金属有机框架化合物对溶剂分子和有机小分子荧光识别与传感研究进展

属-有机框架（MOFs）化合物由于其特定的孔道/孔洞结构以及在气体吸附/存储与分离、化学传感、光学、磁学以及荧光检测等方面的良好性能及潜在应用而成为当前人们关心和研究的热点。本文聚焦MOFs在溶剂分子和有机小分子荧光识别及传感方面的研究工作,着重介绍该领域近期的研究进展,并对该领域今后的发展进行了展望。     

基于金属有机框架的纳米酶及其在生物分析中的应用

纳米酶是一类具有类酶活性的纳米材料,在分析化学和疾病诊疗领域具有良好的发展潜力。金属有机框架（MOFs）材料是由金属节点和有机配体形成的多孔晶体材料,其结构与天然酶有一定的相似性。目前,研究者已经开发了多种基于MOFs的纳米酶,包括具有类过氧化物酶、类氧化酶、类超氧化物歧化酶和类水解酶活性的纳米酶等,并显示出广阔的应用前景。本文根据材料的结构特点,将基于MOFs的纳米酶分为原始MOFs、化学修饰MOFs、MOFs复合材料和MOFs衍生物4类,介绍了这4类纳米酶制备的基本原理与最新研究进展。在此基础上,根据比色传感、荧光传感和电化学传感等分析策略,综述了MOFs基纳米酶在生物分析方面的研究和应用进展,讨论了其在实际应用中所面临的挑战和未来的发展趋势。     

用于铁离子检测的荧光传感材料研究进展

准确、定量检测Fe~(3+)对环境保护和人类健康具有重要意义。目前,荧光传感材料广泛应用于分子传感、气体传感、环境监测等诸多领域。为了实现环境监测领域Fe~(3+)的快速响应、高灵敏和高选择性检测,研究者大力开发了各种新型荧光传感材料,本文重点介绍了金属有机骨架(MOFs)、荧光量子点(QDs)、金属纳米簇、荧光小分子和荧光聚合物等各种新型荧光材料在Fe~(3+)检测中的应用;分析了目前荧光传感材料研究中存在的问题和局限性并对其发展方向进行了展望。     

双发光MOFs的比率型传感和可视化检测应用*

通过[Cu(NH₃)₄]²⁺和EDTA-Ca配合物,引出金属有机骨架(MOFs),揭示刚性多齿配体使MOFs形成无限延展多孔结构的本质。从单一荧光引出双荧光,到比率型荧光传感和可视化检测应用。MOFs丰富的金属离子和配体组成以及多孔结构,为实现双荧光奠定了基础。镧系金属的电子结构使其可以发出可见光。基于此,通过几个多发光MOFs,特别是镧系金属MOFs的比率型荧光和可视化传感应用,将教学知识点与科学前沿结合到一起,一方面加深学生对知识点的理解和掌握,另一方面激发学生运用知识,探索未知的兴趣。     

金属有机框架抗菌材料的研究进展

细菌耐药问题已经成为了中国乃至全球的重大公共健康威胁,设计合成新型抗菌材料以减少抗生素依赖成为当前化学化工、材料和生物医学领域中的重要研究课题.金属有机框架（Metal-organic frameworks,MOFs）材料是由有机配体和金属离子或团簇通过配位键自组装形成的多孔晶态材料,在气体吸附与分离、传感和催化等领域都扮演着重要角色.为了寻求更好应对细菌威胁的方式方法,国内外研究者们纷纷构建出不同结构的MOFs材料,并将其应用于抗菌领域.本综述从细菌耐药性的产生和MOFs抗菌机理等方面出发,分类概述了不同金属中心和配体MOFs材料、MOFs包覆金属纳米粒子材料和药物缓释MOFs材料等在抗菌、促进伤口愈合等方面的应用,归纳概括了MOFs材料在抗菌领域应用中仍需解决的科学问题,并对该领域的发展趋势进行了展望.     

金属有机骨架应用于样品前处理研究的最新进展

作为一类新型多孔晶体材料,金属有机骨架（MOFs）在储能、催化、传感和分离等领域得到了广泛应用。MOFs多样的拓扑结构、大的比表面积和可调的孔径使得其在样品前处理领域拥有广阔的应用前景,基于MOFs及其衍生材料的样品预处理新方法层出不穷。该文总结了近几年MOFs粉末、MOFs膜、MOFs纳米片和MOFs复合材料等应用于固相萃取、固相微萃取和磁固相萃取等样品前处理技术的研究进展,并对该领域研究进行了展望。     

金属有机骨架材料在传感器中的应用

摘 要 金属有机骨架（Metal Organic Framework,MOFs）是由有机配体与金属离子或金属离子簇通过配位作用自组装而成的一种具有永久孔道性的开放结晶骨架,通常也被称为配位聚合物（PCPS）。因为其较大的比表面积、规整的孔道结构、热稳定性和化学可裁剪性,使其在多个领域具有广阔的应用前景。近年来,随着MOFs在传感领域的发展,许多不同的功能基团被引入到MOFs的孔道中,研制出具有荧光识别性能的MOFs。本论文综述了近几年来基于MOFs的化学传感器在离子识别、PH检测、挥发性有机物和气体检测、爆炸物识别和生物分子检测等关键领域的研究进展,并对MOFs在化学传感器的应用前景进行了展望。     

金属有机骨架材料在传感器中的应用

金属有机骨架(MOFs)是由有机配体与金属离子或金属离子簇通过配位作用自组装而成的一种具有永久孔道性的开放结晶骨架,通常也被称为多孔配位聚合物(PCPS)。因为其较大的比表面积、规整的孔道结构、良好的热稳定性和化学可裁剪性,使其在多个领域具有广阔的应用前景。近年来,随着MOFs在传感领域的发展,许多不同的功能基团被引入到MOFs的孔道中,研制出具有荧光识别性能的MOFs。本论文综述了近几年来基于MOFs的化学传感器在离子识别、pH检测、挥发性有机物和气体检测、爆炸物识别和生物分子检测等关键领域的研究进展,并对MOFs在化学传感器的应用前景进行了展望。     

MOFs传感器在癌症及其生物标志物检测中的应用

癌症是世界上最致命的疾病之一,因此癌细胞的有效捕获和敏感检测对基础研究以及临床诊断和治疗都具有重要意义。基于金属有机骨架(MOFs)的催化活性和固有的发光性能等特点,MOFs已被成功地开发为传感平台实现对癌症及其标志物的检测。综述了基于MOFs的电化学、荧光、电化学发光、比色传感器在癌细胞及核酸、蛋白质等生物标志物检测中近3年的研究进展,从MOFs材料,检测物类型,检测方法、检测能力等方面进行了综述,并对各自的特点进行了讨论,对以后MOFs纳米材料在癌症检测中的应用进行了展望。     

金属有机框架材料在环境化学中的研究进展

金属有机框架(MOFs)是一类由有机桥连配体与无机金属中心通过自组装形成的新型多孔材料.相比传统的多孔材料,MOFs具有比表面积高、孔径均一、结构可调节等优点,在基础理论研究和实际应用方面都表现出巨大的潜力.近年来,环境问题日益突出,开发新型材料解决环境问题迫在眉睫,MOFs材料在环境化学中的应用受到了广泛关注.本文主要介绍MOFs材料在催化、气体存储、气体吸附与分离、气敏传感和水体净化等多个领域的理论研究与应用现状,并进一步讨论了MOFs材料在该领域面临的挑战和发展趋势.     

Applications of metal nanoparticles/metal-organic frameworks composites in sensing field

Metal nanoparticles (MNPs) possess size-dependent desirable electronic and optical properties while metal-organic frameworks (MOFs) have an edge over extremely large specific surface areas, homogeneous structure, high porosity and remarkable chemical stability. Their combination (MNPs/MOFs) is a novel nanomaterial with broad application prospect in sensing field. To improve performance in sensing applications, we have paid great attention to synergistic effects between the two compositions above. Because of the synergistic effects between MNPs and MOFs, sensors on the basis of MNPs/MOFs composites show significant sensing enhancement with respect to stability, selectivity and sensitivity. In this review, various applications for MNPs/MOFs composites in electrochemical sensing, fluorescent sensing, colorimetric sensing, surface-enhanced Raman scattering sensing and chemiluminescence/electrochemiluminescence sensing are focused and summarized. Besides, the synergistic interactions between MNPs and MOFs was investigated. Finally, based on theoretical information from the reports as well as experimental experience, this review offers the challenges and opportunities for future research on MNPs/MOFs composites.     

Multicomponent Assembly of Fluorescent‐Tag Functionalized Ligands in Metal–Organic Frameworks for Sensing Explosives

Detection of trace amounts of explosive materials is significantly important for security concerns and pollution control. Four multicomponent metal–organic frameworks ( MOFs‐12 , 13 , 23 , and 123 ) have been synthesized by employing ligands embedded with fluorescent tags. The multicomponent assembly of the ligands was utilized to acquire a diverse electronic behavior of the MOFs and the fluorescent tags were strategically chosen to enhance the electron density in the MOFs. The phase purity of the MOFs was established by PXRD, NMR spectroscopy, and finally by single‐crystal XRD. Single‐crystal structures of the MOFs‐12 and 13 showed the formation of three‐dimensional porous networks with the aromatic tags projecting inwardly into the pores. These electron‐rich MOFs were utilized for detection of explosive nitroaromatic compounds (NACs) through fluorescence quenching with high selectivity and sensitivity. The rate of fluorescence quenching for all the MOFs follows the order of electron deficiency of the NACs. We also showed the detection of picric acid (PA) by luminescent MOFs is not always reliable and can be misleading. This attracts our attention to explore these MOFs for sensing picryl chloride (PC), which is as explosive as picric acid and used widely to prepare more stable explosives like 2,4,6‐trinitroaniline from PA. Moreover, the recyclability and sensitivity studies indicated that these MOFs can be reused several times with parts per billion (ppb) levels of sensitivity towards PC and 2,4,6‐trinitrotoluene (TNT).     

A rht-Type Luminescent Zn (II)-MOF Constructed by Triazine Hexacarboxylate Ligand: Tunable Luminescent Performance and White-light Emission Regulation through doping Eu3+/Tb3+

White-light emitting materials have become a hot research field of luminescent MOF (Metal–Organic Framework) because of its high practical application value. Herein, we successfully synthesized and characterized a rht-type fluorescent MOF Zn-TDPAT [H₆TDPAT = 2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine] with a topology of (3, 24) connected nodes. A series of MOFs materials x%Tb + y%Eu@Zn-TDPAT were prepared by incorporating different concentrations of green emission center Tb³⁺ and red emission center Eu³⁺ into the blue-emitting Zn-MOF. The luminescence properties of MOFs materials x%Tb + y%Eu@Zn-TDPAT can be effectively adjusted by incorporating different concentrations of Tb³⁺ and Eu³⁺ and can obtain multi-color luminescence properties from blue, blue-green, green, yellow green, yellow, blue-red, yellow-red and white. According to trichromatic mechanism, by reasonably matching the intensity of blue light, green light and red light emitted by x%Tb + y%Eu@Zn-TDPAT at 420, 543 and 616 nm, MOFs materials 0.75%Tb + 5%Eu@Zn-TDPAT, 0.65%Tb + 5.5%Eu@Zn-TDPAT and 0.5%Tb + 7.5%Eu@Zn-TDPAT with white-light emission are obtained. Their CIE coordinates are 0.3162, 0.3345 (0.3162, 0.3345), (0.3138, 0.3339) and (0.3329, 0.3222), respectively, which are very close to ideal white-light emission (0.3333,0.3333).     

Magnetic porous carbon nanocomposites derived from metal-organic frameworks as a sensing platform for DNA fluorescent detection

Metal-organic frameworks (MOFs) have emerged as very fascinating functional materials due to their tunable nature and diverse applications. In this work, we prepared a magnetic porous carbon (MPC) nanocomposite by employing iron-containing MOFs (MIL-88A) as precursors through a one-pot thermolysis method. It was found that the MPC can absorb selectively single-stranded DNA (ssDNA) probe to form MPC/ssDNA complex and subsequently quench the labelled fluorescent dye of the ssDNA probe, which is resulted from the synergetic effect of magnetic nanoparticles and carbon matrix. Upon the addition of complementary target DNA, however, the absorbed ssDNA probe could be released from MPC surface by forming double-stranded DNA with target DNA, and accompanied by the recovery of the fluorescence of ssDNA probe. Based on these findings, a sensing platform with low background signal for DNA fluorescent detection was developed. The proposed sensing platform exhibits high sensitivity with detection limit of 1 nM and excellent selectivity to specific target DNA, even single-base mismatched nucleotide can be distinguished. We envision that the presented study would provide a new perspective on the potential applications of MOF-derived nanocomposites in biomedical fields.     

Stimulus‐Responsive Metal–Organic Frameworks

Materials that can recognize the changes in their local environment and respond by altering their inherent physical and/or chemical properties are strong candidates for future “smart” technology materials. Metal–organic frameworks (MOFs) have attracted a great deal of attention in recent years owing to their designable architecture, host–guest chemistry, and softness as porous materials. Despite this fact, studies on the tuning of the properties of MOFs by external stimuli are still rare. This review highlights the recent developments in the field of stimulus‐responsive MOFs or so‐called smart MOFs. In particular, the various stimuli used and the utility of stimulus‐responsive smart MOFs for various applications such as gas storage and separation, sensing, clean energy, catalysis, molecular motors, and biomedical applications are highlighted by using representative examples. Future directions in the developments of stimulus‐responsive smart MOFs and their applications are proposed from a personal perspective.     

功能化金属有机骨架材料在放射性离子检测中的应用

With the shortage of fossil energy and increasing environmental pollution, nuclear energy has received extensive attention by its virtue of high energy density and low emission of greenhouse gases. However, radioactive nuclear waste remains a serious task for its safe and effective disposal due to their harmful effects on human health and the environment. As a new type of multifunctional nanomaterial, metal-organic frameworks (MOFs) are synthesized via the self-assembling combination of inorganic metals and organic ligands. Compared with traditional porous materials, MOFs have broad application prospects in the adsorption and detection of radioactive ions. In this paper, we reviewed the functional modification strategies of MOFs and summarized the progress in the applications of functionalized MOFs in removal and fluorescence sensing of contaminated ions in recent years. Besides, the future development trends are also discussed.     

A roadmap to implementing metal-organic frameworks in electronic devices: challenges and critical directions

Metal-organic frameworks (MOFs) and related material classes are attracting considerable attention for applications such as gas storage, separations, and catalysis. In contrast, research focused on potential uses in electronic devices is in its infancy. Several sensing concepts in which the tailorable chemistry of MOFs is used to enhance sensitivity or provide chemical specificity have been demonstrated, but in only a few cases are MOFs an integral part of an actual device. The synthesis of a few electrically conducting MOFs and their known structural flexibility suggest that MOF-based electronic devices exploiting these properties could be constructed. It is clear, however, that new fabrication methods are required to take advantage of the unique properties of MOFs and extend their use to the realms of electronic circuitry. In this Concepts article, we describe the basic functional elements needed to fabricate electronic devices and summarize the current state of relevant MOF research, and then review recent work in which MOFs serve as active components in electronic devices. Finally, we propose a high-level roadmap for device-related MOF research, the objective of which is to stimulate thinking within the MOF community concerning the development these materials for applications including sensing, photonics, and microelectronics.     

Post-modification of a MOF through a fluorescent-labeling technology for the selective sensing and adsorption of Ag(+) in aqueous solution

A new approach inspired by fluorescent labeling technology to fluorescently functionalize MOFs via post-modification is reported. A fluorescein-containing MOF FITC@BTPY-NH(2) was synthesized for selective sensing and adsorption of Ag(+) in aqueous solution.     

Stimuli-Responsive Luminescent Properties of Tetraphenylethene-Based Strontium and Cobalt Metal–Organic Frameworks

Herein we report two new TPE-based 3D MOFs, that is, Sr-ETTB and Co-ETTB (TPE=Tetraphenylethylene, H₈ETTB=4′,4′′′,4′′′′′,4′′′′′′′-(ethene-1,1,2,2-tetrayl)tetrakis(([1,1′-biphenyl]-3,5-dicarboxylic acid))). Through tailoring outer shell electron configurations of Sr^II and Co^II cations, the fluorescence intensity of the MOFs is tuned from high emission to complete non-emission. Sr-ETTB with strong blue fluorescence shows reversible fluorescence variations in response to pressure and temperature, which is directly related to the reversible deformation of the crystal structure. In addition, non-emissive Co-ETTB counterpart exhibits a turn-on fluorescent enhancement under the stimulation of analyte histidine. In the process, TPE-cored linkers in the MOFs are released through competitive coordination substitution and subsequently reassembled to perform aggregation-induced luminescence behavior originated from the organic linkers.