Synthesis of Water-Soluble Menthol Derivatives Using Response Surface Methodology

Shafaq Nisar; Muhammad Asif Hanif; Umer Rashid; Muhammad Idrees Jilani; Ijaz Ahmad Bhatti; Imtiaz Ali; Bartłomiej Zieniuk

doi:10.22146/ijc.94761

Synthesis of Water-Soluble Menthol Derivatives Using Response Surface Methodology

https://doi.org/10.22146/ijc.94761

Shafaq Nisar⁽¹⁾, Muhammad Asif Hanif⁽²⁾, Umer Rashid^(3*), Muhammad Idrees Jilani⁽⁴⁾, Ijaz Ahmad Bhatti⁽⁵⁾, Imtiaz Ali⁽⁶⁾, Bartłomiej Zieniuk⁽⁷⁾

(1) Nano and Biomaterials Lab, Department of Chemistry, University of Agriculture Faisalabad, Faisalabad 38040, Pakistan
(2) Nano and Biomaterials Lab, Department of Chemistry, University of Agriculture Faisalabad, Faisalabad 38040, Pakistan
(3) Institute of Nanoscience and Nanotechnology (ION2), Universiti Putra Malaysia, 43400 Serdang, Selangor, Malaysia; Center of Excellence in Catalysis for Bioenergy and Renewable Chemicals (CBRC), Faculty of Science, Chulalongkorn University, Pathumwan, Bangkok 10330, Thailand
(4) Punjab Bio-energy Institute (PBI), University of Agriculture Faisalabad, Faisalabad 38040, Pakistan
(5) Nano and Biomaterials Lab, Department of Chemistry, University of Agriculture Faisalabad, Faisalabad 38040, Pakistan
(6) Department of Chemical and Materials Engineering, Faculty of Engineering Rabigh, King Abdulaziz University, Rabigh 21911, Saudi Arabia
(7) Department of Chemistry, Institute of Food Sciences, Warsaw University of Life Sciences, 159C Nowoursynowska Street, 02776 Warsaw, Poland
(*) Corresponding Author

Abstract

In this study, menthol was glycosylated with starch in the presence of α-amylase to produce menthyl maltoside (MenM) as the primary product. Optimization of the experimental parameters, including the menthol-starch ratio, enzyme concentration, temperature, and time, was performed using response surface methodology (RSM). The RSM-generated model displayed adequate accuracy and reasonable predictability for the MenM yield under the specified experimental conditions. Under the optimized reaction conditions of the menthol-to-starch ratio of 1:3 (50 °C, 18 h) and enzyme concentration of 50 U, the highest yield of MenM (23.7%) was obtained. Fourier transform infrared and nuclear magnetic resonance spectroscopies were employed to analyze the synthesized menthol derivative MenM. Compared with standard menthol, the synthesized menthol derivatives displayed various biological activities, including antioxidant, antibacterial, antifungal, and insecticidal properties. The results of this study demonstrate the effectiveness of RSM-optimized synthesis of MenM from the glycosylation of menthol with starch. This study showed that MenM is highly soluble in water and can be easily stored owing to its non-volatile nature.

Keywords

menthol; starch; glycosylation; menthyl maltoside; optimization

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References

[1] Isidorov, V.A., and Masłowiecka, J., 2024, Chemical composition of volatile and extractive organic compounds in the inflorescence litter of five species of woody plants, Plants, 13 (13), 1829.

[2] Choi, H.Y., Kim, B.M., Morgan, A.M.A., Kim, J.S., and Kim, W.G., 2017, Improvement of the pharmacological activity of menthol via enzymatic β-anomer-selective glycosylation, AMB Express, 7 (1), 167.

[3] Chen, H., Jin, X., Zhu, L., Lu, Y., Ma, Z., Liu, S., and Chen, X., 2020, Glycosyl hydrolase catalyzed glycosylation in unconventional media, Appl. Microbiol. Biotechnol., 104 (22), 9523−9534.

[4] Varki, A., and Kornfeld, S., 2022, “Historical Background and Overview”. in Essentials of Glycobiology, Eds. Varki, A., Cummings, R.D., Esko, J.D., Stanley, P., Hart, G.W., Aebi, M., Mohnen, D., Kinoshita, T., Packer, N.H., Prestegard, J.J., Schnaar, R.L., and Seeberger, P.H., Cold Spring Harbor Laboratory Press, New York, US, 4e.1.

[5] Guo, L., Chen, X., Xu, L., Xiao, M., and Lu, L., 2018, Enzymatic synthesis of 6′-sialyllactose, a dominant sialylated human milk oligosaccharide, by a novel exo-α-sialidase from Bacteroides fragilis NCTC9343, Appl. Environ. Microbiol., 84 (13), e00071-18.

[6] Larsson, J., Svensson, D., and Adlercreutz, P., 2005, α-Amylase-catalysed synthesis of alkyl glycosides, J. Mol. Catal. B: Enzym., 37 (1), 84−87.

[7] Tiwari, S.P., Srivastava, R., Singh, C.S., Shukla, K., Singh, R.K., Singh, P., Singh, R., Singh, N.L., and Sharma, R., 2015, Amylases: An overview with special reference to alpha amylase, J Global Biosci., 4 (1), 1886−1901.

[8] Danish, M., Mumtaz, M.W., Fakhar, M., and Rashid, U., 2017, Response surface methodology based optimized purification of the residual glycerol from biodiesel production process, Chiang Mai J. Sci., 44 (4), 1570−1582.

[9] Salama, S.Z., Firdaus, M., and Suryanti, V., 2024, Cellulose ethers from banana (Musa balbisiana Colla) blossom cellulose: Synthesis and multivariate optimization, Indones. J. Chem., 24 (1), 200−212.

[10] Supriyatna, Y.I., Prasetya, A., Astuti, W., Sumardi, S., Natalia, P., Adythia, D.M., and Petrus, H.T.B.M., 2024, Low-grade ilmenite leaching kinetics using hydrochloric acid: RSM and SCM approaches, Indones. J. Chem., 24 (3), 627−637.

[11] Do, H., Sato, T., Kirimura, K., Kino, K., and Usami, S.J., 2002, Enzymatic synthesis of l-menthyl α-maltoside and l-menthyl α-maltooligosides from l-menthyl α-glucoside by cyclodextrin glucanotransferase, J. Biosci. Bioeng., 94 (2), 119−123.

[12] Azizuddin, A., and Ghafoor, S., 2018, The study of changes in physical attributes, chemical composition, phenolic evaluation and antioxidant capacity of pomegranate fruit during storage, Anal. Chem. Lett., 8 (6), 769−781.

[13] Naz, N., Saqib, S., Ashraf, R., Majeed, M.I., and Iqbal, M.A., 2020, Synthesis of new organoselenium compounds: Characterization and biological studies, Maced. J. Chem. Chem. Eng., 39 (1), 1−10.

[14] Pérez-Rosés, R., Risco, E., Vila, R., Peñalver, R., and Cañigueral, S., 2016, Biological and nonbiological antioxidant activity of some essential oils, J. Agric. Food Chem., 64 (23), 4716–4724.

[15] Onanuga, A.O., and Oloyede, G.K., 2021, Two new biologically active steroids from Costus lucanusianus (Costaceae), Steroids, 175, 108913.

[16] Hamza, A.F., Zahran, N.F., and Gad, H.A., 2024, Improving the insecticidal efficacy of Thuja orientalis essential oil by gamma radiation against Trogoderma granarium, Radiat. Phys. Chem., 223, 112035.

[17] Alnaser, A., Tayoub, G., Ghanem, I., and Audeh, A., 2013, Chemical constituents and insecticidal activity of the essential oil from fruits of Foeniculum vulgare Miller on larvae of Khapra beetle (Trogoderma granarium Everts), Herba Pol., 59 (4), 86−96.

[18] Wang, K., Qi, T., Guo, L., Ma, Z., Gu, G., Xiao, M., and Lu, L., 2019, Enzymatic glucosylation of salidroside from starch by α-amylase, J. Agric. Food. Chem., 67, 2012−2019.

[19] Hong, T., Yin, J.Y., Nie, S.P., and Xie, M.Y., 2021, Applications of infrared spectroscopy in polysaccharide structural analysis: Progress, challenge and perspective, Food Chem.: X, 12, 100168.

[20] Kowalczuk, D., and Pitucha, M., 2019, Application of FTIR method for the assessment of immobilization of active substances in the matrix of biomedical materials, Materials, 12 (18), 2972.

[21] Angassa, K., Tesfay, E., Weldmichael, T.G., and Kebede, S., 2023, Response surface methodology process optimization of biodiesel production from castor seed oil, J. Chem., 2023 (1), 6657732.

[22] Shafiq, F., Mumtaz, M.W., Mukhtar, H., Touqeer, T., Raza, S.A., Rashid, U., Nehdi, I.A., and Choong, T.S.Y., 2020, Response surface methodology approach for optimized biodiesel production from waste chicken fat oil, Catalysts, 10 (6), 633.

[23] Penjumras, P., Abdul Rahman, R., Talib, R.A., and Abdan, K., 2015, Response surface methodology for the optimization of preparation of biocomposites based on poly(lactic acid) and durian peel cellulose, Sci. World J., 2015 (1), 293609.

[24] Janeček, Š., Svensson, B., and MacGregor, E.A., 2014, α-Amylase: An enzyme specificity found in various families of glycoside hydrolases, Cell. Mol. Life Sci., 71 (7), 1149−1170.

[25] Hu, Z., Wang, Z., Liu, Y., Wu, Y., Han, X., Zheng, J., Yan, X., and Wang, Y., 2015, Metabolite profile of salidroside in rats by ultraperformance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry and high-performance liquid chromatography coupled with quadrupole-linear ion trap mass spectrometry, J. Agric. Food Chem., 63 (41), 8999−9005.

[26] Noguchi, A., Inohara-Ochiai, M., Ishibashi, N., Fukami, H., Nakayama, T., and Nakao, M., 2008, A novel glucosylation enzyme: Molecular cloning, expression, and characterization of Trichoderma viride JCM22452 α-amylase and enzymatic synthesis of some flavonoid monoglucosides and oligoglucosides, J. Agric. Food Chem., 56 (24), 12016−12024.

[27] Nisar, S., Hanif, M.A., Zahid, M., and Ghaffar, A., 2022, Enzymatic glycosylation of menthol: Optimization of synthesis and extraction processes using response surface methodology and biological evaluation of synthesized product, Chem. Pap., 76 (5), 2649−2675.

[28] Batiha, G.E., Beshbishy, A.M., Ikram, M., Mulla, Z.S., Abd El-Hack, M.E., Taha, A.E., Algammal, A.M., and Elewa, Y.H.A., 2020, The pharmacological activity, biochemical properties, and pharmacokinetics of the major natural polyphenolic flavonoid: Quercetin, Foods, 9 (3), 374.

[29] Ahmad, N., Fazal, H., Ahmad, I., and Abbasi, B.H., 2012, Free radical scavenging (DPPH) potential in nine Mentha species, Toxicol. Ind. Health, 28 (1), 83–89.

[30] Wu, Z., Tan, B., Liu, Y., Dunn, J., Martorell Guerola, P., Tortajada, M., Cao, Z., and Ji, P., 2019, Chemical composition and antioxidant properties of essential oils from peppermint, native spearmint and scotch spearmint, Molecules, 24 (15), 2825.

[31] Cava-Roda, R., Taboada-Rodríguez, A., López-Gómez, A., Martínez-Hernández, G.B., and Marín-Iniesta, F., 2021, Synergistic antimicrobial activities of combinations of vanillin and essential oils of cinnamon bark, cinnamon leaves, and cloves, Foods, 10 (6), 1406.

[32] Tagousop, C.N., Tamokou, J.D., Ekom, S.E., Ngnokam, D., and Voutquenne-Nazabadioko, L., 2018, Antimicrobial activities of flavonoid glycosides from Graptophyllum grandulosum and their mechanism of antibacterial action, BMC Complementary Altern. Med., 18 (1), 252.

[33] Abd El-Bar, M., and Fawki, S., 2021, Fumigant activity and chemical composition of three essential oils used in gelatin capsules for the control of Acanthoscelides obtectus (Say) (Coleoptera: Chrysomelidae) in Egypt, Afr. Entomol., 29 (2), 534−546.

[34] Hanif, M.A., Nisar, S., Khan, G.S., Mushtaq, Z., and Zubair, M., 2019, “Essential Oils” in Essential Oil Research, Ed. Malik, S., Springer International Publishing, Cham, Switzerland, 3−17.

[35] Tong, F., 2010, Investigation of mechanisms of action of monoterpenoid insecticides on insect gamma-aminobutyric acid receptors and nicotinic acetylcholine receptors, Dissertation, Iowa State University, USA.

[36] Samarasekera, R., Weerasinghe, I.S., and Hemalal, K.D.P., 2008, Insecticidal activity of menthol derivatives against mosquitoes, Pest Manage. Sci., 64 (3), 290−295.

DOI: https://doi.org/10.22146/ijc.94761