Ceren ATİLA DİNÇER, Nuray YILDIZ, Ceren GÖKALP, Bengü GETİREN, Atila YILDIZ

Supercritical carbon dioxide extraction of Usnea longissima (L.) Ach.: Optimization by Box-Behnken design (BBD)

Usnic acid (UA) was extracted from Usnea longissima (L.) Ach. in supercritical carbon dioxide $(SC-CO_2 )$ medium. The selected process parameters were extraction temperature (35–45 °C), amount of co-solvent (0%–5%) and extraction time (5–9 h). These parameters were applied to Box-Behnken design (BBD) belonging to response surface methodology (RSM) to determine optimum process parameters for the highest amount of UA in the extract. g UA/100g lichen, extraction yield % and UA content values were calculated in the range of 0.045–0.317, 2.77–5.4 and 71%–82% in different experimental conditions, respectively. The optimum conditions were predicted as 42 °C, 4.3% (ethanol) and 7.48 h. It was determined that the predicted and experimental values of g UA/100g lichen were compatible, and the suggested model was valid.

PDF

___

1. Cocchietto M, Skert N, Nimis PL, Sava G. A review on usnic acid, an interesting natural compound. Naturwissenschaften 2002; 89 (4): 137-146. doi: 10.1007/s00114-002-0305-3
2. Hauck M, Jürgens SR. Usnic acid controls the acidity tolerance of lichens. Environmental Pollution 2008; 156 (1): 115-122. doi: 10.1016/j. envpol.2007.12.033
3. Ingolfsdottir K. Molecules of interest usnic acid. Phytochemistry 2002; 61: 729-736.
4. Oran S, Sahin S, Sahinturk P, Ozturk S, Demir C. Antioxidant and antimicrobial potential, and HPLC analysis of stictic and usnic acids of three Usnea species from Uludag mountain (Bursa, Turkey). Iranian Journal of Pharmaceutical Research 2016; 15: 527-535. doi: 10.22037/ ijpr.2016.1842
5. Fomo G, Madzimbamuto TN, Ojumu TV. Applications of nonconventional green extraction technologies in process industries: challenges, limitations and perspectives, Sustainability 2020; 12 (13): 5244. doi: 10.3390/su12135244
6. Ahangari H, King JW, Ehsani A, Yousefi M. Supercritical fluid extraction of seed oils – A short review of current trends. Trends in Food Science & Technology 2021; 111: 249-260. doi: 10.1016/j.tifs.2021.02.066
7. Arumugham T, Rambabu K, Hasan SW, Show PL, Rinklebe J et al. Supercritical carbon dioxide extraction of plant phytochemicals for biological and environmental applications - A review. Chemosphere 2021; 271: 129525. doi: 10.1016/j.chemosphere.2020.129525
8. Daraee A, Ghoreishi SM, Hedayati A. Supercritical $CO_2$ extraction of chlorogenic acid from sunflower (Helianthus annuus) seed kernels: modeling and optimization by response surface methodology. Journal of Supercritical Fluids 2019; 144: 19-27. doi: 10.1016/j.supflu.2018.10.001
9. Escobedo-Flores Y, Chavez-Flores D, Salmeron I, Molina-Guerrero C et al. Optimization of supercritical fluid extraction of polyphenols from oats (Avena Sativa L.) and their antioxidant activities. Journal of Cereal Science 2018; 80: 198-204. doi: 10.1016/j.jcs.2018.03.002
10. Masghati S, Ghoreishi SM. Supercritical $CO_2$ extraction of cinnamaldehyde and eugenol from cinnamon bark: optimization of operating conditions via response surface methodology. Journal of Supercritical Fluids 2018; 140:62-71. doi: 10.1016/j.supflu.2018.06.002
11. Barzotto ILM, Santos KA, da Silva EA, Sene AC, da Silva NS et al. Supercritical extraction of Eugenia involucrata leaves: Influence of operating conditions on yield and α-tocopherol content. The Journal of Supercritical Fluids 2019; 143: 55-63. doi: 10.1016/j.supflu.2018.08.003
12. Bayrak S, Sökmen M, Aytaç E, Sökmen A. Conventional and supercritical fluid extraction (SFE) of colchicine from Colchicum speciosum. Industrial Crops and Products 2019; 128:80-84. doi: 10.1016/j.indcrop.2018.10.060
13. de Souza ARC, Guedes AR, Rodriguez JMF, Bombardelli MCM, Corazza ML. Extraction of Arctium Lappa leaves using supercritical $CO_2^{+}$ethanol: kinetics, chemical composition, and bioactivity assessments. Journal of Supercritical Fluids 2018; 140: 137-146. doi: 10.1016/j.supflu.2018.06.011
14. Suryawanshi B, Mohanty B. Modeling and optimization: supercritical CO2 extraction of Pongamia pinnata (L.) seed oil. Journal of Environmental Chemical Engineering 2018; 6 (2): 2660-2673. doi: 10.1016/j.jece.2018.04.014
15. Wrona O, Rafińska K, Możeński C, Buszewski B. Supercritical carbon dioxide extraction of Solidago gigantea Ait.: optimization at quarter-technical scale and scale up the process to half-technical plant. Industrial Crops and Products 2019; 130: 316-324. doi: 10.1016/j. indcrop.2018.12.050
16. Kostrzewa D, Dobrzyńska-Inger A, Turczyn A. Optimization of supercritical carbon dioxide extraction of sweet paprika (Capsicum annuum L.) using response surface. Chemical Engineering Research and Design 2020; 160: 39-51. doi: 10.1016/j.cherd.2020.05.005
17. Chaker H, Ameur N, Saidi-Bendahou K, Djennas M, Fourmentin S. Modeling and Box-Behnken design optimization of photocatalytic parameters for efficient removal of dye by lanthanum-doped mesoporous TiO2 . Journal of Environmental Chemical Engineering 2021; 9: 104584. doi: 10.1016/j.jece.2020.104584
18. Khatib I, Chow MY, Ruan J, Cipolla D, Chan HK. Modeling of a spray drying method to produce ciprofloxacin nanocrystals inside the liposomes utilizing a response surface methodology: Box-Behnken experimental design. International Journal of Pharmaceutics 2021; 597: 120277. doi: 10.1016/j.ijpharm.2021.120277
19. Cansaran-Duman D, Aras S, Atakol O. Determination of usnic acid content in some lichen species found in Anatolia. Journal of Applied Biological Sciences 2008; 2: 41-44.
20. Ivanovic J, Meyer F, Misic D, Asanin J, Jaeger P et al. Influence of different pre-treatment methods on isolation of extracts with strong antibacterial activity from lichen Usnea barbata using carbon dioxide as a solvent. Journal of Supercritical Fluids 2013; 76: 1-9. doi: 10.1016/j.supflu.2013.01.005
21. Fanovich MA, Ivanovic J, Misic D, Alvarez MV, Jaeger P et al. Development of polycaprolactone scaffold with antibacterial activity by an integrated supercritical extraction and impregnation process. Journal of Supercritical Fluids 2013; 78: 42-53. doi: 10.1016/j. supflu.2013.03.017
22. Koçer S, Uruş S, Çakır A, Güllüce M, Dığrak M et al. The synthesis, characterization, antimicrobial and antimutagenic activities of hydroxyphenylimino ligands and their metal complexes of usnic acid isolated from Usnea longissima. Journal of the Chemical Society. Dalton Transactions 2014; 43 (16): 6148-6164. doi: 10.1039/C3DT53624F
23. Zugic A, Jeremic I, Isakovic A, Arsic I, Savic S et al. Evaluation of anticancer and antioxidant activity of a commercially available $CO_2$ supercritical extract of old man’s beard (Usnea barbata). PloS One 2016; 11 (1): 0146342. doi: 10.1371/journal.pone.0146342
24. Cansaran D, Çetin D, Halıcı MG, Atakol O. Determination of usnic acid in some Rhizoplaca species from middle anatolia and their antimicrobial activities. Zeitschrift fur Naturforschung - Section C Journal of Biosciences 2006; 61 (1-2): 47-51. doi: 10.1515/znc-2006-1-209
25. Montgomery DC, Runger CR. Applied Statistics and Probability for Engineers. New York, USA: John Wiley & Sons Inc., 2003.
26. Niphadkar SS, Rathod VK. Optimization of ethanol modified supercritical fluid extraction (SFE) of acetyl 11 keto β boswellic acid (AKBA) from Boswellia serrata using Box–Behnken experimental design. Biocatalysis and Agricultural Biotechnology 2018; 13: 304-310. doi : 10.1016/j.bcab.2017.11.013
27. Zeković Z, Pavlić B, Cvetanović A, Đurović S. Supercritical fluid extraction of coriander seeds: process optimization, chemical profile and antioxidant activity of lipid extracts. Industrial Crops and Products 2016; 94: 353-362. doi: 10.1016/j.indcrop.2016.09.008
28. Edwards HGM, Newton EM, Wynn-Williams DD. Molecular structural studies of lichen substances II: atranorin, gyrophoric acid, fumarprotocetraric acid, rhizocarpic acid, calycin, pulvinic dilactone and usnic acid. Journal of Molecular Structure 2003; 651-653: 27-37. doi: 10.1016/S0022-2860(02)00626-9
29. Tabbabi K, Karmous T. Characterization and identification of the components extracted from 28 lichens in Tunisia by high performance thin-layer chromatography (HPTLC), morphologic determination of the species and study of the antibiotic effects of usnic acid. Medicinal & Aromatic Plants 2016; 5 (4): 253. doi: 10.4172/2167-0412.1000253
30. Zizovic I, Ivanovic J, Misic D, Stamenic M, Djordjevic S et al. SFE as a superior technique for isolation of extracts with strong antibacterial activities from lichen Usnea barbata L. Journal of Supercritical Fluids 2012; 72: 7-14. doi: 10.1016/j.supflu.2012.07.018
31. Brovko OS, Ivankhnov AD, Palamarchuk IA, Boitsova TA. Supercritical fluid extraction of usnic acid from lichen of Cladonia genus. Russian Journal of Physical Chemistry B 2017; 11 (8): 1306-1311. doi: 10.1134/S1990793117080024
32. Algan Cavuldak Ö, Vural N, Akay MA, Anlı RE. Optimization of ultrasound-assisted water extraction conditions for the extraction of phenolic compounds from black mulberry leaves (Morus nigra L.). Journal of Food Process Engineering 2019; 42 (5): 1-15. doi: 10.1111/ jfpe.13132
33. Alexandre AMRC, Serra AT, Matias AA, Duarte CMM, Bronze MR. Supercritical fluid extraction of Arbutus unedo distillate residues– Impact of process conditions on antiproliferative response of extracts. Journal of CO2 Utilization 2020; 37:29-38. doi:10.1016/j. jcou.2019.11.002
34. Al-Suod H, Ratiu IA, Krakowska-Sieprawska A, Lahuta L, Górecki R et al. Supercritical fluid extraction in isolation of cyclitols and sugars from chamomile flowers. Journal of Separation Science 2019; 42 (20): 3243-3252. doi: 10.1002/jssc.201900539
35. Peng WL, Mohd-Nasir H, Setapar SHM, Ahmad A, Lokhat D. Optimization of process variables using response surface methodology for tocopherol extraction from Roselle seed oil by supercritical carbon dioxide. Industrial Crops and Products 2020; 143: 111886. doi: 10.1016/j.indcrop.2019.111886