| 1. |
- Zhou, Yuye, et al.
(författare)
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Thiol-ene-based microfluidic chips for glycopeptide enrichment and online digestion of inflammation-related proteins osteopontin and immunoglobulin G
- 2023
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Ingår i: Analytical and Bioanalytical Chemistry. - : Springer Science and Business Media LLC. - 1618-2642 .- 1618-2650. ; 415:6, s. 1173-1185
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Tidskriftsartikel (refereegranskat)abstract
- Proteins, and more specifically glycoproteins, have been widely used as biomarkers, e.g., to monitor disease states. Bottom-up approaches based on mass spectrometry (MS) are techniques commonly utilized in glycoproteomics, involving protein digestion and glycopeptide enrichment. Here, a dual function polymeric thiol-ene-based microfluidic chip (TE microchip) was applied for the analysis of the proteins osteopontin (OPN) and immunoglobulin G (IgG), which have important roles in autoimmune diseases, in inflammatory diseases, and in coronavirus disease 2019 (COVID-19). TE microchips with larger internal surface features immobilized with trypsin were successfully utilized for OPN digestion, providing rapid and efficient digestion with a residence time of a few seconds. Furthermore, TE microchips surface-modified with ascorbic acid linker (TEA microchip) have been successfully utilized for IgG glycopeptide enrichment. To illustrate the use of the chips for more complex samples, they were applied to enrich IgG glycopeptides from human serum samples with antibodies against severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). The dual functional TE microchips could provide high throughput for online protein digestion and glycopeptide enrichment, showing great promise for future extended applications in proteomics and the study of related diseases.
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| 2. |
- Bao, Zijia, et al.
(författare)
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A bimetallic 3D interconnected metal–organic framework with 2D morphology and its derived electrocatalyst for oxygen reduction
- 2023
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Ingår i: CrystEngComm. - : Royal Society of Chemistry (RSC). - 1466-8033. ; 25:13, s. 1869-1873
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Tidskriftsartikel (refereegranskat)abstract
- Metal–organic frameworks (MOFs) are widely used as precursors to generate derivatives for electrocatalysis. However, two-dimensional (2D) MOFs often suffer from the collapse of their 2D structures after being treated at high temperature. Herein, we used the dense ZIF-EC1 as a precursor and doped Co as a secondary metal. The content of Co in ZIF-EC1 can be tuned without changing the crystalline structure. After pyrolysis, the derived carbon-based material maintains the 2D morphology from the parental precursor. The derived ZIF-EC1(ZnCo)-20-900 exhibits the best activity toward the ORR, which is even better than that of Pt/C. This work demonstrates the potential of using a nonporous dense MOF as a precursor and optimizing electrocatalytic ORR activity by tuning the Co content.
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| 3. |
- Brandner, Lea A., et al.
(författare)
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Water sensitivity of heteroepitaxial Cu-MOF films : dissolution and re-crystallization of 3D-oriented MOF superstructures
- 2023
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Ingår i: Chemical Science. - 2041-6520 .- 2041-6539. ; 14:43, s. 12056-12067
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Tidskriftsartikel (refereegranskat)abstract
- 3D-oriented metal–organic framework (MOF) films and patterns have recently emerged as promising platforms for sensing and photonic applications. These oriented polycrystalline materials are typically prepared by heteroepitaxial growth from aligned inorganic nanostructures and display anisotropic functional properties, such as guest molecule alignment and polarized fluorescence. However, to identify suitable conditions for the integration of these 3D-oriented MOF superstructures into functional devices, the effect of water (gaseous and liquid) on different frameworks should be determined. We note that the hydrolytic stability of these heteroepitaxially grown MOF films is currently unexplored. In this work, we present an in-depth analysis of the structural evolution of aligned 2D and 3D Cu-based MOFs grown from Cu(OH)2 coatings. Specifically, 3D-oriented Cu2L2 and Cu2L2DABCO films (L = 1,4-benzenedicarboxylate, BDC; biphenyl-4,4-dicarboxylate, BPDC; DABCO = 1,4-diazabicyclo[2.2.2]octane) were exposed to 50% relative humidity (RH), 80% RH and liquid water. The combined use of X-ray diffraction, infrared spectroscopy, and scanning electron microscopy shows that the sensitivity towards humid environments critically depends on the presence of the DABCO pillar ligand. While oriented films of 2D MOF layers stay intact upon exposure to all levels of humidity, hydrolysis of Cu2L2DABCO is observed. In addition, we report that in environments with high water content, 3D-oriented Cu2(BDC)2DABCO recrystallizes as 3D-oriented Cu2(BDC)2. The heteroepitaxial MOF-to-MOF transformation mechanism was studied with in situ synchrotron experiments, time-resolved AFM measurements, and electron diffraction. These findings provide valuable information on the stability of oriented MOF films for their application in functional devices and highlight the potential for the fabrication of 3D-oriented superstructures via MOF-to-MOF transformations.
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| 4. |
- Chang, Ribooga, et al.
(författare)
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Achieving Molecular Sieving of CO2 from CH4 by Controlled Dynamical Movement and Host–Guest Interactions in Ultramicroporous VOFFIVE-1-Ni by Pillar Substitution
- 2024
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Ingår i: Nano Letters. - 1530-6984 .- 1530-6992. ; 24:25, s. 7616-7622
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Tidskriftsartikel (refereegranskat)abstract
- Engineering the building blocks in metal–organic materials is an effective strategy for tuning their dynamical properties and can affect their response to external guest molecules. Tailoring the interaction and diffusion of molecules into these structures is highly important, particularly for applications related to gas separation. Herein, we report a vanadium-based hybrid ultramicroporous material, VOFFIVE-1-Ni, with temperature-dependent dynamical properties and a strong affinity to effectively capture and separate carbon dioxide (CO2) from methane (CH4). VOFFIVE-1-Ni exhibits a CO2 uptake of 12.08 wt % (2.75 mmol g–1), a negligible CH4 uptake at 293 K (0.5 bar), and an excellent CO2-over-CH4 uptake ratio of 2280, far exceeding that of similar materials. The material also exhibits a favorable CO2 enthalpy of adsorption below −50 kJ mol–1, as well as fast CO2 adsorption rates (90% uptake reached within 20 s) that render the hydrolytically stable VOFFIVE-1-Ni a promising sorbent for applications such as biogas upgrading.
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| 5. |
- Prasad, Ram R. R., et al.
(författare)
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Modulated Self-Assembly of Catalytically Active Metal-Organic Nanosheets Containing Zr6 Clusters and Dicarboxylate Ligands
- 2024
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Ingår i: ACS Applied Materials and Interfaces. - 1944-8244 .- 1944-8252. ; 16:14, s. 17812-17820
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Tidskriftsartikel (refereegranskat)abstract
- Two-dimensional metal–organic nanosheets (MONs) have emerged as attractive alternatives to their three-dimensional metal–organic framework (MOF) counterparts for heterogeneous catalysis due to their greater external surface areas and higher accessibility of catalytically active sites. Zr MONs are particularly prized because of their chemical stability and high Lewis and Brønsted acidities of the Zr clusters. Herein, we show that careful control over modulated self-assembly and exfoliation conditions allows the isolation of the first example of a two-dimensional nanosheet wherein Zr6 clusters are linked by dicarboxylate ligands. The hxl topology MOF, termed GUF-14 (GUF = Glasgow University Framework), can be exfoliated into monolayer thickness hns topology MONs, and acid-induced removal of capping modulator units yields MONs with enhanced catalytic activity toward the formation of imines and the hydrolysis of an organophosphate nerve agent mimic. The discovery of GUF-14 serves as a valuable example of the undiscovered MOF/MON structural diversity extant in established metal–ligand systems that can be accessed by harnessing the power of modulated self-assembly protocols.
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| 6. |
- Sporrer, Lukas, et al.
(författare)
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Near IR Bandgap Semiconducting 2D Conjugated Metal-Organic Framework with Rhombic Lattice and High Mobility
- 2023
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Ingår i: Angewandte Chemie International Edition. - : Wiley. - 1433-7851 .- 1521-3773. ; 62:25
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Tidskriftsartikel (refereegranskat)abstract
- Two-dimensional conjugated metal–organic frameworks (2D c-MOFs) are emerging as a unique class of electronic materials. However, 2D c-MOFs with band gaps in the Vis-NIR and high charge carrier mobility are rare. Most of the reported conducting 2D c-MOFs are metallic (i.e. gapless), which largely limits their use in logic devices. Herein, we design a phenanthrotriphenylene-based, D2h-symmetric π-extended ligand (OHPTP), and synthesize the first rhombic 2D c-MOF single crystals (Cu2(OHPTP)). The continuous rotation electron diffraction (cRED) analysis unveils the orthorhombic crystal structure at the atomic level with a unique slipped AA stacking. The Cu2(OHPTP) is a p-type semiconductor with an indirect band gap of ≈0.50 eV and exhibits high electrical conductivity of 0.10 S cm−1 and high charge carrier mobility of ≈10.0 cm2 V−1 s−1. Theoretical calculations underline the predominant role of the out-of-plane charge transport in this semiquinone-based 2D c-MOF.
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| 7. |
- Zhang, Jianjun, et al.
(författare)
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Wavy Two-Dimensional Conjugated Metal-Organic Framework with Metallic Charge Transport
- 2023
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Ingår i: Journal of the American Chemical Society. - 0002-7863 .- 1520-5126. ; 145:43, s. 23630-23638
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Tidskriftsartikel (refereegranskat)abstract
- Two-dimensional conjugated metal–organic frameworks (2D c-MOFs) have emerged as a new class of crystalline layered conducting materials that hold significant promise for applications in electronics and spintronics. However, current 2D c-MOFs are mainly made from organic planar ligands, whereas layered 2D c-MOFs constructed by curved or twisted ligands featuring novel orbital structures and electronic states remain less developed. Herein, we report a Cu-catecholate wavy 2D c-MOF (Cu3(HFcHBC)2) based on a fluorinated core-twisted contorted hexahydroxy-hexa-cata-hexabenzocoronene (HFcHBC) ligand. We show that the resulting film is composed of rod-like single crystals with lengths up to ∼4 μm. The crystal structure is resolved by high-resolution transmission electron microscopy (HRTEM) and continuous rotation electron diffraction (cRED), indicating a wavy honeycomb lattice with AA-eclipsed stacking. Cu3(HFcHBC)2 is predicted to be metallic based on theoretical calculation, while the crystalline film sample with numerous grain boundaries apparently exhibits semiconducting behavior at the macroscopic scale, characterized by obvious thermally activated conductivity. Temperature-dependent electrical conductivity measurements on the isolated single-crystal devices indeed demonstrate the metallic nature of Cu3(HFcHBC)2, with a very weak thermally activated transport behavior and a room-temperature conductivity of 5.2 S cm–1. Furthermore, the 2D c-MOFs can be utilized as potential electrode materials for energy storage, which display decent capacity (163.3 F g–1) and excellent cyclability in an aqueous 5 M LiCl electrolyte. Our work demonstrates that wavy 2D c-MOF using contorted ligands are capable of intrinsic metallic transport, marking the emergence of new conductive MOFs for electronic and energy applications.
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| 8. |
- Zhou, Guojun, 1990-, et al.
(författare)
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Structure and function tailored metal-organic frameworks for heterogeneous catalysis
- 2022
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Ingår i: Chem Catalysis. - : Elsevier BV. - 2667-1093. ; 2:12, s. 3304-3319
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Tidskriftsartikel (refereegranskat)abstract
- The unlimited combination of building units, tunable structures, and facilitation of tailoring active sites endows metal-organic frame-works (MOFs) with high activity as heterogeneous catalysts in various reactions, such as hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), carbon dioxide reduction reaction (CO2RR), and alcohol -oxidation reactions. Structure-property relationships are at the cen-ter of the development of MOF catalysts with improved activities and stabilities. This perspective highlights recent advances in designing pristine MOF materials for heterogeneous catalysis and emerging state-of-the-art techniques for analyzing structure -prop-erty relationships. We also discuss current barriers, challenges, and future opportunities in this promising and rapidly developing research field.
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| 9. |
- Zhou, Guojun, 1990-, et al.
(författare)
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Structure determination of a low-crystallinity covalent organic framework by three-dimensional electron diffraction
- 2023
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Ingår i: Communications Chemistry. - 2399-3669. ; 6
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Tidskriftsartikel (refereegranskat)abstract
- Covalent organic frameworks (COFs) have been attracting intense research due to their permanent porosity, designable architecture, and high stability. However, COFs are challenging to crystallize and their synthesis often results in tiny crystal sizes and low crystallinities, which hinders an unambiguous structure determination. Herein, we demonstrate that the structure of low-crystallinity COF Py-1P nanocrystals can be solved by coupling three-dimensional electron diffraction (3DED) with simulated annealing (SA). The resulting model is comparable to that obtained from high-crystallinity samples by dual-space method. Moreover, for low-resolution 3DED data, the model obtained by SA shows a better framework than those provided by classic direct method, dual-space method, and charge flipping. We further simulate data with different resolutions to understand the reliability of SA under different crystal quality conditions. The successful determination of Py-1P structure by SA compared to other methods provides new knowledge for using 3DED to analyze low-crystallinity and nanosized materials.
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