ZIF-67@PDA/含氟聚酰亚胺混合基质膜的制备及其气体分离性能

金属有机框架材料(MOF)/聚合物混合基质膜(MMMs)通过结合MOF的分子筛效应和聚合物基质成本较低、加工性能好、机械强度高的特征,使其在气体分离领域展现出巨大的应用前景。然而由于MOF在聚合物基体中存在分散性差问题,极大地限制了其应用。采用溶剂热法合成金属框架材料ZIF-67,并通过溶液氧化法在ZIF-67表面修饰聚多巴胺(PDA)层制备ZIF-67@PDA纳米多孔材料。以4,4’-二氨基二苯醚-2,2’-双(3,4-二羧酸)六氟丙烷二酐(ODA-6 FDA)型含氟聚酰亚胺(FPI)为基体、ZIF-67和ZIF-67@PDA为填料,制备不同质量分数的ZIF-67/FPI和ZIF-67@PDA/FPI。通过FTIR、WAXD、TGA、SEM、比表面和孔径分布分析仪、气体渗透仪等测试对MMMs的结构和性能进行表征并测试了N₂、O₂、CO₂、He 4种气体的渗透性。结果表明：经聚多巴胺修饰后的纳米微孔材料ZIF-67在聚合物基体中能均匀分散并为气体分子的通过提供快速通道,且表现出良好的热稳定性。ZIF-67@PDA对CO<...     

纳米金属有机骨架ZIF-90的制备及载药性能研究

金属有机骨架材料是由金属离子与有机配体通过自组装过程杂化生成的一类具有周期性多维网状结构的多孔材料,在催化、传感、气体储存和载药等方面均表现出了优异的性能.采用一种新的实验方法(超声-搅拌法)并通过优化反应条件制备了粒径在300 nm以下的ZIF-90纳米材料,利用傅里叶红外光谱(FTIR)、粉末X射线衍射(XRD)确定了金属有机骨架的结构,利用扫描电子显微镜(SEM)确定了材料的形貌和粒径.ZIF-90纳米药物载体装载和释放抗癌药物5-氟尿嘧啶的实验结果表明,该材料装载药物的能力最高可达1.245 g/g,药物缓释时长达15h,释放率达到95％以上.该药物载体在不同pH值下的稳定性实验结果表明,该药物载体可在接近肿瘤细胞的酸性条件下通过骨架坍塌的方式快速释放药物,具有肿瘤靶向传递药物的能力.     

纳米金属有机骨架ZIF-90的制备及载药性能研究

金属有机骨架材料是由金属离子与有机配体通过自组装过程杂化生成的一类具有周期性多维网状结构的多孔材料,在催化、传感、气体储存和载药等方面均表现出了优异的性能。采用一种新的实验方法(超声-搅拌法)并通过优化反应条件制备了粒径在300nm以下的ZIF-90纳米材料,利用傅里叶红外光谱(FTIR)、粉末X射线衍射(XRD)确定了金属有机骨架的结构,利用扫描电子显微镜(SEM)确定了材料的形貌和粒径。ZIF-90纳米药物载体装载和释放抗癌药物5-氟尿嘧啶的实验结果表明,该材料装载药物的能力最高可达1.245g/g,药物缓释时长达15h,释放率达到95%以上。该药物载体在不同pH值下的稳定性实验结果表明,该药物载体可在接近肿瘤细胞的酸性条件下通过骨架坍塌的方式快速释放药物,具有肿瘤靶向传递药物的能力。     

离子液体/金属-有机骨架复合材料制备方法、理论计算及应用研究进展

金属-有机骨架(MOF)是一种多孔、高比表面积的新型纳米材料.离子液体(IL)具有稳定性好、功能可设计的特点,将IL负载到MOF的孔中,实现离子液体和MOF材料的有效组合,开发新型功能化复合多孔材料,有利于充分发挥两种材料的优势.本文主要介绍IL/MOF复合材料合成方法、分子模拟及其应用的最新研究.总结目前IL/MOF...     

The applications of zeolitic imidazolate framework-8 in electrical energy storage devices: a review

In order to meet the requirement of electric vehicles (EVs), hybrid electric vehicles (HEVs) and smart grids, effective energy storage devices will become imperative in the future energy technologies. However, it is necessary to further improve the energy density, rate performance and cycle performance of the energy storage devices. Zeolitic imidazolate framework-8 (ZIF-8) is a kind of porous materials that has attracted enormous attention due to its high surface areas, controllable structures and tunable pore sizes. Besides the applications in gas storage and separation, catalysis, sensor, and drug delivery, ZIF-8 is receiving increasing research interest in the field of electrochemical energy storage due to the advantage of synthetic method, such as simplicity and safety. By focusing on recent advances, we summarize the applications of ZIF-8 in electrical energy storage devices, such as rechargeable batteries and supercapacitors. We also list the current problems in applications and give the future study direction.     

Protein-Precoated Surface of Metal-Organic Framework Nanoparticles for Targeted Delivery

Metal-organic framework (MOF) nanoparticles have recently emerged as a promising vehicle for drug delivery with high porosity and feasibility. However, employing a MOF-based drug delivery system remains a challenge due to the difficulty in controlling interfaces of particles in a biological environment. In this paper, protein corona-blocked Zr₆-based MOF (PCN-224) nanoparticles are presented for targeted cancer therapy with high efficiency. The unmodified PCN-224 surface is precoated with glutathione transferase (GST)-fused targetable affibody (GST-Afb) proteins via simple mixing conjugations instead of chemical modifications that can induce the impairment of proteins. GST-Afb proteins are shown to stably protect the surface of PCN-224 particles in a specific orientation with GST adsorbed onto the porous surface and the GST-linked Afb posed outward, minimizing the unwanted interfacial interactions of particles with external biological proteins. The Afb-directed cell-specific targeting ability of particles and consequent induction of cell death is demonstrated both in vitro and in vivo by using two kinds of Afb, which targets the surface membrane receptor, human epidermal growth factor receptor 2 (HER2) or epidermal growth factor receptor (EGFR). This study provides insight into the way of regulating the protein-adhesive surface of MOF nanoparticles and designing a more effective MOF-hosted targeted delivery system.     

A Universal Room-Temperature 3D Printing Approach Towards porous MOF Based Dendrites Inhibition Hybrid Solid-State Electrolytes

Hybrid solid-state electrolytes (HSSEs) provide new opportunities and inspiration for the realization of safer, higher energy-density metal batteries. The innovative application of 3‑dimensional printing in the electrochemical field, especially in solid-state electrolytes, endows energy storage devices with fascinating characteristics. In this paper, effective dendrite-inhibited PEO/MOFs HSSEs is innovatively developed through universal room-temperature 3‑dimensional printing (RT-3DP) strategy. The prepared HSSEs display enhanced dendrite inhibition due to the porous MOF filler promoting homogeneity of lithium deposition and the formation of C-OCO₃Li, ROLi, LiF mesophases, which further improve the migration of Li⁺ in PEO chain and comprehensive performances. This universal strategy realizes the fabrication of different slurry components (PEO with ZIF-67, MOF-74, UIO-66, ZIF-8 fillers) HSSEs at RT environment, providing new inspirations for the exploration of next-generation advanced solid-state batteries.     

Data-driven parameter optimization for the synthesis of high-quality zeolitic imidazolate frameworks via a microdroplet route

As an emerging strategy for the synthesis of metal-organic frameworks (MOFs), a microdroplet-based spray method holds merits of improved heat and mass transfer rates, which allows the formation of MOF crystals in a much faster manner. To optimize the spray route for the MOF synthesis, further exploration is needed to understand the dominant variables controlling the quality of the products. With a series of experiments and advanced computational analysis, we present here general guidance for the synthesis of representative zeolitic imidazolate frameworks (i.e., ZIF-8 and ZIF-67) using the spray route.     

Mechanochemistry: Toward green synthesis of metal–organic frameworks

Metal–organic frameworks (MOFs) have attracted a special attention due to outstanding porosity, adjustable pore sizes, and huge opportunities in varying organic–inorganic compositions. Enormous studies conducted so far on MOFs indicate their high potential in catalysis, gas adsorption, drug delivery, water treatment, energy storage, among others. However, mass production of MOFs is still limited mainly due to the non-economic, non-green and complex synthesis methods. Mechanochemistry is an alternative solution for efficient and environmentally friendly syntheses of various MOFs. Fast and solvent-free or solvent-less mechanosynthesis seems to be a very powerful versatile method for obtaining these advanced porous materials. The mechanochemical concept was used for the preparation of various MOFs including the most popular structures: MOF-5, ZIF-8, HKUST-1, MIL-101, UiO-66. These MOFs feature high specific surface areas, comparable to those prepared by conventional solvent-based methods. Furthermore, mechanochemistry was successfully used for the synthesis of non-conventional multimetallic MOFs and previously unreported solid phases. This review shows the recent developments, challenges and perspectives of green synthesis of diverse MOF structures using mechanochemistry. Besides describing the mechanochemical synthesis of MOFs, some achievements in green applications are also summarized. Importantly, current trends in research suggests for further development of these fields i.e., harmful gas adsorption, water treatment, and energy storage.     

Metal–Organic Framework‐Derived Materials for Sodium Energy Storage

Recently, sodium‐ion batteries (SIBs) are extensively explored and are regarded as one of the most promising alternatives to lithium‐ion batteries for electrochemical energy conversion and storage, owing to the abundant raw material resources, low cost, and similar electrochemical behavior of elemental sodium compared to lithium. Metal–organic frameworks (MOFs) have attracted enormous attention due to their high surface areas, tunable structures, and diverse applications in drug delivery, gas storage, and catalysis. Recently, there has been an escalating interest in exploiting MOF‐derived materials as anodes for sodium energy storage due to their fast mass transport resulting from their highly porous structures and relatively simple preparation methods originating from in situ thermal treatment processes. In this Review, the recent progress of the sodium‐ion storage performances of MOF‐derived materials, including MOF‐derived porous carbons, metal oxides, metal oxide/carbon nanocomposites, and other materials (e.g., metal phosphides, metal sulfides, and metal selenides), as SIB anodes is systematically and completely presented and discussed. Moreover, the current challenges and perspectives of MOF‐derived materials in electrochemical energy storage are discussed.     

High drug loading polymer micelle@ZIF-8 hybrid core–shell nanoparticles through donor–receptor coordination interaction for pH/H2O2-responsive drug release

Smart drug delivery nanocarriers with high drug loading capacity are of great importance in the treatment of diseases, and can improve therapeutic effectiveness as well as alleviate side effects in patients. In this work, a pH and H₂O₂-responsive drug delivery platform with high doxorubicin (DOX) loading capacity has been established through coordination interaction between DOX and phenylboronic acid containing block polymer. A composited drug nanocarrier is further fabricated by growing a zeolitic imidazolate framework 8 (ZIF-8) on the surface of drug-loaded polymer micelles. The study verifies that ZIF-8 shell can act as intelligent “switch” to prevent DOX leaking from core–shell nanoparticles upon H₂O₂ stimulus. However, a burst drug release is detected upon pH and H₂O₂ stimuli due to the further disassociation of ZIF-8 in acid solution. Moreover, the in vitro anti-cancer experiments demonstrate that the DOX-loaded core–shell nanoparticles provide effective treatment towards cancer cells but have negligible effect on normal cells, which results from the high concentration of H₂O₂ and low pH in the microenvironment of tumor cells.     

Improvement in transdermal drug delivery performance by graphite oxide/temperature-responsive hydrogel composites with micro heater

Transdermal drug delivery system (TDDS) was prepared with temperature-responsive hydrogel. The graphite was oxidized and incorporated into hydrogel matrix to improve the thermal response of hydrogel. The micro heater was fabricated to control the temperature precisely by adopting a joule heating method. The drug in hydrogel was delivered through a hairless mouse skin by controlling temperature. The efficiency of drug delivery was improved obviously by incorporation of graphite oxide due to the excellent thermal conductivity and the increased interfacial affinity between graphite oxide and hydrogel matrix. The fabricated micro heater was effective in controlling the temperature over lower critical solution temperature of hydrogel precisely with a small voltage less than 1 V. The cell viability test on graphite oxide composite hydrogel showed enough safety for using as a transdermal drug delivery patch. The performance of TDDS could be improved noticeably based on temperature-responsive hydrogel, thermally conductive graphite oxide, and efficient micro heater.     

Facilitate Gas Transport through Metal‐Organic Polyhedra Constructed Porous Liquid Membrane

Type II porous liquids are demonstrated to be promise porous materials. However, the category of porous hosts is very limited. Here, a porous host metal–organic polyhedra (MOP‐18) is reported to construct type II porous liquids. MOP‐18 is dissolved into 15‐crown‐5 as an individual cage (5 nm). Both the molecular dynamics simulations and experimental gravimetric CO₂ solubility test indicate that the inner cavity of MOP‐18 in porous liquids is unoccupied by 15‐crown‐5 and is accessible to CO₂. Thus, the prepared porous liquids show enhanced gas solubility. Furthermore, the prepared porous liquid is encapsulated into graphene oxide (GO) nanoslits to form a GO‐supported porous liquid membrane (GO‐SPLM). Owing to the empty cavity of MOP‐18 unit cages in porous liquids that reduces the gas diffusion barrier, GO‐SPLM significantly enhances the permeability of gas.     

Zeolitic imidazolate metal organic framework-8 as an efficient pH-controlled delivery vehicle for zinc phthalocyanine in photodynamic therapy

To improve the aqueous solubility and cancer targeting of the photosensitizers in photodynamic therapy (PDT), we encapsulated the photosensitizer in a biocompatibility and pH-sensitive drug delivery system, zeolitic imidazolate frameworks-8 (ZIF-8) nanospheres. Powder X-ray diffraction and electron microscopy show that our nanospheres are uniform and single-crystalline particles. Owing to the cleavage of zinc–ligand coordination bonds, more ZnPc–COOH were released much faster in the mild acidic conditions (pH 5.0 and 6.0) in comparison with physiological environment (pH 7.4). By incorporating ZnPc–COOH in ZIF-8, our nanospheres exhibited high singlet oxygen quantum yield and intracellular ROS generation. Cell viability experiments toward HepG2 cells demonstrated the low toxicity of ZIF-8 and the good anticancer efficacy of the nanospheres with low IC₅₀ values (4.2–4.9 μg/mL) under light illumination (670 nm, 1.5 J/cm²). Collectively, these results suggested that our nanospheres are the promising pH-responsive drug delivery systems for PDT.     

Sustained co-delivery of gemcitabine and cis-platinum via biodegradable thermo-sensitive hydrogel for synergistic combination therapy of pancreatic cancer

Pancreatic cancer is one of the most devastating cancers with poor prognosis and no significant change in the survival rate over the past decades. Localized targeted drug delivery through interventional endoscopic ultrasonography-guided fine-needle injection (EUS-FNI) is an attractive and minimally invasive strategy for inoperable pancreatic cancer. An injectable in-situ formed long-lasting drug delivery system is a promising alternative for the localized treatment of pancreatic cancer via EUS-FNI. Here, a biodegradable thermo-sensitive copolymer hydrogel for the co-delivery of anticancer agents gemcitabine (GEM) and cis-platinum (DDP) was developed. This hydrogel is a free flowable liquid at room temperature that changes into a semi-solid hydrogel following injection in response to the physiological temperature. Both in vitro and in vivo drug release behaviors indicate sustained drug release of this delivery system. Synergistic cellular proliferation inhibition and desirable apoptosis promotion have been found when pancreatic cancer Bxpc-3 cells were co-cultured with this GEM-DDP/hydrogel system. After a single intratumoral injection, the dual-drug loaded hydrogel formulation exhibited superior anti-tumor efficacy and minimized systemic side effect on pancreatic cancer xenograft mouse model in comparison to the intravenously injected free GEM and DDP combination. In addition, a strong synergistic therapeutic effect of the GEM-DDP/hydrogel system against pancreatic cancer has been found in vitro and in vivo compared to the single-drug loaded hydrogel composites. The obtained findings suggest this developed thermo-sensitive copolymer hydrogel system as a potential universal carrier for the localized targeted delivery of multi-drugs, for use in a variety of inoperable solid tumors.

     

Mass Measurements Reveal Preferential Sorption of Mixed Solvent Components in Porous Nanoparticles

The interplay of physical and chemical properties at the nanometer scale provides porous nanoparticles with unique sorption and interaction capabilities. These properties have aroused great interest toward this class of materials for application ranging from chemical and biological sensing to separation and drug delivery. However, so far the preferential uptake of different components of mixed solvents by porous nanoparticles is not measured due to a lack of methods capable of detecting the resulting change in physical properties. Here, a new method, nanomechanical mass correlation spectroscopy, is used to reveal an unexpected dependence of the effective mass density of porous metal–organic framework (MOF) nanoparticles on the chemistry of the solvent system and on the chemical functionalization of the MOF's internal surface. Interestingly, the pore size of the nanoparticles is much too large for the exclusion of small solvent molecules by steric hindrance. The variation of effective density of the nanoparticles with the solvent composition indicates that a complex solvent environment can form within or around the nanoparticles, which may substantially differ from the solvent composition.     

可注射乙酰化乙二醇壳聚糖/泊洛沙姆复合水凝胶的制备及药物缓释研究EI北大核心CSCD

泊洛沙姆(poloxamer)是一种温敏性聚合物,在浓度为15.0%(质量分数,下同)~30.0%时可形成凝胶。为改善泊洛沙姆在体温下的成胶浓度和药物缓释性能,以泊洛沙姆407为基底,与新型温敏性乙酰化乙二醇壳聚糖复合,制得了温敏性乙酰化乙二醇壳聚糖/泊洛沙姆复合水凝胶。通过傅里叶变换红外光谱(FT-IR)、试管倒置法、旋转流变仪、扫描电子显微镜(SEM)和紫外-可见分光光度计(UV-vis)对乙酰化乙二醇壳聚糖/泊洛沙姆的结构、温敏性、力学性能、微观形貌和体外药物释放性能进行表征。结果表明,乙酰化乙二醇壳聚糖/泊洛沙姆溶液具有热可逆温敏性溶胶-凝胶转变行为。通过控制乙酰化乙二醇壳聚糖/泊洛沙姆的质量比,能够使溶胶-凝胶转变温度处于室温与体温(25~37℃)之间,缩短凝胶化时间(382s),降低泊洛沙姆407在体温下的成胶浓度(6%)。乙酰化乙二醇壳聚糖/泊洛沙姆复合水凝胶具有高度孔隙化的三维结构,其孔径大小处于10~60μm范围内,且表现出较高的力学性能。乙酰化乙二醇壳聚糖/泊洛沙姆复合水凝胶对抗癌药物吉西他滨具有缓释作用,载药凝胶的释药时间可达72 h。乙酰化乙二醇壳聚糖/泊洛沙姆复合水凝胶在可注射药物缓释载体方面具有重要的应用前景。     

Chiral nanoporous metal-organic frameworks with high porosity as materials for drug delivery

A chiral nanoporous metal-organic framework (MOF) with high porosity is obtained based on nontoxic zinc and achiral hexadentate ligand. It shows high drug loading and slow release of the proportion of the loaded drug with a complete delivery time of about one week when used as a material for adsorption and delivery of anticancer 5-fluorouracil.     

pH-responsive dual-functional hydrogel integrating localized delivery and anti-cancer activities for highly effective therapy in PDX of OSCC

As one of the most promising localized drug delivery systems for enhancing therapeutic efficacy and reducing systemic toxicity, supramolecular hydrogels self-assembled from natural products have recently attracted tremendous attention. However, the intricate drug loading process, limited drug entrapment efficacy, and lack of stimulus responsiveness considerably impede their potential for biological applications and raise the need for advanced hydrogel-based delivery systems. Therefore, the development of updated materials that integrate localized delivery and drug activity into a single system is extremely desired and has great potential to overcome the aforementioned shortcomings. In this study, a pH-responsive dual-functional isoG-based supramolecular hydrogel with both localized delivery and anti-cancer activity in one molecule is successfully developed in one pot by following a simple and green procedure. The isoguanosine-phenylboronic-guanosine (isoGPBG) hydrogel exhibits exceptional stability (more than one year), outstanding pH-responsiveness and excellent sustained release capability. Both in vitro and in vivo experiments demonstrate that the isoGPBG hydrogel not only shows acceptable biocompatibility and biodegradability but also significantly inhibit tumor growth (approximately 60% inhibition of tumor growth) and improve overall survival, especially in preclinical patient-derived xenograft (PDX) model of oral squamous cell carcinoma (OSCC). Therefore, the isoGPBG hydrogel, to the best of our knowledge, is the first example of pH-responsive dual-functional isoG-based supramolecular hydrogel integrating localized delivery and anti-cancer activity in one molecule. It is implied that the isoGPBG hydrogel could act as a smart dual-functional localized delivery system in the future for clinical cancer therapy.     

Metal‐Organic Frameworks: Metal‐Organic Frameworks: A Rapidly Growing Class of Versatile Nanoporous Materials (Adv. Mater. 2/2011)

Metal‐organic frameworks (MOFs) represent a new class of hybrid organic‐inorganic supramolecular materials comprised of ordered networks formed from organic electron donor linkers and metal cations. They can exhibit extremely high surface areas, as well as tunable pore size and functionality, and can act as hosts for a variety of guest molecules. Since their discovery, MOFs have enjoyed extensive exploration, with applications ranging from gas storage to drug delivery to sensing. This review covers advances in the MOF field from the past three years, focusing on applications, including gas separation, catalysis, drug delivery, optical and electronic applications, and sensing. We also summarize recent work on methods for MOF synthesis and computational modeling.