HPMo@UiO-66-SO3H用于中碳链结构磷脂的高效合成
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1.大连工业大学 轻工与化学工程学院;2.大连工业大学 国家海洋食品工程技术研究中心

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O643.36; O643.322

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国家自然科学基金(32172168,31801546);辽宁省教育厅科学研究项目(J2020039);辽宁省普通本科高等学校校际合作项目(重大科研项目)(21)


Highly effective synthesis of medium-chain structured phospholipids using HPMo@UiO-66-SO3H
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1.School of Light Industry and Chemical Engineering,Dalian Polytechnic University;2.National Engineering Research Center of Seafood,Dalian Polytechnic University

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    摘要:

    以四氯化锆、磷钼酸水合物、1,2,4,5-苯四甲酸和(3-巯基丙基)三甲氧基硅烷为原料,通过原位合成法及接枝共聚法制得负载磷钼酸的磺酸基功能化UiO-66(HPMo@UiO-66-SO3H)。采用XRD、FTIR、SEM、EDS、XPS、N2吸附-脱附和TG-DTG对其进行了结构表征;应用HPMo@UiO-66-SO3H促进大豆卵磷脂与中碳链脂肪酸(辛酸和癸酸)酯交换合成富含辛酸和癸酸的中碳链结构磷脂,通过正交实验优化了反应条件,并对比了HPMo@UiO-66-SO3H与HPMo、UiO-66、HPMo@UiO-66和UiO-66-SO3H的反应活性,考察了HPMo@UiO-66-SO3H的循环利用性。结果表明,HPMo@UiO-66-SO3H具有介孔结构,并含有大量HPMo和磺酸基活性组分,且组分间可显著协同促进中碳链结构磷脂的合成反应;当HPMo@UiO-66-SO3H含量为大豆卵磷脂、辛酸和癸酸总质量的百分之5,m(大豆卵磷脂)∶m(辛酸)∶m(癸酸)=1∶10∶10,50 ℃下反应4 h时,产物的中碳链脂肪酸接入率高达百分之94.31(辛酸和癸酸接入率分别为百分之44.21和百分之50.10);HPMo@UiO-66-SO3H可循环利用5次活性无明显下降。提出了HPMo@UiO-66-SO3H促进酯交换制备中碳链结构磷脂过程的可能反应机理。

    Abstract:

    Sulfonic acid functionalized phosphomolybdic acid incorporated-UiO-66 (HPMo@UiO-66-SO3H) was prepared by an in-situ graft copolymerization method using zirconium (Ⅳ) chloride, phosphomolybdic acid hydrate, 1,2,4,5-benzenetetracarboxylic acid and (3-mercaptopropyl) trimethoxysilane as raw materials, and characterized by XRD, FTIR, SEM, EDS, XPS, N2 adsorption-desorption and TG-DTG. HPMo@UiO-66-SO3H was used to prepare medium-chain structured phospholipids enriched in caprylic acids and capric acids through transesterification between soybean lecithins and medium-chain fatty acids (caprylic acids and capric acids), and the reaction conditions were optimized by orthogonal experiment method. Moreover, the reactivity of HPMo@UiO-66-SO3H was compared with HPMo, UiO-66, HPMo@UiO-66 and UiO-66-SO3H materials, and the recycling of HPMo@UiO-66-SO3H was researched as well. As a result, it was certified that HPMo@UiO-66-SO3H exhibited a mesoporous structure possessing numerous HPMo and sulfonic acid active components, and a promising reactivity for the synthesis of medium-chain structured phospholipids due to the synergistic effect of the two components. The incorporation of medium-chain fatty acids in product reached as high as 94.31percent with 44.21 percent of caprylic acid and 50.10 percent of capric acid at 50 ℃ within 4 h when the HPMo@UiO-66-SO3H dosage was 5 percent of the total mass of soybean lecithins, caprylic acids and capric acids, and the m(soybean lecithins)∶m(caprylic acids)∶m(capric acids) was 1∶10∶10. Noticeably, HPMo@UiO-66-SO3H could be recycled 5 times with no obvious deactivation. A probable reaction mechanism of medium-chain structured phospholipid synthesis using HPMo@UiO-66-SO3H responsible for the process is presented.

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张江华,李子轩,葛艳艳,唐晶晶,周庄,孙乐乐,张华薇,周大勇. HPMo@UiO-66-SO3H用于中碳链结构磷脂的高效合成[J].精细化工,2023,40(7):

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  • 收稿日期:2022-11-29
  • 最后修改日期:2023-02-09
  • 录用日期:2023-02-13
  • 在线发布日期: 2023-05-11
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