Теоретическая и прикладная экология1995-43012618-840610.25750/1995-4301-2026-3-065-078OtherРазработка методики одновременного определения жирных и фенольных кислот - ценных вторичных метаболитов плодов рябины (Sorbus L.)Development of a method for the simultaneous determination of fatty and phenolic acids - valuable secondary metabolites of rowan berries (Sorbus L.)ВеберН. Э.VeberN. E.veber.n@ib.komisc.ruhttps://orcid.org/0000-0003-4165-365XГруздевИ. В.GruzdevI. V.https://orcid.org/0000-0002-6693-3925ШевченкоО. Г.ShevchenkoO. G.https://orcid.org/0000-0001-5331-3201СкроцкаяО. В.SkrotskayaO. V.https://orcid.org/0000-0001-8090-1308Institute of Biology of Komi Science Centre of the Ural Branch of the Russian Academy of SciencesSyktyvkarRussiaИнститут биологии Коми научного центра Уральского отделения Российской академии наукСыктывкарРоссия2909202636578http://www.envjournal.ru/arhvr.php?q=1038

Плоды рябины (Sorbus L.) хорошо известны своими питательными и лечебными свойствами, часть из которых напрямую связана с высоким содержанием органических кислот. Антиоксидантная активность плодов рябины ассоциирована с фенолкарбоновыми кислотами, в то время как биологическая ценность её липидного комплекса определяется наличием в составе липидов незаменимых жирных кислот из рядов ω-3 и ω-6. Для раздельного определения высших карбоновых кислот и фенолкислот при их совместном присутствии в растительных материалах разработана экстракционно-хроматографическая методика, при реализации аналитического цикла которой происходит полное отделение соединений этих двух классов органических кислот. Идентификацию и количественное определение кислот проводят газохроматографическими методами с масс-селективным или пламенно-ионизационным детектором (ГХ-МС/ПИД). Апробация методики проведена на плодах разных видов и сортов рода Sorbus, широко представленных в научной коллекции Ботанического сада ИБ ФИЦ Коми НЦ УрО РАН. В экстрактах из плодов рябины методом ГХ-МС было идентифицировано 18 жирных и 7 фенольных кислот. Проведена сравнительная оценка антиоксидантной активности экстрактов плодов рябины различных видов и сортов. Выявлены образцы (S. aucuparia subsp. phuashanensis), сочетающие высокое содержание феруловой и кофейной кислот с выраженной антиоксидантной активностью. Разработанная методика определения органических кислот в растительных материалах может быть рекомендована для сопровождения селекционного процесса и направленного отбора растений для производства фитопрепаратов и биологически активных добавок.

Rowanberry fruits (Sorbus L.) are well known for their nutritional and medicinal properties, some of which are directly related to their high content of organic acids. The antioxidant activity of rowan fruits is associated with phenolic carboxylic acids, while the biological value of their lipid complex is determined by the presence of essential ω-3 and ω-6 fatty acids. An extraction-chromatographic method was developed to separate the higher carboxylic and phenolic acids in plant raw material. This method allows complete separation of these two classes of organic acids during the analytical cycle. The acids identification and quantification are performed using gas chromatography with a mass-selective or flame-ionization detector (GC-MS/FID). The method was tested on the fruits of Sorbus various species and cultivars, which are widely represented in the scientific collection of the Botanical Garden of the Institute of Biology at the Komi Science Centre of the Ural Branch of the Russian Academy of Sciences. Using GC-MS, 18 fatty acids and 7 phenolic acids were identified in the extracts of rowan fruits. A comparative assessment of the antioxidant activity of extracts from rowan fruits of different species and cultivars was carried out. We identify samples (S. aucuparia subsp. pohuashanensis) that combine high content of ferulic and caffeic acids with pronounced antioxidant activity. The developed method for determining organic acids in plant raw material can be recommended for supporting the breeding process and targeted selection of plants for phytopharmaceuticals and dietary supplements production.

жирные кислотыфенольные кислотырябина (Sorbus L.)газовая хроматографияантиоксидантная активностьfatty acidsphenolic acidsSorbus Lgas chromatographyantioxidant activityРабота выполнена в рамках государственного задания «Оценка влияния климатических условий Севера на процессы репродукции ресурсных растений» (№ 125021302139-3).Gabrielyan E.Ts. Rowan trees (Sorbus L.) of Western Asia and the Himalayas. Erevan: Izdatelstvo AN ArmSSR, 1978. 264 p. (in Russian).Zaikonnikova T.I. Arctic flora of the USSR. Leningrad: Nauka, 1984. 118 p. (in Russian).Petrov E.M. Rowan. M.: Selkhozgiz, 1957. 257 p. (in Russian).Komarov V.L. Flora of the USSR. Moskva: Izdatelstvo AN SSSR, 1939. V. 8. 235 p. (in Russian).Tolmachev A.I. Flora of the North-Eastern European part of the USSR. Leningrad: Nauka, 1976. V. 3. 107 p. (in Russian).Sokolov P.D. Plant resources of the USSR. Flowering plants, their chemical composition, and use. Families of Hydrangeaceae – Haloragaceae. Leningrad: Nauka, 1987. 326 p. (in Russian).Fomenko S.E., Kushnerova N.F., Srygin V.G., Drugova E.S., Momot T.V. Chemical composition and biological activity of the rowanberry extract // Chemistry of plant raw material. 2015. V. 2. P. 161–168 (in Russian). doi: 10.14258/jcprm.201502571Ivanova S.V., Shelepova O.V., Kirichenko E.B. Microelement composition of common mountain ash fruits (Sorbus aucuparia L.) // Vestnik of the Orenburg State University. 2005. No. 2S-2(40). P. 9–10 (in Russian).MikulicPetkovsek M., Krska B., Kiprovski B., Veberic R. Bioactive components and antioxidant capacity of fruits from nine Sorbus genotypes // J. Food Sci. 2017. V. 82. No. 3. P. 647–658. doi: 10.1111/1750-3841.13643Farhoosh R., Johnny S., Asnaashari M., Molaahmadibahraseman N., Sharif A. Structure–antioxidant activity relationships of o-hydroxyl, o-methoxy, and alkyl ester derivatives of p-hydroxybenzoic acid // Food Chem. 2016. V. 194. P. 128–134. doi: 10.1016/j.foodchem.2015.08.003Chen J., Yang J., Ma L., Li J., Shahzad N., Kim C.K. Structure–antioxidant activity relationship of methoxy, phenolic hydroxyl, and carboxylic acid groups of phenolic acids // Sci. Rep. 2020. V. 10. No. 1. Article No. 2611. doi: 10.1038/s41598-020-59451-zSaini R.K., Keum Y.-S. Omega-3 and omega-6 polyunsaturated fatty acids: dietary sources, metabolism, and significance – a review // Life Sci. 2018. V. 203. P. 255–267. doi: 10.1016/j.lfs.2018.04.049Vázquez L., Corzo-Martínez M., Arranz-Martínez P., Barroso E., Reglero G., Torres C.F. Bioactive lipids // Bioactive molecules in food / Eds. J.-M. Mérillon, K.G. Ramawat. Cham: Springer, 2019. P. 467–527. doi: 10.1007/978-3-319-78030-6_58Gladyshev M.I. Essential polyunsaturated fatty acids and their dietary sources for man // Journal of Siberian Federal University. Biology. 2012. V. 5. No. 4. P. 352–386 (in Russian).Lobayeva T.A. Study of the composition and content of fatty acids in herbal remedies // RUDN journal of medicine. 2015. No. 2. P. 9–18 (in Russian).Harwood J.L. Recent advances in the biosynthesis of plant fatty acids // Biochim. Biophys. Acta, Lipids Lipid Metab. 1996. V. 1301. No. 1–2. P. 7–56. doi: 10.1016/0005-2760(95)00242-1Arceusz A., Wesolowski M., Konieczynski P. Methods for extraction and determination of phenolic acids in medicinal plants: a review // Nat. Prod. Commun. 2013. V. 8. No. 12. P. 1821–1829. doi: 10.1177/1934578X1300801238Wu Z., Zhang Q., Li N., Pu Y., Wang B., Zhang T. Comparison of critical methods developed for fatty acid analysis: a review // J. Sep. Sci. 2017. V. 40. No. 1. P. 288–298. doi: 10.1002/jssc.201600707Lima-Pereira Y., de Souza E.M.O., dos Reis D.S., Barcellos-Silva I.G.C., Miki K.S.L., Veiga-Júnior V.F., Teixeira-Costa B.E. Current perspectives on the extraction, isolation, and identification of fats and fatty acids using conventional and green methods // Separations. 2025. V. 12. No. 6. Article No. 160. doi: 10.3390/separations12060160Edo G.I., Nwachukwu S.C., Ali A.B.M., Yousif E., Jikah A.N., Zainulabdeen K., Ekokotu H.A., Isoje E.F., Igbuku U.A., Opiti R.A., Akpoghelie P.O., Owheruo J.O., Essaghah A.E.A. A review on the composition, extraction and applications of phenolic compounds // Ecol. Front. 2025. V. 45. No. 1. P. 7–23. doi: 10.1016/j.ecofro.2024.09.008Ruiz-Rodriguez A., Reglero G., Ibañez E. Recent trends in the advanced analysis of bioactive fatty acids // J. Pharm. Biomed. Anal. 2010. V. 51. No. 2. P. 305–326. doi: 10.1016/j.jpba.2009.05.012.Becerra-Herrera M., Lazzoi M.R., Sayago A., Beltrán R., del Sole R., Vasapollo G. Extraction and determination of phenolic compounds in the berries of Sorbus americana Marsh and Lonicera oblongifolia (Goldie) Hook // Food Anal. Methods. 2015. V. 8. No. 10. P. 2554–2559. doi: 10.1007/s12161-015-0151-5Cui H., Zhou J., Xu F., Lai C.Z., Wan G.H. Determination of phenolic compounds using high-performance liquid chromatography with Ce4+-Tween 20 chemiluminescence detection // Anal. Chim. Acta. 2004. V. 511. No. 2. P. 273–279. doi: 10.1016/j.aca.2004.01.046Kivilompolo M., Obůrka V., Hyötyläinen T. Comparison of GC–MS and LC–MS methods for the analysis of antioxidant phenolic acids in herbs // Anal. Bioanal. Chem. 2007. V. 388. No. 4. P. 881–887. doi: 10.1007/ s00216-007-1298-8Simirgiotis M.J., Silva M., Becerra J., SchmedaHirschmann G. Direct characterisation of phenolic antioxidants in infusions from four Mapuche medicinal plants by liquid chromatography with diode array detection (HPLC-DAD) and electrospray ionisation tandem mass spectrometry (HPLC–ESI–MS) // Food Chem. 2012. V. 131. No. 1. P. 318–327. doi: 10.1016/j.foodchem.2011.07.118Ribas-Agustí A., Gratacós-Cubarsí M., Sárraga C., García-Regueiro J.-A., Castellari M. Analysis of eleven phenolic compounds including novel p-coumaroyl derivatives in lettuce (Lactuca sativa L.) by ultra-high-performance liquid chromatography with photodiode array and mass spectrometry detection // Phytochem. Anal. 2011. V. 22. No. 6. P. 555–563. doi: 10.1002/pca.1318Barros L., Dueñas M., Ferreira I.C.F.R., Baptista P., Santos-Buelga C. Phenolic acids determination by HPLC–DAD–ESI/MS in sixteen different Portuguese wild mushrooms species // Food Chem. Toxicol. 2009. V. 47. No. 6. P. 1076–1079. doi: 10.1016/j.fct.2009.01.039Gruzdev I.V., Zenkevich I.G., Kondratenok B.M. Derivatization in gas chromatographic determination of phenol and aniline traces in aqueous media // Russ. Chem. Rev. 2015. V. 84. No. 6. P. 653–664. doi: 10.1070/RCR4553Parkinson D.R. Analytical derivatization techniques // Reference module in chemistry, molecular sciences and chemical engineering. Elsevier, 2014. 38 p. doi: 10.1016/b978-0-12-409547-2.11454-4Moidoveanu S.C., David V. Derivatization reactions for analytes with various functional groups // Journal of chromatography library. Sample preparation in chromatography / Eds. S.C. Moidoveanu, V. David. Elsevier, 2002. V. 65. P. 639–845. doi: 10.1016/S03014770(02)80020-3Smolarz H.D. Application of GC-MS method for analysis of phenolic acids and their esters in chloroformic extracts from some taxons of Polygonum L. genus // Chem. Anal. 2001. V. 46. No. 3. P. 439–444.Citová I., Sladkovský R., Solich P. Analysis of phenolic acids as chloroformate derivatives using solid phase microextraction–gas chromatography // Anal. Chim. Acta. 2006. V. 573–574. P. 231–241. doi: 10.1016/j. aca.2006.04.077Ichihara K., Fukubayashi Y. Preparation of fatty acid methyl esters for gas-liquid chromatography // J. Lipid Res. 2010. V. 51. No. 3. P. 635–640. doi: 10.1194/ jlr.D001065.Ifeanacho M.O., Ikewuchi C.C., Ikewuchi J.C. Investigation of the profile of phenolic compounds in the leaves and stems of Pandiaka heudelotii using gas chromatography coupled with flame ionization detector // Food Sci. Nutr. 2016. V. 5. No. 3. P. 646–652. doi: 10.1002/fsn3.443Schummer C., Delhomme O., Appenzeller B.M.R., Wennig R., Millet M. Comparison of MTBSTFA and BSTFA in derivatization reactions of polar compounds prior to GC/MS analysis // Talanta. 2009. V. 77. No. 4. P. 1473–1482. doi: 10.1016/j.talanta.2008.09.043Young R.F., Coy D.L., Fedorak P.M. Evaluating MTBSTFA derivatization reagents for measuring naphthenic acids by gas chromatography–mass spectrometry // Anal. Methods. 2010. V. 2. No. 6. P. 765–770. doi: 10.1039/c0ay00014kProestos C., Boziaris I.S., Nychas G.-J.E., Komaitis M. Analysis of flavonoids and phenolic acids in Greek aromatic plants: investigation of their antioxidant capacity and antimicrobial activity // Food Chem. 2006. V. 95. No. 4. P. 664–671. doi: 10.1016/j.foodchem.2005.01.049Proestos C., Sereli D., Komaitis M. Determination of phenolic compounds in aromatic plants by RP-HPLC and GC-MS // Food Chem. 2006. V. 95. No. 1. P. 44–52. doi: 10.1016/j.foodchem.2004.12.016Orata F. Derivatization reactions and reagents for gas chromatography analysis // Advanced gas chromatography – progress in agricultural, biomedical and industrial applications / Ed. M.M. Rijeka. IntechOpen, 2012. P. 83–108. doi: 10.5772/33098Özcan M.M., Al Juhaimi F., Ahmed I.A.M., Babiker E.E., Ghafoor K. Antioxidant activity, fatty acid composition, phenolic compounds and mineral contents of stem, leave and fruits of two morphs of wild myrtle plants // Food Measure. 2020. V. 14. No. 3. P. 1376–1382. doi: 10.1007/s11694-020-00387-3Gruzdev I.V., Veber N.E., Skrotskaya O.V. Isolation and determination of phenolic acids in rowanberry fruits (Sorbus L.) by gas chromatography // Analytics and control. 2024. V. 28. No. 2. P. 87–97 (in Russian). doi: 10.15826/analitika.2024.28.2.002Platonova E.Yu., Golubev D.A., Zemskaya N.V., Shevchenko O.G., Patov S.A., Shaposhnikov M.V., Moskalev A.A. The antioxidant and geroprotective properties of an extract of mountain ash (Sorbus aucuparia L.) fruits // Mol. Biol. 2023. V. 57. No. 6. P. 978–992. doi: 10.1134/S0026893323060134Mikhailova D.V., Shevchenko O.G., Golubev D.A., Platonova E.Y., Zemskaya N.V., Shoeva O.Y., Gordeeva E.I., Patov S.A., Shaposhnikov M.V., Khlestkina E.K., Moskalev A.А. Antioxidant properties and geroprotective potential of wheat bran extracts with increased content of anthocyanins // Antioxidants. 2023. V. 12. No. 11. Article No. 2010. doi: 10.3390/antiox12112010Golubev D., Platonova E., Zemskaya N., Shevchenko O., Shaposhnikov Mi., Nekrasova P., Patov S., Ibragimova U., Valuisky N., Borisov A., Zhukova X., Sorokina S., Litvinov R., Moskalev A. Berberis vulgaris L. extract supplementation exerts regulatory effects on the lifespan and healthspan of Drosophila through its antioxidant activity depending on the sex // Biogerontology. 2024. V. 25. No. 3. P. 507–528. doi: 10.1007/s10522023-10083-6Shevchenko O.G. Investigation of certain aspects of the studies of antioxidants in heterogeneous systems, oil-in-water emulsions // Russ. Chem. Bull. 2024. V. 73. No. 12. P. 3471–3486. doi: 10.1007/s11172-024-4464-7Günter E.A., Popeyko O.V., Shevchenko O.G., Vityazev F.V., Modification of texture and in vitro digestion of pectin and κ-carrageenan food hydrogels with antioxidant properties using plant cells // Int. J. Biol. Macromol. 2025. V. 316. Article No. 144682. doi: 10.1016/j.ijbiomac.2025.144682Adaeva О.I., Demchuk D.V., Shevchenko O.G., Semenova M.N., Semenov V.V Apiol from parsley seeds as a source for the synthesis of coenzyme Q0 propanoic acid conjugates with amines featuring antioxidant activity // ACS Omega. 2026. V. 11. No. 18. P. 26195–26205. doi: 10.1021/acsomega.5c09328Sevgi K., Tepe B., Sarikurkcu C. Antioxidant and DNA damage protection potentials of selected phenolic acids // Food Chem. Toxicol. 2015. V. 77. P. 12–21. doi: 10.1016/j.fct.2014.12.006Celik S.E., Ozyürek M., Güçlü K., Apak R. Solvent effects on the antioxidant capacity of lipophilic and hydrophilic antioxidants measured by CUPRAC, ABTS/ persulphate and FRAP methods // Talanta. 2010. V. 81. No. 4–5. P. 1300–1309. doi: 10.1016/j.talanta.2010.02.025Boulebd H., Zine Y., Khodja I.A., Mermer A., Demir A., Debache A. Synthesis and radical scavenging activity of new phenolic hydrazone/hydrazide derivatives: experimental and theoretical studies // J. Mol. Struct. 2022. V. 1249. Article No. 131546. doi: 10.1016/j.molstruc.2021.131546Romera-Castillo C., Jaffé R. Free radical scavenging (antioxidant activity) of natural dissolved organic matter // Mar. Chem. 2015. V. 177. Pt. 4. P. 668–676. doi: 10.1016/j.marchem.2015.10.008Wu C.R., Lin W.H., Hseu Y.C., Lien J.C., Lin Y.T., Kuo T.P., Ching H. Evaluation of the antioxidant activity of five endemic Ligustrum species leaves from Taiwan flora in vitro // Food Chem. 2011. V. 127. No. 2. P. 564–571. doi:10.1016/j.foodchem.2011.01.041.Kim J.S. Preliminary evaluation for comparative antioxidant activity in the water and ethanol extracts of dried citrus fruit (Citrus unshiu) peel using chemical and biochemical in vitro assays // Food Nutr. Sci. 2013. V. 4. No. 2. P. 177–188. doi: 10.4236/fns.2013.42025Stefanello S.T., Prestes A.S., Ogunmoyole T., Salman S.M., Schwab R.S., Brender C.R., Dornelles L., Rocha J.B.T., Soares F.A.A. Evaluation of in vitro antioxidant effect of new mono and diselenides // Toxicol. in Vitro. 2013. V. 27. No. 5. P. 1433–1439. doi: 10.1016/j. tiv.2013.03.001Korenman Ya.I. Extraction of Phenols. Gorkiy: Volgo-Vyatskoe izdatelstvo, 1973. 214 p. (in Russian).Ribeiro C., Ribeiro A.R., Maia A.S., Gonçalves V.M.F., Tiritan M.E. New trends in sample preparation techniques for environmental analysis // Crit. Rev. Anal. Chem. 2014. V. 44. No. 2. P. 142–185. doi: 10.1080/10408347.2013.833850Mokrani A., Madani K. Effect of solvent, time and temperature on the extraction of phenolic compounds and antioxidant capacity of peach (Prunus persica L.) fruit // Sep. Purif. Technol. 2016. V. 162. P. 68–76. doi: 10.1016/j.seppur.2016.01.043Acquavia M.A., Pascale R., Foti L., Carlucci G., Scrano L., Martelli G., Brienza M., Coviello D., Bianco G., Lelario F. Analytical methods for extraction and identification of primary and secondary metabolites of apple (Malus domestica) fruits: a review // Separations. 2021. V. 8. No. 7. Article No. 91. doi: 10.3390/separations8070091Reichardt C., Welton T. Solvents and solvent effects in organic chemistry. Weinheim: John Wiley & Sons, 2011. 718 p.Jia Y., He Y., Lu F. The structure–antioxidant activity relationship of dehydrodiferulates // Food Chem. 2018. V. 269. P. 480–485. doi: 10.1016/j.foodchem.2018.07.038Kikuzaki H., Hisamoto M., Hirose A., Akiyama K., Taniguchi H. Antioxidant properties of ferulic acid and its related compounds // J. Agric. Food Chem. 2002. V. 50. No. 7. P. 2161–2168. doi: 10.1021/jf011348wKiokias S., Proestos C., Oreopoulou V. Phenolic acids of plant origin – a review on their antioxidant activity in vitro (O/W emulsion systems) along with their in vivo health biochemical properties // Foods. 2020. V. 9. No. 4. Article No. 534. doi: 10.3390/foods9040534

Образцы плодов рябины получены из УНУ « Научная коллекция живых растений Ботанического сада Института биологии Коми НЦ УрО РАН» (№ 507428). Определение химического состава образцов проведено на оборудовании ЦКП «Хроматография» (№ 3297). Исследование антиоксидантной активности экстрактов плодов рябины выполнено на базе ЦКП «Молекулярная биология», в работе использованы мыши из научной коллекции экспериментальных животных Института биологии Коми НЦ УрО РАН (https://ckp-rf.ru/usu/471933/).