Selective Microcrystalline Cellulose Extraction from Chinese Medicine Residues via Direct PMS Oxidation

Jinjing Huang; Xia Liu; Kaixing Fu; Shengyun Yang; Shiqing Zhou; Jinming Luo

doi:10.1016/j.eng.2024.03.008

PDF(1618 KB)

Engineering ›› 2024, Vol. 43 ›› Issue (12) : 139-145. DOI: 10.1016/j.eng.2024.03.008

Research

Article

Selective Microcrystalline Cellulose Extraction from Chinese Medicine Residues via Direct PMS Oxidation

Author information +

History +

Highlights

• A cost-effective one-step PMS oxidation protocol was proposed to extract MCC from CMRs.

• The as-extracted MCC demonstrates high purity of ∼95% and crystallinity of ∼85.4%.

• Selective extraction mechanisms of MCC from CMRs were systematically investigated.

• This versatile cellulose extraction protocol could be extended to various natural wastes.

Abstract

The valorization of Chinese medicine residues (CMRs) into high-value-added products, such as microcrystalline cellulose (MCC), has garnered significant interest in the current post-pandemic era, particularly in regions where Chinese medicine (CM) is widely utilized (i.e., southeast Asia). In this study, we propose a facile and economical protocol for selectively extracting MCC from CMRs via one-step direct peroxymonosulfate (PMS) oxidation without the need for intricate steps. Importantly, our proposed protocol has been verified to be versatile and can be applied to various solid waste sources rich in cellulose, with an average extraction rate of 75%. Analysis using the Fukui index revealed that the β-O-4 bond, the aromatic ring in lignin, specific O sites in hemicellulose, and the amorphous region of cellulose are more susceptible to electrophilic attack by PMS than to reactions involving HO^·, $\mathrm{SO}_{\dot{4}}^{-}$, or ¹O₂. Leveraging this distinct mechanism, the extracted MCC demonstrated ultrahigh purity (∼95%) and crystallinity (∼85.36%). Overall, our work involves transforming solid waste into high-value products through the provision of a technical solution, with the potential for onsite application. This represents a significant advancement to the valorization of CMRs, particularly in providing theoretical guidance for accelerating the recycling of waste materials.

Graphical abstract

Keywords

Chinese medicine residues / Microcrystalline cellulose / PMS oxidation / Electrophilic attacks

Cite this article

EndNote

Ris (Procite)

Bibtex

Download citation ▾

Jinjing Huang, Xia Liu, Kaixing Fu, Shengyun Yang, Shiqing Zhou, Jinming Luo. Selective Microcrystalline Cellulose Extraction from Chinese Medicine Residues via Direct PMS Oxidation. Engineering, 2024, 43(12): 139‒145 https://doi.org/10.1016/j.eng.2024.03.008

References

Publishing order | Descend order by publishing year | Descend order by cited within

[1]	Q. Lu, C. Li. Comprehensive utilization of Chinese medicine residues for industry and environment protection: turning waste into treasure. J Clean Prod, 279 (2021), Article 123856.

[2]	H. Sheridan, B. Kopp, L. Krenn, D. Guo, J. Sendker. Traditional Chinese herbal medicine preparation: invoking the butterfly effect. Science, 350 (2015), pp. S64-S66.

[3]	J. Hou, J. Zhang, C. Yao, R. Bauer, I.A. Khan, W. Wu, et al. Deeper chemical perceptions for better traditional Chinese medicine standards. Engineering, 5 (1) (2019), pp. 83-97.

[4]	Z. Ma, B. Zhang, Y. Fan, M. Wang, D. Kebebe, J. Li, et al. Traditional Chinese medicine combined with hepatic targeted drug delivery systems: a new strategy for the treatment of liver diseases. Biomed Pharmacother, 117 (2019), Article 109128.

[5]	W. Liu, W. Guan, N. Zhong. Strategies and advances in combating COVID-19 in China. Engineering, 6 (10) (2020), pp. 1076-1084.

[6]	W. Feng, H. Ao, C. Peng, D. Yan. Gut microbiota, a new frontier to understand traditional Chinese medicines. Pharmacol Res, 142 (2019), pp. 176-191.

[7]	X. Long, Y. Lu, H. Guo, Y. Tang. Recent advances in solid residues resource utilization in traditional Chinese medicine. ChemistrySelect, 8 (13) (2023), p. 202300383.

[8]	K. Huang, P. Zhang, Z. Zhang, J.Y. Youn, C. Wang, H. Zhang, et al. Traditional Chinese medicine (TCM) in the treatment of COVID-19 and other viral infections: efficacies and mechanisms. Pharmacol Ther, 225 (2021), Article 107843.

[9]	W. Zhu, L. Wang, L. Pan, Z. He, G. Yang. Analysis of the status quo and future prospects of Chinese medicinal resources sustainable development. World Chin Med, 13 (7) (2018), pp. 1752-1755Chinese.

[10]	X.C. Meng. Problems and countermeasures in development of Chinese materia medica resource. Chin Tradit Herbal Drugs, 49 (16) (2018), pp. 3735-3741Chinese.

[11]	W. Tao, J. Jin, Y. Zheng, S. Li. Current advances of resource utilization of herbal extraction residues in China. Waste Biomass Valoriz, 12 (11) (2021), pp. 5853-5868.

[12]	M. Wang, Y. Liu, S. Wang, K. Wang, Y. Zhang. Development of a compound microbial agent beneficial to the composting of Chinese medicinal herbal residues. Bioresource Technol, 330 (2021), Article 124948.

[13]	H. Zhan, X. Yin, Y. Huang, X. Zhang, H. Yuan, J. Xie, et al. Characteristics of NO_x precursors and their formation mechanism during pyrolysis of herb residues. J Fuel Chem Technol, 45 (3) (2017), pp. 279-288.

[14]	Q. He, Y. Bai, Y. Lu, B. Cui, Z. Huang, Q. Yang, et al. Isolation and characterization of cellulose nanocrystals from Chinese medicine residues. Biomass Convers Bior, 14 (2022), pp. 22745-22754.

[15]	A.W. Carpenter, C. de Lannoy, M.R. Wiesner. Cellulose nanomaterials in water treatment technologies. Environ Sci Technol, 49 (9) (2015), pp. 5277-5287.

[16]	M.A.S. Azizi Samir, F. Alloin, A. Dufresne. Review of recent research into cellulosic whiskers, their properties and their application in nanocomposite field. Biomacromolecules, 6 (2) (2005), pp. 612-626.

[17]	N. Johar, I. Ahmad, A. Dufresne. Extraction, preparation and characterization of cellulose fibres and nanocrystals from rice husk. Ind Crops Prod, 37 (1) (2012), pp. 93-99.

[18]	Q. Lin, Y. Huang, W. Yu. Effects of extraction methods on morphology, structure and properties of bamboo cellulose. Ind Crops Prod, 169 (2021), Article 113640.

[19]	A.Q. Almashhadani, C.P. Leh, S. Chan, C.Y. Lee, C.F. Goh. Nanocrystalline cellulose isolation via acid hydrolysis from non-woody biomass: importance of hydrolysis parameters. Carbohydr Polym, 286 (2022), Article 119285.

[20]	X. Chen, X. Deng, W. Shen, M. Jia. Preparation and characterization of the spherical nanosized cellulose by the enzymatic hydrolysis of pulp fibers. Carbohydr Polym, 181 (2018), pp. 879-884.

[21]	Y. Habibi. Key advances in the chemical modification of nanocelluloses. Chem Soc Rev, 43 (5) (2014), pp. 1519-1542.

[22]	J. Wen, Y. Yin, X. Peng, S. Zhang. Using H₂O₂ to selectively oxidize recyclable cellulose yarn with high carboxyl content. Cellulose, 26 (4) (2019), pp. 2699-2713.

[23]	Y. Liu, L. Liu, K. Wang, H. Zhang, Y. Yuan, H. Wei, et al. Modified ammonium persulfate oxidations for efficient preparation of carboxylated cellulose nanocrystals. Carbohydr Polym, 229 (2020), Article 115572.

[24]	P.J. Van Soest, J.B. Robertson, B.A. Lewis. Methods for dietary fiber, neutral detergent fiber, and nonstarch polysaccharides in relation to animal nutrition. J Dairy Sci, 74 (10) (1991), pp. 3583-3597.

[25]	M. Wang, J. Lu, X. Zhang, L. Li, H. Li, N. Luo, et al. Two-step, catalytic C-C bond oxidative cleavage process converts lignin models and extracts to aromatic acids. ACS Catal, 6 (9) (2016), pp. 6086-6090.

[26]	M. Wang, X. Zhang, H. Li, J. Lu, M. Liu, F. Wang. Carbon modification of nickel catalyst for depolymerization of oxidized lignin to aromatics. ACS Catal, 8 (2) (2018), pp. 1614-1620.

[27]	G. Dai, G. Wang, K. Wang, Z. Zhou, S. Wang. Mechanism study of hemicellulose pyrolysis by combining in situ DRIFT, TGA-PIMS and theoretical calculation. Proc Combust Inst, 38 (3) (2021), pp. 4241-4249.

[28]	G. Dai, K. Wang, G. Wang, S. Wang. Initial pyrolysis mechanism of cellulose revealed by in situ DRIFT analysis and theoretical calculation. Combust Flame, 208 (2019), pp. 273-280.

[29]	A.D. Becke. Density-functional exchange-energy approximation with correct asymptotic behavior. Phys Rev A, 38 (6) (1988), pp. 3098-3100.

[30]	C. Lee, W. Yang, R.G. Parr. Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B Condens Matter, 37 (2) (1988), pp. 785-789.

[31]	Y. Tan, H. Chen, J. Li, Q. Wu. Efficacy, chemical constituents, and pharmacological actions of Radix Paeoniae Rubra and Radix Paeoniae Alba. Front Pharmacol, 11 (2020), p. 1054.

[32]	R. Deng, J. Gao, J. Yi, P. Liu. Peony seeds oil by-products: chemistry and bioactivity. Ind Crops Prod, 187 (2022), Article 115333.

[33]	Y. Horikawa, S. Hirano, A. Mihashi, Y. Kobayashi, S. Zhai, J. Sugiyama. Prediction of lignin contents from infrared spectroscopy: chemical digestion and lignin/biomass ratios of Cryptomeria Japonica. Appl Biochem Biotechnol, 188 (4) (2019), pp. 1066-1076.

[34]	M. Roman, W.T. Winter. Effect of sulfate groups from sulfuric acid hydrolysis on the thermal degradation behavior of bacterial cellulose. Biomacromolecules, 5 (5) (2004), pp. 1671-1677.

[35]	A. Chaker, S. Alila, P. Mutje, M.R. Vilar, S. Boufi. Key role of the hemicellulose content and the cell morphology on the nanofibrillation effectiveness of cellulose pulps. Cellulose, 20 (6) (2013), pp. 2863-2875.

[36]	W. Chen, H. Yu, Y. Liu, P. Chen, M. Zhang, Y. Hai. Individualization of cellulose nanofibers from wood using high-intensity ultrasonication combined with chemical pretreatments. Carbohydr Polym, 83 (4) (2011), pp. 1804-1811.

[37]	M.J. Han, D.K. Yoon. Advances in soft materials for sustainable electronics. Engineering, 7 (5) (2021), pp. 564-580.

[38]	J. Gu, Y. Hsieh. Alkaline cellulose nanofibrils from streamlined alkali treated rice straw. ACS Sustain Chem Eng, 5 (2) (2017), pp. 1730-1737.

[39]	M.G. Northolt, H. Boerstoel, H. Maatman, R. Huisman, J. Veurink, H. Elzerman. The structure and properties of cellulose fibres spun from an anisotropic phosphoric acid solution. Polymer, 42 (19) (2001), pp. 8249-8264.

[40]	A.E. Oudiani, Y. Chaabouni, S. Msahli, F. Sakli. Crystal transition from cellulose I to cellulose II in NaOH treated Agave Americana L. fibre. Carbohydr Polym, 86 (3) (2011), pp. 1221-1229.

[41]	A.P. Mangalam, J. Simonsen, A.S. Benight. Cellulose/DNA hybrid nanomaterials. Biomacromolecules, 10 (3) (2009), pp. 497-504.

[42]	B. Deepa, E. Abraham, B.M. Cherian, A. Bismarck, J.J. Blaker, L.A. Pothan, et al. Structure, morphology and thermal characteristics of banana nano fibers obtained by steam explosion. Bioresource Technol, 102 (2) (2011), pp. 1988-1997.

[43]	Y. Yang, G. Banerjee, G.W. Brudvig, J. Kim, J.J. Pignatello. Oxidation of organic compounds in water by unactivated peroxymonosulfate. Environ Sci Technol, 52 (10) (2018), pp. 5911-5919.

[44]	Q. Wu, Z. Yang, Z. Wang, W. Wang. Oxygen doping of cobalt-single-atom coordination enhances peroxymonosulfate activation and high-valent cobalt-oxo species formation. Proc Natl Acad Sci, 120 (16) (2023) e2219923120.

[45]	A.C.W. Leung, S. Hrapovic, E. Lam, Y. Liu, K.B. Male, K.A. Mahmoud, et al. Characteristics and properties of carboxylated cellulose nanocrystals prepared from a novel one-step procedure. Small, 7 (3) (2011), pp. 302-305.

[46]	Y. Zhou, J. Jiang, Y. Gao, J. Ma, S. Pang, J. Li, et al. Activation of peroxymonosulfate by benzoquinone: a novel nonradical oxidation process. Environ Sci Technol, 49 (21) (2015), pp. 12941-12950.

[47]	S. Kutti Rani, S. Nirmal Kumar, C.Y. Wilson, A. Gopi, D. Easwaramoorthy. Oxidation of vanillin by peroxomonosulphate-thermodynamic and kinetic investigation. J Ind Eng Chem, 15 (6) (2009), pp. 898-901.

[48]	J. Kim, C. Huang. Reactivity of peracetic acid with organic compounds: a critical review. ACS EST Water, 1 (1) (2021), pp. 15-33.

[49]	L. Wu, Z. Sun, Y. Zhen, S. Zhu, C. Yang, J. Lu, et al. Oxygen vacancy-induced nonradical degradation of organics: critical trigger of oxygen (O₂) in the Fe-Co LDH/peroxymonosulfate system. Environ Sci Technol, 55 (22) (2021), pp. 15400-15411.

[50]	Y. Jiang, Z. Xiong, J. Huang, F. Yan, G. Yao, B. Lai. Effective E. coli inactivation of core-shell ZnO@ZIF-8 photocatalysis under visible light synergize with peroxymonosulfate: efficiency and mechanism. Chin Chem Lett, 33 (1) (2022), pp. 415-423.

[51]	J. Hu, X. Zeng, G. Wang, B. Qian, Y. Liu, X. Hu, et al. Modulating mesoporous Co₃O₄ hollow nanospheres with oxygen vacancies for highly efficient peroxymonosulfate activation. Chem Eng J, 400 (2020), Article 125869.

[52]	L. Lai, H. Zhou, Y. Hong, M. Luo, Y. Shi, H. Zhang, et al. Activation of peroxymonosulfate by FeVO₃-x for the degradation of carbamazepine: vanadium mediated electron shuttle and oxygen vacancy modulated interface chemistry. Chin Chem Lett, 35 (1) (2024), Article 108580.

[53]	G. Siqueira, A. Várnai, A. Ferraz, A.M.F. Milagres. Enhancement of cellulose hydrolysis in sugarcane bagasse by the selective removal of lignin with sodium chlorite. Appl Energy, 102 (2013), pp. 399-402.

[54]	H. Zhang, C. Xie, L. Chen, J. Duan, F. Li, W. Liu. Different reaction mechanisms of SO₄ center dot-and center dot OH with organic compound interpreted at molecular orbital level in Co(II)/peroxymonosulfate catalytic activation system. Water Res, 229 (2023), Article 119392.

[55]	M. Li, Q. Mei, D. Han, B. Wei, Z. An, H. Cao, et al. The roles of HO center dot, ClO center dot and BrO center dot radicals in caffeine degradation: a theoretical study. Sci Total Environ, 768 (2021), Article 144763.

[56]	Z. Qiu, K. Fu, D. Yu, J. Luo, J. Shang, S. Luo, et al. Radix Astragali residue-derived porous amino-laced double-network hydrogel for efficient Pb (II) removal: performance and modeling. J Hazard Mater, 438 (2022), Article 129418.

[57]	A.A. Houfani, N. Anders, A.C. Spiess, P. Baldrian, S. Benallaoua. Insights from enzymatic degradation of cellulose and hemicellulose to fermentable sugars—a review. Biomass Bioenergy, 134 (2020), Article 105481.

[58]	H. Dong, L. Zheng, P. Yu, Q. Jiang, Y. Wu, C. Huang, et al. Characterization and application of lignin-carbohydrate complexes from lignocellulosic materials as antioxidants for scavenging in vitro and in vivo reactive oxygen species. ACS Sustainable Chem Eng, 8 (1) (2020), pp. 256-266.