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
    An effective electrochemical sensor was developed to detect and determine of the As(III) by modifying the carbon paste electrode (CPE) with graphitic carbon nitride decorated with iron-based metal-organic frameworks (Fe-MOF/g-C3N5). The differential pulse anodic stripping voltammetry (DPASV) method was used to analyze As(III) ions in a phosphate buffer solution (0.10 M, pH = 5). Fe-MOF/g-C3N5/CPE showed high sensitivity (4.24 μA μg-1 L), satisfactory linear range (0.50 μg L-1-5.00 μg L-1 and 5.00 μg L-1-30.00 μg L-1), and low detection limit (LOD, 0.013 μg L-1). The prepared sensor was showed an excellent repeatability and selectivity, and successfully used for determination of the As(III) ion in ambient waters and apple juice samples.
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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
    金属有机骨架(MOFs)是在气体吸附和分离等领域具有潜在应用的材料,催化作用,和生物医学。增强MOFs效用的尝试涉及各种复合材料的制备,包括聚合物接枝的MOFs。通过将聚合物直接接枝到MOFs的外表面,可以克服聚合物和MOF之间的不相容问题。从MOF的表面接枝的聚合物刷可以用于稳定MOF,同时能够通过聚合物-聚合物相互作用将颗粒组装成自组装的金属-有机骨架单层(SAMM)。对接枝聚合物的化学组成和分子量的控制可以允许调节SAMM特性。在这项工作中,提供了关于如何将链转移剂(CTA)固定到MOFUiO-66(UiO=奥斯陆大学)表面上的说明。CTA用作聚合物生长的起始位点。一旦聚合物链从MOF表面生长,SAMM的形成是通过在空气-水界面处的自组装来实现的。通过扫描电子显微镜成像对所得SAMM进行表征并显示为独立的。本文提出的方法有望使SAMM的制备更容易为研究界所用,从而扩大其作为MOF-聚合物复合材料的潜在用途。
    Metal-organic frameworks (MOFs) are materials with potential applications in fields such as gas adsorption and separation, catalysis, and biomedicine. Attempts to enhance the utility of MOFs have involved the preparation of various composites, including polymer-grafted MOFs. By directly grafting polymers to the external surface of MOFs, issues of incompatibility between polymers and MOFs can be overcome. Polymer brushes grafted from the surface of MOFs can serve to stabilize the MOF while enabling particle assembly into self-assembled metal-organic framework monolayers (SAMMs) via polymer-polymer interactions. Control over the chemical composition and molecular weight of the grafted polymer can allow for tuning of the SAMM characteristics. In this work, instructions are provided on how to immobilize a chain transfer agent (CTA) onto the surface of the MOF UiO-66 (UiO = Universitetet i Oslo). The CTA serves as initiation sites for the growth of polymers. Once polymer chains are grown from the MOF surface, the formation of SAMMs is achieved through self-assembly at an air-water interface. The resulting SAMMs are characterized and shown to be freestanding by scanning electron microscopy imaging. The methods presented in this paper are expected to make the preparation of SAMMs more accessible to the research community and thereby expand their potential use as a MOF-polymer composite.
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  • 文章类型: Journal Article
    组织中的基因分型和淀粉样原纤维检测通常被认为是甲状腺素运载蛋白相关淀粉样变性的诊断金标准。患者携带不太稳定的TTR同源四聚体,容易解离成非天然单体,快速自组装成低聚物,最终,淀粉样纤维.因此,淀粉样蛋白级联的初始事件产生最小的转甲状腺素蛋白种类:单体。这创造了仍未探索的诊断工程机会。
    我们假设分子筛代表了一种有前途的方法,用于从血浆样品中存在的四聚体中分离和浓缩痕量TTR单体。随后,免疫检测可用于将单体TTR与吸附部分内的其他低分子量蛋白质区分开。设计了两步法(免疫测定法),结合分子筛分和免疫检测来感知单体转甲状腺素蛋白。该测定法用于分析来自10个人的血浆微样品,包括5名症状前的TTR-V30M携带者,全球最普遍的淀粉样变性相关TTR变异,5健康对照
    Immunosive分析能够灵敏地检测血浆微样品中的单体转甲状腺素蛋白。此外,在淀粉样变性TTR突变的携带者中,循环单体TTR水平显著较高.
    单体TTR可以作为生物标志物用于评估疾病进展和评估对靶向稳定天然TTR的治疗的反应。
    UNASSIGNED: Genotyping and amyloid fibril detection in tissues are generally considered the diagnostic gold standard in transthyretin-related amyloidosis. Patients carry less stable TTR homotetramers prone to dissociation into non-native monomers, which rapidly self-assemble into oligomers and, ultimately, amyloid fibrils. Thus, the initial event of the amyloid cascade produces the smallest transthyretin species: the monomers. This creates engineering opportunities for diagnosis that remain unexplored.
    UNASSIGNED: We hypothesise that molecular sieving represents a promising method for isolating and concentrating trace TTR monomers from the tetramers present in plasma samples. Subsequently, immunodetection can be utilised to distinguish monomeric TTR from other low molecular weight proteins within the adsorbed fraction. A two-step assay was devised (ImmunoSieve assay), combining molecular sieving and immunodetection for sensing monomeric transthyretin. This assay was employed to analyse plasma microsamples from 10 individuals, including 5 pre-symptomatic carriers of TTR-V30M, the most prevalent amyloidosis-associated TTR variant worldwide, and 5 healthy controls.
    UNASSIGNED: The ImmunoSieve assay enable sensitive detection of monomeric transthyretin in plasma microsamples. Moreover, the circulating monomeric TTR levels were significantly higher in carriers of amyloidogenic TTR mutation.
    UNASSIGNED: Monomeric TTR can function as a biomarker for evaluating disease progression and assessing responses to therapies targeted at stabilising native TTR.
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  • 文章类型: Journal Article
    重金属离子和抗生素污染已成为世界范围内的主要环境问题。在水溶液中超低浓度的这些污染物的有效识别策略的开发以及内在传感机制的阐明是具有挑战性的任务。在这项工作中,通过合理的配体设计组装了独特的发光Ln-MOF材料(NIIC-3-Ln)。其中,NIIC-3-Tb在小于7s的亚纳摩尔浓度下表现出对Hg2和磺胺嘧啶(SDI)的高度选择性发光猝灭响应。此外,在单晶X射线衍射分析和Hg2+吸附研究的基础上,提出了一种通过螯合的Hg2+传感机理。使用新开发的方法揭示了NIIC-3-Tb与SDI的相互作用机理,该方法涉及基于(TD-)DFT的MOF分析物超分子复合物模型在基态和激发态下的电荷转移定量。通过气体吸附实验揭示了超声处理对MOF传感性能重要的表面形态的影响。结果表明,NIIC-3-Ln不仅是在超低浓度下有效检测Hg2和SDI的先进传感材料,同时也为在超低浓度下研究分子水平的传感机理开辟了新的途径。
    Heavy metal ions and antibiotic contamination have become a major environmental concern worldwide. The development of efficient recognition strategies of these pollutants at ultra-low concentrations in aqueous solutions as well as the elucidation of the intrinsic sensing mechanism are challenging tasks. In this work, unique luminescent Ln-MOF materials (NIIC-3-Ln) were assembled by rational ligand design. Among them, NIIC-3-Tb demonstrated highly selective luminescence quenching response toward Hg2+ and sulfadiazine (SDI) at subnanomolar concentrations in less than 7 s. In addition, a Hg2+ sensing mechanism through chelation was proposed on the basis of single-crystal X-ray diffraction analysis and Hg2+ adsorption study. The interaction mechanism of NIIC-3-Tb with SDI was revealed using a newly developed approach involving a (TD-)DFT based quantification of the charge transfer of a MOF-analyte supramolecular complex model in the ground and excited states. Effect of ultrasonic treatment on the surface morphology important for MOF sensing performance was revealed by gas adsorption experiments. The presented results indicate that NIIC-3-Ln is not only an advanced sensing material for the efficient detection of Hg2+ and SDI at ultra-low concentrations, but also opens up a new approach to study the sensing mechanism at the molecular level at ultra-low concentrations.
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