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1.
Acta Crystallogr E Crystallogr Commun ; 80(Pt 10): 1059-1063, 2024 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-39372189

RESUMO

Reaction of copper(I)chloride with 2,3-di-methyl-pyrazine in ethanol leads to the formation of the title compound, poly[[µ-chlorido-µ-(2,3-di-methyl-pyrazine)-copper(I)] ethanol hemisolvate], {[CuCl(C6H8N2)]·0.5C2H5OH} n or CuCl(2,3-di-methyl-pyrazine) ethanol hemisolvate. Its asymmetric unit consists of two crystallographically independent copper cations, two chloride anions and two 2,3-di-methyl-pyrazine ligands as well as one ethanol solvate mol-ecule in general positions. The ethanol mol-ecule is disordered and was refined using a split model. The methyl H atoms of the 2,3-di-methyl-pyrazine ligands are also disordered and were refined in two orientations rotated by 60° relative to each other. In the crystal structure, each copper cation is tetra-hedrally coordinated by two N atoms of two bridging 2,3-di-methyl-pyrazine ligands and two µ-1,1-bridg-ing chloride anions. Each of the two copper cations are linked by pairs of bridging chloride anions into dinuclear units that are further linked into layers via bridging 2,3-di-methyl-pyrazine coligands. These layers are stacked in such a way that channels are formed in which the disordered solvent mol-ecules are located. The topology of this network is completely different from that observed in the two polymorphic modifications of CuCl(2,3-di-methyl-pyrazine) reported in the literature [Jess & Näther (2006). Inorg. Chem. 45, 7446-7454]. Powder X-ray diffraction measurements reveal that the title compound is unstable and transforms immediately into an unknown crystalline phase.

2.
Molecules ; 29(17)2024 Sep 06.
Artigo em Inglês | MEDLINE | ID: mdl-39275077

RESUMO

Tetrahedral copper(I) clusters [Cu4(MBIZ)4(PPh3)2] (2), [Cu4(MBOZ)4(PPh3)4] (6) (MBIZ = 2-mercaptobenzimidazole, MBOZ = 2-mercaptobenzoxazole) were prepared by regulation of the copper-thiolate clusters [Cu6(MBIZ)6] (1) and [Cu8(MBOZ)8I]- (5) with PPh3. With the presence of iodide anion, the regulation provided the iodide-containing clusters [CuI4(MBIZ)3(PPh3)3I] (3) and [CuI4(MBOZ)3(PPh3)3I] (7). The cyclic voltammogram of 3 in MeCN (0.1 M nBu4NPF6, 298 K) at a scan rate of 100 mV s-1 shows two oxidation processes at Epa = +0.11 and +0.45 V with return waves observed at Epc = +0.25 V (vs. Fc+/Fc). Complex 3 has a higher capability to lose and gain electrons in the redox processes than complexes 2, 4, 4', 6, and 7. Its thermal stability was confirmed by thermogravimetric analysis. The catalytic performance of 3 was demonstrated by the catalytic transformation of iodobenzenes to benzonitriles using AIBN as the cyanide source. The nitrile products show potential applications in the preparation of 1,3,5-triazine compounds for organic fluorescence materials.

3.
Luminescence ; 39(9): e4902, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39289318

RESUMO

In this paper, we firstly report the synthesis and structural characterization of a discrete coordination metallacycle complex, [CuI (bipy)]2 (1). The x-ray diffraction structure, temperature-dependent electronic absorption, and photoluminescence spectra have been investigated. The solid-state fluorescence at variable temperatures shows that complex 1 exhibits an obvious thermochromic fluorescence. At low temperature, the dual fluorescence with peaks at 590 and 694 nm was observed. The emission color significantly changes from red at 77 K to yellow at 200 K and blue-green at 330 K. The thermochromic fluorescent molecular materials show great potential as temperature sensing.


Assuntos
Cobre , Imidazóis , Temperatura , Cobre/química , Imidazóis/química , Imidazóis/síntese química , Fluorescência , Complexos de Coordenação/química , Complexos de Coordenação/síntese química , Estrutura Molecular , Espectrometria de Fluorescência
4.
Chemistry ; : e202402381, 2024 Sep 04.
Artigo em Inglês | MEDLINE | ID: mdl-39228337

RESUMO

Photoswitchable (pre)catalysts, N,N'-bis-azobenzene-based (NHC)gold(I) and N,N'-bis-azobenzene-derived (NHC)copper(I) complexes are reported. Trans to cis isomerization of the attached photoswitchable moieties in the Au(I) complex enables four-fold decrement in the rate of oxazoline formation reaction. Whereas the progress of the copper(I) catalyzed, azide-alkyne cycloaddition reaction gets reduced by at least threefold. Alternate exposure to UV and blue light could easily toggle the rate of reactions remotely. The catalytic activity of thermodynamically stable trans-trans isomers is found to be similar to the common N-aryl substituted NHC-Au/Cu(I) complexes. NHC-Au(I) and -Cu(I) compounds bearing (trans)azobenzene moieties were characterized by X-ray diffraction. Photoswitching, recyclability studies, and the metastable isomer's thermal half-life in both complexes were studied via UV-visible spectroscopy. Whereas the extent of photoswitching and concomitant formation of geometrical isomers were investigated by using 1H-NMR spectroscopic study. Calculated percentage buried volumes of the three geometrical isomers show the trend trans-trans < trans-cis < cis-cis.

5.
Eur J Med Chem ; 277: 116746, 2024 Nov 05.
Artigo em Inglês | MEDLINE | ID: mdl-39146831

RESUMO

Metal complexes showing dual activity against cancer and bacterial infections are currently the focus of significant interest for their potential in treating life-threatening diseases. Aiming to investigate the impact of ligand substituents on these bioactivity properties of Group 11 d10 metal complexes, we herein present a series of mononuclear Cu(I) and Ag(I) complexes featuring the bis-NH2-substituted heterocyclic thioamide dap2SH (=4,6-diaminopyrimidine-2-thione), namely [AgCl(dap2SH)(PPh3)2] (1), [CuBr(dap2SH)(PPh3)2] (2), [CuBr(dap2SH)(xantphos)] (3), [Ag(dap2S)(xantphos)] (4), and [Cu(dap2S)(xantphos)] (5) (xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene). Complexes were characterized by means of different physicochemical methods (i.e., single crystal X-ray diffraction as well as FTIR, NMR, UV-Vis and fluorescence spectroscopy), and studied in-vitro for their antibacterial and anticancer activity against a variety of bacterial strains and cancer cell lines. Complexes 1-3 effectively inhibited both Gram (+) and Gram (-) bacterial growth, while cellular uptake studies for the most potent complex 1 against E. coli bacteria revealed the accumulation of Ag(I) ions in the periplasm of the bacteria. A high anti-proliferative effect was observed for 1 and 5 against A549, MCF7 and PC3 cancer cell lines, with 1 being capable of inducing apoptosis in A549 cells, as suggested by flow cytometry analysis. DNA interaction studies revealed the capacity of 1 to intercalate between base-pairs of CT DNA. All complexes had a moderate-to-high capacity to scavenge free radicals preventing oxidative stress. Molecular docking calculations, in combination with the experimentally obtained data, provided insights for potential mechanisms of the bioactivity of the complexes.


Assuntos
Antibacterianos , Antineoplásicos , Complexos de Coordenação , Cobre , Ensaios de Seleção de Medicamentos Antitumorais , Escherichia coli , Testes de Sensibilidade Microbiana , Prata , Tioamidas , Antibacterianos/farmacologia , Antibacterianos/química , Antibacterianos/síntese química , Antineoplásicos/farmacologia , Antineoplásicos/química , Antineoplásicos/síntese química , Escherichia coli/efeitos dos fármacos , Humanos , Cobre/química , Cobre/farmacologia , Tioamidas/química , Tioamidas/farmacologia , Tioamidas/síntese química , Complexos de Coordenação/farmacologia , Complexos de Coordenação/química , Complexos de Coordenação/síntese química , Prata/química , Prata/farmacologia , Estrutura Molecular , Relação Estrutura-Atividade , Aminas/química , Aminas/farmacologia , Aminas/síntese química , Proliferação de Células/efeitos dos fármacos , Relação Dose-Resposta a Droga , Linhagem Celular Tumoral , Compostos Heterocíclicos/química , Compostos Heterocíclicos/farmacologia , Compostos Heterocíclicos/síntese química
6.
Molecules ; 29(14)2024 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-39064910

RESUMO

Pentafluorophenyl copper(I)-biarylsulfoxide complexes, existing as [Cu(C6F5)]4L2, both in solution and in the solid state, were prepared and thoroughly characterized. Subsequently, the photochemistry of the complexes was explored, showing inherent photoreactivity of the biarylsulfoxide moiety within the coordination sphere of the copper. Photoinduced cross-coupling reactions between the anthryl moiety of bis-anthracenylsulfoxide and pentafluorobenzene, and synthesis of Cu2O (cuprite), were demonstrated.

7.
Front Chem ; 12: 1338614, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38807978

RESUMO

[Cu(NN1)2]ClO4 is a copper (I) complex, where NN1 is an imine ligand 6-((quinolin-2-ylmethylene) amino)-2H-chromen-2-one obtained by derivatization of natural compound coumarin, developed for the treatment of infectious diseases that affect salmonids. In previous research, we showed that the Cu(I) coordination complex possesses antibacterial activity against Flavobacterium psychrophilum, providing protection against this pathogen in rainbow trout during challenge assays (with an RPS of 50%). In the present study, the effects of administering [Cu(NN1)2]ClO4 to Oncorhynchus mykiss over a 60-days period were evaluated with regard to systemic immune response and its potential to alter intestinal microbiota composition. In O. mykiss, an immunostimulatory effect was evident at days 30 and 45 after administration, resulting in an increment of transcript levels of IFN-γ, IL-12, TNF-α, lysozyme and perforin. To determine whether these immunomodulatory effects correlated with changes in the intestinal microbiota, we analyzed the metagenome diversity by V4 16S rRNA sequencing. In O. mykiss, both [Cu(NN1)2]ClO4 and commercial antibiotic florfenicol had comparable effects at the phylum level, resulting in a predominance of proteobacteria and firmicutes. Nonetheless, at the genus level, florfenicol and [Cu(NN1)2]ClO4 complex exhibited distinct effects on the intestinal microbiota of O. mykiss. In conclusion, our findings demonstrate that [Cu(NN1)2]ClO4 is capable of stimulating the immune system at a systemic level, while inducing alterations in the composition of the intestinal microbiota in O. mykiss.

8.
J Colloid Interface Sci ; 671: 1-14, 2024 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-38788420

RESUMO

The widespread contamination of hexavalent chromium (Cr(VI)), pharmaceuticals and personal care products (PPCPs), and dyes is a growing concern. necessitating the development of convenient and effective technologies for their removal. Copper(I) phenylacetylide (PhC2Cu) has emerged as a promising photocatalyst for environmental remediation. In this study, we introduced a functional Cu-O bond into PhC2Cu (referred to as OrPhC2Cu) by creatively converting the adsorbed oxygen on the surface of PhC2Cu into a Cu-O bond to enhance the efficiency of Cr(VI) photoreduction, PPCPs photodegradation, and dyes photodegradation through a facile vacuum activating method. The incorporation of the Cu-O bond optimized the electron structure of OrPhC2Cu, facilitating exciton dissociation and charge transfer. The exciton dissociation behavior and charge transfer mechanism were systematically investigated for the first time in the OrPhC2Cu system by photoelectrochemical tests, fluorescence and phosphorescence (PH) techniques, and density functional theory (DFT) calculations. Remarkably, the enhanced visible-light response of OrPhC2Cu improved photon utilization and significantly promoted the generation of reactive species (RSs), leading to the highly efficient Cr(VI) photoreduction (98.52% within 25 min) and sulfamethazine photodegradation (94.65% within 60 min), with 3.91 and 5.23 times higher activity compared to PhC2Cu. Additionally, the photocatalytic efficiency of OrPhC2Cu in degrading anionic dyes surpassed that of cationic dyes. The performance of the OrPhC2Cu system in treating electroplating effluent or natural water bodies suggests its potential for practical applications.

9.
Int J Mol Sci ; 25(7)2024 Mar 26.
Artigo em Inglês | MEDLINE | ID: mdl-38612511

RESUMO

Piscirickettsia salmonis is the pathogen that most affects the salmon industry in Chile. Large quantities of antibiotics have been used to control it. In search of alternatives, we have developed [Cu(NN1)2]ClO4 where NN1 = 6-((quinolin-2-ylmethylene)amino)-2H-chromen-2-one. The antibacterial capacity of [Cu(NN1)2]ClO4 was determined. Subsequently, the effect of the administration of [Cu(NN1)2]ClO4 on the growth of S. salar, modulation of the immune system and the intestinal microbiota was studied. Finally, the ability to protect against a challenge with P. salmonis was evaluated. The results obtained showed that the compound has an MIC between 15 and 33.9 µg/mL in four isolates. On the other hand, the compound did not affect the growth of the fish; however, an increase in the transcript levels of IFN-γ, IL-12, IL-1ß, CD4, lysozyme and perforin was observed in fish treated with 40 µg/g of fish. Furthermore, modulation of the intestinal microbiota was observed, increasing the genera of beneficial bacteria such as Lactobacillus and Bacillus as well as potential pathogens such as Vibrio and Piscirickettsia. Finally, the treatment increased survival in fish challenged with P. salmonis by more than 60%. These results demonstrate that the compound is capable of protecting fish against P. salmonis, probably by modulating the immune system and the composition of the intestinal microbiota.


Assuntos
Anti-Infecciosos , Infecções por Piscirickettsiaceae , Salmo salar , Animais , Cobre , Infecções por Piscirickettsiaceae/tratamento farmacológico , Infecções por Piscirickettsiaceae/veterinária , Antibacterianos/farmacologia
10.
Huan Jing Ke Xue ; 45(5): 3037-3046, 2024 May 08.
Artigo em Chinês | MEDLINE | ID: mdl-38629564

RESUMO

Through lettuce potting experiments, the effects of different types of biochar (apple branch, corn straw, and modified sorghum straw biochar with phosphoric acid modification) on lettuce growth under tetracycline (TC) and copper (Cu) co-pollution were investigated. The results showed that compared with those under CK, the addition of biochar treatment significantly increased the plant height, root length, shoot fresh weight, and root fresh weight of lettuce (P < 0.05). The addition of different biochars significantly increased the nitrate nitrogen, chlorophyll, and soluble protein content in lettuce physiological indicators to varying degrees, while also significantly decreasing the levels of malondialdehyde, proline content, and catalase activity. The effects of biochar on lettuce physiological indicators were consistent during both the seedling and mature stages. Compared with those in CK, the addition of biochar resulted in varying degrees of reduction in the TC and Cu contents of both the aboveground and underground parts of lettuce. The aboveground TC and Cu levels decreased by 2.49%-92.32% and 12.79%-36.47%, respectively. The underground TC and Cu levels decreased by 12.53%-55.64% and 22.41%-42.29%, respectively. Correlation analysis showed that nitrate nitrogen, chlorophyll, and soluble protein content of lettuce were negatively correlated with TC content, whereas malondialdehyde, proline content, and catalase activity were positively correlated with TC content. The resistance genes of lettuce were positively correlated with TC content (P < 0.05). In general, modified biochar was found to be more effective in improving lettuce growth quality and reducing pollutant accumulation compared to unmodified biochar, with modified sorghum straw biochar showing the best remediation effect.


Assuntos
Poluentes Ambientais , Poluentes do Solo , Cobre , Lactuca , Poluentes Ambientais/análise , Solo , Catalase , Nitratos/análise , Antibacterianos , Tetraciclina/análise , Carvão Vegetal , Poluentes do Solo/análise , Clorofila/análise , Malondialdeído , Nitrogênio/análise , Prolina
11.
J Colloid Interface Sci ; 666: 57-65, 2024 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-38583210

RESUMO

Modification of oxygen evolution co-catalyst (OEC) on the surface of bismuth vanadate (BiVO4) can effectively improve the kinetics of water oxidation, but it is still limited by the small hole extraction driving force at the BiVO4/OEC interface. Modulating the BiVO4/OEC interface with a hole transfer layer (HTL) is expected to facilitate hole transport from BiVO4 to the OEC surface. Herein, a copper(I) thiocyanate (CuSCN) HTL is inserted between BiVO4 and NiFeOx OEC to create BiVO4/CuSCN/NiFeOx photoanode, resulting in a significant enhancement of photoelectrochemical (PEC) water splitting performance. From electrochemical analyses and density functional theory (DFT) simulations, the markedly enhanced PEC performance is attributed to the insertion of CuSCN as an HTL, which promotes the extraction of holes from BiVO4 surface and boosts the water oxidation kinetics. The optimal photoanode achieves a photocurrent density of 5.6 mA cm-2 at 1.23 V versus the reversible hydrogen electrode (vs. RHE) and an impressive charge separation efficiency of 96.2 %. This work offers valuable insights into the development of advanced photoanodes for solar energy conversion and emphasizes the importance of selecting an appropriate HTL to mitigate recombination at the BiVO4/OEC interface.

12.
Chemistry ; 30(36): e202400817, 2024 Jun 25.
Artigo em Inglês | MEDLINE | ID: mdl-38654445

RESUMO

Luminescent organometallic complexes of earth-abundant copper(I) have long been studied in organic light-emitting diodes (OLED). Particularly, Cu(I)-based carbene-metal-amide (CMA) complexes have recently emerged as promising organometallic emitters. However, blue-emitting Cu(I) CMA complexes have been rarely reported. Here we constructed two blue-emitting Cu(I) CMA emitters, MAC*-Cu-CF3Cz and MAC*-Cu-2CF3Cz, by introducing one or two CF3 substitutes into carbazole ligands. Both complexes exhibited high thermal stability and blue emission colors. Moreover, two complexes exhibited different emission origins rooting from different donor ligands: a distinct thermally activated delayed fluorescence (TADF) from ligand-to-ligand charge transfer excited states for MAC*-Cu-CF3Cz or a dominant phosphorescence nature from local triplet excited state of the carbazole ligand for MAC*-Cu-2CF3Cz. Inspiringly, MAC*-Cu-CF3Cz had high photoluminescence quantum yields of up to 94 % and short emission lifetimes of down to 1.2 µs in doped films, accompanied by relatively high radiative rates in the 105 s-1 order. The resultant vacuum-deposited OLEDs based on MAC*-Cu-CF3Cz delivered pure-blue electroluminescence at 462 nm together with a high external quantum efficiency of 13.0 %.

13.
Antibiotics (Basel) ; 13(3)2024 Mar 21.
Artigo em Inglês | MEDLINE | ID: mdl-38534722

RESUMO

Copper (I) oxide (cuprite) is a material widely used nowadays, and its versatility is further amplified when it is brought to the nanometric size. Among the possible applications of this nanomaterial, one of the most interesting is that in the medical field. This paper presents a cuprite nanopowder study with the aim of employing it in medical applications. With regards to the environmental context, the synthesis used is related to green chemistry since the technique (out-of-phase pulsed electrochemistry) uses few chemical products via electricity consumption and soft conditions of temperature and pressure. After different physico-chemical characterizations, the nanopowder was tested on the Candida albicans to determine its fungicide activity and on human blood to estimate its hemocompatibility. The results show that 2 mg of this nanopowder diluted in 30 µL Sabouraud broth was able to react with Candida albicans. The hemocompatibility tests indicate that for 25 to 100 µg/mL of nanopowder in an aqueous medium, the powder was not toxic for human blood (no hemolysis nor platelet aggregation) but promoted blood coagulation. It appears, therefore, as a potential candidate for the functionalization of matrices for medical applications (wound dressing or operating field, for example).

14.
J Colloid Interface Sci ; 664: 551-560, 2024 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-38484524

RESUMO

Fluorescence quenching induced by photoinduced electron transfer (PET) stands as an effective strategy for identifying water pollutants. Herein, a novel (4, 8)-connected three-dimensional framework Cu(I)-MOF ([Cu2I(tpt)]n) with unique 8-connected [Cu4I2]2+ cationic clusters is designed by employing the nitrogen-rich ligand (Htpt = 5-[4(1H-1,2,4-triazol-1-yl)]phenyl-2H-tetrazole). Water-stabilized Cu(I)-MOF exhibits outstanding fluorescence properties, facilitating its application in detecting organic pollutants in water. Benefiting from the fact that the Cu(I)-MOF possesses a higher lowest unoccupied molecular orbitals (LUMO) energy level than that of the analyte, the rapid d-PET can occur, entitling Cu(I)-MOF to a sensitive fluorescence quenching response to roxarsone (ROX), nitrofurazone (NFZ) and nitrofurantoin (NFT) (with detection limits as low as 0.13 µM, 0.15 µM, and 0.13 µM, respectively). The nitrogen-containing sites of melamine foam (MF) are utilized to facilitate the anchoring and growth of Cu-MOF crystals, which enables the preparation of hierarchical microporous - macroporous Cu(I)-MOF/MF composites. The ordered porous structure of Cu(I)-MOF/MF provides cavities and open sites for the efficient removal of ROX (qmax = 210.6 mg∙g-1), NFZ (qmax = 111.5 mg∙g-1) and NFT (qmax = 238.9 mg∙g-1) from water. This characteristic endows the Cu(I)-MOF/MF with rapid and recyclable adsorption capacity. Therefore, this work provides valuable insights to address the problem of detection and removal of pollutants in the aquatic environment.

15.
Molecules ; 29(5)2024 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-38474457

RESUMO

This study presents a simple and energy-efficient self-assembly LAG synthetic method for novel water-soluble copper(I) complexes [Cu(terpy)(PTA)][PF6] (1) and [Cu(terpy)(PTA)2][PF6] (2). They were characterized by FT-IR, 1H, and 31P{1H} NMR spectroscopy, elemental analysis, and single-crystal/powder X-ray diffraction (for 2). The X-ray analysis of compound 2 indicates a bidentate coordination mode of terpyridine to the metal center. Variable-temperature NMR tests indicate dynamic properties for terpyridine in the case of both compounds, as well as for the PTA ligands in the case of 2. Additionally, compounds 1 and 2 exhibit interesting cytotoxic activity, which was tested on normal human dermal fibroblasts (NHDFs), human lung carcinoma (A549), human breast adenocarcinoma (MCF-7), and human cervix carcinoma (HeLa) established cell lines. In comparison to the other tested compounds, complexes 1 and 2 seem to have significantly lower IC50 values against cancer cells (A549, HeLa, MCF-7), indicating their potential as prospective anticancer agents. Moreover, both compounds show no significant toxicity towards normal skin cells (NHDFs), suggesting a certain selectivity in their action on cancer cells. Cisplatin as a reference compound also exhibited considerable cytotoxicity against cancer cells but with a low level of selectivity, which could lead to unwanted effects on normal cells. Remarkably, compounds 1 and 2 exhibit up to 30 times the cytotoxic activity of cisplatin, with a six-fold lower toxicity to normal cells. They also interact strongly with human serum albumin, suggesting potential therapeutic applications. Overall, these compounds hold significant promise as potential chemotherapeutic agents.


Assuntos
Adamantano/análogos & derivados , Antineoplásicos , Carcinoma , Complexos de Coordenação , Compostos Organofosforados , Feminino , Humanos , Cisplatino/farmacologia , Cobre/química , Linhagem Celular Tumoral , Água , Estudos Prospectivos , Espectroscopia de Infravermelho com Transformada de Fourier , Complexos de Coordenação/química , Antineoplásicos/farmacologia , Ligantes
16.
Small ; 20(31): e2310518, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38429235

RESUMO

Due to their significant capacity and reliable reversibility, transition metal sulphides (TMSs) have received attention as potential anode materials for sodium-ion batteries (SIBs). Nonetheless, a prevalent challenge with TMSs lies in their significant volume expansion and sluggish kinetics, impeding their capacity for rapid and enduring Na+ storage. Herein, a Cu1.96S@NC nanodisc material enriched with copper vacancies is synthesised via a hydrothermal and annealing procedure. Density functional theory (DFT) calculations reveal that the incorporation of copper vacancies significantly boosts electrical conductivity by reducing the energy barrier for ion diffusion, thereby promoting efficient electron/ion transport. Moreover, the presence of copper vacancies creates ample active sites for the integration of sodium ions, streamlines charge transfer, boosts electronic conductivity, and, ultimately, significantly enhances the overall performance of SIBs. This novel anode material, Cu1.96S@NC, demonstrates a reversible capacity of 339 mAh g-1 after 2000 cycles at a rate of 5 A g-1. In addition, it maintains a noteworthy reversible capacity of 314 mAh g-1 with an exceptional capacity retention of 96% even after 2000 cycles at 20 A g-1. The results demonstrate that creating cationic vacancies is a highly effective strategy for engineering anode materials with high capacity and rapid reactivity.

17.
ChemistryOpen ; 13(8): e202300274, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38426697

RESUMO

Nanomaterials based on metal oxides, especially Cu2O, have received much attention in recent years due to the many unique properties of the surface plasmon resonance they provide. The report presented the co-precipitation method, a simple preparation method to produce Cu2O oxide particles. In addition, to improve the unique antibacterial properties of Cu2O, a proposed method is to attach Ag nanoparticles to the surface of Cu2O particles. The Cu2O and Cu2O-Ag particles were synthesized based on redox reactions using ascorbic acid (LAA) as a reducing agent. Moreover, in this experiment, two surfactants, polyethylene glycol 6000 (PEG 6000) and sodium dodecyl sulfate (SDS), were added during the manufacturing process to create particle samples and particle combinations with better properties than the original sample. Changes in the characteristics and properties of particle samples are determined by many different physical and chemical methods such as ultraviolet-visible spectroscopy (UV-Vis), infrared spectroscopy (IR), noise X-ray radiation (XRD), scanning electron microscope (SEM), dynamic light scattering (DLS), energy dispersive X-ray spectroscopy (EDS), and transmission electron microscopy (TEM). Finally, the activity against bacteria, including E. coli and S. aureus, was also tested using the agar well diffusion method to determine the zone of inhibition. The results improved the particle size value, which decreased by half to 200 nm when two additional surfactants, PEG and SDS, were added. In addition, the antibacterial ability has also been shown to increase significantly when the diameter of the bacterial inhibition zone increased significantly, reaching values of 20 mm (Cu2O/Ag/SDS) and 32 mm (Cu2O/Ag/PEG) for the E. coli bacterial strain. The initial test sample was only about 14 mm in size. The S. aureus bacterial strain also had a similar improvement trend after adding Ag to the Cu2O surface with the appearance of two surfactants, SDS and PEG. The inhibition zone diameter values reached the optimal value at 36 mm in the Cu2O/Ag/PEG particle combination sample compared to only the initial 26 mm in the Cu2O particle sample. Finally, the particle samples are added to the acrylic emulsion paint film to evaluate the changes. Positive results were obtained, such as improvement in adhesion (1.22 MPa), relative hardness (240/425), and sand drop resistance (100 L/mil) in the Cu2O/Ag/PEG particle combination sample, which showed the correctness and accuracy of the research.

18.
Chemosphere ; 352: 141340, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38301836

RESUMO

Nanoarchitectured design of the metal sulfides with highly available surface and abundant electroactive centers and using them as electrocatalyst for fabricate the electrochemical sensors for the detection of hydrazine (N2H4) and hydrogen peroxide (H2O2) is challenging and desirable. Herein, Cu2O nanospheres powder is firstly prepared using chemical reduction of copper chloride and then drop-casted on the glassy carbon electrode (GCE) surface. In the next step, CoFeS nanoflakes are electrodeposited on Cu2O nanospheres by cyclic voltammetry method to form CoFeS/Cu2O nanocomposite as a detection platform for measuring N2H4 and H2O2. Accordingly, Cu2O nanospheres are not only used as substrate, but also guided the CoFeS nanoflakes to adhere to the electrode surface without need to any binder or conductive additive, which enhances the electrical conductivity of the sensing active materials. As the hydrazine sensor, the CoFeS/Cu2O/GCE displayed wide linear ranges (0.0001-0.021 mM and 0.021-1.771 mM), low detection limit (0.12 µM), very high sensitivities (103.33 and 21.23 mA mM-1 cm-2), and excellent selectivity. The as-made nanocomposite also exhibited low detection limit of 1.26 µM for H2O2 sensing with very high sensitivities (12.31 and 3.96 mA mM-1 cm-2) for linear ranges of 0.001-0.03 mM and 0.03-2.03 mM, respectively, and negligible response against interfering substances. The superior analytical performance of the CoFeS/Cu2O for N2H4 electro-oxidation and H2O2 electro-reduction can be attributed to structure stability, high electroactive surface area, and good availability to analyte species and electrolyte diffusion. Moreover, to examine the potency of the prepared nanocomposite in real applications, the seawater sample was analyzed and results display that the CoFeS/Cu2O/GCE can be utilized as a reliable and applicable platform for measuring N2H4 and H2O2.


Assuntos
Peróxido de Hidrogênio , Nanosferas , Peróxido de Hidrogênio/química , Cobre/química , Galvanoplastia , Carbono/química , Eletrodos , Técnicas Eletroquímicas/métodos
19.
Environ Sci Technol ; 58(12): 5557-5566, 2024 Mar 26.
Artigo em Inglês | MEDLINE | ID: mdl-38412381

RESUMO

Wet flue gas denitrification offers a new route to convert industrial nitrogen oxides (NOx) into highly concentrated nitrate wastewater, from which the nitrogen resource can be recovered to ammonia (NH3) via electrochemical nitrate reduction reactions (NITRRs). Low-cost, scalable, and efficient cathodic materials need to be developed to enhance the NH3 production rate. Here, in situ electrodeposition was adopted to fabricate a foamy Cu-based heterojunction electrode containing both Cu-defects and oxygen vacancy loaded Cu2O (OVs-Cu2O), which achieved an NH3 yield rate of 3.59 mmol h-1 cm-2, NH3 Faradaic efficiency of 99.5%, and NH3 selectivity of 100%. Characterizations and theoretical calculations unveiled that the Cu-defects and OVs-Cu2O heterojunction boosted the H* yield, suppressed the hydrogen evolution reaction (HER), and served as dual reaction sites to coherently match the tandem reactions kinetics of NO3-to-NO2 and NO2-to-NH3. An integrated system was further built to combine wet flue gas denitrification and desulfurization, simultaneously converting NO and SO2 to produce the (NH4)2SO4 fertilizer. This study offers new insights into the application of low-cost Cu-based cathode for electrochemically driven wet denitrification wastewater valorization.


Assuntos
Amônia , Águas Residuárias , Nitratos/química , Dióxido de Nitrogênio , Desnitrificação , Eletrodos
20.
Small ; 20(28): e2311448, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38326094

RESUMO

The development of a cost-effective, ultra-selective, and room temperature gas sensor is the need of an hour, owing to the rapid industrialization. Here, a new 2D semiconducting Cu(I) coordination polymer (CP) with 1,4-di(1H-1,2,4-triazol-1-yl)benzene (1,4-TzB) ligand is reported. The CP1 consists of a Cu2I2 secondary building unit bridged by 1,4-TzB, and has high stability as well as semiconducting properties. The chemiresistive sensor, developed by a facile drop-casting method derived from CP1, demonstrates a response value of 66.7 at 100 ppm on methanol exposure, accompanied by swift transient (response and recovery time 17.5 and 34.2 s, respectively) behavior. In addition, the developed sensor displays ultra-high selectivity toward methanol over other volatile organic compounds , boasting LOD and LOQ values of 1.22 and 4.02 ppb, respectively. The CP is found to be a state-of-the-art chemiresistive sensor with ultra-high sensitivity and selectivity toward methanol at room temperature.

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