Search Results (36)

Ni-doped amorphous Al₂O₃ catalysts were successfully prepared for the one-step reduction of nitrobenzene to azoxybenzene using NaBH₄ as hydrogen donors under mild conditions. The amorphous Ni₁Al₈₇O_x catalyst achieved a highly efficient azoxybenzene production rate of 1.89 mol·g-Ni⁻¹·h⁻¹, significantly outperforming its Ni/γ-Al₂O₃ counterpart. On the basis of the MAS NMR and XPS characterization results, the enhanced catalytic performance is associated with Ni incorporation during the preparation of amorphous Ni₁Al₈₇O_x, which introduces abundant unsaturated pentacoordinate Al species with oxygen vacancies and stabilizes Ni^δ+ sites against over-reduction. Notably, Ni₁Al₈₇O_x loaded on commercial ZSM-5 supports maintained an azoxybenzene yield of 9.02 mol·g-Ni⁻¹·h⁻¹, highlighting the strong potential for further scalable applications. Full article

Reductive stress, characterized by excessive reducing equivalents such as NADH, NADPH, and reduced glutathione (GSH), is increasingly recognized as a pathophysiological counterpart to oxidative stress. Chronic hyperinsulinemia and insulin resistance promote this over-reduced state by increasing glucose flux, pentose phosphate pathway activity and de novo lipogenesis, thereby elevating NADPH pools and reshaping cellular lipid composition. While reducing equivalents are essential for biosynthesis and antioxidant defense, persistent over-reduction disrupts redox balance, mitochondrial function and metabolic flexibility. Paradoxically, this reductive metabolic environment may increase susceptibility to ferroptosis, an iron-dependent form of regulated cell death driven by lipid peroxidation and failure of glutathione peroxidase 4 (GPX4). Here, we define how reductive stress becomes deregulated in the context of insulin signaling and insulin resistance, and assess whether antioxidant interventions can mitigate ferroptosis, providing a framework for therapeutic strategies to restore redox balance in metabolic disease. Full article

Low temperature combined with fluctuating irradiance frequently co-occurs and suppresses photosynthesis, with irreversible injury to photosystem I (PSI) recognized as a key constraint on growth and yield. To test whether exogenous hydrogen sulfide (H₂S) mitigates this “cold–fluctuating light” stress in mulberry, we established six treatment combinations (room temperature controls, sodium hydrosulfide, and hypotaurine, each with or without low temperature plus fluctuating light). We quantified PSI/PSII photochemical properties, gas exchange, reactive oxygen species (ROS), and antioxidant enzyme activities. Under cold with fluctuating light, PSI was strongly inhibited: Y_NA increased, whereas Y_I and ΔI/I_o decreased, and the P700 re-reduction half-time (t½) was prolonged (ANOVA, Tukey’s HSD, p < 0.05), indicating pronounced acceptor-side over-reduction and impaired electron transport. PSII performance also declined (lower F_v/F_m and PI_ABS, higher ΔV_J; p < 0.05). NaHS pretreatment significantly alleviated these effects relative to the stressed control: PSI/PSII metrics partly recovered, net photosynthetic rate (P_n) and water-use efficiency (WUE) increased, H₂O₂ and MDA decreased, and SOD/POD/CAT activities rose (p < 0.05). Notably, NPQ_high correlated negatively with Y_NA (Pearson r < 0, p < 0.001), consistent with the notion that enhanced energy dissipation relieves PSI acceptor-side limitation. We propose that exogenous H₂S stabilizes electron transport and supports carbon assimilation via a dual strategy—faster engagement of energy dissipation and activation of antioxidant defenses—highlighting its potential utility for managing stress in fruit crops under erratic early-season weather. Full article

Electrocatalytic conversion of CO₂ to high-energy-density multicarbon products (C₂₊) offers a sustainable route for renewable energy storage and carbon neutrality. Precisely modulating Cu-based catalysts to enhance C₂₊ selectivity remains challenging due to uncontrollable reduction of Cu^δ+ active sites. Here, an efficient and stable Ge/Cu catalyst was developed for CO₂ reduction to ethanol via Ge modification. A Cu₂O/GeO₂/Cu core–shell composite was constructed by controlling Ge doping. The structure–performance relationship was elucidated through in situ characterization and theoretical calculations. Ge⁴⁺ stabilized Cu¹⁺ active sites and regulated the surface microenvironment via electronic effects. Ge modification simultaneously altered CO intermediate adsorption to promote asymmetric CO–CHO coupling, optimized water structure at the electrode/electrolyte interface, and inhibited over-reduction of Cu^δ+. This multi-scale synergistic effect enabled a significant ethanol Faradaic efficiency enhancement (11–20%) over a wide potential range, demonstrating promising applicability for renewable energy conversion. This study provides a strategy for designing efficient ECR catalysts and offers mechanistic insights into interfacial engineering for C–C coupling in sustainable fuel production. Full article

Background: For high-grade dislocation of the acromioclavicular (AC) joint, surgical treatment is widely recommended. This study aimed to evaluate the clinical and radiological outcomes after arthroscopic-assisted stabilization of acute high-grade AC joint dislocations using a low-profile suture button (LPSB) combined with percutaneous AC cerclage fixation. A secondary objective was to quantify clavicular tunnel widening (cTW) and explore its correlation with clinical and radiological outcomes. Methods: This retrospective study included 45 patients with acute Rockwood type V injuries treated with the LPSB technique and additional AC cerclage. Clinical outcomes were the Constant Score (CS), Subjective Shoulder Value (SSV), Taft Score (TF), AC Joint Instability Score (ACJI), and VAS for pain upon palpation. Radiological assessment included coracoclavicular (CC) distance and percentage deviations compared to the contralateral side, reclassified according to Rockwood, dynamic posterior translation (DPT), cTW measurements, and assessment of ossifications and AC joint osteoarthritis. Results: After 35.3 months, significant improvements were observed in CC distance and percentage deviation. A total of 27.3% were reclassified as Rockwood type III and 2.3% as type V. Initial overreduction persisted in 18.2%. DPT was observed in 34.1% of cases. The mean CS was 89.64, the SSV was 91.1, and the VAS was 0.8. cTW occurred only below the superior button and increased significantly over time, showing a negative correlation with the SSV but no correlation with any radiological outcome parameter. No implant-related revision surgery was reported. Conclusions: Arthroscopic-assisted stabilization of acute high-grade AC joint dislocations using the LPSB technique with AC cerclage fixation provides excellent clinical outcomes and high patient satisfaction, with minimal implant-related complications and no need for revision surgery due to implant issues. Although cTW occurs, its clinical impact appears limited within this procedure. Full article

High-yielding synthetic routes to five new extremely bulky aminopyridine pro-ligands were developed, viz. (C₅H₃N-6-Ar¹)N(H)Ar²-2; Ar¹ = Trip, Ar² = TCHP (HAmPy¹), Ar* (HAmPy²) or Ar^† (HAmPy³); Ar¹ = TCHP, Ar² = Ar* (HAmPy⁴) or Ar^† (HAmPy⁵) (Trip = 2,4,6-triisopropylphenyl, TCHP = 2,4,6-tricyclohexylphenyl, Ar* = C₆H₂(CHPh₂)₂Me-2,6,4, Ar^† = C₆H₂(CHPh₂)₂Prⁱ-2,6,4. Four of these were deprotonated with LiBuⁿ in diethyl ether to give lithium aminopyridinate complexes which were dimeric for the least bulky ligand, [{Li(AmPy¹)}₂] or monomeric for the bulkier aminopyridinates, i.e., in [Li(AmPy²⁻⁴)(OEt₂)]. One aminopyridine was deprotonated with MeMgI to give monomeric [Mg(AmPy³)I(OEt₂)₂]. When treated with sodium or potassium mirrors or 5% w/w Na/NaCl, over-reduction occurred, leading to the alkali metal aminopyridinates, [M(AmPy³)(η⁶-toluene)] (M = Na or K) or [{Na(AmPy³)}_∞]. An attempted reduction of [Mg(AmPy³)I(OEt₂)₂] with a dimagnesium(I) compound led only to partial loss of diethyl ether and the formation of [(AmPy³)Mg(μ-I)₂Mg(AmPy³)(OEt₂)]. All prepared complexes have potential as ligand transfer reagents in salt metathesis reactions with metal halide complexes. Full article

The diatom Phaeodactylum tricornutum, known for its high triacylglycerol (TAG) content and significant levels of n-3 long chain polyunsaturated fatty acids (LC-PUFAs), such as eicosapentaenoic acid (EPA), has a limited ability to utilize exogenous organic matter. This study investigates the enhancement of acetate utilization in P. tricornutum by introducing an exogenous acetate transport protein. The acetate transporter gene ADY2 from Saccharomyces cerevisiae endowed the organism with the capability to assimilate acetate and accelerating its growth. The transformants exhibited superior growth rates at an optimal NaAc concentration of 0.01 M, with a 1.7- to 2.0-fold increase compared to the wild-type. The analysis of pigments and photosynthetic activities demonstrated a decline in photosynthetic efficiency and maximum electron transport rate. This decline is speculated to result from the over-reduction of the electron transport components between photosystems due to acetate utilization. Furthermore, the study assessed the impact of acetate on the crude lipid content and fatty acid composition, revealing an increase in the crude lipid content and alterations in fatty acid profiles, particularly an increase in C16:1n-7 at the expense of EPA and a decrease in the unsaturation index. The findings provide insights into guiding the biomass and biologically active products production of P. tricornutum through metabolic engineering. Full article

Drought stress is one of the most critical threats to crop productivity and global food security. This review addresses the multiple effects of drought on the process of photosynthesis in major food crops. Affecting both light-dependent and light-independent reactions, drought leads to severe damage to photosystems and blocks the electron transport chain. Plants face a CO₂ shortage provoked by stomatal closure, which triggers photorespiration; not only does it reduce carbon fixation efficiency, but it also causes lower overall photosynthetic output. Drought-induced oxidative stress generates reactive oxygen species (ROS) that damage cellular structures, including chloroplasts, further impairing photosynthetic productivity. Plants have evolved a variety of adaptive strategies to alleviate these effects. Non-photochemical quenching (NPQ) mechanisms help dissipate excess light energy as heat, protecting the photosynthetic apparatus under drought conditions. Alternative electron pathways, such as cyclical electron transmission and chloroplast respiration, maintain energy balance and prevent over-reduction of the electron transport chain. Hormones, especially abscisic acid (ABA), ethylene, and cytokinin, modulate stomatal conductance, chlorophyll content, and osmotic adjustment, further increasing the tolerance to drought. Structural adjustments, such as leaf reordering and altered root architecture, also strengthen tolerance. Understanding these complex interactions and adaptive strategies is essential for developing drought-resistant crop varieties and ensuring agricultural sustainability. Full article

Magnetization reduction roasting is an important method for the utilization of oolitic magnetite. In this study, the magnetization reduction behavior and kinetics of oolitic hematite in gas-based roasting were systematically investigated by X-ray photoelectron spectroscopy (XPS). The results revealed that under optimal roasting conditions of 650 °C, a roasting time of 60 min, and a CO concentration of 30%, the magnetization reduction rate of the roasted product reached 44.34%. Furthermore, the weak magnetic separation concentrate presented a TFe of 58.09% and a concentrate iron recovery of 94.3%. The results of the XPS spectrum indicated that the peak area ratio (Fe²⁺/Fe³⁺) gradually increased with an increase in roasting temperature, roasting time, and CO concentration, while over-reduction occurred when the roasting temperature exceeded 750 °C. The investigation of magnetization roasting kinetics for varying particle sizes demonstrated that the magnetization reduction process is controlled by chemical reaction, with a corresponding activation energy range of 42.96 kJ/mol to 63.29 kJ/mol, indicating the particle size has little effect on the magnetization reduction of oolitic hematite. Full article

Plastid terminal oxidases (PTOXs) are essential for maintaining photosynthetic efficiency and cellular redox homeostasis. Astaxanthin, a carotenoid pigment with antioxidant properties, is synthesized and accumulates in response to oxidative stress induced by high-light intensity or nutrient limitation. It suggests that PTOX may impact astaxanthin biosynthesis under environmental stress conditions due to its involvement in ROS regulation. The ptox1 gene is thought to have a conserved role in safeguarding the photosynthetic apparatus from over-reduction and participating in energy dissipation. On the other hand, the ptox2 gene seems to be involved in the evolution of astaxanthin synthesis and adaptive responses to diverse environmental stressors. Efficient gene silencing strains were developed in Chlamydomonas reinhardtii CC849 for ptox1 and ptox2. The study found that the ptox2 gene correlates highly with resistance to intense light stress. Furthermore, the ptox2 gene showed increased activity under high salt stress conditions, indicating its importance in stress coping mechanisms. The quantification of astaxanthin in the gene-silenced strains revealed that ptox1 acts as a positive regulator, while ptox2 functions as a negative regulator of astaxanthin accumulation. Understanding the coordination between ptox1 and ptox2 could clarify the synergistic actions of these genes in maintaining photosynthetic performance and redox balance under fluctuating environmental conditions. Full article

The adaptation of plants to combined stresses requires unique responses capable of overcoming both the negative effects of each individual stress and their combination. Here, we studied the C₃-C₄ (C₂) halophyte Sedobassia sedoides in response to elevated temperature (35 °C) and salinity (300 mM NaCl) as well as their combined effect. The responses we studied included changes in water–salt balance, light and dark photosynthetic reactions, the expression of photosynthetic genes, the activity of malate dehydrogenase complex enzymes, and the antioxidant system. Salt treatment led to altered water–salt balance, improved water use efficiency, and an increase in the abundance of key enzymes involved in intermediate C₃-C₄ photosynthesis (i.e., Rubisco and glycine decarboxylase). We also observed a possible increase in the activity of the C₂ carbon-concentrating mechanism (CCM), which allowed plants to maintain high photosynthesis intensity and biomass accumulation. Elevated temperatures caused an imbalance in the dark and light reactions of photosynthesis, leading to stromal overreduction and the excessive generation of reactive oxygen species (ROS). In response, S. sedoides significantly activated a metabolic pathway for removing excess NADPH, the malate valve, which is catalyzed by NADP-MDH, without observable activation of the antioxidant system. The combined action of these two factors caused the activation of antioxidant defenses (i.e., increased activity of SOD and POX and upregulation of FDI), which led to a decrease in oxidative stress and helped restore the photosynthetic energy balance. Overall, improved PSII functioning and increased activity of PSI cyclic electron transport (CET) and C₂ CCM led to an increase in the photosynthesis intensity of S. sedoides under the combined effect of salinity and elevated temperature relative to high temperature alone. Full article

The growing demand for new energy sources governs the intensive research into CO₂ hydrogenation to methanol, a valuable liquid fuel. Recently, indium-based catalysts have shown promise in this reaction, but they are plagued by shortcomings such as structural instability during the reaction and low selectivity. Here, we report a new strategy of controlling the selectivity and stability of bimetallic magnetically recoverable indium-based catalysts deposited onto a solid support. This was accomplished by the introduction of a structural promoter: a branched pyridylphenylene polymer (PPP). The selectivity of methanol formation for this catalyst reached 98.5%, while in the absence of PPP, the catalysts produced a large amount of methane, and the selectivity was about 70.2%. The methanol production rate was higher by a factor of twelve compared to that of a commercial Cu-based catalyst. Along with tuning selectivity, PPP allowed the catalyst to maintain a high stability, enhancing the CO₂ sorption capacity and the protection of In against sintering and over-reduction. A careful evaluation of the structure–activity relationships allowed us to balance the catalyst composition with a high level of structural control, providing synergy between the support, magnetic constituent, catalytic species, and the stabilizing polymer layer. We also uncovered the role of each component in the ultimate methanol activity and selectivity. Full article

High-iron and low-silicon red mud is not only an alkaline solid waste from Bayer process alumina production, but it is also a very important secondary iron resource. Magnetization roasting is considered as an effective and typical method for the iron recovery and removal of impurities in red mud. In this work, based on the characteristics of large specific surface area and high porosity of red mud, the kinetics of magnetization roasting and phase transformation of red mud were studied. Thermodynamic analysis results show that the reduction of iron oxide in red mud is more easily promoted by CO as reducing agent at low roasting temperature. The reduction reaction is prone to overreduction, and fayalite and ferrospinel can be formed in the reaction system. The phase transformation and iron reduction mechanism during the roasting process were evaluated. Most of hematite and goethite in the red mud decomposed in the process of magnetization roasting, released CO₂, and transformed into strongly magnetic magnetite. The reaction process has some characteristics controlled by homogeneous reaction. The process of magnetization roasting reduction with CO was controlled by the hybrid control dynamics model, and the apparent activation energy was 38.31 kJ·mol⁻¹. Full article

Boron (B) toxicity is an important stressor that negatively affects maize yield and the quality of the produce. The excessive B content in agricultural lands is a growing problem due to the increase in arid and semi-arid areas because of climate change. Recently, two Peruvian maize landraces, Sama and Pachía, were physiologically characterized based on their tolerance to B toxicity, the former being more tolerant to B excess than Pachía. However, many aspects regarding the molecular mechanisms of these two maize landraces against B toxicity are still unknown. In this study, a leaf proteomic analysis of Sama and Pachía was performed. Out of a total of 2793 proteins identified, only 303 proteins were differentially accumulated. Functional analysis indicated that many of these proteins are involved in transcription and translation processes, amino acid metabolism, photosynthesis, carbohydrate metabolism, protein degradation, and protein stabilization and folding. Compared to Sama, Pachía had a higher number of differentially expressed proteins related to protein degradation, and transcription and translation processes under B toxicity conditions, which might reflect the greater protein damage caused by B toxicity in Pachía. Our results suggest that the higher tolerance to B toxicity of Sama can be attributed to more stable photosynthesis, which can prevent damage caused by stromal over-reduction under this stress condition. Full article

The barley cultivar Sarab 1 (SRB1) can continue photosynthesis despite its low Fe acquisition potential via roots and dramatically reduced amounts of photosystem I (PSI) reaction-center proteins under Fe-deficient conditions. We compared the characteristics of photosynthetic electron transfer (ET), thylakoid ultrastructure, and Fe and protein distribution on thylakoid membranes among barley cultivars. The Fe-deficient SRB1 had a large proportion of functional PSI proteins by avoiding P700 over-reduction. An analysis of the thylakoid ultrastructure clarified that SRB1 had a larger proportion of non-appressed thylakoid membranes than those in another Fe-tolerant cultivar, Ehimehadaka-1 (EHM1). Separating thylakoids by differential centrifugation further revealed that the Fe-deficient SRB1 had increased amounts of low/light-density thylakoids with increased Fe and light-harvesting complex II (LHCII) than did EHM1. LHCII with uncommon localization probably prevents excessive ET from PSII leading to elevated NPQ and lower PSI photodamage in SRB1 than in EHM1, as supported by increased Y(NPQ) and Y(ND) in the Fe-deficient SRB1. Unlike this strategy, EHM1 may preferentially supply Fe cofactors to PSI, thereby exploiting more surplus reaction center proteins than SRB1 under Fe-deficient conditions. In summary, SRB1 and EHM1 support PSI through different mechanisms during Fe deficiency, suggesting that barley species have multiple strategies for acclimating photosynthetic apparatus to Fe deficiency. Full article