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1.
Spectrochim Acta A Mol Biomol Spectrosc ; 324: 124962, 2025 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-39146628

RESUMO

Two isostructural, three-dimensional, interpenetrated amino-functionalized Metal-Organic Frameworks (Co-2AIN-MOF and Cd-2AIN-MOF) based on 2-aminoisonicotinic acid (2AIN) were synthesized, structurally characterized and determined. Based on the PXRD analysis, the solvent exchange hardly changed their framework structure, and the samples fully activated by methanol can be achieved and examined by infrared spectroscopy. Due to the presence of the carbonyl group and free amino groups in the pore of the framework, the NH3 uptakes of Co-2AIN-MOF and Cd-2AIN-MOF are 11.70 and 13.81 mmol/g and at 1 bar, respectively. In-situ Infrared spectroscopy and DFT calculations revealed the different adsorption sites and processes between Co-2AIN-MOF and Cd-2AIN-MOF.

2.
J Colloid Interface Sci ; 678(Pt C): 251-260, 2025 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-39298976

RESUMO

The development of a new system for the electrochemical carbon dioxide reduction reaction (ECO2RR) to methane (CH4) is challenging, and novel conductive metal organic frameworks (c-MOFs) for efficient ECO2RR to CH4 are critical to this system. Here, we report a novel c-MOF, copper-pyromellitic dianhydride-2-methylbenzimidazole (Cu-PD-2-MBI), in which the introduction of electron-withdrawing 2-methylbenzimidazole (2-MBI) into the copper-pyromellitic dianhydride (Cu-PD) interlayer elevated the valence of copper (Cu) ions, which improved the ECO2RR performance of Cu-PD-2-MBI. Cu-PD-2-MBI was tested in a flow cell, and the Faradaic efficiency of CH4 reached 73.7 %, with a corresponding partial current density of -428.3 mA·cm-2 at -1.3 V, which was higher than those of most reported Cu-based catalysts. Further exploration via theoretical calculations indicated that the intercalated 2-MBI in Cu-PD-2-MBI induced a shift in the d-band center in the Cu sites from -2.63 to -1.86 eV and reduced the formation energy of the *COOH and *CHO intermediates in the process of generating CH4 compared with those of the reference Cu-PD catalyst.

3.
J Colloid Interface Sci ; 677(Pt A): 68-78, 2025 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-39083893

RESUMO

Carbon/metal composites derived from metal-organic frameworks (MOFs) have attracted widespread attention due to their excellent electronic conductivity, adjustable porosity, and outstanding stability. However, traditional synthesis methods are limited by the dense stereo geometry and large crystal grain size of MOFs, resulting in many metals active sites are buried in the carbon matrix. While the common strategy involves incorporating additional dispersed media into material, this leads to a decrease in practical metal content. In this study, nanosized copper-metal-organic frameworks (Cu-MOFs) are in-situ grown on surface of carbon spheres by pre-anchoring copper ions, and the hybrid composite of porous carbon/copper oxide with high copper atom utilization rate is prepared through activation and pyrolysis methods. This strategy effectively addresses the issue of insufficient exposure of metal sites, and the obtained composite material exhibits high effective copper atom utilization rate, large specific surface area (2052.3 m2·g-1), diverse pore structure, outstanding specific capacity (1076.5F·g-1 at 0.5 A·g-1), and excellent cycle stability. Furthermore, this highly atom-economical universal method has positive significance in application fields of catalysis, energy storage, and adsorption.

4.
Talanta ; 281: 126844, 2025 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-39277931

RESUMO

Self-powered biosensors with high sensitivity have garnered significant interest for their potential applications in the realm of portable sensing. Herein, a self-powered biosensor with a novel signal amplification strategy was developed by integrating target-controlled release of mediator with an enzyme biofuel cell for the ultrasensitive detection of acetamiprid (ACE). Zeolitic imidazolate framework-67 was utilized as both a nanocontainer for capturing the electron mediator 2,2'-azidobis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), and a precursor for the synthesis of cobalt nanoparticles/nitrogen, sulfur-codoped carbon nanotubes (Co NPs/NS-CNTs), which were employed as the electrode material for constructing both the glucose oxidase-based bioanode and the laccase-based biocathode. The target analyte ACE can specifically bind to its aptamer, leading to the release of ABTS, which cyclically participates in the catalytic reaction of the biocathode, thereby amplifying the electrochemical signal. By leveraging the benefits of ABTS cyclic catalysis and the effective electrocatalysis of bioelectrodes based on Co NPs/NS-CNTs, the self-powered biosensor has a broad detection range of 0.1-1000 fM and a low detection limit of 25 aM toward ACE. The proposed signal amplification approach presents a promising strategy for enhancing sensitivity and enabling portable analysis in applications of food safety, environmental monitoring, and medical diagnostics.


Assuntos
Técnicas Biossensoriais , Eletrodos , Glucose Oxidase , Lacase , Neonicotinoides , Neonicotinoides/análise , Neonicotinoides/química , Técnicas Biossensoriais/métodos , Lacase/química , Lacase/metabolismo , Glucose Oxidase/química , Glucose Oxidase/metabolismo , Nanotubos de Carbono/química , Técnicas Eletroquímicas/métodos , Limite de Detecção , Estruturas Metalorgânicas/química , Cobalto/química , Ácidos Sulfônicos/química , Benzotiazóis/química , Zeolitas/química , Nanopartículas Metálicas/química , Aptâmeros de Nucleotídeos/química , Fontes de Energia Bioelétrica
5.
Talanta ; 281: 126879, 2025 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-39293247

RESUMO

The development of high-performance specific sensors is promising for the rapid detection of harmful residues in animal-derived foods. Recently, luminescent metal-organic framework/molecularly imprinted polymer (LMOF/MIP) materials have been developed as ideal candidates for the analysis of harmful residues. Here, we reported a simple fabrication protocol of paper-based chip through in-situ growth of LMOF on a negatively charged modified filter paper, a paper-based molecularly imprinting layer (FP@BA-Eu@MIP) was thereafter successfully prepared via the boronate affinity-based controllable oriented surface imprinting strategy. The paper-based chips obtained were used to construct a rapid test strip of tetracycline (TC). After addition of TC, significant fluorescence changes on the surface of the FP@BA-Eu@MIP paper-based chip could be observed from blue to red via inner filter effect and photo-induced electron transfer under the excitation of 360 nm. The adsorption kinetics was explored in detail. The presented strip exhibited satisfied selectiveness and sensitivity with a limit of detection of 8.47 µg L-1 for TC. It was confirmed that LMOF/MIP as a biomimetic recognition module can play a crucial role in enrichment and fluorescence response. This study provided a real application case for an in-situ fabricated fluorescence paper-based chip in rapidly detecting harmful residues.


Assuntos
Contaminação de Alimentos , Estruturas Metalorgânicas , Polímeros Molecularmente Impressos , Papel , Tetraciclina , Tetraciclina/análise , Estruturas Metalorgânicas/química , Polímeros Molecularmente Impressos/química , Contaminação de Alimentos/análise , Limite de Detecção , Análise de Alimentos/métodos , Antibacterianos/análise
6.
Talanta ; 281: 126901, 2025 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-39298802

RESUMO

Detection of volatile organic compounds (VOCs) is crucial in industrial production, environmental monitoring, and public safety. VOCs sensors need to be intrinsically safe, given the flammability and toxicity of common VOCs. Fiber optic sensors offer a passive and flexible solution for VOCs detection, attracting significant attention from researchers. In this study, ZIF-8, a subset of metal-organic frameworks, is applied to a side-polished silicon wafer, forming an open-cavity optical fiber Fabry-Pérot interferometer (FPI) with a fiber patch cable and a 3D-printed structural part. The sensing performance for prevalent VOCs, including methylbenzene, methanol, and ethanol, is experimentally explored, exhibiting sensitivities of 0.118 p.m./ppm, 0.177 p.m./ppm, and 0.412 p.m./ppm, respectively. Sensitivity differences are analyzed and demonstrated at the molecular level. The proposed technologies offer advantages such as easy fabrication, intrinsic safety, small size, and good selectivity, providing an alternative for VOCs detection in industrial production.

7.
Talanta ; 281: 126853, 2025 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-39317068

RESUMO

In today's society, heavy metal ions and antibiotic contaminants have caused great harm to water systems and human health. In this study, six isostructural lanthanide metal-organic frameworks [Ln(H3imda)2(TPA)(H2O)2](Tb for CUST-881, Eu for CUST-882, Dy for CUST-883, Er for CUST-884, Nd for CUST-885, Sm for CUST-886) were constructed by selecting terephthalic acid (TPA) and 4,5-Imidazoledicarboxylic acid (H3imda) and lanthanide metal ions via solvethermal method. Among them, CUST-881 and CUST-882 can selectively detect Fe3+, Cr2O72-, CrO42, and ceftriaxone sodium (CRO) in water systems and uric acid in urine. CUST-881 shows very low detection limits for these five substances. Furthermore, Principal Component Analysis (PCA) was used to distinguish Fe3+, Cr2O72-, CrO42-, and CRO in water. To our knowledge, this is the first time that they have been able to be simultaneously distinguished. In addition, the possible sensing mechanism was studied through UV-visible spectroscopy, Infrared spectroscopy, and PXRD analysis. Furthermore, the probe also showed satisfactory repeatability and recovery when applied to UA samples that simulated urine. Based on the above results, lanthanide metal-organic frameworks have great potential for practical monitoring of contaminants in water environments.


Assuntos
Elementos da Série dos Lantanídeos , Estruturas Metalorgânicas , Poluentes Químicos da Água , Estruturas Metalorgânicas/química , Elementos da Série dos Lantanídeos/química , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/urina , Biomarcadores/urina , Biomarcadores/análise , Medições Luminescentes/métodos , Humanos , Ácidos Ftálicos/química , Ácido Úrico/urina , Ácido Úrico/química , Limite de Detecção , Análise de Componente Principal
8.
Talanta ; 281: 126924, 2025 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-39326115

RESUMO

A large number of Chinese herbal medicines (CHMs) are included in daily recipes, but their pesticide residues have aroused more and more concerns. In this paper, an electrochemiluminescence aptasensor was constructed for the trace detection of acetamiprid (ACE) in Angelica sinensis and Lycium barbarum. Possessing a large specific surface area, UiO-66 was modified with amino groups to improve biocompatibility, and the addition of AuNPs allowed UiO-66-NH2 to catalyze the formation of excited states of luminescent molecules (TPrA⁎; Ru(bpy)32+⁎), and AuNPs@UiO-66-NH2 was used to bridge the aptamer (Au-S) and luminescent substrate (peptide bond). The conventional luminescent reagent Ru(bpy)32+ was doped with multi-walled carbon nanotubes (MWCNTs) to obtain a more powerful and stable light signal. After optimizing the experimental parameters, the aptasensor could give results in 10 min with a detection range from 1×10-2-1×104 nM and a lower limit of detection (LOD) of 0.8 pM. The LOD of the study was at least one order of magnitude lower than that of the fluorescence detection method. Furthermore, the accuracy of the aptasensor was validated for spiked recovery experiments.


Assuntos
Aptâmeros de Nucleotídeos , Medicamentos de Ervas Chinesas , Técnicas Eletroquímicas , Ouro , Medições Luminescentes , Nanopartículas Metálicas , Resíduos de Praguicidas , Aptâmeros de Nucleotídeos/química , Nanopartículas Metálicas/química , Ouro/química , Medicamentos de Ervas Chinesas/química , Medicamentos de Ervas Chinesas/análise , Técnicas Eletroquímicas/métodos , Medições Luminescentes/métodos , Resíduos de Praguicidas/análise , Lycium/química , Estruturas Metalorgânicas/química , Angelica sinensis/química , Técnicas Biossensoriais/métodos , Neonicotinoides/análise , Neonicotinoides/química , Limite de Detecção , Nanotubos de Carbono/química
9.
J Colloid Interface Sci ; 678(Pt A): 540-548, 2025 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-39214006

RESUMO

The energy system of lithium-sulfur batteries is quite promising, however, lithium-sulfur batteries still suffer from considerable problems, such as the abominable shuttle effect of polysulfides (LiPSs), the low conductivity of the solid-phase products, the slow redox kinetics during charging and discharging, and the volume expansion. Herein, the hybridization pattern between the d-orbitals of various transition metal atoms and the p-orbitals of sulfides is revealed grounded in the theory of density function, which explains the high adsorption strength of two-dimensional metal-organic frameworks (MOFs) with LiPSs and accelerates the screening of high-performance anchoring and catalytic materials. The results elucidate that the coordinated transition metal-organic frameworks (Mo-NH MOF) monolayers increase the capacity of LiPSs to anchor by forming more π-bonds from the hybridization of the S p orbitals and Mo d orbitals. Notably, Mo-NH MOF exhibits bifunctional catalytic activity for sulfur reduction as well as Li2S decomposition reactions during charging and discharging, which improves the conversion efficiency of redox reactions. As a result, new MOF materials featuring unique active centers and the potential mechanism by which the active centers modulate the performance of the substrate materials are revealed, and this finding may accelerate the development of high-performance Li-S batteries.

10.
J Colloid Interface Sci ; 678(Pt A): 795-805, 2025 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-39217695

RESUMO

Metal-organic frameworks (MOFs) have gained tremendous notice for the application in alkaline water/seawater oxidation due to their tunable structures and abundant accessible metal sites. However, exploring cost-effective oxygen evolution reaction (OER) electrocatalysts with high catalytic activity and excellent stability remains a great challenge. In this work, a promising strategy is proposed to regulate the crystalline structures and electronic properties of NiFe-metal-organic frameworks (NiFe-MOFs) by altering the organic ligands. As a representative sample, NiFe-BDC (BDC: C8H6O4) synthesized on nickel foam (NF) shows extraordinary OER activity in alkaline condition, delivering ultralow overpotentials of 204, 234 and 273 mV at 10, 100, and 300 mA cm-2, respectively, with a small Tafel slope of 21.6 mV dec-1. Only a slight decrease is observed when operating in alkaline seawater. The potential attenuation is barely identified at 200 mA cm-2 over 200 h continuous test, indicating the remarkable stability and corrosion resistance. In-situ measurements indicate that initial Ni2+/Fe2+ goes through oxidation process into Ni3+/Fe3+ during OER, and eventually presents in the form of NiFeOOH/NiFe-BDC heterojunction. The unique self-reconstructed surface is responsible for the low reaction barrier and fast reaction kinetics. This work provides an effective strategy to develop efficient MOF-based electrocatalysts and an insightful view on the dynamic structural evolution during OER.

11.
J Colloid Interface Sci ; 678(Pt A): 979-986, 2025 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-39226838

RESUMO

Precise deposition of metal-organic framework (MOF) materials is important for fabricating high-performing MOF-based devices. Electric-field assisted drop-casting of poly(3,4-ethylenedioxythiophene)-functionalized (PEDOT) MIL-101(Cr) nanoparticles onto interdigitated electrodes allowed their precise spatioselective deposition as percolating nanoparticle chains in the interelectrode gaps. The resulting aligned materials were investigated for resistive and capacitive humidity sensing and compared with unaligned samples prepared via regular drop-casting. The spatioselective deposition of MOFs resulted in up to over 500 times improved conductivity and approximately 6 times increased responsivity during resistive humidity sensing. The aligned samples also showed good capacitive humidity sensing performance, with up to 310 times capacitance gain at 10 versus 90 % relative humidity. In contrast, the resistive behavior of the unaligned samples rendered them unsuitable for capacitive sensing. This work demonstrates that applying an alternating potential during drop-casting is a simple yet effective method to control MOF deposition for greater efficiency, conductivity, and enhanced humidity sensing performance.

12.
J Colloid Interface Sci ; 678(Pt B): 88-94, 2025 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-39241450

RESUMO

Considerable attention has been paid to the preparation of single-atom solid base catalysts (SASBCs) owing to their high activity and maximized utilization of basic sites. At present, the reported fabrication methods of SASBCs, such as two-step reduction strategy and sublimation capture strategy, require high temperature. Such a high activation temperature is easy to cause the sublimation loss of alkali or alkaline earth metal atoms and destructive to the support structure. Herein, a new SASBC, Ca1/UiO-67-BPY, is fabricated, in which the alkaline earth metal Ca sites are immobilized onto N-rich metal-organic framework UiO-67-BPY at room temperature. The results show that the atomic configuration of Ca single atoms is coordinated by two N atoms in the framework. The obtained Ca SASBC possesses ordered structure and exhibits high product yield of 87.2% in the Knoevenagel reaction between benzaldehyde and malononitrile. Furthermore, thanks to the Ca single atoms sites anchored on UiO-67-BPY, the Ca1/UiO-67-BPY catalyst also shows good stability during cycles. This work might offer new insight in designing SASBCs for different base-catalyzed reactions.

13.
J Colloid Interface Sci ; 677(Pt B): 111-119, 2025 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-39137560

RESUMO

Electrochemical carbon dioxide reduction reaction (CO2RR) is a promising technology to establish an artificial carbon cycle. Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) with high electrical conductivity have great potential as catalysts. Herein, we designed a range of 2D c-MOFs with different transition metal atoms and organic ligands, TMNxO4-x-HDQ (TM = Cr∼Cu, Mo, Ru∼Ag, W∼Au; x  = 0, 2, 4; HDQ = hexadipyrazinoquinoxaline), and systematically studied their catalytic performance using density functional theory (DFT). Calculation results indicated that all of TMNxO4-x-HDQ structures possess good thermodynamic and electrochemical stability. Notably, among the examined 37 MOFs, 6 catalysts outperformed the Cu(211) surface in terms of catalytic activity and product selectivity. Specifically, NiN4-HDQ emerged as an exceptional electrocatalyst for CO production in CO2RR, yielding a remarkable low limiting potential (UL) of -0.04 V. CuN4-HDQ, NiN2O2-HDQ, and PtN2O2-HDQ also exhibited high activity for HCOOH production, with UL values of -0.27, -0.29, and -0.27 V, respectively, while MnN4-HDQ, and NiO4-HDQ mainly produced CH4 with UL values of -0.58 and -0.24 V, respectively. Furthermore, these 6 catalysts efficiently suppressed the competitive hydrogen evolution reaction. Machine learning (ML) analysis revealed that the key intrinsic factors influencing CO2RR performance of these 2D c-MOFs include electron affinity (EA), electronegativity (χ), the first ionization energy (Ie), p-band center of the coordinated N/O atom (εp), the radius of metal atom (r), and d-band center (εd). Our findings may provide valuable insights for the exploration of highly active and selective CO2RR electrocatalysts.

14.
J Colloid Interface Sci ; 677(Pt B): 429-440, 2025 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-39153246

RESUMO

MicroRNAs (miRNAs) are small noncoding RNAs that are critical for the regulation of multiple physiological and pathological processes, thus holding great clinical potential. However, the therapeutic applications of miRNAs are severely limited by their biological instability and poor intracellular delivery. Herein, we describe a dual-layers surface engineering strategy to design an efficient miRNA delivery nanosystem based on metal-organic frameworks (MOFs) incorporating lipid coating. The resulting nanoparticle system was demonstrated to protect miRNA from ribonuclease degradation, enhance cellular uptake and facilitate lysosomal escape. These ensured effective miRNA mediated gene therapy, which synergized with MOF-specific photodynamic therapy and pre-encapsulated doxorubicin (Dox) chemotherapy to provide a multifunctional with therapeutic effectiveness against cencer cells The mechanisms of miRNA binding and Dox loading were revealed, demonstrating the potential of the present MOFs surface-engineered strategy to overcome their inherent pore-size restriction for macromolecular miRNA carrying, enableefficient co-delivery. In vitro studies revealed the potential of our multifunctional system for miRNA delivery and the demonstrated the therapeutic effectiveness against cancer cells, thereby providing a versatile all-in-one MOFs strategy for delivery of nucleic acids and diverse therapeutic molecules in synergistic therapy.


Assuntos
Doxorrubicina , Portadores de Fármacos , Estruturas Metalorgânicas , MicroRNAs , Nanopartículas , Propriedades de Superfície , Estruturas Metalorgânicas/química , MicroRNAs/genética , MicroRNAs/química , Humanos , Doxorrubicina/farmacologia , Doxorrubicina/química , Nanopartículas/química , Portadores de Fármacos/química , Estabilidade de RNA , Fotoquimioterapia , Tamanho da Partícula , Sobrevivência Celular/efeitos dos fármacos , Linhagem Celular Tumoral , Ensaios de Seleção de Medicamentos Antitumorais
15.
J Colloid Interface Sci ; 677(Pt B): 862-871, 2025 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-39173518

RESUMO

Two-dimensional metal-organic frameworks (2D MOFs) hold great promise as electrochemically active materials. However, their application in MOF nanocomposite electrodes in solution engineering is limited by structural self-stacking and imperfect conductive pathways. In this study, we used meso-tetra(4-carboxyphenyl) porphine (TCPP) with off-domain π-bonds to reconstitute Zn-TCPP (ZMOF) and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) through an interfacial modulation strategy involving electrostatic coupling and hydrogen bonding, creating a conductive composite with a nanosheet structure. The negatively charged PSS and ZMOF formed a three-dimensional interconnected conductive network with excellent interfaces. The positively charged PEDOT, fine tuned with the lamellar structure, established strong π-π stacking interactions between the porphyrin and thiophene rings. ZMOF also induced changes in the PEDOT chain structure, weakening PSS entanglement and enhancing charge-transport properties. The specific capacitance of the prepared supercapacitor was as high as 967.8 F g-1. Flexible supercapacitors produced on a large scale using dispensing printing technology exhibited an energy density of 1.85 µWh cm-2 and a power density of 7.08 µW cm-2. This interfacial modulation strategy also exhibited excellent wearable properties, with 96 % capacitance retention at a 180° bending angle and stable cycling performance. This study presented a significant advancement in the functionalization of 2D materials, highlighting their potential for device-grade capacitive architectures.

16.
Biomaterials ; 312: 122755, 2025 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-39151270

RESUMO

Copper-catalyzed click chemistry offers creative strategies for activation of therapeutics without disrupting biological processes. Despite tremendous efforts, current copper catalysts face fundamental challenges in achieving high efficiency, atom economy, and tissue-specific selectivity. Herein, we develop a facile "mix-and-match synthetic strategy" to fabricate a biomimetic single-site copper-bipyridine-based cerium metal-organic framework (Cu/Ce-MOF@M) for efficient and tumor cell-specific bioorthogonal catalysis. This elegant methodology achieves isolated single-Cu-site within the MOF architecture, resulting in exceptionally high catalytic performance. Cu/Ce-MOF@M favors a 32.1-fold higher catalytic activity than the widely used MOF-supported copper nanoparticles at single-particle level, as first evidenced by single-molecule fluorescence microscopy. Furthermore, with cancer cell-membrane camouflage, Cu/Ce-MOF@M demonstrates preferential tropism for its parent cells. Simultaneously, the single-site CuII species within Cu/Ce-MOF@M are reduced by upregulated glutathione in cancerous cells to CuI for catalyzing the click reaction, enabling homotypic cancer cell-activated in situ drug synthesis. Additionally, Cu/Ce-MOF@M exhibits oxidase and peroxidase mimicking activities, further enhancing catalytic cancer therapy. This study guides the reasonable design of highly active heterogeneous transition-metal catalysts for targeted bioorthogonal reactions.


Assuntos
Materiais Biomiméticos , Cobre , Humanos , Cobre/química , Materiais Biomiméticos/química , Catálise , Estruturas Metalorgânicas/química , Neoplasias/tratamento farmacológico , Neoplasias/terapia , Cério/química , Linhagem Celular Tumoral , Animais , Química Click/métodos , Biomimética/métodos , Camundongos
17.
J Environ Sci (China) ; 149: 374-385, 2025 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-39181650

RESUMO

Electrocatalytic reduction of nitrate to ammonia has been considered a promising and sustainable pathway for pollutant treatment and ammonia has significant potential as a clean energy. Therefore, the method has received much attention. In this work, Cu/Fe 2D bimetallic metal-organic frameworks were synthesized by a facile method applied as cathode materials without high-temperature carbonization. Bimetallic centers (Cu, Fe) with enhanced intrinsic activity demonstrated higher removal efficiency. Meanwhile, the 2D nanosheet reduced the mass transfer barrier between the catalyst and nitrate and increased the reaction kinetics. Therefore, the catalysts with a 2D structure showed much better removal efficiency than other structures (3D MOFs and Bulk MOFs). Under optimal conditions, Cu/Fe-2D MOF exhibited high nitrate removal efficiency (87.8%) and ammonium selectivity (89.3%) simultaneously. The ammonium yielded up to significantly 907.2 µg/(hr·mgcat) (7793.8 µg/(hr·mgmetal)) with Faradaic efficiency of 62.8% at an initial 100 mg N/L. The catalyst was proved to have good stability and was recycled 15 times with excellent effect. DFT simulations confirm the reduced Gibbs free energy of Cu/Fe-2D MOF. This study demonstrates the promising application of Cu/Fe-2D MOF in nitrate reduction to ammonia and provides new insights for the design of efficient electrode materials.


Assuntos
Amônia , Cobre , Ferro , Estruturas Metalorgânicas , Nitratos , Poluentes Químicos da Água , Amônia/química , Cobre/química , Nitratos/química , Estruturas Metalorgânicas/química , Ferro/química , Poluentes Químicos da Água/química , Catálise , Modelos Químicos , Oxirredução , Cinética
18.
J Colloid Interface Sci ; 680(Pt A): 25-32, 2024 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-39488896

RESUMO

Proton-conducting materials have gained popularity owing to their extensive applications in biologic/chemical sensors, supercapacitors, proton sieving, and proton-exchange-membrane fuel cells. To date, the most commercially used polymer membrane has been the Nafion series that exhibits conductivity exceeding 0.1 S cm-1, however, this series is expensive, has poor dimensional stability, and requires a complex synthesis process. The key criterion for selecting Nafion alternatives is to achieve the systematic integration of high proton conductivity with high stability through a simple and efficient approach. In this study, we used an aliovalent metal substitution strategy to design serial metal-organic frameworks (MOFs), including tetragonal T-Cd-BTC (CH3NH2CH3)2[Cd(BTC)](H2O) and quasi-cubic quasi-C-In-BTC (C4H7N2)[In(BTC)] and Im@quasi-C-In-BTC (C3H5N2)2[In(BTC)] frameworks, with 2-methylimidazolium and imidazolium cations as templates, respectively. Because of the aliovalent substitution of In(III) for Cd(II), both the metal-oxygen bond strength and unit cell symmetry gradually increased, resulting in an increase in the thermal stability of quasi-C-In-BTC and Im@quasi-C-In-BTC at temperatures of up to 700 K. Compared with in situ loaded 2-methylimidazolium quasi-C-In-BTC, Im@quasi-C-In-BTC prepared by incorporating the imidazolium cation into the pores of activated quasi-C-In-BTC exhibited a higher proton conductivity of 7.1 × 10-2 S cm-1 at 338 K and 95 % relative humidity. Thus, Im@quasi-C-In-BTC demonstrated real-life application. This result was confirmed by integrating Im@quasi-C-In-BTC with a poly(vinyl pyrrolidone)-poly(vinylidene fluoride) polymer matrix. Density functional theory simulations indicated that Im@quasi-C-In-BTC was strongly acidic and had high water-adsorption capacities, which contributed to extensive hydrogen-bond networks and strong host-guest interactions, in accordance with the experimental finding.

19.
Angew Chem Int Ed Engl ; : e202417137, 2024 Nov 06.
Artigo em Inglês | MEDLINE | ID: mdl-39501776

RESUMO

Paper crafts, such as origami and kirigami, have become an interdisciplinary research theme transportable from art to science, and further to engineering. Kirigami-inspired architectural design strategies allow the establishment of three-dimensional (3D) mechanical linkages with unprecedented mechanical properties. Herein, we report a crystalline zeolitic imidazolate framework (ZIF), displaying folding mechanics based on a kirigami tessellation, originated from the double-corrugation surface (DCS) pattern. Pressure- and guest-induced responses demonstrate the kirigami mechanism of the ZIF, wherein imidazolate linkers act as hinges, controlling pore dimensionality, resembling the check valve-adapted mechanical manifold. This discovery of the kirigami tessellation inside a flexible ZIF reveals foldable mechanics at the molecular level.

20.
Asian J Pharm Sci ; 19(5): 100951, 2024 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-39493807

RESUMO

Metal-organic frameworks (MOFs) offer innovative solutions to the limitations of traditional oral drug delivery systems through their unique combination of metal ions and organic ligands. This review systematically examines the structural properties and principles of MOFs, setting the stage for their application in drug delivery. It discusses various classes of MOFs, including those based on zirconium, iron, zinc, copper, titanium, aluminum, potassium, and magnesium, assessing their drug-loading capacities, biocompatibility, and controlled release mechanisms. The effectiveness of MOFs is illustrated through case studies that highlight their capabilities in enhancing drug solubility, providing protection against the harsh gastrointestinal environment, and enabling precise drug release. The review addresses potential challenges, particularly the toxicity concerns associated with MOFs, and calls for further research into their biocompatibility and interactions with biological systems. It concludes by emphasizing the potential of MOFs in revolutionizing oral drug delivery, highlighting the critical need for comprehensive research to harness their full potential in clinical applications.

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