Editorial Material
Chemistry, Multidisciplinary
Linfang Lu, Baizeng Fang
Summary: Scientists have reported an efficient catalyst that can produce cyclohexanone oxime with high selectivity (>95%) through in-situ generated H2O2, comparable to the current industrial route. The use of in-situ generated H2O2 can achieve significant cost savings in current oxime production and is believed to have promising prospects in other industrial chemical reactions requiring H2O2.
Article
Chemistry, Physical
Joseph Brehm, Richard J. Lewis, Thomas Richards, Tian Qin, David J. Morgan, Thomas E. Davies, Liwei Chen, Xi Liu, Graham J. Hutchings
Summary: The combination of an evolved unspecific peroxygenase (UPO) from Agrocybe aegerita and bimetallic Pd-based catalysts shows high efficiency in the oxidation of cyclohexane. The alloying of Pd with Zn greatly enhances the catalytic performance, attributed to the formation of PdZn alloys and electronic modification of Pd. This system inhibits competitive chemo-catalyzed H2O2 degradation reactions and overoxidation of cyclohexanol.
Article
Chemistry, Physical
Joseph Brehm, Richard J. Lewis, Thomas Richards, Tian Qin, David J. Morgan, Thomas E. Davies, Liwei Chen, Xi Liu, Graham J. Hutchings
Summary: The combination of an evolved unspecific peroxygenase (UPO) and bimetallic Pd-based catalysts is highly effective for the oxidative valorization of cyclohexane. Alloying Pd with Zn enhances catalytic performance, while the large population of Pd-only clusters in other catalysts promotes undesired oxidation products.
Article
Chemistry, Physical
Alex Stenner, Richard J. Lewis, Joseph Brehm, Tian Qin, Angeles Lopez-Martin, David J. Morgan, Thomas E. Davies, Liwei Chen, Xi Liu, Graham J. Hutchings
Summary: This study demonstrates that the introduction of dopant concentrations of Pt into supported AuPd nanoparticles, when used with an evolved unspecific peroxygenase (UPO) from Agrocybe aegerita (PaDa-I), offers high efficacy for the selective oxidation of cyclohexane to KA oil (cyclohexanol and cyclohexanone) via in-situ synthesis of H2O2. The optimized AuPdPt/TiO2/PaDa-I system shows significant improvements over analogous AuPd or Pd-only formulations or the use of commercially available H2O2, attributed to the increased rate of H2O2 production by the chemo-catalyst resulting from electronic modification of Pd species through Pt incorporation upon the formation of trimetallic nanoalloys.
Article
Chemistry, Organic
Huifang Lai, Jiexin Xu, Jin Lin, Biling Su, Daijun Zha
Summary: The Ritter-type reaction is an efficient tool for constructing amides, but the issue of chemical selectivity limits its efficiency and yield. We discovered that the inorganic salt hydrate MgSO4·2H2O can control chemical selectivity and overcome the shortcomings of other synthesis methods. It has a wide range of applications and significantly improves yield.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Multidisciplinary Sciences
Jiwon Kim, Jae Hyung Kim, Cheoulwoo Oh, Hyewon Yun, Eunchong Lee, Hyung-Suk Oh, Jong Hyeok Park, Yun Jeong Hwang
Summary: An electro-assisted approach using acid-treated carbon electrocatalyst and in-situ cathodically generated reactive oxygen species is proposed for the partial oxidation of methane at ambient temperature and pressure. Reactive oxygen species activate methane and methanol, leading to selective methane partial oxidation. This study presents a method for the electrochemically assisted partial oxidation of methane to produce liquid oxygenate, HCOOH, selectively.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Ming-Hao Guan, Ling-Yu Dong, Tao Wu, Wen-Cui Li, Guang-Ping Hao, An-Hui Lu
Summary: We have established an integrated pathway for oxidizing ethylene into ethylene glycol using mesoporous carbon catalyst and titanium silicalite-1 catalyst. This pathway exhibits remarkable activity, achieving 86% H2O2 conversion, 99% ethylene glycol selectivity, and a production rate of 51.48 mmol g(ecat)(-1) h(-1) at 0.4 V vs. reversible hydrogen electrode. In addition to using generated H2O2 as an oxidant, there is also an (OOH)-O-center dot intermediate that eliminates the step of absorbing and dissociating H2O2, showing faster reaction kinetics compared to the ex situ approach. This work not only provides a new idea for ethylene glycol synthesis but also demonstrates the advantage of in situ generated H2O2 in the tandem route.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Daniel Schwendenwein, Anna K. Ressmann, Marcello Entner, Viktor Savic, Margit Winkler, Florian Rudroff
Summary: This study focused on the synthesis of chiral fragrance aldehydes using a combination of chemo-catalysis and multi-enzymatic in vivo cascade reaction, as well as the development of a highly versatile high-throughput assay for enzymatic reduction of carboxylic acids. A biocompatible metal-catalyzed synthesis was used to prepare alpha or beta substituted cinnamic acid derivatives, which were then fed into a biocatalytic system for the synthesis of target molecules through enzymatic cascade reactions. The production of fragrance aldehydes was achieved by combining a biocompatible oxidative Heck protocol with specific enzymes expressed in cells.
Article
Chemistry, Organic
Yiming Zhao, Run Yang, Canming Wu, Shihan Wang, Xinghua Liu, Jihui Li, Shuying Xu
Summary: In this study, an unprecedented copper and in situ-generated triflic acid relay-promoted four-component cascade reaction was established for the rapid and concise construction of diverse five-membered cycloguanidines. The reaction involved cyanamides, diaryliodonium triflates, propargylic amines, and water, and resulted in the simultaneous formation of six new bonds with high yields. This reaction provides an alternative strategy for the highly efficient utilization of diaryliodonium triflates by serving as both an arylation reagent and an internal acid promoter.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Caixia Zhu, Zhixin Zhou, Xuejiao J. Gao, Yanhong Tao, Xuwen Cao, Yuan Xu, Yanfei Shen, Songqin Liu, Yuanjian Zhang
Summary: This article reports a nanozyme-based chemical reaction network (CRN) with feedback and feedforward functions, which can generate multiple responses to a single H2O2 stimulus. By confining this nanozymatic network to a microfluidic chip, it exhibits remarkable selectivity and linearity in perceiving H2O2 stimulus and provides an instructive platform for studying primordial life-like processes.
Article
Multidisciplinary Sciences
Danping Tian, Ruipeng Hao, Xiaoming Zhang, Hu Shi, Yuwei Wang, Linfeng Liang, Haichao Liu, Hengquan Yang
Summary: Bioinspired multicompartment architectures are desired in synthetic biology and metabolic engineering due to their cell-like structures and ability of assembling catalytic species. This study describes a Pickering double emulsion-directed interfacial synthesis method to fabricate multicompartmental MOF microreactors, enabling tailor-made inner architectures and selective permeability. The microreactor demonstrates enhanced efficiency in chemo-enzymatic cascade reactions, showcasing its potential in complex cellular transformations.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Yuan Zhong, Guichen Li, Dan Zhang, Long Hao, Zhengjun Cai
Summary: The present study describes a multicomponent all-carbon cascade and sequential annulation reaction that produces highly functionalized decalin derivatives using benzoylacetonitrile derivatives and 2-arylidene-1,3-indanediones. The reaction strategy involves a consecutive Michael/Michael/tautomerization/Michael/Aldol annulation sequence with organic amine catalysts, mild conditions, and high stereoselectivity. This one-pot approach allows for the formation of four C-C bonds and the construction of fused carbocyclic decalin derivatives.
Article
Chemistry, Multidisciplinary
Chao Zhang, Jia Huang, Xusheng Guo, Xuwen Da, Zhifei Dai, Moustapha Hassan, Yingjie Yu, Xuesong Wang, Qianxiong Zhou
Summary: Chemodynamic therapy (CDT) is a promising cancer treatment that uses H2O2 to kill cancer cells. However, limited H2O2 in tumor cells limits its clinical application. In this study, a supramolecule (Ru1) was synthesized to efficiently generate H2O2. When loaded onto nanoparticles and exposed to near-infrared light, the intracellular H2O2 level increased by 2.8 times. This enhanced CDT and also stimulated immune response by reprogramming the tumor microenvironment.
Article
Chemistry, Inorganic & Nuclear
Jordan Santiago Martinez, Jaime Mazario, Silvia Gutierrez-Tarrino, Carmen Galdeano-Ruano, Jose Gaona-Miguelez, Marcelo E. Domine, Pascual Ona-Burgos
Summary: Alcohol oxidation is an important industrial organic reaction. Pd, Pt, and Au supported nanoparticles have traditionally been the best catalysts. In recent years, the research community has been developing strategies for synthesizing carbon-supported Pd/Au bimetallic nanoparticles to enhance activity and selectivity.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Rok Narobe, Kathiravan Murugesan, Christoph Haag, Tobias Emanuel Schirmer, Burkhard Koenig
Summary: Visible light excitation of iodine(iii)-BF3 complex enables the formation of carbocations from C(sp(3))-H bonds. The complexes are generated catalytically from iodoarene, carboxylate ligand, the oxidizing agent Selectfluor, and the Lewis acid BF3. This modular catalytic system allows the formation of synthetically valuable amine derivatives without a metal- or photocatalyst.
CHEMICAL COMMUNICATIONS
(2022)
Article
Biotechnology & Applied Microbiology
Martha Sophia Smit, Mpeyake Jacob Maseme, Jacqueline van Marwijk, Jasmin Cara Aschenbrenner, Diederik Johannes Opperman
Summary: Cytochrome P450 monooxygenases (CYP450s) are crucial in the synthesis and breakdown of secondary metabolites in eukaryotes, especially in plants and fungi. CYP505E3 from Aspergillus terreus demonstrates remarkable omega-7 hydroxylase activity, making it a promising catalyst for delta-dodecalactone synthesis. Other CYP505Es also display similar activity, but their occurrence is limited to certain species like Aspergillus and Penicillium.
APPLIED MICROBIOLOGY AND BIOTECHNOLOGY
(2023)
Article
Metallurgy & Metallurgical Engineering
Michael D. Odidi, Marijke A. Fagan-Endres, Susan T. L. Harrison
Summary: Preferential flow is a key factor in the failure to achieve optimal metal recovery rates in drip-irrigated leaching packed beds. Capillary tests were conducted to investigate the impact of particle size distribution, porosity, wettability, and fluid viscosity on moisture absorption via capillary action. The results showed that particle size distribution had the greatest influence on the strength of capillary forces. Higher wettability and porosity also contributed to increased capillary action.
Article
Chemistry, Multidisciplinary
Patricia Gomez de Santos, Ivan Mateljak, Manh Dat Hoang, Sarel J. Fleishman, Frank Hollmann, Miguel Alcalde
Summary: In this study, a diverse repertoire of active, stable, and enantiodivergent fungal peroxidases was designed using the FuncLib algorithm based on phylogenetic and Rosetta calculations. Several designs showed unprecedented enantiodivergence, changing regioselectivity, and increasing catalytic efficiencies up to 10-fold, with improvements in total turnover numbers. Beneficial epistasis among the mutations and extensive reorganization of the heme channel contributed to this functional divergence. This work demonstrates the rapid design of highly functional peroxygenase libraries using FuncLib for various biotechnological applications, which are not naturally existing.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Richard J. Lewis, Kenji Ueura, Xi Liu, Yukimasa Fukuta, Tian Qin, Thomas E. Davies, David J. Morgan, Alex Stenner, James Singleton, Jennifer K. Edwards, Simon J. Freakley, Christopher J. Kiely, Liwei Chen, Yasushi Yamamoto, Graham J. Hutchings
Summary: The in-situ production of H2O2 enables the ammoximation of ketones to oximes, providing a feasible alternative for industrial-scale production, especially for synthesizing cyclohexanone oxime as a key precursor to Nylon-6. By using a bifunctional catalyst consisting of Pd-based bimetallic nanoparticles immobilized onto a TS-1 carrier, the considerable condition gap between the direct synthesis of H2O2 and ketone ammoximation can be bridged. The formation of PdAu nanoalloys is crucial for achieving high reactivity and catalytic stability, with the monometallic Pd analogue being optimal.
Article
Chemistry, Multidisciplinary
Gabriela C. Schroeder, Martha S. Smit, Diederik J. Opperman
Summary: CYPs/P450s are versatile hemethiolate proteins with high stereo- and regio-selectivity, making them powerful biocatalysts for synthesizing value-added compounds. This review highlights recent advances in P450-mediated syntheses, including enzyme engineering strategies to enhance selectivity and facilitate bond formation, as well as approaches to overcome limitations of P450 catalysis for improved efficiency and biotechnological viability.
CURRENT OPINION IN GREEN AND SUSTAINABLE CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Xiaomin Xu, Jacob M. A. van Hengst, Yejia Mao, Mireia Martinez, Sergi Roda, Martin Floor, Victor Guallar, Caroline E. Paul, Miguel Alcalde, Frank Hollmann
Summary: A peroxygenase-catalysed hydroxylation of organosilanes has been reported, demonstrating efficient conversion of various silane starting materials and high catalyst performance. Molecular modelling of the enzyme-substrate interaction provides a basis for understanding the selectivity of AaeUPO.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Yinqi Wu, Caroline E. Paul, Thomas Hilberath, Ewald P. J. Jongkind, Wuyuan Zhang, Miguel Alcalde, Frank Hollmann
Summary: The utilization of fatty acids can be expanded by adding new functionalities to the hydrocarbon part. In this study, a peroxygenase mutant AaeUPO-Fett is demonstrated to selectively oxyfunctionalize fatty acids, leading to the production of ?-1 hydroxy fatty acid (esters). These hydroxy fatty acid (esters) can be further transformed into lactones, alcohols, esters, and amines through multi-enzyme cascades, providing new pathways for fatty acid valorisation.
Article
Chemistry, Multidisciplinary
Jonathan Ruiz Esquius, David J. Morgan, Gerardo Algara Siller, Diego Gianolio, Matteo Aramini, Leopold Lahn, Olga Kasian, Simon A. Kondrat, Robert Schloegl, Graham J. Hutchings, Rosa Arrigo, Simon J. Freakley
Summary: The oxygen evolution reaction (OER) is crucial for future energy systems based on water electrolysis. Iridium oxides show promise as catalysts due to their corrosion resistance in acidic and oxidizing conditions. The transformation of highly active iridium (oxy)-hydroxides prepared using alkali metal bases into rutile IrO2 at high temperatures (>350 degrees C) results in poor activity, but the transformation into Li-intercalated IrOx retains comparative activity and improved stability. This nanocrystalline lithium iridate form could be more resistant to industrial procedures and help stabilize the high populations of redox active sites in amorphous iridium (oxy)hydroxides.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Applied
Thomas Hilberath, Remco van Oosten, Juliet Victoria, Hugo Brasselet, Miguel Alcalde, John M. Woodley, Frank Hollmann
Summary: This study reports the mol-scale oxyfunctionalization of cyclohexane to cyclohexanol/cyclohexanone (KA-oil) using an unspecific peroxygenase. By utilizing AaeUPO from Agrocybe aegerita and simple H2O2 as an oxidant, cyclohexanol concentrations of more than 300 mM (>60% yield) with attractive productivities (157 mM h(-1), approx. 15 g L-1 h(-1)) were achieved. The current limitations of the proposed biooxidation system have been identified, paving the way for future improvements and implementation.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2023)
Article
Chemistry, Multidisciplinary
Dianelis T. Monterrey, Andrea Menes-Rubio, Merve Keser, David Gonzalez-Perez, Miguel Alcalde
Summary: Fungal unspecific peroxygenases (UPOs) are promising biocatalysts for synthetic chemistry due to their ability to catalyze a wide range of oxyfunctionalization reactions. However, there are challenges to overcome, including poor expression levels, unwanted peroxidase activity, overoxidation reactions, and oxidative inactivation. Specific protein engineering and reaction optimization are being used to address these challenges and generate highly active, selective, and stable UPO variants. This review discusses recent developments and trends in converting UPOs into industrial biocatalysts.
CURRENT OPINION IN GREEN AND SUSTAINABLE CHEMISTRY
(2023)
Article
Chemistry, Organic
Ana C. Ebrecht, Thato M. Mofokeng, Frank Hollmann, Martha S. Smit, Diederik J. Opperman
Summary: γ- and δ-lactones are important flavor and fragrance compounds, and their synthesis relies on suitable hydroxy fatty acid precursors. Three short unspecific peroxygenases were found to selectively hydroxylate C4 and C5 positions of C8-C12 fatty acids, leading to the corresponding γ- and δ-lactones after lactonization. The preference for C4 hydroxylation resulted in γ-lactones as the major products. Overoxidation of the hydroxy fatty acids was addressed by reducing the resulting oxo acids using an alcohol dehydrogenase in a bienzymatic cascade reaction.
Article
Chemistry, Multidisciplinary
Lars-Erik Meyer, Dorottya Horvath, Sonja Vaupel, Johanna Meyer, Miguel Alcalde, Selin Kara
Summary: This study demonstrates the immobilization of enzymes in a novel 3D printable synthetic hydrogel and its application in continuous oxidation reactions. The average immobilization yield was 6.1%, and the continuous synthesis reaction lasted for 24 hours with a space-time yield of 3.1 x 10(-2) g L-1 h(-1).
REACTION CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Patricia Gomez de Santos, Ivan Mateljak, Manh Dat Hoang, Sarel J. Fleishman, Frank Hollmann, Miguel Alcalde
Summary: In this study, we used the FuncLib algorithm based on phylogenetic and Rosetta calculations to design a diverse repertoire of active, stable, and enantiodivergent fungal perox-ygenases. These designs, which carried 4-5 mutations in the catalytic core, were functionally expressed in yeast and showed remarkable improvements in catalytic efficiency and enantiodivergence compared to the parental enzyme. The functional divergence was attributed to beneficial epistasis among the mutations and extensive reorganization of the heme channel. This work highlights the potential of FuncLib in designing highly functional libraries of enantioselective peroxygenases for biotechnological applications.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
