Chia-Her Lin

Metal organic framework-organic polymer monolith stationary phases for capillary electrochromatography and nano-liquid chromatography.

In this study, metal organic framework (MOF)-organic polymer monoliths prepared via a 5-min microwave-assisted polymerization of ethylene dimethacrylate (EDMA), butyl methacrylate (BMA), and 2-acrylamido-2-methylpropane sulfonic acid (AMPS) with the addition of various weight percentages (30-60%) of porous MOF (MIL-101(Cr)) were developed as stationary phases for capillary electrochromatography (CEC) and nano-liquid chromatography (nano-LC). Powder X-ray diffraction (PXRD) patterns and nitrogen adsorption/desorption isotherms of these MOF-organic polymer monoliths showed the presence of the inherent characteristic peaks and the nano-sized pores of MIL-101(Cr), which confirmed an unaltered crystalline MIL-101(Cr) skeleton after synthesis; while energy dispersive spectrometer (EDS) and micro-FT-IR spectra suggested homogenous distribution of MIL-101(Cr) in the MIL-101(Cr)-poly(BMA-EDMA) monoliths. This hybrid MOF-polymer column demonstrated high permeability, with almost 800-fold increase compared to MOF packed column, and efficient separation of various analytes (xylene, chlorotoluene, cymene, aromatic acids, polycyclic aromatic hydrocarbons and trypsin digested BSA peptides) either in CEC or nano-LC. This work demonstrated high potentials for MOF-organic polymer monolith as stationary phase in miniaturized chromatography for the first time.

A mesoporous aluminium metal–organic framework with 3 nm open pores

A mesoporous metal–organic framework of [Al(OH)(SDC)] (CYCU-3) (H2SDC = 4,4′-stilbenedicarboxylic acid) was synthesised by using Al(III) ions and H2SDC under solvothermal conditions. The structure forms 3D mesoporous frameworks in which the carboxylate oxygen on each terminus of the ligand forms octahedral AlO6 by corner-sharing. As verified by N2 sorption measurements, the CYCU-3 exhibits the largest pore volume and open channels (3.0 nm) in the system of Al-MOFs reported to date. This mesoporous Al-MOF also displays highly porous properties and uptake capacities of H2 (8.22 mmol g−1 at 77 K and 1 atm) and CO2 (2.83 mmol g−1 CO2 at 273 K and 1 atm).

A Novel Hybrid Metal–Organic Framework–Polymeric Monolith for Solid‐Phase Microextraction

This study describes the fabrication of a novel hybrid metal-organic framework- organic polymer (MOF-polymer) for use as a stationary phase in fritless solid-phase microextraction (SPME) for validating analytical methods. The MOF-polymer was prepared by using ethylene dimethacrylate (EDMA), butyl methacrylate (BMA), and an imidazolium-based ionic liquid as porogenic solvent followed by microwave-assisted polymerization with the addition of 25 % MOF. This novel hybrid MOF-polymer was used to extract penicillin (penicillin G, penicillin V, oxacillin, cloxacillin, nafcillin, dicloxacillin) under different conditions. Quantitative analysis of the extracted penicillin samples using the MOF-organic polymer for SPME was conducted by using capillary electrochromatography (CEC) coupled with UV analysis. The penicillin recovery was 63-96.2 % with high reproducibility, sensitivity, and reusability. The extraction time with the proposed fabricated SPME was only 34 min.

Microwave synthesis and gas sorption of calcium and strontium metal–organic frameworks with high thermal stability

Two new calcium and strontium metal–organic frameworks [Ca(SBA)] (CYCU-1) and [Sr(SBA)] (CYCU-2) were prepared by microwave-assisted reactions. Both rigid frameworks are thermally stable up to about 450 °C. As verified by N2, CO2, and H2sorption measurements, the thermally activated CYCU-1 and CYCU-2 exhibit significant microporosity.

Aluminum based metal-organic framework-polymer monolith in solid-phase microextraction of penicillins in river water and milk samples

In this study, aluminum based metal-organic framework (Al-MOF)-organic polymer monoliths were prepared via microwave-assisted polymerization of ethylene dimethacrylate (EDMA), butyl methacrylate (BMA) with different weight percentages of Al-MOF (MIL-53; 37.5-62.5%) and subsequently utilized as sorbent in solid-phase microextraction (SPME) of penicillins (penicillin G, penicillin V, oxacillin, cloxacillin, dicloxacillin, nafcillin). The Al-MOF-polymer was characterized using Fourier transform infrared (FTIR) spectroscopy, powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and SEM-energy-dispersive X-ray spectroscopy (SEM-EDS) to clarify the retained crystalline structure well as the homogeneous dispersion of Al-MOF (MIL-53) in polymer monolith. The developed Al-MOF-polymer (MIL-53) monolithic column was evaluated according to its extraction recovery of penicillins. Several parameters affecting the extraction recoveries of penicillins using fabricated Al-MOF-polymer (MIL-53) monolithic column including different MIL-53 weight percentages, column length, pH, desorption solvent, and mobile phase flow rate were investigated. For comparison, different Al-based MOFs (MIL-68, CYCU-4 and DUT-5) were fabricated using the optimized condition for MIL-53-polymer (sample matrix at pH 3, 200μL desorption volume using methanol, 37.5% of MOF, 4-cm column length at 0.100mLmin(-1) flow rate). Among all the Al-MOF-polymers, MIL-53(Al)-polymer still afforded the best extraction recovery for penicillins ranging from 90.5 to 95.7% for intra-day with less than 3.5% relative standard deviations (RSDs) and inter-day precision were in the range of 90.7-97.6% with less than 4.2% RSDs. Meanwhile, the recoveries for column-to-column were in the range of 89.5-93.5% (<3.4% RSDs) while 88.5-90.5% (<5.8% RSDs) for batch-to-batch (n=3). Under the optimal conditions, the limit of detections were in the range of 0.06-0.26μgL(-1) and limit of quantifications between 0.20 and 0.87μgL(-1). Finally, the MIL-53-polymer was applied for the extraction of penicillin in river water and milk by spiking trace-level penicillin for as low as 50μgL(-1) and 100μgL(-1) with recoveries ranging from 80.8% to 90.9% (<6.7% RSDs) in river water and 81.1% to 100.7% (<7.1% RSDs) in milk sample, respectively.

Metal–organic frameworks: new matrices for surface-assisted laser desorption–ionization mass spectrometry

The cage-type MIL-100(Fe) metal-organic frameworks (MOFs) were used as matrices for surface assisted laser desorption-ionization mass spectrometry. The unique 3D cage frameworks and the iron-center feature good reproducibility of MS intensity and a high signal-to-noise ratio compared to organic or other nanoparticle matrices.

Improvement of conversion efficiency for multi-junction solar cells by incorporation of Au nanoclusters.

We studied the photoluminescence (PL) and photovoltaic current-voltage characteristics of the three-junction InGaP/InGaAs/Ge solar cells by depositing Au nanoclusters on the cell surface. The increases of the PL intensity and short-circuit current after incorporation of Au nanoclusters are evident. An increase of 15.3% in energy conversion efficiency (from 19.6 to 22.6%) is obtained for the three-junction solar cells in which Au nanoclusters have been incorporated. We suggest that the increased light trapping due to radiative scattering from Au nanoclusters is responsible for improving the performance of the three-junction solar cells.

Fast Multipoint Immobilized MOF Bioreactor

An enzyme-NBD@MOF bioreactor with exemplary proteolytic performance, even after successive reuse and storage, was produced through a novel, rapid and simple multipoint immobilization technique without chemical modification of the solid support. Enzyme loading and distribution could be directly monitored from the fluorescence emission of the bioreactor. The dye molecular dimension plays a role in its overall performance.

Immobilization of Protein on Nanoporous Metal-Organic Framework Materials

Recently, metal-organic frameworks (MOFs) have been gaining attention as attractive support materials for the immobilization of proteins. They possess well-ordered pore structures, aperture channel distributions, great surface area, high stability, and can be modified with various functional groups. In this review, we present an overview of the reported fabrication methods of these materials along with the advantages and limitations of different approaches to immobilizing enzymes using MOF materials as support. GRAPHICAL ABSTRACT

Lipase‐Supported Metal–Organic Framework Bioreactor Catalyzes Warfarin Synthesis

A green and sustainable strategy synthesizes clinical medicine warfarin anticoagulant by using lipase-supported metal-organic framework (MOF) bioreactors (see scheme). These findings may be beneficial for future studies in the industrial production of chemical, pharmaceutical, and agrochemical precursors.