Preliminary Study on Laccase-Catalyzed Oxidative Transformation of Anethole: Evidence from GC-MS Analysis
Abstract
Purpose of the study: This research was conducted with the aim of synthesizing anethole dimers using the laccase enzyme biocatalyst.
Methodology: In this study, anise oil containing 90% anethole, laccase enzyme as a biocatalyst, and hydroquinone as a mediator were used. The laccase enzyme used was isolated from white oyster mushroom (Pleurotus ostreatus) which has an activity of 712.758 U/L. The anethole dimer formation reaction was carried out in a biphasic medium (ethyl acetate: phosphate buffer = 4:1) which was carried out for 24 hours and 48 hours. The reaction results were then extracted with ethyl acetate and produced a thick brownish liquid with a more intense color intensity in the 48-hour reaction.
Main Findings: Comparison of the GC test results on anise oil, 24-hour reaction, and 48-hour reaction showed an increase in peaks and changes in peak height in the 48-hour reaction. Anethole and p-anisaldehyde compounds had a smaller % area than in the 24-hour reaction. It is suspected that the 48-hour reaction produced a new compound derived from the oxidation reaction, namely caryophyllene oxide, but the compound that is the anethole dimer has not been identified.
Novelty/Originality of this study: This study introduces a biocatalytic approach for anethole transformation using laccase from Pleurotus ostreatus, integrating mechanistic insights with product characterization. It reveals the limited reactivity of anethole under laccase catalysis while identifying alternative oxidation pathways, such as caryophyllene oxide formation. These findings advance understanding of substrate specificity and expand knowledge of laccase-mediated transformations in non-phenolic systems.
References
U. Hanefeld, F. Hollmann, and C. E. Paul, “Biocatalysis making waves in organic chemistry,” Chem. Soc. Rev., vol. 51, no. 2, pp. 594–627, 2022, doi: 10.1039/d1cs00100k.
C. K. Winkler, J. H. Schrittwieser, and W. Kroutil, “Power of biocatalysis for organic synthesis,” ACS Cent. Sci., vol. 7, no. 1, pp. 55–71, Jan. 2021, doi: 10.1021/acscentsci.0c01496.
Y. Ding, G. Perez-Ortiz, J. Peate, and S. M. Barry, “Redesigning enzymes for biocatalysis: Exploiting structural understanding for improved selectivity,” Front. Mol. Biosci., vol. 9, no. July, pp. 1–17, 2022, doi: 10.3389/fmolb.2022.908285.
R. Mu et al., “Application of enzymes in regioselective and stereoselective organic reactions,” Catalysts, vol. 10, no. 8, pp. 1–25, 2020, doi: 10.3390/catal10080832.
L. E. Zetzsche et al., “Biocatalytic oxidative cross-coupling reactions for biaryl bond formation,” HHS Public Access, vol. 603, no. 7899, pp. 79–85, 2022, doi: 10.1038/s41586-021-04365-7.Biocatalytic.
L. Lu, H. Li, and A. Lei, “Oxidative cross-coupling reactions between two nucleophiles,” Chinese J. Chem., vol. 40, no. 2, pp. 256–266, Jan. 2022, doi: 10.1002/cjoc.202100396.
P. Aza and S. Camarero, “Fungal laccases: Fundamentals, engineering and classification update,” Biomolecules, vol. 13, no. 1716, pp. 1–21, 2023, doi: 10.3390/biom13121716.
M. Mahuri, M. Paul, and H. Thatoi, “A review of microbial laccase production and activity toward different biotechnological applications,” Syst. Microbiol. Biomanufacturing, vol. 3, no. 4, pp. 533–551, Oct. 2023, doi: 10.1007/s43393-023-00163-6.
J. Jayakumar, D. Priyadarshini, A. Parthasarathy, and S. R. Reddy, “Recent advances in molecular oxygen assisted laccase catalyzed sustainable organic transformations,” Asian J. Org. Chem., vol. 12, no. 1, pp. 1–27, Jan. 2023, doi: 10.1002/ajoc.202200564.
C. Garrido and S. Leimkühler, “The inactivation of human aldehyde oxidase 1 by hydrogen peroxide and superoxide,” Drug Metab. Dispos., vol. 49, no. 9, pp. 729–735, Sep. 2021, doi: 10.1124/dmd.121.000549.
D. M. Scheibel, I. P. I. Gitsov, and I. Gitsov, “Enzymes in ‘green’ synthetic chemistry: Laccase and lipase,” Molecules, vol. 29, no. 5, pp. 1–33, 2024, doi: 10.3390/molecules29050989.
T. Itoh and Y. Takagi, “Laccase-catalyzed reactions in ionic liquids for green sustainable chemistry,” ACS Sustain. Chem. Eng., vol. 9, no. 4, pp. 1443–1458, 2021, doi: 10.1021/acssuschemeng.0c07097.
A. Zayed, M. Sobeh, and M. A. Farag, “Dissecting dietary and semisynthetic volatile phenylpropenes: A compile of their distribution, food properties, health effects, metabolism and toxicities,” Crit. Rev. Food Sci. Nutr., vol. 63, no. 32, pp. 11105–11124, Dec. 2023, doi: 10.1080/10408398.2022.2087175.
M. Sharafan et al., “Illicium verum (star anise) and trans-anethole as valuable raw materials for medicinal and cosmetic applications,” Molecules, vol. 27, no. 650, pp. 1–16, 2022, doi: 10.3390/molecules27030650.
S. M. Umer, M. Solangi, K. M. Khan, and R. S. Z. Saleem, “Indole-containing natural products 2019–2022: Isolations, reappraisals, syntheses, and biological activities,” Molecules, vol. 27, no. 21, pp. 1–45, 2022, doi: 10.3390/molecules27217586.
W. Hou and H. Xu, “Incorporating selenium into heterocycles and natural products─from chemical properties to pharmacological activities,” J. Med. Chem., vol. 65, no. 6, pp. 4436–4456, Mar. 2022, doi: 10.1021/acs.jmedchem.1c01859.
A. V. Atoki, P. M. Aja, E. N. Ondari, and T. S. Shinkafi, “Advances in alzheimer’s disease therapeutics: Biochemistry, exploring bioactive compounds and novel approaches,” Int. J. Food Prop., vol. 26, no. 1, pp. 2091–2127, 2023, doi: 10.1080/10942912.2023.2243050.
I. Lopes, C. Campos, R. Medeiros, and F. Cerqueira, “Antimicrobial activity of dimeric flavonoids,” Compounds, vol. 4, no. 2, pp. 214–229, 2024, doi: 10.3390/compounds4020011.
S. K. Sinha et al., “Transition-metal catalyzed C–H activation as a means of synthesizing complex natural products,” Chem. Soc. Rev., vol. 52, no. 21, pp. 7461–7503, 2023, doi: 10.1039/D3CS00282A.
S. E. Dibrell, Y. Tao, and S. E. Reisman, “Synthesis of complex diterpenes: Strategies guided by oxidation pattern analysis,” Acc. Chem. Res., vol. 54, no. 6, pp. 1360–1373, Mar. 2021, doi: 10.1021/acs.accounts.0c00858.
J. Teržan, A. Sedminek, Ž. Lavrič, M. Grilc, M. Huš, and B. Likozar, “Selective oxidation of biomass-derived carbohydrate monomers,” Green Chem., vol. 25, no. 6, pp. 2220–2240, 2023, doi: 10.1039/d2gc04623g.
G. D. Yadav, R. K. Mewada, D. P. Wagh, and H. G. Manyar, “Advances and future trends in selective oxidation catalysis: a critical review,” Catal. Sci. Technol., vol. 12, no. 24, pp. 7245–7269, 2022, doi: 10.1039/D2CY01322C.
D. den Boer, H. C. de Heer, F. Buda, and D. G. H. Hetterscheid, “Challenges in elucidating the free energy scheme of the laccase catalyzed reduction of oxygen,” ChemCatChem, vol. 15, no. 1, pp. 1–27, Jan. 2023, doi: 10.1002/cctc.202200878.
D. Zhu et al., “Insight into depolymerization mechanism of bacterial laccase for lignin,” ACS Sustain. Chem. Eng., vol. 8, no. 34, pp. 12920–12933, 2020, doi: 10.1021/acssuschemeng.0c03457.
S. G. Newman, “Optimizing chemical reactions,” Chem. Rev., vol. 124, no. 7, pp. 3645–3647, Apr. 2024, doi: 10.1021/acs.chemrev.4c00231.
L. Y. Chen and Y. P. Li, “Machine learning-guided strategies for reaction conditions design and optimization,” Beilstein J. Org. Chem., vol. 20, pp. 2476–2492, 2024, doi: 10.3762/bjoc.20.212.
N. F. Shamsudin et al., “Flavonoids as antidiabetic and anti-inflammatory agents: A review on structural activity relationship-based studies and meta-analysis,” Int. J. Mol. Sci., vol. 23, no. 20, pp. 1–35, 2022, doi: 10.3390/ijms232012605.
Ç. Karabacak Atay, Ö. Dilek, T. Tilki, and B. Dede, “A novel imidazole-based azo molecule: synthesis, characterization, quantum chemical calculations, molecular docking, molecular dynamics simulations and ADMET properties,” J. Mol. Model., vol. 29, no. 8, p. 226, Aug. 2023, doi: 10.1007/s00894-023-05625-1.
K. P. Baviskar et al., “A Review on hyphenated techniques in analytical chemistry,” Curr. Anal. Chem., vol. 18, no. 9, pp. 956–976, Nov. 2022, doi: 10.2174/1573411018666220818103236.
M. S. J. Maftuh, U. S. Lawal, M. Ade, A. V. Lama, and A. F. Adzim, “Understanding learning strategies: A comparison between contextual learning and problem-based learning,” Educ. J. Educ. Learn., vol. 01, no. 01, pp. 54–65, 2023, doi: 10.61987/educazione.v1i1.496 Understanding.
A. Syafawi and M. Rahmi, “Formation of anethole dimer compound using biocatalyst laccase from white oyster mushroom,” Chem Trendz J., vol. 1, no. 1, pp. 1–16, 2024.
S. Sfameni, G. Rando, and M. R. Plutino, “Sustainable secondary-raw materials, natural substances and eco-friendly nanomaterial-Based approaches for improved surface performances: An overview of What They Are and How They Work,” Int. J. Mol. Sci., vol. 24, no. 6, pp. 1–33, 2023, doi: 10.3390/ijms24065472.
A. Khosravi, A. Zarepour, S. Iravani, R. S. Varma, and A. Zarrabi, “Sustainable synthesis: natural processes shaping the nanocircular economy,” Environ. Sci. Nano, vol. 11, no. 3, pp. 688–707, 2024, doi: 10.1039/D3EN00973D.
B. Cochachin-Carrera, J. Moreno-Cuevas, and N. Carvajal-Mena, “Effects of concentration by block freezing and vacuum evaporation on the physicochemical properties and digestibility of whey,” CYTA - J. Food, vol. 21, no. 1, pp. 313–320, 2023, doi: 10.1080/19476337.2023.2196321.
K. Gandhi, N. Sharma, P. B. Gautam, R. Sharma, B. Mann, and V. Pandey, “Centrifugation,” 2022, pp. 85–102. doi: 10.1007/978-1-0716-1940-7_3.
R. Maulini, D. Sahlinal, and O. Arifin, “Monitoring of pH, amonia (NH3) and temperature parameters aquaponic water in the 4.0 revolution era,” IOP Conf. Ser. Earth Environ. Sci., vol. 1012, no. 1, pp. 1–10, 2021, doi: 10.1088/1755-1315/1012/1/012087.
N. M. Hussein, Y. M. Mohialden, and S. A. Salman, “Impact of IoT-based environmental monitoring on lab safety and sustainability,” Babylonian J. Internet Things, vol. 2024, pp. 16–26, Mar. 2024, doi: 10.58496/BJIoT/2024/003.
M. Grzybowski, B. Sadowski, H. Butenschön, and D. T. Gryko, “Synthetic applications of oxidative aromatic coupling—from biphenols to nanographenes,” Angew. Chemie - Int. Ed., vol. 59, no. 8, pp. 2998–3027, 2020, doi: 10.1002/anie.201904934.
Z. Qiu, H. Zeng, and C.-J. Li, “Coupling without coupling reactions: En route to developing phenols as sustainable coupling partners via dearomatization–rearomatization processes,” Acc. Chem. Res., vol. 53, no. 10, pp. 2395–2413, Oct. 2020, doi: 10.1021/acs.accounts.0c00479.
D. L. Golden, S. Suh, and S. S. Stahl, “Radical C(sp3)–H functionalization and cross-coupling reactions,” HHS Public Access, vol. 6, no. 6, pp. 405–427, 2023, doi: 10.1038/s41570-022-00388-4.Radical.
N. Bekavac et al., “Advancements in aqueous two-phase systems for enzyme extraction, purification, and biotransformation,” Molecules, vol. 29, no. 16, pp. 1–30, 2024, doi: 10.3390/molecules29163776.
H.-M. Huang, P. Bellotti, and F. Glorius, “Merging carbonyl addition with photocatalysis,” Acc. Chem. Res., vol. 55, no. 8, pp. 1135–1147, Apr. 2022, doi: 10.1021/acs.accounts.1c00799.
H. Choi, S. E. Suh, and H. Kang, “Advances in exploring mechanisms of oxidative phenolic coupling reactions,” Adv. Synth. Catal., vol. 366, no. 21, pp. 4347–4384, 2024, doi: 10.1002/adsc.202400895.
J. Wu and M. C. Kozlowski, “Catalytic oxidative coupling of phenols and related compounds,” HHS Public Access, vol. 12, no. 11, pp. 6532–6549, 2019, doi: 10.1021/acscatal.2c00318.Catalytic.
S. R. Maji, C. Roy, and S. K. Sinha, “Gas chromatography-mass spectrometry (GC-MS): a comprehensive review of synergistic combinations and their applications in the past two decades,” J. Anal. Sci. Appl. Biotechnol., vol. 5, no. 2, pp. 72–85, 2023, doi: 10.48402/IMIST.PRSM/jasab-v5i2.40209.
B. Pulver et al., “Structure elucidation of the novel synthetic cannabinoid Cumyl‐Tosyl‐Indazole‐3‐Carboxamide (Cumyl‐TsINACA) found in illicit products in Germany,” Drug Test. Anal., vol. 14, no. 8, pp. 1387–1406, Aug. 2022, doi: 10.1002/dta.3261.
Copyright (c) 2024 Siti Zainatur Rahmah, Wimonnan Pongpatrakant
This work is licensed under a Creative Commons Attribution 4.0 International License.
Authors who publish with this journal agree to the following terms:
- Authors retain copyright and acknowledge that the Journal of Chemical Learning Innovation is the first publisher licensed under a Creative Commons Attribution 4.0 International License.
- Authors are able to enter into separate, additional contractual arrangements for the non-exclusive distribution of the journal's published version of the work (e.g., post it to an institutional repository or publish it in a book), with an acknowledgment of its initial publication in this journal.
- Authors are permitted and encouraged to post their work online (e.g., in institutional repositories or on their website) prior to and during the submission process, as it can lead to productive exchanges and earlier and greater citation of published work.
.png)
.png)
