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1.
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
2.
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.

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.
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.

5.
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
6.
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.

7.
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
8.
Small Methods ; : e2400968, 2024 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-39351807

RESUMO

Solid-state electrolytes (SSEs) based on metal-organic frameworks (MOFs) are an ideal material for constructing high-performance lithium metal batteries (LMBs). However, the low ion conductivity and poor interface contact (especially at low temperatures) still seriously hinder its further application. Herein, inspired by the Na+/K+ conduction in biology systems, a series (NH2, OH, NH-(CH2)3-SO3H)-modified MIL-53-X as SSEs is reported. These functional groups are similar to anions suspended in biological ion channels, partially repelling anions while allowing cations to be effectively transported through pore channels. Subsequently, MIL-53-X with hierarchical pore structure (H-MIL-53-X) is obtained by introducing lauric acid as a regulator, and then the effects of structural design and morphology control on its performance are explored. The conductivity of H-MIL-53-NH-SO3Li with multi-level pore structure and modified by sulfonic acid groups reached 2.2 × 10-3 S cm-1 at 25 °C, lithium-ion transference number of 0.78. Besides, the H-MIL-53-NH-SO3Li still has an excellent conductivity of 10-4 S cm-1 at -40 °C. Additionally, LiFePO4/Li batteries equipped with H-MIL-53-NH-SO3Li SSEs could operate stably for over 200 cycles at 0.1 C. The strategy of combining structural and morphological design of MOFs with biomimetic ion channels opens new avenues for the design of high-performance SSEs.

9.
Adv Sci (Weinh) ; : e2407297, 2024 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-39352306

RESUMO

Metal-organic frameworks (MOFs) deliver potential applications in electrochromism and energy storage. However, the poor intrinsic conductivity of MOFs in electrolytes seriously hampers the development of the above-mentioned electrochemical applications, especially in one MOF electrode. Herein, a new Ni-based MOF (denoted Ni-DPNDI) is proposed with enhanced conductivity by π-delocalized DPNDI connectors. Predictably, the obtained Ni-DPNDI MOF achieves a conductivity of up to 4.63 S∙m-1 at 300 K. Profiting from its unique electronic structure, the Ni-DPNDI MOF delivers excellent electrochromic and energy storage performance with a great optical modulation (60.8%), a fast switching speed (tc = 7.9 s and tb = 6.4 s), a moderate specific capacitance (25.3 mAh·g-1) and good cycle stability over 2000 times. Meanwhile, energy storage capacity is visual by the coloration states of Ni-DPNDI film. As a proof of the potential application, a large-area (100 cm2) electrochromic energy storage smart window is further designed and displayed. The strategy provides an interesting alternative to porous multifunctional materials for the new generation of electronic devices with diverse applications.

10.
Front Pharmacol ; 15: 1462368, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-39359247

RESUMO

As a novel class of smart biomaterials with promising potentials, metal-organic frameworks (MOFs) are widely utilized in the field of biomedicine. Current researches indicate that the therapeutic strategies for osteoarthritis (OA) are highly limited to achieving symptom improvement and reducing both pain and inflammation. Together, the introduction of MOFs into the treatment of OA holds the potential to offer significant benefits. This is because MOFs not only have intrinsic biological activities, but also act as carriers to facilitate controlled drug delivery and prolong the duration in the management of OA. This paper presents a review of the recent studies that have explored the potential usage of MOFs as drugs or carriers in the treatment of OA, which also examines the progress of MOFs in tissue engineering for the treatment of OA. These studies are anticipated to not only enhance the comprehension of MOFs but also provide strong evidence in favor of their utilization in the treatment of OA.

11.
Angew Chem Int Ed Engl ; : e202414770, 2024 Oct 02.
Artigo em Inglês | MEDLINE | ID: mdl-39355946

RESUMO

Developing high-performance lithium-sulfur batteries is a promising way to attain higher energy density at lower cost beyond the state-of-the-art lithium-ion battery technology. However, the major issues blocking their practical application are the sluggish kinetics and parasitic shuttling reactions for sulfur and polysulfides. Here, pillaring multilayer graphene with the metal-organic framework (MOF) demonstrates the substantial impact of a versatile interlayer design in tackling those issues. Unlike regular composite separators reported so far, the participation of tri-metallic Ni-Co-Mn MOF (NCM-MOF) as pillars supports the construction of an ion-channel interconnected interlayer structure, unexpectedly balancing the interfacial concentration polarization, spatially confining the soluble polysulfides and vastly affording lithiophilic sites for highly efficient polysulfide sieving/conversion. As a demonstration, we show that the MOF-pillared interlayer structure enables outstanding capacity (1634 mAh g-1 at 0.1C) and longevity (average capacity decay of 0.034% per cycle in 2000 cycles) of lithium-sulfur batteries. Besides, the multilayer separator can be readily integrated into the high-nickel cathode (LiNi0.91Mn0.03Co0.06O2)-based lithium-ion batteries, which efficiently suppresses the undesired phase evolution upon cycling. These findings suggest the potential of "gap-filling" materials in fabricating multi-functional separators, bring forward the pillared interlayer structure for energy-storage applications.

12.
Mikrochim Acta ; 191(11): 640, 2024 Oct 02.
Artigo em Inglês | MEDLINE | ID: mdl-39356328

RESUMO

Chiral compounds are abundantly distributed in both the natural world and biological systems. It is crucial to identify and detect chiral compounds in living systems or to separate and determine them in the natural environment. Many researchers have developed a range of chiral materials with different functionalizations to separate and detect chiral substances. Chiral metal-organic frameworks (CMOFs) have the potential to be used in enantioselective separation and detection due to their large surface areas, regulated framework topologies, particular substrate interactions, and accessible chiral sites. CMOFs contribute significantly to the development of enantiomer separation and detection in medicine, agriculture, food, environment, and other fields. This review focuses on four synthesis methods of CMOFs and their applications in chiral separation and chiral sensing in the past five years, mainly including chromatographic separation, membrane separation, optical sensing, electrochemical sensing, and other sensing methods. Finally, the challenges and potential growth direction of CMOFs in enantiomer separation and detection are discussed and prospected.

13.
Angew Chem Int Ed Engl ; : e202416367, 2024 Oct 11.
Artigo em Inglês | MEDLINE | ID: mdl-39392381

RESUMO

The addition of polar functional groups to porous structures is an effective strategy for increasing the ability of metal-organic frameworks (MOFs) to capture CO2 by enhancing interactions between the dipoles of the polar functional groups and the quadrupoles of CO2. However, the potential of MOFs grafted to polar functional group to activate CO2 has not been investigated in the context of CO2 electrolysis. In this study, we report a mixed-ligand strategy to incorporate various functional groups in the MOFs. We found that substituents with strong polarity led to increased catalytic performance of electrochemical CO2 reduction for these polarized MOFs. Both experimental and theoretical evidence indicates that the presence of polar functional groups induces a charge redistribution in the micropores of MOFs. We have shown that higher electron densities of sp2-carbon atoms in benzimidazolate ligands reduces the energy barrier to generate *COOH, which is simultaneously controlled by the mass transfer of CO2. Our research offers an effective method of disrupting local electron neutrality in the pores of electrocatalysts/supports to activate CO2 under electrochemical conditions.

14.
Int J Nanomedicine ; 19: 9943-9959, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-39355653

RESUMO

Introduction: Alzheimer's disease (AD), a neurodegenerative condition, stands as the most prevalent form of dementia. Its complex pathological mechanisms and the formidable blood-brain barrier (BBB) pose significant challenges to current treatment approaches. Oxidative stress is recognized as a central factor in AD, underscoring the importance of antioxidative strategies in its treatment. In this study, we developed a novel brain-targeted nanoparticle, Ce/Zr-MOF@Cur-Lf, for AD therapy. Methods: Layer-by-layer self-assembly technology was used to prepare Ce/Zr-MOF@Cur-Lf. In addition, the effect on the intracellular reactive oxygen species level, the uptake effect by PC12 and bEnd.3 cells and the in vitro BBB permeation effect were investigated. Finally, the mouse AD model was established by intrahippocampal injection of Aß1-42, and the in vivo biodistribution, AD therapeutic effect and biosafety of the nanoparticles were researched at the animal level. Results: As anticipated, Ce/Zr-MOF@Cur-Lf demonstrated efficient BBB penetration and uptake by PC12 cells, leading to attenuation of H2O2-induced oxidative damage. Moreover, intravenous administration of Ce/Zr-MOF@Cur-Lf resulted in rapid brain access and improvement of various pathological features of AD, including neuronal damage, amyloid-ß deposition, dysregulated central cholinergic system, oxidative stress, and neuroinflammation. Conclusion: Overall, Ce/Zr-MOF@Cur-Lf represents a promising approach for precise brain targeting and multi-target mechanisms in AD therapy, potentially serving as a viable option for future clinical treatment.


Assuntos
Doença de Alzheimer , Barreira Hematoencefálica , Cério , Curcumina , Estresse Oxidativo , Zircônio , Animais , Doença de Alzheimer/tratamento farmacológico , Células PC12 , Barreira Hematoencefálica/efeitos dos fármacos , Barreira Hematoencefálica/metabolismo , Zircônio/química , Zircônio/farmacocinética , Camundongos , Ratos , Curcumina/química , Curcumina/farmacocinética , Curcumina/farmacologia , Curcumina/administração & dosagem , Estresse Oxidativo/efeitos dos fármacos , Cério/química , Cério/farmacocinética , Cério/farmacologia , Cério/administração & dosagem , Peptídeos beta-Amiloides/metabolismo , Peptídeos beta-Amiloides/química , Distribuição Tecidual , Espécies Reativas de Oxigênio/metabolismo , Nanopartículas/química , Modelos Animais de Doenças , Estruturas Metalorgânicas/química , Estruturas Metalorgânicas/farmacocinética , Estruturas Metalorgânicas/farmacologia , Masculino , Portadores de Fármacos/química , Portadores de Fármacos/farmacocinética , Humanos , Encéfalo/efeitos dos fármacos , Encéfalo/metabolismo
15.
Angew Chem Int Ed Engl ; : e202417027, 2024 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-39375150

RESUMO

The activation of the stimulator of interferon genes (STING) protein by cyclic dinucleotide metabolites plays a critical role in antitumor immunity. However, synthetic STING agonists like 4-(5,6-dimethoxybenzo[b]thiophen-2-yl)-4-oxobutanoic acid (MSA-2) exhibit suboptimal pharmacokinetics and fail to sustain STING activation in tumors for effective antitumor responses. Here, we report the design of MOF/MSA-2, a bifunctional MSA-2 conjugated nanoscale metal-organic framework (MOF) based on Hf6 secondary building units (SBUs) and hexakis(4'-carboxy[1,1'-biphenyl]-4-yl)benzene bridging ligands, for potent cancer radio-immunotherapy. By leveraging the high-Z properties of the Hf6 SBUs, the MOF enhances the therapeutic effect of X-ray radiation and elicits potent immune stimulation in the tumor microenvironment. MOF/MSA-2 further enhances radiotherapeutic effects of X-rays by enabling sustained STING activation and promoting the infiltration and activation of immune cells in the tumors. MOF/MSA-2 plus low-dose X-ray irradiation elicits strong STING activation and potent tumor regression, and when combined with an immune checkpoint inhibitor, effectively suppresses both primary and distant tumors through systemic immune activation.

16.
ChemSusChem ; : e202401760, 2024 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-39375533

RESUMO

The conversion of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) is a promising approach for enhancing biomass utilization. Nevertheless, traditional methods using noble metal catalysts face challenges due to high costs and poor selectivity towards DFF. Herein, we developed a novel catalytic electrode integrating N-hydroxyphthalimide (NHPI) into a metal-organic framework on a hydrophilic carbon cloth. This design significantly enhances the selective adsorption of HMF due to stronger hydrogen-bond interaction between the electrode's hydrophilic surface and the C(sp3)-OH group in HMF compared to the C(sp2)=O in DFF. Additionally, the electro-driven dissociation of the NHPI-linker generates stabilized N-Oxyl radicals that promote selective semi-oxidation of HMF under neutral conditions. As a result, this approach achieves a high yield rate of 138.2 mol molcat-1 h-1 with a selectivity of 96.7% for the HMF-to-DFF conversion. This work introduces a novel strategy for designing catalytic electrodes with stabilized N-Oxyl radicals, and offers a promising method for electrocatalytic DFF synthesis, leveraging hydrogen-bond interaction between electrode surface and HMF.

17.
Food Chem ; 463(Pt 4): 141496, 2024 Sep 30.
Artigo em Inglês | MEDLINE | ID: mdl-39378721

RESUMO

Rapid and effective analysis of foodborne bacteria is crucial for preventing and controlling bacterial infections. Here, we present the synthesis of a self-reporting molecularly imprinted polymer (MIP) as an inner reference probe (IR), and the in-situ growth of metal-organic frameworks on transition metal carbon nitrides (MOF/Ti3C2TX-MXene) as a signaling nanoprobe (SP). These advancements are then applied in a ratiometric electrochemical bioassay for Staphylococcus aureus (S. aureus) using a hybrid recognition mechanism. When S. aureus is present, the aptamer-integrated MIP (MIP@Apt) efficiently captures it, followed by binding with SP to form a sandwich structure. This leads to decreased current response of IR (IIR) and increased current intensity of SP (Isp), enabling quantification through utilization of the ISP to IIR ratio. The biosensor shows a wide detection range (10-108 CFU mL-1) and low detection limit of 1.2 CFU mL-1. Its feasibility for testing complex samples indicates the potential application in food analysis.

18.
Angew Chem Int Ed Engl ; : e202417072, 2024 Oct 08.
Artigo em Inglês | MEDLINE | ID: mdl-39379790

RESUMO

Efficient removal of acetylene (C2H2) impurities from polymer-grade ethylene (C2H4) in a simple, clean manner remains a challenging goal in industry. The use of porous materials such as metal-organic frameworks (MOFs) is promising for this aim but the acquisition of high purification performance is still hindered by few knowledge on the purification process because the previous conclusions were derived basically from the non-breakthrough tests or ignored the influence of structural difference (crystal structure, morphology, or defect). Here we propose an unprecedented in situ stimulus response strategy to minimize the influence of structural difference, obtain the gas-loading crystal structures of the same MOF before and after light or heat stimulation, directly observe the evolution of pore charge distribution and pore×××gas interactions under light/heat induction, and finally summarizes the favorable structure for highly efficient purification of C2H4. This study opens a new route to understand the relationship between the structure and separation performance for porous materials.

19.
ChemSusChem ; : e202401456, 2024 Oct 08.
Artigo em Inglês | MEDLINE | ID: mdl-39377744

RESUMO

Polyoxometalates@metal-organic frameworks (POMs@MOFs) have attracted much attention as multifunctional materials in biomass catalysis. Individual POMs and MOFs are hindered by their respective defects, such as poor stability and single catalytic active site, which make it difficult to realize large-scale applications. However, the combination of POMs and MOFs can be used to maximize the catalytic advantages of each. MOFs with high specific surface area and rich pore structure can effectively stabilize and uniformly disperse POMs, while the introduction of POMs also provides more catalytic possibilities for POMs@MOFs. Therefore, POMs@MOFs with ultra-high porosity, large specific surface area and excellent acid catalytic activity have unique catalytic advantages in the field of biomass catalytic conversion. In this work, we provide an overview of the current development of POMs@MOFs in the field of biomass catalysis. The synthesis strategies of POMs@MOFs are summarized and discussed, highlighting the in-situ synthesis methods. We focus on the nanostructure engineering of POMs@MOFs, and explore the "structure-property" relationship in depth. In addition, the representative work of POMs@MOFs in the catalysis of biomass derivatives is summarized. Filially, the prospects, and challenges for the future development of POMs@MOFs in the field of biomass catalysis are also presented.

20.
J Appl Crystallogr ; 57(Pt 5): 1270-1281, 2024 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-39387073

RESUMO

Metal-organic frameworks (MOFs) have garnered significant attention in recent years owing to their exceptional properties. Understanding the intricate relationship between the structure of a material and its properties is crucial for guiding the synthesis and application of these materials. (Scanning) Transmission electron microscopy (S)TEM imaging stands out as a powerful tool for structural characterization at the nanoscale, capable of detailing both periodic and aperiodic local structures. However, the high electron-beam sensitivity of MOFs presents substantial challenges in their structural characterization using (S)TEM. This paper summarizes the latest advancements in low-dose high-resolution (S)TEM imaging technology and its application in MOF material characterization. It covers aspects such as framework structure, defects, and surface and interface analysis, along with the distribution of guest molecules within MOFs. This review also discusses emerging technologies like electron ptychography and outlines several prospective research directions in this field.

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