JOURNAL OF MOLECULAR CATALYSIS B-ENZYMATIC
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2013
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IF 2.823
Xiaolin Pei,Lirong Yang,Gang Xu,Qiuyan Wang,Jianping Wu
Microbial nitrile hydratases (NHases) are important industrial catalysts to produce valuable amides. However, only some NHase genes have been reported and studied at the molecular level. In this study, we developed a genome mining method to discover Fe-type NHases from GenBank. The putative NHase gene from Pseudomonas putida F1 was cloned and functionally expressed in Escherichia coli BL21 (DE3) by assisting of a putative activator gene adjacent to β-subunit region. Three recombinant plasmids containing NHase gene or the activator gene were designed and constructed. Maximal enzyme activity was obtained when the structural and activator genes were transcribed as one unit in plasmid pCDFDuet-1 at 18 °C. However, the expressed product did not show any NHase activity when the downstream activator gene was ignored, and the product completely existed in insoluble inclusion body. The activator gene might be involved in protein folding of the α- and β-subunits of NHase. In addition, the Fe-type NHase exhibited broad substrate specificity. The enzyme can efficiently hydrate aromatic nitriles, such as 3-cyanopyridine, 4-cyanopyridine, and benzonitrile, asides from aliphatic nitriles preferentially. Therefore, the recombinant NHase shows potential applications in some amides preparation.
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JOURNAL OF CHROMATOGRAPHY A
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2024
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IF 3.8
Yibo Yan,Ruilin Yang,Yanan Wang,Yinan Wu,Xiaofei Gu,Xiaoqiang Qiao
Styrene-maleic acid (SMA) copolymer has received much attention for its excellent solubilization characteristics. In this work, SMA copolymer brush-based chromatographic stationary phases were exploited and developed for the first time. First, SMA copolymer brush was in situ grown on the surface of spherical silica via living/controlled reversible addition-fragmentation chain transfer (RAFT) polymerization method. Subsequently, as a proof-of-concept demonstration, the copolymer was esterified by diethylene glycol mono-2-ethylhexyl ether (DGME) and 2-(2-ethylhexyloxy) ethanol (EHOE), respectively. The obtained Sil-SMA-DGME and Sil-SMA-EHOE copolymer-brush chromatographic stationary phases were characterized by transmission electron microscopy, Fourier transform infrared spectrometer, X-ray photoelectron spectroscopy, and thermogravimetric analysis, respectively. The chromatographic retention mechanism indicated that both the two packed columns exhibited hydrophilic/reverse mixed-mode retention modes. The maximum column efficiency was up to 71,000 N/m. The chromatographic separation performance evaluation indicated that the novel kind of stationary phases had excellent separation capabilities for hydrophilic, hydrophobic compounds and phospholipid standards. In addition, by combination with mass spectrometry identification, the Sil-SMA-DGME column was further exploited for separation and identification of phospholipids in human lung cancer cells. Totally, 9 classes including 186 phospholipid species were successfully identified. The results demonstrated the promising application prospects of the novel kind of SMA copolymer-brush chromatographic stationary phases.
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Catalysts
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2024
·Vol. 14
·期 1
·70
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IF 3.8
Min Zhang,Hongwei Xiang,Xiaodong Wen
This investigation explores the synthesis of advanced catalysts for epoxidizing long-chain linear α-olefins, a pivotal process in the chemical industry for generating critical intermediates. Employing a hydrothermal technique, we developed four distinct catalysts (CS-1–4), methodically modulating the Ca/Sn ratio to elucidate its impact on the catalysts’ physicochemical properties. Our research uncovered that an escalated Ca/Sn ratio induces a morphological shift from octagonal to cubic structures, concomitant with a diminution in particle size and an enhancement in specific surface area. Significantly, the CS-3 catalyst outperformed others in 1-octene epoxidation, an efficacy attributed to its augmented surface alkalinity and proliferation of medium-strength alkaline sites, likely emanating from increased surface oxygen defects. Subsequent hydrogen reduction of CS-3 further amplified these oxygen defects, yielding a 10% uptick in catalytic activity. This correlation underscores the potential of oxygen defect manipulation in optimizing catalytic efficiency. Our findings contribute a novel perspective to the development of robust, high-performance catalysts for α-olefin epoxidation, seamlessly aligning with the principles of sustainable chemistry.Keywords:long-chain linear alpha-olefin;perovskite oxide;CaSnO3;oxygen vacancy;epoxidation
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ACS Catalysis
·
2025
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IF 13.1
Jia-qi Bai,Mei Ma,Huangfei Liu,Zhangkai Qian,Durui Liu,Yuncai Zhao,Yijing Gao,Jingshuai Chen,Mengdie Cai,Song Sun
The hydrogenation of nitriles is an environmentally friendly and atom-economical route to prepare high-value amines; however, it is still a challenge to control selectivity because of the occurrence of hydrogenation, self-coupling, and hydrogenolysis reactions during the hydrogenation process. It is highly desirable to develop efficient non-noble-metal catalysts for the hydrogenation of nitriles to secondary amines, although several noble metal catalysts have been reported. Herein, we successfully prepared a Cu–Ni/W20O58 catalyst and found that the Cu4.4–Ni0.6/W20O58 catalyst showed a 92.3% yield with initial TOFs of 270.0 h–1 at 373 K and 3 MPa H2 for the hydrogenation of benzonitrile (BN) to dibenzylamine (DBA), which was much superior to that of the monometallic Cu4.4/W20O58 and Ni0.6/W20O58 catalysts. Moreover, the Cu4.4–Ni0.6/W20O58 catalyst could be reused at least 4 times and was effective for the hydrogenation of various nitriles with superior selectivity to secondary amines. Furthermore, the reaction mechanism of BN hydrogenation for the Cu–Ni alloy of Cu4.4–Ni0.6/W20O58 was proposed on the basis of spectroscopic studies such as XRD, TPR, TEM, XAFS, and XPS, kinetic studies such as the effect of BN concentration and H2 pressure, the isotopic effect of hydrogen, and the effect of the reaction temperature and DFT calculations. The rate-determining step was the hydrogenation of benzylidenamine (BI) to the half-hydrogenated intermediate by one H atom over the Cu4.4–Ni0.6/W20O58 catalyst. The Ni–W20O58 interface was responsible for the adsorption and activation of BN, and the electron-rich Cu acted as the site for H2 dissociation; the synergistic effect of Cu and Ni led to the superior catalytic performance of the Cu4.4–Ni0.6/W20O58 catalyst.
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Nano Research
·
2024
·Vol. 17
·期 7
·6119-6126
·
IF 9.5
Li Ziwei,Yu Yue,Yang Dongyue,Wang Jin,Yan Junmin,Huang Gang,Liu Tong,Zhang Xinbo
Li-O 2 batteries with high energy density hold significant promise as next-generation energy storage systems. However, Li-O 2 batteries have poor cycling performance at high current densities and large capacities, primarily due to the high impedance caused by the instability of the lithium anode and the sluggish kinetics in the discharge products decomposition on the cathode. Herein, we investigated a bifunctional nitrile additive (2-methoxy benzonitrile (2-MBN)) with good chemical/electrochemical stability to improve the performances of Li-O 2 batteries. The 2-MBN could actively modify the anode by ensuring uniform Li + deposition and optimizing the composition of solid electrolyte interphase (SEI). Meanwhile, it could also facilitate the decomposition of discharge products by inducing the formation of sheet-like Li 2 O 2 , significantly reducing the battery charge overpotential. The bifunctional effects of 2-MBN for the anode and cathode enable Li-O 2 batteries to achieve a stable lifetime of 97 cycles at a current density of 600 mA·g −1 with a fixed capacity of 2000 mAh·g −1 , much better than that of Li-O 2 batteries without 2-MBN (28 cycles). The inclusion of 2-MBN provides an effective approach for attaining high-performance Li-O 2 batteries.
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FOOD CHEMISTRY
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2025
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IF 9.8
Run Liu,Yi Zhang,Yuanzhi Xu,Zhonghui Liu,Jinhang Chen,Kheng-Lim Goh,Yufei Zhang,Mingming Zheng
Diacylglycerol (DAG) is a functional lipid that is naturally present in vegetable oils in limited concentrations (1 %–5 %). This study proposed an enzymatic method to afford high-content-DAG vegetable oils via a reaction catalyzed by an immobilized lipase, PS@OMS-C 8 , using high-speed homogenization and molecular distillation. Results indicated that 48.6 % DAG was initially obtained through the enzymatic glycerolysis of rapeseed oil with glycerol, of which 90.2 % was sn -1,3-DAG. PS@OMS-C 8 maintained 35.5 % DAG content after 10 reuse cycles, confirming its catalytic stability; this was attributed to lipase immobilization on the ordered mesoporous silica that significantly improve the secondary protein structures, including α-helix and β-sheet, thereby strengthening the rigidity of PS@OMS-C 8 . In addition to producing DAG-enriched rapeseed oil, other edible oils with 39.4 %–50.2 % DAG content were obtained, as revealed via molecular docking simulation. This study offers new strategies for the sustainable synthesis of vegetable oils with a high content of functional lipids high-content functional lipids.
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JOURNAL OF CHEMICAL AND ENGINEERING DATA
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2025
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IF 2.1
Mingya Wang,Hongxia Pan,Yongzheng Liu,Jun Chen,Duanlin Cao,Linxiu Zhao
3(5)-Nitropyrazole is obtained by rearrangement of 1-nitropyrazole in high boiling organic solvents. In this paper, the solubility of 3(5)-nitropyrazole in 12 high boiling solvents (anisole, benzonitrile, mesitylene, o-dichlorobenzene, 1-octanol, benzyl alcohol, 2-ethylhexyl acetate, dimethyl glutarate, cyclohexanone, N,N-dimethylformamide, N-methylformamide, and isophorone) was determined using the static gravimetric method over the temperature range of 283.15–323.15 K. The experimental results revealed that the solubility of 3(5)-nitropyrazole exhibited a positive correlation with temperature. Under ambient conditions at 298.15 K, the solubility decreased in the following order: N,N-dimethylformamide (37.705 × 10–2), N-methylformamide (20.131 × 10–2), cyclohexanone (13.469 × 10–2), isophorone (11.957 × 10–2), dimethyl glutarate (6.667 × 10–2), benzyl alcohol (3.909 × 10–2), benzonitrile (2.915 × 10–2), 1-octanol (1.916 × 10–2), 2-ethylhexyl acetate (1.220 × 10–2), o-dichlorobenzene (0.666 × 10–2), anisole (0.688 × 10–2), and mesitylene (0.246 × 10–2). The solubility of 3(5)-nitropyrazole was fitted using the Apelblat equation, λh equation, NRTL model, and van’t Hoff model. The fitting results were evaluated using average relative deviation and RMSD. The NRTL model exhibited the best overall performance. The use of Hansen solubility parameters for solubility prediction and analysis has certain limitations.
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY
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2025
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IF 3.8
Yang Ruilin,Wang Ping,Guan Xinhui,Gu Xiaofei,Qiao Xiaoqiang
Phospholipids have been considered biomarkers for diagnosing many diseases in recent years. However, the isolation and analysis of phospholipids still face many difficulties. Styrene-maleic acid (SMA) copolymer is currently considered suitable for the separation and analysis of phospholipids due to its ability to enhance and improve the solubility of phospholipid bilayers on cell membranes. In this work, metal-free atom transfer radical polymerization was first exploited to graft SMA copolymer onto the surface of silica gel. With glycerol monolaurate (GML) as the derivatization reagent, Sil-SMA-GML polymer-brush silica-based stationary phase was first developed. The chromatographic retention mechanism revealed that the Sil-SMA-GML column is of hydrophilic/reversed-phase mixed-mode retention modes. The chromatographic separation performance evaluation indicated that the Sil-SMA-GML column had excellent separation capabilities for both hydrophilic and hydrophobic compounds. The maximum column efficiency was up to 78,600 N/m. The Sil-SMA-GML column could also achieve simultaneous separation and analysis of different phospholipid classes and species as well as complex phospholipid extracts from human serum and exosomal phospholipid extracts, demonstrating the good potential of the developed stationary phase. Graphical
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APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Jiaxin Li,Ganceng Yang,Yanqing Jiao,Hongyan Sun,Jiaqi Wang,Yue Liu,Chungui Tian,Haijing Yan,Honggang Fu
Selective electroreduction of nitrobenzene (NB) to generate valuable azoxybenzene (AOB) is an important electrochemical N-N coupling reaction, but suffering from low selectivity at low potential. Herein, we constructed a Mo-incorporated NiFe bimetallic nitride on nickel foam (Mo-Fe 2 Ni 2 N/NF), effectively catalyzing selective electroreduction of NB (NSR) to generate AOB. Experimental and theoretical findings reveal that incorporating Mo into Fe 2 Ni 2 N triggers a rational charge redistribution, which induces a moderate hydrogen affinity, alongside enhances the adsorption of nitrosobenzene and phenylhydroxylamine intermediates so as to lower energy barrier of potential-determining step (PDS) for formation of AOB and higher energy barriers of PDS for formation of by-products (amine and azobenzene) can be achieved, thus leading to desired tandem reactions of partial hydrogenation reduction and bimolecular coupling for selective electrosynthesis of AOB. As a result, Mo-Fe 2 Ni 2 N/NF exerts an ultralow potential (0.341 V@100 mA cm −2 ) along with 100 % conversion of NB and 97.2 % yield of AOB. Remarkably, an anion exchange membrane flow electrolyzer of pairing cathodic NSR with anodic benzylamine oxidation by using Mo-Fe 2 Ni 2 N/NF cathode and Mo x Ni y N/NF anode is integrated, and simultaneous synthesis of value-added, easy-separation AOB and benzonitrile can be accomplished with low voltage (1.50 V@100 mA cm −2 ) and high productivity (> 90 %), highlighting its large potential for industrial application. This work showcases a new route to design efficient electrocatalysts for organic electrosynthesis via manipulating adsorption of key reaction species of constructing multicomponent nitrides.
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LANGMUIR
·
2025
·
IF 3.9
Chen Shen,Binyu Zhang,Haiyong Wang,Mi Luo,Tianhan Zhu,Tianyu Gao,Tong Zhang,Xiaoli Chen,Chenguang Wang
Precise modulation of interfacial electronic structures is crucial for enhancing the catalytic activity and selectivity in heterogeneous catalysis. The electron penetration effect (EPE), involving electron transfer from a metal core through a protective shell to surface active sites, has emerged as an effective strategy for tuning surface electronic properties and promoting catalytic performance. However, controlled manipulation of EPE remains challenging, particularly in regulating the phase structure of the metal core and the characteristics of the encapsulating shell. In this work, nitrogen-doped graphene-coated Ni nanoparticles were synthesized from a Ni-based metal–organic framework (Ni-MOF-T/t) by systematically adjusting the reduction temperature (T) and time (t). Subsequent deposition of Pd species yielded Pd/Ni-MOF-T/t catalysts. Among them, the optimized Pd/Ni-MOF-400 °C/2 h catalyst, featuring a hexagonal Ni core, exhibited enhanced electron penetration across the graphitic shell to the Pd sites, effectively modulating the surface electronic structure and boosting catalytic activity. The catalyst demonstrated excellent performance in both thermocatalytic hydrogenation of benzonitrile (90% conversion, 99.0% selectivity) and electrochemical hydrogenation of 4-nitrophenol (96.5% conversion, 90.5% Faradaic efficiency). These findings highlight that phase-controlled electron penetration provides a versatile and generalizable approach for constructing multifunctional catalysts with superior activity under mild conditions. This work establishes phase engineering of MOF-derived metal–carbon interfaces as an effective strategy to manipulate electron penetration effects and optimize catalytic performance.
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