Oxygen Tolerance Research Articles

Aerobic-Controlled Radical Polymerization: Full Oxygen Tolerance Enabled by Air-Stable Amine–Borane

Aerobic-Controlled Radical Polymerization: Full Oxygen Tolerance Enabled by Air-Stable Amine–Borane

The Selenoproteome as a Dynamic Response Mechanism to Oxidative Stress in Hydrogenotrophic Methanogenic Communities.

Methanogenesis is a critical process in the carbon cycle that is applied industrially in anaerobic digestion and biogas production. While naturally occurring in diverse environments, methanogenesis requires anaerobic and reduced conditions, although varying degrees of oxygen tolerance have been described. Microaeration is suggested as the next step to increase methane production and improve hydrolysis in digestion processes; therefore, a deeper understanding of the methanogenic response to oxygen stress is needed. To explore the drivers of oxygen tolerance in methanogenesis, two parallel enrichments were performed under the addition of H2/CO2 in an environment without reducing agents and in a redox-buffered environment by adding redox mediator 9,10-anthraquinone-2,7-disulfonate disodium. The cellular response to oxidative conditions is mapped using proteomic analysis. The resulting community showed remarkable tolerance to high-redox environments and was unperturbed in its methane production. Next to the expression of pathways to mitigate reactive oxygen species, the higher redox potential environment showed an increased presence of selenocysteine and selenium-associated pathways. By including sulfur-to-selenium mass shifts in a proteomic database search, we provide the first evidence of the dynamic and large-scale incorporation of selenocysteine as a response to oxidative stress in hydrogenotrophic methanogenesis and the presence of a dynamic selenoproteome.

Light-Mediated Polymerization Catalyzed by Carbon Nanomaterials.

Carbon nanomaterials, specifically carbon dots and carbon nitrides, play a crucial role as heterogeneous photoinitiators in both radical and cationic polymerization processes. These recently introduced materials offer promising solutions to the limitations of current homogeneous systems, presenting a novel approach to photopolymerization. This review highlights the preparation and photocatalytic performance of these nanomaterials, emphasizing their application in various polymerization techniques, including photoinduced i) free radical, ii) RAFT, iii) ATRP, and iv) cationic photopolymerization. Additionally, it discusses their potential in addressing contemporary challenges and explores prospects in this field. Moreover, carbon nitrides, in particular, exhibit exceptional oxygen tolerance, underscoring their significance in radical polymerization processes and allowing their applications such as 3D printing, surface modification of coatings, and hydrogel engineering.

Atlantic salmon Salmo salar do not prioritize digestion when energetic budgets are constrained by warming and hypoxia.

During summer, farmed Atlantic salmon (Salmo salar) can experience prolonged periods of warming and low aquatic oxygen levels due to climate change. This often results in a drop in feed intake; however, the physiological mechanism behind this behaviour is unclear. Digestion is a metabolically expensive process that can demand a high proportion of an animal's energy budget and might not be sustainable under future warming scenarios. We investigated the effects of elevated temperature and acute hypoxia on specific dynamic action (SDA; the energetic cost of digestion), and how much of the energy budget (i.e. aerobic scope, AS) was occupied by SDA in juvenile Atlantic salmon. AS was 9% lower in 21°C-acclimated fish compared to fish reared at their optimum temperature (15°C) and was reduced by ~50% by acute hypoxia (50% air saturation) at both temperatures. Furthermore, we observed an increase in peak oxygen uptakerate during digestion which occupied ~13% of the AS at 15°C and ~20% of AS at 21°C, and increased the total cost of digestion at 21°C. The minimum oxygen tolerance threshold in digesting fish was ~42% and ~53% at 15 and 21°C, respectively, and when digesting fish were exposed to acute hypoxia, gut transit was delayed. Thus, these stressors result in a greater proportion of the available energy budget being directed away from digestion. Moderate environmental hypoxia under both optimal and high temperatures severely impedes digestion and should be avoided to limit exacerbating temperature effects on fish growth.

Young-of-the-year fish as bioindicators of eutrophication and temperature regime of water bodies.

Young-of-the-year fish communities are widely used as bioindicators of various environmental disturbances. This study was conducted from 1997 to 2015 and aims to develop fish trait-based indices of changes in the temperature regime and eutrophication of water bodies in the Dnipro River basin. We identified fish traits that significantly correlate with both temperature and chlorophyll-a concentration optimum: reproduction habitat, oxygen tolerance, and toxicity tolerance. Compared to other ecological groups, lithophilic species exhibited the lowest degree of thermal and eutrophication optimum, indicating this species' greater vulnerability to environmental alteration. Fish species that are intolerant to water quality and low oxygen concentration were the most sensitive to changes in temperature regime and eutrophication level. Salinity preferences and water quality tolerance emerged as reliable predictors of temperature optimum. Freshwater fish had an average temperature optimum that was 4.5% higher than that of freshwater-brackish and freshwater-brackish-marine fish. Species tolerance to the temperature factors and nutrient loads correlated only with rheophily, with rheophilic species having an average 13.8% higher temperature tolerance than other fish species and a 10.4% higher chlorophyll-a concentration tolerance. The fish temperature index increased over time during the study period in all the studied water bodies, consistent with ongoing warming affecting all sites. In contrast, the Fish Eutrophication Index showed greater temporal heterogeneity in studied water bodies, indicating various adaptative potentials of fish communities to eutrophication. These indices can be relevant for assessing disturbed situations caused by changes in climatic and anthropogenic impacts on water bodies.

Erratum to “Photoenzymatic RAFT Emulsion Polymerization with Oxygen Tolerance”

Erratum to “Photoenzymatic RAFT Emulsion Polymerization with Oxygen Tolerance”

Oxygen Extraction Efficiency and Tolerance to Hypoxia in Sponges

Sponges have always been filter feeders, in contrast to all the other filter-feeding invertebrate groups for which this feeding mode is a secondary adaptation. This study calls attention to this aspect, which explains why sponges are tolerant to hypoxia, but probably not more tolerant than the other filter-feeding invertebrates. The measurement of respiration rates at decreasing oxygen concentrations along with an estimation of the oxygen extraction efficiency in the marine demosponge Halichondria panicea have been used to understand why sponges are tolerant to low oxygen concentrations. It was found that the respiration rate was constant down to about 1.5 mL O2 L−1, which shows that the extraction efficiency increases with a decreasing oxygen concentration. It is argued that the relationship between the filtration rate and oxygen consumption in filter feeders is controlled by the resistance to the diffusion of oxygen across the boundary layer between the feeding current and the tissues of the body. A high tolerance to hypoxia is a consequence of the adaptation to filter feeding, and sponges do not have a special capacity to overcome hypoxic events.

Examining the resistance and resilience of anode-respiring Shewanella oneidensis biohybrid using microsensors

Immobilizing electro-active microbes within polymer matrices (thereby forming biohybrids) is a promising approach to accelerate microbial attachment to electrodes and increase the biofilm robustness. However, little is known on the fine scale chemical environment that develops within the electro-active biohybrids. Herein, we develop a biohybrid by immobilizing a culture of Shewanella oneidensis MR1 in agar matrix on the surface of a graphite electrode poised at +0.25 V. The resulting bioanode (3–6 mm thick) was grown under anoxic conditions and produced a steady current of 40 μA. Oxygen and pH distribution within the biohybrid were characterized in-situ using microsensors. As Shewanella is a facultative aerobe, it will halt the current production in the presence of oxygen. Thus, in addition, we investigated the alteration of the microenvironment during and after aeration of the medium to evaluate the oxygen tolerance of the system. During aeration, oxygen was effectively consumed in the top layers of the biofilm, leaving a 400–900 μm thick anoxic zone on the anode surface, that sustained >60% of the initial current. Current production recovered to pre-oxic condition within 5 h after the aeration was stopped, showing that immobilization can promote both high resistance and resilience of the system. Despite the absence of strong buffering conditions, pH profiles indicated a maximum drop of 0.2 units across the biohybrid. Characterizing the chemical microenvironment helps to elucidate the mechanistic functioning of artificial biofilms and hold a great potential for the designing of future, more effective biohybrid electrodes.

Outer-sphere effects on the O2 sensitivity, catalytic bias and catalytic reversibility of hydrogenases.

The comparison of homologous metalloenzymes, in which the same inorganic active site is surrounded by a variable protein matrix, has demonstrated that residues that are remote from the active site may have a great influence on catalytic properties. In this review, we summarise recent findings on the diverse molecular mechanisms by which the protein matrix may define the oxygen tolerance, catalytic directionality and catalytic reversibility of hydrogenases, enzymes that catalyse the oxidation and evolution of H2. These mechanisms involve residues in the second coordination sphere of the active site metal ion, more distant residues affecting protein flexibility through their side chains, residues lining the gas channel and even accessory subunits. Such long-distance effects, which contribute to making enzymes efficient, robust and different from one another, are a source of wonder for biochemists and a challenge for synthetic bioinorganic chemists.

Enhanced Oxygen Tolerance in CO2 Electroreduction to Formic Acid on SnO2/CN Catalyst through Alkali-Heat Treatment

Enhanced Oxygen Tolerance in CO2 Electroreduction to Formic Acid on SnO2/CN Catalyst through Alkali-Heat Treatment

A novel system to culture human intestinal organoids under physiological oxygen content to study microbial-host interaction.

Mechanistic investigation of host-microbe interactions in the human gut are hindered by difficulty of co-culturing microbes with intestinal epithelial cells. On one hand the gut bacteria are a mix of facultative, aerotolerant or obligate anaerobes, while the intestinal epithelium requires oxygen for growth and function. Thus, a coculture system that can recreate these contrasting oxygen requirements is critical step towards our understanding microbial-host interactions in the human gut. Here, we demonstrate Intestinal Organoid Physoxic Coculture (IOPC) system, a simple and cost-effective method for coculturing anaerobic intestinal bacteria with human intestinal organoids (HIOs). Using commensal anaerobes with varying degrees of oxygen tolerance, such as nano-aerobe Bacteroides thetaiotaomicron and strict anaerobe Blautia sp., we demonstrate that IOPC can successfully support 24-48 hours HIO-microbe coculture. The IOPC recapitulates the contrasting oxygen conditions across the intestinal epithelium seen in vivo. The IOPC cultured HIOs showed increased barrier integrity, and induced expression of immunomodulatory genes. A transcriptomic analysis suggests that HIOs from different donors show differences in the magnitude of their response to coculture with anaerobic bacteria. Thus, the IOPC system provides a robust coculture setup for investigating host-microbe interactions in complex, patient-derived intestinal tissues, that can facilitate the study of mechanisms underlying the role of the microbiome in health and disease.

Response of Arctic benthic foraminiferal traits to past environmental changes

The Arctic is subjected to all-encompassing disruptions in marine ecosystems caused by anthropogenic warming. To provide reliable estimates of how future changes will affect the ecosystems, knowledge of Arctic marine ecosystem responses to past environmental variability beyond the instrumental era is essential. Here, we present a novel approach on how to evaluate the state of benthic marine biotic conditions during the deglacial and Holocene period on the Northeast Greenland shelf. Benthic foraminiferal species were assigned traits (e.g., oxygen tolerance, food preferences) aiming to identify past faunal changes as a response to external forcing mechanisms. This approach was applied on sediment cores from offshore Northeast Greenland. We performed numerical rate-of-change detection to determine significant changes in the benthic foraminiferal traits. That way, the significant abrupt trait changes can be assessed across sites, providing a better understanding of the impact of climate drivers on the traits. Our results demonstrate that during the last ~ 14,000 years, bottom water oxygen is the main factor affecting the variability in the benthic foraminiferal faunas in this area. Our results show that significant changes in the traits correspond to drastic climate perturbations. Specifically, the deglacial-Holocene transition and mid-Holocene warm period exhibited significant change, with several trait turnovers.

Recent advances in aggregation-induced emission-active type I photosensitizers with near-infrared fluorescence: From materials design to therapeutic platform fabrication.

Near-infrared (NIR) fluorescence imaging-guided photodynamic therapy (PDT) technology plays an important role in treating various diseases and still attracts increasing research interests for developing novel photosensitizers (PSs) with outstanding performances. Conventional PSs such as porphyrin and rhodamine derivatives have easy self-aggregation properties in the physiological environment due to their inherent hydrophobic nature caused by their rigid molecular structure that induces strong intermolecular stacking π-π interaction, leading to serious fluorescence quenching and cytotoxic reactive oxygen species (ROS) reduction. Meanwhile, hypoxia is an inherent barrier in the microenvironment of solid tumors, seriously restricting the therapeutic outcome of conventional PDT. Aforementioned disadvantages should be overcome urgently to enhance the therapeutic effect of PSs. Novel NIR fluorescence-guided type I PSs with aggregation-induced emission (AIE), which features the advantages of improving fluorescent intensity and ROS generation efficiency at aggregation as well as outstanding oxygen tolerance, bring hope for resolving aforementioned problems simultaneously. At present, plenty of research works fully demonstrates the advancement of AIE-active PDT based on type I PSs. In this review, cutting-edge advances focusing on AIE-active NIR type I PSs that include the aspects of the photochemical mechanism of type I ROS generation, various molecular structures of reported type I PSs with NIR fluorescence and their design strategies, and typical anticancer applications are summarized. Finally, a brief conclusion is obtained, and the underlying challenges and prospects of AIE-active type I PSs are proposed.

Oxygen tolerance in triplet-excited-state-based photocatalysis through compartmentalization

Oxygen tolerance in triplet-excited-state-based photocatalysis through compartmentalization

Contrasting response strategies of sulfate-reducing bacteria in a microbial consortium to As3+ stress under anaerobic and aerobic environments

The sulfate-reducing efficiency of sulfate-reducing bacteria (SRB) is strongly influenced by the presence of oxygen, but little is known about the oxygen tolerance mechanism of SRB and the effect of oxygen on the metalliferous immobilization by SRB. The performance evaluation, identification of bioprecipitates, and microbial and metabolic process analyses were used here to investigate the As3+ immobilization mechanisms and survival strategies of the SRB1 consortium under different oxygen-containing environments. Results indicated that the sulfate reduction efficiency was significantly decreased under aerobic (47.37%) compared with anaerobic conditions (66.72%). SEM analysis showed that under anaerobic and aerobic conditions, the morphologies of mineral particles were different, whereas XRD and XPS analyses showed that the most of As3+ bioprecipitates under both conditions were arsenic minerals such as AsS and As4S4. The abundances of Clostridium_sensu_stricto_1, Desulfovibrio, and Thiomonas anaerobic bacteria were significantly higher under anaerobic than aerobic conditions, whereas the aerobic Pseudomonas showed an opposite trend. Network analysis revealed that Desulfovibrio was positively correlated with Pseudomonas. Metabolic process analysis confirmed that under aerobic conditions the SRB1 consortium generated additional extracellular polymeric substances (rich in functionalities such as Fe-O, SO, CO, and -OH) and the anti-oxidative enzyme superoxide dismutase to resist As3+ stress and oxygen toxicity. New insights are provided here into the oxygen tolerance and detoxification mechanism of SRB and provide a basis for the future remediation of heavy metal(loid)-contaminated environments.

An allosteric redox switch involved in oxygen protection in a CO2 reductase.

Metal-dependent formate dehydrogenases reduce CO2 with high efficiency and selectivity, but are usually very oxygen sensitive. An exception is Desulfovibrio vulgaris W/Sec-FdhAB, which can be handled aerobically, but the basis for this oxygen tolerance was unknown. Here we show that FdhAB activity is controlled by a redox switch based on an allosteric disulfide bond. When this bond is closed, the enzyme is in an oxygen-tolerant resting state presenting almost no catalytic activity and very low formate affinity. Opening this bond triggers large conformational changes that propagate to the active site, resulting in high activity and high formate affinity, but also higher oxygen sensitivity. We present the structure of activated FdhAB and show that activity loss is associated with partial loss of the metal sulfido ligand. The redox switch mechanism is reversible in vivo and prevents enzyme reduction by physiological formate levels, conferring a fitness advantage during O2 exposure.

Red-Light-Driven Atom Transfer Radical Polymerization for High-Throughput Polymer Synthesis in Open Air.

Photoinduced reversible-deactivation radical polymerization (photo-RDRP) techniques offer exceptional control over polymerization, providing access to well-defined polymers and hybrid materials with complex architectures. However, most photo-RDRP methods rely on UV/visible light or photoredox catalysts (PCs), which require complex multistep synthesis. Herein, we present the first example of fully oxygen-tolerant red/NIR-light-mediated photoinduced atom transfer radical polymerization (photo-ATRP) in a high-throughput manner under biologically relevant conditions. The method uses commercially available methylene blue (MB+) as the PC and [X-CuII/TPMA]+ (TPMA = tris(2-pyridylmethyl)amine) complex as the deactivator. The mechanistic study revealed that MB+ undergoes a reductive quenching cycle in the presence of the TPMA ligand used in excess. The formed semireduced MB (MB•) sustains polymerization by regenerating the [CuI/TPMA]+ activator and together with [X-CuII/TPMA]+ provides control over the polymerization. This dual catalytic system exhibited excellent oxygen tolerance, enabling polymerizations with high monomer conversions (>90%) in less than 60 min at low volumes (50-250 μL) and high-throughput synthesis of a library of well-defined polymers and DNA-polymer bioconjugates with narrow molecular weight distributions (Đ < 1.30) in an open-air 96-well plate. In addition, the broad absorption spectrum of MB+ allowed ATRP to be triggered under UV to NIR irradiation (395-730 nm). This opens avenues for the integration of orthogonal photoinduced reactions. Finally, the MB+/Cu catalysis showed good biocompatibility during polymerization in the presence of cells, which expands the potential applications of this method.

Novel Co-MOF/GO triggered peroxymonosulfate activation: Insight into singlet oxygen generation mechanism from peroxymonosulfate self-decomposition and secondary radical conversion

Peroxymonosulfate (PMS)-triggered non-radical pathways have potential for environmental application due to the high activity and pH tolerance of singlet oxygen (1O2). However, the mechanism of 1O2 generation remains unclear. Herein, new insights into 1O2 generation are discussed based on the postulated precursors of PMS, DO, O2–, SO4−, and OH with Co-MOF/GO catalyst. According to experimental results and theoretical calculation, Co (II) and Co (III) were identified as dominant active sites for PMS attachment, leading to the simultaneous breakage of S-O and O-O bonds and the generation of SO4−, OH, and 1O2. SO4− and OH were critical precursors for 1O2 generation, while PMS self-decomposition had a small contribution. DO and O2– acted more likely as quenchers than vital precursors of 1O2. Results provide in-depth understanding of the mechanism of 1O2 generation to broaden the application prospects of PMS oxidation technology.

Design of oxygen-tolerant Photo-RAFT system for protein-polymer conjugation achieving high bioactivity.

Protein-polymer conjugates have significant potential in pharmaceutical and biomedical applications. To enable their widespread use, robust conjugation techniques are crucial. This study introduces a photo-initiated reversible addition-fragmentation chain-transfer (Photo-RAFT) polymerization system that exhibits excellent oxygen tolerance. This system allows for the synthesis of protein-polymer conjugates with high bioactivity under mild and aerobic conditions. Three photocatalytic systems utilizing Eosin Y (EY) as the photocatalyst with two different cocatalysts (ascorbic acid and triethanolamine) were investigated, each generating distinct reactive oxygen species (ROS) such as singlet oxygen, superoxide, hydrogen peroxide, and hydroxyl radicals. The impact of these ROS on three model proteins (lysozyme, albumin, and myoglobin) was evaluated, demonstrating varying bioactivities based on the ROS produced. The EY/TEOA system was identified as the optimal photo-RAFT initiating system, enabling the preparation of protein-polymer conjugates under aerobic conditions while maintaining high protein enzymatic activity. To showcase the potential of this approach, lysozyme-poly(dimethylaminoethyl acrylate) conjugates were successfully prepared and exhibited enhanced antimicrobial property against gram-positive and gram-negative bacteria.

Design of an Oxygen‐Tolerant Photo‐RAFT System for Protein‐Polymer Conjugation Achieving High Bioactivity

AbstractProtein‐polymer conjugates have significant potential in pharmaceutical and biomedical applications. To enable their widespread use, robust conjugation techniques are crucial. This study introduces a photo‐initiated reversible addition‐fragmentation chain‐transfer (Photo‐RAFT) polymerization system that exhibits excellent oxygen tolerance. This system allows for the synthesis of protein‐polymer conjugates with high bioactivity under mild and aerobic conditions. Three photocatalytic systems utilizing Eosin Y (EY) as the photocatalyst with two different cocatalysts (ascorbic acid and triethanolamine) were investigated, each generating distinct reactive oxygen species (ROS) such as singlet oxygen, superoxide, hydrogen peroxide, and hydroxyl radicals. The impact of these ROS on three model proteins (lysozyme, albumin, and myoglobin) was evaluated, demonstrating varying bioactivities based on the ROS produced. The EY/TEOA system was identified as the optimal photo‐RAFT initiating system, enabling the preparation of protein‐polymer conjugates under aerobic conditions while maintaining high protein enzymatic activity. To showcase the potential of this approach, lysozyme‐poly(dimethylaminoethyl acrylate) conjugates were successfully prepared and exhibited enhanced antimicrobial property against Gram‐positive and Gram‐negative bacteria.