Metal-organic framework

金属 - 有机骨架
  • 文章类型: Journal Article
    产生磁性FenUiO-66吸附剂以实现高磷酸盐吸附能力。Fe3O4的掺入促进了结晶过程中UiO-66的沉淀和生长,导致吸附位点向多层非均相分布的转变。Fe3O4含量的增加显着提高了FenUiO-66的磁性能,而对其吸附性能的影响可忽略不计。Fe1.5UiO-66具有出色的磷酸盐吸附能力(136.54mg/g),出色的选择性,和持续的可重用性,经过九个循环的实际水处理后,去除率为80%。FenUiO-66吸附磷酸盐的机理涉及静电吸引,配体交换,和链接器交换。值得注意的是,虽然接头交换显著有助于高吸附能力,它导致了FenUiO-66晶体的不可逆损伤。这些明确的发现将为进一步研究奠定坚实的基础,并强调接头在磷酸盐吸附过程中的关键作用。
    A magnetic FenUiO-66 adsorbent was created to achieve high phosphate adsorption capacity. The incorporation of Fe3O4 facilitated the precipitation and growth of UiO-66 during crystallization, resulting in a shift towards a multilayer heterogeneous distribution of adsorption sites. The increased Fe3O4 content notably enhanced the magnetic properties of FenUiO-66, while negligibly affecting its adsorption performance. The Fe1.5UiO-66 demonstrated exceptional phosphate adsorption capacity (136.54 mg/g), outstanding selectivity, and sustained reusability, with an 80% removal efficiency after nine cycles of treating actual water. The mechanism of phosphate adsorption by FenUiO-66 involved electrostatic attraction, ligand exchange, and linker exchange. Notably, while linker exchange significantly contributed to high adsorption capacity, it resulted in irreversible damage to the FenUiO-66 crystal. These unequivocal findings will serve as a solid foundation for further research and underline the critical role of linkers in the process of phosphate adsorption.
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  • 文章类型: Journal Article
    在CO2电还原中,突变中间体和具有挑战性的CC偶联需要活性位点之间的空间相互作用,并通过动态优化配置。在这里,我们将乙二胺四乙酸(EDTA)键合的Cux/Bi3对锚定在UiO-66中,以进行自发的空间优化CO2到C2H4的电还原。从头算分子动力学(AIMD)模拟显示这种金属对与中间体自适应相互作用。密度泛函理论(DFT)引发了组分协同作用,其中Cu的上移d带激活被质子化为*COOH的CO2,而Bi位点稳定氧化的二聚体以进行深度氢化。这种对的动态特征为各种中间体的吸附和迁移提供了很大的自由度,因此,使UiO-66-EDTA/CuBi的最大[公式:见正文]为47%,并且在流动池中的总电流密度超过100mAcm-2。
    In CO2 electroreduction, mutative intermediates and the challenging CC coupling necessitate the spatial interplay between active sites and through dynamically optimizing configurations. Herein, we anchor ethylenediaminetetraacetic acid (EDTA)-bonded Cux+/Bi3+ pair within UiO-66 for a spontaneous spatial-optimizing CO2-to-C2H4 electroreduction. Ab initio molecular dynamic (AIMD) simulation visualizes that such metal pair adaptively interacts with intermediates. Density functional theory (DFT) elicits the componential synergy, in which an upshift d-band of Cu activates CO2 being protonated into *COOH while Bi site stabilizes oxygenated dimers for deep hydrogenation. The dynamic feature of such pair affords large freedom for sorption and migration of various intermediates, which consequently bestows UiO-66-EDTA/CuBi a maximal [Formula: see text] of 47 % and a total current density over 100 mA cm-2 in the flow cell.
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  • 文章类型: Journal Article
    在这项研究中,开发了一种衍生自金属有机框架(PCMOF)的多孔碳,作为用诺卡氏菌特定的反义ssDNA寡核苷酸(ssDNA捕获探针)官能化的靶标响应材料,以基于生物饲养者策略构建简单的基因传感器,用于灵敏检测复杂生物样品中的诺卡氏菌。具有合适孔体积的PCMOF用于包封电活性染料亚甲基蓝(MB),ssDNA捕获探针用作capPCMOF的看门人。没有诺卡氏菌靶的存在,捕获的MB的电化学信号很高。添加目标后,ssDNA捕获探针和靶的杂交导致形成探针-靶双链(dsDNA)结构,其从PCMOF解离并允许MB分子被释放。因此,基因传感器的电化学信号下降。诺卡氏菌的检测是通过观察MB峰值电流强度以剂量依赖性方式的变化来完成的。对于这个基因传感器,合成ssDNA靶标的线性范围为10-18至10-7M,两个标准分离株的线性范围为10至108拷贝/mL,观察到诺卡氏菌PTCC1309和巴西诺卡氏菌ATCC19296以及临床分离株(鉴定为耳道诺卡氏菌),分别。合成ssDNA靶标的检出限(DL)值为0.54aM,而法西诺拉黑则为5、7和4拷贝/mL,巴西奈斯,和耳道奈瑟菌,分别。这种基因传感器还具有良好的特异性,再现性,和稳定性。
    In this study, a porous carbon derived from a metal-organic framework (PCMOF) as a target-responsive material functionalized with Nocardia particular antisense ssDNA oligonucleotide (ssDNA capture probe) was developed to construct a simple genosensor based on biogatekeeper strategy for sensitive detection of Nocardia in complex biological samples. The PCMOF with suitable pores volume was used to encapsulate electroactive dye methylene blue (MB), and the ssDNA capture probe was used as a gatekeeper to cap PCMOF. Without the presence of Nocardia target, the electrochemical signal of trapped MB was high. Upon adding the target, the hybridization of ssDNA capture probe and target led to the formation of a probe-target double-stranded (dsDNA) structure which dissociated from PCMOF and allowed MB molecules to be released. Therefore, the electrochemical signal of the genosensor decreased. The detection of Nocardia was accomplished by observing variations in the MB peak current intensity in a dose-dependent manner. For this genosensor, a linearity range from 10-18 to 10-7 M for synthetic ssDNA target and 10 to 108 copies/mL for two standard isolates, Nocardia farcinica PTCC 1309 and Nocardia brasiliensis ATCC 19296 as well as for clinical isolates (identified as Nocardia otitidiscaviarum) was observed, respectively. The detection limit (DL) values were 0.54 aM for synthetic ssDNA target and 5, 7, and 4 copies/mL for N. farcinica, N. brasiliensis, and N. otitidiscaviarum, respectively. This genosensor was also characterized by good specificity, reproducibility, and stability.
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  • 文章类型: Journal Article
    MOF-199被认为是一种优良的CO2吸附剂,由于其相当大的比表面积,合适的孔隙结构和丰富的吸附位点。然而,粉状MOF-199易于团聚,可回收性差。在这里,将MOF合成工艺与传统造纸工艺相结合,提出了一种MOF-199基吸附剂。通过这样的设计,MOF-199颗粒粘附在木浆纤维的表面上。纤维素的足够的羟基和静电力促进MOF晶体的均匀和紧密粘附。最佳的MP-4样品具有较高的CO2吸附能力(在25°C时为1.80mmol·g-1)和良好的CO2/N2选择性(30.06)。此外,复合吸附剂可以容易地再生。通过密度泛函理论方法分析了吸附机理。模拟结果表明,含有大量氧原子和活性金属位点的羧基官能团是提高CO2吸附性能的关键。
    MOF-199 is considered to be an excellent CO2 adsorbent owing to its substantial specific surface area, suitable pore structure and abundant sorption sites. However, powdered MOF-199 is prone to agglomeration and has poor recyclability. Herein, we proposed a MOF-199-based adsorbent by combining the MOF synthesis process with traditional papermaking process. Through such a design, MOF-199 particles are adhered on the surface of wood pulp fiber. The sufficient hydroxyl groups and electrostatic forces of cellulose facilitates the homogeneous and tight adhesion of MOF crystals. The optimal MP-4 sample demonstrated a high CO2 adsorption capacity (1.80 mmol·g-1 at 25 °C) and good CO2/N2 selectivity (30.06). Moreover, the composite sorbent can be easily regenerated. The adsorption mechanism was analyzed by the density functional theory approach. The simulation results showed that the carboxyl functional groups with a large number of oxygen atoms and active metal sites are the key to boost the CO2 adsorption performance.
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  • 文章类型: Journal Article
    伤口易于感染,这可能对患者的生命是致命的。抗生素的使用对于控制伤口中的细菌感染至关重要,但是长期使用高剂量的抗生素可能会导致细菌耐药性,甚至产生超级细菌。因此,制定针对性的抗菌治疗策略和减少抗生素的使用是当务之急.在这项研究中,通过Zn2+的自组装合成了一种用于治疗抑菌感染的多功能纳米药物递送系统(Cef-rhEGF@ZIF-8@ConA),头孢拉定(Cef)和重组人表皮生长因子(rhEGF),然后与伴刀豆球蛋白(ConA)缀合,其经历pH响应性降解以释放药物。首先,ConA能与细菌特异性结合,抑制Zn2+离子的快速释放,从而达到长效抗菌效果。Cef通过抑制细菌膜蛋白的合成发挥其抗菌作用。最后,从Zn-金属-有机骨架(MOF)释放的Zn2离子通过增强细菌细胞膜的渗透性而表现出抑菌特性。此外,rhEGF上调血管生成相关基因,从而促进血管生成,上皮再生和伤口愈合过程。结果表明,Cef-rhEGF@ZIF-8@ConA具有良好的生物相容性,对金黄色葡萄球菌和大肠杆菌的抗菌效果分别为99.61%和99.75%,分别。这些纳米材料可以抑制炎症细胞因子的释放,促进抗炎细胞因子的释放,同时还刺激成纤维细胞的增殖以促进伤口愈合。一起来看,Cef-rhEGF@ZIF-8@ConA纳米系统是抑菌感染和伤口愈合的临床治疗的优秀候选者。
    Wounds are prone to infection which may be fatal to the life of the patient. The use of antibiotics is essential for managing bacterial infections in wounds, but the long-term use of high doses of antibiotics may lead to bacterial drug resistance and even to creation of superbacteria. Therefore, the development of targeted antimicrobial treatment strategies and the reduction in antibiotic usage are of utmost urgency. In this study, a multifunctional nanodrug delivery system (Cef-rhEGF@ZIF-8@ConA) for the treatment of bacteriostatic infection was synthesized through self-assembly of Zn2+, cefradine (Cef) and recombinant human epidermal growth factor (rhEGF), then conjugated with concanavalin (ConA), which undergoes pH-responsive degradation to release the drugs. First, ConA can specifically combine with bacteria and inhibit the rapid release of Zn2+ ions, thus achieving a long-acting antibacterial effect. Cef exerts its antibacterial effect by inhibiting the synthesis of bacterial membrane proteins. Finally, Zn2+ ions released from the Zn-metal-organic framework (MOF) demonstrate bacteriostatic properties by enhancing the permeability of the bacterial cell membrane. Furthermore, rhEGF upregulates angiogenesis-associated genes, thereby promoting angiogenesis, re-epithelialization and wound healing processes. The results showed that Cef-rhEGF@ZIF-8@ConA has good biocompatibility, with antibacterial efficacy against Staphylococcus aureus and Escherichia coli of 99.61 % and 99.75 %, respectively. These nanomaterials can inhibit the release of inflammatory cytokines and promote the release of anti-inflammatory cytokines, while also stimulating the proliferation of fibroblasts to facilitate wound healing. Taken together, the Cef-rhEGF@ZIF-8@ConA nanosystem is an excellent candidate in clinical therapeutics for bacteriostatic infection and wound healing.
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  • 文章类型: Journal Article
    锆基金属有机骨架(UiO-66)由于其广泛的应用而获得了相当多的关注。在目前的研究中,UiO-66是通过缺陷工程方法合成的,并探讨了其毒性特征。通过FTIR和拉曼光谱等光谱学方法对合成的纳米材料进行了广泛的表征,这证实了框架的形成。X射线衍射(XRD)和透射电子显微镜(TEM)用于确定结晶度,纳米制剂的形状和尺寸。热重分析,使用1HNMR光谱和Brunauer-Emmett-Teller(BET)表面积分析来鉴定原始和有缺陷的UiO-66之间的差异。此外,将合成的MOF暴露于各种pH条件下,血清蛋白和DMEM。使用5-氟尿嘧啶作为模型抗癌药物评估药物加载和释放研究。合成的MOFs用透明质酸通过贻贝启发聚合进行修饰以增加其摄取和稳定性。更重要的是,通过各种毒性研究研究了纳米制剂的毒性,如溶血测定和细胞活力测定,从Wistar大鼠获得的体内急性和亚急性毒性数据进一步支持。还使用177Lu进行了放射性标记和生物分布研究,以探索UiO-66的生物分布特征。
    Zirconium-based metal-organic frameworks (UiO-66) have gained considerable attention owing to their versatile application. In the present research, UiO-66 was synthesized via a defect engineering approach, and its toxicity profile was explored. The synthesized nanomaterial was extensively characterized via spectroscopic methods such as FTIR and Raman spectroscopy, which confirmed the formation of the framework. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to determine the crystallinity, shape and size of the nanoformulations. Thermal gravimetric analysis, 1H NMR spectroscopy and Brunauer-Emmett-Teller (BET) surface area analysis were used to identify the differences between pristine and defective UiO-66. Furthermore, the synthesized MOF was exposed to various pH conditions, serum protein and DMEM. Drug loading and release studies were evaluated using 5-fluorouracil as a model anticancer drug. The synthesized MOFs were modified with hyaluronic acid via mussel-inspired polymerization to increase their uptake and stability. More importantly, the toxicity of the nanoformulation was investigated via various toxicity studies, such as hemolysis assays and cell viability assays, and was further supported by in vivo acute and subacute toxicity data obtained from Wistar rats. Radiolabelling and bio-distribution studies were also performed using 177Lu to explore the bio-distribution profile of UiO-66.
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  • 文章类型: Journal Article
    新鲜固相萃取剂的开发对于选择性分离和纯化特殊蛋白质至关重要。在这里,我们证明了带有His标签的重组葡萄球菌蛋白G(rSPG)修饰了新型单金属有机框架(rSPG@Ni-MOF-74)。提出的固相萃取材料具有均匀的纺锤形结构,大表面积(709.60m2g-1)和孔体积(0.08m3g-1),高金属含量(22.57wt%),这促进了主人和客人之间的互动。作为结果,该复合材料对IgG表现出优异的选择性识别和吸附,由于rSPG与IgGFc区结合能力的协同作用,通过氢键和静电引力保持,以及疏水相互作用。研究了rSPG@Ni-MOF-74的吸附性能和机理。此外,rSPG@Ni-MOF-74复合物能有效分离健康人血清中的IgG,通过SDS-PAGE分析验证分离的IgG的纯度。此外,LC-MS/MS分析鉴定出rSPG@Ni-MOF-74的洗脱液中IgG含量高(55.3%),表明rSPG@Ni-MOF-74在从复杂基质中分离和富集IgG方面具有巨大潜力。
    Development of fresh solid phase extractant is critical for selective separation and purification of special proteins. Herein, we demonstrated a recombinant Staphylococcal Protein G (rSPG) with a His-tag modified the novel single-metal organic framework (rSPG@Ni-MOF-74). The proposed solid-phase extraction material possessed a uniform spindle-shaped structure, large surface area (709.60 m2 g-1) and pore volume (0.08 m3 g-1), high metal content (22.57 wt%), which facilitated the interaction between host and guest. As results, the composite displayed outstanding selective recognition and adsorption of IgG, due to synergistic effect of the binding ability of rSPG with the Fc region of IgG, maintained through hydrogen bonding and electrostatic attraction, as well as hydrophobic interaction. The adsorption performance and mechanism of rSPG@Ni-MOF-74 have been fully investigated. Additionally, the rSPG@Ni-MOF-74 composite could effectively separate IgG from serum obtained from healthy humans, with the purity of the separated IgG verified through SDS-PAGE analysis. Furthermore, LC-MS/MS analysis identified a high content of IgG (55.3 %) in the eluate from rSPG@Ni-MOF-74, suggesting the great potential of rSPG@Ni-MOF-74 in IgG separation and enrichment from complex matrix.
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  • 文章类型: Journal Article
    使用[Rh(Cp*)(bpy)Cl]还原的烟酰胺腺嘌呤二核苷酸(NADH)的电化学再生在手性化学品的工业合成中具有重要的前景。然而,由于NADH的高消耗和循环再生的有限效率,挑战依然存在,这阻碍了目前的广泛应用。为了解决这些障碍,基于三维有序金属有机骨架(NU-1000)在石墨毡表面的原位生长,[Rh(Cp*)(bpy)Cl]通过溶剂辅助配体掺入(SALI)固定在NU-1000的Zr6节点上,并应用于流动生物反应器中。此外,我们使用气体扩散电极(GDE)氧化H2,为NADH的电化学再生提供清洁的质子源。因此,当与L-乳酸脱氢酶(LDH)偶联作为模型反应时,可以实现高效的酶电催化合成L-乳酸,48h后[Rh(Cp*)(bpy)Cl]+和NAD+的总周转数(TTN)达到19600和1750,对应于[Rh(Cp*)(bpy)Cl]和NAD+的2350h-1和210h-1的高周转频率(TOF),分别。这项工作为工业生产中高效的酶电合成系统的构建提供了新的见解。
    The electrochemical regeneration of reduced nicotinamide adenine dinucleotide (NADH) using [Rh(Cp*)(bpy)Cl]+ holds significant promise for the industrial synthesis of chiral chemicals. However, challenges persist due to the high consumption of NADH and the limited efficiency of its cyclic regeneration, which currently hinder widespread application. To address these obstacles, based on in-situ growth of 3D ordered metal-organic framework (NU-1000) on the surface of graphite felt, [Rh(Cp*)(bpy)Cl]+ were immobilized on the Zr6 nodes of NU-1000 by solvent-assisted ligand incorporation (SALI), and applied in a flow bioreactor. Moreover, we employ a gas diffusion electrode (GDE) to oxidize H2, providing a clean proton source for the electrochemical regeneration of NADH. Consequently, highly efficient enzymatic electrocatalytic synthesis of L-lactate was achieved when coupled with L-lactate dehydrogenases (LDH) as a model reaction, and the total turnover number (TTN) reached 19600 and 1750 for [Rh(Cp*)(bpy)Cl]+ and NAD+ after 48 h, corresponding to a high turnover frequency (TOF) of 2350 h-1 and 210 h-1 for [Rh(Cp*)(bpy)Cl]+ and NAD+, respectively. This work provides new insights for the construction of efficient enzymatic electrosynthesis systems in industrial production.
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  • 文章类型: Journal Article
    二甲苯分离至关重要但具有挑战性,特别是用于从二甲苯混合物中优先分离中等尺寸的间二甲苯。在这里,利用二甲苯分子长度和烷基分布的差异,我们提出了一个长度匹配的金属有机框架,配制为Al(OH)[O2C-C4H2O-CO2],具有与间二甲苯分子长度相对应的有效孔径,并结合多个负O氢键供体分布,可以作为分子阱有效地优先分离中等尺寸的间二甲苯。实现了从间二甲苯/邻二甲苯/对二甲苯的三元混合物中分离间二甲苯的基准分离性能,在液相竞争吸附中同时具有创纪录的高间二甲苯吸收(1.3mmolg-1)和间二甲苯/对二甲苯选择性(5.3)。气相和液相固定床测试均证实了其具有基准动态间二甲苯/对二甲苯和间二甲苯/邻二甲苯选择性的实际分离能力,以及出色的再生能力。通过模拟进一步阐明了二甲苯分子之间的选择性和强的间二甲苯结合亲和力,验证这种孔隙环境对中等尺寸分子分离的有效性。
    Xylene separation is crucial but challenging, especially for the preferential separation of the intermediate-size m-xylene from xylene mixtures. Herein, exploiting the differences in molecular length and alkyl distribution among xylenes, we present a length-matched metal-organic framework, formulated as Al(OH)[O2C-C4H2O-CO2], featuring an effective pore size corresponding to m-xylene molecular length combined with multiple negative O hydrogen bond donors distribution, can serve as a molecular trap for efficient preferential separation of the intermediate-size m-xylene. Benchmark separation performance was achieved for separating m-xylene from a ternary mixture of m-xylene/o-xylene/p-xylene, with simultaneous record-high m-xylene uptake (1.3 mmol g-1) and m-xylene/p-xylene selectivity (5.3) in the liquid-phase competitive adsorption. Both vapor- and liquid-phase fixed-bed tests confirmed its practical separation capability with benchmark dynamic m-xylene/p-xylene and m-xylene/o-xylene selectivities, as well as excellent regenerability. The selective and strong m-xylene binding affinity among xylene molecules was further elucidated by simulations, validating the effectiveness of such a pore environment for the separation of intermediate-size molecules.
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  • 文章类型: Journal Article
    在畜牧业生产中滥用四环素会带来严重的健康风险。因此,建立方便的检测方法来取代复杂的实验室检测对食品安全至关重要。在这项研究中,开发了异质结构Zn-BTC/IRMOF-3(表示为ZBI)异步响应荧光传感器,用于定性和定量检测食品中的四环素。ZBI溶液在紫外激发下表现出蓝色荧光;引入四环素后,ZBI通过电子转移选择性识别四环素分子,π-π堆叠,和螯合,导致蓝色荧光猝灭和绿色荧光增强。用于四环素检测的ZBI传感器在食品样品中的回收率为93.91%至111.91%,检测限低至0.086μmol/L。最后,我们构建了一种使用支持向量分类器的便携式传感装置,用于在真实场景中检测四环素.我们的发现为制造荧光传感器提供了一种新的方法,并提供了一种检测四环素的新方法。
    The misuse of tetracyclines in livestock production poses significant health risks. Thus, establishing convenient detection methods to replace complex laboratory tests for food safety is crucial. In this study, a heterostructure Zn-BTC/IRMOF-3 (denoted as ZBI) asynchronous response fluorescence sensor was developed for the qualitative and quantitative detection of tetracyclines in foods. The ZBI solution exhibited blue fluorescence under UV excitation; upon the introduction of tetracyclines, ZBI selectively recognized the tetracycline molecules through electron transfer, π-π stacking, and chelation, resulting in blue fluorescence quenching and green fluorescence enhancement. The ZBI sensor for tetracycline detection achieved recovery rates ranging from 93.91 to 111.91% in food samples, with a detection limit of as low as 0.086 μmol/L. Lastly, a portable sensing device using support vector classifier was constructed for detecting tetracyclines in real-life scenarios. Our findings introduce a new approach for fabricating fluorescence sensors and offer a novel method for detecting tetracyclines.
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