Comparative Analysis of Alkylresorcinols Homologue Composition in Whole Wheat Flour and Refined Wheat Flour
ZOU YanYu, FANG Yong,, LI Peng, HUANG QinQin, XIA Ji, LIU Qin, XIE MinHao, HU QiuHuiCollege of Food Science and Engineering, Nanjing University of Finance and Economics/Collaborative Innovation Center for Modern Grain Circulation and Safety of Jiangsu Province/Key Laboratory of Grains and Oils Control and Processing of Jiangsu Province, Nanjing 210023
Abstract 【Objective】 In order to realize the authenticity discrimination of whole wheat flour, a high performance liquid chromatography (HPLC) detection and analysis method was established to explore the composition of alkylresorcinols (ARs) homologues in whole wheat flour and refined wheat flour. 【Method】 The HPLC conditions were investigated to determine five kinds of ARs homologues, including 5-heptadecylresorcinol (C17:0), 5-nonadecylresorcinol (C19:0), 5-heneicosylresorcino (C21:0), 5-tricosylresorcinol (C23:0) and 5-hentacosylresorcinol (C25:0), and then a methodological evaluation was processed. The contents and composition of ARs homologues in 47 samples, including whole wheat flour, refined wheat flour and wheat bran from home and abroad, were determined and conducted by heat map and principal component analysis (PCA).【Result】 The chromatographic column of ZORBAX SB-C18 (150 mm×4.6 mm, 5 μm, Agilent ) was used for gradient elution, and the column was eluted with 0.1% formic acid aqueous solution and 0.1% formic acid methanol solution. The ARs homologues could be effectively separated within 35 minutes under the UV detection wavelength at 280 nm. The column temperature was 35℃, and the flow rate was 0.5 mL·min-1with 20 μL injection. The peak shape of each homologue was symmetrical without interference, and the detected resolution was exactly. After methodological evaluation, the method was proved that it had good precision and sensitivity, the linear correlation coefficients of the standard curves were more than 0.999, the detection limit was 0.06-0.19 μg·mL -1, the recovery rate was 81.16%-112.92%, and the precision standard deviation was 0.02%-4.02%. Therefore, this method could be applied to determine the composition of ARs homologues. The composition of ARs homologues and total amount of ARs in different samples were found significantly after thermal cluster analysis (P<0.05). Among the ARs homologues of wheat flour samples, C21:0 was the highest, which accounted for 33%-61%; followed by C19:0, which accounted for 12%-44%; while the ratio of C17:0, C23:0 and C25:0 were the least. The content and abundance of ARs homologues in the whole wheat flour of United States and Canada were similar. The content of ARs homologues in abroad whole wheat flour was higher than the whole wheat flour in domestic. The composition of ARs homologues in domestic whole wheat flour was more abundant than refined wheat flour, except for individual refined wheat flour samples. The composition of homologous and total content of ARs in wheat bran F1 were significantly higher than whole wheat flour and refined wheat flour (P<0.05). The total content of ARs in wheat bran F1 was 1 795.78 μg·g-1, which was the most significantly difference compared with other samples (P<0.05). The results of PCA showed that the main difference index between wheat flour samples was the composition of ARs homologues. As the first principal component, the cumulative contribution rate was 98.40%. The relative dispersion between wheat bran and other wheat flour samples was the farthest, while the dispersion of Chinese refined wheat flour was the largest. Even the whole wheat flour of United States and Canada could nearly overlapped, the whole wheat flour and part of refined wheat flour of China could only partially overlapped.【Conclusion】 The HPLC method could be employed to effectively and rapidly quantify the ARs in whole wheat flour products. Moreover, the abundance of ARs homologues in whole wheat flour was better than that of ARs homologues in refined wheat flour under comparative analysis. In summary, the results could provide a theoretical basis for authenticity discrimination and quality control for whole wheat flour by exploring the composition of ARs homologues. Keywords:wheat;whole wheat flour;alkylresorcinols;high performance liquid chromatography;homologues;authenticity discrimination
PDF (831KB)元数据多维度评价相关文章导出EndNote|Ris|Bibtex收藏本文 本文引用格式 邹燕羽, 方勇, 李彭, 黄沁沁, 夏季, 刘琴, 谢旻皓, 胡秋辉. 全麦粉和小麦粉中烷基间苯二酚同系物组成的对比分析[J]. 中国农业科学, 2020, 53(10): 2055-2065 doi:10.3864/j.issn.0578-1752.2020.10.012 ZOU YanYu, FANG Yong, LI Peng, HUANG QinQin, XIA Ji, LIU Qin, XIE MinHao, HU QiuHui. Comparative Analysis of Alkylresorcinols Homologue Composition in Whole Wheat Flour and Refined Wheat Flour[J]. Scientia Acricultura Sinica, 2020, 53(10): 2055-2065 doi:10.3864/j.issn.0578-1752.2020.10.012
5-十五烷基间苯二酚标准品(C15:0,纯度≥95%)、5-十七烷基间苯二酚(C17:0,纯度≥95%)、5-十九烷基间苯二酚(C19:0,纯度≥95%)、5-二十一烷基间苯二酚(C21:0,纯度≥95%)、5-二十三烷基间苯二酚(C23:0,纯度≥95%)和5-二十五烷基间苯二酚(C25:0,纯度≥95%)标准品均购于美国Sigma公司;重氮盐Fast blue B Zn(纯度≥95%)购于阿拉丁试剂有限公司;乙酸乙酯(分析纯),购于上海山浦化工有限公司;甲醇(色谱纯)购于美国Tedia公司;甲酸(色谱纯),购于美国ACS公司。
Table 1 表1 表15种烷基间苯二酚同系物线性方程、相关系数、检出限、定量限及精密度 Table 1Linear regression equation, determination coefficient, LOD, LOQ and precision of five kinds ARs homologues
U1—U7代表美国全麦粉;C1—C6代表加拿大全麦粉;Q1—Q13代表中国全麦粉;X1—X16代表中国小麦粉;F1—F5代表自制小麦麸皮 Fig. 2The abundance heat map of the composition of five kinds ARs homologues in wheat flour at the level of content
U1-U7 represents whole wheat flour collected from America; C1-C6 represents whole wheat flour collected from Canada; Q1-Q13 represents whole wheat flour collected from China; X1-X16 represents refined wheat flour collected from China; F1-F5 represents wheat bran collected from China
U代表美国全麦粉;C代表加拿大全麦粉;Q代表中国全麦粉;X代表中国小麦粉;F代表自制小麦麸皮 Fig. 3The principal component analysis of ARs homologues composition in 47 kinds wheat flour samples
U represent whole wheat flour collected from America; C represent whole wheat flour collected from Canada; Q represent whole wheat flour collected from China; X represent refined wheat flour collected from China; F represent wheat bran collected from China
GOHILS, PETTERSSOND, SALOMONSSON AC, ?MANP . Analysis of alkyl- and alkenylresorcinols in triticale, wheat and rye Journal of the Science of Food and Agriculture, 1988,45(1):43-52. [本文引用: 1]
KOZUBEKA, TYMAN J HP . Cereal grain resorcinolic lipids: Mono and dienoic homologues are present in rye grains Chemistry and Physics of Lipids, 1995,78(1):29-35. [本文引用: 1]
LIYANA-PATHIRANA CM, SHAHIDIF . The antioxidant potential of milling fractions from breadwheat and durum Journal of Cereal Science, 2007,45(3):238-247. [本文引用: 1]
KOZUBEKA, TYMAN J HP . Resorcinolic lipids, the natural non-isoprenoid phenolic amphiphiles and their biological activity Chemical Reviews, 1999,99(1):1-26. [本文引用: 1]
GARCIAS, GARCíAC, HEINZENH, MOYNAP . Chemical basis of the resistance of barley seeds to pathogenic fungi Phytochemistry, 1997,44(3):415-418. [本文引用: 1]
PARIKKAK, ROWLAND IR, WELCH RW, WAHALAK . In vitro antioxidant activity and antigenotoxicity of 5-n-alkylresorcinols Journal of Agricultural and Food Chemistry, 2006,54(5):1646-1650. [本文引用: 1]
WANGZ . Scientific Evidence and Research Frontier of the Impact of "Whole Grain" Consumption on Human Health The 5th High Level Symposium on Nutrition Communication-Exchange the Evidence of Food and Health, Beijing, China, 2014. (in Chinese) [本文引用: 1]
WANG LP, WU FM, TIAN XH, LIUM, LIU YX, TANB . Research progress on whole wheat flour at home and abroad Cereal and Food Industry, 2013,20(4):4-8. (in Chinese) [本文引用: 1]
DOBLADO-MALDONADO AF, PIKE OA, SWELEY JC, ROSE DJ . Key issues and challenges in whole wheat flour milling and storage Journal of Cereal Science, 2012,56(2):119-126. [本文引用: 1]
MARQUARTL, WIEMER KL, JONES JM, JACOBB . Whole grain health claims in the USA and other efforts to increase whole-grain consumption Proceedings of the Nutrition Society, 2003,62(1):151-160. [本文引用: 1]
ROSS AB, SHEPHERD MJ, SCHUPPHAUSM, SINCLAIRV, ALFAROB, KAMAL-ELDINA, ?MANP . Alkylresorcinols in cereals and cereal products Journal of Agricultural and Food Chemistry, 2003,51(14):4111-4118. [本文引用: 1]
LANDBERGR, KAMAL-ELDINA, ANDERSSONR, ?MANP . Alkylresorcinol content and homologue composition in durum wheat (Triticum durum) kernels and pasta products Journal of Agricultural and Food Chemistry, 2006,54(8):3012-3014. DOI:10.1021/jf0530805URL [本文引用: 2]
LANDBERGR, KAMAL-ELDINA, SALMENKALLIO-MARTTILASM, ROUAUX, ?MANP . Localization of alkylresorcinols in wheat, rye and barley kernels Journal of Cereal Science, 2008,48(2):401-406. [本文引用: 1]
ROSS AB, KAMAL-ELDINA, JUNGC, SHEPHERD MJ, ?MANP . Gas chromatographic analysis of alkylresorcinols in rye ( Secale cereale L) grains Journal of the Science of Food and Agriculture, 2001,81(14):1405-1411. [本文引用: 1]
GUNENCA, HADINEZHADM, FARAHI, HASHEMA, HOSSEINIANF . Impact of supercritical CO2 and traditional solvent extraction systems on the extractability of alkylresorcinols, phenolic profile and their antioxidant activity in wheat bran Journal of Functional Foods, 2015,12:109-119. [本文引用: 1]
PENG TY, ZHAO RY, WANG XY . Optimization of ultrasound- assisted extraction of alkylresorcinols from whole wheat flour Journal of Henan University of Technology (Natural Science Edition), 2017,38(4):14-19. (in Chinese) [本文引用: 1]
WU SY, QIU TQ, FAN XD . Advances in the application of ultrasound in the extraction of active ingredients from Chinese herbal medicines Jiangsu Journal of Traditional Chinese Medicine, 2008,40(7):93-94. (in Chinese) [本文引用: 1]
WANG YF, ZHANG XS, XIANG XS, GAOC, WANGZ . Establishment of the liquid fluorometric method for determination of alkylresorcinols in whole wheat Acta Nutrimenta Sinica, 2018,40(4):86-91. (in Chinese) [本文引用: 2]
BORDIGAM, LOCATELLIM, TRAVAGLIAF, ARLORIOM, REYNERIA, BLANDINOM, COISSON JD . Alkylresorcinol content in whole grains and pearled fractions of wheat and barley Journal of Cereal Science, 2016,70:38-46. [本文引用: 2]
CHENY, ROSS AB, ?MANP, KAMAL-ELDINA . Alkylresorcinols as markers of whole grain wheat and rye in cereal products Journal of Agricultural and Food Chemistry, 2004,52(26):8242-8246. [本文引用: 2]
LIUJ, HAO YM, WANG ZY, NIF, WANGY, GONG LX, SUN BG, WANGJ . Identification, quantification, and anti-inflammatory activity of 5-n-alkylresorcinols from 21 different wheat varieties Journal of Agricultural and Food Chemistry, 2018,66(35):9241-9247. [本文引用: 1]
ZHANGJ, YAN YF, YANL, ZHAO YX, ZHANG AF, ZHANGZ . Establishment and optimization of high performance liquid chromatography-mass spectrometry/mass spectrometry for the determination of progesterone residues in fresh milk Heilongjiang Animal Science and Veterinary Medicine, 2018 (17):201-204. (in Chinese) [本文引用: 1]
GUO YZ, YANG XM, LI YY . Alkylresorcinols from wheat bran induced autophagy and apoptosis of HepG2 cells Food Science, 2019,41(5):102-107. (in Chinese) [本文引用: 1]
KNODLERM, KAISERA, CARLER, SCHIBERA . Profiling of Alk (en) ylresorcinols in cereals by HPLC-DAD-APcI-MSn Analytical and Bioanalytical Chemistry, 2008,391(1):221. [本文引用: 1]
ZHANG YY, PEIF, FANGY, LIP, ZHAOY, SHENF, ZOU YY, HU QH . Comparison of concentration and health risks of 9 Fusarium mycotoxins in commercial whole wheat flour and refined wheat flour by multi-IAC-HPLC Food Chemistry, 2019,275:763-769. [本文引用: 1]
ROSS AB, SHEPHERD MJ, SCHUPPHAUSM, SINCLAIRV, ALFAROB, KAMAL-ELDINA, AMANP . Alkylresorcinols in Cereals and Cereal Products Journal of Agricultural and Food Chemistry, 2003,51(14):4111-4118. [本文引用: 2]
WIERZBICKAR, WUH, FRANEKM, KAMAL-ELDINA, LANDBERGR . Determination of alkylresorcinols and their metabolites in biological samples by gas chromatography-mass spectrometry Journal of Chromatography B, 2015,1000:120-129. [本文引用: 1]
KNODLERM, BERARDININ, KAMMERER DR, CARLER, SCHIEBERA . Characterization of major and minor alk (en) ylresorcinols from mango ( Mangifera indica L.) peels by high- performance liquid chromatography/atmospheric pressure chemical ionization mass spectrometry Rapid Communications in Mass Spectrometry, 2007,21(6):945-951. [本文引用: 1]
GENGP, HARNLY JM, CHEN PG . Differentiation of whole grain from refined wheat ( T. aestivum) flour using lipid profile of wheat bran, germ, and endosperm with UHPLC-HRAM mass spectrometry Journal of Agricultural and Food Chemistry, 2015,63(27):6189-6211. [本文引用: 1]
GENGP, HARNLY JM, CHEN PG . Differentiation of bread made with whole grain and refined wheat ( T. aestivum) flour using LC/MS-based chromatographic fingerprinting and chemometric approaches Journal of Food Composition and Analysis, 2016,47:92-100. [本文引用: 1]
ANDERSSON A AM, KAMAL-ELDINA, FRASA, BOROSD, AMANP . Alkylresorcinols in wheat varieties in the health grain diversity screen Journal of Agricultural and Food Chemistry, 2008,56(21):9722-9725. [本文引用: 1]
TANB . Thoughts on the definition, labeling and standard system construction of whole grain in China Science and Technology of Food Industry, 2013 (4):1-4. (in Chinese) [本文引用: 1]
ZHAOX, REN CG, CHEN JJ, YU WZ . Main milling processes of whole wheat flour and their merits and demerits analysis Cereals and Oils Processing (Electronic Version), 2014(11):55-57. (in Chinese) [本文引用: 1]
WANG LP, LIUH, TIAN XH, LIU YX, LIUM, CHEN YH, TANB . Research of influence on quality of bran, germ and whole-wheat flour by extrusion processing Science and Technology of Food Industry, 2012,33(16):141-144. (in Chinese) [本文引用: 1]
TANB, TAN HZ, LIUM, TIAN XH, LI AK, LIN JY . The development status and trend of whole grain food at home and abroad Food and Nutrition in China, 2009 (9):4-7. (in Chinese) [本文引用: 1]
LIANGY, LIY, ZHANG LJ, LIU XJ, LU BY . Discussion on the definition and screening method of characteristic quality indicators of edible agricultural products Scientia Agricultura Sinica, 2019,52(18):3155-3162. (in Chinese) [本文引用: 1]
ZHUH, LIANG KH, XU HQ, QIUJ, GUO YZ, HUANG JZ, ZHU DZ, SUN JM . Review and suggestion for nutrition standard of agricultural products in China Scientia Agricultura Sinica, 2019,52(18):3145-3154. (in Chinese) [本文引用: 1]
TANB, TAN HZ, LIUM, TIAN XH, LI AK, LIN JY . Significance and challenges of development of wholegrain foods in China Cereal and Food Industry, 2009,16(4):4-8. (in Chinese) [本文引用: 1]
WANG LP, TANB, TIAN XH, LIU YX, LIUM . Study on quality analysis of whole wheat flour from domestic and foreign market Grain Science and Technology and Economy, 2012,37(6):8-10. (in Chinese) [本文引用: 1]
CHEN JJ, XIET, REN CG, HUAN ML . Application status and prospect of whole wheat flour in food industry in China Cereal & Feed Industry, 2018(7):4-8. (in Chinese) [本文引用: 1]