Methoxylated Flavonols and ent-Kaurane Diterpenes from the South African Helichrysum rutilans and Their Cosmetic Potential
Abstract
:1. Introduction
2. Materials and Methods
2.1. Reagents and Organic Solvents
2.2. Preparation of Plant Extracts
2.3. Extraction and Purification of Chemical Constituents
2.4. Antioxidant and Biological Characterization
2.4.1. Ferric-Ion-Reducing Antioxidant Power (FRAP) Assay
2.4.2. Automated Oxygen Radical Absorbance Capacity (ORAC) Assay
2.4.3. Trolox Equivalent Absorbance Capacity (TEAC) Assay
2.4.4. Inhibition of Fe (II)-Induced Microsomal Lipid Peroxidation Assay
2.4.5. Tyrosinase Enzyme Assay
2.4.6. Elastase Inhibition Assay
2.5. Statistical Analysis
3. Results
3.1. Spectroscopic Measurements
3.2. Total Antioxidant Capacities
3.3. Skin Enzyme Inhibitory Activities
4. Discussion
5. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
- Banjarnahor, S.D.S.; Artanti, N. Antioxidant properties of flavonoids. Med. J. Indones. 2014, 23, 239–244. [Google Scholar] [CrossRef] [Green Version]
- Fisher, G.J.; Wang, Z.; Datta, S.C.; Varani, J.; Kang, S.; Voorhees, J.J. Pathophysiology of Premature Skin Aging Induced by Ultraviolet Light. N. Engl. J. Med. 1997, 337, 1419–1429. [Google Scholar] [CrossRef] [PubMed]
- Barmaverain, D.; Hasler, S.; Kalbermatten, C.; Plath, M.; Kalbermatten, R. Oxidation during Fresh Plant Processing: A Race against Time. Processes 2022, 10, 1335. [Google Scholar] [CrossRef]
- Zemour, K.; Labdelli, A.; Adda, A.; Dellal, A.; Talou, T.; Merah, O. Phenol Content and Antioxidant and Antiaging Activity of Safflower Seed Oil (Carthamus Tinctorius L.). Cosmetics 2019, 6, 55. [Google Scholar] [CrossRef] [Green Version]
- Wang, X.; Ding, G.; Liu, B.; Wang, Q. Flavonoids and antioxidant activity of rare and endangered fern: Isoetes sinensis. PLoS ONE 2020, 15, e0232185. [Google Scholar] [CrossRef]
- Panche, A.N.; Diwan, A.D.; Chandra, S.R. Flavonoids: An overview. J. Nutr. Sci. 2016, 5, e47. [Google Scholar] [CrossRef] [Green Version]
- Quan, V.V.; Nguyen, M.T.; Le, T.H.; Mai, V.B.; Nguyen, M.T.; Trinh, L.H.; Nguyen, T.H.; Adam, M. The Antioxidant Activity of Natural Diterpenes, Theoretical Insights. R. Soc. Chem. 2020, 10, 14937–14943. [Google Scholar] [CrossRef]
- Nagarajan, A.; Brindha, P. Diterpenes—A Review on Therapeutic Uses with Special Emphasis on Antidiabetic Activity. J. Pharm. Res. 2012, 5, 4530–4540. [Google Scholar]
- POWO. Plants of the World Online. Facilitated by the Royal Botanical Gardens, Kew. Available online: http://www.plantoftheworldonline.org (accessed on 8 July 2023).
- Popoola, O.K. Chemical and Biological Characterization of South African Helichrysum Species. Ph.D. Thesis, University of the Western Cape, Cape Town, South Africa, 2015; pp. 82–238. [Google Scholar]
- Benzie, I.F.F.; Strain, J.J. The ferric reducing ability of plasma (FRAP) as a measure of “antioxidant power”: The FRAP assay. Anal. Biochem. 1996, 239, 70–76. [Google Scholar] [CrossRef] [Green Version]
- Prior, R.L.; Hoang, H.A.; Gu, L.; Wu, X.; Bacchiocca, M.; Howard, L.; Hampsch-Woodill, M.; Huang, D.; Ou, B.; Jacob, R. Assays for Hydrophilic and Lipophilic Antioxidant Capacity (oxygen radical absorbance capacity (ORACFL)) of Plasma and Other Biological and Food Samples. J. Agric. Food Chem. 2003, 51, 3273–3279. [Google Scholar] [CrossRef]
- Cao, G.; Sofic, E.; Prior, R.L. Antioxidant and Prooxidant Behavior of Flavonoids: Structure-Activity Relationships. Free Radic. Biol. Med. 1997, 22, 749–760. [Google Scholar] [CrossRef] [PubMed]
- Cao, G.; Prior, R.L. Measurement of oxygen radical absorbance capacity in biological samples. Methods Enzymol. 1998, 299, 50–62. [Google Scholar] [CrossRef]
- Fellegrini, N.; Ke, R.; Yang, M.; Rice-Evans, C. Screening of dietary carotenoids and carotenoid-rich fruit extracts for antioxidant activities applying 2,2′-azinobis(3-ethylenebenzothiazoline-6-sulfonic acid radical cation decolorization assay. Meth. Enzymol. 1999, 299, 379–389. [Google Scholar]
- Re, R.; Pellegrini, N.; Proteggente, A.; Pannala, A.; Yang, M.; Rice-Evans, C. Antioxidant activity applying an improved ABTS radical cation decolorization assay. Free Radic. Biol. Med. 1999, 26, 1231–1237. [Google Scholar] [CrossRef]
- Snijman, P.W.; Joubert, E.; Ferreira, D.; Li, X.-C.; Ding, Y.; Green, I.R.; Gelderblom, W.C.A. Antioxidant Activity of the Dihydrochalcones Aspalathin and Nothofagin and Their Corresponding Flavones in Relation to Other Rooibos (Aspalathus linearis) Flavonoids, Epigallocatechin Gallate, and Trolox. J. Agric. Chem. 2009, 57, 6678–6684. [Google Scholar] [CrossRef] [PubMed]
- Chompoo, J.; Upadhyay, A.; Fukuta, M.; Tawata, S. Effect of Alpinia zerumbet components on antioxidant and skin diseases-related enzymes. BMC Complement. Altern. Med. 2012, 12, 106. [Google Scholar] [CrossRef] [Green Version]
- Vardhan, A.; Khan, S.; Pandey, B. Screening of Plant Parts for Anti-tyrosinase Activity by Tyrosinase Assay using Mushroom Tyrosinase. Indian J. Sci. Res. 2014, 4, 134–139. [Google Scholar]
- Urzúa, A.; Mendoza, L.; Tojo, E.; Rial, M.E. Acylated Flavonoids from Pseudognaphalium Species. J. Nat. Prod. 1999, 62, 381–382. [Google Scholar] [CrossRef] [PubMed]
- Tomás-Lorente, F.; Iniesta-Sanmartín, E.; Tomás-Barberán, F.A.; Trowitzsch-Kienast, W.; Wray, V. Antifungal phloroglucinol derivatives and lipophilic flavonoids from Helichrysum decumbens. Phytochemistry 1989, 28, 1613–1615. [Google Scholar] [CrossRef]
- Jakupovic, J.; Kuhnke, J.; Schuster, A.; Metwally, M.A.; Bohlmann, F. Phloroglucinol derivatives and other constituents from South African Helichrysum species. Phytochemistry 1986, 25, 1133–1142. [Google Scholar] [CrossRef]
- Hutchison, M.; Lewer, P.; MacMillan, J. Carbon-13 Nuclear Magnetic Resonance Spectra of eighteen Derivatives of ent-kaur-16-ene-19-oic acid. J. Chem. Soc. 1984, 1, 2363–2366. [Google Scholar] [CrossRef]
- Bohlmann, F.; Zdero, C.; Zeisberg, R.; Sheldrick, W.S. Naturally occurring Terpene Derivatives. Part 213. Hydroxyhelifulvanoic Acid, a new Diterpene with an Anomalous Carbon Skeleton from Helichrysum fulvum. Phytochemistry 1979, 18, 1359–1362. [Google Scholar] [CrossRef]
- Lobitz, G.O.; Tamayo-Castillo, G.; Poveda, L.; Merfort, I. Phytochemical and Biological Studies on Costa Rica Asteraceae II. New kaurene Derivatives from Milkania vitifolia. Phytochemistry 1998, 49, 805–809. [Google Scholar] [CrossRef]
- Thibane, V.; Ndhlala, A.; Abdelgadir, H.; Finnie, J.; Van Staden, J. The cosmetic potential of plants from the Eastern Cape Province traditionally used for skincare and beauty. S. Afr. J. Bot. 2019, 122, 475–483. [Google Scholar] [CrossRef]
- Soobrattee, M.A.; Neergheen, V.S.; Luximon-Ramma, A.; Aruoma, O.I.; Bahorun, T. Phenolics as potential antioxidant therapeutic agents: Mechanism and actions. Mutat. Res. Fund. Mol. Mech. Mutagen. 2005, 579, 200–213. [Google Scholar] [CrossRef]
- Heim, K.E.; Tagliaferro, A.R.; Bobilya, D.J. Flavonoid antioxidants: Chemistry, metabolism and structure-activity relationships. J. Nutr. Biochem. 2002, 13, 572–584. [Google Scholar] [CrossRef]
- Dugas, J.A.J.; Castañeda-Acosta, J.; Bonin, G.C.; Price, K.L.; Fischer, N.H.; Winston, G.W. Evaluation of the Total Peroxyl Radical-Scavenging Capacity of Flavonoids: Structure−Activity Relationships. J. Nat. Prod. 2000, 63, 327–331. [Google Scholar] [CrossRef]
- Burda, S.; Oleszek, W. Antioxidant and Antiradical Activities of Flavonoids. J. Agric. Food Chem. 2001, 49, 2774–2779. [Google Scholar] [CrossRef]
- Morita, A. Tobacco smoke causes premature skin aging. J. Dermatol. Sci. 2007, 48, 169–175. [Google Scholar] [CrossRef]
- Popoola, O.K.; Marnewick, J.L.; Rautenbach, F.; Ameer, F.; Iwuoha, E.I.; Hussein, A.A. Inhibition of Oxidative Stress and Skin Aging-Related Enzymes by Prenylated Chalcones and Other Flavonoids from Helichrysum teretifolium. Molecules 2015, 20, 7143–7155. [Google Scholar] [CrossRef] [Green Version]
- Liguori, I.; Russo, G.; Curcio, F.; Bulli, G.; Aran, L.; Della-Morte, D.; Gargiulo, G.; Testa, G.; Cacciatore, F.; Bonaduce, D.; et al. Oxidative stress, aging, and diseases. Clin. Interv. Aging 2018, 13, 757–772. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Kumar, S.; Pandey, A.K. Chemistry and Biological Activities of Flavonoids: An Overview. Sci. World J. 2013, 2013, 162750. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Wolfe, K.L.; Liu, R.H. Structure−Activity Relationships of Flavonoids in the Cellular Antioxidant Activity Assay. J. Agric. Food Chem. 2008, 56, 8404–8411. [Google Scholar] [CrossRef]
- Georgiev, L.; Chochkova, M.; Totseva, I.; Seizova, K.; Marinova, E.; Ivanova, G.; Ninova, M.; Najdenski, H.; Milkova, T. Anti-tyrosinase, antioxidant and antimicrobial activities of hydroxycinnamoylamides. Med. Chem. Res. 2012, 22, 4173–4182. [Google Scholar] [CrossRef]
- Catalá, A. An overview of lipid peroxidation with emphasis in outer segments of photoreceptors and the chemiluminescence assay. Int. J. Biochem. Cell Biol. 2006, 38, 1482–1495. [Google Scholar] [CrossRef] [PubMed]
- Myron, G. Flavonoids and Cardiovascular Disease. Pharm. Biol. 2004, 42, 21–35. [Google Scholar]
- Fahran, S.A. Study on the Interaction of Copper (II) Complex of Morin and its Antimicrobial Effect. Int. J. Chem. Sci. 2013, 11, 1247–1255. [Google Scholar]
- Katan, M.B.; Hollman, P.C.H. Dietary Flavonoids and Cardiovascular Disease. Nutr. Metabol. Cardiovasc. Dis. 1998, 8, 1–4. [Google Scholar] [CrossRef]
- Narayanaswamy, N.; Duraisamy, A.; Balakrishnan, K.P. Screening of some Medicinal Plants for their Antityrosinase and Antioxidant Activities. Intl. J. PharmTech. Res. 2011, 3, 1107–1112. [Google Scholar] [CrossRef]
- Karim, A.A.; Azlan, A.; Ismail, A.; Hashim, P.; Gani, S.S.A.; Zainudin, B.H.; Abdullah, N.A. Phenolic Composition, Antioxidant, Anti-wrinkles and Tyrosinase Inhibitory Activities of Cocoa Pod Extract. BMC Complement. Altern. Med. 2014, 14, 1–28. [Google Scholar] [CrossRef] [Green Version]
- Cao, X.; Yang, L.; Xue, Q.; Yao, F.; Sun, J.; Yang, F.; Liu, Y. Antioxidant evaluation-guided chemical profiling and structure-activity analysis of leaf extracts from five trees in Broussonetia and Morus (Moraceae). Sci. Rep. 2020, 10, 4808. [Google Scholar] [CrossRef] [Green Version]
- Nijveldt, R.J.; van Nood, E.; van Hoorn, D.E.C.; Boelens, P.G.; van Norren, K.; van Leeuwen, P.A.M. Flavonoids: A review of probable mechanisms of action and potential applications. Am. J. Clin. Nutr. 2001, 74, 418–425. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Morita, A.; Torii, K.; Maeda, A.; Yamaguchi, Y. Molecular Basis of Tobacco Smoke-Induced Premature Skin Aging. J. Investig. Dermatol. Symp. Proc. 2009, 14, 53–55. [Google Scholar] [CrossRef] [PubMed]
- Xiao, J.; Ni, X.; Kai, G.; Chen, X. A Review on Structure–Activity Relationship of Dietary Polyphenols Inhibiting α-Amylase. Crit. Rev. Food Sci. Nutr. 2013, 53, 497–506. [Google Scholar] [CrossRef] [PubMed]
No. | C-1 | C-2 | C-3 | C-4 | ||||
---|---|---|---|---|---|---|---|---|
13C | 1H | 13C | 1H | 13C | 1H | 13C | 1H | |
2 | 155.8 s | 155.8 s | 156.1 s | |||||
3 | 139.2 s | 139.3 s | 139.5 s | |||||
4 | 179.1 s | 179.5 s | 179.5 s | |||||
5 | 149.9 s | 148.9 s | 153.1 s | |||||
6 | 131.2 s | 130.5 s | 130.6 s | |||||
7 | 149.6 s | 148.1 s | 149.2 s | |||||
8 | 118.2 s | 127.2 s | 136.2 s | 6.61 s | ||||
9 | 144.3 s | 145.1 s | 145.1 s | |||||
10 | 104.3 s | 105.2 s | 107.6 s | |||||
1′ | 130.1 s | 128.5 s | 132.9 s | |||||
2′ | 128.1 d | 7.29 br s | 128.3 d | 8.15 br s | 128.4 d | 8.17 br s | 8.19 d, 7.2 | |
3′ | 128.4 d | 8.02 br s | 128.8 d | 7.65 br s | 128.8 d | 7.56 br s | 7.45 m | |
4′ | 130.9 d | 7.29 br s | 131.1 d | 7.65 br s | 131.2 d | 7.56 br s | 7.45 m | |
5′ | 128.4 d | 8.02 br s | 128.8 d | 7.65 br s | 128.8 d | 7.56 br s | 7.45 m | |
6′ | 128.1 d | 7.29 br s | 128.3 d | 8.15 br s | 128.4 d | 8.17 br s | 8.19 d, 7.2 | |
1″ | 165.5 s | |||||||
2″ | 126.4 s | |||||||
3″ | 140.9 d | 6.36 q, 6.8 | ||||||
4″ | 15.8 q | 2.13 d, 6.8 | ||||||
5″ | 20.3 q | 2.16 s | ||||||
OMe-3 | 60.2 q | 3.88 s | 60.4 q | 3.90 s | 60.4 q | 3.91 s | 3.89 s | |
OMe-6 | 60.6 q | 4.11 s | 61.1 q | 4.09 s | 61.2 q | 3.98 s | 3.92 s | |
OMe-7 | 62.2 q | 4.14 q | 4.06 s | |||||
OMe-8 | 61.8 q | 4.02 s | 61.7 q | 3.98 s | ||||
5-OH | 12.65 s | 12.55 s | 12.37 | 11.37 | ||||
7-OH | 6.58 br s | 6.80 br s |
Sample | FRAP µM AAE/g | TEAC µM TE/g | ORAC Peroxyl µM TE/g | ORAC Hydroxyl × 106 µM TE/g | LPO |
---|---|---|---|---|---|
HR | 906.71 ± 5.18 | 765.23 ± 2.43 | 2935.16 ± 3.92 | 1.817 ± 1.72 | 61.09 ± 4.19 |
C-1 | 1251.45 ± 4.18 | 1131.80 ± 6.41 | 3523.51 ± 3.22 | 2.114 ± 4.01 | 13.123 ± 0.34 |
C-2 | 1402.62 ± 5.77 | 1276.11 ± 1.32 | 2935.47 ± 0.13 | 2.413 ± 6.20 | 16.42 ± 0.92 |
C-3 | 1314.42 ± 2.42 | 1378.10 ± 9.06 | 2431.30 ± 8.63 | 1.924 ± 16.40 | 11.64 ± 1.72 |
C-4 | 1119.44 ± 11.89 | 1207.11 ± 7.21 | 2814.51 ± 5.20 | 1.917 ± 3.91 | 14.90 ± 0.06 |
C-5 | 19.66 ± 8.12 | 1105.00 ± 3.09 | 364.44 ± 6.71 | 0.429 ± 12.00 | >100 |
C-6 | 29.39 ± 5.84 | 1361.90 ± 0.35 | 914.29 ± 2.74 | 0.531 ± 10.24 | >100 |
C-7 | 60.90 ± 7.90 | 1424.51 ± 0.70 | 93.10 ± 13.68 | 0.845 ± 13.34 | >100 |
EGCG | 3326.45 ± 5.76 | 11545.44 ± 17.28 | 14693.09 ± 5.53 | 3.862 ± 4.65 | 0.929 ± 4.11 |
Sample | TYR | ELA |
---|---|---|
HR | 74.15 ± 3.92 | >100 |
C-1 | 25.735 ± 9.62 | >100 |
C-2 | 24.062 ± 0.61 | >100 |
C-3 | 39.03 ± 13.12 | >100 |
C-4 | 37.67 ± 0.98 | >100 |
C-5 | >100 | >100 |
C-6 | >100 | >100 |
C-7 | >100 | >100 |
KJA | 3.425 ± 2.37 | >100 |
OLEAN | NA | 12.77 ± 0.97 |
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Popoola, O.K.; Marnewick, J.L.; Iwuoha, E.I.; Hussein, A.A. Methoxylated Flavonols and ent-Kaurane Diterpenes from the South African Helichrysum rutilans and Their Cosmetic Potential. Plants 2023, 12, 2870. https://doi.org/10.3390/plants12152870
Popoola OK, Marnewick JL, Iwuoha EI, Hussein AA. Methoxylated Flavonols and ent-Kaurane Diterpenes from the South African Helichrysum rutilans and Their Cosmetic Potential. Plants. 2023; 12(15):2870. https://doi.org/10.3390/plants12152870
Chicago/Turabian StylePopoola, Olugbenga K., Jeanine L. Marnewick, Emmanuel I. Iwuoha, and Ahmed A. Hussein. 2023. "Methoxylated Flavonols and ent-Kaurane Diterpenes from the South African Helichrysum rutilans and Their Cosmetic Potential" Plants 12, no. 15: 2870. https://doi.org/10.3390/plants12152870