RESUMEN
Currently, mitochondrial dysfunction caused by oxidative stress is a growing concern in degenerative diseases, notably intervertebral disc degeneration (IVDD). Dysregulation of the balance of mitochondrial quality control (MQC) has been considered the key contributor, while it's still challenging to effectively harmonize different MQC components in a simple and biologically safe way. Hydrogen gas (H2) is a promising mitochondrial therapeutic molecule due to its bio-reductivity and diffusibility across cellular membranes, yet its relationship with MQC regulation remains unknown. Herein, we propose a mitochondrial 'Birth-Death' coordinator achieved by an intelligent hydrogen nanogenerator (Fe@HP-OD), which can sustainably release H2 in response to the unique microenvironment in degenerated IVDs. Both in vitro and in vivo results prove alleviation of cellular oxidative stress and restoration of nucleus pulposus cells function, thereby facilitating successful IVD regeneration. Significantly, this study for the first time proposes the mitochondrial 'Birth-Death' coordination mechanism: 1) attenuation of overactivated mitochondrial 'Death' process (UPRmt and unselective mitophagy); and 2) activation of Adenosine 5'-monophosphate-activated protein kinase (AMPK) signaling pathway for mitochondrial 'Birth-Death' balance (mitochondrial biogenesis and controlled mitophagy). These pioneering findings can fill in the gaps in molecular mechanisms for H2 regulation on MQC homeostasis, and pave the way for future strategies towards restoring equilibrium of MQC system against degenerative diseases.
Asunto(s)
Hidrógeno , Degeneración del Disco Intervertebral , Mitocondrias , Estrés Oxidativo , Hidrógeno/química , Animales , Mitocondrias/metabolismo , Mitocondrias/efectos de los fármacos , Estrés Oxidativo/efectos de los fármacos , Regeneración/efectos de los fármacos , Disco Intervertebral/efectos de los fármacos , Humanos , Mitofagia/efectos de los fármacos , Ratas Sprague-Dawley , Masculino , Núcleo Pulposo/metabolismo , RatasRESUMEN
Li6ZnO4 was chemically modified by nickel addition, in order to develop different compositions of the solid solution Li6Zn1-xNixO4. These materials were evaluated bifunctionally; analyzing their CO2 capture performances, as well as on their catalytic properties for H2 production via dry reforming of methane (DRM). The crystal structures of Li6Zn1-xNixO4 solid solution samples were determined through X-ray diffraction, which confirmed the integration of nickel ions up to a concentration around 20 mol%, meanwhile beyond this value, a secondary phase was detected. These results were supported by XPS and TEM analyses. Then, dynamic and isothermal thermogravimetric analyses of CO2 capture revealed that Li6Zn1-xNixO4 solid solution samples exhibited good CO2 chemisorption efficiencies, similarly to the pristine Li6ZnO4 chemisorption trends observed. Moreover, a kinetic analysis of CO2 isothermal chemisorptions, using the Avrami-Erofeev model, evidenced an increment of the constant rates as a function of the Ni content. Since Ni2+ ions incorporation did not reduce the CO2 capture efficiency and kinetics, the catalytic properties of these materials were evaluated in the DRM process. Results demonstrated that nickel ions favored hydrogen (H2) production over the pristine Li6ZnO4 phase, despite a second H2 production reaction was determined, methane decomposition. Thereby, Li6Zn1-xNixO4 ceramics can be employed as bifunctional materials.
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Dióxido de Carbono , Hidrógeno , Metano , Hidrógeno/química , Metano/química , Dióxido de Carbono/química , Níquel/química , Catálisis , Modelos QuímicosRESUMEN
Developing cost-effective and high-performance catalyst systems for dry reforming of methane (DRM) is crucial for producing hydrogen (H2) sustainably. Herein, we investigate using iron (Fe) as a promoter and major alumina support in Ni-based catalysts to improve their DRM performance. The addition of iron as a promotor was found to add reducible iron species along with reducible NiO species, enhance the basicity and induce the deposition of oxidizable carbon. By incorporating 1 wt.% Fe into a 5Ni/10ZrAl catalyst, a higher CO2 interaction and formation of reducible "NiO-species having strong interaction with support" was observed, which led to an â¼80% H2 yield in 420 min of Time on Stream (TOS). Further increasing the Fe content to 2wt% led to the formation of additional reducible iron oxide species and a noticeable rise in H2 yield up to 84%. Despite the severe weight loss on Fe-promoted catalysts, high H2 yield was maintained due to the proper balance between the rate of CH4 decomposition and the rate of carbon deposit diffusion. Finally, incorporating 3 wt.% Fe into the 5Ni/10ZrAl catalyst resulted in the highest CO2 interaction, wide presence of reducible NiO-species, minimum graphitic deposit and an 87% H2 yield. Our findings suggest that iron-promoted zirconia-alumina-supported Ni catalysts can be a cheap and excellent catalytic system for H2 production via DRM.
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Óxido de Aluminio , Hidrógeno , Hierro , Metano , Níquel , Circonio , Metano/química , Circonio/química , Catálisis , Hierro/química , Hidrógeno/química , Óxido de Aluminio/química , Níquel/químicaRESUMEN
Nucleosides with a substituent at the 4'-position have received much attention as antiviral drugs and as raw materials for oligonucleotide therapeutics. 4'-Modified nucleosides are generally synthesized using ionic reactions through the introduction of electrophilic or nucleophilic substituents at the 4'-position. However, their synthetic methods have some drawbacks; e.g., (i) it is difficult to control stereoselectivity at the 4'-position; (ii) complex protection-deprotection processes are required; (iii) the range of electrophiles and nucleophiles is limited. With this background, we considered that a carbon radical generated at the 4'-position would be a useful intermediate for the synthesis of 4'-modified nucleosides. In this review, two novel methods for the generation of 4'-carbon radicals are summarized. The first utilizes radical deformylation involving ß-fragmentation of a hydroxymethyl group at the 4'-position. The other utilizes radical decarboxylation and 1,5-hydrogen atom transfer (1,5-HAT), which enables the generation of 4'-carbon radicals while retaining the hydroxymethyl group at the 4'-position. These methods enable the rapid and facile generation of 4'-carbon radicals and provide various 4'-modified nucleosides including 2',4'-bridged structures.
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Antivirales , Carbono , Nucleósidos , Nucleósidos/síntesis química , Nucleósidos/química , Carbono/química , Radicales Libres/química , Radicales Libres/síntesis química , Antivirales/síntesis química , Antivirales/química , Técnicas de Química Sintética/métodos , Hidrógeno/químicaRESUMEN
Although the past decade has witnessed a rapid development of oxidoreductase-mimicking nanozymes, the mimicry of cofactors that play key roles in mediating electron and proton transfer remains limited. This study explores how surface Au-H species conjugated to Au nanoparticles (NPs) that imitate formate dehydrogenase (FDH) can serve as cofactors, analogous to NADH in natural enzymes, offering diverse possibilities for FDH-mimicking Au nanozymes to mimic various enzymes. Once O2 is present, Au-H species assist Au NPs to complete the on-demand H2O2 generation for cascade reactions. Alternatively, when oxidizing organic molecules are introduced as substrates, Au-H species confer nitro reductase- and aldehyde reductase-like activities on Au NPs under anaerobic conditions. Furthermore, similar to the dehydrogenase-NADH complex, Au NPs possessing Au-H species are gifted with esterase-like activity for ester hydrolysis. By revealing that Au-H species are prosthetic groups for FDH-mimicking Au nanozymes, this work may inspire explorations into future self-generated cofactor mimics for nanozymes, thereby circumventing the need for exogenous cofactors.
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Formiato Deshidrogenasas , Oro , Nanopartículas del Metal , Oro/química , Formiato Deshidrogenasas/metabolismo , Formiato Deshidrogenasas/química , Nanopartículas del Metal/química , Propiedades de Superficie , Hidrógeno/química , Hidrógeno/metabolismo , Peróxido de Hidrógeno/química , Peróxido de Hidrógeno/metabolismo , Materiales Biomiméticos/química , Materiales Biomiméticos/metabolismo , Oxidación-ReducciónRESUMEN
Graphitic carbon nitride (g-C3N4)-based photocatalysts have garnered significant interest as a promising photocatalyst for hydrogen generation under visible light, to address energy and environmental challenges owing to their favorable electronic structure, affordability, and stability. In spite of that, issues such as high charge carrier recombination rates and low quantum efficiency impede its broader application. To overcome these limitations, structural and morphological modification of the g-C3N4-based photocatalysts is a novel frontline to improve the photocatalytic performance. Therefore, we briefly summarize the current preparation methods of g-C3N4. Importantly, this review highlights recent advancements in crafting high-performance g-C3N4-based photocatalysts, focusing on strategies like elemental doping, nanostructure design, bandgap engineering, and heterostructure construction. Notably, sophisticated doping techniques have propelled hydrogen production rates to a 104-fold increase. Ingenious nanostructure designs have expanded the surface area by a factor of 26, concurrently extending the fluorescence lifetime of charge carriers by 50%. Moreover, the strategic assembly of heterojunctions has not only elevated charge carrier separation efficiency but also preserved formidable redox properties, culminating in a dramatic hundredfold surge in hydrogen generation performance. This work provides a reliable and brief overview of the controlled modification engineering of g-C3N4-based photocatalyst systems, paving the way for more efficient hydrogen production.
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Grafito , Hidrógeno , Compuestos de Nitrógeno , Procesos Fotoquímicos , Hidrógeno/química , Catálisis , Grafito/química , Compuestos de Nitrógeno/química , Luz , Nanoestructuras/químicaRESUMEN
Plastic waste poses a critical environmental challenge for the world. The proliferation of waste plastic coffee pods exacerbates this issue. Traditional disposal methods such as incineration and landfills are environmentally unfriendly, necessitating the exploration of alternative management strategies. One promising avenue is the pyrolysis in-line reforming process, which converts plastic waste into hydrogen. However, traditional pyrolysis methods are costly due to inefficiencies and heat losses. To address this, for the first time, our study investigates the use of microwave to enhance the pyrolysis process. We explored microwave pyrolysis for polypropylene (PP), high-density polypropylene (HDPE), and waste coffee pods, with the latter primarily comprising polypropylene. Additionally, catalytic ex-situ pyrolysis of coffee pod pyrolysis over a nickel-based catalyst was investigated to convert the evolved gas into hydrogen. The single-stage microwave pyrolysis results revealed the highest gas yield at 500 °C for HDPE, and 41 % and 58 % (by mass) for waste coffee pods and polypropylene at 700 °C, respectively. Polypropylene exhibited the highest gaseous yield, suggesting its readiness for pyrolytic degradation. Waste coffee pods uniquely produced carbon dioxide and carbon monoxide gases because of the oxygen present in their structure. Catalytic reforming of evolved gas from waste coffee pods using a 5 % nickel loaded activated carbon catalyst, yielded 76 % (by volume) hydrogen at 900 °C. These observed results were supported by elemental balance analysis. These findings highlight that two-stage microwave and catalysis assisted pyrolysis could be a promising method for the efficient management of waste coffee pods, particularly for producing clean energy.
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Café , Hidrógeno , Microondas , Polietileno , Polipropilenos , Pirólisis , Polipropilenos/química , Hidrógeno/química , Café/química , Catálisis , Polietileno/química , Eliminación de Residuos/métodosRESUMEN
This work is primarily focused on overcoming the limitations of polymeric membranes in achieving the balance between permeability and selectivity of the separation performance. The filler, Zeolitic imidazole framework -67 (ZIF-67) nanoparticles were synthesised in cubical morphology using hexadecyltrimethylammonium bromide (CTAB) as a surfactant via the wet-chemical method. The uniform particles with particle sizes ranging between 120-180 nm were incorporated into the polyvinylidene fluoride (PVDF) matrix to fabricate mixed matrix membranes via the phase inversion method. These mixed matrix membranes were systematically characterised to confirm the chemical, structural and morphological properties of the materials and membranes. Furthermore, the membranes showed a 56.5% improvement in their mechanical properties. The results confirm that 5 wt.% ZIF-67/PVDF membrane showed the best separation results compared to its pure counterpart. The permeability of H2 gas was reported to be 1,094,511 Barrer, with selectivities of 3.03 for H2/CO2 and 3.06 for H2/N2. This represents a 210.6% increase in the permeability of H2 gas. These results demonstrate the influence of ZIF-67 loading in the PVDF polymer matrix along with the potential of ZIF-67/PVDF mixed matrix membranes in the field of hydrogen separation and purification.
Asunto(s)
Hidrógeno , Membranas Artificiales , Polivinilos , Zeolitas , Polivinilos/química , Zeolitas/química , Hidrógeno/química , Permeabilidad , Polímeros/química , Imidazoles/química , Polímeros de FluorocarbonoRESUMEN
Photocatalytic degradation of pollutants coupled with hydrogen (H2) evolution has emerged as a promising solution for environmental and energy crises. However, the fast recombination of photoexcited electrons and holes limits photocatalytic activities. Herein, an S-scheme heterojunction carbon doped-TiO2/ZnIn2S4 (C-TiO2/ZnIn2S4) was designed by substituting oxygen sites within C-TiO2 by ZnIn2S4. Under visible light irradiation, the optimal C-TiO2/ZnIn2S4 exhibits a higher degradation efficiency (88.6%) of microcystin-LR (MC-LR), compared to pristine C-TiO2 (72.9%) and ZnIn2S4 (66.8%). Furthermore, the H2 yield of the C-TiO2/ZnIn2S4 reaches 1526.9 µmol g-1 h-1, which is 3.83 times and 2.87 times that of the C-TiO2 and ZnIn2S4, respectively. Experimental and theoretical investigations reveal that an internal electric field (IEF) informed in the C-TiO2/ZnIn2S4 heterojunction, accelerates the separation of photogenerated charge pairs, thereby enhancing photocatalytic efficiency of MC-LR degradation and H2 production. This work highlights a new perspective on the development of high-performance photocatalysts for wastewater treatment and H2 generation.
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Carbono , Hidrógeno , Toxinas Marinas , Microcistinas , Titanio , Microcistinas/química , Titanio/química , Toxinas Marinas/química , Catálisis , Hidrógeno/química , Carbono/química , Fotólisis , Contaminantes Químicos del Agua/química , Aguas Residuales/química , Luz , Procesos Fotoquímicos , Zinc/químicaRESUMEN
The escalating levels of plastic waste and energy crises underscore the urgent need for effective waste-to-energy strategies. This study focused on converting polypropylene wastes into high-value products employing various iron-based catalysts and microwave radiative thermal processing. The Al-Fe catalysts exhibited exceptional performance, achieving a hydrogen utilization efficiency of 97.65% and a yield of 44.07 mmol/g PP. The gas yields increased from 19.99 to 94.21 wt % compared to noncatalytic experiments. Furthermore, this catalytic system produced high-value bamboo-shaped carbon nanotubes that were absent in other catalysts. The mechanism analysis on catalytic properties and product yields highlighted the significance of oxygen vacancies in selecting high-value products through two adsorption pathways. Moreover, the investigation examined the variations in product distribution mechanisms between conventional and microwave pyrolysis, in which microwave conditions resulted in 4 times higher hydrogen yields. The technoeconomic assessment and Monte Carlo risk analysis further compared the disparity. The microwave technique had a remarkable internal rate of return (IRR) of 39%, leading to an income of $577/t of plastic with a short payback period of 2.5 years. This research offered sustainable solutions for the plastic crisis, validating the potential applicability of commercializing the research outcomes in real-world scenarios.
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Hidrógeno , Microondas , Nanotubos de Carbono , Plásticos , Nanotubos de Carbono/química , Hidrógeno/química , CatálisisRESUMEN
Low concentrations of nitrate (NO3-) widely exist in wastewater, post-treated wastewater, and natural environments; its further disposal is a challenge but meaningful for its discharge goals. Electroreduction of NO3- is a promising method that allows to eliminate NO3- and even generate higher-value NH3. However, the massive side reaction of hydrogen evolution has raised great obstacles in the electroreduction of low concentrations of NO3-. Herein, we present an efficient electroreduction method for low or even ultralow concentrations of NO3- via NO3- self-enrichment and active hydrogen (H*) inducement on the Ce(IV)-Co3O4 cathode. The key mechanism is that the strong oxytropism of Ce(IV) in Co3O4 resulted in two changes in structures, including loose nanoporous structures with copious dual adsorption sites of Ce-Co showing strong self-enrichment of NO3- and abundant oxygen vacancies (Ovs) inducing substantial H*. Ultimately, the bifunctional role synergistically promoted the selective conversion of NH3 rather than H2. As a result, Ce(IV)-Co3O4 demonstrated a NO3- self-enrichment with a 4.3-fold up-adsorption, a 7.5-fold enhancement of NH3 Faradic efficiency, and a 93.1% diminution of energy consumption when compared to Co3O4, substantially exceeding other reported electroreduction cathodes for NO3- concentrations lower than 100 mg·L-1. This work provides an effective treatment method for low or even ultralow concentrations of NO3-.
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Electrodos , Nitratos , Nitratos/química , Hidrógeno/química , Cerio/químicaRESUMEN
Partial least squares (PLS) regression is a valuable chemometric tool for property prediction when coupled with gas chromatography (GC). Since the separation run time and stationary phase selection are crucial for effective PLS modeling, we study these GC parameters on the prediction of viscosity, density and hydrogen content for 50 aerospace fuels. Due to the diversity of compounds in the fuels (primarily alkanes, cycloalkanes, and aromatics), we explore both polar and non-polar stationary phase columns. The robustness for the PLS models was evaluated by their normalized root mean square error of cross-validation (NRMSECV). PLS models built for viscosity across 1-min, 3-min, 7-min, and 10-min time window (TW) high-speed GC separations produced nearly the same NRMSECV with the polar column data with an average (standard deviation) of 4.41 % (0.34 %) versus the non-polar column data of 4.69 % (0.15 %). In contrast, while the NRMSECV of density modeling with the polar column data varied more than the viscosity models, averaging 7.54 % (0.67 %), the non-polar column data produced a significantly higher average NRMSECV of 10.06 % (0.35 %). Similarly, for hydrogen content, the NRMSECV with the polar column data averaged 9.50 % (0.87 %), which was significantly lower than the NRMSECV with the non-polar column data averaging 12.10 % (0.88 %). We also investigated the impact of smoothing the GC data on the corresponding PLS models. By applying varying degrees of smoothing, we can effectively obtain similar chromatographic peak patterns in a shorter TW. For example, a 10-min smoothed chromatogram appears like the 1-min separation with no smoothing but resulted in nearly the same NRMSECV. Overall, the fast separation with a 1-min TW produced robust PLS models for viscosity with either stationary phase column, whereas for density and hydrogen content the polar stationary phase column produced superior PLS models, thus with proper stationary phase selection, a fast separation run time could be readily applied with optimal PLS property modeling results.
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Hidrógeno , Análisis de los Mínimos Cuadrados , Cromatografía de Gases/métodos , Viscosidad , Hidrógeno/química , Hidrógeno/análisis , Modelos Químicos , Alcanos/análisis , Alcanos/químicaRESUMEN
Aluminumlithium (AlLi) alloy polishing and grinding processes in wet dust collector systems could cause hydrogen fire and explosion. From the fundamental perspective of preventing hydrogen explosions, a safe, nontoxic, and sustainable modified green hydrogen inhibitor based on chitosan (CS) and sodium alginate (SA) was developed in this study and was used as a hydrogen evolution inhibitor for the processing of waste dust from AlLi alloys. The structure and elemental distribution of the synthesized material were characterized through characterization experiments. Hydrogen evolution experiments and a hydrolysis kinetic model were used to explore the inhibitory effect of modified CS/SA on AlLi alloy dust, and the results revealed that the inhibitory concentration of the hydrogen explosion lower limit was 0.40 wt%, with an inhibition efficiency of 91.93 %, indicating an 11.88-61.44 % improvement over that of CS and SA. As the inhibitor concentration increased and the temperature decreased, the hydrogen inhibition effect increased. Characterization experiments and density functional theory showed that CS/SA primarily formed a dense physical protective barrier on the dust surface through chemical adsorption and complexation reactions, interrupting the hydrogen evolution reaction between the metal and water. This study introduces a novel green modified hydrogen inhibitor that fundamentally addresses hydrogen generation and explosion.
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Alginatos , Aleaciones , Quitosano , Hidrógeno , Quitosano/química , Hidrógeno/química , Alginatos/química , Aleaciones/química , Polvo/análisis , Biopolímeros/química , Cinética , Tecnología Química VerdeRESUMEN
Water microdroplets containing dissolved ammonia (30-300 µM) are sprayed through a copper oxide mesh with a 200 µm average pore size, resulting in the formation of nitrate (NO3-) and the release of molecular hydrogen (H2). The products result from a redox process that takes place at the liquid-solid interface through contact electrification, where no external potential is applied. Oxidation is initiated by superoxide radical anions (O2-) that originate from the oxygen in the air surrounding the microdroplets and from the hydroxyl radicals (OHâ¢) originating from the water-air interface. Two spin traps (TEMPO and DMPO) capture these radicals as well as NH2OH+â¢, HNO, NOâ¢, NO2â¢, and NOOH, which are detected by mass spectrometry. We also directly observed N2O2-⢠by the same means. We found that the hydrogen atom from the ammonia molecule can be set free not only in the form of H⢠but also as H2, which is detected using a residue gas analyzer. The oxidation process can be significantly enhanced by a factor of 3 when the sprayed microdroplets are irradiated with ultraviolet light (265 nm, 5 W). 35% of 300 µM ammonia can be degraded within 20 µs, and the nitrate conversion rate is estimated to be 15 nmol·mg-1·h-1.
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Amoníaco , Hidrógeno , Nitratos , Oxidación-Reducción , Agua , Amoníaco/química , Hidrógeno/química , Nitratos/química , Agua/químicaRESUMEN
Carbon capture and utilization (CCU) covers an array of technologies for valorizing carbon dioxide (CO2). To date, most mature CCU technology conducted with capture agents operates against the CO2 gradient to desorb CO2 from capture agents, exhibiting high energy penalties and thermal degradation due to the requirement for thermal swings. This Perspective presents a concept of Bio-Integrated Carbon Capture and Utilization (BICCU), which utilizes methanogens for integrated release and conversion of CO2 captured with capture agents. BICCU hereby substitutes the energy-intensive desorption with microbial conversion of captured CO2 by the methanogenic CO2-reduction pathway, utilizing green hydrogen to generate non-fossil methane.
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Archaea , Dióxido de Carbono , Metano , Dióxido de Carbono/metabolismo , Dióxido de Carbono/química , Metano/metabolismo , Metano/química , Archaea/metabolismo , Oxidación-Reducción , Hidrógeno/metabolismo , Hidrógeno/química , Carbono/metabolismo , Carbono/química , Secuestro de CarbonoRESUMEN
An H-bond involves the sharing of a hydrogen atom between an electronegative atom to which it is covalently bound (the donor) and another electronegative atom serving as an acceptor. Such bonds represent a critically important geometrical force in biological macromolecules and, as such, have been characterized extensively. H-bond formation invariably leads to a weakening within the acceptor moiety due to the pulling exerted by the donor hydrogen. This phenomenon can be compared to a spring connecting two masses; pulling one mass stretches the spring, similarly affecting the bond between the two masses. Herein, we describe the opposite phenomenon when investigating the energetics of the C-H···O=C bond. This bond underpins the most prevalent protein transmembrane dimerization motif (GxxxG) in which a glycine Cα-H on one helix forms a hydrogen bond with a carbonyl in a nearby helix. We use isotope-edited FT-IR spectroscopy and corroborating computational approaches to demonstrate a surprising strengthening of the acceptor C=O bond upon binding with the glycine Cα-H. We show that electronic factors associated with the Cα-H bond strengthen the C=O oscillator by increasing the s-character of the σ-bond, lowering the hyperconjugative disruption of the π-bond. In addition, a reduction of the acceptor C=O bond's polarity is observed upon the formation of the C-H···O=C bond. Our findings challenge the conventional understanding of H-bond dynamics and provide new insights into the structural stability of inter-helical protein interactions.
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Enlace de Hidrógeno , Hidrógeno/química , Espectroscopía Infrarroja por Transformada de Fourier , Glicina/química , Modelos Moleculares , TermodinámicaRESUMEN
ConspectusLife is an exergonic chemical reaction. The same was true when the very first cells emerged at life's origin. In order to live, all cells need a source of carbon, energy, and electrons to drive their overall reaction network (metabolism). In most cells, these are separate pathways. There is only one biochemical pathway that serves all three needs simultaneously: the acetyl-CoA pathway of CO2 fixation. In the acetyl-CoA pathway, electrons from H2 reduce CO2 to pyruvate for carbon supply, while methane or acetate synthesis are coupled to energy conservation as ATP. This simplicity and thermodynamic favorability prompted Georg Fuchs and Erhard Stupperich to propose in 1985 that the acetyl-CoA pathway might mark the origin of metabolism, at the same time that Steve Ragsdale and Harland Wood were uncovering catalytic roles for Fe, Co, and Ni in the enzymes of the pathway. Subsequent work has provided strong support for those proposals.In the presence of Fe, Co, and Ni in their native metallic state as catalysts, aqueous H2 and CO2 react specifically to formate, acetate, methane, and pyruvate overnight at 100 °C. These metals (and their alloys) thus replace the function of over 120 enzymes required for the conversion of H2 and CO2 to pyruvate via the pathway and its cofactors, an unprecedented set of findings in the study of biochemical evolution. The reactions require alkaline conditions, which promote hydrogen oxidation by proton removal and are naturally generated in serpentinizing (H2-producing) hydrothermal vents. Serpentinizing hydrothermal vents furthermore produce natural deposits of native Fe, Co, Ni, and their alloys. These are precisely the metals that reduce CO2 with H2 in the laboratory; they are also the metals found at the active sites of enzymes in the acetyl-CoA pathway. Iron, cobalt and nickel are relicts of the environments in which metabolism arose, environments that still harbor ancient methane- and acetate-producing autotrophs today. This convergence indicates bedrock-level antiquity for the acetyl-CoA pathway. In acetogens and methanogens growing on H2 as reductant, the acetyl-CoA pathway requires flavin-based electron bifurcation as a source of reduced ferredoxin (a 4Fe4S cluster-containing protein) in order to function. Recent findings show that H2 can reduce the 4Fe4S clusters of ferredoxin in the presence of native iron, uncovering an evolutionary precursor of flavin-based electron bifurcation and suggesting an origin of FeS-dependent electron transfer in proteins. Traditionally discussed as catalysts in early evolution, the most common function of FeS clusters in metabolism is one-electron transfer, also in radical SAM enzymes, a large and ancient enzyme family. The cofactors and active sites in enzymes of the acetyl-CoA pathway uncover chemical antiquity in metabolism involving metals, methyl groups, methyl transfer reactions, cobamides, pterins, GTP, S-adenosylmethionine, radical SAM enzymes, and carbon-metal bonds. The reaction sequence from H2 and CO2 to pyruvate on naturally deposited native metals is maximally simple. It requires neither nitrogen, sulfur, phosphorus, RNA, ion gradients, nor light. Solid-state metal catalysts tether the origin of metabolism to a H2-producing, serpentinizing hydrothermal vent.
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Acetilcoenzima A , Acetilcoenzima A/metabolismo , Acetilcoenzima A/química , Metano/química , Metano/metabolismo , Dióxido de Carbono/metabolismo , Dióxido de Carbono/química , Hidrógeno/química , Hidrógeno/metabolismo , TermodinámicaRESUMEN
Various applications related to glucose catalysis have led to the development of functional nanozymes with glucose oxidase (GOX)-like activity. However, the unsatisfactory catalytic activity of nanozymes is a major challenge for their practical applications due to their inefficient hydrogen and electron transfer. Herein, we present the synthesis of AuFe/polydopamine (PDA) superparticles that exhibit photothermal-enhanced GOX-like activity. Experimental investigations and theoretical calculations reveal that the glucose oxidation process catalyzed by AuFe/PDA follows an artificial-cofactor-mediated hydrogen atom transfer mechanism, which facilitates the generation of carbon-centered radical intermediates. Rather than depending on charged Au surfaces for thermodynamically unstable hydride transfer, Fe(III)-coordinated PDA with abundant amino and phenolic hydroxyl groups serves as cofactor mimics, facilitating both hydrogen atom and electron transfer in the catalytic process. Finally, leveraging the photothermal-enhanced GOX-like and catalase-like activities of AuFe/PDA, we establish a highly sensitive and accurate point-of-care testing blood glucose determination with exceptional anti-jamming capabilities.
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Glucosa Oxidasa , Oro , Hidrógeno , Indoles , Polímeros , Glucosa Oxidasa/química , Glucosa Oxidasa/metabolismo , Oro/química , Hidrógeno/química , Transporte de Electrón , Indoles/química , Polímeros/química , Glucosa/química , Catálisis , Oxidación-Reducción , Glucemia/análisis , Hierro/química , HumanosRESUMEN
Water splitting has emerged as a promising route for sustainable hydrogen production. In this research paper, adsorption and dissociation of H2O accompanied with dissociated constituents reactions with CO2 and CO have been investigated on Fe modified Cu(100) surface employing density functional theory (DFT) at GGA-PW91 level. The adsorption and other reactions carried out on Fe2-Cu(100) surfaces gave very promising results. The adsorption of H2O on Fe top of this surface occurs yielding Eads -1.73 eV, which highlights a favorable adsorption on the Fe-modified Cu(100) surface. The activation energy for the water splitting reaction is found to be 0.65 eV, suggesting a feasible pathway for hydrogen evolution. The process also accompanies reaction energy of -0.54 eV. Furthermore, the interaction between carbon dioxide (CO2) and the H-atom on the surface lead to the formation of COOH through surmounting an activation barrier of 1.09 eV. The final position of COOH gets further stabilization having exothermicity of -0.43 eV. Another route for COOH formation from CO + OH operates on the Cu(100) part of the surface with a small activation barrier of 0.14 eV through exothermic process of -0.29 eV, however, diffusion of CO and OH from Fe to Cu is energetically expensive. This study signifies the consumption of CO and CO2 in addition to water splitting giving birth to useful products.
Asunto(s)
Dióxido de Carbono , Cobre , Teoría Funcional de la Densidad , Hierro , Propiedades de Superficie , Agua , Agua/química , Cobre/química , Hierro/química , Adsorción , Dióxido de Carbono/química , Modelos Moleculares , Termodinámica , Monóxido de Carbono/química , Hidrógeno/químicaRESUMEN
3-chloro-4-fluoraniline (FCA) is an important intermediate for the synthesis of antibiotics, herbicides and insecticides, and has significant environmental health hazards. Catalytic hydrogenation technology is widely used in pretreatment of halogenated organics due to its simple process and excellent performance. However, compared with the research of high activity hydrogenation catalyst, the research of efficient utilization of hydrogen source under mild conditions is not sufficient. In this work, micro-nano H2 bubbles are produced in situ by electrolytic water and active metal replacement, and their apparent properties are studied. The result show that the H2 bubbles have a size distribution in the range of 150-900 nm, which can rapidly reduce the REDOX potential of the water and maintain it in a hydrogen-rich state for a long time. Under the action of Pd/C catalyst, atomic hydrogen (Hâ¢) produced by dissociative adsorption can sequentially hydrogenate FCA to aniline. The H⢠utilization ratios of the above two hydrogen supply pathways reach 6.20% and 4.94% respectively, and H2 consumption is reduced by tens of times (≥50 â ≈1.0 mL/min). The research provides technical support for the efficient removal of halogenated refractory pollutants in water and the development of hydrogen economy.