Mathematical planning of experiments to optimize the extraction of extractive substances from needles of Pinus sylvestris

The presented work is devoted to the determination of the optimal conditions for the isolation of the sum of extractives from wood greenery (WG) of Pinus sylvestris by the method of emulsion extraction. The environmentally friendly emulsion method for the extraction of plant raw materials in an aqueous-alkaline medium is not inferior to the traditional methods of extracting low molecular weight components and makes it possible to effectively isolate both hydrophilic and hydrophobic compounds. The object of this study is logging waste – woody greenery of Pinus sylvestris – a source of natural biologically active substances that have practical application. The determination of the optimal conditions for the extraction of WG pine by the emulsion method in this study was carried out by the response surface method using a rotatable compositional uniform plan of the second order, which included 13 experiments with all possible combinations of the levels of two studied factors: the concentration of an aqueous solution of NaOH and the hydromodule – ratio of the volume of water-alkaline solution to the mass of raw materials. Analysis of the research results showed that in a given range of variation of factors, the greatest influence on the yield of extractive substances is exerted by the hydromodule, with an increase of which to 10: 1, the yield increases, then an equilibrium concentration is established in the "raw material – extractant" system. The optimal conditions for emulsion extraction of WG pine were established: concentration of an aqueous solution of NaOH – 5%, hydromodule 10:1. Under optimal conditions, the yield of extractive substances was 9,84% of the weight of the dry raw material, which is comparable with the results obtained by traditional methods of raw material extraction with organic solvents.

1. Anashenkov S.Ju., Roshhin V.I., Chernyshova O.A. Vodno-shhelochnaja jekstrakcija drevesnoj zeleni. I. Vlijanie konstruktivnyh osobennostej jekstraktorarotorno-pul'sacionnogo tipa i gidromodulja na vyhod jekstraktivnyh veshhestv. Himija rastitel'nogo syr'ja, 2008, no. 3, pp. 65–70. (In Russ.)

2. Arrabal Carlos, Concepcion Garcia-Vallejo Maria, Cadahia Estrella, Manuel Cortijo. Seasonal variations of lipophilic compounds in needles of two chemotypes of Pinus pinaster. Plant Syst Evol., 2014, pp. 359–367. URL: https://doi.org/10.1007/s00606-013-0888-5.

3. Bogdanovich N.I., Kuznecova L.N., Tret'jakov S.I., Zhabin V.I. Planirovanie jeksperimenta v primerah i raschetah: uchebnoe posobie. [Planning an experiment in examples and calculations: a tutorial]. Arhangel'sk: AGTU, 2010. 126 p. (In Russ.)

4. Chemat F., Vian M.A., & Cravotto G. Green extraction of natural products: Concept and principles. International Journal of Molecules Sciences, 2012, no. 13, pp. 8615–8627. URL: https://doi.org/10.3390/ijms13078615.

5. Hou K., Bao M., Wang L., Zhang H., Yang L., Zhao H., & Wang Z. Aqueous enzymatic pretreatment ionic liquid–lithium salt based microwave–assisted extraction of essential oil and procyanidins from pinecones of Pinus koraiensis. Journal of Cleaner Production, 2019, vol. 236, pp. 1–13. URL: https://doi.org/10.1016/j.jclepro.2019.07.056.

6. Hurshkajnen T.V., Skripova N.N., Kuchin A.V. Sravnitel'naja ocenka jekstrakcionnogo oborudovanija dlja jeffektivnogo vydelenija jekstraktivnyh veshhestv hvojnoj drevesnoj zeleni. Teoreticheskaja i prikladnaja jekologija, 2017, no. 1, pp. 25–30. (In Russ.)

7. Karmanova L.P., Kuchin A.V., Koroljova A.A., Hurshkajnen T.V., Kuchin V.A. Jekstrakcija vodnym rastvorom osnovanija kak osnova novoj tehnologii poluchenija fungicidov i stimuljatorov rosta rastenij. Himija i komp'juternoe modelirovanie. Butlerovskie soobshhenija, 2002, no. 7, pp. 61–64. (In Russ.)

8. Kilic A., Hafizoglu H., Dönmez I.E., Tümen I., Sivrikaya H., Reunanen M., Hemming J. HolzalsRoh- und Werkstoff. Extractives in the cones of Pinus species. Eur. J. Wood Prod., 2011, vol. 69, no. 1, pp. 37–40. https://doi.org/10.1007/s00107-010-0421-2.

9. Kolesnikov A.L. Tehnicheskij analiz produktov organicheskogo sinteza. M.: Vysshaja shkola, 1966, p.22. (In Russ.)

10. Kuchin A.V., Karmanova L.P., Koroljova A.A., Hurshkajnen T.V., Sychjov R.L. Patent № 2298327 Rossijskaja Federacija, MPK A01N 65/00 (2006.01), A01P 21/00, A01P 3/00 Reguljator rosta rastenij s fungicidnym dejstviem «Vjerva» : № 2006101648/04 : zajavl. 20.01.2006 : opubl. 10.05.2007. 10 p. (In Russ.)

11. Kuchin A.V., Karmanova L.P., Koroljova A.A., Hurshkajnen T.V., Sychjov R.L. Patent № 2117487 Rossijskaja Federacija, MPK A61K 35/78 (1995.01) Jemul'sionnyj sposob vydelenija lipidov : № 96120436/14 : zajavl. 04.10.1996 : opubl. 20.08.1998. 3 p. (In Russ.)

12. Levin B.D., Fedjulin A.S. Vlijanie gidromodulja na vyhod biologicheski aktivnyh veshhestv. Vestnik KrasGAU, 2006, no. 2, pp. 266–269. (In Russ.)

13. Metsamuuronen Sari., Heli Sire´n. Bioactive phenolic compounds, metabolism and properties: a review on valuable chemical compounds in Scots pine and Norway spruce. Phytochemistry Reviews, 2019, no. 18(3), pp. 623–664. URL: https://doi.org/10.1007/s11101-019-09630-2.

14. Mihajlov K.L., Gushhin V.A., Tarakanov A.M. Organizacija sbora i pererabotki lesosechnyh othodov i drov na lesoseke. Izvestija vysshih uchebnyh zavedenij. Lesnoj zhurnal, 2016, no. 4, p. 98. DOI: 10.17238/issn0536-1036.20 16.6.98. (In Russ.)

15. Oliveira dos Santos A., Izumi E., Ueda-Nakamura T., Prado Dias-Filho B., Valdir Florencio da Veiga-Junior, Celso Vataru Nakamura. Antileishmanial activity of diterpene acids in copaiba oil. Mem Inst Oswaldo Cruz, 2013, vol. 108, pp. 59–64. URL: https://doi.org/10.1590/S0074-02762013000100010.

16. Permjakova G.V., Loskutov S.R., Semenovich A.V. Jekstrakcija kory hvojnyh vodoj s dobavleniem monojetanolamina. Himija rastitel'nogo syr'ja, 2008, no. 1, pp. 37–40. (In Russ.)

17. Ponomarev V.O. Jekstragirovanie lekarstvennogo syr'ja. M., 1976, p. 73. (In Russ.)

18. Repjah S.M., Ushanova V.M., Ushanov V.S., Ushanov S.V. Zakonomernosti izmenenija sostava drevesnoj zeleni hvojnyh ot diametra pobegov. Himija rastitel'nogo syr'ja, 2000, no. 1, pp. 37–42. (In Russ.)

19. Rombaut N., Tixier A.-S., Bily A., Chemat F. Green extraction processes of natural products as tools for biorefinery. Biofuels, Bioproducts and Biorefining, 2014, no. 8, pp. 530–544. URL: https://doi.org/10.1002/bbb.1486

20. Roshhin V.I., Kolodynskaja L.A., Pavluckaja I.S., Solov'ev V.A., Nagibina N.Ju., Vasil'ev S.N. Patent № SU 1650681 MPK C09F 1/00(2006.01), C11B 1/10(2006.01) Sposob pererabotki sosnovoj drevesnoj zeleni : no. 4432710 : zajavl. 15.03.1988 : opubl. 23.05. 1991. 4 p. (In Russ.)

21. Roshhin V.I., Sultanov V.S. Patent № 2238291 Rossijskaja Federacija, MPK C 09F 1/00, C 11B 1/10 Sposob pererabotki rastitel'nogo syr'ja : no. 2003117227/04 : zajavl. 06.06.2003 : opubl. : 20.10.2004. 14p. (In Russ.)

22. Routa Johanna, Brännström Hanna, Hellström Jarkko, Laitila Juha. Influence of storage on the physical and chemical properties of Scots pine bark. BioEnergy Research. PagesAhead of Print, 2020. URL: https://doi.org/10.1007/s12155-020-10206-8

23. Sultanov V.S., Kuljashova L.B., Nikitina T.V. Patent № 2677686 Rossijskaja Federacija, MPK A61K 36/15(2006.01), A61K 31/00(2006.01), A61P 13/00(2006.01)

24. Lekarstvennoe sredstvo, farmacevticheskaja kompozicija, sposob lechenija urogenital'nyh zabolevanij organizma cheloveka, vyzvannyh mikroorganizmami vida Ureaplasma urealyticum: no. 2017141869 : zajavl. 30.11.2017: opubl. 21.01.2019. 16 p. (In Russ.)

25. Tanaka R., Tokuda H., Ezaki Y. Cancer chemopreventive activity of “rosin” constuents of Pinus spez. and their derivatives in two-stage mouse skin carcinogenesis test. Phytomedicine, 2008, no. 15, pp. 985–992. URL: https://doi.org/10.1016/j.phymed.2008.02.020.

26. Teng Jie, Zhang Rong, Zhang Yan-Wen, Hong-Quan Duan and Yoshihisa Takaishi. A new labdanic norditerpene from Pinus sylvestris. Natural Product Research, 2010, vol. 24, pp. 1587–1591. DOI: 10.1080/14786410802696684.

27. Tjul'kova Ju. A., Rjazanova T. V., Eremenko O. N., Ushanov S. V. Modelirovanie processa jekstrakcii kory sosny vodno-shhelochnym rastvorom. Zhurnal sibirskogo federal'nogo universiteta. Serija: Himija, 2013, no. 6(3), pp. 321–327. (In Russ.)

28. Tranquilino-Rodriguez E., Martinez-Flores H.E., Rodiles-Lopez J.O. Optimization in the extraction of polyphenolic compounds and antioxidant activity from Opuntia ficus-indica using response surface methodology. Journal of Food Processing and Preservation, 2020, no. 44(6). URL: https://doi.org/10.1111/jfpp.14485

29. Ucar M.B., Ucar G. Lipophilic extractives and main components of black pine cones. Chemistry of Natural Compounds, 2008, vol. 44, no. 3, pp. 380–383. https://doi.org/10.1007/s10600-008-9071-6.

30. Ushanova V.M., Chencova L.I., Gorchakovskij V.K. Vlijanie vida jekstragenta na kolichestvennyj i kachestvennyj sostav jekstraktov, poluchaemyh iz kory hvojnyh. Izvestija vysshih uchebnyh zavedenij. Serija: Himija i himicheskaja tehnologija, 2006, vol. 49, no. 6, pp. 82-87. (In Russ.)

31. Vasil'ev S.N., Roshhin V.I., Jagodin V.I. Jekstraktivnye veshhestva drevesnoj zeleni Pinus Sylvrstris L. Rastitel'nye resursy, 1995, vol. 31, B.2, pp. 79–119. (In Russ.)

32. Venkatesan T., Choi Y.-W., & Kim Y.-K. Impact of Different Extraction Solvents on Phenolic Content and Antioxidant Potential of Pinus densiflora Bark Extract. BioMed Research International, 2019, pp. 1–14. URL: https://doi.org/10.1155/2019/3520675.

33. Yim H.S., Chye F.Y., Koo S.M., Matanjun P., How S.E., & Ho C.W. Optimization of extraction time and temperature for antioxidant activity of edible wild mushroom Pleurotus porrigens. Food and Bioproducts Processing, 2012, no. 2, pp. 235–242. URL: https://doi.org/10.1016/j. fbp.2011.04.001