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1. Cascade/Parallel Biocatalysis via Multi-enzyme Encapsulation on Metal–Organic Materials for Rapid and Sustainable Biomass Degradation

   https://doi.org/https://doi.org/10.1021/acsami.1c12209  

   Li, Q. ; Pan, Y. ; Li, H. ; Lenertz, M. ; Reed, K. ; Jordahl, D. ; Bjerke, T. ; Ugrinov, A. ; Chen, B. ; Yang, Z. ( September 2021 , ACS applied materials interfaces)

   Multiple-enzyme cooperation simultaneously is an effective approach to biomass conversion and biodegradation. The challenge, however, lies in the interference of the involved enzymes with each other, especially when a protease is needed, and thus, the difficulty in reusing the enzymes; while extracting/synthesizing new enzymes costs energy and negative impact on the environment. Here, we present a unique approach to immobilize multiple enzymes, including a protease, on a metal–organic material (MOM) via co-precipitation in order to enhance the reusability and sustainability. We prove our strategy on the degradation of starch-containing polysaccharides (require two enzymes to degrade) and food proteins (require amore »protease to digest) before the quantification of total dietary fiber. As compared to the widely adopted “official” method, which requires the sequential addition of three enzymes under different conditions (pH/temperature), the three enzymes can be simultaneously immobilized on the surface of our MOM crystals to allow for contact with the large substrates (starch), while MOMs offer sufficient protection to the enzymes so that the reusability and long-term storage are improved. Furthermore, the same biodegradation can be carried out without adjusting the reaction condition, further reducing the reaction time. Remarkably, the simultaneous presence of all enzymes enhances the reaction efficiency by a factor of ∼3 as compared to the official method. To our best knowledge, this is the first experimental demonstration of using aqueous-phase co-precipitation to immobilize multiple enzymes for large-substrate biocatalysis. The significantly enhanced efficiency can potentially impact the food industry by reducing the labor requirement and enhancing enzyme cost efficiency, leading to reduced food cost. The reduced energy cost of extracting enzymes and adjusting reaction conditions minimize the negative impact on the environment. The strategy to prevent protease damage in a multi-enzyme system can be adapted to other biocatalytic reactions involving proteases.« less
2. One-pot synthesis of enzyme@metal–organic material (MOM) biocomposites for enzyme biocatalysis

   https://doi.org/DOI https://doi.org/10.1039/D1GC00775K  

   Pan, Y. ; Li, H. ; Lenertz, M. ; Han, Y. ; Ugrinov, A. ; Kilin, D. ; Chen, B. ; Yang, Z. ( March 2021 , Green chemistry)

   Metal–organic frameworks/materials (MOFs/MOMs) are advanced enzyme immobilization platforms that improve biocatalysis, materials science, and protein biophysics. A unique way to immobilize enzymes is co-crystallization/co-precipitation, which removes the limitation on enzyme/substrate size. Thus far, most enzyme@MOF composites rely on the use of non-sustainable chemicals and, in certain cases, heavy metals, which not only creates concerns regarding environmental conservation but also limits their applications in nutrition and biomedicine. Here, we show that a dimeric compound derived from lignin, 5,5′-dehydrodivanillate (DDVA), co-precipitates with enzymes and low-toxicity metals, Ca2+ and Zn2+, and forms stable enzyme@Ca/Zn–MOM composites. We demonstrated this strategy on four enzymes withmore »different isoelectric points (IEPs), molecular weights, and substrate sizes. Furthermore, we found that all enzymes displayed slightly different but reasonable catalytic efficiencies upon immobilization in the Ca–DDVA and Zn–DDVA MOMs, as well as reasonable reusability in both composites. We then probed the structural basis of such differences using a representative enzyme and found enhanced restriction of enzymes in Zn–DDVA than in Ca–DDVA, which might have caused the activity difference. To the best of our knowledge, this is the first aqueous-phase, one-pot synthesis of a lignin-derived “green” enzyme@MOF/MOM platform that can host enzymes without any limitations on enzyme IEP, molecular weight, and substrate size. The different morphologies and crystallinities of the composites formed by Ca–DDVA and Zn–DDVA MOMs broaden their applications depending on the problem of interest. Our approach of enzyme immobilization not only improves the sustainability/reusability of almost all enzymes but also reduces/eliminates the use of non-sustainable resources. This synthesis method has a negligible environmental impact while the products are non-toxic to living things and the environment. The biocompatibility also makes it possible to carry out enzyme delivery/release for nutritional or biomedical applications via our “green” biocomposites.« less
3. Rapid mechanochemical encapsulation of biocatalysts into robust metal–organic frameworks

   https://doi.org/10.1038/s41467-019-12966-0  

   Wei, Tz-Han ; Wu, Shi-Hong ; Huang, Yi-Da ; Lo, Wei-Shang ; Williams, Benjamin P. ; Chen, Sheng-Yu ; Yang, Hsun-Chih ; Hsu, Yu-Shen ; Lin, Zih-Yin ; Chen, Xin-Hua ; et al ( November 2019 , Nature Communications)

   Metal–organic frameworks (MOFs) have recently garnered consideration as an attractive solid substrate because the highly tunable MOF framework can not only serve as an inert host but also enhance the selectivity, stability, and/or activity of the enzymes. Herein, we demonstrate the advantages of using a mechanochemical strategy to encapsulate enzymes into robust MOFs. A range of enzymes, namely β-glucosidase, invertase, β-galactosidase, and catalase, are encapsulated in ZIF-8, UiO-66-NH₂, or Zn-MOF-74 via a ball milling process. The solid-state mechanochemical strategy is rapid and minimizes the use of organic solvents and strong acids during synthesis, allowing the encapsulation of enzymes intomore »three prototypical robust MOFs while maintaining enzymatic biological activity. The activity of encapsulated enzyme is demonstrated and shows increased resistance to proteases, even under acidic conditions. This work represents a step toward the creation of a suite of biomolecule-in-MOF composites for application in a variety of industrial processes.

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4. Functional CeOx nanoglues for efficient and robust atomically dispersed catalysts

   Li X, Hernandez XIP ( June 2021 , Research square)

   Single-atom catalysts (SACs) exhibit unique catalytic property and maximum atom efficiency of rare, expensive metals. A critical barrier to applications of SACs is sintering of active metal atoms under operating conditions. Anchoring metal atoms onto oxide supports via strong metal-support bonds may alleviate sintering. Such an approach, however, usually comes at a cost: stabilization results from passivation of metal sites by excessive oxygen ligation—too many open coordination sites taken up by the support, too few left for catalytic action. Furthermore, when such stabilized metal atoms are activated by reduction at elevated temperatures they become unlinked and so move and sinter,more »leading to loss of catalytic function. We report a new strategy, confining atomically dispersed metal atoms onto functional oxide nanoclusters (denoted as nanoglues) that are isolated and immobilized on a robust, high-surface-area support—so that metal atoms do not sinter under conditions of catalyst activation and/or operation. High-number-density, ultra-small and defective CeOx nanoclusters were grafted onto high-surface-area SiO2 as nanoglues to host atomically dispersed Pt. The Pt atoms remained on the CeOx nanoglue islands under both O2 and H2 environment at high temperatures. Activation of CeOx supported Pt atoms increased the turnover frequency for CO oxidation by 150 times. The exceptional stability under reductive conditions is attributed to the much stronger affinity of Pt atoms for CeOx than for SiO2—the Pt atoms can move but they are confined to their respective nanoglue islands, preventing formation of larger Pt particles. The strategy of using functional nanoglues to confine atomically dispersed metal atoms and simultaneously enhance catalytic performance of localized metal atoms is general and takes SACs one major step closer to practical applications as robust catalysts for a wide range of catalytic transformations.« less
5. Enzymatic synthesis of supported CdS quantum dot/reduced graphene oxide photocatalysts

   https://doi.org/10.1039/C9GC00097F  

   Spangler, Leah C. ; Cline, Joseph P. ; Sakizadeh, John D. ; Kiely, Christopher J. ; McIntosh, Steven ( July 2019 , Green Chemistry)

   Photocatalysis is an attractive, sustainable, and potentially low-cost route to capture solar energy as fuel. However, current photocatalytic materials synthesis routes are not easily scaled-up to the magnitude required to impact our energy consumption due to both economic and environmental concerns. While the elements utilized are often earth abundant, typical synthetic routes utilize organic solvents at elevated temperatures with relatively expensive precursors. Herein, we demonstrate the fully biomineralized synthesis of a quantum confined CdS/reduced graphene oxide (CdS/rGO) photocatalyst catalyzed by the single enzyme cystathionine γ-lyase (CSE). The synthesis is performed at pH 9 in a buffered aqueous solution, under ambientmore »conditions, and utilizes the low-cost precursors Cd acetate, l -cysteine, graphene oxide, and a poly- l -lysine linker molecule. CSE actively decomposes l -cysteine to generate reactive HS − in aqueous solution at pH 9. Careful selection and control of the synthesis conditions enable both reduction of graphene oxide to rGO, and control over the mean CdS nanocrystal size. The CdS is conjugated to the rGO via a poly- l -lysine crosslinker molecule introduced during rGO formation. The completed CdS/rGO photocatalyst is capable of producing H 2 , without the aid of a noble metal co-catalyst, at a rate of 550 μmol h −1 g −1 for an optimized CdS/rGO ratio. This rate is double that measured for unsupported CdS and is comparable to CdS/rGO photocatalysts produced using more typical chemical synthesis routes. Single enzyme biomineralization by CSE can produce a range of metal chalcogenides without altering the enzyme or benign approach, making this an easily adaptable procedure for the sustainable production of a wide variety of important photocatalyst systems.« less