Nature uses catalysis as an indispensable tool to control assembly and reaction cycles in vital non-equilibrium supramolecular processes. For instance, enzymatic methionine oxidation regulates actin (dis-)assembly, and catalytic guanosine triphosphate hydrolysis is found in tubulin (dis-)assembly. Here we present a completely artificial reaction cycle which is driven by a chemical fuel that is catalytically obtained from a "pre-fuel". The reaction cycle controls the dis-assembly and re-assembly of a hydrogel, where the rate of pre-fuel turnover dictates the morphology as well as the mechanical properties. By addition of additional fresh aliquots of fuel and removal of waste, the hydrogels can be re-programmed time after time. Overall, we show how catalytic fuel generation can control reaction/assembly kinetics and materials' properties in life-like non-equilibrium systems.
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http://dx.doi.org/10.1021/jacs.9b11503 | DOI Listing |
ChemSusChem
January 2025
Zittau/Görlitz University of Applied Sciences: Hochschule Zittau/Gorlitz, Faculty of Natural and Environmental Sciences, Theodor-Körner-Allee 16, 02763, Zittau, GERMANY.
Life cycle assessment (LCA) was used, next to green chemistry concepts, to compare the full environmental impacts of the epoxidation of a bio-based monomer, which can be used for the synthesis of vitrimers. On a laboratory scale, the synthesis of the monomer can either be done via a petrochemical route or via an enzymatic reaction pathway. Both reaction pathways were initially optimized to minimize the impact of suboptimal routes on the sustainability evaluation.
View Article and Find Full Text PDFSmall
January 2025
Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, School of Chemistry and Materials Science, Jiangsu Normal, University Xuzhou, Jiangsu, 221116, P. R. China.
Fabricating visible-light-responsive metal-organic frameworks (MOFs) with high stability and effective catalytic functionality remains a long-term pursuit yet a great challenge. Herein, a strategy of increasing ligand and cluster connectivity is developed to construct highly stable fluorescein MOFs, La-CFL, presenting a new (4,8)-connected topological structure compared to Cd-FL constructed using 6-connected dinuclear clusters and 3-connected tritopic ligands. La(CFL) containers like Chinese "Ritual Wine Vessels (Jue)" resemble linear arrangements interconnected by the [La(COO)] clusters.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Georgia Institute of Technology, School Of Chemistry and Biochemistry, 901 Atlantic Drive, 30332, United States, 30332, Atlanta, UNITED STATES OF AMERICA.
The development of chemically recyclable polymers for sustainable 3D printing is crucial to reducing plastic waste and advancing towards a circular polymer economy. Here, we introduce a new class of polythioenones (PCTE) synthesized via Michael addition-elimination ring-opening polymerization (MAEROP) of cyclic thioenone (CTE) monomers. The designed monomers are straightforward to synthesize, scalable and highly modular, and the resulting polymers display mechanical performance superior to commodity polyolefins such as polyethylene and polypropylene.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Central South University, chemistry, CHINA.
The two-dimensional lamellar materials disperse platinum sites and minimize noble-metal usage for fuel cells, while mass transport resistance at the stacked layers spurs device failure with a significant performance decline in membrane electrode assembly (MEA). Herein, we implant porous and rigid sulfonated covalent organic frameworks (COF) into the graphene-based catalytic layer for the construction of steric mass-charge channels, which highly facilitates the activity of oxygen reduction reactions in both the rotating disk electrode (RDE) measurements and MEA device tests. Specifically, the normalized mass activity is remarkably boosted by 3.
View Article and Find Full Text PDFJ Mater Chem A Mater
January 2025
MESA+ Institute for Nanotechnology, University of Twente 7500 AE Enschede Netherlands
The advancement of rapid-response grid energy storage systems and the widespread adoption of electric vehicles are significantly hindered by the charging times and energy densities associated with current lithium-ion battery technology. In state-of-the-art lithium-ion batteries, graphite is employed as the standard negative electrode material. However, graphite suffers from polarization and deteriorating side-reactions at the high currents needed for fast charging.
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