超高效液质联用技术解析黑果枸杞超临界CO2萃取物中黄酮类天然产物结构

摘要/Abstract

摘要： 解析黑果枸杞中黄酮组分及其结构对于其高值化开发具有重要意义。以青海柴达木黑枸杞作为研究材料，对其超临界CO2萃取物，通过超高效液质联用技术（ultra-high performance liquid chromatography & mass spectrometry，UPLC-MS）和Peakview色谱工作站拟合、二级质谱解析和紫外光谱及质谱数据比对，解析其中的黄酮组分及其结构。共鉴定出黑果枸杞果超临界CO2萃取物中含有13种黄酮类化合物（7种黄酮醇苷元及黄酮醇苷，3种二氢黄酮醇苷元，2种黄酮苷元和1种二氢黄酮苷元），包括芦丁、槲皮素-3-β-葡萄糖醛酸苷、金丝桃苷即槲皮素-3-O-吡喃半乳糖苷、二氢槲皮素、二氢异鼠李素、二氢山奈酚、槲皮素、芹菜素、橙皮素、苜蓿素、山奈酚、异鼠李素、山奈素，其中橙皮素和苜蓿素之前在黑果枸杞未被发现过。

关键词: 黑果枸杞, 黄酮, 超临界CO2萃取物, 超高效液相色谱-质谱联用

Abstract: It is of great significance for developing high-valued black goji products to determine its flavonoid composition and structures. The supercritical CO2 extract of black goji was analyzed by ultra-high performance liquid chromatography & mass spectrometry (UPLC-MS), Peakview work station matching, two-dimensional mass spectrometry, ultraviolet spectrum and mass spectral data comparison, to illustrate the flavonoid composition and structures. 13 flavonoid chemicals were determined, i.e. 7 flavonol aglycones and flavonol glycosides, 3 dihydroflavonol aglycones, 2 flavonoid aglycones and 1 dihydroflavonoid aglycon, including rutin, quercetin-3-β-glucuronide, hyperoside i.e. quercetin-3-O-galactopyranoside, dihydroquercetin, dihydroisorhamnetin, dihydrogen Kaempferol, quercetin, apigenin, hesperetin, alizarin, kaempferol, isorhamnetin, kaempferide, among which hesperetin and alizarin are never found in black goji.

Key words: Black goji, Flavonoid, Supercritical CO2 extract, Ultra-high performance liquid chromatography and mass spectrometry (UPLC-MS)

中图分类号:

TS201.2

束彤丁丽娜王茜贾彩惠邱亦亦阮晖. 超高效液质联用技术解析黑果枸杞超临界CO2萃取物中黄酮类天然产物结构[J]. 食品科学, 0, (): 0-0.

Li NaDING Hui Ruan. Determination of Flavonoids in the Supercritical CO2 Extract of Black Goji Fruit by Using Ultra-High Performance Liquid Chromatography and Mass Spectrometry[J]. FOOD SCIENCE, 0, (): 0-0.

参考文献

Chen SS, Zeng Z, Hu N, et al. Simultaneous optimization of the ultrasound-assisted extraction for phenolic compounds content and antioxidant activity of Lycium ruthenicum Murr. fruit using response surface methodology [J]. Food Chemistry,2018,242:1-8. DOI:10.1016/j.foodchem.2017.08.105.

Chen SS, Zhou HN, Zhang G, et al. Anthocyanins from Lycium ruthenicum Murr. ameliorated D-galactose-induced memory impairment, oxidative stress, and neuroinflammation in adult rats [J]. Journal of Agricultural and Food Chemistry,2019,67(11): 3140-3149. DOI:10.1021/acs.jafc.8b06402.

Liu Y, Gong GP, Sun YJ, et al. Isolation, structural characterization, and immunological activity of a polysaccharide LRLP4-A from the leaves of Lycium ruthenicum [J]. Journal of Carbohydate Chemistry,2016,35(1):40-56. DOI:10.1080/07328303.2015.1120875.

Liu ZG, Dang J, Wang QL, et al. Optimization of polysaccharides from Lycium ruthenicum fruit using RSM and its anti-oxidant activity [J]. International Journal of Biological Macromolecules,2014,61:127-134. DOI:10.1016/j.ijbiomac.2013.06.042.

Liu ZG, Liu BL, Kang HL, et al. Subcritical fluid extraction of Lycium ruthenicum seeds oil and its antioxidant activity [J]. International Journal of Food Science and Technology,2019,54(1): 161-169. DOI:10.1111/ijfs.13920.

Peng Q, Liu HJ, Shi SH, et al. Lycium ruthenicum polysaccharide attenuates inflammation through inhibiting TLR4/NF-B-kappa signaling pathway [J]. International Journal of Biological Macromolecules,2014,67:330-335. DOI:10.1016/j.ijbiomac.2014.03.023.

Peng Q, Xu QS, Yin H, et al. Characterization of an immunologically active pectin from the fruits of Lycium ruthenicum [J]. International Journal of Biological Macromolecules,2014,64: 69-75. DOI:10.1016/j.ijbiomac.2013.11.030.

Qin BL, Liu XC, Cui HM, et al. Aqueous two-phase assisted by ultrasound for the extraction of anthocyanins from Lycium ruthenicum Murr [J]. Preparative Biochemistry and Biotechnology, 2017,47(9):881-888. DOI:10.1080/10826068.2017.1350980.

Tang JL, Yan YM, Ran LW, et al. Isolation, antioxidant property and protective effect on PC12 cell of the main anthocyanin in fruit of Lycium ruthenicum Murray [J]. Journal of Functional Food,2017,30: 97-107. DOI:10.1016/j.jff.2017.01.015.

Tang PP & Giusti M. Black goji as a potential source of natural color in a wide pH range [J]. Food Chemistry,2018.269:419-426. DOI:10.1016/j.foodchem.2018.07.034.

Tian ZH, Aierken A, Pang HH, et al. Constituent analysis and quality control of anthocyanin constituents of dried Lycium ruthenicum Murray fruits by HPLC-MS and HPLC-DAD [J]. Journal of Liquid Chromotography and Related Technology,2016,39(9):453-458. DOI:10.1080/10826076.2016.1179201.

Wang HQ, Li JN, Tao WW, et al. Lycium ruthenicum studies: Molecular biology, phytochemistry and pharmacology [J]. Food Chemistry,2018,240:759-766. DOI:10.1016/j.foodchem.2017.08.026.

Wang YW, Luan GX, Zhou W, et al. Subcritical water extraction, UPLC-Triple-TOF/MS analysis and antioxidant activity of anthocyanins from Lycium ruthenicum Murr [J]. Food Chemistry,2018,249:119-126. DOI:10.1016/j.foodchem.2017.12.078.

Zhang G, Chen SS, Zhou W, et al. Anthocyanin composition of fruit extracts from Lycium ruthenicum and their protective effect for gouty arthritis [J]. Industrial Crops and Products,2019, 129:414-423. DOI:10.1016/j.indcrop.2018.12.026.

Zhang G, Chen SS, Zhou W, et al. Rapid qualitative and quantitative analyses of eighteen phenolic compounds from Lycium ruthenicum Murray by UPLC-Q-Orbitrap MS and their antioxidant activity [J]. Food Chemistry,2018,269:150-156. DOI:10.1016/j.foodchem.2018.06.132.

Zheng J, Ding CX, Wang LS, et al. Anthocyanins composition and antioxidant activity of wild Lycium ruthenicum Murr. from Qinghai-Tibet Plateau [J]. Food Chemistry,2011,126(3): 859-865. DOI:10.1016/j.foodchem.2010.11.052.

白红进,河滨,罗锋. 黑果枸杞色素的提取及其清除DPPH自由基作用的研究 [J]. 西北农业学报,2007,16(2):190-192. DOI:10.3969/j.issn.1004-1389.2007.02.045.

丁玉静,刘俊秀,李金红等. 黑果枸杞生理活性成分及作用研究进展 [J]. 中国临床药理学杂志,2017,33(13):1280-1283. DOI:10.13699/j.cnki.1001-6821.2017.13.031.

冯小雨,蔡瑜,燕雪莹等. 响应面法优化超声辅助提取黑枸杞色素 [J]. 吉林医药学院学报,2018,39(6):401-404.

耿丹丹,谭亮,肖远灿等. 离子色谱法测定黑果枸杞中的甜菜碱 [J]. 食品科学,2015, 36(20):145-147. DOI:10.7506/spkx1002-6630-201520027.

韩爱芝,蒋卉,贾清华等. 响应面试验优化黑果枸杞花色苷微胶囊制备工艺及其稳定性分析 [J]. 食品科学,2016,37(10):82-87. DOI:10.7506/spkx1002-6630-201610014

李进,瞿伟菁. 大孔树脂吸附分离黑果枸杞色素的研究 [J]. 食品科学,2005,26(6):47-51. DOI:10.3321/j.issn:1002-6630.2005.06.006.

李进,赵红艳,原惠等.黑果枸杞色素性质研究 [J]. 食品科学,2006,27(10):146-151. DOI:10.3321/j.issn:1002-6630.2006.10.032.

李淑珍,李进,杨志江等. 大孔树脂分离纯化黑果枸杞总黄酮的研究 [J]. 食品科学,2009, 30(1):19-24. DOI:10.3321/j.issn:1002-6630.2009.01.003.

林丽,李进,丁成丽. 高效液相色谱法测定黑果枸杞果实中花色苷的含量 [J]. 食品科学, 2013,34(6):164-166.

楼舒婷,程焕,林雯雯等.SPME-GC/MS联用测定黑果枸杞中挥发性物质 [J]. 中国食品学报,2016,16(10):245-250. DOI:10.16429/j.1009-7848.2016.10.034.

孙晓红,王潼,吕康文等. 黑枸杞与普通红枸杞营养成分和相关活性物质的分析与评价 [J]. 营养学报,2016,38(5):509-511.

唐骥龙,闫亚美,曹有龙等. 黑果枸杞中一种花色苷类物质的分离纯化及抗氧化活性 [J]. 食品科学,2016,37(15):113-117. DOI:10.7506/spkx1002-6630-201615019

汪河滨,白红进,王金磊. 超声-微波协同萃取法提取黑果枸杞多糖的研究 [J]. 西北农业学报,2007,16(1):157-158,175. DOI:10.3969/j.issn.1004-1389.2007.01.037.

王琪,唐惠儒. 黑果构杞和宁夏枸杞果实中多酚类物质组成的差异研究 [J]. 上海交通大学学报(医学版),2019,39(1):39-46. DOI:10.3969/j.issn.1674-8115.2019.01.008.

杨萍,李哲. pH示差法与HPLC测定黑枸杞花青素方法比较 [J]. 中国农机化学报,2017, 38(7):74-78. DOI:10.13733/j.jcam.issn.2095-5553.2017.07.014.

张晶,杨慧海,刘芳芳等. 黑果枸杞的化学成分药理作用及栽培技术的研究现状 [J]. 食品与生物技术学报,2018,37(7):673-678. DOI:10.3969/j.issn.1673-1689.2018.07.001.

[1]	张欣珂, 赵旭, 刘沛通, 段长青, 段雪荣, 杨健, 李德美, 范雪梅. 红葡萄酒的花色苷：来源、呈色与反应[J]. 食品科学, 2023, 44(23): 342-364.
[2]	谭华强, 铁曼曼, 李丽平, 鲁荣海, 潘绍坤, 唐有万. 紫色辣椒HN191与二荆条的比较代谢组分析[J]. 食品科学, 2023, 44(22): 304-312.
[3]	米佳, 张渌淘, 禄璐, 魏佳仪, 金波, 罗青, 闫亚美, 曹有龙. 中压制备色谱法分离黑果枸杞中2 个矮牵牛素花色苷及其对胰脂肪酶的抑制活性[J]. 食品科学, 2023, 44(22): 16-23.
[4]	丁健, 阮成江, 杨红, 关莹, 李贺, 陈叶, 唐克, 吴立仁. 基于UPLC-MS技术分析沙棘果肉成熟过程中生物活性成分差异[J]. 食品科学, 2023, 44(22): 276-286.
[5]	罗悦，刘瑞山，王志远，柴丽娟，陆震鸣，史劲松，张晓娟，许正宏. 不同β-葡萄糖苷酶活性乳酸菌发酵豆乳特性分析[J]. 食品科学, 2023, 44(20): 155-164.
[6]	周汉琛，王辉，刘亚芹，雷攀登. 基于UPLC-MS/MS方法分析绿茶非挥发性代谢物在常温贮藏中的动态变化[J]. 食品科学, 2023, 44(16): 301-311.
[7]	王卫华，杨晓琴，桑正林，杨顺强，赵平，刘云，朱国磊，叶夏英. 比较代谢组学揭示不同生长期筇竹笋的代谢物差异[J]. 食品科学, 2023, 44(14): 237-244.
[8]	李静，张居舟，刘毅，余晓娟，王欣. 全自动固相萃取结合UPLC-MS/MS同时测定蜂蜜中26 种内源性组分[J]. 食品科学, 2023, 44(10): 265-272.
[9]	刘佳，李勇，木其尔，田菊，张希平，余向阳. 非靶向代谢组学研究3 种树胶代谢轮廓差异[J]. 食品科学, 2023, 44(10): 273-280.
[10]	曾文燊，黄达荣，谢斯威，杜冰，黎攀. 葛根异黄酮组成、结构及功效机制研究进展[J]. 食品科学, 2023, 44(1): 353-361.
[11]	赵萍，刘俊霞，兰阿峰，裴金金，陈德经，金文刚. 基于UPLC-MS非靶向代谢组学分析大鲵肉冷藏过程中代谢物的变化[J]. 食品科学, 2022, 43(22): 267-280.
[12]	邓珂，陈镠，杨良缘，胡钰，许光治，张有做，王艳，倪勤学. 豆芋异黄酮的制备及其对RIN-m5F细胞氧化损伤的保护作用[J]. 食品科学, 2022, 43(19): 200-207.
[13]	周一鸣，马思佳，蒋晴怡，周小理，李云龙. 苦荞中芦丁和槲皮素对淀粉消化酶的抑制能力[J]. 食品科学, 2022, 43(18): 30-37.
[14]	陈超，谭书明，王画，杨笙，代晓桐. 刺梨及其活性成分对2型糖尿病小鼠糖脂代谢的影响[J]. 食品科学, 2022, 43(13): 146-154.
[15]	王凤，肖楚翔，刘淑珍，王凤舞. 榴莲核黄酮的提取及其对秀丽隐杆线虫氧化和衰老的影响[J]. 食品科学, 2021, 42(9): 123-129.