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1.
J Am Chem Soc ; 146(8): 5232-5241, 2024 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-38350439

RESUMO

In pursuit of potent pharmaceutical candidates and to further improve their chemical traits, small ring systems can serve as a potential starting point. Small ring units have the additional merit of loaded strain at their core, making them suitable reactants as they can capitalize on this intrinsic driving force. With the introduction of cyclobutenone as a strained precursor to ketene, the photocycloaddition with another strained unit, bicyclo[1.1.0]butane (BCB), enables the reactivity of both π-units in the transient ketene. This double strain-release driven [2π+2σ]-photocycloaddition promotes the synthesis of diverse heterobicyclo[2.1.1]hexane units, a pharmaceutically relevant bioisostere. The effective reactivity under catalyst-free conditions with a high functional group tolerance defines its synthetic utility. Experimental mechanistic studies and density functional theory (DFT) calculations suggest that the [2π+2σ]-photocycloaddition takes place via a triplet mechanism.

2.
Environ Sci Technol ; 58(17): 7445-7456, 2024 Apr 30.
Artigo em Inglês | MEDLINE | ID: mdl-38622030

RESUMO

The tandem application of CO2 electrolysis with syngas fermentation holds promise for achieving heightened production rates and improved product quality. However, the significant impact of syngas composition on mixed culture-based microbial chain elongation remains unclear. Additionally, effective methods for generating syngas with an adjustable composition from acidic CO2 electrolysis are currently lacking. This study successfully demonstrated the production of medium-chain fatty acids from CO2 through tandem acidic electrolysis with syngas fermentation. CO could serve as the sole energy source or as the electron donor (when cofed with acetate) for caproate generation. Furthermore, the results of gas diffusion electrode structure engineering highlighted that the use of carbon black, either alone or in combination with graphite, enabled consistent syngas generation with an adjustable composition from acidic CO2 electrolysis (pH 1). The carbon black layer significantly improved the CO selectivity, increasing from 0% to 43.5% (0.05 M K+) and further to 92.4% (0.5 M K+). This enhancement in performance was attributed to the promotion of K+ accumulation, stabilizing catalytically active sites, rather than creating a localized alkaline environment for CO2-to-CO conversion. This research contributes to the advancement of hybrid technology for sustainable CO2 reduction and chemical production.


Assuntos
Dióxido de Carbono , Eletrólise , Ácidos Graxos , Fermentação , Dióxido de Carbono/química , Ácidos Graxos/metabolismo
3.
Appl Opt ; 63(12): 3242-3249, 2024 Apr 20.
Artigo em Inglês | MEDLINE | ID: mdl-38856473

RESUMO

Traditional long-wave infrared polarimetry usually relies on complex optical setups, making it challenging to meet the increasing demand for system miniaturization. To address this problem, we design an all-silicon broadband achromatic polarization-multiplexing metalens (BAPM) operating at the wavelength range of 9-12 µm. A machine-learning-based design method is developed to replace the tedious and computationally intensive simulation of a large number of meta-atoms. The results indicate that the coefficients of variation in focal length of the BAPM are 3.95% and 3.71%, and the average focusing efficiencies are 41.3% and 40.5% under broadband light incidence with x- and y-polarizations, respectively.

4.
J Sci Food Agric ; 104(7): 4226-4233, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38299755

RESUMO

BACKGROUND: Dried shrimp is a high-value fishery product worldwide, but rapid and accurate assessment of its quality remains challenging. In the present study, a new method based on Raman spectroscopy was developed for assessing the quality changes in dried shrimp (Parapenaeopsis hardwickii) during storage. RESULTS: A high-quality Raman spectrum of astaxanthin (AST) was obtained from the third abdominal segment of dried shrimp. The intensity ratio (I1520/I1446) of the band from 1520 cm-1 to that at 1446 cm-1, which was ascribed to AST and protein/lipid, respectively, was calculated. I1520/I1446 can probe AST degradation in dried shrimp during storage at both 37 and 4 °C and further reflect quality changes of dried shrimp, as indicated by indices including total volatile basic nitrogen, pH and thiobarbituric acid reactive substances. CONCLUSION: Compared to conventional methods, the proposed method avoids complex and time-consuming preprocessing and provides significant advantages including cost-effectiveness and rapid detection. © 2024 Society of Chemical Industry.


Assuntos
Penaeidae , Análise Espectral Raman , Animais , Alimentos Marinhos , Xantofilas/química , Penaeidae/química
5.
J Am Chem Soc ; 145(1): 260-267, 2023 01 11.
Artigo em Inglês | MEDLINE | ID: mdl-36538618

RESUMO

Persistent organic pollutants (POPs) exist widely in the environment and place significant impact on human health by bioaccumulation. Efficient recognition of POPs and their removal are highly challenging tasks because their specific structures interact often very weakly with the capture materials. Herein, a molecular nanocage (1) is studied as an efficient sensing and sorbent material for POPs, which is demonstrated by a representative and stable perfluorooctane sulfonate (PFOS) substrate containing a hydrophilic sulfonic group and a hydrophobic fluoroalkyl chain. A highly sensitive and unusual turn-on fluorescence response within 10 s and a 97% total removal of PFOS from water in 20 min have been achieved owing to the strong host-guest interactions between 1 and PFOS. The binding constant of 1 to PFOS is 2 orders of magnitude higher than state-of-the-art adsorbents for PFOS and thus represents a new benchmark material for the recognition and removal of PFOS. The host-guest interaction has been elucidated by solid-state NMR spectroscopy and single-crystal X-ray diffraction, which provide key insights at a molecular level for the design of new advanced sensing/sorbent materials for POPs.


Assuntos
Ácidos Alcanossulfônicos , Poluentes Ambientais , Fluorocarbonos , Poluentes Químicos da Água , Humanos , Poluentes Orgânicos Persistentes , Poluentes Químicos da Água/química , Adsorção , Poluentes Ambientais/química , Água , Fluorocarbonos/química , Ácidos Alcanossulfônicos/química
6.
Pharmacology ; 108(4): 394-399, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37271128

RESUMO

INTRODUCTION: The aim of the study was to investigate the role of D-cycloserine (DCS) in the adaptation process and maintenance of motion sickness (MS). METHODS: In experiment 1, 120 SD rats were used to study the promoting effect of DCS on the adaptation process of MS in rats. They were randomly divided into four groups, DCS-rotation (DCS-Rot), DCS-static, saline-rotation (Sal-Rot), and saline-static, and further divided into three subgroups according to the adaptation time (4 days, 7 days, and 10 days) in each group. After being given DCS (0.5 mg/kg) or 0.9% saline, they were rotated or kept static according to the group. Their fecal granules, total distance, and total activity of spontaneous activity were recorded and analyzed. In experiment 2, other 120 rats were used. The experimental grouping and specific experimental method were the same as experiment 1. According to the grouping of the adaptive maintenance duration, the animals of 14 days, 17 days, and 21 days groups were measured on the corresponding date of the changes in the animals' exploratory behavior. RESULTS: In experiment 1, the fecal granules, total distance, and total activity of spontaneous activity of Sal-Rot returned to the control level on 9 days, and the DCS-Rot group returned to the control level on 6 days, indicating that DCS could shorten the adaptation time of MS rats from 9 days to 6 days. In experiment 2, the Sal-Rot could not maintain the adaptive state after 14 days' absence from the seasickness environment. The fecal granules of DCS-Rot increased significantly, and total distance and total activity of spontaneous activity of DCS-Rot decreased significantly from 17 days. These illustrate that DCS can prolong the adaptive maintenance time from within 14 days to 17 days in MS rats. CONCLUSION: 0.5 mg/kg DCS injected intraperitoneally can shorten the MS adaptation process and extend the maintenance time of adaptation of SD rats.


Assuntos
Ciclosserina , Extinção Psicológica , Ratos , Animais , Ciclosserina/farmacologia , Ciclosserina/uso terapêutico , Ratos Sprague-Dawley , Comportamento Animal , Receptores de N-Metil-D-Aspartato
7.
Angew Chem Int Ed Engl ; 61(6): e202115265, 2022 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-34874598

RESUMO

A series of solid supramolecules based on acrylamide-phenylpyridium copolymers with various substituent groups (P-R: R=-CN, -CO2 Et, -Me, -CF3 ) and cucurbit[7]uril (CB[7]) are constructed to exhibit tunable second-level (from 0.9 s to 2.2 s) room-temperature phosphorescence (RTP) in the amorphous state. Compared with other solid supramolecules P-R/CB[7] (R=-CN, -CO2 Et, -Me), P-CF3 /CB[7] displays the longest lifetime (2.2 s), which is probably attributed to the fluorophilic interaction of cucurbiturils leading to a uncommon host-guest interaction between 4-phenylpyridium with -CF3 and CB[7]. Furthermore, the RTP solid supramolecular assembly (donors) can further react with organic dyes Eosin Y or SR101 (acceptors) to form ternary supramolecular systems featuring ultralong phosphorescence energy transfer (PpET) and visible delayed fluorescence (yellow for EY at 568 nm and red for SR101 at 620 nm). Significantly, the ultralong multicolor PpET supramolecular assembly can be further applied in fields of anti-counterfeiting and information encryption and painting.

8.
Phys Chem Chem Phys ; 23(43): 24579-24588, 2021 Nov 10.
Artigo em Inglês | MEDLINE | ID: mdl-34704573

RESUMO

The low photoluminescence (PL) quantum yields of transition metal dichalcogenide monolayers have been a limiting factor for their optoelectronic applications. Various and even inconsistent mechanisms have been proposed to modulate their PL efficiencies. Herein, we use PL/Raman microspectroscopy and the corresponding in situ mapping, atomic force microscopy, and field-effect transistor (FET) characterization to investigate the changes in the structural and optical properties of monolayer MoS2. Relatively low power density (<4.08 × 105 W cm-2) of laser irradiation in ambient air can cause a slight PL suppression effect on monolayer MoS2, whereas relatively high power density (∼1.02 × 106 W cm-2) of laser irradiation brings significant PL enhancement. Experiments under different atmospheres reveal that the laser-irradiation-induced enhancement only occurs in the atmosphere containing O2 and is more remarkable in pure O2. In addition, physically adsorbed water can also induce PL enhancement of monolayer MoS2. FET devices suggest that the adsorbed water produces a p-doping effect on MoS2, and the laser irradiation in ambient air generates an n-doping effect, and both types of doping can enhance the PL intensity. The island-shaped defects caused by laser irradiation can be stabilized by oxygen atoms and act as trapping centers for excited trions or electrons, thus reducing the non-radiative recombination ratio and enhancing the PL intensity. The physically adsorbed water works in a similar way. A low power density of laser irradiation can sweep away the originally adsorbed H2O on the surface, thus reducing the PL.

9.
J Med Virol ; 92(9): 1542-1548, 2020 09.
Artigo em Inglês | MEDLINE | ID: mdl-32181901

RESUMO

During an outbreak of respiratory diseases including atypical pneumonia in Wuhan, a previously unknown ß-coronavirus was detected in patients. The newly discovered coronavirus is similar to some ß-coronaviruses found in bats but different from previously known SARS-CoV and MERS-CoV. High sequence identities and similarities between 2019-nCoV and SARS-CoV were found. In this study, we searched the homologous templates of all nonstructural and structural proteins of 2019-nCoV. Among the nonstructural proteins, the leader protein (nsp1), the papain-like protease (nsp3), the nsp4, the 3C-like protease (nsp5), the nsp7, the nsp8, the nsp9, the nsp10, the RNA-directed RNA polymerase (nsp12), the helicase (nsp13), the guanine-N7 methyltransferase (nsp14), the uridylate-specific endoribonuclease (nsp15), the 2'-O-methyltransferase (nsp16), and the ORF7a protein could be built on the basis of homology templates. Among the structural proteins, the spike protein (S-protein), the envelope protein (E-protein), and the nucleocapsid protein (N-protein) can be constructed based on the crystal structures of the proteins from SARS-CoV. It is known that PL-Pro, 3CL-Pro, and RdRp are important targets for design antiviral drugs against 2019-nCoV. And S protein is a critical target candidate for inhibitor screening or vaccine design against 2019-nCoV because coronavirus replication is initiated by the binding of S protein to cell surface receptors. It is believed that these proteins should be useful for further structure-based virtual screening and related computer-aided drug development and vaccine design.


Assuntos
Betacoronavirus/genética , Biologia Computacional , Simulação de Dinâmica Molecular , SARS-CoV-2/genética , Proteínas Virais/genética , Biologia Computacional/métodos , Humanos , Coronavírus da Síndrome Respiratória do Oriente Médio/genética , Fases de Leitura Aberta , Alinhamento de Sequência/métodos , Relação Estrutura-Atividade , Proteínas Virais/química
10.
Phys Chem Chem Phys ; 22(24): 13713-13720, 2020 Jun 24.
Artigo em Inglês | MEDLINE | ID: mdl-32525501

RESUMO

By using density-functional theory, we have systematically investigated the structural stabilities, electronic structures, and optical properties of monolayer fibrous red phosphorene. We find the monolayer fibrous red phosphorene lattice to be dynamically and thermodynamically stable based on phonon spectra calculation and ab initio molecular dynamics simulation. A small cleavage energy of approximately 0.88 J m-2 is required for creating it from its bulk, suggesting the possibility of exfoliation in experiments. Furthermore, we find that monolayer fibrous red phosphorene is a semiconductor with an indirect bandgap of approximately 2.46 eV, and the bandgap is less susceptible to the number of stacked atomic layers. Moreover, the monolayer is expected to have highly directional anisotropy effective masses and high carrier mobilities (∼104 cm2 V-1 s-1), comparable with those of monolayer black phosphorene. In addition, fibrous red phosphorene nanosheets can absorb visible light as well as their band edge alignments are well positioned for the feasibility of both photo-oxidation and photo-reduction of water within the range of -5 to 5% biaxial strains. These combined properties make the fibrous red phosphorene nanosheets an alternative to diverse nanodevices, and pave the way for a potential photocatalyst.

11.
Phys Chem Chem Phys ; 20(17): 11967-11975, 2018 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-29670965

RESUMO

Utilizing density functional theory, we investigate the structural stabilities, electronic structures, and optical properties of monolayer violet phosphorene, i.e., Hittorfene, under an external vertical electric field and upon in-layer biaxial strain control. We find that compared with monolayer black phosphorene, monolayer violet phosphorene has a significantly larger direct band gap of 2.50 eV, and it is sensitive to an external vertical electric field, under which it undergoes an intriguing direct-indirect and insulator-metal transition. By applying an in-layer biaxial strain, the semiconductor characteristic of monolayer violet phosphorene is found to be robust and stable over a wide range of strains (-10 to 10%), with a minimum bulk gap still being up to 0.90 eV at a tensile strain of 10%. This demonstrates that the band edges of monolayer violet phosphorene not only can straddle water redox potentials in the equilibrium state but can also be available within the strain range of -7 to 7% for facilitating photocatalytic water splitting. In particular, the suitable band edges and intensive absorption of visible light suggest that a strain ratio of -7% would be the more favorable condition for water splitting under visible light.

12.
Phys Chem Chem Phys ; 17(33): 21149-57, 2015 Sep 07.
Artigo em Inglês | MEDLINE | ID: mdl-25478906

RESUMO

A new type of surface-enhanced Raman scattering (SERS) substrate consisting of ß-cyclodextrin (ß-CD) coated SiO2@Au@Ag nanoparticles (SiO2@Au@Ag@CD NPs) has been achieved. Our protocol was a simplified approach as the fabrication and modification of the silver shell were realized in a single-step reaction by taking advantage of ß-CD as both the reducing and stabilizing agents. The as-synthesized SiO2@Au@Ag@CD NPs were uniform in size and demonstrated high SERS activity and reproducibility. The substrates consisting of the SiO2@Au@Ag@CD NPs were employed for SERS detection of polychlorinated biphenyls (PCBs) including PCB-3, PCB-29 and PCB-77. The SERS detection sensitivity was significantly improved due to enrichment of more PCB molecules captured by ß-CD on the substrate surface, as confirmed by the appearance of the new Raman bands which are attributed to the complexes between ß-CD and PCBs according to the theoretical simulation. Therefore, this work presents a novel approach to the fabrication of effective SERS substrates that can be employed for rapid determination of trace amounts of PCBs in the environment with high detection sensitivity and recognition selectivity.


Assuntos
Nanopartículas Metálicas/química , Bifenilos Policlorados/análise , Análise Espectral Raman , beta-Ciclodextrinas/química , Ouro/química , Nanopartículas Metálicas/ultraestrutura , Reprodutibilidade dos Testes , Dióxido de Silício/química , Prata/química
13.
Analyst ; 139(12): 3083-7, 2014 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-24776730

RESUMO

A label-free approach to selective detection of 3,3',4,4'-tetrachlorobiphenyl (PCB77) using aptamer modified silica-Au/core-shell nanoparticles (denoted as SiO2@Au core/shell NPs) through surface enhanced Raman scattering (SERS) spectroscopy was proposed. The devised system consisted of SiO2@Au core/shell NPs fixed on the amino-silane functionalized glass slides with the PCB77-binding aptamers attached covalently to the gold surfaces through a thiol linker. The aptamers made of single-stranded DNA (ssDNA) oligomers with one end standing on the Au surface changed the conformation upon conjugation with PCB77, which correspondingly caused the spectral response of the ssDNA oligomers. The intensity ratio I(660 cm(-1))/I(736 cm(-1)) decreased with the amount of PCB77 added, which thus allowed us to measure trace amounts of PCB77 in a selective and quantitative way. This work therefore demonstrates that the design of aptamer-modified SiO2@Au core/shell NPs can be utilized for label-free SERS detection of persistent organic pollutants (POPs) in the environment.


Assuntos
Aptâmeros de Nucleotídeos , Nanopartículas , Bifenilos Policlorados/análise , Dióxido de Silício/química , Sequência de Bases
14.
Mater Today Bio ; 26: 101105, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38933416

RESUMO

In tumor treatment, the deposition of nanoenzymes in normal tissues and cause potential side effects are unavoidable. Here, we designed an intelligent biomimetic nanoenzymes carrier platform (MSCintelligent) that endows the carrier platform with "wisdom" by introducing Affibody-Notch(core)-VP64-GAL4/UAS-HSV-TK artificial signal pathways to mesenchymal stem cells (MSCs). This intelligent nanoenzymes carrier platform is distinguished from the traditional targeting tumor microenvironment or enhancing affinity with tumor, which endue MSCintelligent with tumor signal recognition capacity, so that MSCintelligent can autonomously distinguish tumor from normal tissue cells and feedback edited instructions. In this study, MSCintelligent can convert tumor signals into HSV-TK instructions through artificial signal pathway after recognizing Her2 (+) tumor. Subsequently, the synthesized HSV-TK can rupture MSCintelligent under the mediation of ganciclovir, and release the preloaded Cu/Fe nanocrystal clusters to kill the tumor accurately. Meanwhile, MSCintelligent without recognizing tumors will not initiate the HSV-TK instructions, thus being unresponsive to GCV and blocking the release of nanoenzymes in normal tissues. Consequently, MSCintelligent is the first intelligent biomimetic nanoenzymes carrier platform, which represents a new biomimetic nanoenzymes targeting mode.

15.
J Hazard Mater ; 473: 134663, 2024 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-38788575

RESUMO

In Southern China, the co-occurrence of arsenic (As) and antimony (Sb) contamination in soils around Sb mines presents an environmental challenge. During the flooding period of mining-impacted soils, anaerobic reduction of iron (Fe) oxides enhances the mobilization and bioavailability of Sb and As, further elevating the risk of Sb and As entering the food chain. To address this problem, activated carbon (AC) and biochar (BC) were applied to remediate flooded mining-impacted soils. Our results explored that AC can significantly decrease mobilization by 9-97 % for Sb and 9-67 % for As through inhibiting Fe(III) mineral reduction and dissolution in flooded soils. In contrast, there was no significant effect of BC. This was attributed to the strong adsorption of soil dissolved organic matter (DOM) by AC compared to BC, while DOM as electron shuttle is crucial for microbial Fe(III) reduction. Consequently, the DOM sequestration by AC effectively mitigates Sb and As leaching in contaminated mining soils.


Assuntos
Antimônio , Arsênio , Carvão Vegetal , Mineração , Poluentes do Solo , Antimônio/química , Arsênio/química , Poluentes do Solo/química , Carvão Vegetal/química , Adsorção , Inundações , Solo/química , Recuperação e Remediação Ambiental/métodos
16.
Natl Sci Rev ; 11(2): nwad324, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38314400

RESUMO

Iron catalysts are ideal transition metal catalysts because of the Earths abundant, cheap, biocompatible features of iron salts. Iron catalysts often have unique open-shell structures that easily undergo spin crossover in chemical transformations, a feature rarely found in noble metal catalysts. Unfortunately, little is known currently about how the open-shell structure and spin crossover affect the reactivity and selectivity of iron catalysts, which makes the development of iron catalysts a low efficient trial-and-error program. In this paper, a combination of experiments and theoretical calculations revealed that the iron-catalyzed hydrosilylation of alkynes is typical spin-crossover catalysis. Deep insight into the electronic structures of a set of well-defined open-shell active formal Fe(0) catalysts revealed that the spin-delocalization between the iron center and the 1,10-phenanthroline ligand effectively regulates the iron center's spin and oxidation state to meet the opposite electrostatic requirements of oxidative addition and reductive elimination, respectively, and the spin crossover is essential for this electron transfer process. The triplet transition state was essential for achieving high regioselectivity through tuning the nonbonding interactions. These findings provide an important reference for understanding the effect of catalyst spin state on reaction. It is inspiring for the development of iron catalysts and other Earth-abundant metal catalysts, especially from the point of view of ligand development.

17.
ACS Biomater Sci Eng ; 2024 Jun 29.
Artigo em Inglês | MEDLINE | ID: mdl-38943566

RESUMO

Metal peroxide nanomaterials as efficient hydrogen peroxide (H2O2) self-supplying agents have attracted the attention of researchers for antitumor treatment. However, relying solely on metal peroxides to provide H2O2 is undoubtedly insufficient to achieve optimal antitumor effects. Herein, we construct novel hyaluronic acid (HA)-modified nanocomposites (MgO2/Pd@HA NCs) formed by decorating palladium nanoparticles (Pd NPs) onto the surfaces of a magnesium peroxide (MgO2) nanoflower as a highly effective nanoplatform for the tumor microenvironment (TME)-responsive induction of ferroptosis in tumor cells and tumor photothermal therapy (PTT). MgO2/Pd@HA NC could be well endocytosed into tumor cells with CD44 expression depending on the specific recognition of HA with CD44, and then, the nanocomposites can be rapidly decomposed in mild acid and hyaluronidase overexpressed TME, and plenty of H2O2 was released. Simultaneously, Pd NPs catalyze self-supplied H2O2 to generate abundant hydroxyl radicals (•OH) and catalyze glutathione (GSH) into glutathione disulfide owing to its peroxidase and glutathione oxidase mimic enzyme activities, while the abundant •OH could also consume GSH in tumor cells and disturb the defense pathways of ferroptosis leading to the accumulation of lipid peroxidation and resulting in the occurrence of ferroptosis. Additionally, the superior photothermal conversion performance of Pd NPs in near-infrared II could also be used for PTT, synergistically cooperating with nanocomposite-induced ferroptosis for tumor inhibition. Consequently, the successfully prepared TME-responsive MgO2/Pd@HA NCs exhibited marked antitumor effect without obvious biotoxicity, contributing to thoroughly explore the nanocomposites as a novel and promising treatment for tumor therapy.

18.
J Hazard Mater ; 470: 134214, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38603908

RESUMO

Fe(II) regeneration is decisive for highly efficient H2O2-based Fenton-like processes, but the role of cobalt-containing reactive sites in promoting Fe(II) regeneration was overlooked. Herein, a single atom Co-N-C catalyst was employed in Fe(II)/H2O2 system to promote the degradation of diverse organic contaminants. The EPR and quenching experiments indicated Co-N-C significantly enhanced the generation of superoxide species, and accelerated hydroxyl radical generation for pollutant degradation. The electrochemical and surface composition analyses demonstrated the enhanced H2O2 activation and Fe(III)/Fe(II) recycling on the catalyst. Furthermore, in-situ Raman characterization with shell-isolated gold nanoparticles was employed to visualize the interfacial reactive intermediates and their time-resolved interaction. The accumulation of interfacial CoOOH* was confirmed when Co-N-C activated H2O2 alone, but it rapidly transformed into FeOOH* upon Fe(II) addition. Besides, the temporal variation of OOH* intermediates and the relative intensity of Co(III)-O and Co(IV)=O peaks depicted the dynamic interaction of reactive intermediates along the H2O2 consumption. With this basis, we proposed a mechanism of interfacial OOH* mediated Fe(II) regeneration, which overcame the kinetical limitation of Fe(II)/H2O2 system. Therefore, this study provided a primary effort to elucidate the overlooked role of interfacial CoOOH* in the Fenton-like processes, which may inspire the design of more efficient catalysts.

19.
Reprod Sci ; 31(6): 1719-1731, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38396297

RESUMO

Diabetes is known to negatively affect male reproduction. Recent clinical results have confirmed that mesenchymal stem cell (MSC)-based therapies are safe and effective for the treatment of diabetes. However, the effect and potential mechanism through which MSC transplantation improves diabetes-derived male reproductive dysfunction are still unknown. In the present study, we first established a male T1D mouse model through intraperitoneal injection of streptozotocin for five consecutive days. Subsequently, we evaluated the blood glucose levels, fertility, and histology and immunology of the pancreas, testes, and penis of T1D mice with or without transplantation of menstrual blood-derived endometrial stem cells (MenSCs) or umbilical cord mesenchymal stem cells (UCMSCs). Glucose was added to the medium in which the Leydig cells were cultured to imitate high glucose-injured cell viability. Subsequently, we evaluated the cellular viability, ROS levels, and mitochondrial membrane potential of Leydig cells treated with or without MenSC-conditioned medium (MenSC-CM) using a CCK8 assay, immunofluorescence, and flow cytometry. The targeted proteins are involved in the potential mechanism underlying MenSC-derived improvements, which was further validated via Western blotting. Collectively, our results indicated that MenSC transplantation significantly ameliorated reproductive dysfunction in male T1D mice by enhancing cellular antioxidative capacity and promoting angiogenesis. This study provides solid evidence and support for the application of MSCs to improve diabetes-induced male reproductive dysfunction.


Assuntos
Diabetes Mellitus Experimental , Endométrio , Animais , Masculino , Camundongos , Diabetes Mellitus Experimental/terapia , Feminino , Endométrio/metabolismo , Endométrio/patologia , Células Intersticiais do Testículo/metabolismo , Antioxidantes/farmacologia , Infertilidade Masculina/terapia , Diabetes Mellitus Tipo 1/metabolismo , Diabetes Mellitus Tipo 1/terapia , Transplante de Células-Tronco Mesenquimais/métodos , Espécies Reativas de Oxigênio/metabolismo , Camundongos Endogâmicos C57BL
20.
Sci Total Environ ; 879: 163042, 2023 Jun 25.
Artigo em Inglês | MEDLINE | ID: mdl-36965722

RESUMO

The extensive usage of ammonium sulfate as the leaching agent to extract rare earth elements led to widespread ammonia nitrogen (NH4+-N) pollution in the tailing soils of ion-adsorbed rare earth deposits in southern China. However, the cost-effective technologies to tackle with the long-term retention of NH4+-N in the rare earth mining soil have been largely unresolved. In this study, we developed a cost-effective approach to activate soil nitrification by the co-application of alkaline materials and organic fertilizer. The co-application of 0.3 % of organic fertilizer and 0.1 % âˆ¼ 0.2 % of CaO or MgO or Mg(OH)2 stimulated a soil NH4+-N decrease rate of 2.01-7.58 mg kg-1 d-1 and a soil NO3--N accumulation rate of 1.56-7.09 mg kg-1 d-1. Noting that only if the soil pH was elevated to 7.81-9.00, the NH4+-N decrease rate and NO3--N accumulation rate were dependent on the proton consumption capacity of the alkaline materials. The application of CaCO3 could not stimulate soil nitrification possibly due to the soil pH was uncapable to be elevated to above 7.68. The qPCR, amplicon sequencing, and nitrification inhibitor batch incubation results demonstrated that organic fertilizer supplied active ammonia-oxidizing bacteria Nitrosomonas europaea. The proliferation of Nitrosomonas europaea in the alkaline materials and organic fertilizer co-applied soil was responsible for the soil nitrification. Furthermore, the application of commercial denitrifying bacteria inoculum promoted the removal of accumulated NO3--N. The findings of this study provide a lost-cost technology to remove NH4+-N from the rare earth mining soil.

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