MOFs材料对普洱茶中总黄酮的吸附
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摘要
为有效分离纯化普洱茶中的黄酮类化合物,采用水热反应法合成MIL-101-Fe、MIL-101-Cr和NH2-MIL-101-Cr等3种金属有机骨架(MOFs)材料对其进行富集分离,研究振荡时间、pH值和样品初始质量浓度等工艺参数对MOFs对普洱茶总黄酮吸附纯化作用的影响,并分析不同解吸剂、解吸附时间对MOFs上普洱茶总黄酮解吸附作用的影响。结果表明:MOFs材料对普洱茶总黄酮的吸附量随着振荡时间的延长而增加,随着pH值和样品初始质量浓度的增加先增大后减小;3种MOFs材料中MIL-101-Fe对总黄酮的吸附效果最好,最佳吸附工艺条件为振荡时间40 min,pH值5.56,样品初始质量浓度0.127 mg/mL,此时吸附量为10.16 mg/g;振荡时间为30 min时,无水乙醇对普洱茶中总黄酮的解吸附效果最好,对MIL-101-Fe、MIL-101-Cr和NH2-MIL-101-Cr上总黄酮的最大解吸附率分别为90.04%、79.76%和89.09%。
In order to effectively separate and purify the flavonoids from Pu′er tea, three kinds of metal organic framework(MOFs) materials, including MIL-101-Fe, MIL-101-Cr and NH2-MIL-101-Cr, were synthesized by hydrothermal reaction to enrich and separate them. The effects of process parameters such as shaking time, pH value and initial mass concentration on the adsorption and purification of total flavonoids from Pu′er tea by MOFs were studied. The effects of different desorbents and desorption time on the desorption of total flavonoids on the MOFs were analyzed. The results showed that the adsorption amount of total flavonoids from Pu′er tea increased with the increase of the shaking time, first increased and then decreased with the increase of pH value and initial mass concentration. Among the three kinds of MOFs, MIL-101-Fe had the best adsorption effect on total flavonoids. The optimum adsorption conditions are shaking time is 40 min, pH value is 5.56, and the initial mass concentration of the sample is 0.127 mg/mL, the amount of adsorption is 10.16 mg/g. When the shaking time is 30 min, the desorption of total flavonoids by ethanol is the best, and the maximum desorption rates on MIL-101-Fe, MIL-101-Cr and NH2-MIL-101-Cr are 90.04%, 79.76% and 89.09%, respectively.
In order to effectively separate and purify the flavonoids from Pu′er tea, three kinds of metal organic framework(MOFs) materials, including MIL-101-Fe, MIL-101-Cr and NH2-MIL-101-Cr, were synthesized by hydrothermal reaction to enrich and separate them. The effects of process parameters such as shaking time, pH value and initial mass concentration on the adsorption and purification of total flavonoids from Pu′er tea by MOFs were studied. The effects of different desorbents and desorption time on the desorption of total flavonoids on the MOFs were analyzed. The results showed that the adsorption amount of total flavonoids from Pu′er tea increased with the increase of the shaking time, first increased and then decreased with the increase of pH value and initial mass concentration. Among the three kinds of MOFs, MIL-101-Fe had the best adsorption effect on total flavonoids. The optimum adsorption conditions are shaking time is 40 min, pH value is 5.56, and the initial mass concentration of the sample is 0.127 mg/mL, the amount of adsorption is 10.16 mg/g. When the shaking time is 30 min, the desorption of total flavonoids by ethanol is the best, and the maximum desorption rates on MIL-101-Fe, MIL-101-Cr and NH2-MIL-101-Cr are 90.04%, 79.76% and 89.09%, respectively.
引文
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[14]张贺,李国良,张可刚,等.金属有机骨架材料在吸附分离研究中的应用进展[J].化学学报,2017,75(9):841-859.ZHANG H,LI G L,ZHANG K G,et al. Advances of metalorganic frameworks in adsorption and separation applications[J].Acta Chimica Sinica,2017,75(9):841-859(in Chinese).
[15] LI X H,GUO W L,LIU Z H,et al. Fe-based MOFs for efficient adsorption and degradation of acid orange 7 in aqueous solution via persulfate activation[J]. Applied Surface Science,2016,369:130-136.
[16] SHAFIEI M,ALIVAND M S,RASHIDI A,et,al. Synthesis and adsorption performance of a modified micro-mesoporous MIL-101(Cr)for VOCs removal at ambient conditions[J].Chemical Engineering Journal,2018,341:164-174.
[17] HWANG Y K,HONG D Y,CHANG J S,et al. Amine grafting on coordinatively unsaturated metal centers of MOFs:Consequences for catalysis and metal encapsulation[J]. Angewandte Chemie International Edition,2008,47(22):4144-4148.
[18]赵红昆,杜晓蕊,杨翰文,等. MOFs材料在以氢键作用为主导的吸附分离中的应用研究进展[J].天津师范大学学报(自然科学版),2018,38(1):1-6.ZHAO H K,DU X R,YANG H W,et al. Application progress on the MOFs in adsorption/separation processes via hydrogen bond interactions[J]. Journal of Tianjin Normal University(Natural Science Edition),2018,38(1):1-6(in Chinese).
[19] LYU H P,ZHANG Y J,LIN Z,et al. Processing and chemical constituents of Pu-erh tea:A review[J]. Food Research International,2013,53(2):608-618.
[20]李志平,尹笃林,石爱华,等.两种茵陈总黄酮提取方法的对比研究[J].生命科学仪器,2007,5(9):50-52.LI Z P,YIN D L,SHI A H,et al. Contrast of two extraction methods for artemisia capillaries thunb′s total flavones[J]. Life Science Instruments,2007(5):50-52(in Chinese).
[21]饶秋林. Fe-MIL-101、Fe-MIL-53及Fe/MIL-125(Ti)非均相Fenton反应降解罗丹明B溶液[D].昆明:云南大学,2015.RAO Q L. Fe-MIL-101,Fe-MIL-53 and Fe/MIL-125(Ti)heterogeneous Fenton reaction degradation of Rhodamine B solution[D]. Kunming:Yunnan University,2015(in Chinese).
[22]郭金涛,陈勇,荆钰,等.以醋酸盐为矿化剂合成金属有机骨架MIL-101[J].高等学校化学学报,2012,33(4):668-672.GUO J T,CHEN Y,JING Y,et al. Synthesis of metal organic framework MIL-101 with acetate as mineralizer[J]. Chemical Journal of Chinese Universities,2012,33(4):668-672(in Chinese).
[23]周晶晶,刘开宇,孔春龙,等.金属有机骨架材料MIL-101(Cr)-NH2的合成及其气体吸附性能[J].过程工程学报,2013,13(1):146-151.ZHOU J J,LIU K Y,KONG C L,et al. Synthesis and gas adsorption properties of metal organic framework material MIL-101(Cr)-NH2[J]. Chinese Journal of Process Engineering,2013,13(1):146-151(in Chinese).
[24] ASIABI M,MEHDINIA A,JABBARI A. Electrospun biocompatible Chitosan/MIL-101(Fe)composite nanofibers for solidphase extraction ofΔ9-tetrahydrocannabinol in whole blood samples using Box-Behnken experimental design[J]. Journal of Chromatography A,2017,1479:71-80.
[25] CHEN M,YAN J Q,TAN Y,et al. Hydroxyalkylation of phenol with formaldehyde to bisphenol F catalyzed by Keggin phosphotungstic acid encapsulated in metal-organic frameworks MIL-100(Fe or Cr)and MIL-101(Fe or Cr)[J]. Industrial&Engineering Chemistry Research,2015,54(47):11804-11813.
[2]吴礼辉.普洱茶概述[J].茶叶科学技术,2005,46(3):44-45.WU L H. Pu′er tea overview[J]. Acta Tea Sinica,2005,46(3):44-45(in Chinese).
[3]顾睿,李瑞明,张兰兰,等.普洱茶化学成分及药理研究进展[J].天津药学,2011,23(1):47-51.GU R,LI R M,ZHANG L L,et al. Advances in study on chemical composition and pharmacological properties of Pu-erh tea[J]. Tianjin Pharmacy,2011,23(1):47-51(in Chinese).
[4] ZHOU Z H,ZHANG Y J,XU M,et al. Puerins A and B,two new 8-C substituted flavan-3-ols from Pu-er tea[J]. Journal of Agricultural and Food Chemistry,2005,53(22):8614-8617.
[5]王淑敏,门田重利,刘志强,等.沱茶中抗自由基化学成分的研究[J].天然产物研究与开发,2005,17(2):131-137.WANG S M,KADOTA S,LIU Z Q,et al. Studies on the antifree radical compounds in Tuocha[J]. Natural Product Research and Development,2005,17(2):131-137(in Chinese).
[6]魏红,丰帆,陈旭丹,等. 4种中药黄酮提取物清除自由基活性的研究[J].天津师范大学学报(自然科学版),2008,28(2):14-17.WEI H,FENG F,CHEN X D,et al. Study on flavonoid extracts from 4 kinds of Chinese traditional medicine scavenging free radicals[J]. Journal of Tianjin Normal University(Natural Science Edition),2008,28(2):14-17(in Chinese).
[7]苏凡,杨小波,李东海,等.五指山水满茶的茶多酚、总黄酮含量与抗氧化活性研究[J].热带作物学报,2018,39(4):675-680.SU F,YANG X B,LI D H,et al. The concent of tea flavonoids,total phenols and antioxidant activities of Wuzhishan-Shuiman Tea[J]. Chinese Journal of Tropical Crops,2018,39(4):675-680(in Chinese).
[8]许丽璇.普洱茶中黄酮类化合物提取方法和抗氧化性初步研究[J].安徽农业科学,2009,37(30):14875-14878.XU L X. Preliminary study on the flavonoids extraction methods and oxidation resistance in Pu′er Tea[J]. Journal of Anhui Agricultural Sciences,2009,37(30):14875-14878(in Chinese).
[9]王丽,邵金良,魏茂琼,等.普洱茶中黄酮类化合物含量的测定方法[J].江苏农业学报,2016,32(6):1410-1415.WANG L,SHAO J L,WEI M Q,et al. Method for the determination of flavonoids in Pu-erh tea by HPLC[J]. Jiangsu Journal of Agricultural Sciences,2016,32(6):1410-1415(in Chinese).
[10] LYU C,YANG J,LIU R,et al. A comparative study on the adsorption and desorption characteristics of flavonoids from honey by six resins[J]. Food Chemistry,2018,268:424-430.
[11] LI A F,SUN A L,LIU R M,et al. An efficient preparative procedure for main flavonoids from the peel of Trichosanthes kirilowii Maxim,using polyamide resin followed by semipreparative high performance liquid chromatography[J]. Journal of Chromatography B:Analytical Technologies in the Biomedical and Life Science,2014,965:150-157.
[12] DONG F P,HA C S. Multifunctional materials based on polysilsesquioxanes[J]. Macromolecular Research,2012,20(4):335-343.
[13]王硕,白丽明.金属-有机骨架材料的制备及吸附应用进展[J].高师理科学刊,2018,38(5):49-52.WANG S,BAI L M. Progress in preparation and adsorption of metal-organic frameworks[J]. Journal of Science of Teachers′College and University,2018,38(5):49-52(in Chinese).
[14]张贺,李国良,张可刚,等.金属有机骨架材料在吸附分离研究中的应用进展[J].化学学报,2017,75(9):841-859.ZHANG H,LI G L,ZHANG K G,et al. Advances of metalorganic frameworks in adsorption and separation applications[J].Acta Chimica Sinica,2017,75(9):841-859(in Chinese).
[15] LI X H,GUO W L,LIU Z H,et al. Fe-based MOFs for efficient adsorption and degradation of acid orange 7 in aqueous solution via persulfate activation[J]. Applied Surface Science,2016,369:130-136.
[16] SHAFIEI M,ALIVAND M S,RASHIDI A,et,al. Synthesis and adsorption performance of a modified micro-mesoporous MIL-101(Cr)for VOCs removal at ambient conditions[J].Chemical Engineering Journal,2018,341:164-174.
[17] HWANG Y K,HONG D Y,CHANG J S,et al. Amine grafting on coordinatively unsaturated metal centers of MOFs:Consequences for catalysis and metal encapsulation[J]. Angewandte Chemie International Edition,2008,47(22):4144-4148.
[18]赵红昆,杜晓蕊,杨翰文,等. MOFs材料在以氢键作用为主导的吸附分离中的应用研究进展[J].天津师范大学学报(自然科学版),2018,38(1):1-6.ZHAO H K,DU X R,YANG H W,et al. Application progress on the MOFs in adsorption/separation processes via hydrogen bond interactions[J]. Journal of Tianjin Normal University(Natural Science Edition),2018,38(1):1-6(in Chinese).
[19] LYU H P,ZHANG Y J,LIN Z,et al. Processing and chemical constituents of Pu-erh tea:A review[J]. Food Research International,2013,53(2):608-618.
[20]李志平,尹笃林,石爱华,等.两种茵陈总黄酮提取方法的对比研究[J].生命科学仪器,2007,5(9):50-52.LI Z P,YIN D L,SHI A H,et al. Contrast of two extraction methods for artemisia capillaries thunb′s total flavones[J]. Life Science Instruments,2007(5):50-52(in Chinese).
[21]饶秋林. Fe-MIL-101、Fe-MIL-53及Fe/MIL-125(Ti)非均相Fenton反应降解罗丹明B溶液[D].昆明:云南大学,2015.RAO Q L. Fe-MIL-101,Fe-MIL-53 and Fe/MIL-125(Ti)heterogeneous Fenton reaction degradation of Rhodamine B solution[D]. Kunming:Yunnan University,2015(in Chinese).
[22]郭金涛,陈勇,荆钰,等.以醋酸盐为矿化剂合成金属有机骨架MIL-101[J].高等学校化学学报,2012,33(4):668-672.GUO J T,CHEN Y,JING Y,et al. Synthesis of metal organic framework MIL-101 with acetate as mineralizer[J]. Chemical Journal of Chinese Universities,2012,33(4):668-672(in Chinese).
[23]周晶晶,刘开宇,孔春龙,等.金属有机骨架材料MIL-101(Cr)-NH2的合成及其气体吸附性能[J].过程工程学报,2013,13(1):146-151.ZHOU J J,LIU K Y,KONG C L,et al. Synthesis and gas adsorption properties of metal organic framework material MIL-101(Cr)-NH2[J]. Chinese Journal of Process Engineering,2013,13(1):146-151(in Chinese).
[24] ASIABI M,MEHDINIA A,JABBARI A. Electrospun biocompatible Chitosan/MIL-101(Fe)composite nanofibers for solidphase extraction ofΔ9-tetrahydrocannabinol in whole blood samples using Box-Behnken experimental design[J]. Journal of Chromatography A,2017,1479:71-80.
[25] CHEN M,YAN J Q,TAN Y,et al. Hydroxyalkylation of phenol with formaldehyde to bisphenol F catalyzed by Keggin phosphotungstic acid encapsulated in metal-organic frameworks MIL-100(Fe or Cr)and MIL-101(Fe or Cr)[J]. Industrial&Engineering Chemistry Research,2015,54(47):11804-11813.