The selective oxidative C−C bond cleavage is essential for the production of functional molecules. Herein, a sustainable and efficient heterogeneous catalytic protocol is developed to facilitate the aerobic oxidative C−C bond cleavage, in which the selective conversion of vicinal diols to the corresponding aldehydes was achieved under a near-room-temperature condition with NH 3 -treated cobalt catalysts. Hydrobenzoin was selectively transformed to generate benzaldehyde with the solid Co m O n /C−N catalyst, where the conversion and product selectivity reached 96.7 and 99.0% under an oxygen atmosphere, respectively. Further investigations revealed that the high catalytic activity of the catalyst is contributed to numerous oxygen defects, which lead to efficient generation of active 1 O 2 species. Moreover, the Co m O n /C−N catalyst still exhibited a very high catalytic activity after it was continuously recycled five times. Finally, the oxidative cleavages of the C−C bond in the different 1,2-diols were also studied where more than 96.5% conversion of substrates and 99% selectivity of aldehydes were acquired under the optimal conditions.
With the increasing demand for the regulation of CRISPR systems, a considerable number of studies have been conducted to control their excessive activity levels. In this context, we propose a method that involves a bioorthogonal cleavage reaction between isonitrile and tetrazine to modulate the cleavage activity of the CRISPR system. Importantly, isonitrile demonstrates significant potential for modifying sgRNAs, making it a promising candidate for bioorthogonal reactions, a phenomenon that has not been previously reported. Our approach utilizes the 3-isocyanopropyl-carbonate group as a caging group to deactivate the CRISPR systems, while tetrazine acts as an activator to restore their activities. Through the implementation of post-synthetic modifications and click-and-release chemistry, we have successfully achieved the regulation of RNA-guided nucleic acid cleavage, which holds great promise for controlling gene editing in human cells.
Relying on the excellent properties of high-entropy materials (HEMs), the high-entropy alloys (HEAs) and high-entropy oxides (HEOs) are considered as the novel heterogeneous catalysts for the valorization of biomass feedstock and biomass-derived platform compounds. HEAs and HEOs are opening up a vast, unknown field of alloy or oxide composition and can realize the catalyst stability with the rocksalt crystal structure by means of configurational entropy. In this paper, the general component and structure of lignocellulosic biomass are concisely introduced. Then, the fundamental character of HEMs including the inherent merit and regulatable property as promising catalytic materials is discussed. Therein, the inherent merits of HEMs are defined as the high entropy effect in thermodynamics, lattice distortion in the structure, sluggish diffusion in dynamics, and the cocktail effect in performance; correspondingly, the regulatable property contains the surface area, the applicability of the element, and the size of nanoparticles. In addition, the valorization of biomass feedstocks including the direct pyrolysis of biomass, the selective transformation of cellulose and hemicelluloses, the utilization of lignin, and the catalytic valorization of furfural (FUR) and 5-hydroxymethylfurfural (5-HMF) as the representative biomass-based platform compounds is discussed, and the obtained valuable reaction products are briefly summarized. Finally, further research orientations for the selective volarization of biomass by the use of HEMs as heterogeneous catalysts is prospected, and the recommendable HEAs and HEOs catalysts including the potential metallic elements are proposed for the biomass pyrolysis, the conversion of (hemi)cellulose, and the transformation of lignin, respectively.
The selective oxidative C-C and C-O bond cleavage is of significance to the efficient ulitization of biomass and biomass-derived platform compounds. In this work, the selective oxidative cleavage of C-C...
The number of carbon atoms is closely related to the properties of liquid fuels. As for furfural (FUR)-based biofuels, the regulation of carbon chain length is greatly significant to improve the quality. In this work, the C7–C17 fuel precursor has been successfully synthesized via the oxidative condensation processes of biomass-derived FUR with aliphatic alcohols. With the promotion of the MgLaFeMnCu high entropy catalyst (HECAT), the carbon chain increase of FUR is adjustable by changing the carbon number of aliphatic alcohols. Typically, 2-(furan-2-yl-methylene) butanal (FMB, C9) could be prepared from the reaction of furfural with n-butanol, in which a 99.7% conversion and 93.8% selectivity of FMB were obtained at 80 °C for 2 h. Especially, a 94.3% conversion of FUR with 95.1% selectivity of FMB could be achieved at room temperature for a suitable reaction time. Moreover, all the oxidative condensation reactions of FUR with C2–C12 alcohols have been successfully performed to generate the C7–C17 precursor in the presence of MgLaFeMnCu HECAT. Further investigations revealed that the occurrence of active O2 –· species plays a crucial role during the oxidative condensation reactions. Meanwhile, the high activity of HECAT is attributed to the abundant oxygen vacancies, high surface area, and synergistic effects of the numerous metallic components.
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