塔拉粉酶解废液HPLC指纹图谱及2个主成分含量测定方法研究

doi:10.3969/j.issn.0253-2417.2023.05.003

林产化学与工业 ›› 2023, Vol. 43 ›› Issue (5): 17-24.doi: 10.3969/j.issn.0253-2417.2023.05.003

塔拉粉酶解废液HPLC指纹图谱及2个主成分含量测定方法研究

管勤昊¹^,², 汤丽华¹, 张亮亮³^,*(), 徐曼¹, 刘义稳⁴, 黄立新¹^,*()

1. 中国林业科学研究院林产化学工业研究所；江苏省生物质能源与材料重点实验室；国家林业和草原局林产化学工程重点实验室；林木生物质低碳高效利用国家工程研究中心，江苏南京 210042
2. 南京林业大学江苏省林业资源高效加工利用协同创新中心，江苏南京 210037
3. 华侨大学先进碳转化技术研究院，福建厦门 361021
4. 五峰赤诚生物科技股份有限公司，湖北宜昌 443000

收稿日期:2023-01-12 出版日期:2023-10-28 发布日期:2023-10-27
通讯作者: 张亮亮,黄立新 E-mail:zhll20086@163.com;l_x_huang@163.com
作者简介:黄立新，研究员，博士生导师，研究领域为天然资源化学利用，E-mail：l_x_huang@163.com
张亮亮，研究员，博士，硕士生导师，主要从事单宁化学研究, E-mail：zhll20086@163.com
管勤昊(1999—)，男，山东德州人，硕士生，研究方向为单宁化学
基金资助:
国家重点研发计划项目(2022YFD1300903);华侨大学科研启动费项目(22BS133)

HPLC Fingerprint and Content Determination of Two Principal Components in Waste Liquid of Tara Enzymatic Hydrolysis

Qinhao GUAN¹^,², Lihua TANG¹, Liangliang ZHANG³^,*(), Man XU¹, Yiwen LIU⁴, Lixin HUANG¹^,*()

1. Institute of Chemical Industry of Forest Products, CAF; Key Lab. of Biomass Energy and Material, Jiangsu Province; Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; National Engineering Research Center of Low-Carbon Processing and Utilization of Forest Biomass, Nanjing 210042, China
2. Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Najing Forestry University, Nanjing 210037, China
3. Institute of Advanced Carbon Conversion Technology, Huaqiao University, Xiamen 361021, China
4. Wufeng Chicheng Biotechnology Co., Ltd., Yichang 443000, China

Received:2023-01-12 Online:2023-10-28 Published:2023-10-27
Contact: Liangliang ZHANG,Lixin HUANG E-mail:zhll20086@163.com;l_x_huang@163.com

摘要/Abstract

摘要：

建立了一种同时分析塔拉粉酶解废液中奎宁酸(QA)与没食子酸(GA)的HPLC方法，并进行方法学验证，进一步绘制其HPLC指纹图谱，结合相似度、聚类分析等手段对不同批次塔拉粉酶解废液进行评价。研究结果表明：该方法选择215 nm、流动相乙腈-0.1%三氟乙酸水溶液、乙腈梯度5%~20%、流速1.0 mL/min、柱温30 ℃作为奎宁酸与没食子酸的色谱分析条件；奎宁酸标准曲线线性范围为1.25~20 g/L、其检测限为0.5 g/L，没食子酸标准曲线线性范围为0.062 5~1 g/L、其检测限为5 mg/L；该方法精密度、重复性、稳定性、加样回收试验的RSD均小于5%；奎宁酸与没食子酸平均加样回收率分别为100.87%、99.65%；12批次废液试样指纹图谱分析相似度均大于0.95；可通过聚类分析分为两类，10号和11号样品聚为一类，其余样品聚为一类；计算得到奎宁酸质量浓度为482.3 g/L，没食子酸质量浓度为35.7 g/L。

关键词: 方法学验证, 指纹图谱, 奎宁酸, 没食子酸

Abstract:

An HPLC method was developed for the simultaneous analysis of quinic acid(QA) and gallic acid(GA) in tara powder enzymatic digestion waste solution, and the methodological verification was carried out. The HPLC fingerprints were further drawn and the different batches of tara powder enzymatic digestion waste solution were evaluated by combining similarity and cluster analysis. The results showed that the detection wavelength at 215 nm, mobile phase acetonitrile-0.1% aqueous trifluoroacetic acid aqueous solution, acetonitrile gradient of 5%-20%, flow rate of 1.0 mL/min and column temperature of 30 ℃ were selected as the chromatographic analysis conditions for quinic acid and gallic acid. The linear range of quinic acid standard curve was 1.25-20 g/L, and the detection limit was 0.5 g/L. The linear range of gallic acid standard curve was 0.062 5-1 g/L, and the detection limit was 5 mg/L. The RSD of precision, repeatability, stability, and the spiked recovery test were less than 5%.The average spiked recoveries of quinic acid and gallic acid were 100.87% and 99.65%, respectively. The similarity of the fingerprint profiles of the 12 batches of waste samples was greater than 0.95. The samples could be divided into two categories by cluster analysis, with samples No.10 and No.11 were clustered into one category, and the rest samples were clustered into one category. The mass concentrations of quinic acid and gallic acid were calculated to be 482.3 g/L and 35.7 g/L, respectively.

Key words: methodological verification, fingerprint, quinic acid, gallic acid

中图分类号:

TQ35

管勤昊, 汤丽华, 张亮亮, 徐曼, 刘义稳, 黄立新. 塔拉粉酶解废液HPLC指纹图谱及2个主成分含量测定方法研究[J]. 林产化学与工业, 2023, 43(5): 17-24.

Qinhao GUAN, Lihua TANG, Liangliang ZHANG, Man XU, Yiwen LIU, Lixin HUANG. HPLC Fingerprint and Content Determination of Two Principal Components in Waste Liquid of Tara Enzymatic Hydrolysis[J]. Chemistry and Industry of Forest Products, 2023, 43(5): 17-24.

图/表 9

图1

图2

图3

表1

表2

图4

图5

表3

图6

参考文献 21

1	李志国, 杨文云, 夏定久, 等. 塔拉生物生态学习性初步研究[J]. 林业科学研究, 1997, 10 (1): 6- 9. doi: 10.3321/j.issn:1001-1498.1997.01.002
	LI Z G , YANG W Y , XIA D J , et al. A preliminary study on the bioecology of tara[J]. Forest Research, 1997, 10 (1): 6- 9. doi: 10.3321/j.issn:1001-1498.1997.01.002
2	孙先玉, 孙博, 李冬玲, 等. 塔拉及塔拉单宁的研究与加工技术进展[J]. 林产化学与工业, 2011, 31 (1): 119- 126.
	SUN X Y , SUN B , LI D L , et al. Progress of research and processing technologies on tara and tara tannin[J]. Chemistry and Industry of Forest Products, 2011, 31 (1): 119- 126.
3	张建云, 李志国, 夏定久, 等. 塔拉单宁和塔拉多糖研究现状[J]. 天然产物研究与开发, 2009, 21 (1): 6- 10. doi: 10.3969/j.issn.1001-6880.2009.01.002
	ZHANG J Y , LI Z G , XIA D J , et al. Investigating actuality and the vista of tara tannin and tara polysaccharide[J]. Natural Products Research and Development, 2009, 21 (1): 6- 10. doi: 10.3969/j.issn.1001-6880.2009.01.002
4	BELLOTTI N , AMO B D , ROMAGNOLI R . Tara tannin a natural product with antifouling coating application[J]. Progress in Organic Coatings, 2012, 74 (3): 411- 417. doi: 10.1016/j.porgcoat.2011.11.014
5	陈培旭, 刘春利, 王思渊, 等. 塔拉单宁酶解生产没食子酸的工艺优化[J]. 现代食品科技, 2020, 36 (12): 60- 68.
	CHEN P X , LIU C L , WANG S Y , et al. Optimization of gallic acid production by enzymatic hydrolysis of tara tannin[J]. Modern Food Science and Technology, 2020, 36 (12): 60- 68.
6	秦清, 仲崇茂, 徐浩, 等. 塔拉单宁提取和精制工艺对络合沉锗率影响[J]. 林产化学与工业, 2012, 32 (2): 79- 82.
	QIN Q , ZHONG C M , XU H , et al. Effects of extraction and refining technology of tara tannin on complexing precipitation of geranium[J]. Chemistry and Industry of Forest Products, 2012, 32 (2): 79- 82.
7	曾维丽, 姚开, 贾冬英, 等. 塔拉单宁水解酶产生条件的研究[J]. 天然产物研究与开发, 2006, 18 (4): 592- 595. doi: 10.3969/j.issn.1001-6880.2006.04.014
	ZENG W L , YAO K , JIA D Y , et al. Study on the conditions of tara tannin hydrolase production[J]. Natural Products Research and Development, 2006, 18 (4): 592- 595. doi: 10.3969/j.issn.1001-6880.2006.04.014
8	周道兵, 陈笳鸿, 汪咏梅, 等. 塔拉单宁水解废液回收奎尼酸的工艺试验[J]. 林产化工通讯, 2001, 35 (1): 17- 19.
	ZHOU D B , CHEN J H , WANG Y M , et al. Experiment of recovering quinic acid from liquid waste of tara tannin hydrolysis[J]. Journal of Chemical Industry of Forest Products, 2001, 35 (1): 17- 19.
9	黄永林, 陈月圆, 刘金磊, 等. 红背山麻杆叶的化学成分研究(Ⅲ)——奎宁酸类化合物[J]. 广西植物, 2015, 35 (1): 105- 108.
	HUANG Y L , CHEN Y Y , LIU J L , et al. Chemical constituents from the leaves of Alchornea trewioides(Ⅲ): Quinic acids[J]. Guihaia, 2015, 35 (1): 105- 108.
10	张维冰, 王智聪, 张凌怡. 超高效液相色谱-二极管阵列检测-串联质谱法测定菊花中的10种咖啡酰基奎宁酸和22种黄酮类化合物[J]. 分析化学, 2013, 41 (12): 1851- 1861.
	ZHANG W B , WANG Z C , ZHANG L Y . Determination of 10 caffeoylquinic acids and 22 flavonoids in chrysanthemum samples by ultra-high performance liquid chromatography-diode array detection-tandem mass spectrometry[J]. Chinese Journal of Analytical Chemistry, 2013, 41 (12): 1851- 1861.
11	王静, 邢海洋, 瞿玲娜. 没食子酸对铜绿假单胞菌生物膜的抑制作用研究[J]. 中国基层医药, 2021, 28 (10): 1555- 1559.
	WANG J , XING H Y , QU L N . Inhibitory effect of gallic acid on Pseudomonas aeruginosa biofilm[J]. Chinese Journal of Primary Medicine and Pharmacy, 2021, 28 (10): 1555- 1559.
12	韩雪琴, 黄立新, 郝娟, 等. 没食子酸与大米淀粉的相互作用[J]. 现代食品科技, 2021, 37 (10): 103- 111.
	HAN X Q , HUANG L X , HAO J , et al. Interactions between gallic acid and rice starch[J]. Modern Food Science and Technology, 2021, 37 (10): 103- 111.
13	申娜, 骆树瑜, 乔晓丞, 等. 没食子酸对过敏性鼻炎小鼠的抗过敏作用研究[J]. 中国临床药理学杂志, 2022, 38 (5): 409- 412.
	SHEN N , LUO S Y , QIAO X C , et al. Study on the anti-allergic effect of gallic acid in mice with allergic rhinitis[J]. The Chinese Journal of Clinical Pharmacology, 2022, 38 (5): 409- 412.
14	LI G Z, RWO K H. Hydrophilic molecularly imprinted chitosan based on deep eutectic solvents for the enrichment of gallic acid in red ginseng tea[J/OL]. Polymers, 2019, 11(9): 1434[2022-02-25]. https://doi.org/10.3390/polym11091434.
15	葛亮, 李娜, 杨明翰, 等. 沙棘果高效薄层色谱分析及抗氧化能力研究[J]. 食品与发酵工业, 2021, 48 (6): 263- 269.
	GE L , LI N , YANG M H , et al. Study on high-performance thin-layer chromatography analysis and antioxidant ability of Hippophae rhamnoides L.fruits[J]. Food and Fermentation Industries, 2021, 48 (6): 263- 269.
16	覃国新, 李慧玲, 何洁, 等. 固相萃取净化HPLC法同时检测荔枝皮中的几种原花青素[J]. 现代食品科技, 2021, 37 (7): 310- 314.
	QIN G X , LI H L , HE J , et al. Determination of several procyanidins in litchi pericarp by HPLC with pass-through extraction[J]. Modern Food Science and Technology, 2021, 37 (7): 310- 314.
17	汤丽华, 张亮亮, 张禾. 紫外法和皮粉法测定塔拉单宁含量的对比研究[J]. 生物质化学工程, 2022, 56 (6): 31- 35.
	TANG L H , ZHANG L L , ZHANG H . Comparison on the determination of tara tannin content with UV spectrophotometry and hide powder method[J]. Biomass Chemical Engineering, 2022, 56 (6): 31- 35.
18	张亮亮, 汪咏梅, 徐曼, 等. 高效液相色谱-内标法测定焦性没食子酸含量[J]. 生物质化学工程, 2015, 49 (2): 12- 16.
	ZHANG L L , WANG Y M , XU M , et al. Determination of pyrogallol using reversed-phase HPLC and internal standard method[J]. Biomass Chemical Engineering, 2015, 49 (2): 12- 16.
19	朱拓, 陈国庆, 虞锐鹏, 等. 甲醇溶液吸收光谱与荧光光谱的研究[J]. 激光技术, 2005, 29 (5): 470- 472.
	ZHU T , CHEN G Q , YU R P , et al. An experiment study of methanol absorption and fluorescent spectra induced by UV-light[J]. Laser Technology, 2005, 29 (5): 470- 472.
20	刘妍妍, 张慧文, 白云霞, 等. 蒙药三子散HPLC指纹图谱结合化学模式识别研究[J]. 中国药房, 2022, 33 (3): 319- 325.
	LIU Y Y , ZHANG H W , BAI Y X , et al. Study on HPLC fingerprint and chemical pattern recognition of Mongolian medicine Sanzisan[J]. China Pharmacy, 2022, 33 (3): 319- 325.
21	周冰倩, 高喜梅, 杨颖, 等. 不同来源竹茹药材HPLC指纹图谱和化学计量学分析[J]. 中草药, 2022, 53 (3): 853- 857.
	ZHOU B Q , GAO X M , YANG Y , et al. Quality analysis of Caulis bambusae in Taeniam from different origins by HPLC coupled with chemometrics[J]. Chinese Traditional and Herbal Drugs, 2022, 53 (3): 853- 857.

样品¹⁾ sample	峰面积peak area		质量浓度mass concentration/(g·L^-1)
样品¹⁾ sample	奎宁酸quinic acid	没食子酸gallic acid	奎宁酸quinic acid	没食子酸gallic acid
S1	1 281 357	17 398 945	4.823	0.357
S2	1 374 108	18 399 532	5.154	0.380
S3	1 466 215	17 948 876	5.482	0.370
MR1	6 215 462	35 699 746	22.400	0.781
MR2	3 406 330	26 959 533	12.393	0.579

样品 sample	理论值/(g·L^-1) theoretical value		实际值/(g·L^-1) actual value		加样回收率/% sample recovery
样品 sample	奎宁酸 quinic acid	没食子酸 gallic acid	奎宁酸 quinic acid	没食子酸 gallic acid	奎宁酸 quinic acid	没食子酸 gallic acid
S1+MR1	13.612	0.569	14.243	0.563	104.64	98.91
S1+MR2	8.608	0.468	8.641	0.449	100.38	96.02
S2+MR1	13.777	0.581	14.159	0.587	102.77	101.04
S2+MR2	8.773	0.480	8.477	0.473	96.62	98.62
S3+MR1	13.941	0.576	14.414	0.597	103.40	103.66
S3+MR2	8.937	0.474	8.706	0.473	97.41	99.64

编号 No.	S1	S2	S3	S4	S5	S6	S7	S8	S9	S10	S11	S12	R
S1	1.000	0.992	0.989	0.981	0.996	0.982	0.987	0.983	0.989	0.992	0.999	0.997	0.989
S2	0.991	1.000	0.983	0.979	0.996	0.996	0.998	0.980	0.985	0.980	0.997	0.979	0.994
S3	0.983	0.992	1.000	0.998	0.995	0.986	0.985	0.989	0.997	0.979	0.997	0.986	0.979
S4	0.985	0.980	0.996	1.000	0.984	0.983	0.993	0.979	0.985	0.993	0.989	0.991	0.989
S5	0.998	0.980	0.989	0.996	1.000	0.991	0.982	0.983	0.992	0.995	0.981	0.984	0.991
S6	0.982	0.996	0.985	0.992	0.990	1.000	0.994	0.996	0.982	0.994	0.982	0.992	0.982
S7	0.992	0.984	0.992	0.987	0.996	0.983	1.000	0.994	0.991	0.996	0.995	0.993	0.983
S8	0.996	0.999	0.996	0.981	0.989	0.988	0.991	1.000	0.991	0.986	0.985	0.990	0.989
S9	0.989	0.981	0.984	0.984	0.992	0.985	0.983	0.996	1.000	0.997	0.987	0.984	0.982
S10	0.992	0.984	0.996	0.998	0.997	0.984	0.979	0.983	0.990	1.000	0.981	0.993	0.982
S11	0.999	0.998	0.999	0.987	0.996	0.991	0.998	0.990	0.990	0.995	1.000	0.988	0.997
S12	0.995	0.988	0.994	0.987	0.981	0.997	0.981	0.985	0.989	0.989	0.979	1.000	0.994
R	0.984	0.991	0.997	0.983	0.984	0.988	0.995	0.992	0.989	0.999	0.997	0.988	1.000

[1]	雷响, 张闽峰, 胡可欣, 柯宇, 郑德勇. 1, 2, 3, 5, 6, 7-六羟基-9, 10-蒽醌的合成及其抗氧化活性研究[J]. 林产化学与工业, 2022, 42(6): 64-68.
[2]	齐志文,周昊,薛兴颖,颜洋洋,王成章. 三甲氧基没食子酸1, 2, 4-噻二唑-3, 5-二酮衍生物的合成及其对HL60细胞增殖的抑制作用[J]. 林产化学与工业, 2020, 40(3): 123-129.
[3]	徐曼, 汪咏梅, 张亮亮. 产焦性没食子酸菌株筛选及其培养条件优化[J]. 林产化学与工业, 2018, 38(3): 97-102.
[4]	刘贵锋, 吴国民, 陈健, 孔振武. 有机硅改性没食子酸非异氰酸酯聚氨酯的制备及性能研究[J]. 林产化学与工业, 2018, 38(1): 39-46.
[5]	黄永林, 陈月圆, 颜小捷, 刘金磊, 王亚凤, 何瑞杰, 李典鹏. 栲树皮乙醇提取物中多酚类化学成分的鉴定[J]. 林产化学与工业, 2016, 36(4): 135-139.
[6]	欧阳文, 曹庸, 陈雪香, 杜方麓. 三氟化硼催化合成2,3,4,4’-四羟基二苯甲酮新方法研究[J]. 林产化学与工业, 2014, 34(4): 21-24.
[7]	裴建军;姚凌菱;李迅;赵林果;. 黑曲霉全细胞生物催化制备没食子酸丙酯的研究[J]. 林产化学与工业, 2012, 32(6): 52-56.
[8]	郭满满;肖卓炳;彭密军;于华忠;郭瑞轲. 没食子酸的热稳定性研究[J]. 林产化学与工业, 2012, 32(4): 58-62.
[9]	徐曼;汪咏梅;张亮亮;吴冬梅;陈笳鸿. 没食子酸辛酯标准样品的研制[J]. 林产化学与工业, 2012, 32(3): 47-50.
[10]	秦清;徐浩;钱星;杜运平. Hoesch反应法合成2,3,4,4'-四羟基二苯甲酮的研究[J]. 林产化学与工业, 2012, 32(2): 71-74.
[11]	吴晓雯;张俊梅;潘再法;王丽丽. MC顶空萃取-热解吸-GC/MS法研究香附指纹图谱[J]. 林产化学与工业, 2012, 32(1): 93-98.
[12]	李森林;张建斌;张正付;魏雄辉. 湿地松松针中鞣质的提取与分离工艺研究[J]. 林产化学与工业, 2010, 30(5): 99-102.
[13]	陈茜文;谷文众. 无带水剂合成没食子酸正辛酯的研究[J]. 林产化学与工业, 2010, 30(2): 57-60.
[14]	黄莉;谢晖;陶波;张赛南. 活性炭负载杂多酸催化合成没食子酸甲酯的研究[J]. 林产化学与工业, 2010, 30(2): 99-102.
[15]	薄采颖;毕良武;赵振东;张秋格;李冬梅;古研;王婧;王玉民;周永红. 多酚酸酯稳定剂对生物柴油高温稳定性的影响[J]. 林产化学与工业, 2009, 29(S1): 23-28.

塔拉粉酶解废液HPLC指纹图谱及2个主成分含量测定方法研究

HPLC Fingerprint and Content Determination of Two Principal Components in Waste Liquid of Tara Enzymatic Hydrolysis

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 9

参考文献 21

相关文章 15

编辑推荐

Metrics

本文评价

关于本刊

投稿指南

在线期刊

相关单位

联系我们