金属有机框架材料光催化还原CO2的应用

金属有机框架材料(MOFs)是由金属原子或原子团簇与有机配体构成的多孔材料,具有良好的吸附性和光催化活性。基于对植物光合作用的模拟,MOFs材料光催化将CO2还原转化为系列碳氢化合物燃料在环境保护和未来能源供应方面具有广阔的应用前景。本文简述了MOFs光催化还原CO2的机理,通过对催化剂进行设计,如：能带结构工程(掺杂、配体取代、构建异质结等),形貌结构功能化以及协同催化等方式,实现材料的较强光捕获、较高的气体吸附量、产物选择性、稳定性和光催化效率。并提出了光催化还原CO2的发展趋势。     

金属有机框架、功能核酸及在生物检测中的应用

简述了金属有机框架材料最新研究进展,综述了其特点、合成方法及应用,重点介绍了其在生物领域的应用。同时又阐述了常与金属有机框架交联制备新型复合材料的功能核酸的基本情况、筛选技术,详细介绍了几种功能核酸生物分析方法及其在各个领域的应用。综述了DNA(脱氧核糖核酸)功能化材料的研究进展,并分析了其应用前景。     

Metal-organic frameworks for analytical chemistry: from sample collection to chromatographic separation

In modern analytical chemistry researchers pursue novel materials to meet analytical challenges such as improvements in sensitivity, selectivity, and detection limit. Metal-organic frameworks (MOFs) are an emerging class of microporous materials, and their unusual properties such as high surface area, good thermal stability, uniform structured nanoscale cavities, and the availability of in-pore functionality and outer-surface modification are attractive for diverse analytical applications. This Account summarizes our research on the analytical applications of MOFs ranging from sampling to chromatographic separation. MOFs have been either directly used or engineered to meet the demands of various analytical applications. Bulk MOFs with microsized crystals are convenient sorbents for direct application to in-field sampling and solid-phase extraction. Quartz tubes packed with MOF-5 have shown excellent stability, adsorption efficiency, and reproducibility for in-field sampling and trapping of atmospheric formaldehyde. The 2D copper(II) isonicotinate packed microcolumn has demonstrated large enhancement factors and good shape- and size-selectivity when applied to on-line solid-phase extraction of polycyclic aromatic hydrocarbons in water samples. We have explored the molecular sieving effect of MOFs for the efficient enrichment of peptides with simultaneous exclusion of proteins from biological fluids. These results show promise for the future of MOFs in peptidomics research. Moreover, nanosized MOFs and engineered thin films of MOFs are promising materials as novel coatings for solid-phase microextraction. We have developed an in situ hydrothermal growth approach to fabricate thin films of MOF-199 on etched stainless steel wire for solid-phase microextraction of volatile benzene homologues with large enhancement factors and wide linearity. Their high thermal stability and easy-to-engineer nanocrystals make MOFs attractive as new stationary phases to fabricate MOF-coated capillaries for high-resolution gas chromatography (GC). We have explored a dynamic coating approach to fabricate a MOF-coated capillary for the GC separation of important raw chemicals and persistent organic pollutants with high resolution and excellent selectivity. We have combined a MOF-coated fiber for solid-phase microextraction with a MOF-coated capillary for GC separation, which provides an effective MOF-based tandem molecular sieve platform for selective microextraction and high-resolution GC separation of target analytes in complex samples. Microsized MOFs with good solvent stability are attractive stationary phases for high-performance liquid chromatography (HPLC). These materials have shown high resolution and good selectivity and reproducibility in both the normal-phase HPLC separation of fullerenes and substituted aromatics on MIL-101 packed columns and position isomers on a MIL-53(Al) packed column and the reversed-phase HPLC separation of a wide range of analytes from nonpolar to polar and acidic to basic solutes. Despite the above achievements, further exploration of MOFs in analytical chemistry is needed. Especially, analytical application-oriented engineering of MOFs is imperative for specific applications.     

Metal-organic frameworks constructed from monomeric,dimeric and trimeric phenanthroline citrate zinc building units

Adduct of mononuclear and dinuclear citrate zinc complex [Zn(Hcit)(phen)(H₂O)][Zn₂(Hcit)(phen)₂(H₂O)₃]·13.5H₂O (1) and its aggregate [Zn₃(Hcit)₂(phen)₄]_n·14nH₂O (2) (H₄cit = citric acid, phen = 1,10-phenanthroline) were synthesized in weak acidic solutions. The former was obtained from the reaction of zinc nitrate, citric acid and phenanthroline in a molar ratio of 3:2:3, while a slightly excess of phenanthroline results in the formation of the polymeric product 2 in a molar ratio of 3:2:4. Transformation of 1 to 2 was finished by the reaction of 1 with an equimolar of phenanthroline in 72% yield. Reverse conversion of 2 to 1 is obtained in 77% yield, showing an equilibrium between 1 and 2. Neutral compound 1 consists of one monomeric anionic unit [Zn(Hcit)(phen)(H₂O)]^? and one dimeric cationic unit [Zn₂(Hcit)(phen)₂(H₂O)₃]⁺ that connect each other by strong hydrogen bonds [O6?O4w 2.636(2); O7?O3w 2.630(3) Å]. In 2, the citrate ligand links each trinuclear unit [Zn₃(Hcit)₂(phen)₄] to generate an infinite 1D chain that extents into a 3D supramolecular structure by intra- and inter-molecular hydrogen bonds. Moreover, 1 and 2 exhibit strong fluorescence at room temperature.     

金属-有机框架基柔性复合材料研究进展

金属-有机框架材料(MOFs)作为近年来的研究热点,在气体储存、分离、催化等多个领域表现出优越的性能。但材料本身存在的缺陷和特性使得单一MOFs在实际应用中仍存在较多困难。将MOFs与其他材料复合制备具有一定柔性的新型材料成为扩宽其实际应用的有效途径。从制备方法角度出发,综述了前沿MOFs柔性复合材料的制备及其应用,并对MOFs复合材料的优势与存在的问题展开讨论,指出柔性基底材料为MOFs实际应用提供了支持。进一步开发和研制新型MOFs复合材料,提高MOFs实际应用的可能性与多样性,仍是研究者们需要努力的方向。     

金属有机骨架材料在催化中的研究进展

简介了金属有机骨架材料（MOFs）的合成方法,主要介绍了MOFs应用于Lewis酸、碱和手性催化中的研究进展,对MOFs材料在催化领域的应用进行了展望。     

Metal-organic framework UiO-66 membranes

Metal-organic frameworks (MOFs) have emerged as a class of promising membrane materials. UiO-66 is a prototypical and stable MOF material with a number of analogues. In this article, we review five approaches for fabricating UiO-66 polycrystalline membranes including in situ synthesis, secondary synthesis, biphase synthesis, gas-phase deposition and electrochemical deposition, as well as their applications in gas separation, pervaporation, nanofiltration and ion separation. On this basis, we propose possible methods for scalable synthesis of UiO-66 membranes and their potential separation applications in the future.     

金属有机骨架材料在催化领域的研究进展

金属有机骨架(Metal-organic frameworks)材料属于新一代纳米多孔材料,因其具有比表面积大,孔隙率高,结构及功能多样等特点而被广泛应用于气体吸附与分离、传感器、药物缓释、催化反应等领域中.尤其在催化领域,与传统无机材料相比,MOFs因其含有有机配体组分,可以通过有机转化引入各种有机官能团;因其具有多孔性,可以同时实现材料表面与内部的改性,比无机材料只能表面改性更具优势,MOFs作为催化材料为催化领域的发展提供了新的思路.本文综述了MOFs材料作为催化材料的特点和的合成方法以及应用,并对今后的发展进行了展望.     

金属-有机框架的机械化学合成研究进展

金属-有机框架的机械化学合成方法,与常规的基于溶液法相比,具有快速,绿色及简单等的诸多优点,使得极具工业应用前景的金属–有机框架化合物的大规模制备成为可能。同时,利用高效的机械化学合成金属-有机框架是对于此类材料应用研究的极大促进。在这里,我们对于当前这个研究热点的研究进展给予介绍。     

点击化学及其在生物医学领域的应用研究进展

点击化学实质是指通过可靠、高效而又具选择性的化学反应来实现碳杂原子连接,从而快速合成大量新化合物的一套强大且实用的合成方法。它具有反应条件温和、产物收率高、速率快、产物易分离以及高度选择性等优点,已经成为国内外研究的热点之一。主要综述了点击化学作为一种新的合成方法在合成基因载体、药物载体、药物设计以及荧光标记领域等生物医学领域的国内外最新进展,最后对其发展前景进行了展望。     

陶瓷纳米颗粒在生物医学中的应用进展

近年来,纳米技术成为科学技术领域最重要与最激动人心的前沿领域之一.随着纳米技术的发展,纳米材料在生产和生活的各方面发挥着越来越重要的作用.陶瓷纳米颗粒作为一类重要的纳米材料,拥有体积效应、介电限域效应、量子尺寸效应和量子隧道效应等,使其在生物医学领域具有广阔的应用前景.本文综述了羟基磷灰石、磷酸钙、氧化铁、氧化锌和氧化铈陶瓷纳米颗粒的特点及其在肿瘤成像与治疗、骨组织工程和安全评价等生物医学领域的应用进展,并对陶瓷纳米颗粒在生物医学中的发展提出了几点建议.     

酶催化超分子自组装及其在癌症诊疗中的应用研究进展

自组装是自然界的普遍现象,也是构建超分子生物材料的有力工具。在众多方法中,酶催化超分子自组装具有优异的肿瘤靶向性及良好的生物安全性,是近年来癌症诊疗的一个重要新方向。针对这一趋势,本文简介了酶催化超分子自组装在细胞内、外的构建方法,详细总结了其在癌症诊疗中的应用。研究表明,酶催化超分子自组装材料在生物医学成像、选择性杀死癌细胞、药物递送和克服药物不良反应方面具有潜在的应用价值。提出了体内超分子组装体的微观形貌需要明确表征、构建自组装方法的酶范围需要扩展以及需要探索酶催化超分子自组装（EISA）与亚细胞器的相互作用等解决其发展中的问题的思路和方向,并对其在抗菌药物开发、免疫调节、创伤修复和组织再生领域的潜在应用作出了展望。     

Metal-organic Frameworks Incorporating Multiple Metal Elements

The obtaining of materials incorporating multiple metal elements is of interest because the combination of various metal cations results in the achievement of new and enhanced properties. Metal-organic frameworks (MOFs) offer a suitable platform to combine multiple metal elements due to their modular nature and highly controllable structure. The incorporation of various metal elements into MOFs might be accomplished by following different synthetic approaches, which in turn determine the way in which the various metal elements are arranged in the framework. In this contribution, we will overview the formation of multi-metal MOFs by the introduction of new metal sites in the organic linkers, or in the inorganic secondary building units through cation exchange process, or one-pot synthesis.