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Food Bioscience · 2025 · IF 5.9

Highly purified pinolenic acid from pine nut oil: A novel approach combining urea complexation, lipase-catalyzed esterification, and rapid preparative reversed-phase liquid chromatography

Chunhao Qian,Yiren Zhang,Hui Li,Jun Jin,Hui Zhang,Qingzhe Jin,Xingguo Wang

Pinolenic acid (PLA) from pine nut oil was purified through a three-step process involving urea complexation (UC), lipase-catalyzed selective esterification, and rapid preparative reversed-phase liquid chromatography (RP-RPLC). UC was optimized with response surface methodology (RSM) under optimized conditions: fatty acid/urea (w/w) of 1:3.114, 95 % ethanol/urea (B, v/w) of 3.892:1, complexation time (h) of 12.303, and complexation temperature of −9.84 °C, achieving the optimal concentration of 62.19 ± 0.33 % and the yield of 46.55 ± 0.43 %. The one-step purified PLA was further purified through lipase-catalyzed selective esterification, resulting in purity and yield at 81.50 ± 0.32 % and 45.83 ± 0.2 % for the two-step purified PLA. The two-step purified PLA was then eluted from a C18 column to achieve the product with purity of 99.52 ± 0.08 % and yield of 71.93 ± 0.03 %. This study introduces an innovative PLA purification strategy for high-purity products suitable for nutritional and pharmaceutical uses.

CAS / MDL: 110-54-3 67-56-1
研究领域: 食品科学 · 生物化学 · 制药工程
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CHEMICAL ENGINEERING JOURNAL · 2018 · IF 6.735

Covalently linked organo-sulfonic acid modified titanate nanotube hybrid nanostructures for the catalytic esterification of levulinic acid with n-butyl alcohol

Shuolin Zhou,Xianxiang Liu,Jinhua Lai,Min Zheng,WenZhu Liu,Qiong Xu,Dulin Yin

A novel inorganic-organic hybrid nanocatalyst has been prepared by initially functionalizing titanate nanotubes with 3-amino-propyltrimethoxysilane and subsequently introducing sulfonic acid groups with 1,4-butane-sultone. The as-prepared hybrid catalyst was characterized by FT-IR, XRD, TEM, SEM-EDX, TG-DTG, and N 2 adsorption isotherm techniques, and its catalytic performance was evaluated by esterification of levulinic acid with n -butyl alcohol under solvent-free conditions. The experimental design and study were carried out by response surface methodology (RSM) to test the effects of reaction conditions on the catalytic process. Up to 82.7% yield of n -butyl levulinate was obtained under the optimal reaction conditions. Furthermore, the catalyst showed an excellent reusability without the loss of reactivity after several runs.

研究领域: 材料科学 · 催化化学
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NEW JOURNAL OF CHEMISTRY · 2022 ·Vol. 46 ·期 44 ·21287-21300 · IF 3.925

Synthesis of lipase-hydrogel microspheres and their application in deacidification of high-acid rice bran oil

Yawen Yin,Xu Fei,Jing Tian,Longquan Xu,Yao Li,Yi Wang

The main challenge of rice bran oil (RBO) as a highly nutritional edible oil is the high content of free fatty acids. Biocatalytic esterification is an effective strategy to reduce acid value of RBO. In this study, polydopamine/hydroxyethyl methacrylate/acrylamide hydrogel microspheres (PHAMs) are designed and synthesized to immobilize lipase. The PHAMs have excellent water retention and provide an oil–water interface for the biocatalytic esterification of lipase. The catalytically active center of lipase is induced to open by the oil–water interface and its catalytic activity is fully developed. At the same time, the micro-water environment provided by hydrogel microspheres prevents hydrolysis of lipid products. Lipase-polydopamine/hydroxyethyl methacrylate/acrylamide hydrogel microspheres (L-PHAMs) exhibit strong immobilization capacity (enzymatic loading is 13.34 mg g−1), enhanced activity (1.11-fold that of free lipase), and excellent reusability (it maintained 37.8% of the free lipase activity after 10 cycles). The L-PHAMs still maintain 86.24% of the initial enzymatic activity after 15 days, while the free lipase activity is only 25.31%. In addition, kinetic determination shows an increased affinity between L-PHAMs and the substrate (Km is 1.07 μmol L−1). High-acid rice bran oil (HBRO) is successfully deacidified by an esterification reaction using L-PHAMs as catalysts. This process enabled an unprecedented deacidification efficiency of up to 98.19% in a short time (2 h). Overall, biocatalytic esterification by L-PHAMs is an economical and sustainable deacidification method.

研究领域: 生物化学 · 食品科学 · 材料科学
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Catalysts · 2020 ·Vol. 10 ·期 4 ·384 · IF 3.52

Active, Selective, and Recyclable Zr(SO4)2/SiO2 and Zr(SO4)2/Activated Carbon Solid Acid Catalysts for Esterification of Malic Acid to Dimethyl Malate

Pei Yu,Can Chen,Guangci Li,Zhong Wang,Xuebing Li

The esterification of malic acid using traditional homogenous catalysts suffers from the difficulty in reuse of the catalyst and undesirable side reactions. In this work, Zr(SO4)2/SiO2and Zr(SO4)2/activated carbon (AC) as solid acid catalysts were prepared for malic acid esterification with methanol. The conversion of malic acid over these two catalysts is comparable to that over H2SO4and unsupported Zr(SO4)2∙4H2O catalysts; however; a 99% selectivity of dimethyl malate can be realized on these two supported catalysts, which is much higher than that of conventional H2SO4(75%) and unsupported Zr(SO4)2∙4H2O (80%) catalysts, highlighting the critical role of AC and SiO2supports in tuning the selectivity. We suggest that the surface hydroxyls of AC or lattice O2−ions from SiO2donate electrons to Zr4+in Zr(SO4)2/AC and Zr(SO4)2/SiO2catalysts, which results in the increase in electron density on Zr4+. The enhanced electron density on Zr4+reduces the degree of H delocalization from crystal water and then decreases the Brønsted acid strength. Consequently, the reduced Brønsted acid strength of Zr(SO4)2/AC and Zr(SO4)2/SiO2catalysts suppresses the intermolecular dehydration side reaction. In addition, these two supported catalysts can be easily separated from the reaction system by simple filtration with almost no loss of activity.Keywords:malic acid;catalytic esterification;solid acid catalyst;Zr(SO4)2;intermolecular dehydration

研究领域: 催化 · 化学工程 · 有机化学
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ACS Sustainable Chemistry & Engineering · 2020 · IF 7.632

Self-Solidifying Quaternary Phosphonium-Containing Ionic Liquids as Efficient and Reusable Catalysts for Biodiesel Production

Jinyi Chen,Meichen Li,Mantian Li,Xiaocheng Lin,Ting Qiu

Unusual self-solidifying tris(2,4,6-trimethoxyphenyl)phosphonium-containing ionic liquids were synthesized for biodiesel production via the catalytic esterification of a variety of free fatty acids. These ionic liquids were synthesized by a two-step method involving the reaction between tris(2,4,6-trimethoxyphenyl)phosphine and 1,3-propanesulfonate to form a TTMPP-PS zwitterion followed by acidification with different acids. The obtained solid-state ionic liquids were soluble during the reaction to conduct homogeneous catalysis and precipitated after the reaction, which was followed by alcohol evaporation, indicating the great ease of heterogeneous recovery; therefore, the ionic liquids had the combined advantages of both homogeneous and heterogeneous catalysts. As a result, such ionic liquids show great potential for biodiesel production because of their pronounced activity, excellent stability, and recyclability.

研究领域: 化学工程 · 能源科学
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2017 · IF 2.843

High Conversion of Methyl Acetate Hydrolysis in a Reactive Dividing Wall Column by Weakening the Self-Catalyzed Esterification Reaction

Xiaoda Wang,Hongxing Wang,Jinyi Chen,Weiyue Zheng,Ting Qiu

We show the superiority of reactive dividing wall column (RDWC) to the single reactive distillation (RD) column in improving the conversion of reactant, taking the hydrolysis of methyl acetate (MA) as example. It is difficult to achieve above 99% conversion for MA in a traditional reactive distillation column (TRDC) due to the existence of self-catalyzed methanol (MeOH)-acetic acid (HAc) esterification reaction in the column bottom. In this work, more than 99% conversion of MA hydrolysis was realized experimentally in an RDWC by separating MeOH from the hydrolysis mixture. The effects of several operation parameters on hydrolysis conversion were systematically investigated, including feedwater–MA mole ratio, heat duty, mole flow rate of feed MA, and vapor distribution. The simulation results by Aspen Plus showed that RDWC has several improvements in MA hydrolysis over TRDC, including lower energy consumption, lower water–MA mole ratio, and larger production capacity. With the increase in MA conversion, the superiorities became more obvious and contribute to the weaker self-catalyzed MeOH–HAc esterification reaction in the RDWC.

研究领域: 化学工程 · 工业化学
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JOURNAL OF PHYSICAL CHEMISTRY B · 2024 · IF 2.8

Machine-Learning-Based Kinetic-Free Hybrid Gray-Box Model to Predict Sulfuric-Acid-Catalyzed Esterification Reaction

Xingyu Wen,Wenshuai Bai,Dayu Zhang

The sulfuric–acid-catalyzed esterification reaction of 2-butanol and propionic anhydride is a vital industrial process. In this paper, several experiments are conducted via reaction calorimetry to validate that both sulfuric and propionic acids have discernible catalytic effects on the reaction. This finding complicates the accurate description of the reaction kinetics through traditional methods. So this paper turns to a kinetic-free black-box model, Gaussian process regression (GPR) model via 24 experiments, as a more adaptable approach. Besides, the best GPR model is combined with traditional heat balance model to generate a hybrid gray-box model, which can give complete knowledge of reaction process. The hybrid gray-box model finally achieves maximum root-mean-square error (RMSE) of 0.0069 for conversion, 0.6535 for temperature, and 10.6087 for heat flow rate, underscoring its pretty good predictive ability.

研究领域: 化学工程 · 机器学习 · 反应动力学建模
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ChemistrySelect · 2023 ·Vol. 8 ·期 9 ·e202203501 · IF 2.1

Nanocrystalline HZSM-5prepared by supercritical hydrothermal synthesis and its catalytic esterification performances

Br. Yundi Zhang,Mingyu Cui,Yidong Zhang,Wei Xu,Min Wang,Rong Shao,Jianfei Ding

Graphical The PMD conversion, TBPM selectivity, yield and the catalytic stability were obviously improved on the nanocrystalline HZSM-5 (Z-1) prepared by supercritical hydrothermal synthesis, because it had more amount of framework tetrahedral Al species and the total acidity, higher surface area and pore volume than those of HZSM-5 (Z-2) prepared by conventional hydrothermal synthesis. The nanocrystalline HZSM-5 was synthesized by supercritical hydrothermal synthesis for the first time and investigated in catalytic esterification of pyromellitic dianhydride(PMD)and n-butanol to tetrabutyl pyromellitate(TBPM). The HZSM-5 prepared by conventional hydrothermal synthesis was also examined for comparison. The catalysts were studied using XRD, N 2 adsorption, NH 3 -TPD, Pyridine-adsorption FT-IR, SEM, [27] Al MAS NMRandCHNS analysis. According to the results of characterization, the supercritical hydrothermal condition was helpful to reduce the size of crystal particles and improve the crystallinity of HZSM-5, and shorten the crystallization time. The surface area, especially external surface area, and pore volume were increased, and the total acidity was increased. The strong acid sites were transformed into the weak acid sites, and the strength of weak and strong acid was weakened. The amount of framework tetrahedral Al species and Brönsted acid sites were increased. Therefore, the formation of coke was retarded, and thePMD conversion, the TBPM selectivity and the catalytic stability were obviously improved.

研究领域: 化学 · 催化 · 材料科学
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CONSTRUCTION AND BUILDING MATERIALS · 2023 · IF 7.4

A novel approach to methoxy polyethylene glycol-grafted sulfonated poly(maleic anhydride-alt-styrene) as superplasticizers in cement pastes

Bingzheng Jiang,Dong Chen,Li Wang,Wantai Yang

In this research, a novel method was developed to synthesize methoxy polyethylene glycol-grafted sulfonated poly(maleic anhydride- alt -styrene) (SPMS-g-mPEG) as cement superplasticizers. The method includes three main steps: 1) self-stabilized precipitation polymerization (2SP) of styrene and maleic anhydride for PMS microspheres; 2) gas-solid heterogeneous sulfonation reaction (GSR) of gaseous SO 3 with PMS microspheres; 3) intramolecular sulfonic acid-catalyzed esterification reaction of mPEG with sulfonated PMS (SPMS). GSR can achieve uniform sulfonation of PMS microspheres, while overcoming the inherent drawbacks of the traditional homogeneous solution sulfonation process. SPMS and SPMS-g-mPEG with different structural parameters and uniform structure were successfully prepared and their effects on the fluidity and fluidity retention of cement pastes were systematically compared. For the samples demonstrating the best dispersing ability, the hydration heat and setting time of cement pastes, adsorption kinetics and compressive strength of mortar samples were determined further. Our work provides an innovative and effective approach to superplasticizers with outstanding properties and its uniform structure facilitates the investigation on the relationship between structure and properties.

研究领域: 材料科学 · 化学工程 · 土木工程
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