Metal-Organic Frameworks

金属 - 有机框架
  • 文章类型: Journal Article
    An intelligent nanodrug delivery system (Cu/ZIF-8@GOx-DOX@HA, hereafter CZGDH) consisting of Cu-doped zeolite imidazolate framework-8 (Cu/ZIF-8, hereafter CZ), glucose oxidase (GOx), doxorubicin (DOX), and hyaluronic acid (HA) was established for targeted drug delivery and synergistic therapy of tumors. The CZGDH specifically entered tumor cells through the targeting effect of HA and exhibited acidity-triggered biodegradation for subsequent release of GOx, DOX, and Cu2+ in the tumor microenvironment (TME). The GOx oxidized the glucose (Glu) in tumor cells to produce H2O2 and gluconic acid for starvation therapy (ST). The DOX entered the intratumoral cell nucleus for chemotherapy (CT). The released Cu2+ consumed the overexpressed glutathione (GSH) in tumor cells to produce Cu+. The generated Cu+ and H2O2 triggered the Fenton-like reaction to generate toxic hydroxyl radicals (·OH), which disrupted the redox balance of tumor cells and effectively killed tumor cells for chemodynamic therapy (CDT). Therefore, synergistic multimodal tumor treatment via TME-activated cascade reaction was achieved. The nanodrug delivery system has a high drug loading rate (48.3 wt%), and the three-mode synergistic therapy has a strong killing effect on tumor cells (67.45%).
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  • 文章类型: Journal Article
    Human epididymis protein 4 (HE4), a diagnostic biomarker of ovarian cancer, is crucial for monitoring the early stage of the disease. Hence, it is highly important to develop simple, inexpensive, and user-friendly biosensors for sensitive and quantitative HE4 assays. Herein, a new sandwich-type electrochemical immunosensor based on Prussian blue (PB) as a signal indicator and functionalized metal-organic framework nanocompositesas efficient signal amplifiers was fabricated for quantitative analysis of HE4. In principle, ketjen black (KB) and AuNPs modified on TiMOF (TiMOF-KB@AuNPs) could accelerate electron transfer on the electrode surface and act as a matrix for the immobilization of antibodies via cross-linking to improve the determination sensitivity. The PB that covalently binds to labeled antibodies endows the biosensors with intense electrochemical signals. Furthermore, the concentration of HE4 could be indirectly detected by monitoring the electroactivity of PB. Benefiting from the high signal amplification ability of the PB and MOF nanocomposites, this strategy displayed a wide linear range (0.1-80 ng mL-1) and a lower detection limit (0.02 ng mL-1). Hence, this study demonstrated great promise for application in clinical ovarian cancer diagnosis and treatment, and provided a new platform for detecting other cancer biomarkers.
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  • 文章类型: Journal Article
    CoFe@C首先通过煅烧CoFe-金属-有机骨架-74(CoFe-MOF-74)的前体来制备,然后构建了用于测定新橙皮苷二氢查耳酮(NHDC)的电化学传感器,它源于新型CoFe@C/Nafion复合膜修饰玻碳电极(GCE)。通过场发射扫描电子显微镜(FE-SEM)和透射电子显微镜(TEM)验证了CoFe@C/Nafion复合材料。电化学阻抗谱(EIS)用于评估其作为电化学传感器的改性材料的电性能。与CoFe-MOF-74前驱体修饰电极相比,CoFe@C/Nafion电极表现出很大的协同催化作用,极大地增加了NHDC的氧化峰信号。研究了各种实验条件对NHDC氧化的影响,并测试了校准图。结果表明,在最佳实验条件下,CoFe@C/NafionGCE具有良好的重现性和抗干扰性。此外,NHDC的差分脉冲电流响应与其浓度在0.08~20μmol/L范围内呈线性关系,线性回归系数为0.9957。检出限低至14.2nmol/L(S/N=3)。为了进一步验证该方法的可行性,它被成功地用于测定中药中NHDC的含量,结果令人满意,与高效液相色谱(HPLC)的结果一致。
    CoFe@C was first prepared by calcining the precursor of CoFe-metal-organic framework-74 (CoFe-MOF-74), then an electrochemical sensor for the determination of neohesperidin dihydrochalcone (NHDC) was constructed, which was stemmed from the novel CoFe@C/Nafion composite film modified glassy carbon electrode (GCE). The CoFe@C/Nafion composite was verified by field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). Electrochemical impedance spectroscopy (EIS) was used to evaluate its electrical properties as a modified material for an electrochemical sensor. Compared with CoFe-MOF-74 precursor modified electrode, CoFe@C/Nafion electrode exhibited a great synergic catalytic effect and extremely increased the oxidation peak signal of NHDC. The effects of various experimental conditions on the oxidation of NHDC were investigated and the calibration plot was tested. The results bespoken that CoFe@C/Nafion GCE has good reproducibility and anti-interference under the optimal experimental conditions. In addition, the differential pulse current response of NHDC was linear with its concentration within the range 0.08 ~ 20 µmol/L, and the linear regression coefficient was 0.9957. The detection limit was as low as 14.2 nmol/L (S/N = 3). In order to further verify the feasibility of the method, it was successfully used to determine the content of NHDC in Chinese medicine, with a satisfactory result, good in accordance with that of high performance liquid chromatography (HPLC).
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  • 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
    半胱氨酸尿症是一种遗传性疾病,在严重的情况下,可能会导致肾衰竭.作为胱氨酸尿症的重要生物标志物,尿液中精氨酸(Arg)的水平是筛查胱抑素尿的重要指标。因此,迫切需要高选择性和灵敏度的Arg检测。在这项工作中,硼酸官能化的Zr基金属有机骨架UiO-PhbA通过使用共价合成后改性(CPSM)策略通过席夫碱反应将苯基硼酸接枝到UiO-66-NH2上来制备。制备的UiO-PhbA对Arg表现出灵敏和特异性的荧光“开启”响应,可用于检测人血清和尿液样品中的Arg,其线性范围为0.6-350µM,检测限(LOD)为18.45nM。本研究为亚硫酸盐氧化酶缺乏相关疾病的快速筛查提供了一种新的可靠的方法。
    Cystinuria is a genetic disorder, and in severe cases, it might lead to kidney failure. As an important biomarker for cystinuria, the level of arginine (Arg) in urine is a vital indicator for cystinuria screening. Therefore, it is urgently needed to detect Arg with high selectivity and sensitivity. In this work, a boric acid functionalized Zr-based metal-organic framework UiO-PhbA is prepared by grafting phenylboronic acid on UiO-66-NH2 through a Schiff base reaction using a covalent post-synthesis modification (CPSM) strategy. The prepared UiO-PhbA exhibits a sensitive and specific fluorescence \"turn-on\" response to Arg and can be exploited to detect Arg in human serum and urine samples with a broad linear range of 0.6-350 µM and low limit of detection (LOD) of 18.45 nM. This study provides a new and reliable rapid screening protocol for sulfite oxidase deficiency-related diseases.
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  • 文章类型: Journal Article
    这项工作研究了应用顶空固相微萃取-气相色谱-质谱(HS-SPME-GC/MS)结合嗅觉可视化表征黑蒜风味的可行性。进行挥发性有机化合物(VOCs)分析以选择黑蒜加工过程中重要的差异VOCs。然后开发了与两个多孔金属有机框架组装的多通道纳米复合材料CSA,以表征黑蒜加工过程中的风味变化,大蒜样品在加工过程中可以分为五组,与VOCs分析一致。人工神经网络(ANN)模型在区分处理阶段优于其他模式识别方法。此外,气味感官评分的SVR模型的预测相关系数为0.8919,表现出比PLS模型更好的性能。表明对气味质量有较好的预测能力。这项工作表明,结合适当的化学计量学的纳米复合材料CSA可以为客观,快速地表征黑蒜或其他食品基质的风味质量提供有效的工具。
    This work investigated the feasibility of applying headspace solid phase microextraction-gas chromatography-mass spectrometry (HS-SPME-GC/MS) combining olfactory visualization for flavor characterization of black garlic. Volatile organic compounds (VOCs) analysis was performed to select important differential VOCs during black garlic processing. A multi-channels nanocomposite CSA assembled with two porous metal-organic frameworks was then developed to characterize flavor profiles changes during black garlic processing, and garlic samples during processing could be divided into five clusters, consistent with VOCs analysis. Artificial neural network (ANN) model outperformed other pattern recognition methods in discriminating processing stages. Furthermore, SVR model for odor sensory scores with the correlation coefficient for prediction set of 0.8919 exhibited a better performance than PLS model, indicating a preferable prediction ability for odor quality. This work demonstrated that the nanocomposite CSA combining appropriate chemometrics can offer an effective tool for objectively and rapidly characterizing flavor quality of black garlic or other food matrixes.
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  • 文章类型: Journal Article
    次磷酸铝(AHP)作为阻燃剂已经使用了很长时间。以往关于AHP在阻燃材料中应用的研究主要集中在涂层,修改,复杂的系统。探索用AHP和金属有机骨架(MOFs)制备纳米杂化物的简单实验步骤是有价值的。我们发现酸性物质可以蚀刻沸石咪唑酯骨架67(ZIF-67)以获得MOF衍生物。不幸的是,AHP和ZIF-67不能直接形成杂交体。因此,羧甲基纤维素(CMC)作为双功能层(缓冲层和载体)引入。CMC抵抗由磷酸蚀刻的ZIF-67完全转化为无定形磷酸钴水合物(ACP)。同时,含有羟基的CMC通过静电相互作用和配位键与AHP结合。通过这种一石双鸟策略合成了双层空心MOF衍生物。由于多种阻燃元素和独特的纳米结构,这种MOF衍生物赋予环氧(EP)树脂优异的阻燃性。添加2.0wt%时,EP/AHP/ACP@CMC的峰值放热率(pHRR)和总放热(THR)分别降低了47.8和21.0%,分别。本研究提出了一种将AHP转化为MOF衍生物作为高性能FR的新方案。
    Aluminum hypophosphite (AHP) has been used as a flame retardant for a long time. Previous studies about AHP employed in flame retardant materials mostly focus on coating, modification, and complex system. It is valuable to explore simple experimental steps to prepare nano hybrids with AHP and metal-organic frameworks (MOFs). We found acidic substances could etch zeolitic imidazolate framework-67 (ZIF-67) to obtain MOF derivatives. Unfortunately, AHP and ZIF-67 could not directly form a hybrid. Therefore, carboxymethylcellulose (CMC) is introduced as a dual function layer (buffer and support). The CMC resists the complete conversion of ZIF-67 etched by phosphoric acid to amorphous cobalt phosphate hydrate (ACP). Meanwhile, CMC containing hydroxyl groups combines with AHP through electrostatic interaction and coordination bonds. A double-layer hollow MOF derivative is synthesized through this one-stone-two-birds strategy. Due to multiple flame retardant elements and unique nanostructure, this MOF derivative endows epoxy (EP) resin with excellent flame retardancy. With 2.0 wt% addition, the peak heat release rate (pHRR) and total heat release (THR) of EP/AHP/ACP@CMC are decreased by 47.8 and 21.0 %, respectively. This study proposes a novel scheme that converts AHP into MOF derivatives as high-performance FRs.
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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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