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Hypothetical chloroplast open reading frames (ycfs) are putative genes in the plastid genomes of photosynthetic eukaryotes. Many ycfs are also conserved in the genomes of cyanobacteria, the presumptive ancestors of present-day chloroplasts. The functions of many ycfs are still unknown. Here, we generated knock-out mutants for ycf51 (sll1702) in the cyanobacterium Synechocystis sp. PCC 6803. The mutants showed reduced photoautotrophic growth due to impaired electron transport between photosystem II (PSII) and PSI. This phenotype results from greatly reduced PSI content in the ycf51 mutant. The ycf51 disruption had little effect on the transcription of genes encoding photosynthetic complex components and the stabilization of the PSI complex. In vitro and in vivo analyses demonstrated that Ycf51 cooperates with PSI assembly factor Ycf3 to mediate PSI assembly. Furthermore, Ycf51 interacts with the PSI subunit PsaC. Together with its specific localization in the thylakoid membrane and the stromal exposure of its hydrophilic region, our data suggest that Ycf51 is involved in PSI complex assembly. Ycf51 is conserved in all sequenced cyanobacteria, including the earliest branching cyanobacteria of the Gloeobacter genus, and is also present in the plastid genomes of glaucophytes. However, Ycf51 has been lost from other photosynthetic eukaryotic lineages. Thus, Ycf51 is a PSI assembly factor that has been functionally replaced during the evolution of oxygenic photosynthetic eukaryotes.
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Proteínas Bacterianas , Sistemas de Lectura Abierta , Complejo de Proteína del Fotosistema I , Synechocystis , Complejo de Proteína del Fotosistema I/metabolismo , Complejo de Proteína del Fotosistema I/genética , Synechocystis/genética , Synechocystis/metabolismo , Sistemas de Lectura Abierta/genética , Proteínas Bacterianas/metabolismo , Proteínas Bacterianas/genética , Cloroplastos/metabolismo , Fotosíntesis/genética , Tilacoides/metabolismo , Complejo de Proteína del Fotosistema II/metabolismo , Complejo de Proteína del Fotosistema II/genética , MutaciónRESUMEN
Selective oxidation of methane to organic oxygenates over metal-organic frameworks (MOFs) catalysts at low temperature is a challenging topic in the field of C1 chemistry because of the inferior stability of MOFs. Modifying the surface of Cu-BTC via hydrophobic polydimethylsiloxane (PDMS) at 235 °C under vacuum not only can dramatically improve its catalytic cycle stability in a liquid phase but also generate coordinatively unsaturated Cu(I) sites, which significantly enhances the catalytic activity of Cu-BTC catalyst. The results of spectroscopy characterizations and theoretical calculation proved that the coordinatively unsaturated Cu(I) sites made H2O2 dissociative into â¢OH, which formed Cu(II)-O active species by combining with coordinatively unsaturated Cu(I) sites for activating the C-H bond of methane. The high productivity of C1 oxygenates (CH3OH and CH3OOH) of 10.67 mmol gcat.-1h-1 with super high selectivity of 99.6% to C1 oxygenates was achieved over Cu-BTC-P-235 catalyst, and the catalyst possessed excellent reusability.
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Hitherto, sulfur poisoning and hydrothermal aging have still been the challenges faced in practical applications of the Cu-SSZ-13 catalyst for the selective catalytic reduction (SCR) of NOx from diesel engine exhaust. Here, we elaborately design and conduct an in-depth investigation of the synthetic effects of hydrothermal aging and SO2 poisoning on pristine Cu-SSZ-13 and Cu-SSZ-13@Ce0.75Zr0.25O2 core@shell structure catalysts (Cu@CZ). It has been discovered that Cu@CZ susceptible to 750 °C with 5 vol % H2O followed by 200 ppm SO2 with 5 vol % H2O (Cu@CZ-A-S) could still maintain nearly 100% NOx conversion across the significantly wider temperature region of 200-425 °C, which is remarkably broader than that of the Cu-SSZ-13-A-S (300-400 °C) counterpart. The experimental results show that the hydrothermal aging process results in the migration of highly active Cu species within the cage of Cu-SSZ-13 to the CZ surface, forming CuO/CZ with abundant interfaces, which significantly enhances the adsorption and subsequent activation of NO, leading to the generation of reactive N2O3 and HONO intermediates. Moreover, density functional theory (DFT) calculations reveal that the H of the HONO* species can function as Brønsted acid sites, effectively adsorbing NH3 to generate the active NH4NO2* intermediate, which readily decomposes into N2 and H2O. Furthermore, this pathway is the rate-determining step with an energy barrier of 0.93 eV, notably lower than that of the "standard SCR" pathway (1.42 eV). Therefore, the formation of the new CuO/CZ interface profoundly boosts the low-temperature NH3-SCR activity and improves the coresistance of the Cu@CZ catalyst to sulfur poisoning and hydrothermal aging.
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Great efforts have been made to expand the application fields of nanozymes, which puts forward requirements for nanozymes with both superior catalytic activity and specificity. Herein, we reported the high-indexed intermetallic Pt3Sn (H-Pt3Sn) with high peroxidase-like activity and specificity. The resultant H-Pt3Sn exhibits a specific activity of 345.3 U/mg, which is 1.82 times higher than Pt. Moreover, H-Pt3Sn possesses negligible oxidase-like and catalase-like activities, achieving superior catalytic specificity toward H2O2 activation. Experimental and theoretical calculations reveal both the splitting energy for adsorbed H2O2 and the energy barrier for the rate-determining step of H-Pt3Sn are significantly decreased compared with Pt3Sn and Pt. Finally, a nanozyme-linked immunosorbent assay is successfully developed, achieving the sensitive and accurate colorimetric detection for carcinoembryonic antigen with a low detection limit of 0.49 pg/mL and showing practical feasibility in serum sample detection.
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Peróxido de Hidrógeno , Peroxidasa , Peroxidasas , Inmunoensayo , ColorimetríaRESUMEN
The electrocatalytic nitrogen reduction reaction (NRR) on metal-free catalysts is an attractive alternative to the industrial Haber-Bosch process. However, the state-of-the-art metal-free electrocatalysts still suffer from low Faraday efficiencies and low ammonia yields. Herein, we present a molecular design strategy to develop a defective boron carbon nitride (BCN) catalyst with the abundant unsaturated B and N atoms as Lewis acid and base sites, which upgrades the catalyst from a single "Lewis acid catalysis" to "frustrated Lewis pairs (FLPs) catalysis." 14 N2 /15 N2 exchange experiments and density functional theory (DFT) calculations reveal that FLPs can adsorb an N2 molecule to form a six-membered ring intermediate, which enables the cleavage of N2 via a pull-pull effect, thereby significantly reducing the energy barrier to -0.28â eV. Impressively, BCN achieves a high Faraday efficiency of 18.9 %, an ammonia yield of 20.9â µg h-1 mg-1 cat. , and long-term durability.
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The development of highly active single-atom catalysts (SACs) and identifying their intrinsic active sites in oxidizing industrial hazardous hydrocarbons are challenging prospects. Tuning the electronic metal-support interactions (EMSIs) is valid for modulating the catalytic performance of SACs. We propose that the modulation of the EMSIs in a Pt1 -CuO SAC significantly promotes the activity of the catalyst in acetone oxidation. The EMSIs promote charge redistribution through the unified Pt-O-Cu moieties, which modulates the d-band structure of atomic Pt sites, and strengthens the adsorption and activation of reactants. The positively charged Pt atoms are superior for activating acetone at low temperatures, and the stretched Cu-O bonds facilitate the activation of lattice oxygen atoms to participate in subsequent oxidation. We believe that this work will guide researchers to engineer efficient SACs for application in hydrocarbon oxidation reactions.
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The inorganic lead-free Cs2AgBiBr6 double perovskite structure is the promising development direction in perovskite solar cells (PSCs) to solve the problem of the instability of the APbX3 structure and lead toxicity. However, the low short-circuit current and power conversion efficiency (PCE) caused by the low crystallization of Cs2AgBiBr6 greatly limit the optoelectronic application. Herein, we adopt a simple strategy to dope single-layered MXene nanosheets into titania (Ti3C2Tx@TiO2) as a multifunctional electron transport layer for stable and efficient Cs2AgBiBr6 double PSCs. The single-layered MXene nanosheets significantly improve the electrical conductivity and electron extraction rate of TiO2; meanwhile, the single-layered MXene nanosheets change the surface wettability of the electron transport layer and promote the crystallization of the Cs2AgBiBr6 double perovskite in solar cell devices. Therefore, the PCE went up by more than 40% to 2.81% compared to that of a TiO2 based device, and the hysteresis was greatly suppressed. Furthermore, the device based on Ti3C2Tx@TiO2 showed the long-term operating stability. After storing the device for 15 days under ambient air conditions, the PCE still remained a retention rate of 93% of the initial one. Our finding demonstrates the potential of Ti3C2Tx@TiO2 in electron transfer material of high-performance double PSCs.
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Inspired by the key role of the coordination environment in the catalytic activity of enzymes, a rational design of the coordination structure of active sites at the atom scale is expected to develop high-performance enzyme-like catalysts. Here, we design a simple model system involving pentacoordinated and tetracoordinated Fe-N-C single-atom catalysts (named NG-Heme and G-Heme, respectively) to investigate structure-activity relationships. NG-Heme with axial ligand-engineered Fe sites exhibits superior enzyme-like activity to G-Heme, achieving the goal of vivid mimicking of the active sites of peroxidase. Experiments and theoretical studies reveal that the enhanced intrinsic catalytic activity originates from the "push effect" of the additional axial ligand, which can strengthen the interaction between the active site and the intermediate. Based on the outstanding catalytic activity, an NG-Heme-linked immunosorbent assay was constructed for colorimetric detection of carcinoembryonic antigen, exhibiting satisfactory sensitivity and feasibility in the analysis of clinical samples.
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Hemo , Peroxidasa , Catálisis , Inmunoensayo , LigandosRESUMEN
Rational design and construction of advanced sensing platforms for sensitive detection of H2O2 released from living cells is one of the challenges in the field of physiology and pathology. Noble metal clusters are a kind of nanomaterials with well-defined chemical composition and special atomic structures, which have been widely explored in catalysis, biosensing, and therapy. Compared with noble metal nanoparticles, noble metal clusters exhibit great potential in electrochemical biosensing due to their high atom utilization efficiency and abundant reactive active sites. Herein, Pt nanoclusters anchored on hollow carbon spheres (PtNCS/HCS) were successfully prepared for sensitive detection of H2O2. By tuning the ratio of Pt(0)/Pt(II) at different annealing temperatures, the optimized PtNCS/HCS-550 showed higher H2O2 reduction and oxidation catalytic activities than other control samples. Density functional theory calculations revealed that H2O2*can be better activated and dissociated in the Pt0II model featured with the co-existence of Pt(0)/Pt(II) and the key intermediates OOH*/OH* have a stronger interaction with the Pt0II model. As a concept application, the electrochemical biosensing platform was successfully applied to sensitive detection of H2O2 released from the cells.
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Técnicas Biosensibles , Nanopartículas del Metal , Técnicas Electroquímicas , Peróxido de Hidrógeno , Oxidación-Reducción , Platino (Metal)RESUMEN
The rational construction of advanced sensing platforms to sensitively detect H2O2 produced by living cells is one of the challenges in both physiological and pathological fields. Owing to the extraordinary catalytic performances and similar metal coordination to natural metalloenzymes, single atomic site catalysts (SASCs) with intrinsic peroxidase (POD)-like activity have shown great promise for H2O2 detection. However, there still exists an obvious gap between them and natural enzymes because of the great challenge in rationally modulating the electronic and geometrical structures of central atoms. Note that the deliberate modulation of the metal-support interaction may give rise to the promising catalytic activity. In this work, an extremely sensitive electrochemical H2O2 biosensor based on single atomic Fe sites coupled with carbon-encapsulated Fe3C crystals (Fe3C@C/Fe-N-C) is proposed. Compared with the conventional Fe SASCs (Fe-N-C), Fe3C@C/Fe-N-C exhibits superior POD-like activity and electrochemical H2O2 sensing performance with a high sensitivity of 1225 µA/mM·cm2, fast response within 2 s, and a low detection limit of 0.26 µM. Significantly, sensitive monitoring of H2O2 released from living cells is also achieved. Moreover, the density functional theory calculations reveal that the incorporated Fe3C nanocrystals donate electrons to single atomic Fe sites, endowing them with improved activation ability of H2O2 and further enhancing the overall activity. This work provides a new design of synergistically enhanced single atomic sites for electrochemical sensing applications.
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Técnicas Biosensibles , Peróxido de Hidrógeno , Carbono , Catálisis , Oxidación-ReducciónRESUMEN
Water splitting to H2 by photocatalysis remains an effective strategy to alleviate the energy crisis. Unfortunately, single-component photocatalyst still suffers from sluggish reaction kinetics. In this work, a noble-metal free photocatalytic system of nitrogen-doped carbon@Co embedded in carbon nanotubes (NC@Co-NCT)/cadmium sulfide (CdS) is fabricated by coupling CdS nanorods with the metal-organic framework-derived Co encapsulated nitrogen-doped carbon (NC) material. The optimal photocatalytic activity of NC@Co-NCT/CdS is determined to be 3.8 mmol h-1 g-1 , which is ≈5.8 times of CdS. By combining the experimental evidences and density functional theory calculations, a novel photoelectron transfer channel in the heterojunction interfaces is revealed, expediting the migration and separation of photo-induced charge carriers of CdS. Moreover, the presence of Co nanoclusters can act as the active sites, boosting the H2 evolution reaction. This study can present a new avenue to design advanced photocatalysts with high-efficiency electrons and holes separation.
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Maintaining the structural integrity of the photosynthetic apparatus during dehydration is critical for effective recovery of photosynthetic activity upon rehydration in a variety of desiccation-tolerant plants, but the underlying molecular mechanism is largely unclear. The subaerial cyanobacterium Nostoc flagelliforme can survive extreme dehydration conditions and quickly recovers its photosynthetic activity upon rehydration. In this study, we found that the expression of the molecular chaperone NfDnaK2 was substantially induced by dehydration, and NfDnaK2 proteins were primarily localized in the thylakoid membrane. NfDnaJ9 was identified to be the cochaperone partner of NfDnaK2, and their encoding genes shared similar transcriptional responses to dehydration. NfDnaJ9 interacted with the NfFtsH2 protease involved in the degradation of damaged D1 protein. Heterologous expression of NfdnaK2 enhanced PSII repair and drought tolerance in transgenic Nostoc sp. PCC 7120. Furthermore, the nitrate reduction (NarL)/nitrogen fixation (FixJ) family transcription factors response regulator (NfRre1) and photosynthetic electron transport-dependent regulator (NfPedR) were identified as putative positive regulators capable of binding to the promoter region of NfdnaK2 and they may mediate dehydration-induced expression of NfdnaK2 in N. flagelliforme Our findings provide novel insights into the molecular mechanism of desiccation tolerance in some xerotolerant microorganisms, which could facilitate future synthetic approaches to the creation of extremophiles in microorganisms and plants.
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Proteínas Bacterianas/metabolismo , Cianobacterias/metabolismo , Complejo de Proteína del Fotosistema II/metabolismo , Deshidratación , Desecación , Sequías , Nitratos/metabolismo , Fijación del Nitrógeno , Fotosíntesis/fisiología , Tilacoides/metabolismoRESUMEN
Dual-atom site catalysts (DACs) have emerged as a new frontier in heterogeneous catalysis because the synergistic effect between adjacent metal atoms can promote their catalytic activity while maintaining the advantages of single-atom site catalysts (SACs), like 100 % atomic utilization efficiency and excellent selectivity. Herein, a supported Pd2 DAC was synthesized and used for electrochemical CO2 reduction reaction (CO2 RR) for the first time. The as-obtained Pd2 DAC exhibited superior CO2 RR catalytic performance with 98.2 % CO faradic efficiency at -0.85â V vs. RHE, far exceeding that of Pd1 SAC, and coupled with long-term stability. The density functional theory (DFT) calculations revealed that the intrinsic reason for the superior activity of Pd2 DAC toward CO2 RR was the electron transfer between Pd atoms at the dimeric Pd sites. Thus, Pd2 DAC possessed moderate adsorption strength of CO*, which was beneficial for CO production in CO2 RR.
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Tetrahedral NiS2 /NiSe2 heterocages with rich-phase boundaries are synthesized through a simultaneous sulfuration/selenylation process using Ni-based acetate hydroxide prisms as precursor. Such a nanocage-like NiS2 /NiSe2 heterostructure can expose more active sites, accelerate the mass transport of the ions/gas, and optimize the interfacial electronic structure, which shows a significantly lower overpotential of 290 mV at 20 mA cm-2 than those of NiS/NiS2 and NiSe2 as counterparts. The experimental characterizations and theoretical density functional theory (DFT) calculations unveil that the interfacial electron transfer from NiSe2 to NiS2 at the heterointerface can modulate the electronic structure of NiS2 /NiSe2 , which further cooperates synergistically to change the Gibbs free energy of oxygen-containing intermediates as the rate-determining step (RDS) from 2.16 eV (NiSe2 ) and 2.10 eV (NiS2 ) to 1.86 eV (NiS2 /NiSe2 heterostructures) during the oxygen evolution reaction (OER) process. And as a result, tetrahedral NiS2 /NiSe2 heterocages with dual-phase synergy efficiently trigger the OER process, and accelerate the OER kinetics. This work provides insights into the roles of the interfacial electron transfer in electrocatalysis, and can be an admirable strategy to modulate the electronic structure for developing highly active electrocatalysts.
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Two cAMP receptor proteins (CRPs), Sycrp1 (encoded by sll1371) and Sycrp2 (encoded by sll1924), exist in the cyanobacterium Synechocystis sp. strain PCC 6803. Previous studies have demonstrated that Sycrp1 has binding affinity for cAMP and is involved in motility by regulating the formation of pili. However, the function of Sycrp2 remains unknown. Here, we report that sycrp2 disruption results in the loss of motility of Synechocystis sp. PCC 6803, and that the phenotype can be recovered by reintroducing the sycrp2 gene into the genome of sycrp2-disrupted mutants. Electron microscopy showed that the sycrp2-disrupted mutant lost the pilus apparatus on the cell surface, resulting in a lack of cell motility. Furthermore, the transcript level of the pilA9-pilA11 operon (essential for cell motility and regulated by the cAMP receptor protein Sycrp1) was markedly decreased in sycrp2-disrupted mutants compared with the wild-type strain. Moreover, yeast two-hybrid analysis and a pulldown assay demonstrated that Sycrp2 interacted with Sycrp1 to form a heterodimer and that Sycrp1 and Sycrp2 interacted with themselves to form homodimers. Gel mobility shift assays revealed that Sycrp1 specifically binds to the upstream region of pilA9 Together, these findings indicate that in Synechocystis sp. PCC 6803, Sycrp2 regulates the formation of pili and cell motility by interacting with Sycrp1.IMPORTANCE cAMP receptor proteins (CRPs) are widely distributed in cyanobacteria and play important roles in regulating gene expression. Although many cyanobacterial species have two cAMP receptor-like proteins, the functional links between them are unknown. Here, we found that Sycrp2 in the cyanobacterium Synechocystis sp. strain PCC 6803 is essential for twitching motility and that it interacts with Sycrp1, a known cAMP receptor protein involved with twitching motility. Our findings indicate that the two cAMP receptor-like proteins in cyanobacteria do not have functional redundancy but rather work together.
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Proteínas Bacterianas/genética , Fimbrias Bacterianas/metabolismo , Genes Bacterianos , Receptores de AMP Cíclico/genética , Synechocystis/genética , Proteínas Bacterianas/metabolismo , Regulación Bacteriana de la Expresión Génica , Movimiento , Receptores de AMP Cíclico/metabolismo , Synechocystis/metabolismoRESUMEN
Carbonate intermediates have been reported to play an active role in CO oxidation over ceria-based catalysts in recent experimental studies. However, the detailed CO oxidation mechanism involving carbonate intermediates over ceria-based catalysts remains obscure. In this work, we carried out systematic density functional theory calculations corrected by on-site Coulomb interactions (DFT+U) to investigate the complete CO oxidation mechanism involving carbonate intermediates over cobalt-doped CeO2 catalysts, aiming to unravel how the carbonate participates in CO oxidation and shed light on the underlying factors that control the carbonate-mediated reaction mechanism. A novel carbonate-mediated Mars-van Krevelen (M-vK) mechanism was proposed, in which the carbonate acts as an active intermediate rather than a spectator and can react with CO to form CO2. This carbonate-mediated M-vK mechanism is facet-dependent because it is predominant on the (110) surface whereas the conventional M-vK mechanism is more favorable on (111) and (100) surfaces. The origin of facet-dependence was discussed by analyzing the geometric and electronic structures. It is found that the negatively charged bent CO2- intermediate formed on the (110) surface plays a critical role in the carbonate-mediated M-vK mechanism, whereas the formation of a neutral linear CO2 intermediate on (111) and (100) surfaces hinders the carbonate-mediated M-vK mechanism. The surface oxygen vacancy hinders the formation of carbonate intermediates, indicating that the carbonate-mediated M-vK mechanism is also vacancy-dependent. The formation of carbonate intermediates on different metal (Ti, V, W, Mo and Re) doped CeO2(110) surfaces was studied and the results indicate that the coordination environment of the dopant species is a key factor that determines the carbonate-mediated M-vK mechanism. This study provides atomic-scale insights into the reaction mechanism involving carbonate intermediates and the structure-mechanism relationship for CO oxidation over cobalt-ceria catalysts.
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MAIN CONCLUSION: The sulfur-formation ( suf ) genes play important roles in both photosynthesis and respiration of cyanobacteria, but the organism prioritizes Fe-S clusters for respiration at the expense of photosynthesis. Iron-sulfur (Fe-S) clusters are important to all living organisms, but their assembly mechanism is poorly understood in photosynthetic organisms. Unlike non-photosynthetic bacteria that rely on the iron-sulfur cluster system, Synechocystis sp. PCC 6803 uses the Sulfur-Formation (SUF) system as its major Fe-S cluster assembly pathway. The co-expression of suf genes and the direct interactions among SUF subunits indicate that Fe-S assembly is a complex process in which no suf genes can be knocked out completely. In this study, we developed a condition-controlled SUF Knockdown mutant by inserting the petE promoter, which is regulated by Cu2+ concentration, in front of the suf operon. Limited amount of the SUF system resulted in decreased chlorophyll contents and photosystem activities, and a lower PSI/PSII ratio. Unexpectedly, increased cyclic electron transport and a decreased dark respiration rate were only observed under photoautotrophic growth conditions. No visible effects on the phenotype of SUF Knockdown mutant were observed under heterotrophic culture conditions. The phylogenetic distribution of the SUF system indicates that it has a co-evolutionary relationship with photosynthetic energy storing pathways.
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Metabolismo Energético , Proteínas Hierro-Azufre/genética , Fotosíntesis/fisiología , Azufre/metabolismo , Synechocystis/genética , Procesos Autotróficos , Proteínas Bacterianas/genética , Proteínas Bacterianas/metabolismo , Clorofila/metabolismo , Transporte de Electrón , Técnicas de Inactivación de Genes , Procesos Heterotróficos , Proteínas Hierro-Azufre/metabolismo , Luz , Mutación , Operón/genética , Oxígeno/metabolismo , Fenotipo , Filogenia , Transpiración de Plantas/fisiología , Synechocystis/crecimiento & desarrollo , Synechocystis/fisiología , Synechocystis/efectos de la radiaciónRESUMEN
MAIN CONCLUSION: The Ycf46 mutant of Synechocystis showed growth inhibition under low dissolved CO 2 conditions, suggesting a role for the Ycf46 protein in the process of photosynthetic CO 2 uptake and utilization. Hypothetical chloroplast open reading frame Ycf46 proteins are highly conserved in all cyanobacterial lineages and most algal chloroplast genomes, but their exact function is still unknown. In the cyanobacterium Synechocystis sp. PCC 6803, the Ycf46 encoding gene slr0374 is part of an operon (with slr0373 and slr0376) and responds to many environmental stresses. Transcript levels of the slr0373, slr0374 and slr0376 genes were increased under a low concentration of dissolved inorganic carbon (Ci). Compared with the wild type, the mutant lacking slr0374 showed growth arrest under Ci-deficient conditions but not under iron-deficient or low-light conditions. In addition, the mutant grew more slowly than the wild type under pH 6.0 conditions in which CO2 was the dominant Ci source, indicating the mutant cells had weak CO2 uptake and/or utilization ability. Supplying a high concentration of CO2 (5 %, v/v) to the mutant restored its phenotype to the wild type level. The photosynthetic activity of the mutant was inhibited to a lesser extent by a carbonic anhydrase inhibitor than that of the wild type, which specifically blocked CO2 uptake. Inactivation of slr0374 decreased expression of the ecaB gene and reduced carbonic anhydrase activity. A subcellular localization assay indicated that the Ycf46 protein was soluble. By co-immunoprecipitation assay using Slr0374 as a bait-protein, potential interacting proteins in the size range of 30 kDa were identified. These results suggest that the Ycf46 protein plays a role in the regulation of photosynthesis in cyanobacteria, especially in CO2 uptake and utilization.
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Proteínas Bacterianas/metabolismo , Dióxido de Carbono/metabolismo , Operón , Synechocystis/metabolismo , Proteínas Bacterianas/genética , Carbono/metabolismo , Regulación Bacteriana de la Expresión Génica , Concentración de Iones de Hidrógeno , Inmunoprecipitación , Mutación , Fotosíntesis/genética , Fotosíntesis/fisiología , Unión Proteica , Synechocystis/genéticaRESUMEN
The development of low-cost and high-efficiency electrocatalysts for the oxygen evolution reaction (OER) is essential to produce high-purity hydrogen in large scale. Herein, a three-dimensional (3D) seaweed-like hierarchical structure was fabricated using two-dimensional (2D) NiMn LDH nanosheets wrapped on one-dimensional (1D) NiSe nanowires with nickel foam (NF) as a substrate (NiSe@NiMn LDH/NF) via hydrothermal and electrodeposition processes. Owing to the strong interfacial synergy, 3D seaweed-like hierarchical structure, higher conductivity, and strong structural stability, the NiSe@NiMn LDH/NF exhibited superior OER performance with an overpotential of 287 mV at 100 mA cm-2, and stably operated for 160 h at large current. Moreover, the overall water splitting system with NiSe@NiMn LDH/NF as the anode and Pt/C/NF as the cathode exhibited a low cell voltage of 1.59/1.64 V to reach 50/100 mA cm-2, and excellent stability for 110 h at 300 mA cm-2. The density function theory (DFT) calculations unveiled that NiSe@NiMn LDH enabled the interfacial synergy, reallocating the electron density at the interface, and further weakening the energy barrier of OH* by strengthening chemical bonds with OH* intermediates to improve the intrinsic OER activity.
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Incorporating donor doping into Mg3Sb1.5Bi0.5 to achieve n-type conductivity is one of the crucial strategies for performance enhancement. In pursuit of higher thermoelectric performance, we herein report co-doping with Te and Y to optimize the thermoelectric properties of Mg3Sb1.5Bi0.5, achieving a peak ZT exceeding 1.7 at 703 K in Y0.01Mg3.19Sb1.5Bi0.47Te0.03. Guided by first-principles calculations for compositional design, we find that Te-doping shifts the Fermi level into the conduction band, resulting in n-type semiconductor behavior, while Y-doping further shifts the Fermi level into the conduction band and reduces the bandgap, leading to enhanced thermoelectric performance with a power factor as high as >20 µW cm-1 K-2. Additionally, through detailed micro/nanostructure characterizations, we discover that Te and Y co-doping induces dense crystal and lattice defects, including local lattice distortions and strains caused by point defects, and densely distributed grain boundaries between nanocrystalline domains. These defects efficiently scatter phonons of various wavelengths, resulting in a low thermal conductivity of 0.83 W m-1 K-1 and ultimately achieving a high ZT. Furthermore, the dense lattice defects induced by co-doping can further strengthen the mechanical performance, which is crucial for its service in devices. This work provides guidance for the composition and structure design of thermoelectric materials.