Graphite paste electrodes modified with a sulfo-functionalized metal-organic framework (type MIL-101) for voltammetric sensing of dopamine.

The metal-organic frameworks MIL-101 and sulfo-MIL-101 were used to modify graphite paste electrodes (GPEs) to obtain sensors for determination of dopamine (DA). Taking advantage of the catalytic activity of metal-organic frameworks (MOFs) and of the electrical conductivity of graphite, the modified GPEs show enhanced voltammetric responses, and the GPE modified with the sulfo-MOF displays superior sensitivity when operated at a working potential of -0.4 to 0.8 V (vs. Ag/AgCl). The sensor works in the 0.07 to100 µM DA concentration range and has a 43 nM detection limit. It is concluded that the sulfo group provides open sites for efficient electrostatic and hydrogen bonding interactions, which facilitates electron transfer. Graphical abstractSchematic representation of the structure of the sulfo-functionalized MOF (sulfo-MIL-101) and the different voltammetric signals of dopamine at the graphite paste electrodes (GPEs) modified with sulfo-MIL-101 and the parent MOF (MIL-101).

Fluorescence Turn-On Response Amplified by Space Confinement in Metal-Organic Frameworks.

Sensitive fluorescence turn-on response to specific substances is highly desired for development of chemical sensors and switches. Here we utilized a "two-in-one" strategy to prepare ionic metal-organic frameworks (MOFs) functionalized with the cationic bipyridinium receptors at the frameworks and anionic fluorescent indicators in the pores. The MOFs are rendered a fluorescence-resting state because the indicator's fluorescence is efficiently quenched by the ground-state charge-transfer (CT) complexation between the indicator and receptor. Addition of an alkylamine efficiently turns on the fluorescence because the indicator is displaced by the CT complexation between alkylamine with receptor. The turn-on response is highly specific to alkylamines. The MOFs can be used as recyclable sensors for selective and sensitive detection of alkylamines, with ultralow detection limits (0.5 nM). The fluorescence in solid state can be reversibly switched on and off with high contrast. The sensitive and high-contrast response can be attributed to the space confinement effects of the porous frameworks. The confined space can significantly enhance indicator-receptor and analyte-receptor interactions, and thereby both the quenching efficiency in the off state and the displacement efficiency in the on state are amplified.

A Facile and Versatile "Click" Approach Toward Multifunctional Ionic Metal-organic Frameworks for Efficient Conversion of CO2.

Ionic metal-organic frameworks (IMOFs) that integrate synergistic Lewis-acid sites (intrinsic metal centers of the frameworks) and nucleophilic anions (halides encapsulated within pores) are intriguing platforms for the design of fully heterogeneous catalytic systems for cycloaddition of CO2 to epoxides. A new, facile and versatile synthetic approach has been used to fabricate triazolium-based IMOFs for the first time. The approach makes use of azide-alkyne click chemistry and subsequent N-alkylation to post-synthetically create a cationic triazolium ring and introduce exchangeable counteranions at the same time. The IMOFs are efficient and recyclable heterogeneous catalysts for CO2 conversion under mild and cocatalyst-free conditions. In particular, the click-accessible triazolium ring provides a handle to incorporate further functionality. The MIL-101-tzmOH-Br catalyst, which integrates hydrogen-bonding hydroxy groups besides metal centers and bromide anions, shows superior catalytic performance under mild conditions.