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Molecular Catalysis · 2023 · IF 4.6

Biosynthesis of cyclic ketones by a H2O2 self-sufficient cascade reaction

Bin Wu,Xiangyun Wang,Bo Yang,Yunjian Ma,Frank Hollmann,Yonghua Wang

In the present work we propose a bienzymatic cascade for the oxyfunctionalisation of cycloalkanes to cyclic alcohols/cyclic ketones. By combining a H 2 O 2 -dependent peroxygenase with a O 2 -consuming and H 2 O 2 -producing alcohol oxidase an overall aerobic oxidation system was established. A convincing proof-of-concept is presented and some current limitations are outlined.

研究领域: 生物化学 · 酶工程
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FUEL PROCESSING TECHNOLOGY · 2023 · IF 7.5

Hydrogen source controlled hydrodeoxygenation of phenolic compounds to cycloalkanes/cycloalkanols over NiFeAlOx catalysts

Fa-Peng Wu,Le-Le Qiu,Yun-Peng Zhao,Zong-Pin Fu,Jian Xiao,Jian Li,Fang-Jing Liu,Jing Liang,Jing-Pei Cao

Catalytic hydrodeoxygenation (HDO) of phenolic compounds is a promising strategy for bio-oil upgradation to produce high-value chemicals and fuels. Herein, a series of NiFeAlO x catalysts prepared by a co-precipitation method were applied in HDO of guaiacol as a typical model compound. The characterization results revealed that the catalyst with Ni/Fe/Al ratio of 3/0.5/2.5 possessed developed textural properties, small metal particles, abundant oxygen vacancies and acid sites. HDO of guaiacol occurred in two pathways with different hydrogen sources : the direct hydrogenation of benzene ring to 2-methoxycyclohexanone and the further hydrogenolysis and dehydration of intermediates to cyclohexane at 260 °C in n -hexane under H 2 for 6 h, while demethoxylation affording phenol followed by hydrogenation of phenol to cyclohexanol at 220 °C in isopropanol under N 2 for 2 h. The different product composition results from the type of reactive H species, where active hydrogen species are hydrogen radicals using H 2 as the hydrogen source and hydrogen ions with opposite charges using isopropanol as the H-donor solvent, respectively. The Ni 3 Fe 0.5 Al 2.5 O x catalyst maintained good performance after five recycle experiments with a slight decrease in the conversion of guaiacol. Moreover, the catalyst showed excellent universality for selective HDO of other phenolic compounds to cycloalkanes or cycloalkanols.

CAS / MDL: 108-95-2
研究领域: 催化化学 · 能源化学
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Reaction Chemistry & Engineering · 2021 ·Vol. 6 ·期 3 ·559-571 · IF 4.239

Efficient Ni-based catalysts for the hydrotreatment of lignin dimer model compounds to cycloalkanes/cycloalkanols

Changzhou Chen,Dichao Wu,Peng Liu,Haihong Xia,Minghao Zhou,Xinglong Hou,Jianchun Jiang

The noble-metal catalytic cleavage of ether bonds in lignin to obtain aromatic chemicals has achieved great success, and the development of a low-cost efficient catalyst is crucial. Herein, NixLay/CNT was designed for the hydrogenolysis of benzyl phenyl ether (BPE), diphenyl ether (DPE) and 2-phenethyl phenyl ether (PPE) under a relatively mild condition. Owing to the synergistic effect of Ni with La, the Ni–La catalyst was especially active. Moreover, not only could the Ni–La catalyst fracture the C–O bond, but it could also transform aromatic rings to produce cycloalkanes. Physicochemical characterizations were carried out by means of XRD, TEM, H2-TPR, NH3-TPD, pyridine-IR and XPS analyses. Based on the optimal reaction condition (240 °C, 4 h, 2.0 MPa H2), various model compounds could also be effectively hydrotreated to produce corresponding products. A mechanistic study revealed that cyclohexanol and methylcyclohexane were major products for the transfer cleavage of BPE. Furthermore, it has been illustrated that aryl groups played a significant role in the hydrogenation of phenol from the competitive catalytic hydrogenation reaction of phenol. This study opened up the possibility of the valorization of lignin using a rare earth metal as the co-catalyst for the selective cleavage of lignin model compounds to value-added chemicals.

CAS / MDL: 13478-00-7 100587-94-8
研究领域: 化学工程 · 催化科学
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CARDIOVASCULAR DRUGS AND THERAPY · 2023 · IF 3.4

Bicyclol Alleviates Streptozotocin-induced Diabetic Cardiomyopathy By Inhibiting Chronic Inflammation And Oxidative Stress

Zhang Lingxi,Hu Chenghong,Jin Bo,Bai Bin,Liao Jing,Jin Leiming,Wang Minxiu,Zhu Weiwei,Wu Xuedan,Zheng Li,Xu Xuelian,Jiang Yongsheng,Wang Yi,He Ying

Purpose Diabetic cardiomyopathy (DCM) is a common and severe complication of diabetes. Inflammation and oxidative stress play important roles in DCM development. Bicyclol is a hepatoprotective drug in China that exerts anti-inflammatory effects by inhibiting the MAPK and NF-κB pathways to prevent obesity-induced cardiomyopathy. Our purpose was to explore the effect and mechanism of bicyclol on DCM. Methods A type 1 diabetes mouse model was established using C57BL/6 mice by intraperitoneal injection of STZ. The therapeutic effect of bicyclol was evaluated in both heart tissues of diabetic mice and high concentration of glucose (HG)-stimulated H9c2 cells. Results We showed that bicyclol significantly attenuated diabetes-induced cardiac hypertrophy and fibrosis, which is accompanied by the preservation of cardiac function in mice. In addition, bicyclol exhibited anti-inflammatory and anti-oxidative effects both in vitro and in vivo. Furthermore, bicyclol inhibited the hyperglycemia-induced activation of MAPKs and NF-κB pathways, while upregulating the Nrf-2/HO-1 pathway to exhibit protective effects. Conclusion Our data indicate that bicyclol could be a promising cardioprotective agent in the treatment of DCM.

CAS / MDL: 14431-43-7
研究领域: 药理学 · 心脏病学 · 糖尿病研究 · 分子生物学
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ACS Sustainable Chemistry & Engineering · 2023 · IF 8.4

Enhanced Upgrading of Crude Lignin Bio-Oil to Jet Fuel Precursors with a Moderate Organic Acid-Modified Copper Catalyst

Xiangchen Kong,Chao Liu,Yuyang Fan,Ming Li,Rui Xiao

The conversion of crude lignin bio-oil to jet fuels is a highly desirable target for biorefineries, especially in light of the global energy crisis. The key to achieving this goal is the realistic tuning of catalyst efficiency and selectivity for expected products. Herein, a copper catalyst with enhanced activity for hydrodeoxygenation (HDO) of crude lignin bio-oil to jet fuel precursors was developed in this work. The copper catalyst, a copper-doped porous metal oxide, was modified with a series of moderate organic acids to graft the acidic O-groups as potential Brønsted acid sites for HDO reactions. The copper catalyst modified with propanoic acid exhibited exceptional catalytic performance for the upgrading of lignin pyrolysis bio-oil, giving yields of jet fuel precursor range cycloalkanes and cycloalcohols of 10.04 and 14.20 C%, which were improved by 88.0 and 42.7% compared with those from the blank. Meanwhile, the corresponding hydrogenation and deoxygenation degrees of the products reached 91.5 and 65.9%, respectively, which were improved by 17.3 and 31.8%. Likewise, the overall double bond equivalence and aromaticity index of the products given by the modified copper catalyst were as low as 2.8 and 0.1, which were substantially reduced by 18.0 and 50%, correlating to higher HDO efficiency. The abundant Brønsted acid sites with proper strength and the affluent pore structures of the propanoic acid-modified copper catalyst mainly contributed to its outstanding catalytic activity. The findings suggest promising avenues for increasing the efficiency of heterogeneous catalysts in the HDO of lignin-based bio-oil to alternative fuels.

研究领域: 化学工程 · 催化 · 可再生能源 · 生物炼制
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APPLIED ENERGY · 2022 · IF 11.446

Production of oxygen-containing fuels via supercritical methanol hydrodeoxygenation of lignin bio-oil over Cu/CuZnAlOx catalyst

Xiangchen Kong,Chao Liu,Xing Wang,Yuyang Fan,Weicong Xu,Rui Xiao

Practical, economical, and high-selectivity methods of lignin bio-oil upgrading could greatly increase biorefinery productivity and profitability. Herein, we report the efficient production of oxygen-containing fuel via supercritical methanol hydrodeoxygenation (SCM-HDO) of lignin bio-oil with a well-defined Cu/CuZnAlO x catalyst. The fuel range cyclic alcohols were majorly produced from guaiacol and corncob lignin pyrolysis bio-oil with selectivity of 66.67 and 15.90% at 300 °C in 8 h, respectively, via Cu species induced hydrogenation of aromatics rings and inhibited over-deoxygenation of alcoholic hydroxyl groups. The catalyst activity decreased by 28% after five runs of bio-oil HDO due to the oxidation of Cu species and carbon deposit, where the oxidation of Cu species played the dominant role as the carbon deposit was restrained to as low as 3.64 wt% with the mild catalyst acidity. Meanwhile, the catalyst activity could be easily recovered through a calcination-reduction process to remove the carbon deposit and reactivate the Cu species. The results offered appealing opportunities for tailoring more efficient approaches for the upgrading of lignin bio-oil to alternative biofuels.

研究领域: 化学工程 · 催化 · 生物能源 · 可再生能源
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