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1.
Proc Natl Acad Sci U S A ; 120(11): e2218987120, 2023 Mar 14.
Artículo en Inglés | MEDLINE | ID: mdl-36877842

RESUMEN

Selective electroreduction of carbon dioxide (CO2RR) into ethanol at an industrially relevant current density is highly desired. However, it is challenging because the competing ethylene production pathway is generally more thermodynamically favored. Herein, we achieve a selective and productive ethanol production over a porous CuO catalyst that presents a high ethanol Faradaic efficiency (FE) of 44.1 ± 1.0% and an ethanol-to-ethylene ratio of 1.2 at a large ethanol partial current density of 501.0 ± 15.0 mA cm-2, in addition to an extraordinary FE of 90.6 ± 3.4% for multicarbon products. Intriguingly, we found a volcano-shaped relationship between ethanol selectivity and nanocavity size of porous CuO catalyst in the range of 0 to 20 nm. Mechanistic studies indicate that the increased coverage of surface-bounded hydroxyl species (*OH) associated with the nanocavity size-dependent confinement effect contributes to the remarkable ethanol selectivity, which preferentially favors the *CHCOH hydrogenation to *CHCHOH (ethanol pathway) via yielding the noncovalent interaction. Our findings provide insights in favoring the ethanol formation pathway, which paves the path toward rational design of ethanol-oriented catalysts.

2.
J Am Chem Soc ; 146(11): 7575-7583, 2024 Mar 20.
Artículo en Inglés | MEDLINE | ID: mdl-38466222

RESUMEN

Electrocatalytic reactions taking place at the electrified electrode-electrolyte interface involve processes of proton-coupled electron transfer. Interfacial protons are delivered to the electrode surface via a H2O-dominated hydrogen-bond network. Less efforts are made to regulate the interfacial proton transfer from the perspective of interfacial hydrogen-bond network. Here, we present quaternary ammonium salt cationic surfactants as electrolyte additives for enhancing the H2O2 selectivity of the oxygen reduction reaction (ORR). Through in situ vibrational spectroscopy and molecular dynamics calculation, it is revealed that the surfactants are irreversibly adsorbed on the electrode surface in response to a given bias potential range, leading to the weakening of the interfacial hydrogen-bond network. This decreases interfacial proton transfer kinetics, particularly at high bias potentials, thus suppressing the 4-electron ORR pathway and achieving a highly selective 2-electron pathway toward H2O2. These results highlight the opportunity for steering H2O-involved electrochemical reactions via modulating the interfacial hydrogen-bond network.

3.
Small ; 20(7): e2305396, 2024 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-37797184

RESUMEN

Efficient manufacture of electroactive vertically-oriented nanosheets with enhanced electrolyte mass diffusion and strong interfacial redox dynamics is critical for realizing high energy density of miniature supercapacitor (SC), but still challenging. Herein, microfluidic droplet printing is developed to controllably construct vertically-oriented graphene/ZIF-67 hetero-microsphere (VAGS/ZIF-67), where the ZIF-67 is coordinately grown on vertically-oriented graphene framework via Co─O─C bonds. The VAGS/ZIF-67 shows ordered porous channel, high electroactivity and strong interfacial interaction, providing rapid electrolyte diffusion dynamics and high faradaic capacitance in KOH solution (1674 F g-1 , 1004 C g-1 ), which are verified by computational fluid dynamics (CFD) and density functional theory (DFT). Moreover, the VAGS/ZIF-67 based SC exhibits large energy density (100 Wh kg-1 ), excellent durability (10 000 cycles and high/low temperature), and robust power-supply applications in portable electronics.

4.
Small ; : e2408688, 2024 Oct 15.
Artículo en Inglés | MEDLINE | ID: mdl-39410729

RESUMEN

The electrochemical activation of inert CO2 molecules through C─C coupling reactions under ambient conditions remains a significant challenge but holds great promise for sustainable development and the reduction of CO2 emission. Lewis pairs can capture and react with CO2, offering a novel strategy for the electrosynthesis of high-value-added C2 products. Herein, an electron-beam irradiation strategy is presented for rapidly synthesizing a metal-organic framework (MOF) with well-defined Lewis pairs (i.e., Cu- Npyridinic). The synthesized MOFs exhibit a total C2 product faradic efficiency of 70.0% at -0.88 V versus RHE. In situ attenuated total reflection Fourier transform infrared and Raman spectra reveal that the electron-deficient Lewis acidic Cu sites and electron-rich Lewis basic pyridinic N sites in the ligand facilitate the targeted chemisorption, activation, and conversion of CO2 molecules. DFT calculations further elucidate the electronic interactions of key intermediates in the CO2 reduction reaction. The work not only advances Lewis pair-site MOFs as a new platform for CO2 electrochemical conversion, but also provides pioneering insights into the underlying mechanisms of electron-beam irradiated synthesis of advanced nanomaterials.

5.
Langmuir ; 40(14): 7723-7732, 2024 Apr 09.
Artículo en Inglés | MEDLINE | ID: mdl-38554094

RESUMEN

Liquid crystal emulsion is a new type of emulsion, in which the emulsifier molecules are located at the oil/water (O/W) interface and form a long-range ordered and short-range disordered lamellar liquid crystal. The lamellar liquid crystal formed by the emulsifier is similar to the skin stratum corneum lipid structure, which enables it to have a broad application prospect in the fields of cosmetics, pharmaceuticals, etc. In this work, a liquid crystal nanoemulsion was obtained by passing a liquid crystal emulsion stabilized by hydrogenated lecithin and phytosterol combination through a microfluidizer. The microstructure of the prepared liquid crystal nanoemulsion was investigated experimentally by dynamic light scattering, transmission electron microscopy, and small-angle X-ray scattering. The results have shown that the nanoemulsion inherited the liquid crystal emulsion property, namely, the long-range ordered and short-range disordered lamellar structure still existed at the oil/water interface even though they underwent extrusion, friction, and acceleration. At the same time, the underlying mechanisms of the existence of lamellar liquid crystal between the oil phase and the water phase for the nanoemulsion were explored theoretically by molecular dynamics simulations. The simulation results elucidated that the hydrogenated lecithin and phytosterol combination improved the flexibility of the bilayer structure composed of emulsifiers. The bilayers were the basic structure units of lamellar liquid crystals, and thus, the improved flexibility of bilayers provided insurance for the existence of lamellar liquid crystals with larger curvature around the oil droplets. In addition, the applicable properties of liquid crystal nanoemulsion were studied, and the results have shown that the liquid crystal nanoemulsion presented better slow-release and moisturizing properties than traditional nanoemulsions due to the existence of multilayers between oil and water phases. This work not only provides necessary information for the development and effective application of liquid crystal emulsions but also is helpful for in-depth understanding the inner properties of lamellar liquid crystal at molecular level.

6.
Langmuir ; 2024 Oct 16.
Artículo en Inglés | MEDLINE | ID: mdl-39415458

RESUMEN

Surfactants, which are widely used in skin care products and cleansers, can cause skin irritation. The skin irritation potential of surfactants is fundamentally determined by their molecular structure and is directly related to their microscopic aggregation structure and specific interactions with the skin. The microscopic origin of the irritation of the surfactants remains unknown. In this work, irritation properties of four surfactant solutions were measured, and their microscopic aggregation behavior was systematically analyzed. The results indicate that the surfactants self-assembled in aqueous solution to form aggregates with different morphologies, where the head groups of surfactants were closer to each other. Furthermore, surfactants that can form larger and more stable aggregate structures in aqueous solutions will exhibit less irritation. These findings hold significant implications for the design and expanded applications of mild surfactants.

7.
Langmuir ; 40(1): 594-603, 2024 01 09.
Artículo en Inglés | MEDLINE | ID: mdl-38115608

RESUMEN

The application of alcohols as permeation enhancers in pharmaceutical and cosmetic formulations has attracted considerable attention, owing to their skin permeation-enhancing effect. Nonetheless, the elucidation of the fundamental mechanisms underlying the skin permeation-enhancing effect remains elusive. In this study, molecular dynamics (MD) simulations were employed to investigate the effect of 1,2-propanediol (1,2-PDO), 1,2-butanediol (1,2-BDO), and ethanol (EtOH) on the stratum corneum (SC) model membrane. The results showed that the effect of alcohols on the SC model membrane displayed a concentration-dependent nature. The alcohols can interact with SC lipids and exhibit a remarkable ability to selectively extract free fatty acid (FFA) molecules from the SC model membrane and make the SC looser. Meanwhile, 1,2-BDO and EtOH can penetrate into SC lipid bilayers at higher concentrations, leading to the formation of continuous hydrophilic defects in SC. The FFA extraction and the formation of continuous hydrophilic defects induced ceramide (CER) tail chains to become more disordered and fluid and also weakened the hydrogen bonding (H-bonding) network among SC lipids. Both the FFA extraction and the continuous hydrophilic defect formation endowed alcohols with the permeation-enhancing effect. The constrained simulations revealed that the free energy barriers decreased for the permeation of the hydrophilic model molecule (COL) across the SC model membranes containing alcohols, particularly for 1,2-BDO and EtOH. The possible permeation-enhancing mechanisms of alcohols were proposed correspondingly. This work not only provided a deep understanding of the transdermal permeation-enhancing behavior of alcohols at the molecular level but also provided necessary reference information for designing effective transdermal drug delivery systems in applications.


Asunto(s)
Simulación de Dinámica Molecular , Piel , Permeabilidad , Administración Cutánea , Etanol , Membrana Dobles de Lípidos
8.
BMC Pediatr ; 24(1): 352, 2024 May 22.
Artículo en Inglés | MEDLINE | ID: mdl-38778342

RESUMEN

BACKGROUND: Galactosemia is an autosomal recessive disorder resulting from an enzyme defect in the galactose metabolic pathway. The most severe manifestation of classic galactosemia is caused by galactose-1-phosphate uridylyltransferase (GALT) deficiency, and this condition can be fatal during infancy if left untreated. It also may result in long-term complications in affected individuals. CASE PRESENTATION: This report describes a patient whose initial clinical symptoms were jaundice and liver dysfunction. The patient's liver and coagulation functions did not improve after multiple admissions and treatment with antibiotics, hepatoprotective and choleretic agents and blood transfusion. Genetic analysis revealed the presence of two variants in the GALT gene in the compound heterozygous state: c.377 + 2dup and c.368G > C (p.Arg123Pro). Currently, the variant locus (c.377 + 2dup) in the GALT gene has not been reported in the Human Gene Mutation Database (HGMD), while c.368G > C (p.Arg123Pro) has not been reported in the Genome Aggregation Database (GnomAD) nor the HGMD in East Asian population. We postulated that the two variants may contribute to the development of classical galactosemia. CONCLUSIONS: Applications of whole-exome sequencing to detect the two variants can improve the detection and early diagnosis of classical galactosemia and, more specifically, may identify individuals who are compound heterozygous with variants in the GALT gene. Variants in the GALT gene have a potential therapeutic significance for classical galactosemia.


Asunto(s)
Galactosemias , UTP-Hexosa-1-Fosfato Uridililtransferasa , Humanos , Galactosemias/genética , Galactosemias/diagnóstico , UTP-Hexosa-1-Fosfato Uridililtransferasa/genética , Masculino , Femenino , Mutación , Lactante
9.
Chem Soc Rev ; 52(5): 1697-1722, 2023 Mar 06.
Artículo en Inglés | MEDLINE | ID: mdl-36779328

RESUMEN

Antimicrobial photodynamic therapy (APDT) is a promising approach to fight the growing problem of antimicrobial resistance that threatens health care, food security and agriculture. APDT uses light to excite a light-activated chemical (photosensitiser), leading to the generation of reactive oxygen species (ROS). Many APDT studies confirm its efficacy in vitro and in vivo against bacteria, fungi, viruses and parasites. However, the development of the field is focused on exploring potential targets and developing new photosensitisers. The role of light, a crucial element for ROS production, has been neglected. What are the main parameters essential for effective photosensitiser activation? Does an optimal light radiant exposure exist? And finally, which light source is best? Many reports have described the promising antibacterial effects of APDT in vitro, however, its application in vivo, especially in clinical settings remains very limited. The restricted availability may partially be due to a lack of standard conditions or protocols, arising from the diversity of selected photosensitising agents (PS), variable testing conditions including light sources used for PS activation and methods of measuring anti-bacterial activity and their effectiveness in treating bacterial infections. We thus sought to systematically review and examine the evidence from existing studies on APDT associated with the light source used. We show how the reduction of pathogens depends on the light source applied, radiant exposure and irradiance of light used, and type of pathogen, and so critically appraise the current state of development of APDT and areas to be addressed in future studies. We anticipate that further standardisation of the experimental conditions will help the field advance, and suggest key optical and biological parameters that should be reported in all APDT studies. More in vivo and clinical studies are needed and are expected to be facilitated by advances in light sources, leading to APDT becoming a sustainable, alternative therapeutic option for bacterial and other microbial infections in the future.


Asunto(s)
Antiinfecciosos , Fotoquimioterapia , Especies Reactivas de Oxígeno , Fotoquimioterapia/métodos , Antiinfecciosos/farmacología , Antiinfecciosos/uso terapéutico , Fármacos Fotosensibilizantes/farmacología , Fármacos Fotosensibilizantes/uso terapéutico , Antibacterianos/farmacología , Antibacterianos/uso terapéutico , Bacterias
10.
Nano Lett ; 23(5): 1645-1651, 2023 Mar 08.
Artículo en Inglés | MEDLINE | ID: mdl-36795963

RESUMEN

The assembly of polyoxometalate (POM) metal-oxygen clusters into ordered nanostructures is attracting a growing interest for catalytic and sensing applications. However, assembly of ordered nanostructured POMs from solution can be impaired by aggregation, and the structural diversity is poorly understood. Here, we present a time-resolved small-angle X-ray scattering (SAXS) study of the co-assembly in aqueous solutions of amphiphilic organo-functionalized Wells-Dawson-type POMs with a Pluronic block copolymer over a wide concentration range in levitating droplets. SAXS analysis revealed the formation and subsequent transformation with increasing concentration of large vesicles, a lamellar phase, a mixture of two cubic phases that evolved into one dominating cubic phase, and eventually a hexagonal phase formed at concentrations above 110 mM. The structural versatility of co-assembled amphiphilic POMs and Pluronic block copolymers was supported by dissipative particle dynamics simulations and cryo-TEM.

11.
Angew Chem Int Ed Engl ; : e202418447, 2024 Oct 18.
Artículo en Inglés | MEDLINE | ID: mdl-39422288

RESUMEN

Structure and properties of the electrode/electrolyte interface significantly influence the electrochemical processes of energy storage and conversion, yet the challenge lies in accurate description of both molecular characteristics and external field effects. Here, we develop a mesoscopic thermodynamic model that calculates the thermodynamic properties of electrolytes based on chemical potential, and its efficiency is enhanced by a deep neutral network. The deep neutral network enhanced mesoscopic thermodynamic (DeepMT) model effectively bridges the gap between micro-level characteristics of ions and macro-level effects of external field, enabling precise presentation of ion density distributions over complex conditions. Our result indicates that the DeepMT model not only demonstrates a computational efficiency improvement of approximately four orders of magnitude over direct theoretical calculations, but also accurately predicts interface properties including ion adsorption, surface charge, and differential capacitance through the statistical analysis of density distributions.

12.
J Am Chem Soc ; 145(11): 6516-6525, 2023 Mar 22.
Artículo en Inglés | MEDLINE | ID: mdl-36913524

RESUMEN

Electrochemical alkynol semi-hydrogenation has emerged as a sustainable and environmentally benign route for the production of high-value alkenols, featuring water as the hydrogen source instead of H2. It is highly challenging to design the electrode-electrolyte interface with efficient electrocatalysts and their matched electrolytes to break the selectivity-activity stereotype. Here, boron-doped Pd catalysts (PdB) and surfactant-modified interface are proposed to enable the simultaneous increase in alkenol selectivity and alkynol conversion. Typically, compared to pure Pd and commercial Pd/C catalysts, the PdB catalyst achieves both higher turnover frequency (139.8 h-1) and specific selectivity (above 90%) for the semi-hydrogenation of 2-methyl-3-butyn-2-ol (MBY). Quaternary ammonium cationic surfactants that are employed as electrolyte additives are assembled at the electrified interface in response to applied bias potential, establishing an interfacial microenvironment that can facilitate alkynol transfer and hinder water transfer suitably. Eventually the hydrogen evolution reaction is inhibited and alkynol semi-hydrogenation is promoted, without inducing the decrease of alkenol selectivity. This work offers a distinct perspective on creating a suitable electrode-electrolyte interface for electrosynthesis.

13.
Phys Rev Lett ; 131(11): 118201, 2023 Sep 15.
Artículo en Inglés | MEDLINE | ID: mdl-37774307

RESUMEN

Using classical density functional theory, we investigate the influence of solvent on the structure and ionic screening of electrolytes under slit confinement and in contact with a reservoir. We consider a symmetric electrolyte with implicit and explicit solvent models and find that spatially resolving solvent molecules is essential for the ion structure at confining walls, excess ion adsorption, and the pressure exerted on the walls. Despite this, we observe only moderate differences in the period of oscillations of the pressure with the slit width and virtually coinciding decay lengths as functions of the scaling variable σ_{ion}/λ_{D}, where σ_{ion} is the ion diameter and λ_{D} the Debye length. Moreover, in the electrostatic-dominated regime, this scaling behavior is practically independent of the relative permittivity and its dependence on the ion concentration. In contrast, the crossover to the hard-core-dominated regime depends sensitively on all three factors.

14.
Faraday Discuss ; 246(0): 520-539, 2023 Oct 12.
Artículo en Inglés | MEDLINE | ID: mdl-37602784

RESUMEN

Screening of electrostatic interactions in room-temperature ionic liquids and concentrated electrolytes has recently attracted much attention as surface force balance experiments have suggested the emergence of unanticipated anomalously large screening lengths at high ion concentrations. Termed underscreening, this effect was ascribed to the bulk properties of concentrated ionic systems. However, underscreening under experimentally relevant conditions is not predicted by classical theories and challenges our understanding of electrostatic correlations. Despite the enormous effort in performing large-scale simulations and new theoretical investigations, the origin of the anomalously long-range screening length remains elusive. This contribution briefly summarises the experimental, analytical and simulation results on ionic screening and the scaling behaviour of screening lengths. We then present an atomistic simulation approach that accounts for the solvent and ion exchange with a reservoir. We find that classical density functional theory (DFT) for concentrated electrolytes under confinement reproduces ion adsorption at charged interfaces surprisingly well. With DFT, we study confined electrolytes using implicit and explicit solvent models and the dependence on the solvent's dielectric properties. Our results demonstrate how the absence vs. presence of solvent particles and their discrete nature affect the short and long-range screening in concentrated ionic systems.

15.
Inorg Chem ; 62(43): 17678-17690, 2023 Oct 30.
Artículo en Inglés | MEDLINE | ID: mdl-37856236

RESUMEN

Regulating the chemical/thermal stability and catalytic activity of coordination polymers (CPs) to achieve high catalytic performance is topical and challenging. The CPs are competent in promoting oxidative cross-coupling, yet they have not received substantial attention. Here, the ligand effect of the secondary ligand of CPs for oxidative cross-coupling reactions was investigated. Specifically, four new isostructural CPs [Co(Fbtx)1.5(4-R-1,2-BDC)]n (denoted as Co-CP-R, Fbtx = 1,4-bis(1,2,4-triazole-1-ylmethyl)-2,3,5,6-tetrafluorobenzene, 4-R-1,2-BDC = 4-R-1,2-benzenedicarboxylate, R = F, Cl, Br, CF3) were prepared. It was found that in the reactions of oxidative amination of benzoxazoles with secondary amines and the oxidative coupling of styrenes with benzaldehydes, both the chemical and thermal stabilities of the four Co-CPs with the R group followed the trend of -CF3 > -Br > -Cl > -F. Density functional theory (DFT) calculations suggested that the difference in reactivity may be ascribed to the effect of substituent groups on the electron transition energy of the cobalt(II) center of these Co-CPs. These findings highlight the secondary ligand effect in regulating the stability and catalytic performance of coordination networks.

16.
J Chem Inf Model ; 63(20): 6423-6435, 2023 10 23.
Artículo en Inglés | MEDLINE | ID: mdl-37782627

RESUMEN

A major cause of prion infectivity is the early formation of small, fibril-like aggregates consisting of the heptapeptide GNNQQNY. The prion aggregates exhibit a unique stacking mode in which the hydrophobic tyrosine (Y) is exposed outward, forming a bilayer ß-sheet-stacking zipper structure. This stacking mode of the prion peptides, termed "Y-outward" structure for convenience, goes against the common understanding that, for other amyloid-forming peptides, the hydrophobic residues should be hidden within the peptide fibril, referred to as "Y-inward" structure. To explore the extraordinary stacking behaviors of the prion GNNQQNY peptides, two fibril models are constructed in a fashion of "Y-outward" and "Y-inward" stackings and then studied in silico to examine their thermodynamic stabilities and disaggregation pathways. The "Y-inward" structure indeed exhibits stronger thermodynamic stability than the "Y-outward" structure, according to potential energy and stacking energy calculations. To show how the peptide fibrils dissociate, we illustrated two disaggregation pathways. A dihedral-based free energy landscape was then calculated to examine the conformational degrees of freedom of the GNNQQNY chains in the "Y-outward" and "Y-inward" structures. Peptide chains lose more configurational entropy in the "Y-inward" structure than in the "Y-outward" structure, indicating that the prion peptides are prone to aggregate in a fashion of "Y-outward" stacking pattern due to its low conformational constraints. The prion-like aggregation of the GNNQQNY peptides into amyloid fibrils is primarily governed by the configuration entropy.


Asunto(s)
Nanofibras , Priones , Priones/química , Entropía , Estructura Secundaria de Proteína , Péptidos/química , Amiloide/química , Proteínas Amiloidogénicas
17.
Acta Pharmacol Sin ; 44(10): 2004-2018, 2023 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-37225844

RESUMEN

Doxorubicin is a common chemotherapeutic agent in clinic, but myocardial toxicity limits its use. Fibroblast growth factor (FGF) 10, a multifunctional paracrine growth factor, plays diverse roles in embryonic and postnatal heart development as well as in cardiac regeneration and repair. In this study we investigated the role of FGF10 as a potential modulator of doxorubicin-induced cardiac cytotoxicity and the underlying molecular mechanisms. Fgf10+/- mice and an inducible dominant negative FGFR2b transgenic mouse model (Rosa26rtTA; tet(O)sFgfr2b) were used to determine the effect of Fgf10 hypomorph or blocking of endogenous FGFR2b ligands activity on doxorubicin-induced myocardial injury. Acute myocardial injury was induced by a single injection of doxorubicin (25 mg/kg, i.p.). Then cardiac function was evaluated using echocardiography, and DNA damage, oxidative stress and apoptosis in cardiac tissue were assessed. We showed that doxorubicin treatment markedly decreased the expression of FGFR2b ligands including FGF10 in cardiac tissue of wild type mice, whereas Fgf10+/- mice exhibited a greater degree of oxidative stress, DNA damage and apoptosis as compared with the Fgf10+/+ control. Pre-treatment with recombinant FGF10 protein significantly attenuated doxorubicin-induced oxidative stress, DNA damage and apoptosis both in doxorubicin-treated mice and in doxorubicin-treated HL-1 cells and NRCMs. We demonstrated that FGF10 protected against doxorubicin-induced myocardial toxicity via activation of FGFR2/Pleckstrin homology-like domain family A member 1 (PHLDA1)/Akt axis. Overall, our results unveil a potent protective effect of FGF10 against doxorubicin-induced myocardial injury and identify FGFR2b/PHLDA1/Akt axis as a potential therapeutic target for patients receiving doxorubicin treatment.


Asunto(s)
Factor 10 de Crecimiento de Fibroblastos , Receptor Tipo 2 de Factor de Crecimiento de Fibroblastos , Animales , Ratones , Doxorrubicina , Factor 10 de Crecimiento de Fibroblastos/metabolismo , Factores de Crecimiento de Fibroblastos/metabolismo , Ratones Transgénicos , Proteínas Proto-Oncogénicas c-akt/metabolismo , Receptor Tipo 2 de Factor de Crecimiento de Fibroblastos/metabolismo , Transducción de Señal/fisiología , Factores de Transcripción
18.
J Insect Sci ; 23(3)2023 May 01.
Artículo en Inglés | MEDLINE | ID: mdl-37294686

RESUMEN

Thrips hawaiiensis (Morgan) (Thysanoptera: Thripidae) is a sap-sucking pest that seriously damages several crops and reduces their economic value. Exposure to low concentrations of insecticides may have a sublethal effect on surviving insects. In order to provide a reference for the rational application of emamectin benzoate, its sublethal effects on the development and reproduction of T. hawaiiensis were evaluated. Pupal development time was significantly shorter in T. hawaiiensis treated with sublethal concentrations of emamectin benzoate (LC10 and LC20) than in control. Female adult longevity and female total longevity were significantly longer following LC20 treatment than in the control and LC10 treatment groups. Nevertheless, male adult longevity and male total longevity were significantly shorter in the LC10 treatment group than in the control and LC20 treatment groups. The sublethal concentration of emamectin benzoate (LC20) significantly shortened the preadult stages and the mean generation. Meanwhile, it significantly increased the finite rate of increase, intrinsic rate of increase, and net reproductive rate. The fecundity was significantly higher after LC20 treatment than after LC10 and control treatments. Compared with the control group, the LC10 and LC20 groups of T. hawaiiensis adults showed a significantly higher expression of the vitellogenin (Vg) and vitellogenin receptor (VgR) genes, which played a key role in increasing their fecundity. These findings suggest that short-term exposure to sublethal concentrations of emamectin benzoate may lead to a resurgence and secondary outbreak of T. hawaiiensis infestation. The results have practical applications for the management of this important and noxious pest.


Asunto(s)
Insecticidas , Thysanoptera , Femenino , Masculino , Animales , Thysanoptera/genética , Vitelogeninas/genética , Reproducción , Insecticidas/toxicidad , Expresión Génica
19.
Angew Chem Int Ed Engl ; 62(21): e202301563, 2023 May 15.
Artículo en Inglés | MEDLINE | ID: mdl-36920707

RESUMEN

Tuning the strong metal-support interaction (SMSI) in metal catalysts is a promising strategy to improve their catalytic performance. In this article, we systematically investigated the influences of different alcohol/water mixtures on the evolution of the interfacial structure of Cu/ZnO catalysts in the reduction stage. A series of in situ characterization and theoretical simulation studies were performed to elucidate the various mechanisms of alcohol induced SMSI. It was found that when methanol/water is added to H2 during the reduction pretreatment, more oxygen vacancies are formed on the ZnO support, which facilitates the dissociation of H2 O and the hydroxylation of ZnO species. Such promotion eventually favors the SMSI between Cu and ZnO and increases the catalytic activity for the methanol steam reforming reaction. In contrast, the addition of ethanol/water and 1-propanol/water during reduction leads to a physical blockage of the catalyst by alcohol molecules, poisoning the active Cu sites and limiting the migration of ZnO species.

20.
Angew Chem Int Ed Engl ; 62(2): e202215342, 2023 Jan 09.
Artículo en Inglés | MEDLINE | ID: mdl-36404275

RESUMEN

Supercapacitor represents an important electrical energy storage technology with high-power performance and superior cyclability. However, currently commercialized supercapacitors still suffer limited energy densities. Here we report an unprecedentedly respiring supercapacitor with chlorine gas iteratively re-inspires in porous carbon materials, that improves the energy density by orders of magnitude. Both electrochemical results and theoretical calculations show that porous carbon with pore size around 3 nm delivers the best chlorine evolution and adsorption performance. The respiring supercapacitor with multi-wall carbon nanotube as the cathode and NaTi2 (PO4 )3 as the anode can store specific energy of 33 Wh kg-1 with negligible capacity loss over 30 000 cycles. The energy density can be further improved to 53 Wh kg-1 by replacing NaTi2 (PO4 )3 with zinc anode. Furthermore, thanks to the extraordinary reaction kinetics of chlorine gas, this respiring supercapacitor performs an extremely high-power density of 50 000 W kg-1 .

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