HPMo@UiO-66-SO_(3)H用于中碳链结构磷脂的高效合成

Highly efficient synthesis of medium-chain structured phospholipids using HPMo@UiO-66-SO_(3)H

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了负载磷钼酸的磺酸基功能化UiO-66(HPMo@UiO-66-SO_(3)H)。采用XRD、FTIR、SEM、EDS、XPS、N2吸附-脱附和TG-DTG对其进行了表征,将HPMo@UiO-66-SO_(3)H用于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,考察了HPMo@UiO-66-SO_(3)H的循环利用性。结果表明,HPMo@UiO-66-SO_(3)H具有介孔结构,并含有大量HPMo和磺酸基活性组分,且组分间的协同作用促进了中碳链结构磷脂的生成;当HPMo@UiO-66-SO_(3)H含量为大豆卵磷脂、辛酸和癸酸总质量的5%,m(大豆卵磷脂)∶m(辛酸)∶m(癸酸)=1∶10∶10,50℃下反应4 h时,中碳链脂肪酸接入率高达94.31%(辛酸和癸酸接入率分别为44.21%和50.10%);HPMo@UiO-66-SO_(3)H循环利用5次后,活性略微下降。

Sulfonic acid-functionalized phosphomolybdic acid incorporated-UiO-66(HPMo@UiO-66-SO_(3)H)was prepared from in-situ graft copolymerization method of zirconium tetrachloride,phosphomolybdic acid hydrate,1,2,4,5-benzenetetracarboxylic acid and(3-mercaptopropyl)trimethoxysilane,and characterized by XRD,FTIR,SEM,EDS,XPS,N2 adsorption-desorption and TG-DTG.HPMo@UiO-66-SO_(3)H was then applied in the synthesis of medium-chain structured phospholipids enriched in caprylic acids and capric acids via transesterification of soybean lecithins and medium-chain fatty acids(caprylic acids and capric acids),of which the reaction conditions were optimized through orthogonal experiment and the reusability of was investigated.The results showed that HPMo@UiO-66-SO_(3)H exhibited a mesoporous structure with numerous HPMo and sulfonic acid active components,and the synergistic interaction between the components promoted the formation of medium-chain structured phospholipids.The incorporation of medium-chain fatty acids in product reached as high as 94.31%with 44.21%of caprylic acid and 50.10%of capric acid at 50℃within 4 h when the HPMo@UiO-66-SO_(3)H dosage was 5%of the total mass of soybean lecithins,caprylic acids and capric acids,and m(soybean lecithins)∶m(caprylic acids)∶m(capric acids)was 1∶10∶10.Meanwhile,HPMo@UiO-66-SO_(3)H showed no obvious deactivation after being recycled 5 times.