Zirconium metal-organic cages (Zr-MOCs) that assemble from zirconocence-based clusters and carboxylate-based ligands have been widely used as building blocks for constructing various MOC-based materials with diverse applications because of their high stability and solubilities. However, in this work, we found that the structures of a series of Zr-MOCs are quite flexible when heated at 60 °C in an ,'-dimethylformamide solution, in which they are completely disassembled into fragments and reassembled into amorphous metal-organic gels (MOGs). The transformation mechanism was investigated via proton nuclear magnetic resonance, electrospray ionization mass spectrometry, infrared spectroscopy, X-ray photoelectron spectroscopy, and other techniques, which revealed that cyclopentadiene (CP) breaks out of the [ZrCP(μ-OH)(μ-O)] cluster and remains in solution, whereas the trinuclear [Zr(μ-OH)(μ-O)] cluster dimerizes into a hexanuclear [Zr(μ-OH)(μ-O)] cluster and forms amorphous MOGs with terephthalic acid-based ligands. The reported Zr-MOCs based on terephthalic acid-based ligands with different substituent groups, longer biphenyl dicarboxylic acids, and trimesic acids all undergo such MOC-to-MOG transformations, indicating good versatility for this transformation. In addition, the posttreatment of amorphous MOGs with an appropriate amount of acetic acid could regulate the crystallinity of the MOGs, thus giving rise to MOGs containing nano-UiO-66-type MOF crystals and xerogels with improved porosity.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.inorgchem.4c05077 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Transformation of Zirconium Metal-Organic Cages to Metal-Organic Gels.
Inorg Chem
March 2025
GDMPA Key Laboratory for Process Control and Quality Evaluation of Chiral Pharmaceuticals, and Guangzhou Key Laboratory of Analytical Chemistry for Biomedicine, School of Chemistry, South China Normal University, Guangzhou 510006, P. R. China.
Zirconium metal-organic cages (Zr-MOCs) that assemble from zirconocence-based clusters and carboxylate-based ligands have been widely used as building blocks for constructing various MOC-based materials with diverse applications because of their high stability and solubilities. However, in this work, we found that the structures of a series of Zr-MOCs are quite flexible when heated at 60 °C in an ,'-dimethylformamide solution, in which they are completely disassembled into fragments and reassembled into amorphous metal-organic gels (MOGs). The transformation mechanism was investigated via proton nuclear magnetic resonance, electrospray ionization mass spectrometry, infrared spectroscopy, X-ray photoelectron spectroscopy, and other techniques, which revealed that cyclopentadiene (CP) breaks out of the [ZrCP(μ-OH)(μ-O)] cluster and remains in solution, whereas the trinuclear [Zr(μ-OH)(μ-O)] cluster dimerizes into a hexanuclear [Zr(μ-OH)(μ-O)] cluster and forms amorphous MOGs with terephthalic acid-based ligands.
View Article and Find Full Text PDFUltrafast cell-free DNA extraction from body fluids using UiO-66-NH hydrogel packed syringe.
Talanta
March 2025
Clinical Stem Cell Center, Nanjing Drum Tower Hospital, Affiliated Hospital of Medical School, Nanjing University, Nanjing, 210008, China; Clinical Stem Cell Center, Nanjing Drum Tower Hospital, Clinical Medical College of Traditional Chinese and Western Medicine, Nanjing University of Chinese Medicine, Nanjing, 210008, China. Electronic address:
Liquid biopsy represents a noninvasive or minimally invasive diagnostic approach relevant for both the organ-specific changes and systemic health conditions, whereas cell-free DNA (cfDNA) extraction from body liquids has attracted much attention in liquid biopsy, especially. Nowadays, metal-organic frameworks (MOF) such as UiO-66-NH has been demonstrated efficient extraction property for DNA molecular, whereas the disadvantages of MOF for solid-phase extraction (SPE) still remain. Herein, one macro-pored MOF hydrogel formation strategy was constructed in this study to achieve superb extraction performance of cfDNAs from body fluids.
View Article and Find Full Text PDFEffect of magnetized solvent on the porosity of magnetic graphene oxide@zirconium-based metal-organic framework sorbent for efficient extraction of remdesivir.
J Chromatogr A
March 2025
Department of Chemistry, Faculty of Science, Ferdowsi University of Mashhad, Mashhad, 9177948974, Iran.
In this study, the effect of magnetized solvent on the synthesis and properties of magnetic graphene oxide@UiO-66 (MGO@UiO-66) nanocomposite as sorbent was investigated. The prepared sorbent was used for the magnetic solid-phase extraction (MSPE) of remdesivir drug from water and plasma samples. The extracted remdesivir was quantitatively determined by high-performance liquid chromatography with a photodiode array detector (HPLC-PDA).
View Article and Find Full Text PDFLinkage Position-Controlled Synthesis of Diverse Zirconium Metal-Organic Frameworks with Prominent Intrinsic Proton Conductivities.
Inorg Chem
March 2025
Key Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM), Nanjing Tech University, Nanjing 211816, China.
Herein, by engineering the geometries of the organic linkers, two pyrrolo-pyrrole-based low-symmetry tetracarboxylate linkers (TAPPs) were successfully designed and subsequently used for the construction of two new zirconium-based metal-organic frameworks (Zr-MOFs) ( and ). The reduction of the linker symmetry arises from both the asymmetric pyrrolo-pyrrole core and the integration of both the - and -benzoate coordination groups on the linkers. Both MOFs are composed of 8-connected Zr nodes and 4-connected highly deformed TAPP linkers with the same topology, but distinct linker arrangements can be observed in two structures.
View Article and Find Full Text PDFLight-Responsive Nanoemulsion-Guided Assembly of Honeycomb Hierarchically Macro/mesoporous Metal-Organic Framework Nanoarchitectures.
Small
March 2025
Key Laboratory of Analytical Chemistry for Life Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, 620 West Chang'an Street, Xi'an, 710119, China.
Despite that soft template pathways are promising avenues for synthesizing hierarchically porous metal-organic framework (MOF) nanoparticles, smart-responsive-directed assembly strategies have been rarely extended to fabricate well-defined hierarchical macro/mesoporosities in MOF architectures. Herein, a novel light-responsive nanoemulsion-guided strategy is reported to prepare honeycomb hierarchically porous UiO-66 nanoparticles (UiO-66 HHPNPs) with macro/mesoporosities transition using poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (F127, PEOPPOPEO) and azobenzene (Azo) as a light-responsive soft template. By facilely tuning the concentration of Azo and light irradiation (e.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!