Fa-Kuen Shieh

Imparting Functionality to Biocatalysts via Embedding Enzymes into Nanoporous Materials by a de Novo Approach: Size-Selective Sheltering of Catalase in Metal–Organic Framework Microcrystals

We develop a new concept to impart new functions to biocatalysts by combining enzymes and metal-organic frameworks (MOFs). The proof-of-concept design is demonstrated by embedding catalase molecules into uniformly sized ZIF-90 crystals via a de novo approach. We have carried out electron microscopy, X-ray diffraction, nitrogen sorption, electrophoresis, thermogravimetric analysis, and confocal microscopy to confirm that the ~10 nm catalase molecules are embedded in 2 μm single-crystalline ZIF-90 crystals with ~5 wt % loading. Because catalase is immobilized and sheltered by the ZIF-90 crystals, the composites show activity in hydrogen peroxide degradation even in the presence of protease proteinase K.

Water-based synthesis of zeolitic imidazolate framework-90 (ZIF-90) with a controllable particle size.

The ZIF code: ZIF-90 materials were successfully synthesized in an optimized water-based system. The particle size, ranging from micro- to nanoscales, could be controlled by different amounts of polyvinylpyrrolidone (PVP), Zn/imidazole-2-carboxaldehyde ratio and alcohol.

Synthesis, Bifunctionalization, and Remarkable Adsorption Performance of Benzene-Bridged Periodic Mesoporous Organosilicas Functionalized with High Loadings of Carboxylic Acids

Highly ordered benzene-bridged periodic mesoporous organosilicas (PMOs) that were functionalized with exceptionally high loadings of carboxylic acid groups (COOH), up to 80 mol % based on silica, have been synthesized and their use as adsorbents for the adsorption of methylene blue (MB), a basic dye pollutant, and for the loading and release of doxorubicin (DOX), an anticancer drug, is demonstrated. These COOH-functionalized benzene-silicas were synthesized by the co-condensation of 1,4-bis(triethoxysilyl) benzene (BTEB) and carboxyethylsilanetriol sodium salt (CES), an organosilane that contained a carboxylic acid group, in the presence of non-ionic oligomeric surfactant Brij 76 in acidic medium. The materials thus obtained were characterized by a variety of techniques, including powder X-ray diffraction (XRD), nitrogen-adsorption/desorption isotherms, TEM, and (13)C and (29)Si solid-state NMR spectroscopy. Owing to the exceptionally high loadings of COOH groups, their high surface areas, and possible π-π-stacking interactions, these adsorbents have very high adsorption capacities and extremely rapid adsorption rates for MB removal and for the controlled loading/release of DOX, thus manifesting their great potential for environmental and biomedical applications.

Synthesis of hierarchical micro/mesoporous structures via solid-aqueous interface growth: zeolitic imidazolate framework-8 on siliceous mesocellular foams for enhanced pervaporation of water/ethanol mixtures.

A new hierarchical micro/mesoporous composite is synthesized via direct growth of microporous zeolitic imidazolate framework-8 (ZIF-8) on siliceous mesocellular foams (MCF). Depending on different synthetic conditions, ZIF-8 with two different particle sizes, i.e., ZIF-8 microparticles and ZIF-8 nanoparticles, were successfully formed on the external surface of amine-functionalized MCF (denoted as microZIF-8@MCF and nanoZIF-8@MCF, respectively). The synthesized hierarchical micro/mesoporous ZIF-8@MCF structures were characterized with several spectroscopic techniques including X-ray diffraction (XRD), solid-state NMR, and FT-IR and electron microscopic techniques (scanning electron microscope, SEM, and transmission electron microscopy, TEM). In addition, the pervaporation measurements of the liquid water/ethanol mixture show that nanoZIF-8@MCF/PVA (poly(vinyl alcohol) mixed-matrix membrane exhibits enhanced performance both on the permeability and separation factor. Compared to conventional routes for chemical etching, this study demonstrates a promising and simple strategy for synthesizing novel hierarchical porous composites exhibiting both advantages of mesoporous materials and microporous materials, which is expected to be useful for gas adsorption, separation, and catalysis.

Strategies for Improving the Functionality of Zeolitic Imidazolate Frameworks: Tailoring Nanoarchitectures for Functional Applications

Zeolitic imidazolate frameworks (ZIFs), a subclass of metal-organic frameworks (MOFs) built with tetrahedral metal ions and imidazolates, offer permanent porosity and high thermal and chemical stabilities. While ZIFs possess some attractive physical and chemical properties, it remains important to enhance their functionality for practical application. Here, an overview of the extensive strategies which have been developed to improve the functionality of ZIFs is provided, including linker modifications, functional hybridization of ZIFs via the encapsulation of guest species (such as metal and metal oxide nanoparticles and biomolecules) into ZIFs, and hybridization with polymeric matrices to form mixed matrix membranes for industrial gas and liquid separations. Furthermore, the developed strategies for achieving size and shape control of ZIF nanocrystals are considered, which are important for optimizing the textural characteristics as well as the functional performance of ZIFs and their derived materials/hybrids. Moreover, the recent trends of using ZIFs as templates for the derivation of nanoporous hybrid materials, including carbon/metal, carbon/oxide, carbon/sulfide, and carbon/phosphide hybrids, are discussed. Finally, some perspectives on the potential future research directions and applications for ZIFs and ZIF-derived materials are offered.

Shielding against Unfolding by Embedding Enzymes in Metal–Organic Frameworks via a de Novo Approach

We show that an enzyme maintains its biological function under a wider range of conditions after being embedded in metal-organic framework (MOF) microcrystals via a de novo approach. This enhanced stability arises from confinement of the enzyme molecules in the mesoporous cavities in the MOFs, which reduces the structural mobility of enzyme molecules. We embedded catalase (CAT) into zeolitic imidazolate frameworks (ZIF-90 and ZIF-8), and then exposed both embedded CAT and free CAT to a denature reagent (i.e., urea) and high temperatures (i.e., 80 °C). The embedded CAT maintains its biological function in the decomposition of hydrogen peroxide even when exposed to 6 M urea and 80 °C, with apparent rate constants kobs (s-1) of 1.30 × 10-3 and 1.05 × 10-3, respectively, while free CAT shows undetectable activity. A fluorescence spectroscopy study shows that the structural conformation of the embedded CAT changes less under these denaturing conditions than free CAT.

Phosphine oxide-based conjugated microporous polymers with excellent CO2 capture properties

Three novel phosphine oxide-based conjugated microporous polymers TEPO-1, TEPO-2 and TEPO-3 are designed and synthesized, which are constructed using the phosphine-based building unit tris(4-ethynylphenyl)phosphine oxide with linkers tris(4-ethynylphenyl)phosphine oxide, triphenylphosphine oxide and tri(thiophen-2-yl)phosphine oxide via Sonogashira–Hagihara homo-coupling or cross-coupling condensation reaction. The adsorption isotherms of N2 reveal that the Brunauer–Emmett–Teller (BET) specific surface areas of TEPO-1, TEPO-2 and TEPO-3 are 485 m2 g−1, 534 m2 g−1 and 592 m2 g−1, respectively. However, these three polymers have strong affinity for CO2, which exhibit relatively high sorption abilities for CO2 (273 K/1.0 bar: 6.52 wt%, 7.62 wt%, and 8.40 wt%). Meanwhile, the TEPOs demonstrate ultrahigh hydrogen uptake and outstanding CO2/CH4 selectivity compared to analogous materials with similar BET surface areas using C, Si and N as the nodes. This work reveals clearly that the gas uptake capacity of material is highly dependent on the length of the rigid skeleton and the modification of functional groups in the monomer structure.

Benzouracil-coumarin-arene conjugates as inhibiting agents for chikungunya virus.

Chikungunya virus (CHIKV) is an arbovirus that was first recognized in an epidemic form in East Africa in 1952-1953. The virus is primarily transmitted through mosquitoes and the resulting disease, chikungunya fever, is found in nearly 40 countries. Neither an effective vaccine nor a specific antiviral drug exists for treatments of chikungunya fever. Thus 22 new conjugated compounds of uracil-coumarin-arene were designed and synthesized as potential inhibiting agents. Their chemical structures were determined unambiguously by spectroscopic methods, including single-crystal X-ray diffraction crystallography. The three units in these conjugates were connected by specially designed -SCH2- and -OSO2- joints. Five of these new conjugates were found to inhibit CHIKV in Vero cells with significant potency (EC50 = 10.2-19.1 μM) and showed low toxicity (CC50 = 75.2-178 μM). The selective index values were 8.8-11.5 for three conjugates. By analysis of the data from the anti-viral assays, the structure-activity relationship is derived on the basis of the nature of the uracil, the functional groups attached to the arene, and the joints between the ring units.

Dendrimer-like conjugated microporous polymers

Four dendrimer-like polycarbazole conjugated polymer networks P-G1-T, P-G2-T, P-G1-Fo and P-G2-Fo were designed and synthesized by FeCl3 oxidative coupling polymerization. Aromatic thiophene and fluorenone units were employed as the linkers between carbazole units to construct the building blocks. The first generation polymers (1st) were produced from the monomers containing two carbazole units, while the second generation polymers (2nd) were produced from the monomers with six carbazole units, which feature double oxidative polymerization sites compared with the monomers for the 1st generation. It was found that the 2nd generation polymers show a higher Brunauer–Emmett–Teller (BET) surface area and a higher gas adsorption performance than the 1st generation polymers because of more reactive sites and larger torsion angles in the monomers for the 2nd generation, which led to a highly crosslinked polymer structure and thus a high surface area. All of the polymers show high isosteric heats of CO2 adsorption over 33 kJ mol−1 because the incorporation of heteroatoms (N, S and/or O) into the skeleton of the polymers enhanced the interaction between the pore wall and CO2 molecules.

Cytotoxicity of Postmodified Zeolitic Imidazolate Framework-90 (ZIF-90) Nanocrystals: Correlation between Functionality and Toxicity.

Using a simple method, the aldehyde groups of zeolitic imidazolate framework-90 (ZIF-90) nanocrystals were converted into carboxyl, amino, and thiol groups, without affecting the integrity of the framework. Notably, for the first time, correlations between functionality and cytotoxicity are also demonstrated via in vitro cytotoxicity assays. The positive charged aminated-ZIF-90 presumably results in either perturbation of cell membrane, more efficient cell uptake, or both. Therefore, the half-maximal effective (EC50 ) concentration of aminated-ZIF-90 has a higher cytotoxicity of about 30 μg mL(-1) .