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1.
J Hazard Mater ; 472: 134520, 2024 May 03.
Artigo em Inglês | MEDLINE | ID: mdl-38718512

RESUMO

Polyethylene (PE) microplastic, which is detected in various environmental media worldwide, also inevitably enters wastewater treatment plants, which may have an impact on anaerobic processes in wastewater treatment. In this work, the effect of PE microplastics on anaerobic sulfur transformation was explored. Experimental results showed that PE microplastics addition at 0.1%- 0.5% w/w promoted H2S production by 14.8%-27.4%. PE microplastics enhanced the release of soluble organic sulfur and inorganic sulfate, and promoted the bioprocesses of organosulfur compounds hydrolysis and sulfate reduction. Mechanism analysis showed that PE microplastics increased the content of electroactive components (e.g., protein and humic acids) contained in extracellular polymeric substances (EPS). In particular, PE microplastics increased the proportion and the dipole moment of α-helix, an important component involved in electron transfer contained in extracelluar protein, which provided more electron transfer sites and promoted the α-helix mediated electron transfer. These enhanced the direct electron transfer ability of EPSs, which might explain why PE microplastics facilitated the bioprocesses of organosulfur compounds hydrolysis and sulfate reduction. Correspondingly, metagenomic analysis revealed that PE microplastics increased the relative abundance of S2- producers (e.g., Desulfobacula and Desulfonema) and the relative abundance of functional genes involved in anaerobic sulfur transformation (e.g., PepD and cysD), which were beneficial to H2S production in anaerobic system.

2.
J Mol Cell Cardiol ; 191: 76-87, 2024 May 06.
Artigo em Inglês | MEDLINE | ID: mdl-38718920

RESUMO

The reactivated adult epicardium produces epicardium-derived cells (EPDCs) via epithelial-mesenchymal transition (EMT) to benefit the recovery of the heart after myocardial infarction (MI). SMARCA4 is the core catalytic subunit of the chromatin re-modeling complex, which has the potential to target some reactivated epicardial genes in MI. However, the effects of epicardial SMARCA4 on MI remain uncertain. This study found that SMARCA4 was activated over time in epicardial cells following MI, and some of activated cells belonged to downstream differentiation types of EPDCs. This study used tamoxifen to induce lineage tracing and SMARCA4 deletion from epicardial cells in Wt1-CreER;Smarca4fl/fl;Rosa26-RFP adult mice. Epicardial SMARCA4 deletion reduces the number of epicardial cells in adult mice, which was related to changes in the activation, proliferation, and apoptosis of epicardial cells. Epicardial SMARCA4 deletion reduced collagen deposition and angiogenesis in the infarcted area, exacerbated cardiac injury in MI. The exacerbation of cardiac injury was related to the inhibition of generation and differentiation of EPDCs. The alterations in EPDCs were associated with inhibited transition between E-CAD and N-CAD during the epicardial EMT, coupled with the down-regulation of WT1, SNAIL1, and PDGF signaling. In conclusion, this study suggests that Epicardial SMARCA4 plays a critical role in cardiac injury caused by MI, and its regulatory mechanism is related to epicardial EMT. Epicardial SMARCA4 holds potential as a novel molecular target for treating MI.

3.
ACS Macro Lett ; : 632-637, 2024 May 06.
Artigo em Inglês | MEDLINE | ID: mdl-38709177

RESUMO

Sulfur is a massive byproduct of the petrochemicals industry and hardly employed as a building block for porous organic polymers (POPs). Here, a new family of sulfur-bridged POPs has been prepared via a C-H insertion reaction between sulfur and polycyclic aromatic hydrocarbons. Sulfur works as a solvent, external cross-linker, and porogen simultaneously during the polymerization process. The products demonstrate high porosity and maximum surface area of 1050 m2 g-1 with abundant accessible active sites, contributing to the nanometerization of sulfur and significantly enhancing the inherent affinity between heteroatoms toward soft metal ions. Therefore, they exhibit a high absorption capacity for Au(III) of 3287 mg g-1 and excellent absorption selectivity and removal efficiency via a performance evaluation even in real electronic wastewater. This synthetic strategy to prepare high added-value functional POPs with sulfur not only sheds light on designing high-performance gold adsorption materials and emerging POPs, but also promotes a sustainable development protocol.

4.
Environ Sci Technol ; 58(18): 8043-8052, 2024 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-38648493

RESUMO

Bisphenol A (BPA), as a typical leachable additive from microplastics and one of the most productive bulk chemicals, is widely distributed in sediments, sewers, and wastewater treatment plants, where active sulfur cycling takes place. However, the effect of BPA on sulfur transformation, particularly toxic H2S production, has been previously overlooked. This work found that BPA at environmentally relevant levels (i.e., 50-200 mg/kg total suspended solids, TSS) promoted the release of soluble sulfur compounds and increased H2S gas production by 14.3-31.9%. The tryptophan-like proteins of microbe extracellular polymeric substances (EPSs) can spontaneously adsorb BPA, which is an enthalpy-driven reaction (ΔH = -513.5 kJ mol-1, ΔS = -1.60 kJ mol-1K -1, and ΔG = -19.52 kJ mol-1 at 35 °C). This binding changed the composition and structure of EPSs, which improved the direct electron transfer capacity of EPSs, thereby promoting the bioprocesses of organic sulfur hydrolysis and sulfate reduction. In addition, BPA presence enriched the functional microbes (e.g., Desulfovibrio and Desulfuromonas) responsible for organic sulfur mineralization and inorganic sulfate reduction and increased the abundance of related genes involved in ATP-binding cassette transporters and sulfur metabolism (e.g., Sat and AspB), which promoted anaerobic sulfur transformation. This work deepens our understanding of the interaction between BPA and sulfur transformation occurring in anaerobic environments.


Assuntos
Enxofre , Enxofre/metabolismo , Anaerobiose , Sulfeto de Hidrogênio/metabolismo , Fenóis/metabolismo , Compostos Benzidrílicos/metabolismo
5.
Langmuir ; 40(17): 9001-9011, 2024 Apr 30.
Artigo em Inglês | MEDLINE | ID: mdl-38627239

RESUMO

The enrichment and recovery of gold from wastewater are an alternative method to obtain this noble metal, which benefits reducing hazardous emissions from the conventional ore mining process and reserving natural gold for sustainable development. Inspired by our previous work (Lei et al., Macromol. Rapid Comm. 2022, 2200712), four families of microporous polyureas (mPPUs) with a large surface area (690 m2 g-1) and abundant heteroatom sites have been prepared via the factor-optimized solvothermal protocol. The resultant sample NPU-A starting from 1,5-naphthalene diisocyanate (NDI) and tri(4-aminophenyl) amine (TAPA) exhibits the maximum Au(III) adsorption capacity of 1300 mg g-1 and high selectivity even when the Au(III) concentration is as low as 0.1 mg L-1. This study not only demonstrates the robustness of the high-throughput synthetic strategy but also promotes the investigation of the structure-activity correlation between the mPPU chemical structure and Au(III) adsorption performance.

6.
Environ Pollut ; 346: 123564, 2024 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-38367693

RESUMO

Histone modifications maintain genomic stability and orchestrate gene expression at the chromatin level. Benzo [a]pyrene (BaP) is the ubiquitous carcinogen widely spread in the environment, but the role and regulatory mechanism of histone modification in its toxic effects remain largely undefined. In this study, we found a dose-dependent reduction of histone H3 methylations at lysine4, lysine9, lysine27, lysine36 in HBE cells treated with BaP. We observed that inhibiting H3K27 and H3K36 methylation impaired cell proliferation, whereas the loss of H3K4, H3K9, H3K27, and H3K36 methylation led to increased genomic instability and delayed DNA repair. H3K36 mutation at both H3.1 and H3.3 exhibited the most significant impacts. In addition, we found that the expression of SET domain containing 2 (SETD2), the unique methyltransferase catalyzed H3K36me3, was downregulated by BaP dose-dependently in vitro and in vivo. Knockdown of SETD2 aggravated DNA damage of BaP exposure, which was consistent with the effects of H3K36 mutation. With the aid of chromatin immunoprecipitation (ChIP) -seq and RNA-seq, we found that H3K36me3 was responsible for transcriptional regulation of genes involved in pathways related to cell survival, lung cancer, metabolism and inflammation. The enhanced enrichment of H3K36me3 in genes (CYP1A1, ALDH1A3, ACOXL, WNT5A, WNT7A, RUNX2, IL1R2) was positively correlated with their expression levels, while the reduction of H3K36me3 distribution in genes (PPARGC1A, PDE4D, GAS1, RNF19A, KSR1) were in accordance with the downregulation of gene expression. Taken together, our findings emphasize the critical roles and mechanisms of histone lysine methylation in mediating cellular homeostasis during BaP exposure.


Assuntos
Benzo(a)pireno , Histonas , Humanos , Histonas/metabolismo , Benzo(a)pireno/toxicidade , Metilação , Instabilidade Genômica , Células Epiteliais/metabolismo , Ubiquitina-Proteína Ligases/genética , Ubiquitina-Proteína Ligases/metabolismo
7.
Org Lett ; 26(9): 1775-1779, 2024 Mar 08.
Artigo em Inglês | MEDLINE | ID: mdl-38408019

RESUMO

Herein, BF3·Et2O-promoted O-insertion/spirocyclization/fluorination/ring-expansion of unsaturated amides to synthesis of spiro[benzo[b]-[1,4]dioxepine-3,5'-oxazole] skeletons in the presence of natural light and O2 (3Σg-) was reported. Air was the oxygen source of the 1O2-generation and O-insertion reaction under metal-free and mild conditions. BF3·Et2O played multiple roles, such as Lewis acid, activating reagent, and fluorine source in the reported cascade. A mechanism involving 1O2 generation/activation of double bond/O-insertion/spirocyclization/fluorination/ring expansion was supposed.

8.
ACS Appl Mater Interfaces ; 16(8): 11013-11025, 2024 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-38353218

RESUMO

Industrial robots are the main piece of equipment of intelligent manufacturing, and array-type tactile sensors are considered to be the core devices for their active sensing and understanding of the production environment. A great challenge for existing array-type tactile sensors is the wiring of sensing units in a limited area, the contradiction between a small number of sensing units and high resolution, and the deviation of the overall output pattern due to the difference in the performance of each sensing unit itself. Inspired by the human somatosensory processing hierarchy, we combine tactile sensors with artificial intelligence algorithms to simplify the sensor architecture while achieving tactile resolution capabilities far greater than the number of signal channels. The prepared 8-electrode carbon-based conductive network achieves high-precision identification of 32 regions with 97% classification accuracy assisted by a quadratic discriminant analysis algorithm. Notably, the output of the sensor remains unchanged after 13,000 cycles at 60 kPa, indicating its excellent durability performance. Moreover, the large-area skin-like continuous conductive network is simple to fabricate, cost-effective, and can be easily scaled up/down depending on the application. This work may address the increasing need for simple fabrication, rapid integration, and adaptable geometry tactile sensors for use in industrial robots.

9.
ISA Trans ; 147: 511-526, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38336511

RESUMO

To address the trajectory tracking issue of upper-limb rehabilitation exoskeleton with uncertainties and external disturbances, this paper proposes a fractional-order ultra-local model-based model-free finite-time robust controller (FO-FTRC) using predefined performance sliding surface. Different from previous model-free control strategies, a novel multi-input multi-output (MIMO) fractional-order ultra-local model which is a virtual model is proposed to approximate the complex uncertain nonlinear exoskeleton dynamics in a short sliding time window. This allows the design of controller to be independent of any exoskeleton model information and reduces the difficulty of controller design. The developed robust model-free control method incorporates a fractional-order quasi-time delay estimator (FO-QTDE), unknown disturbance estimator (UDE) as well as prescribed performance sliding mode control (PPSMC). The FO-QTDE is utilized to estimate the unknown lumped uncertainties which employs short time delayed knowledge only about the control input. However, the low-pass filter is always added for FO-QTDE when disturbances change fast, which leads to unavoidable estimation error. Then, UDE is designed to further eliminate the estimation error of FO-QTDE to enhance control performance. The PPSMC is constructed to converge sliding surface to zero in a finite time. Besides, the sliding surface is always limited in performance boundaries. After that, the overall system stability and convergence analyses are demonstrated by using the Lyapunov theorem. Finally, with the comparison to other methods of α-variable adaptive model free control (α-AMFC), time-delay estimation-based continuous nonsingular fast terminal sliding mode controller (TDE-CNFTSMC), time delay estimation (TDE)-based model-free fractional-order nonsingular fast terminal sliding mode control (MFF-TSM) and fractional-order proportion-differential (PDß), the co-simulation results on 7-degree-of-freedom (DOF) iReHave upper-limb exoskeleton virtual prototype and experiment results on 2-DOF upper-limb exoskeleton are obtained to illustrate the effectiveness and superiority of the proposed FO-FTRC method.

10.
Chemistry ; 30(11): e202303505, 2024 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-38143237

RESUMO

The catalysis performance of metal nanoparticles (NPs) will be significantly deteriorated because of their spontaneous agglomeration during practical applications. Covalent-organic frameworks (COFs) materials with functional groups and well-defined channels benefit for the dispersion and anchor of metal ions and the confined growth of metal NPs, working as an ideal platform to compose catalytic systems. In this article, we report a one-pot strategy for the preparation of metal NPs loaded COFs without the need of post-modification. During the polymerization process, the pre-added metal ions were stabilized by the rapidly formed COF oligomers and hardly disturb the construction of COFs. After reduction, metal NPs are uniformly anchored on the COF matrix. Eventually, a wide spectrum of metal NPs, including Au, Pd, Pt, AuPd, CuPd, CuPt and CuPdPt, loaded COFs are successfully prepared. The versatility and metal ions anchoring mechanism are verified with four different COF matrixes. Taking AuPd NPs as example, the resultant AuPd NPs loaded COF materials can selectively decompose ammonium formate and produce hydrogen in-situ, exhibiting over 99 % conversion of hydrodechlorination for chlorobenzenes and nitro-reduction reaction for nitroaromatic compounds under ambient temperature in aqueous solution.

11.
Talanta ; 270: 125557, 2024 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-38128284

RESUMO

As the development of global population and industry civilization, the accurate and sensitive detection of intended analytes is becoming an important and great challenge in the field of environmental, medical, and public safety. Recently, electrochemical biosensors have been constructed and used in sensing fields, such as antibiotics, pesticides, specific markers of cancer, and so on. Functional materials have been designed and prepared to enhance detection performance. Among all reported materials, covalent organic frameworks (COFs) are emerging as porous crystalline materials to construct electrochemical biosensors, because COFs have many unique advantages, including large surface area, high stability, atom-level designability, and diversity, to achieve a far better sensing performance. In this comprehensive review, we not only summarize state-of-the-art electrochemical biosensors based on COFs and their hybrid materials but also highlight and discuss some typical examples in detail. We finally provide the challenge and future perspective of COFs-based electrochemical biosensors.

12.
Appl Opt ; 62(33): 8769-8779, 2023 Nov 20.
Artigo em Inglês | MEDLINE | ID: mdl-38038022

RESUMO

As the feature size of integrated circuits continues to decrease, optical proximity correction (OPC) has emerged as a crucial resolution enhancement technology for ensuring high printability in the lithography process. Recently, level set-based inverse lithography technology (ILT) has drawn considerable attention as a promising OPC solution, showcasing its powerful pattern fidelity, especially in advanced processing. However, the massive computational time consumption of ILT limits its applicability to mainly correcting partial layers and hotspot regions. Deep learning (DL) methods have shown great potential in accelerating ILT. However, the lack of domain knowledge of inverse lithography limits the ability of DL-based algorithms in process window (PW) enhancement, etc. In this paper, we propose an inverse lithography physics-informed deep neural level set (ILDLS) approach for mask optimization. This approach utilizes level set-based ILT as a layer within the DL framework and iteratively conducts mask prediction and correction to significantly enhance printability and PW in comparison with results from pure DL and ILT. With this approach, the computational efficiency is significantly improved compared with ILT. By gearing up DL with the knowledge of inverse lithography physics, ILDLS provides a new and efficient mask optimization solution.

13.
J Am Chem Soc ; 145(48): 26374-26382, 2023 Dec 06.
Artigo em Inglês | MEDLINE | ID: mdl-37992232

RESUMO

The electrochemical conversion of CO2 into multicarbon (C2) products on Cu-based catalysts is strongly affected by the surface coverage of adsorbed CO (*CO) intermediates and the subsequent C-C coupling. However, the increased *CO coverage inevitably leads to strong *CO repulsion and a reduced C-C coupling efficiency, thus resulting in suboptimal CO2-to-C2 activity and selectivity, especially at ampere-level electrolysis current densities. Herein, we developed an atomically ordered Cu9Ga4 intermetallic compound consisting of Cu square-like binding sites interspaced by catalytically inert Ga atoms. Compared to Cu(100) previously known with a high C2 selectivity, the Ga-spaced, square-like Cu sites presented an elongated Cu-Cu distance that allowed to reduce *CO repulsion and increased *CO coverage simultaneously, thus endowing more efficient C-C coupling to C2 products than Cu(100) and Cu(111). The Cu9Ga4 catalyst exhibited an outstanding CO2-to-C2 electroreduction, with a peak C2 partial current density of 1207 mA cm-2 and a corresponding Faradaic efficiency of 71%. Moreover, the Cu9Ga4 catalyst demonstrated a high-power (∼200 W) electrolysis capability with excellent electrochemical stability.

14.
J Phys Condens Matter ; 35(38)2023 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-37295439

RESUMO

γ-GeSe is a new type of layered bulk material that was recently successfully synthesized. By means of density functional theory first-principles calculations, we systematically studied the physical properties of two-dimensional (2D) few-layerγ-GeSe. It is found that few-layerγ-GeSe are semiconductors with band gaps decreasing with increasing layer number; and 2Dγ-GeSe with layer numbern⩾ 2 are ferroelectric with rather low transition barriers, consistent with the sliding ferroelectric mechanism. Particularly, spin-orbit coupling induced spin splitting is observed at the top of valence band, which can be switched by the ferroelectric reversal; furthermore, their negative piezoelectricity also enables the regulation of spin splitting by strain. Finally, excellent optical absorption was also revealed. These intriguing properties make 2D few-layerγ-GeSe promising in spintronic and optoelectric applications.

15.
Mol Nutr Food Res ; 67(11): e2200755, 2023 06.
Artigo em Inglês | MEDLINE | ID: mdl-37002873

RESUMO

SCOPE: The purpose of this research is to investigate the specific role of HSP90 paralogs in ulcerative colitis (UC), and to explore the mechanisms behind the inhibitory effects of galangin (Gal) on UC by inhibiting HSP90ß in vivo. METHODS AND RESULTS: In order to achieve this, publicly available gene expression data and molecular biology techniques are used. The results show that the expression of HSP90ß is significantly increased in the mucosal biopsies of UC patients and in the colons of colitis mice, and that there is a significant correlation between HSP90ß levels and disease severity. Then, Gal is found to bind directly to HSP90ß and downregulates the level of p-AKT, as well as the stability and oligomerization of HSP90ß, indicating Gal as an HSP90ß inhibitor. Moreover, the findings reveal that HSP90ß plays a critical role in controlling UC, and that Gal can alleviate colitis by inhibiting HSP90ß and perturbing fatty acid synthesis-mediated NLRP3 inflammasome activation. CONCLUSION: These results not only provide insight into the potential therapeutic use of Gal in the treatment of UC, but also offer new perspectives on the role of HSP90ß in this disease.


Assuntos
Colite Ulcerativa , Colite , Camundongos , Animais , Colite Ulcerativa/genética , Inflamassomos/metabolismo , Proteína 3 que Contém Domínio de Pirina da Família NLR/metabolismo , Colite/genética , Ácidos Graxos , Sulfato de Dextrana/toxicidade , Camundongos Endogâmicos C57BL
16.
ACS Appl Mater Interfaces ; 15(15): 19032-19042, 2023 Apr 19.
Artigo em Inglês | MEDLINE | ID: mdl-37026992

RESUMO

Electrochemical synthesis of ammonia is deemed as an alternative to the fossil-fuel-driven Haber-Bosch (HB) process, in which Li-mediated nitrogen reduction (LiNR) is the most promising scheme. Continuous lithium-mediated nitrogen reduction for ammonia synthesis (C-LiNR) has recently been reported in high-level journals with many foggy internal reactions. Synthesizing ammonia in a separate way may be profitable for understanding the mechanism of LiNR. Herein, an intermittent lithium-mediated nitrogen reduction for ammonia synthesis (I-LiNR) was proposed, three steps required for I-LiNR were achieved in the cathode chamber of a Li-N2 battery. Discharge, stand, and charge in the Li-N2 battery correspond to N2 lithification, protonation, and lithium regeneration, respectively. It can also realize the quasi-continuous process with practical significance because it could be carried out through identical batteries. Products such as Li3N, LiOH, and NH3 are detected experimentally, which demonstrate a definite reaction pathway. The mechanism of the Li-N2 battery, the Li-mediated synthesis of ammonia, and LiOH decomposition are explored through density functional theory calculations. The role of Li in dinitrogen activation is highlighted. It expands the range of LiOH-based Li-air batteries and may guide the study from Li-air to Li-N2; attention has been given to the reaction mechanism of Li-mediated nitrogen reduction. The challenges and opportunities of the procedure are discussed in the end.

17.
BMC Plant Biol ; 23(1): 188, 2023 Apr 10.
Artigo em Inglês | MEDLINE | ID: mdl-37032339

RESUMO

BACKGROUND: Phosphorus (P) deficiency in desert ecosystems is widespread. Generally, desert species may allocate an enormous proportion of photosynthetic carbon to their root systems to adjust their P-acquisition strategies. However, root P-acquisition strategies of deep-rooted desert species and the coordination response of root traits at different growth stages to differing soil P availability remains unclear. In this study, a two-year pot experiment was performed with four soil P-supply treatments (0, 0.9, 2.8, and 4.7 mg P kg-1 y-1 for the control, low-, intermediate-, and high-P supply, respectively). Root morphological and physiological traits of one- and two-year-old Alhagi sparsifolia seedlings were measured. RESULTS: For two-year-old seedlings, control or low-P supply significantly increased their leaf Mn concentration, coarse and fine roots' specific root length (SRL), specific root surface area (SRSA), and acid phosphatase activity (APase), but SRL and SRSA of one-year-old seedlings were higher under intermediate-P supply treatment. Root morphological traits were closely correlated with root APase activity and leaf Mn concentration. One-year-old seedlings had higher root APase activity, leaf Mn concentration, and root tissue density (RTD), but lower SRL and SRSA. Two-year-old seedlings had higher root APase activity, leaf Mn concentration, SRL and SRSA, but a lower RTD. Root APase activity was significantly positively correlated with the leaf Mn concentration, regardless of coarse or fine roots. Furthermore, root P concentrations of coarse and fine roots were driven by different root traits, with root biomass and carboxylates secretion particularly crucial root traits for the root P-acquisition of one- and two-year-old seedlings. CONCLUSIONS: Variation of root traits at different growth stages are coordinated with root P concentrations, indicating a trade-off between root traits and P-acquisition strategies. Alhagi sparsifolia developed two P-activation strategies, increasing P-mobilizing phosphatase activity and carboxylates secretion, to acclimate P-impoverished in soil. The adaptive variation of root traits at different growth stages and diversified P-activation strategies are conducive to maintaining the desert ecosystem productivity.


Assuntos
Ecossistema , Fabaceae , Fósforo , Solo , Raízes de Plantas , Plantas , Plântula , Ácidos Carboxílicos
18.
Adv Sci (Weinh) ; 10(15): e2300841, 2023 May.
Artigo em Inglês | MEDLINE | ID: mdl-36950758

RESUMO

There is an urgent need for cost-effective strategies to produce hydrogen from renewable net-zero carbon sources using renewable energies. In this context, the electrochemical hydrogen evolution reaction can be boosted by replacing the oxygen evolution reaction with the oxidation of small organic molecules, such as ethylene glycol (EG). EG is a particularly interesting organic liquid with two hydroxyl groups that can be transformed into a variety of C1 and C2 chemicals, depending on the catalyst and reaction conditions. Here, a catalyst is demonstrated for the selective EG oxidation reaction (EGOR) to formate on nickel selenide. The catalyst nanoparticle (NP) morphology and crystallographic phase are tuned to maximize its performance. The optimized NiS electrocatalyst requires just 1.395 V to drive a current density of 50 mA cm-2 in 1 m potassium hydroxide (KOH) and 1 m EG. A combination of in situ electrochemical infrared absorption spectroscopy (IRAS) to monitor the electrocatalytic process and ex situ analysis of the electrolyte composition shows the main EGOR product is formate, with a Faradaic efficiency above 80%. Additionally, C2 chemicals such as glycolate and oxalate are detected and quantified as minor products. Density functional theory (DFT) calculations of the reaction process show the glycol-to-oxalate pathway to be favored via the glycolate formation, where the CC bond is broken and further electro-oxidized to formate.

19.
J Org Chem ; 88(7): 4359-4371, 2023 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-36939669

RESUMO

Herein, hypervalent iodine-catalyzed halogenation of aryl-activated alkenes using BX3 (X = Cl, Br) as the halogen source and activating reagents was reported. Various halogenated 1,3-oxazine/2-oxazoline derivatives were obtained in good-to-high yields. Using BF3 resulted in different substitute sites from BBr3 and BCl3 of the products, indicating different reactive intermediates and reaction pathways. The reaction underwent a "ligand coupling/oxidative addition/intermolecular nucleophilic attack/1,2-aryl migration/reductive elimination/intramolecular nucleophilic attack" cascade when BF3 was applied as the halogen source, while 1,2-aryl migration has "disappeared" when the halogen source was BBr3 or BCl3. Possible catalytic cycles were proposed, and DFT calculations were conducted to demonstrate the differences among BX3 (X = F, Cl, Br) in the hypervalent iodine-catalyzed halogenations.

20.
Nano Lett ; 23(2): 685-693, 2023 Jan 25.
Artigo em Inglês | MEDLINE | ID: mdl-36594847

RESUMO

While tuning the electronic structure of Pt can thermodynamically alleviate CO poisoning in direct methanol fuel cells, the impact of interactions between intermediates on the reaction pathway is seldom studied. Herein, we contrive a PtBi model catalyst and realize a complete inhibition of the CO pathway and concurrent enhancement of the formate pathway in the alkaline methanol electrooxidation. The key role of Bi is enriching OH adsorbates (OHad) on the catalyst surface. The competitive adsorption of CO adsorbates (COad) and OHad at Pt sites, complementing the thermodynamic contribution from alloying Bi with Pt, switches the intermediate from COad to formate that circumvents CO poisoning. Hence, 8% Bi brings an approximately 6-fold increase in activity compared to pure Pt nanoparticles. This notion can be generalized to modify commercially available Pt/C catalysts by a microwave-assisted method, offering opportunities for the design and practical production of CO-tolerance electrocatalysts in an industrial setting.

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