstrates that biochar can confer robust resilience to ammonia toxicity in functional microbes, paving a way for efficient and sustainable n-caproic acid production.

A perspective on three sustainable hydrogen production technologies with a focus on technology readiness level, cost of production and life cycle environmental impacts.

Hydrogen will play an indispensable role as both an energy vector and as a molecule in essential products in the transition to climate neutrality. However, the optimal sustainable hydrogen production system is not definitive due to challenges in energy conversion efficiency, economic cost, and associated marginal abatement cost. This review summarises and contrasts different sustainable hydrogen production technologies including for their development, potential for improvement, barriers to large-scale industrial application, capital and operating cost, and life-cycle environmental impact. Polymer electrolyte membrane water electrolysis technology shows significant potential for large-scale application in the near-term, with a higher technology readiness level (expected to be 9 by 2030) and a levelized cost of hydrogen expected to be 4.15-6 €/kg H2 in 2030; this equates to a 50% decrease as compared to 2020. The four-step copper-chlorine (Cu-Cl) water thermochemical cycle can perform better in terms of life cycle environmental impact than the three- and five-step Cu-Cl cycle, however, due to system complexity and high capital expenditure, the thermochemical cycle is more suitable for long-term application should the technology develop. Biological conversion technologies (such as photo/dark fermentation) are at a lower technology readiness level, and the system efficiency of some of these pathways such as biophotolysis is low (less than 10%). Biomass gasification may be a more mature technology than some biological conversion pathways owing to its higher system efficiency (40%-50%). Biological conversion systems also have higher costs and as such require significant development to be comparable to hydrogen produced via electrolysis.

Local Dipole Modulation Toward High Fill Factor in Organic Solar Cells.

Dipole moment arrangement in organic semiconductors plays a critical role in affecting the intermolecular packing, determining optoelectronic properties and device performance. Here, to get the desired fill factor (FF) values in organic solar cells (OSCs), the local dipole of non-fullerene acceptors (NFAs) is modulated by changing the molecular asymmetries. Two NFAs, AA-1 and AA-2 are designed and synthesized, which have different substitutions of alkyl and alkoxyl groups. The unidirectional asymmetry in AA-2 creates distinct local dipoles, while the bidirectional asymmetry in AA-1 mitigates dipole variation. Despite the minimal impact on monomolecular properties, the local dipole moment significantly influences terminal group packing modes in the film state. This, in turn, enhances the relative dielectric constant, prolongs exciton lifetime, and reduces sub-bandgap defect states. Consequently, PBDB-TF:AA-2-based OSCs achieve an exceptional FF of 0.830 and a power conversion efficiency (PCE) of 18.3%, with a ternary device reaching a PCE of 19.3%. This work highlights the potential of dipole modulation in material design to get ideal FF values for high-performance OSCs.

Hydrothermal Valorization of Biosugars with Heterogeneous Catalysts: Advances, Catalyst Deactivation, Mitigation Strategies and Perspectives.

Sustainable production of valuable biochemicals and biofuels from lignocellulosic biomass necessitates the development of durable and high-performance catalysts. To assist the next-stage catalyst design for hydrothermal treatment of biosugars, this paper provides a critical review of (1) recent advances in biosugar hydrothermal valorization using heterogeneous catalysts, (2) the deactivation process of catalysts based on recycling tests of representative biosugar hydrothermal treatments, (3) state-of-the-art understandings of the deactivation mechanisms of heterogeneous catalysts, and (4) strategies for preparing durable catalysts and the regeneration of deactivated catalysts. Based on the review, challenges and perspectives are proposed. Some remarkable achievements in heterogeneous catalysis of biosugars are highlighted. The understanding of catalyst durability needs to be further enhanced based on full examination of the catalytic performance based on the conversion of substrates, the yield, and selectivity of products. Further, a full examination of the physiochemical changes based on multiple characterization techniques is required to eclucidate the relationships between treatment variables and catalyst durability. Collectively, a clear understanding of the relationships between chemical reaction pathways, treatment variables, and the physiochemistry of catalysts is encouraged to be gained to advise the development of heterogeneous catalysts for long-term and efficient hydrothermal upgrading of biosugars.

A perspective on the combination of alkali pre-treatment with bioaugmentation to improve biogas production from lignocellulose biomass.

Anaerobic digestion (AD) is a bioprocess technology that integrates into circular economy systems, which produce renewable energy and biofertilizer whilst reducing greenhouse gas emissions. However, improvements in biogas production efficiency are needed in dealing with lignocellulosic biomass. The state-of-the-art of AD technology is discussed, with emphasis on feedstock digestibility and operational difficulty. Solutions to these challenges including for pre-treatment and bioaugmentation are reviewed. This article proposes an innovative integrated system combining alkali pre-treatment, temperature-phased AD and bioaugmentation techniques. The integrated system as modelled has a targeted potential to achieve a biodegradability index of 90% while increasing methane production by 47% compared to conventional AD. The methane productivity may also be improved by a target reduction in retention time from 30 to 20 days. This, if realized has the potential to lower energy production cost and the levelized cost of abatement to facilitate an increased resource of sustainable commercially viable biomethane.

An assessment of how the properties of pyrochar and process thermodynamics impact pyrochar mediated microbial chain elongation in steering the production of medium-chain fatty acids towards n-caproate.

Microbial chain elongation fermentation is an alternative technology for medium-chain fatty acid (MCFA) production. This paper proposed the addition of pyrochar and graphene in chain elongation to improve MCFA production using ethanol and acetate as substrates. Results showed that the yield of, and selectivity towards, C6 n-caproate were significantly enhanced with pyrochar addition. At the optimal mass ratio of pyrochar to substrate of 2 g/g, the maximum n-caproate yield of 13.67 g chemical oxygen demand/L and the corresponding selectivity of 56.8% were obtained; this represents an increase of 115% and 128% respectively as compared with no pyrochar addition. Such improvements were postulated as due to the high electrical conductivity and surface redox groups of pyrochar. The optimal ethanol to acetate molar ratio of 2 mol/mol achieved the highest MCFA yield under pyrochar mediated chain elongation conditions. Thermodynamic calculations modelled an energy benefit of 93.50 kJ/mol reaction for pyrochar mediated n-caproate production.

Design, Commissioning, and Performance Assessment of a Lab-Scale Bubble Column Reactor for Photosynthetic Biogas Upgrading with Spirulina platensis.

The two-step bubble column-photobioreactor photosynthetic biogas upgrading system can enable simultaneous production of biomethane and value-added products from microalgae. However, due to the influence of a large number of variables, including downstream processes and the presence of microalgae, no unanimity has been reached regarding the performance of bubble column reactors in photosynthetic biogas upgrading. To investigate this further, the present work documents in detail, the design and commissioning of a lab-scale bubble column reactor capable of treating up to 16.3 L/h of biogas while being scalable. The performance of the bubble column was assessed at a pH of 9.35 with different algal densities of Spirulina platensis at 20 °C in the presence of light (3-5 klux or 40.5-67.5 µmol m-2 s-1). A liquid/gas flow (L/G) ratio of 0.5 allowed consistent CO2 removal of over 98% irrespective of the algal density or its photosynthetic activity. For lower concentrations of algae, the volumetric O2 concentration in the upgraded biomethane varied between 0.05 and 0.52%, thus providing grid quality biomethane. However, for higher algal concentrations, increased oxygen content in the upgraded biomethane due to both enhanced O2 stripping and the photosynthetic activity of the microalgae as well as clogging and foaming posed severe operational challenges.

Production of Bio-alkanes from Biomass and CO2.

Bioelectrochemical technologies such as electro-fermentation and microbial CO2 electrosynthesis are emerging interdisciplinary technologies that can produce renewable fuels and chemicals (such as carboxylic acids). The benefits of electrically driven bioprocesses include improved production rate, selectivity, and carbon conversion efficiency. However, the accumulation of products can lead to inhibition of biocatalysts, necessitating further effort in separating products. The recent discovery of a new photoenzyme, capable of converting carboxylic acids to bio-alkanes, has offered an opportunity for system integration, providing a promising approach for simultaneous product separation and valorisation. Combining the strengths of photo/bio/electrochemical catalysis, we discuss an innovative circular cascading system that converts biomass and CO2 to value-added bio-alkanes (CnH2n+2, n = 2 to 5) whilst achieving carbon circularity.

Zeolitic imidazolate framework-derived porous carbon enhances methanogenesis by facilitating interspecies electron transfer: Understanding fluorimetric and electrochemical responses of multi-layered extracellular polymeric substances.

Modulating microbial electron transfer during anaerobic digestion can significantly improve syntrophic interactions for enhanced biogas production. As a carbonaceous conductive material, zeolite imidazolate framework-67 (ZIF-67)-derived porous carbon (PC) was hypothesized to act as a microbial electron transfer highway and assessed with respect to understanding the fluorimetric and electrochemical responses of multilayered extracellular polymeric substances (EPS). The highest biomethane yield (614.0 mL/g) from ethanol was achieved in the presence of 100 mg/L PC prepared at a carbonization temperature of 800 °C (PC-800), which was 28.2% higher than that without PC addition. Electrochemical analysis revealed that both the redox peak currents and conductivity of the methanogenic sludge increased, while the free charge transfer resistance decreased with PC-800 addition. The conductive PC-800 potentially functioned as an abiotic electron conduit to promote direct interspecies electron transfer, thereby resulting in decreased expression of functional genes associated with electrically conductive pili (e-pili) and hemeproteins. Additionally, PC-800 stimulated the secretion of redox-active humic substances (HSs), and excitation emission matrix spectra analysis indicated that the largest increase in percent fluorescence response of HSs occurred in the tightly bound EPS (TB-EPS) with addition of PC-800. This was attributed to the strong complexation ability of PC-800 particles to hydroxyl/carboxylic/phenolic moieties of HSs contained in the TB-EPS. Microbial analysis revealed that syntrophic/exoelectrogenic bacteria such as Pelotomaculum and Syntrophomonas, as well as hydrogenotrophic/electrotrophic methanogens such as Methanoculleus and Methanobacterium, were enriched in methanogenic sludge with adding PC-800. This study provided comprehensive insights for understanding the interactions among ZIF-derived PC, methanogenic microorganisms and their multilayered EPS.

How can ethanol enhance direct interspecies electron transfer in anaerobic digestion?

Anaerobic digestion (AD) of organic waste to produce biogas is a mature biotechnology commercialised for decades. However, the relatively recent discovery of direct interspecies electron transfer (DIET) brings a new opportunity to improve the efficiency of biogas technology. DIET may replace mediated interspecies electron transfer (MIET) by efficient electron transfer between exoelectrogens and electrotrophic methanogens, thereby enhancing yields and rates of biogas production. Ethanol, as the initial electron donor in the discovery of the DIET pathway, is now a "hot topic" in the literature. Recent studies have indicated that ethanol in AD functions not only as the substrate, but also as the precursor to stimulate DIET by enriching exoelectrogens and electrotrophic methanogens for co-digesting complex organic wastes. This review aims to highlight the state of the art and recent advances in ethanol-based DIET in AD. The DIET associated reactions of ethanol oxidation and carbon dioxide reduction are assessed by thermodynamic analysis to reveal the extent of the potential for improvement of the AD processes that utilizes DIET pathways. Three ethanol-based DIET strategies are discussed: (1) ethanol as the sole substrate supplemented with conductive materials in AD, (2) ethanol co-digestion with complex substrates and (3) ethanol-type fermentation prior to AD. This review aims to chart the pathways for improved AD performance by utilizing ethanol-based DIET in specific treatments of biological wastes.

Emerging bioelectrochemical technologies for biogas production and upgrading in cascading circular bioenergy systems.

Biomethane is suggested as an advanced biofuel for the hard-to-abate sectors such as heavy transport. However, future systems that optimize the resource and production of biomethane have yet to be definitively defined. This paper assesses the opportunity of integrating anaerobic digestion (AD) with three emerging bioelectrochemical technologies in a circular cascading bioeconomy, including for power-to-gas AD (P2G-AD), microbial electrolysis cell AD (MEC-AD), and AD microbial electrosynthesis (AD-MES). The mass and energy flow of the three bioelectrochemical systems are compared with the conventional AD amine scrubber system depending on the availability of renewable electricity. An energy balance assessment indicates that P2G-AD, MEC-AD, and AD-MES circular cascading bioelectrochemical systems gain positive energy outputs by using electricity that would have been curtailed or constrained (equivalent to a primary energy factor of zero). This analysis of technological innovation, aids in the design of future cascading circular biosystems to produce sustainable advanced biofuels.

A perspective on novel cascading algal biomethane biorefinery systems.

Synergistic opportunities to combine biomethane production via anaerobic digestion whilst cultivating microalgae have been previously suggested in literature. While biomethane is a promising and flexible renewable energy vector, microalgae are increasingly gaining importance as an alternate source of food and/or feed, chemicals and energy for advanced biofuels. However, simultaneously achieving, grid quality biomethane, effective microalgal digestate treatment, high microalgae growth rate, and the most sustainable use of the algal biomass is a major challenge. In this regard, the present paper proposes multiple configurations of an innovative Cascading Algal Biomethane-Biorefinery System (CABBS) using a novel two-step bubble column-photobioreactor photosynthetic biogas upgrading technology. To overcome the limitations in choice of microalgae for optimal system operation, a microalgae composition based biorefinery decision tree has also been conceptualised to maximise profitability. Techno-economic, environmental and practical aspects have been discussed to provide a comprehensive perspective of the proposed systems.

Effects of foam nickel supplementation on anaerobic digestion: Direct interspecies electron transfer.

Stimulating direct interspecies electron transfer with conductive materials is a promising strategy to overcome the limitation of electron transfer efficiency in syntrophic methanogenesis of industrial wastewater. This paper assessed the impact of conductive foam nickel (FN) supplementation on syntrophic methanogenesis and found that addition of 2.45 g/L FN in anaerobic digestion increased the maximum methane production rate by 27.4 % (on day 3) while decreasing the peak production time by 33 % as compared to the control with no FN. Cumulative methane production from day 2 to 6 was 14.5 % higher with addition of 2.45 g/L FN than in the control. Levels of FN in excess of 2.45 g/L did not show benefits. Cyclic voltammetry results indicated that the biofilm formed on the FN could generate electrons. The dominant bacterial genera in suspended sludge were Dechlorobacter and Rikenellaceae DMER64, whereas that in the FN biofilm was Clostridium sensu stricto 11. The dominant archaea Methanosaeta in the FN biofilm was enriched by 14.1 % as compared to the control.

How to optimise photosynthetic biogas upgrading: a perspective on system design and microalgae selection.

Photosynthetic biogas upgrading using microalgae provides a promising alternative to commercial upgrading processes as it allows for carbon capture and re-use, improving the sustainability of the process in a circular economy system. A two-step absorption column-photobioreactor system employing alkaline carbonate solution and flat plate photobioreactors is proposed. Together with process optimisation, the choice of microalgae species is vital to ensure continuous performance with optimal efficiency. In this paper, in addition to critically assessing the system design and operation conditions for optimisation, five criteria are selected for choosing optimal microalgae species for biogas upgrading. These include: ability for mixotrophic growth; high pH tolerance; external carbonic anhydrase activity; high CO2 tolerance; and ease of harvesting. Based on such criteria, five common microalgae species were identified as potential candidates. Of these, Spirulina platensis is deemed the most favourable species. An industrial perspective of the technology further reveals the significant challenges for successful commercial application of microalgal upgrading of biogas, including: a significant land footprint; need for decreasing microalgae solution recirculation rate; and selecting preferable microalgae utilisation pathway.

Enhancing fermentative hydrogen production with the removal of volatile fatty acids by electrodialysis.

A three-chamber electrodialysis bioreactor comprising fermentation, cathode and anode chambers was proposed to remove in situ volatile fatty acids during hydrogen fermentation. The electrodialysis voltage of 4 V resulted in a volumetric hydrogen productivity of 1878.0 mL/L from the fermentation chamber, which is 55.4% higher than that (1208.5 mL/L) of the control group without voltage applied. Gas production was not observed in the cathode and anode chambers throughout fermentation. By applying different voltages (0-6 V), the hydrogen content accumulated to 54.6%-84.7%, and it exhibited increases of 7.1%-66.4% compared with that of the control. Meanwhile, the maximum concentrations of acetate and butyrate in the fermentation chamber decreased to 10.3 and 13.1 mmol/L at a voltage of 4 V, respectively, which are 68.0% and 62.4% lower than that for the control.

Graphene Facilitates Biomethane Production from Protein-Derived Glycine in Anaerobic Digestion.

Interspecies electron transfer is a fundamental factor determining the efficiency of anaerobic digestion (AD), which involves syntrophy between fermentative bacteria and methanogens. Direct interspecies electron transfer (DIET) induced by conductive materials can optimize this process offering a significant improvement over indirect electron transfer. Herein, conductive graphene was applied in the AD of protein-derived glycine to establish DIET. The electron-producing reaction via DIET is thermodynamically more favorable and exhibits a more negative Gibbs free energy value (-60.0 kJ/mol) than indirect hydrogen transfer (-33.4 kJ/mol). The Gompertz model indicated that the kinetic parameters exhibited linear correlations with graphene addition from 0.25 to 1.0 g/L, leading to the highest increase in peak biomethane production rate of 28%. Sedimentibacter (7.8% in abundance) and archaea Methanobacterium (71.1%) and Methanosarcina (11.3%) might be responsible for DIET. This research can open up DIET to a range of protein-rich substrates, such as algae.

Ionic-liquid pretreatment of cassava residues for the cogeneration of fermentative hydrogen and methane.

An ionic liquid of N-methylmorpholine-N-oxide (NMMO) was used to effectively pretreat cassava residues for the efficient enzymatical hydrolysis and cogeneration of fermentative hydrogen and methane. The reducing sugar yield of enzymolysed cassava residues with NMMO pretreatment improved from 36 to 42g/100g cassava residues. Scanning electron microscopy images revealed the formation of deep grooves (∼4µm wide) and numerous pores in the cassava residues pretreated with NMMO. X-ray diffraction patterns showed that the crystallinity coefficient of NMMO-pretreated cassava residues decreased from 40 to 34. Fourier transform infrared spectra indicated that crystal cellulose I was partially transformed to amorphous cellulose II in the NMMO-pretreated cassava residues. This transformation resulted in a reduced crystallinity index from 0.85 to 0.77. Hydrogen yield from the enzymolysed cassava residues pretreated with NMMO increased from 92.3 to 126mL/gTVS, and the sequential methane yield correspondingly increased from 79.4 to 101.6mL/g TVS.

Boosting biomethane yield and production rate with graphene: The potential of direct interspecies electron transfer in anaerobic digestion.

Interspecies electron transfer between bacteria and archaea plays a vital role in enhancing energy efficiency of anaerobic digestion (AD). Conductive carbon materials (i.e. graphene nanomaterial and activated charcoal) were assessed to enhance AD of ethanol (a key intermediate product after acidogenesis of algae). The addition of graphene (1.0g/L) resulted in the highest biomethane yield (695.0±9.1mL/g) and production rate (95.7±7.6mL/g/d), corresponding to an enhancement of 25.0% in biomethane yield and 19.5% in production rate. The ethanol degradation constant was accordingly improved by 29.1% in the presence of graphene. Microbial analyses revealed that electrogenic bacteria of Geobacter and Pseudomonas along with archaea Methanobacterium and Methanospirillum might participate in direct interspecies electron transfer (DIET). Theoretical calculations provided evidence that graphene-based DIET can sustained a much higher electron transfer flux than conventional hydrogen transfer.