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
    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
    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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  • 文章类型: Journal Article
    合成染料的广泛使用对环境和人类健康都有严重影响。因此,迫切需要发展小说,这些染料的高效吸附剂。在这项研究中,通过溶剂热法在细菌纳米纤维素(BC)上原位生长具有可控形态的锆基金属有机骨架(MOF)。所得的BC@MOF复合纳米纤维具有651m2/g的高比表面积,并且可以在钙离子的辅助下通过真空过滤组装成自支撑多孔膜(BMMCa)。Ca(Ⅱ)的加入通过分散作用和静电相互作用,显著提高了膜的力学性能,以及通过盐析效应增强其吸附性能。BMMCa膜,具有分层的多孔结构和高通量,对刚果红(CR)具有高选择性,具有3518.6mg/g的超高吸附能力。此外,自支撑膜通过循环过滤吸附实现了快速便捷的去除CR。通过MaterialsStudio(MS)软件进行分子动力学模拟计算,验证了吸附机理和选择性。这种膜基吸附剂,具有超高的吸附能力,良好的选择性,和回收能力,在实际废水处理应用中具有巨大的潜力。
    The widespread use of synthetic dyes has serious implications for both the environment and human health. Therefore, there is an urgent need for the development of novel, high-efficiency adsorbents for these dyes. In this study, a Zirconium-based metal-organic framework (MOF) with controllable morphology was in-situ grown on bacterial nanocellulose (BC) via a solvothermal method. The resulting BC@MOF composite nanofibers have a high specific surface area of 651 m2/g and can be assembled into a self-supported porous membrane (BMMCa) through vacuum filtration with the assistance of calcium ions. The addition of Ca(II) significantly enhanced the mechanical properties of the membrane through dispersion effect and electrostatic interactions, as well as enhancing its adsorption performance through the salting-out effect. The BMMCa membrane, with its hierarchical porous structure and high flux, exhibits high selectivity for Congo red (CR) with an ultra-high adsorption capacity of 3518.6 mg/g. Furthermore, the self-supporting membrane achieved rapid and convenient removal of CR through circulating filtration adsorption. The adsorption mechanism and selectivity were verified through the molecular dynamics simulation calculations by Materials Studio (MS) software. This membrane-based adsorbent, with its ultra-high adsorption capacity, good selectivity, and recycling ability, has great potential for practical wastewater treatment applications.
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  • 文章类型: Journal Article
    本研究利用计算模拟和表面分子印迹技术来开发能够选择性识别和检测多种氟喹诺酮(FQs)的磁性金属-有机骨架分子印迹聚合物(Fe3O4@ZIF-8@SMIP)。Fe3O4@ZIF-8@SMIP材料是使用“普通”模板氧氟沙星合成的,通过计算模拟识别,证明所有测试的FQ具有显著的吸附容量(88.61-212.93mgg-1)和快速传质特征(平衡时间:2-3分钟),符合Langmuir吸附模型。随后,该材料被用作磁性固相萃取吸附剂,通过与高效液相色谱相结合来吸附和检测多个FQ。所开发的方法在0.1-500μgL-1的浓度范围内对各种FQ表现出良好的线性,具有低的检测限(0.0605-0.1529μgL-1)和定量限(0.2017-0.5097μgL-1)。当应用于加标食品样品时,获得了令人满意的回收率(88.38-103.44%),证明了这种Fe3O4@ZIF-8@SMIP材料用于快速富集和鉴定多个FQs残基的巨大潜力。
    This study utilized computational simulation and surface molecular imprinting technology to develop a magnetic metal-organic framework molecularly imprinted polymer (Fe3O4@ZIF-8@SMIP) capable of selectively recognizing and detecting multiple fluoroquinolones (FQs). The Fe3O4@ZIF-8@SMIP material was synthesized using the \"common\" template-ofloxacin, identified by computational simulation, demonstrating notable adsorption capacity (88.61-212.93 mg g-1) and rapid mass-transfer features (equilibration time: 2-3 min) for all tested FQs, consistent with Langmuir adsorption model. Subsequently, this material was employed as a magnetic solid-phase-extraction adsorbent for adsorption and detection of multiple FQs by combining with high performance liquid chromatography. The developed method exhibited good linearity for various FQs within the concentration range of 0.1-500 μg L-1, with low limit of detection (0.0605-0.1529 μg L-1) and limit of quantitation (0.2017-0.5097 μg L-1). Satisfactory recoveries (88.38-103.44%) were obtained when applied to spiked food samples, demonstrating the substantial potential of this Fe3O4@ZIF-8@SMIP material for rapid enrichment and identification for multiple FQs residues.
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