Mechanism of extracellular electron transport and reactive oxygen mediated Sb(III) oxidation by Klebsiella aerogenes HC10.

Microbial oxidation and the mechanism of Sb(III) are key governing elements in biogeochemical cycling. A novel Sb oxidizing bacterium, Klebsiella aerogenes HC10, was attracted early and revealed that extracellular metabolites were the main fractions driving Sb oxidation. However, linkages between the extracellular metabolite driven Sb oxidation process and mechanism remain elusive. Here, model phenolic and quinone compounds, i.e., anthraquinone-2,6-disulfonate (AQDS) and hydroquinone (HYD), representing extracellular oxidants secreted by K. aerogenes HC10, were chosen to further study the Sb(III) oxidation mechanism. N2 purging and free radical quenching showed that oxygen-induced oxidation accounted for 36.78% of Sb(III) in the metabolite reaction system, while hydroxyl free radicals (·OH) accounted for 15.52%. ·OH and H2O2 are the main driving factors for Sb oxidation. Radical quenching, methanol purification and electron paramagnetic resonance (EPR) analysis revealed that ·OH, superoxide radical (O2•-) and semiquinone (SQ-•) were reactive intermediates of the phenolic induced oxidation process. Phenolic-induced ROS are one of the main oxidants in metabolites. Cyclic voltammetry (CV) showed that electron transfer of quinone also mediated Sb(III) oxidation. Part of Sb(V) was scavenged by the formation of the secondary Sb(V)-bearing mineral mopungite [NaSb(OH)6] in the incubation system. Our study demonstrates the microbial role of oxidation detoxification and mineralization of Sb and provides scientific references for the biochemical remediation of Sb-contaminated soil.

Construction of eco-friendly dual carbon dots ratiometric fluorescence probe for highly selective and efficient sensing mercury ion.

In present work, blue carbon dots (b-CDs) were derived from ammonium citrate and guanidine hydrochloride, and red carbon dots (r-CDs) were stemmed from malonate, ethylenediamine and meso­tetra (4-carboxyphenyl) porphin based on facile hydrothermal method. Eco-friendly ratiometric fluorescence probe was innovatively constructed to effectively measure Hg2+ utilizing b-CDs and r-CDs. The developed probe displayed two typical emission peaks at 450 nm from b-CDs and 650 nm from r-CDs under the excitation at 360 nm. Mercury ion has strong quenching effect on the fluorescence intensity at 450 nm due to the electron transfer process and the fluorescence change at 450 nm was used as the response signal, whereas the fluorescence intensity at 650 nm kept unchangeable which resulted from the chemical inertness between Hg2+ and r-CDs, serving as the reference signal in the sensing system. Under optimal circumstances, this probe exhibited an excellent linearity between the fluorescence response values of ΔF450/F650 and Hg2+ concentrations over range of 0.01-10 µmol/L, and the limit of detection was down to 5.3 nmol/L. Furthermore, this probe was successfully employed for sensing Hg2+ in practical environmental water samples with satisfied recoveries of 98.5%-105.0%. The constructed ratiometric fluorescent probe provided a rapid, environmental-friendly, reliable, and efficient platform for measuring trace Hg2+ in environmental field.

Top-down mass spectrometry analysis of capsid proteins of recombinant adeno-associated virus using multiple ion activations and proton transfer charge reduction.

Adeno-associated viruses (AAVs) are common vectors for emerging gene therapies due to their lack of pathogenicity in humans. Here, we present our investigation of the viral proteins (i.e., VP1, VP2, and VP3) of the capsid of AAVs via top-down mass spectrometry (MS). These proteins, ranging from 59 to 81 kDa, were chromatographically separated using hydrophilic interaction liquid chromatography and characterized in the gas-phase by high-resolution Orbitrap Fourier transform MS. Complementary ion dissociation methods were utilized to improve the overall sequence coverage. By reducing the overlap of product ion signals via proton transfer charge reduction on the Orbitrap Ascend BioPharma Tribrid mass spectrometer, the sequence coverage of each VP was significantly increased, reaching up to ∼40% in the case of VP3. These results showcase the improvements in the sequencing of proteins >30 kDa that can be achieved by manipulating product ions via gas-phase reactions to obtain easy-to-interpret fragmentation mass spectra.

The evolution of structural characteristics and redox properties of humin during the composting of sludge and corn straw.

Humins (HMs), the insoluble faction of humic substances (HSs), play a pivotal role in the bioremediation of pollutants by acting as electron shuttles that modulate the interactions between microorganisms and pollutants. This crucial function is intricately linked to their structural composition and electron transfer capabilities. However, the dynamics of the electron transfer capacity (ETC) of HM extracted during the composting process and its determinants have yet to be fully elucidated. This study undertakes a comprehensive analysis of the ETC of HM derived from composting, employing electrochemical techniques alongside spectroscopic methods and elemental analysis to explore the influencing factors, including the electron accepting capacity (EAC), electron donating capacity (EDC), and electron reversible rate (ERR). Our findings reveal substantial variations in the EAC and EDC of HM throughout the composting process, with EAC values ranging from 133.03-220.98 µmol e- gC-1 and EDC values from 111.17-229.33 µmol e- gC-1. Notably, the composting process enhances the ERR and EDC of HM while diminishing their EAC. This shift is accompanied by an augmented presence of aromatic structures, polar functional groups, quinones, and nitrogen - and sulfur-containing moieties, thereby boosting the HM's EDC. Conversely, the reduction in EAC is associated with a decline in lignin carbon content and the abundance of oxygen-containing moieties, as well as the diminishment of visible fulvic-like and protein-like substances within HM. Importantly, humic-like substances and nitrogen-containing moieties within HM demonstrated the capacity for repeated electron transfer, underscoring their significance in the context of environmental remediation.

3D Bioprinting of Engineered Living Materials with Extracellular Electron Transfer Capability for Water Purification.

Attention is widely drawn to the extracellular electron transfer (EET) process of electroactive bacteria (EAB) for water purification, but its efficacy is often hindered in complex environmental matrices. In this study, the engineered living materials with EET capability (e-ELMs) were for the first time created with customized geometric configurations for pollutant removal using three-dimensional (3D) bioprinting platform. By combining EAB and tailored viscoelastic matrix, a biocompatible and tunable electroactive bioink for 3D bioprinting was initially developed with tuned rheological properties, enabling meticulous manipulation of microbial spatial arrangement and density. e-ELMs with different spatial microstructures were then designed and constructed by adjusting the filament diameter and orientation during the 3D printing process. Simulations of diffusion and fluid dynamics collectively showcase internal mass transfer rates and EET efficiency of e-ELMs with different spatial microstructures, contributing to the outstanding decontamination performances. Our research propels 3D bioprinting technology into the environmental realm, enabling the creation of intricately designed e-ELMs and providing promising routes to address the emerging water pollution concerns.

Sludge-derived hydrochar modulates complete nonradical electron transfer in peroxydisulfate activation via pyrrolic-N and carbon defect: Implication for degrading electron-rich ionizable anilines compounds.

Nonradical electron transfer process (ETP) is a promising pathway for pollutant degradation in peroxydisulfate-based advanced oxidation processes (PDS-AOPs). However, there is a critical bottleneck to trigger ETP by sludge-derived hydrochar due to its negatively charged surface, inferior porosity and electrical conductivity. Herein, pyrrolic-N doped and carbon defected sludge-derived hydrochar (SDHC-N) was constructed for PDS activation to degrade anilines ionizable organic compounds (IOC) through complete nonradical ETP oxidation. Degradation of anilines IOC was not only affected by the electron-donating capacity but also proton concentration in solution because of the ionizable amino group (-NH2). Diverse effects including proton favor, insusceptible and inhibition were observed. Impressively, addition of HCO3 with strong proton binding capacity boosted aniline degradation nearly 10 times. Moreover, characterizations and theoretical calculations demonstrated that pyrrolic-N increased electron density and created positively charged surface, profoundly promoting generation of SDHC-N-S2O82-* complexes. More delocalized electrons around carbon defect could enhance electron mobility. This work guides a rational design of sludge-derived hydrochar to mediate nonradical ETP oxidation, and provides insights into the impacts of proton on anilines IOC degradation.

Photomodulation of Charge Transfer through Excited-State Processes: Directing Donor-Acceptor Binding Dynamics.

Modulating charge transfer (CT) interactions between donor and acceptor molecules may give rise to unique dynamic changes in physicochemical properties, exhibiting great importance in supramolecular chemistry and materials science. In this work, we demonstrate the first instance of reversible photomodulation of donor-acceptor (D-A) CT interaction in the solid state.Pyridinium-based chromophore featuring π-conjugated D-A structures can not only function as a good electron acceptor to undergo photoinduced electron transfer (ET) or engage in intermolecular CT interaction, but also exhibit unique dual emission depending on the excitation wavelengths. The rotatable C-C single bonds within D-A pairs enhance the tunability of molecular structure. Through the synergy of a photoinduced ET and an excited-state conformational change, the intermolecular CT interaction can be switched on and off by alternate light irradiation to enables reversibly modulation of the affinity between donor and acceptor molecules, accompanied by visual color switching and fluorescence on-off as feedback signals.

Engineered Cell Elongation Promotes Extracellular Electron Transfer of Shewanella Oneidensis.

To investigate how cell elongation impacts extracellular electron transfer (EET) of electroactive microorganisms (EAMs), the division of model EAM Shewanella oneidensis (S. oneidensis) MR-1 is engineered by reducing the formation of cell divisome. Specially, by blocking the translation of division proteins via anti-sense RNAs or expressing division inhibitors, the cellular length and output power density are all increased. Electrophysiological and transcriptomic results synergistically reveal that the programmed cell elongation reinforces EET by enhancing NADH oxidation, inner-membrane quinone pool, and abundance of c-type cytochromes. Moreover, cell elongation enhances hydrophobicity due to decreased cell-surface polysaccharide, thus facilitates the initial surface adhesion stage during biofilm formation. The output current and power density all increase in positive correction with cellular length. However, inhibition of cell division reduces cell growth, which is then restored by quorum sensing-based dynamic regulation of cell growth and elongation phases. The QS-regulated elongated strain thus enables a cell length of 143.6 ± 40.3 µm (72.6-fold of that of S. oneidensis MR-1), which results in an output power density of 248.0 ± 10.6 mW m-2 (3.41-fold of that of S. oneidensis MR-1) and exhibits superior potential for pollutant treatment. Engineering cellular length paves an innovate avenue for enhancing the EET of EAMs.

Nitrogen-doped carbon dots boost microbial electrosynthesis via efficient extracellular electron uptake of acetogens.

This study investigated the molecular mechanism behind the highly efficient performance of nitrogen-doped carbon dots (NCDs)-assisted microbial electrosynthesis systems (MESs). The impact of NCDs (C:N precursor = 1:0.5-1:3) on acetogens was examined in the biocathode. The highest electrocatalytic performance was observed with NCDs1:1. The maximum acetate production rate of 1.9 ± 0.1 mM d-1 was achieved in NCDs1:1-modified MESs, which was 26.7-216.7 % higher than other MESs (0.6-1.5 mM d-1). With NCDs1:1 modified, the biocathode exhibited a 129.3-186.8 % increase in the abundance of Sporomusa, and 38.5-104.6 % increase in cytochrome expression (cydAB, cybH). Transcriptome confirmed that cytochromes played a crucial role in the extracellular electron uptake (EEU) of NCDs1:1-modified Sporomusa. NCDs1:1 enhanced EEU efficiency, thereby increasing the two H+-pumping steps and accelerating microbial CO2 fixation. These results provide valuable insights into increasing CO2 fixation by maximizing EEU efficiency in acetogens.

Long-lasting organics removal via •OH adsorbed transition metal flocs: Electron transfer-mediated H-bond and van der Waals force.

Homogenous advanced oxidation processes (AOPs) based on transition metal catalysts toward the activation of H2O2 to hydroxyl radical (•OH) have been widely applied to organic pollutants removal, such as Fenton and Fenton-like processes. These transition metal catalysts mostly flocculate as the pH increases. It's worth noting that the formed transition metal flocs are complex heterogeneous aggregations with active substances, providing diverse reaction spaces and interfaces. However, it is a challenge to distinguish the roles of transition metal flocs in the organic pollutants removal from homogeneous catalytic reactions. Herein, we unveiled a pathway for the long-lasting removal of organic pollutants via Cr flocs adsorbed with •OH (HO•-Cr flocs) using a stepwise method. First, adsorbed •OH (•OHads) within the HO•-Cr flocs was proved to be the active site forming hydrogen bond (H-bond) and van der Waals force with organic pollutants. Then, the presence of switchable electron transfer between Cr and OH groups within the HO•-Cr flocs was revealed, contributing to the persistent existence of •OHads and consequently ensuring the long-lasting organics removal. Further, this removal pathway of organic pollutants was confirmed during the leather wastewater treatment. These findings will complement a different pathway for organic pollutants removal via transition metal flocs and extend the lifetime of homogeneous AOPs based on transition metal catalysts, providing significant implications for their design and optimization.

Reversed I1Cu4 single-atom sites for superior neutral ammonia electrosynthesis with nitrate.

Electrochemical ammonia (NH3) synthesis from nitrate reduction (NITRR) offers an appealing solution for addressing environmental concerns and the energy crisis. However, most of the developed electrocatalysts reduce NO3- to NH3 via a hydrogen (H*)-mediated reduction mechanism, which suffers from undesired H*-H* dimerization to H2, resulting in unsatisfactory NH3 yields. Herein, we demonstrate that reversed I1Cu4 single-atom sites, prepared by anchoring iodine single atoms on the Cu surface, realized superior NITRR with a superior ammonia yield rate of 4.36 mg h-1 cm-2 and a Faradaic efficiency of 98.5% under neutral conditions via a proton-coupled electron transfer (PCET) mechanism, far beyond those of traditional Cu sites (NH3 yield rate of 0.082 mg h-1 cm-2 and Faradaic efficiency of 36.5%) and most of H*-mediated NITRR electrocatalysts. Theoretical calculations revealed that I single atoms can regulate the local electronic structures of adjacent Cu sites in favor of stronger O-end-bidentate NO3- adsorption with dual electron transfer channels and suppress the H* formation from the H2O dissociation, thus switching the NITRR mechanism from H*-mediated reduction to PCET. By integrating the monolithic I1Cu4 single-atom electrode into a flow-through device for continuous NITRR and in situ ammonia recovery, an industrial-level current density of 1 A cm-2 was achieved along with a NH3 yield rate of 69.4 mg h-1 cm-2. This study offers reversed single-atom sites for electrochemical ammonia synthesis with nitrate wastewater and sheds light on the importance of switching catalytic mechanisms in improving the performance of electrochemical reactions.

Protein-driven interaction enhanced electrochemiluminescence biosensor of hydrogen-bonded biohybrid organic frameworks for sensitive immunoassay of disease markers.

The oriented design of reticular materials as emitters can significantly enhance the sensitivity of electrochemiluminescence (ECL) sensing analysis for disease markers. However, due to the structural fragility of hydrogen bonds, relational research on hydrogen-bonded organic frameworks (HOFs) has not been thoroughly conducted. Additionally, the modulation of luminescence behavior through HOFs has been rarely reported. In view of this, hydrogen-bonded biohybrid organic frameworks (HBOFs) were synthesized and recruited for ECL immunoassay applications. HBOFs was easily prepared using 6,6',6″,6‴-(pyrene-1,3,6,8-tetrayl)tetrakis(2-naphthoic acid) as linkers via bovine serum albumin (BSA) activated hydrogen-bonded cross-linking. The material exhibited good fluorescence emission characteristics. And the highly ordered topological structure and molecular motion limitation mediated by BSA overcome aggregation-caused quenching and generate strong aggregation induced emission, expressing hydrogen-bond interaction enhanced ECL (HIE-ECL) activity with the participation of tri-n-propylamine. Furthermore, a sandwich immunosensor was constructed employing cobalt-based metal-phenolic network (CMPN) coated ferrocene nanoparticles (FNPs) as quenchers (CMPN@FNPs). Signal closure can be achieved by annihilating the excited state through electron transfer from both CMPN and FNPs. Using a universal disease marker, carcinoembryonic antigen, as the analysis model, the signal-off sensor obtained a detection limit of 0.47 pg/mL within the detection range of 1 pg/mL - 50 ng/mL. The synthesis and application of highly stable HBOFs triggered by proteins provide a reference for the development of new reticular ECL signal labels, and electron transfer model provides flexible solutions for more sensitive sensing analysis.

Functional biochar accelerates peroxymonosulfate activation for organic contaminant degradation via the specific B-C-N configuration.

Functional biochar designed with heteroatom doping facilitates the activation of peroxymonosulfate (PMS), triggering both radical and non-radical systems and thus augmenting pollutant degradation efficiency. A sequence of functional biochar, derived from hyperaccumulator (Sedum alfredii) residues, was synthesized via sequential doping with boron and nitrogen. The SABC-B@N-2 exhibited outstanding catalytic effectiveness in activating PMS to degrade the model pollutant, acid orange 7 ( =0.0655 min-1), which was 6.75 times more active than the pristine biochar and achieved notable mineralization efficiency (71.98%) at reduced PMS concentration (0.1 mM). Relative contribution evaluations, using steady-state concentrations combined with electrochemical and in situ Raman analyses, reveal that co-doping with boron and nitrogen alters the reaction pathway, transitioning from PMS activation through multiple reactive oxygen species (ROSs) to a predominantly non-radical process facilitated by electron transfer. Moreover, the previously misunderstood concept that singlet oxygen (1O2) plays a central role in the degradation of AO7 has been clarified. Correlation analysis and density functional theory calculations indicate that the distinct BCN configuration, featuring the BC2O group and pyridinic-N, is fundamental to the active site. This research substantially advances the sustainability of phytoremediation by offering a viable methodology to synthesize highly catalytic functional biochar utilizing hyperaccumulator residues.

D1-Tyr246 and D2-Tyr244 in photosystem II: Insights into bicarbonate binding and electron transfer from QA•- to QB.

In photosystem II (PSII), D1-Tyr246 and D2-Tyr244 are symmetrically located at the binding site of the bicarbonate ligand of the non-heme Fe complex. Here, we investigated the role of the symmetrically arranged tyrosine pair, D1-Tyr246 and D2-Tyr244, in the function of PSII, by generating four chloroplast mutants of PSII from Chlamydomonas reinhardtii: D1-Y246F, D1-Y246T, D2-Y244F, and D2-Y244T. The mutants exhibited altered photoautotrophic growth, reduced PSII protein accumulation, and impaired O2-evolving activity. Flash-induced fluorescence yield decay kinetics indicated a significant slowdown in electron transfer from QA•- to QB in all mutants. Bicarbonate reconstitution resulted in enhanced O2-evolving activity, suggesting destabilization of bicarbonate binding in the mutants. Structural analyses based on a quantum mechanical/molecular mechanical approach identified the existence of a water channel that leads to incorporation of bulk water molecules and destabilization of the bicarbonate binding site. The water intake channels, crucial for bicarbonate stability, exhibited distinct paths in the mutants. These findings shed light on the essential role of the tyrosine pair in maintaining bicarbonate stability and facilitating efficient electron transfer in native PSII.

Metabolic evolution and bottleneck insights into simultaneous autotroph-heterotroph anammox system for real municipal wastewater nitrogen removal.

When biological nitrogen removal (BNR) systems shifted from treating simulated wastewater to real wastewater, a microbial succession occurred, often resulting in a decline in efficacy. Notably, despite their high nitrogen removal efficiency for real wastewater, anammox coupled systems operating without or with minimal carbon sources also exhibited a certain degree of performance reduction. The underlying reasons and metabolic shifts within these systems remained elusive. In this study, the simultaneous autotrophic/heterotrophic anammox system demonstrated remarkable metabolic resilience upon exposure to real municipal wastewater, achieving a nitrogen removal efficiency (NRE) of 82.83 ± 2.29 %. This resilience was attributed to the successful microbial succession and the complementary metabolic functions of heterotrophic microorganisms, which fostered a resilient microbial community. The system's ability to harness multiple electron sources, including NADH oxidation, the TCA cycle, and organics metabolism, allowed it to establish a stable and efficient electron transfer chain, ensuring effective nitrogen removal. Despite the denitrification channel's nitrite supply capability, the analysis of the interspecies correlation network revealed that the synergistic metabolism between AOB and AnAOB was not fully restored, resulting in selective functional bacterial and genetic interactions and the system's PN/A performance declined. Additionally, the enhanced electron affinity of PD increased interconversion of NO3--N and NO2--N, limiting the efficient utilization of electrons and thereby constraining nitrogen removal performance. This study elucidated the metabolic mechanism of nitrogen removal limitations in anammox-based systems treating real municipal wastewater, enhancing our understanding of the metabolic functions and electron transfer within the symbiotic bacterial community.

Regulating the Scaling Relations in Ammonia Synthesis through a Light-driven Bendable Seesaw Effect on Tailored Iron Catalyst.

Advancing the energy-intensive Haber-Bosch process faces significant challenges due to the intrinsic constraints of scaling relations in heterogeneous catalysis. Herein, we reported an approach of bending the "seesaw effect" to regulate the scaling relations over a tailored α-Fe metallic material (α-Fe-110s), realizing highly efficient light-driven thermal catalytic ammonia synthesis rate of 1260 µmol gcatalyst-1 h-1 without additional heating. Specifically, the thermal catalytic activity of α-Fe-110s was significantly enhanced by the novel stepped {110} surface, exhibiting a 3.8-fold increase compared to the commercial fused-iron catalyst with promoters at 350 °C. The photo-induced hot electron transfer further accelerates the dinitrogen dissociation and hydrogenation simultaneously, effectively overcoming the limitation of scaling relation over identical sites. Consequently, the ammonia production rate of α-Fe-110s was further enhanced by 30 times at the same temperature with irradiation. This work designs an efficient and sustainable system for ammonia synthesis and provides a novel approach for regulating the scaling relations in heterogeneous catalysis.

Anthraquinones-based photocatalysis: A comprehensive review.

In recent years, there has been significant interest in photocatalytic technologies utilizing semiconductors and photosensitizers responsive to solar light, owing to their potential for energy and environmental applications. Current efforts are focused on enhancing existing photocatalysts and developing new ones tailored for environmental uses. Anthraquinones (AQs) serve as redox-active electron transfer mediators and photochemically active organic photosensitizers, effectively addressing common issues such as low light utilization and carrier separation efficiency found in conventional semiconductors. AQs offer advantages such as abundant raw materials, controlled preparation, excellent electron transfer capabilities, and photosensitivity, with applications spanning the energy, medical, and environmental sectors. Despite their utility, comprehensive reviews on AQs-based photocatalytic systems in environmental contexts are lacking. In this review, we thoroughly describe the photochemical properties of AQs and their potential applications in photocatalysis, particularly in addressing key environmental challenges like clean energy production, antibacterial action, and pollutant degradation. However, AQs face limitations in practical photocatalytic applications due to their low electrical conductivity and solubility-related secondary contamination. To mitigate these issues, the design and synthesis of graphene-immobilized AQs are highlighted as a solution to enhance practical photocatalytic applications. Additionally, future research directions are proposed to deepen the understanding of AQs' theoretical mechanisms and to provide practical applications for wastewater treatment. This review aims to facilitate mechanistic studies and practical applications of AQs-based photocatalytic technologies and to improve understanding of these technologies.

Geobatteries in environmental biogeochemistry: Electron transfer and utilization.

The efficiency of direct electron flow from electron donors to electron acceptors in redox reactions is significantly influenced by the spatial separation of these components. Geobatteries, a class of redox-active substances naturally present in soil-water systems, act as electron reservoirs, reversibly donating, storing, and accepting electrons. This capability allows the temporal and spatial decoupling of redox half-reactions, providing a flexible electron transfer mechanism. In this review, we systematically examine the critical role of geobatteries in influencing electron transfer and utilization in environmental biogeochemical processes. Typical redox-active centers within geobatteries, such as quinone-like moieties, nitrogen- and sulfur-containing groups, and variable-valent metals, possess the potential to repeatedly charge and discharge. Various characterization techniques, ranging from qualitative methods like elemental analysis, imaging, and spectroscopy, to quantitative techniques such as chemical, spectroscopic, and electrochemical methods, have been developed to evaluate this reversible electron transfer capacity. Additionally, current research on the ecological and environmental significance of geobatteries extends beyond natural soil-water systems (e.g., soil carbon cycle) to engineered systems such as water treatment (e.g., nitrogen removal) and waste management (e.g., anaerobic digestion). Despite these advancements, challenges such as the complexity of environmental systems, difficulties in accurately quantifying electron exchange capacity, and scaling-up issues must be addressed to fully unlock their potential. This review underscores both the promise and challenges associated with geobatteries in responding to environmental issues, such as climate change and pollutant transformation.

Regulation of Microalgal Photosynthetic Electron Transfer.

The global ecosystem relies on the metabolism of photosynthetic organisms, featuring the ability to harness light as an energy source. The most successful type of photosynthesis utilizes a virtually inexhaustible electron pool from water, but the driver of this oxidation, sunlight, varies on time and intensity scales of several orders of magnitude. Such rapid and steep changes in energy availability are potentially devastating for biological systems. To enable a safe and efficient light-harnessing process, photosynthetic organisms tune their light capturing, the redox connections between core complexes and auxiliary electron mediators, ion passages across the membrane, and functional coupling of energy transducing organelles. Here, microalgal species are the most diverse group, featuring both unique environmental adjustment strategies and ubiquitous protective mechanisms. In this review, we explore a selection of regulatory processes of the microalgal photosynthetic apparatus supporting smooth electron flow in variable environments.

Light-Driven H2 Production in Chlamydomonas reinhardtii: Lessons from Engineering of Photosynthesis.

In the green alga Chlamydomonas reinhardtii, hydrogen production is catalyzed via the [FeFe]-hydrogenases HydA1 and HydA2. The electrons required for the catalysis are transferred from ferredoxin (FDX) towards the hydrogenases. In the light, ferredoxin receives its electrons from photosystem I (PSI) so that H2 production becomes a fully light-driven process. HydA1 and HydA2 are highly O2 sensitive; consequently, the formation of H2 occurs mainly under anoxic conditions. Yet, photo-H2 production is tightly coupled to the efficiency of photosynthetic electron transport and linked to the photosynthetic control via the Cyt b6f complex, the control of electron transfer at the level of photosystem II (PSII) and the structural remodeling of photosystem I (PSI). These processes also determine the efficiency of linear (LEF) and cyclic electron flow (CEF). The latter is competitive with H2 photoproduction. Additionally, the CBB cycle competes with H2 photoproduction. Consequently, an in-depth understanding of light-driven H2 production via photosynthetic electron transfer and its competition with CO2 fixation is essential for improving photo-H2 production. At the same time, the smart design of photo-H2 production schemes and photo-H2 bioreactors are challenges for efficient up-scaling of light-driven photo-H2 production.