Active Nanointerfaces Based on Enzyme Carbonic Anhydrase and Metal–Organic Framework for Carbon Dioxide Reduction

Abstract

Carbonic anhydrases are enzymes capable of transforming carbon dioxide into bicarbonate to maintain functionality of biological systems. Synthetic isolation and implementation of carbonic anhydrases into membrane have recently raised hopes for emerging and efficient strategies that could reduce greenhouse emission and the footprint of anthropogenic activities. However, implementation of such enzymes is currently challenged by the resulting membrane’s wetting capability, overall membrane performance for gas sensing, adsorption and transformation, and by the low solubility of carbon dioxide in water, the required medium for enzyme functionality. We developed the next generation of enzyme-based interfaces capable to efficiently adsorb and reduce carbon dioxide at room temperature. For this, we integrated carbonic anhydrase with a hydrophilic, user-synthesized metal–organic framework; we showed how the framework’s porosity and controlled morphology contribute to viable enzyme binding to create functional surfaces for the adsorption and reduction of carbon dioxide. Our analysis based on electron and atomic microscopy, infrared spectroscopy, and colorimetric assays demonstrated the functionality of such interfaces, while Brunauer–Emmett–Teller analysis and gas chromatography analysis allowed additional evaluation of the efficiency of carbon dioxide adsorption and reduction. Our study is expected to impact the design and development of active interfaces based on enzymes to be used as green approaches for carbon dioxide transformation and mitigation of global anthropogenic activities.

Diverse Applications of Biomass‐Derived 5‐Hydroxymethylfurfural and Derivatives as Renewable Starting Materials

“…Since then, other MOFs with FDCA linkers have been made with Gd, [91] as well as with Cu, [88,89] Cr, [92] Fe, [89,93] Zr, [89,92,93] Zn, [94] various lanthanides, [90,91,95] and, most commonly, Al. [89,93,[96][97][98][99][100][101][102][103][104][105][106][107] The polarity and conjugation of the FDCA ligands confers desirable properties in MOFs designed for metal binding and detection through photoluminescence. In 2017, Sapchenko et al created a MOF complex (H 3 O) 2 [Zn 4 (urotropine) (FDCA) 2 (FDCA 2À ) 4 ] with cryptand-like cavities that can be used to separate and detect Rb and Cs cations optically.…”

“…Subsequent investigations have demonstrated that MIL-160's porosity and hydrophilic environment is crucial for CO 2 adsorption and reduction. [101] A silver-adhered MIL-160 framework (Ag/MIL-160) has also shown promising catalytic activity for the photocatalytic reduction of nitrophenol, which can be used for detection of this prevalent pollutant. [104] The morphology of synthesized Ag/MIL-160 hybrid was shown to be similar to MIL-160 (Figure 6).…”

“…The washed and collected MOFs exhibited gas adsorption capabilities for N 2 , H 2 , and CO 2 and magnetic properties. Since then, other MOFs with FDCA linkers have been made with Gd, [91] as well as with Cu, [88,89] Cr, [92] Fe, [89,93] Zr, [89,92,93] Zn, [94] various lanthanides, [90,91,95] and, most commonly, Al [89,93,96–107] …”

“…These CA‐MIL‐160 conjugates exhibit excellent biocatalytic activity, and improved kinetics relative to enzymes immobilized on hydrophobic supports. Subsequent investigations have demonstrated that MIL‐160’s porosity and hydrophilic environment is crucial for CO 2 adsorption and reduction [101] . A silver‐adhered MIL‐160 framework (Ag/MIL‐160) has also shown promising catalytic activity for the photocatalytic reduction of nitrophenol, which can be used for detection of this prevalent pollutant [104] .…”

Assessment of Enzyme Functionality at Metal–Organic Framework Interfaces Developed through Molecular Simulations

“…37 On the other hand, the hydrophilicity of MIL-160 has solidified this hybrid as a strong candidate for the reversible adsorption of water to be adapted to heat reallocation systems for a more economical maintenance of indoor temperatures. 28 The interest in CA is motivated by the intrinsic activity of this specific catalyst for the green-based mitigation of CO 2 emissions as well as the transformation to benign, and potentially valuable, chemical products 25,38,39 while the interest in MPO is motivated by its known enzymatic activity in the transformation of halides (Cl − , namely) and hydrogen peroxide (H 2 O 2 ) to hypochlorous acid (HOCl), which plays a critical role in the control of microbial behavior via the killing of neutrophils, 40 thereby solidifying MPO as a particularly prominent biocatalyst in industrial surface decontamination. 41 Additionally, MPO has been shown to be an effective agent in the biodegradation of aqueously dispersed graphene particles, indicating that the enzyme can be useful in the treatment of industrial wastewater.…”