Abstract
2,2,6,6-tetramethylpiperidine-1-oxyl-radical (TEMPO) oxidation is a classical method to obtain carboxyl chitin nanomaterials, but when the traditional TEMPO/NaBr/NaClO (TBN) oxidation system was oxidizing β-chitin, it was only suitable for β-chitin with a degree of deacetylation (DD) of 1%. Herein, the high yield carboxyl β-chitin nanofibers (CO-ChNFs) were successfully prepared from squid pen β-chitin with partially deacetylated (DD: 5–30%) using the TEMPO/NaClO/NaClO2 (TNN) oxidation system. The results show that the DD of purified β-chitin has a great impact on the yield of CO-ChNFs, and the yield is as high as 98% when the DD of β-chitin was 11%. XRD results showed that β-chitin undergoes slight of β–α transformation after TNN TEMPO oxidation, and the 010 crystal planes are arranged more closely. AFM characterization suggests that thus prepared CO-ChNFs have a diameter of 2–6 nm and a length in the micrometer range. The proposed preparation method breaks through the previous limitation of TEMPO oxidation for β-chitin, and will facilitate the in-depth research and application of carboxyl β-chitin nanofibers.
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References
Anitha A et al (2014) Chitin and chitosan in selected biomedical applications. Prog Polym Sci 39:1644–1667. https://doi.org/10.1016/j.progpolymsci.2014.02.008
Bogdanova OI, Polyakov DK, Streltsov DR, Bakirov AV, Blackwell J, Chvalun SN (2016) Structure of beta-chitin from Berryteuthis magister and its transformation during whisker preparation and polymerization filling. Carbohydr Polym 137:678–684. https://doi.org/10.1016/j.carbpol.2015.11.027
Chen YJ, Zhang Q, Zhong Y, Wei PD, Yu XJ, Huang JC, Cai J (2021) Super-strong and super-stiff chitosan filaments with highly ordered hierarchical structure. Adv Funct Mater 31:2104368. https://doi.org/10.1002/adfm.202104368
Fan Y, Saito T, Isogai A (2008) Chitin nanocrystals prepared by TEMPO-mediated oxidation of α-chitin. Biomacromolecules 9:192–198. https://doi.org/10.1021/bm700966g
Fan YM, Saito T, Isogai A (2008) Preparation of chitin nanofibers from squid pen beta-chitin by simple mechanical treatment under acid conditions. Biomacromolecules 9:1919–1923. https://doi.org/10.1021/bm800178b
Fan YM, Saito T, Isogai A (2009) TEMPO-mediated oxidation of beta-chitin to prepare individual nanofibrils. Carbohydr Polym 77:832–838. https://doi.org/10.1016/j.carbpol.2009.03.008
Fan YM, Saito T, Isogai A (2010) Individual chitin nano-whiskers prepared from partially deacetylated alpha-chitin by fibril surface cationization. Carbohydr Polym 79:1046–1051. https://doi.org/10.1016/j.carbpol.2009.10.044
Fang Y, Xu Y, Wang Z, Zhou W, Yan L, Fan X, Liu H (2020) 3D porous chitin sponge with high absorbency, rapid shape recovery, and excellent antibacterial activities for noncompressible wound. Chem Eng J 388:124169. https://doi.org/10.1016/j.cej.2020.124169
Gonzalez-Gonzalez M, Mayolo-Deloisa K, Rito-Palomares M, Winkler R (2011) Colorimetric protein quantification in aqueous two-phase systems. Process Biochem 46:413–417. https://doi.org/10.1016/j.procbio.2010.08.026
Huang J, Zhong Y, Zhang L, Cai J (2017) Extremely strong and transparent chitin films: a high-efficiency, energy-saving, and “Green” route using an aqueous KOH/Urea solution. Adv Funct Mater 27:1701100. https://doi.org/10.1002/adfm.201701100
Jiang J, Yu J, Liu L, Wang ZG, Fan YM, Satio T, Isogai A (2018) Preparation and hydrogel properties of pH-sensitive amphoteric chitin nanocrystals. J Agr Food Chem 66:11372–11379. https://doi.org/10.1021/acs.jafc.8b02899
Jin J et al (2016) Chitin nanofiber transparent paper for flexible green electronics. Adv Mater 28:5169–5175. https://doi.org/10.1002/adma.201600336
Jin T et al (2020) Carboxylated chitosan nanocrystals: a synthetic route and application as superior support for gold-catalyzed reactions. Biomacromolecules 21:2236–2245. https://doi.org/10.1021/acs.biomac.0c00201
Jin T, Liu T, Lam E, Moores A (2021) Chitin and chitosan on the nanoscale. Nanoscale Horizons 6:505–542. https://doi.org/10.1039/D0NH00696C
Lasseuguette E, Roux D, Nishiyama Y (2008) Rheological properties of microfibrillar suspension of TEMPO-oxidized pulp. Cellulose 15:425–433. https://doi.org/10.1007/s10570-007-9184-2
Lu Y, Ye G, She X, Wang S, Yang D, Yin Y (2017) Sustainable route for molecularly thin cellulose nanoribbons and derived nitrogen-doped carbon electrocatalysts. ACS Sustain Chem Eng 5:8729–8737. https://doi.org/10.1021/acssuschemeng.7b01511
Ma QY, Pang K, Wang K, Huang SS, Ding BB, Duan YX, Zhang JM (2019) Ultrafine and carboxylated beta-chitin nanofibers prepared from squid pen and its transparent hydrogels. Carbohydr Polym 211:118–123. https://doi.org/10.1016/j.carbpol.2019.02.001
Ma H, Liu L, Yu J, Fan Y (2021) One-step preparation of chitin nanofiber dispersion in full pH surroundings using recyclable solid oxalic acid and evaluation of redispersed performance. Biomacromolecules 22:4373–4382. https://doi.org/10.1021/acs.biomac.1c00938
Pang K, Ding BB, Liu XT, Wu H, Duan YX, Zhang JM (2017) High-yield preparation of a zwitterionically charged chitin nanofiber and its application in a doubly pH-responsive Pickering emulsion. Green Chem 19:3665–3670. https://doi.org/10.1039/c7gc01592e
Pillai CKS, Paul W, Sharma CP (2009) Chitin and chitosan polymers: chemistry, solubility and fiber formation. Prog Polym Sci 34:641–678. https://doi.org/10.1016/j.progpolymsci.2009.04.001
Saito T, Hirota M, Tamura N, Kimura S, Fukuzumi H, Heux L, Isogai A (2009) Individualization of nano-sized plant cellulose fibrils by direct surface carboxylation using TEMPO catalyst under neutral conditions. Biomacromolecules 10:1992–1996. https://doi.org/10.1021/bm900414t
Suenaga S, Nikaido N, Totani K, Kawasaki K, Ito Y, Yamashita K, Osada M (2016) Effect of purification method of β-chitin from squid pen on the properties of β-chitin nanofibers. Int J Biol Macromol 91:987–993. https://doi.org/10.1016/j.ijbiomac.2016.06.060
Thomas B et al (2018) Nanocellulose, a versatile green platform: from biosources to materials and their applications. Chem Rev 118:11575–11625. https://doi.org/10.1021/acs.chemrev.7b00627
Tolaimate A, Desbrières J, Rhazi M, Alagui A, Vincendon M, Vottero P (2000) On the influence of deacetylation process on the physicochemical characteristics of chitosan from squid chitin. Polymer 41:2463–2469. https://doi.org/10.1016/S0032-3861(99)00400-0
Wu Q, Jungstedt E, Soltesova M, Mushi NE, Berglund LA (2019) High strength nanostructured films based on well-preserved beta-chitin nanofibrils. Nanoscale 11:11001–11011. https://doi.org/10.1039/c9nr02870f
Wu Q, Engstrom J, Li LW, Sehaqui H, Mushi NE, Berglund LA (2021) High-strength nanostructured film based on beta-chitin nanofibrils from squid illex argentinus pens by 2,2,6,6-tetramethylpiperidin-1-yl oxyl-mediated reaction. ACS Sustain Chem Eng 9:5356–5363. https://doi.org/10.1021/acssuschemeng.0c09406
Xu H, Fang Z, Tian W, Wang Y, Ye Q, Zhang L, Cai J (2018) Green fabrication of amphiphilic quaternized β-chitin derivatives with excellent biocompatibility and antibacterial activities for wound healing. Adv Mater 30:1801100. https://doi.org/10.1002/adma.201801100
Yang QL, Saito T, Berglund LA, Isogai A (2015) Cellulose nanofibrils improve the properties of all-cellulose composites by the nano-reinforcement mechanism and nanofibril-induced crystallization. Nanoscale 7:17957–17963. https://doi.org/10.1039/c5nr05511c
Yang X, Liu J, Pei Y, Zheng X, Tang K (2020) Recent progress in preparation and application of nano-chitin material. Energy Environ Mater 3:492–515. https://doi.org/10.1002/eem2.12079
Ye WB, Hu YL, Ma HZ, Liu L, Yu J, Fan YM (2020) Comparison of cast films and hydrogels based on chitin nanofibers prepared using TEMPO/NaBr/NaClO and TEMPO/NaClO/NaClO2 systems. Carbohydr Polym 237:116125. https://doi.org/10.1016/j.carbpol.2020.116125
Ye WB, Yokota S, Fan YM, Kondo T (2021) A combination of aqueous counter collision and TEMPO-mediated oxidation for doubled carboxyl contents of alpha-chitin nanofibers. Cellulose 28:2167–2181. https://doi.org/10.1007/s10570-021-03676-2
Yokoi M, Tanaka R, Saito T, Isogai A (2017) Dynamic viscoelastic functions of liquid-crystalline chitin nanofibril dispersions. Biomacromolecules 18:2564–2570. https://doi.org/10.1021/acs.biomac.7b00690
Acknowledgments
This work was supported by the National Natural Science Foundation of China (Grant Numbers 51573082 and 21774068), and State Key Laboratory of Bio-Fibers and Eco-Textiles (Qingdao University) (K2019-09).
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Funding was provided by the National Natural Science Foundation of China (Grant Numbers 51573082 and 21774068).
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Conceptualization: [DL]; Methodology: [DL]; Investigation : [DL], [SH], [HW]; Data curation: [DL]; Writing—original draft preparation: [DL]; Writing—review and editing: [JZ]; Supervision: [JZ]
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Liu, D., Huang, S., Wu, H. et al. Using TEMPO oxidation to tailor deacetylation of carboxyl β-chitin nanofibers from squid pen. Cellulose 29, 8539–8549 (2022). https://doi.org/10.1007/s10570-022-04817-x
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DOI: https://doi.org/10.1007/s10570-022-04817-x