Metal-Organic Frameworks

金属 - 有机框架
  • 文章类型: Journal Article
    金属-有机骨架(MOFs)是由自组装的金属离子或簇和有机配体组成的金属-有机骨架化合物。MOF材料通常具有多孔结构,高比表面积,均匀和可调节的毛孔,表面活性高,易于改性,具有广泛的应用前景。MOFs已被广泛使用。近年来,随着MOF材料的不断膨胀,它们在抗菌剂领域也取得了显著的成果。在这次审查中,详细介绍了MOF材料的结构组成和合成改性,描述了这些材料在感染伤口愈合中的抗菌机制和应用。此外,提出了MOF材料发展中遇到的机遇和挑战,我们预计未来将开发更多具有高生物安全性和高效抗菌能力的MOF材料。
    Metal-organic frameworks (MOFs) are metal-organic skeleton compounds composed of self-assembled metal ions or clusters and organic ligands. MOF materials often have porous structures, high specific surface areas, uniform and adjustable pores, high surface activity and easy modification and have a wide range of prospects for application. MOFs have been widely used. In recent years, with the continuous expansion of MOF materials, they have also achieved remarkable results in the field of antimicrobial agents. In this review, the structural composition and synthetic modification of MOF materials are introduced in detail, and the antimicrobial mechanisms and applications of these materials in the healing of infected wounds are described. Moreover, the opportunities and challenges encountered in the development of MOF materials are presented, and we expect that additional MOF materials with high biosafety and efficient antimicrobial capacity will be developed in the future.
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  • 文章类型: Journal Article
    细胞和酶的共固定对于工业规模可行性的级联生物催化过程通常是必不可少的,但仍然是一个巨大的挑战。在这里,我们创建了一个简单的共固定平台,将酶和细胞整合到共价有机框架(COFs)中,以实现菊粉酶和大肠杆菌的高效级联,用于天然产物的生物转化。酶可以均匀地固定在COF装甲中,它覆盖在细胞表面以产生高效的级联生物催化剂,稳定性和可回收性。此外,这种一锅原位合成方法促进了酶细胞生物催化剂的克规模制造,可以产生将菊粉转化为D-阿洛酮糖的连续流动装置,实现161.28gL-1d-1的时空产率和高稳定性(连续反应7天后保持>90%的初始催化效率)。创建的平台适用于各种单元格(例如,大肠杆菌,酵母)和酶,表现出极好的普遍性。这项研究为打破细胞外催化和细胞内催化的瓶颈铺平了道路,为酶-细胞级联生物制造创造了一个高性能和可定制的平台,扩大了生物催化过程强化的范围。
    Co-immobilization of cells and enzymes is often essential for the cascade biocatalytic processes of industrial-scale feasibility but remains a vast challenge. Herein, we create a facile co-immobilization platform integrating enzymes and cells in covalent organic frameworks (COFs) to realize the highly efficient cascade of inulinase and E. coli for bioconversion of natural products. Enzymes can be uniformly immobilized in the COF armor, which coats on the cell surface to produce cascade biocatalysts with high efficiency, stability and recyclability. Furthermore, this one-pot in situ synthesis process facilitates a gram-scale fabrication of enzyme-cell biocatalysts, which can generate a continuous-flow device conversing inulin to D-allulose, achieving space-time yield of 161.28 g L-1 d-1 and high stability (remaining >90% initial catalytic efficiency after 7 days of continuous reaction). The created platform is applied for various cells (e.g., E. coli, Yeast) and enzymes, demonstrating excellent universality. This study paves a pathway to break the bottleneck of extra- and intracellular catalysis, creates a high-performance and customizable platform for enzyme-cell cascade biomanufacturing, and expands the scope of biocatalysis process intensification.
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  • 文章类型: Journal Article
    结合了二维(2D)无机纳米片的物理优势以及金属有机框架(MOFs)的模块化设计和编程结构,2DMOFs仍然处于功能材料研究的前沿。尽管付出了巨大的努力,在2D非分层MOFs的合成与所需应用的预先设计的拓扑的精确控制仍然具有挑战性。通过配体交换成功地自下而上地合成2D非层状MOF,促使我们将部分BTC(BTC=1,3,5-苯三羧酸酯)配体解离和CO2封端的配位纳入块状Cu-BTCMOF的自上而下处理中,导致3D非分层网络成功转换为2D基于Cu的拓扑结构。值得注意的是,使用超临界含CO2的溶剂混合物来提供所需的缺陷和协调工程。因此,我们的工作引入了一种基于调制合成的自上而下的新概念,以首次制造高质量的2D非分层MOFs。
    Combining the physical advantages of two-dimensional (2D) inorganic nanosheets and the modular design and programmed structure of metal-organic frameworks (MOFs), 2D MOFs remain at the forefront of functional material research. Despite tremendous efforts, precise control in the synthesis of 2D nonlayered MOFs with predesigned topology for desired applications remains challenging. Success in the bottom-up synthesis of 2D nonlayered MOFs via ligand exchange motivated us to incorporate partial BTC (BTC = 1,3,5-benzenetricarboxylate) ligand dissociation and CO2 capped coordination into the top-down treatment of bulk Cu-BTC MOF, leading to successful conversion of a 3D nonlayered network to a 2D Cu-based topological structure. Notably, a supercritical CO2-containing solvent mixture is employed to provide the desired defect and coordination engineering. Thus, our work introduces a new top-down concept based on modulated synthesis to fabricate high-quality 2D nonlayered MOFs for the first time.
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  • 文章类型: Journal Article
    2,6-吡啶二羧酸(DPA)是臭名昭著的炭疽孢子的特殊生物标志物。因此,快速,敏感,选择性定量检测DPA具有极其重要的意义和紧迫性。本文报道了式为{[Zn6(NDA)6(DPBT)3]2H2O·3DMF}n(MOF-1)的Zn(II)金属有机骨架,由2,6-萘二羧酸(2,6-NDA)组成,4,7-二(4-吡啶基)-2,1,3-苯并噻二唑(DPBT),和Zn(II)离子。结构分析表明,MOF-1是在单斜晶系中结晶的三维(3D)网络,具有C2/c空间群,显示高pH值,溶剂,和热稳定性。发光传感研究表明,MOF-1具有高选择性,敏感,和可回收荧光传感器用于识别DPA。此外,制作荧光试纸,以快速检测颜色变化的DPA。通过MOF-1和DPA分子之间的氢键相互作用和光诱导电子转移跃迁建立了增强机制。
    2,6-pyridine dicarboxylic acid (DPA) is an exceptional biomarker of notorious anthrax spores. Therefore, the rapid, sensitive, and selective quantitative detection of DPA is extremely significant and urgent. This paper reports a Zn(II) metal-organic framework with the formula of {[Zn6(NDA)6(DPBT)3] 2H2O·3DMF}n (MOF-1), which consists of 2,6-naphthalenedicarboxylic acid (2,6-NDA), 4,7-di(4-pyridyl)-2,1,3-benzothiadiazole (DPBT), and Zn(II) ions. Structural analysis indicated that MOF-1 is a three-dimensional (3D) network which crystallized in the monoclinic system with the C2/c space group, revealing high pH, solvent, and thermal stability. Luminescence sensing studies demonstrated that MOF-1 had the potential to be a highly selective, sensitive, and recyclable fluorescence sensor for the identification of DPA. Furthermore, fluorescent test paper was made to detect DPA promptly with color changes. The enhancement mechanism was established by the hydrogen-bonding interaction and photoinduced electron transfer transition between MOF-1 and DPA molecules.
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  • 文章类型: Journal Article
    从N2中有效分离CH4对于从氮气中纯化甲烷是必不可少的。为了解决这个问题,合成了由棒状SBA-15基UiO-66-Br2组成的复合材料,用于分离CH4/N2混合物。通过PXRD对材料进行了表征,N2吸附-解吸,SEM,TEM,FT-IR,和TGA。确定了CH4和N2在标准压力条件下对复合材料的吸附等温线,然后进行了比较。研究表明,复合材料是通过MOF纳米晶体在SBA-15基体表面的生长形成的。杂化材料的表面积和吸附能力的增强归因于表面硅烷醇基团与金属中心之间的相互作用引起的结构修饰。利用Langmuir吸附方程评估了复合材料对CH4和N2气体混合物的选择性。分析结果表明,与其他样品相比,U6B2S5/SBA-15样品对CH4/N2吸附的选择性最大,吸附选择性参数(S)为20.06。需要进行其他研究,以使用SBA-15基金属有机骨架材料增强CH4/N2混合物中甲烷的富集。
    Efficient separation of CH4 from N2 is essential for the purification of methane from nitrogen. In order to address this problem, composite materials consisting of rod-shaped SBA-15-based UiO-66-Br2 were synthesized for the purpose of separating a CH4/N2 mixture. The materials were characterized via PXRD, N2 adsorption-desorption, SEM, TEM, FT-IR, and TGA. The adsorption isotherms of CH4 and N2 under standard pressure conditions for the composites were determined and subsequently compared. The study revealed that the composites were formed through the growth of MOF nanocrystals on the surfaces of the SBA-15 matrix. The enhancements in surface area and adsorption capacity of hybrid materials were attributed to the structural modifications resulting from the interactions between surface silanol groups and metal centers. The selectivity of the composites towards a gas mixture of CH4 and N2 was assessed utilizing the Langmuir adsorption equation. The results of the analysis revealed that the U6B2S5/SBA-15 sample exhibited the greatest selectivity for CH4/N2 adsorption compared to the other samples, with an adsorption selectivity parameter (S) of 20.06. Additional research is necessary to enhance the enrichment of methane from CH4/N2 mixtures using SBA-15-based metal-organic framework materials.
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  • 文章类型: Journal Article
    醛在温和条件下的氧化酯化仍然是一个重大挑战。这项研究引入了一种独特的缺陷UiO-66,以实现在温和条件下有效的醛氧化的金纳米簇(AuNC)。通过XRD技术对这些材料的结构和表征进行了深入的研究,SEM和TEM图像,FT-IR,拉曼,和XPS光谱,强调缺陷型UiO-66中独特的微孔有利于AuNC的制造。系统地评价了所制备材料在醛氧化反应中的催化性能,证明了分散的Au@UiO-66-25具有高含量(9.09wt%)Au负载和超小尺寸(〜2.7nm)的显着效率。此外,提供了在温和条件下(70°C持续1小时)对催化过程的机械见解,阐明在AuNC的有限制造和随后的糠醛吸附中确定有缺陷的UiO-66,这是管理观察到的增强功能的原则的基础。这项研究为使用有缺陷的MOFs作为平台合成高度分散和催化活性的金属纳米颗粒奠定了基础,将糠醛催化酯化反应提高到一个新的水平。
    The oxidative esterification of aldehydes under mild conditions remains a significant challenge. This study introduces a unique defective UiO-66 to achieve gold nanoclusters (AuNCs) for efficient aldehyde oxidation under mild conditions. The construction and characterization of these materials are thoroughly investigated by techniques of XRD, SEM and TEM images, FT-IR, Raman, and XPS spectrum, emphasizing the unique microporous in defective UiO-66 are conducive to the fabrication of AuNCs. The catalytic performance of the prepared materials in aldehyde oxidation reactions is systematically evaluated, demonstrating the remarkable efficiency of dispersed Au@UiO-66-25 with high-content (9.09 wt%) Au-loading and ultra-small size (~2.7 nm). Moreover, mechanistic insights into the catalytic process under mild conditions (70 °C for 1 h) are provided, elucidating the determination of defective UiO-66 in the confined fabrication of AuNCs and subsequent furfural adsorption, which underlie the principles governing the observed enhancements. This study establishes the groundwork for the synthesis of highly dispersed and catalytically active metal nanoparticles using defective MOFs as a platform, advancing the catalytic esterification reaction of furfural to the next level.
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  • 文章类型: Journal Article
    在环境化学中,用于消除水中有机污染物的光催化剂已经获得了极大的兴趣。我们的研究引入了结合MIL-101(Cr)和碘化铋(Bi5O7I)的独特异质结构。我们评估了这种纳米结构在可见光下吸附和降解四环素(TC)的效率。Bi5O7I@MIL-101(Cr)复合材料,表面积为637m2/g,防止在其组件中看到的自聚集,增强可见光的吸收。其光催化效率分别超过Bi5O7I和MIL-101(Cr)的33.4和9.2倍,分别。综合分析,包括扫描电子显微镜(SEM)和透射电子显微镜(TEM),证实了具有明确形态特征的异质结构的成功形成。BET分析表明其高表面积,而X射线衍射(XRD)证实了其结晶度。电子自旋共振(ESR)测试表明,在光下会产生大量的活性氧(ROS),例如h和··O2-。对TC降解至关重要。该材料在五个周期内保持了优异的耐久性。密度泛函理论(DFT)模拟和经验研究揭示了Bi5O7I和MIL-101(Cr)之间的I型异质结,促进有效的电子-空穴对分离。这项研究强调了Bi5O7I@MIL-101(Cr)的优异光催化活性和稳定性,提供对设计用于水净化的创新光催化剂的见解。
    In environmental chemistry, photocatalysts for eliminating organic contaminants in water have gained significant interest. Our study introduces a unique heterostructure combining MIL-101(Cr) and bismuth oxyiodide (Bi5O7I). We evaluated this nanostructure\'s efficiency in adsorbing and degrading tetracycline (TC) under visible light. The Bi5O7I@MIL-101(Cr) composite, with a surface area of 637 m2/g, prevents self-aggregation seen in its components, enhancing visible light absorption. Its photocatalytic efficiency surpassed Bi5O7I and MIL-101(Cr) by 33.4 and 9.2 times, respectively. Comprehensive analyses, including scanning electron microscopy (SEM) and transmission electron microscopy (TEM), confirmed the successful formation of the heterostructure with defined morphological characteristics. BET analysis demonstrated its high surface area, while X-ray diffraction (XRD) confirmed its crystallinity. Electron spin resonance (ESR) tests showed significant generation of reactive oxygen species (ROS) like h+ and·•O2- under light, crucial for TC degradation. The material maintained exceptional durability over five cycles. Density functional theory (DFT) simulations and empirical investigations revealed a type I heterojunction between Bi5O7I and MIL-101(Cr), facilitating efficient electron-hole pair separation. This study underscores the superior photocatalytic activity and stability of Bi5O7I@MIL-101(Cr), offering insights into designing innovative photocatalysts for water purification.
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  • 文章类型: Journal Article
    Omega-3多不饱和脂肪酸(ω-3PUFA)提供多种健康益处,比如支持心血管健康,改善认知功能,促进关节和肌肉骨骼健康,并促进健康衰老。尽管他们的优势,像氧化敏感性这样的挑战,低生物利用度,高剂量的潜在不良反应持续存在。纳米粒子封装成为解决这些限制同时保持稳定性的有希望的途径。提高生物利用度,和控制释放。这篇全面的综述探讨了ω-3脂肪酸的治疗作用,批判性地评估它们的缺点,并深入研究现代封装策略。此外,它探讨了金属有机框架纳米颗粒(MOFNP)与其他常用纳米颗粒相比,在改善药物递送系统(DDS)中omega-3脂肪酸的治疗效果方面的潜在优势。此外,它概述了未来的研究方向,以充分利用这些封装的omega-3制剂用于心血管疾病治疗的治疗益处。
    Omega-3 polyunsaturated fatty acids (ω-3 PUFAs) offer diverse health benefits, such as supporting cardiovascular health, improving cognitive function, promoting joint and musculoskeletal health, and contributing to healthy aging. Despite their advantages, challenges like oxidation susceptibility, low bioavailability, and potential adverse effects at high doses persist. Nanoparticle encapsulation emerges as a promising avenue to address these limitations while preserving stability, enhanced bioavailability, and controlled release. This comprehensive review explores the therapeutic roles of omega-3 fatty acids, critically appraising their shortcomings and delving into modern encapsulation strategies. Furthermore, it explores the potential advantages of metal-organic framework nanoparticles (MOF NPs) compared to other commonly utilized nanoparticles in improving the therapeutic effectiveness of omega-3 fatty acids within drug delivery systems (DDSs). Additionally, it outlines future research directions to fully exploit the therapeutic benefits of these encapsulated omega-3 formulations for cardiovascular disease treatment.
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  • 文章类型: Journal Article
    金属有机骨架(MOF)经常用作传感材料。不幸的是,MOFs的低电导率阻碍了其在电化学测定中的进一步应用。为了克服这个限制,提出了一种新的MOFs修饰策略,建立了白酒中氰化物的电化学测定方法。Co和Ni协同用作金属活性中心,以内消旋四(4-羧基苯基)卟啉(TCPP)和二茂铁羧酸(Fc-COOH)为主要配体,通过水热法合成Ni/Co-MOF-TCPP-Fc。制备的MOF表现出改善的电导率和稳定的比率信号,使氰化物的快速和灵敏的测定。丝网印刷碳电极(SPCE)由于其便携性,适用于通过电化学传感器原位和实时测定氰化物,低成本,易于大规模生产。该方法在0.196~44ng/mL范围内呈对数线性响应,检测限(LOD)为0.052ng/mL。与其他方法相比,传感器是通过一步合成法构建的,这大大简化了分析过程,所需的测定时间仅为4分钟。在自然氰化物测定过程中,推荐读数与GC-MS匹配良好,相对误差小于5.9%。此外,该电化学传感器为评价白酒中氰化物的安全性提供了一种有前景的方法。
    Metal-organic frameworks (MOFs) are frequently utilized as sensing materials. Unfortunately, the low conductivity of MOFs hinder their further application in electrochemical determination. To overcome this limitation, a novel modification strategy for MOFs was proposed, establishing an electrochemical determination method for cyanides in Baijiu. Co and Ni were synergistically used as the metal active centers, with meso-Tetra(4-carboxyphenyl)porphine (TCPP) and Ferrocenecarboxylic acid (Fc-COOH) serving as the main ligands, synthesizing Ni/Co-MOF-TCPP-Fc through a hydrothermal method. The prepared MOF exhibited improved conductivity and stable ratio signals, enabling rapid and sensitive determination of cyanides. The screen-printed carbon electrodes (SPCE) were suitable for in situ and real-time determination of cyanide by electrochemical sensors due to their portability, low cost, and ease of mass production. A logarithmic linear response in the range of 0.196~44 ng/mL was demonstrated by this method, and the limit of detection (LOD) was 0.052 ng/mL. Compared with other methods, the sensor was constructed by a one-step synthesis method, which greatly simplifies the analysis process, and the determination time required was only 4 min. During natural cyanide determinations, recommended readouts match well with GC-MS with less than 5.9% relative error. Moreover, this electrochemical sensor presented a promising method for assessing the safety of cyanides in Baijiu.
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  • 文章类型: Journal Article
    金属有机骨架(MOF)由于其独特的性能而作为传感材料获得了显着的重视。然而,了解形态之间的相关性,属性,这些基于MOF的传感器的传感性能仍然是一个挑战,限制了它们的应用和改进的潜力。在这项研究中,选择Zr-MOF作为理想模型来探索MOF形态对传感性能的影响,鉴于其显著的稳定性和结构变异性。三个发光MOF(即棒状Zr-LMOF,棱柱状Zr-LMOF,通过调节苯甲酸的用量和反应时间,合成了椭球状Zr-LMOF)。更重要的是,彻底检查了这些Zr-LMOFs对黄曲霉毒素B1(AFB1)的传感性能。值得注意的是,与其他Zr-LMOF相比,椭球状Zr-LMOF表现出明显更高的灵敏度,归因于其大的比表面积和孔体积。此外,对Zr-LMOFs对AFB1的检测机制进行了深入研究。基于这些见解,通过将Eu3+与椭球状Zr-LMOF协调,开发了比率荧光传感器,AFB1的检测限明显较低,为2.82nM。这项研究有助于更好地理解MOF形态与传感特性之间的关系,同时提出了一种有效的AFB1检测方法。
    Metal-organic frameworks (MOFs) have gained significant prominence as sensing materials owing to their unique properties. However, understanding the correlation between the morphology, properties, and sensing performance in these MOF-based sensors remains a challenge, limiting their applications and potential for improvement. In this study, Zr-MOF was chosen as an ideal model to explore the impact of the MOF morphology on the sensing performance, given its remarkable stability and structural variability. Three luminescent MOFs (namely rod-like Zr-LMOF, prismoid-like Zr-LMOF, and ellipsoid-like Zr-LMOF) were synthesized by adjusting the quantities of the benzoic acid and the reaction time. More importantly, the sensing performance of these Zr-LMOFs in response to aflatoxin B1 (AFB1) was thoroughly examined. Notably, the ellipsoid-like Zr-LMOF exhibited significantly higher sensitivity compared to other Zr-LMOFs, attributed to its large specific surface area and pore volume. Additionally, an in-depth investigation into the detection mechanism of AFB1 by Zr-LMOFs was conducted. Building upon these insights, a ratiometric fluorescence sensor was developed by coordinating Eu3+ with ellipsoid-like Zr-LMOF, achieving a remarkably lower detection limit of 2.82 nM for AFB1. This study contributes to an improved comprehension of the relationship between the MOF morphology and the sensing characteristics while presenting an effective approach for AFB1 detection.
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