Determination of Limonene Chirality in Oils Obtained from Different Types of Citrus Waste Peels in Türkiye

Year 2024, , 453 - 460, 15.05.2024

Barış Güzel , Oltan Canlı , Beyza Yüce , Selda Murat Hocaoglu

https://doi.org/10.18596/jotcsa.1363425

Cited By: 1

Abstract

Limonene constitutes a significant amount in citrus oils. It has a chiral structure and has two different optically active isomers, R-limonene and S-limonene, which are symmetrical to each other. Determining the chiral configurations of limonene plays an important role in determining the beneficial use areas of essential oils. Citrus oils are used in a wide variety of industrial areas, depending on their limonene content. This paper presents the analytical method optimization, validation, and chirality studies of limonene in the citrus oils acquired from different citrus waste peels in Türkiye. An inlet temperature of 250 °C and an injection volume of 2 µL were decided as the optimal conditions for the most accurate measurement of both limonenes in the citrus oil. This method produced results for linearity, sensitivity (LODs and LOQs), repeatability, and reproducibility that were acceptable within the scope of the validation studies. The chirality of limonene was investigated in twenty-six citrus oils (fifteen orange oils, six lemon oils, four mandarin oils, and one grapefruit oil) in Türkiye. While the content of R-limonene in orange oil varied between 56.39% and 72.85%, the content of S-limonene changed from 2.53% to 5.71%. Whereas the constituent of R-limonene in lemon oils ranged from 54.73% to 73.99%, the content of S-limonene varied between 3.78-4.79%. In mandarin oils, the content of R-limonene was determined to be 58.02% and 65.05%, while the content of S-limonene was found as 3.05% and 4.87%. In single grapefruit oil, R-limonene content was 60.69% and S-limonene content was 3.12%.

Keywords

Chirality, Citrus peel, Essential oil, Gas Chromatography, Mass Spectrometry, Limonene

Supporting Institution

TÜBİTAK

Project Number

220N255

Thanks

This work was performed within the development of a process for the production of a bio-based two-component epoxy resin from renewable raw materials project - CORNET multi-collaboration programme, funded by TUBITAK with Project Number: 220N255

References

• 1. Pourbafrani M, Forgács G, Horváth IS, Niklasson C, Taherzadeh MJ. Production of biofuels, limonene and pectin from citrus wastes. Bioresour Technol [Internet]. 2010 Jun;101(11):4246–50. Available from: <URL>.
• 2. Ciriminna R, Lomeli-Rodriguez M, Demma Carà P, Lopez-Sanchez JA, Pagliaro M. Limonene: a versatile chemical of the bioeconomy. Chem Commun [Internet]. 2014;50(97):15288–96. Available from: <URL>.
• 3. Siddiqui SA, Pahmeyer MJ, Assadpour E, Jafari SM. Extraction and purification of d-limonene from orange peel wastes: Recent advances. Ind Crops Prod [Internet]. 2022 Mar;177:114484. Available from: <URL>.
• 4. Wei F, Xu Y, Guo Y, Liu S, Wang H. Quantitative Surface Chirality Detection with Sum Frequency Generation Vibrational Spectroscopy: Twin Polarization Angle Approach. Chinese J Chem Phys [Internet]. 2009 Dec 1;22(6):592–600. Available from: <URL>.
• 5. Friedman L, Miller JG. Odor Incongruity and Chirality. Science (80- ) [Internet]. 1971 Jun 4;172(3987):1044–6. Available from: <URL>.
• 6. Boelens MH, Boelens H, Van Gemert LJ. Sensory properties of optical isomers. Perfum Flavorist [Internet]. 1993;18(6):1–16. Available from: <URL>.
• 7. Chaudhary S, Siddiqui M, Athar M, Alam MS. D-Limonene modulates inflammation, oxidative stress and Ras-ERK pathway to inhibit murine skin tumorigenesis. Hum Exp Toxicol [Internet]. 2012 Aug 8;31(8):798–811. Available from: <URL>.
• 8. Hakim IA, Harris RB, Ritenbaugh C. Citrus Peel Use Is Associated With Reduced Risk of Squamous Cell Carcinoma of the Skin. Nutr Cancer [Internet]. 2000 Jul 18;37(2):161–8. Available from: <URL>.
• 9. Lu X-G, Zhan L-B, Feng B-A, Qu M-Y, Yu L-H, Xie J-H. Inhibition of growth and metastasis of human gastric cancer implanted in nude mice by d -limonene. World J Gastroenterol [Internet]. 2004;10(14):2140–4. Available from: <URL>.
• 10. Hirota R, Roger NN, Nakamura H, Song H, Sawamura M, Suganuma N. Anti‐inflammatory Effects of Limonene from Yuzu ( Citrus junos Tanaka) Essential Oil on Eosinophils. J Food Sci [Internet]. 2010 Apr 5;75(3):H87–92. Available from: <URL>.
• 11. Rufino AT, Ribeiro M, Sousa C, Judas F, Salgueiro L, Cavaleiro C, et al. Evaluation of the anti-inflammatory, anti-catabolic and pro-anabolic effects of E-caryophyllene, myrcene and limonene in a cell model of osteoarthritis. Eur J Pharmacol [Internet]. 2015 Mar;750:141–50. Available from: <URL>.
• 12. Yoon W-J, Lee NH, Hyun C-G. Limonene Suppresses Lipopolysaccharide-Induced Production of Nitric Oxide, Prostaglandin E2, and Pro-inflammatory Cytokines in RAW 264.7 Macrophages. J Oleo Sci [Internet]. 2010;59(8):415–21. Available from: <URL>.
• 13. Yu L, Yan J, Sun Z. D-limonene exhibits anti-inflammatory and antioxidant properties in an ulcerative colitis rat model via regulation of iNOS, COX-2, PGE2 and ERK signaling pathways. Mol Med Rep [Internet]. 2017 Mar;15(4):2339–46. Available from: <URL>.
• 14. Pizzino G, Irrera N, Cucinotta M, Pallio G, Mannino F, Arcoraci V, et al. Oxidative Stress: Harms and Benefits for Human Health. Oxid Med Cell Longev [Internet]. 2017;2017:8416763. Available from: <URL>.
• 15. Mizrahi B, Shapira L, Domb AJ, Houri‐Haddad Y. Citrus Oil and MgCl2 as Antibacterial and Anti‐Inflammatory Agents. J Periodontol [Internet]. 2006 Jun;77(6):963–8. Available from: <URL>.
• 16. Naveed R, Hussain I, Tawab A, Tariq M, Rahman M, Hameed S, et al. Antimicrobial activity of the bioactive components of essential oils from Pakistani spices against Salmonella and other multi-drug resistant bacteria. BMC Complement Altern Med [Internet]. 2013 Dec 14;13(1):265. Available from: <URL>.
• 17. Asikin Y, Shimizu K, Iwasaki H, Oku H, Wada K. Stress amelioration and anti-inflammatory potential of Shiikuwasha (Citrus depressa Hayata) essential oil, limonene, and γ-terpinene. J Food Drug Anal [Internet]. 2022 Sep 14;30(3):454–65. Available from: <URL>.
• 18. Eddin LB, Jha NK, Meeran MFN, Kesari KK, Beiram R, Ojha S. Neuroprotective Potential of Limonene and Limonene Containing Natural Products. Molecules [Internet]. 2021 Jul 27;26(15):4535. Available from: <URL>.
• 19. Güzel B, Canlı O, Murat Hocaoğlu S. Method development and validation for accurate and sensitive determination of terpenes in bio-based (citrus) oils by single quadrupole gas chromatography-mass spectrometry (GC/MS). Microchem J [Internet]. 2023 Aug;191:108903. Available from: <URL>.
• 20. Bernart MW. Ultra-High Performance Liquid Chromatography (UHPLC) Method for the Determination of Limonene in Sweet Orange (Citrus sinensis) Oil: Implications for Limonene Stability. J AOAC Int [Internet]. 2015 Jan 1;98(1):94–7. Available from: <URL>.
• 21. Agatonovic-Kustrin S, Ristivojevic P, Gegechkori V, Litvinova TM, W. Morton D. Essential Oil Quality and Purity Evaluation via FT-IR Spectroscopy and Pattern Recognition Techniques. Appl Sci [Internet]. 2020 Oct 19;10(20):7294. Available from: <URL>.
• 22. Marti G, Boccard J, Mehl F, Debrus B, Marcourt L, Merle P, et al. Comprehensive profiling and marker identification in non-volatile citrus oil residues by mass spectrometry and nuclear magnetic resonance. Food Chem [Internet]. 2014 May;150:235–45. Available from: <URL>.
• 23. Magnusson B, Örnemark U. Eurachem Guide: The Fitness forPurpose of Analytical Methods – A Laboratory Guide to Method Validation and Related Topics. 2014; Available from: <URL>.
• 24. AOAC. Guidelines for Standard Method Performance Requirements Appendix F. 2016; Available from: <URL>.
• 25. Al-Alam J, Baroudi F, Chbani A, Fajloun Z, Millet M. A multiresidue method for the analysis of pesticides, polycyclic aromatic hydrocarbons, and polychlorinated biphenyls in snails used as environmental biomonitors. J Chromatogr A [Internet]. 2020 Jun;1621:461006. Available from: <URL>.
• 26. Canlı O, Oktem Olgun E, Güzel B, Kaplan M. Sensitive and accurate determination of 168 micropollutants including pharmaceuticals and pesticides in surface water and wastewater samples with direct injection using jet stream ESI LC-MS/MS. Int J Environ Anal Chem [Internet]. 2022 Mar 23;(Article in Press):1–27. Available from: <URL>.
• 27. Canlı O, Güzel B, Çetintürk K. Determination of Ethylenediaminetetraacetic acid (EDTA) levels in surface waters by high performance liquid chromatography (HPLC)-Ultraviolet/Visible (UV/VIS) detector. Turkish J Anal Chem [Internet]. 2022 Dec 29;4(2):76–9. Available from: <URL>.
• 28. Güzel B, Canlı O, Öktem Olgun E. Gas Chromatography Method Validation Study for Sensitive and Accurate Determination of Volatile Aromatic Hydrocarbons (VAHs) in Water. Cumhur Sci J [Internet]. 2018 Dec 24;39(4):970–82. Available from: <URL>.
• 29. Güzel B. Method validation for the sensitive and simultaneous detection of fifty-five volatile organic compounds (VOCs) with human health hazards in environmental waters. In: Çoğun HY, Parlar İ, Üzmuş H, editors. Current Debates on Natural and Engineering Sciences 9 [Internet]. Bilgin Kültür Sanat Yayınları; 2023. p. 456–74. Available from: <URL>.
• 30. de Souza SVC, Junqueira RG. A procedure to assess linearity by ordinary least squares method. Anal Chim Acta [Internet]. 2005 Nov;552(1–2):25–35. Available from: <URL>.
• 31. Giese MW, Lewis MA, Giese L, Smith KM. Method for the Analysis of Cannabinoids and Terpenes in Cannabis. J AOAC Int [Internet]. 2015 Nov 1;98(6):1503–22. Available from: <URL>.
• 32. Nguyen T-D, Riordan-Short S, Dang T-TT, O’Brien R, Noestheden M. Quantitation of Select Terpenes/Terpenoids and Nicotine Using Gas Chromatography–Mass Spectrometry with High-Temperature Headspace Sampling. ACS Omega [Internet]. 2020 Mar 17;5(10):5565–73. Available from: <URL>.
• 33. Ponce-Rodríguez HD, Herráez-Hernández R, Verdú-Andrés J, Campíns-Falcó P. Quantitative Analysis of Terpenic Compounds in Microsamples of Resins by Capillary Liquid Chromatography. Molecules [Internet]. 2019 Nov 10;24(22):4068. Available from: <URL>.
• 34. Huang C, Bian C, Wang L, Zhou W, Li Y, Li B. Development and validation of a method for determining d-limonene and its oxidation products in vegetables and soil using GC–MS. Microchem J [Internet]. 2022 Aug;179:107470. Available from: <URL>.
• 35. Sayed R, Hussein OE, Omran AA. Method optimization and validation for the determination of mancozeb in chamomile by modified QuEChERS and liquid chromatography–tandem mass spectrometry. J Food Compos Anal [Internet]. 2022 Aug;111:104646. Available from: <URL>.
• 36. Ibrahim E, Wang M, Radwan M, Wanas A, Majumdar C, Avula B, et al. Analysis of Terpenes in Cannabis sativa L. Using GC/MS: Method Development, Validation, and Application. Planta Med [Internet]. 2019 Mar 15;85(05):431–8. Available from: <URL>.
• 37. Emberger ME, Lin J, Pika J, Christ I, Eigenbrodt B. Automated Solid‐Phase Microextraction GC-MS/MS Method for Quantification of Volatile Limonene Oxidation Products in Encapsulated Orange Oil. Flavour Fragr J [Internet]. 2019 Jan 5;34(1):52–62. Available from: <URL>.
• 38. Marine SS, Clemons J. Determination of Limonene Oxidation Products Using SPME and GC-MS. J Chromatogr Sci [Internet]. 2003 Jan 1;41(1):31–5. Available from: <URL>.