Cellulose Degradation by Calcium Thiocyanate
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials
2.2. Dissolution of Cellulose and Preparation of Cellulose Aerogel
2.3. Fluorescence Labeling of Functional Groups and Dissolution of Cellulose Aerogels
2.4. SEC–MALS Analysis
2.5. Brunauer–Emmett–Teller (BET) Surface Area Analysis
3. Results and Discussion
3.1. Solubility Characteristics of Cellulose
3.2. Evaluation of Cellulose Hydrolysis during Dissolving Process
3.3. Evaluation of Cellulose Oxidation during Dissolving Process
3.4. BET Surface Area Analysis
4. Conclusions
Author Contributions
Funding
Conflicts of Interest
References
- Li, J.; Lu, Y.; Yang, D.; Sun, Q.; Liu, Y.; Zhao, H. Lignocellulose aerogel from wood-ionic liquid solution (1-allyl-3-methylimidazolium chloride) under freezing and thawing conditions. Biomacromolecules 2011, 12, 1860–1867. [Google Scholar] [CrossRef] [PubMed]
- Klemm, D.; Heublein, B.; Fink, H.-P.; Bohn, A. Cellulose: Fascinating biopolymer and sustainable raw material. Angew. Chem. Int. Ed. 2005, 44, 3358–3393. [Google Scholar] [CrossRef] [PubMed]
- Henniges, U.; Vejdovszky, P.; Siller, M.; Jeong, M.-J.; Rosenau, T.; Potthast, A. Finally dissolved! Activation procedures to dissolve cellulose in DMAc/LiCl prior to size exclusion chromatography analysis—A review. Curr. Chromatogr. 2014, 1, 52–68. [Google Scholar] [CrossRef]
- Klemm, D.; Cranston, E.D.; Fischer, D.; Gama, M.; Kedzior, S.A.; Kralisch, D.; Kramer, F.; Kondo, T.; Lindström, T.; Nietzsche, S.; et al. Nanocellulose as a natural source for groundbreaking applications in materials science: today’s state. Mater. Today 2018, 21, 720–748. [Google Scholar] [CrossRef]
- Geng, L.; Peng, X.; Zhan, C.; Naderi, A.; Sharma, P.R.; Mao, Y.; Hsiao, B.S. Structure characterization of cellulose nanofiber hydrogel as functions of concentration and ionic strength. Cellulose 2017, 24, 5417–5429. [Google Scholar] [CrossRef]
- Sharma, P.R.; Sharma, S.K.; Antoine, R.; Hsiao, B.S. Efficient removal of arsenic using zinc oxide nanocrystal-decorated regenerated microfibrillated cellulose scaffold. ACS Sustain. Chem. Eng. 2019, 7, 6140–6151. [Google Scholar] [CrossRef]
- Sharma, P.R.; Rajamohanan, P.R.; Varma, A.J. Supramolecular transitions in native cellulose-I during progressive oxidation reaction leading to quasi-spherical nanoparticles of 6-carboxycellulose. Carbohyd. Polym. 2014, 113, 615–623. [Google Scholar] [CrossRef] [PubMed]
- Sharma, P.R.; Kamble, S.; Sarkar, D.; Anand, A.; Varma, A. Shape and size engineered cellulosic nanomaterials as broad spectrum anti-microbial compounds. Int. J. Biol. Macromol. 2016, 87, 460–465. [Google Scholar] [CrossRef] [PubMed]
- Sharma, P.R.; Zheng, B.; Sharma, S.K.; Zhan, C.; Wang, R.; Bhatia, S.R.; Hsiao, B.S. High aspect ratio carboxycellulose nanofibers prepared by nitro-oxidation method and their nanopaper properties. ACS Appl. Nano Mater. 2018, 1, 3969–3980. [Google Scholar] [CrossRef]
- Golmohammadi, H.; Morales-Narváez, E.; Naghdi, T.; Merkoc, A. Nanocellulose in sensing and biosensing. Chem. Mater. 2017, 29, 5426–5446. [Google Scholar] [CrossRef]
- Sabo, R.; Yermakov, A.; Law, C.T.; Elhajjar, R. Nanocellulose-enabled electronics, energy harvesting devices, smart materials and sensors: A review. J. Renew. Mater. 2016, 4, 297–312. [Google Scholar] [CrossRef]
- Sharma, P.R.; Joshi, R.; Sharma, S.K.; Hsiao, B.S. A simple approach to prepare carboxycellulose nano fibers from untreated biomass. Biomacromolecules 2017, 18, 2333–2342. [Google Scholar] [CrossRef] [PubMed]
- Sharma, P.R.; Chattopadhyay, A.; Sharma, S.K.; Geng, L.; Amiralian, N.; Martin, D.; Hsiao, B.S. Nanocellulose from Spinifex as an effective adsorbent to remove cadmium(II) from water. ACS Sustain. Chem. Eng. 2018, 6, 3279–3290. [Google Scholar] [CrossRef]
- Sharma, P.R.; Chattopadhyay, A.; Sharma, S.K.; Hsiao, B.S. Efficient removal of UO22+ from water using carboxycellulose nano fibers prepared by the nitro-oxidation method. Ind. Eng. Chem. Res. 2017, 56, 13885–13893. [Google Scholar] [CrossRef]
- Moon, R.J.; Martini, A.; Nairn, J.; Simonsen, J.; Youngblood, J. Cellulose nanomaterials review: Structure, properties and nanocomposites. Chem. Soc. Rev. 2011, 40, 3941–3994. [Google Scholar] [CrossRef] [PubMed]
- Tan, C.; Fung, B.M.; Newman, J.K.; Vu, C. Organic aerogels with very high impact strength. Adv. Mater. 2001, 13, 644–646. [Google Scholar] [CrossRef]
- Jin, H.; Nishiyama, Y.; Wada, M.; Kuga, S. Nanofibrillar cellulose aerogels. Colloid Surf. A Physicochem. Eng. Asp. 2004, 240, 63–67. [Google Scholar] [CrossRef]
- Hoepfner, S.; Ratke, L.; Milow, B. Synthesis and characterisation of nanofibrillar cellulose aerogels. Cellulose 2008, 15, 121–129. [Google Scholar] [CrossRef]
- Gupta, P.; Singh, B.; Agrawal, A.K.; Maji, P.K. Low density and high strength nanofibrillated cellulose aerogel for thermal insulation application. Mater. Des. 2018, 158, 224–236. [Google Scholar] [CrossRef]
- Long, L.-Y.; Weng, Y.-X.; Wang, Y.-Z. Cellulose aerogels: Synthesis, applications, and prospects. Polymers 2018, 10, 623. [Google Scholar] [CrossRef]
- Seantier, B.; Bendahou, D.; Bendahou, A.; Grohens, Y.; Kaddami, H. Multi-scale cellulose based new bio-aerogel composites with thermal super-insulating and tunable mechanical properties. Carbohydr. Polym. 2016, 138, 335–348. [Google Scholar] [CrossRef] [PubMed]
- Sai, H.; Xing, L.; Xiang, J.; Cui, L.; Jiao, J.; Zhao, C.; Li, Z.; Li, F.; Zhang, T. Flexible aerogels with interpenetrating network structure of bacterial cellulose-silica composite from sodium silicate precursor via freeze drying process. RSC Adv. 2014, 4, 30453–30461. [Google Scholar] [CrossRef]
- Jin, H.; Kettunen, M.; Laiho, A.; Pynnönen, H.; Paltakari, J.; Marmur, A.; Ikkala, O.; Ras, R.H.A. Superhydrophobic and superoleophobic nanocellulose aerogel membranes as bioinspired cargo carriers on water and oil. Langmuir 2011, 27, 1930–1934. [Google Scholar] [CrossRef] [PubMed]
- Martins, B.F.; de Toledo, P.V.O.; Petri, D.F.S. Hydroxypropyl methylcellulose based aerogels: Synthesis, characterization and application as adsorbents for wastewater pollutants. Carbohydr. Polym. 2017, 155, 173–181. [Google Scholar] [CrossRef] [PubMed]
- Panzella, L.; Melone, L.; Pezzella, A.; Rossi, B.; Pastori, N.; Perfetti, M.; D’Errico, G.; Punta, C.; D’Ischia, M. Surface-functionalization of nanostructured cellulose aerogels by solid state eumelanin coating. Biomacromolecules 2016, 17, 564–571. [Google Scholar] [CrossRef] [PubMed]
- Wang, Y.; Yadav, S.; Heinlein, T.; Konjik, V.; Breitzke, H.; Buntkowsky, G.; Schneider, J.J.; Zhang, K. Ultra-light nanocomposite aerogels of bacterial cellulose and reduced graphene oxide for specific absorption and separation of organic liquids. RSC Adv. 2014, 4, 21553–21558. [Google Scholar] [CrossRef] [Green Version]
- Jiang, F.; Hsieh, Y.-L. Amphiphilic superabsorbent cellulose nanofibril aerogels. J. Mater. Chem. A 2014, 2, 6337–6342. [Google Scholar] [CrossRef] [Green Version]
- Shen, Z.; Mitragotri, S. Intestinal patches for oral drug delivery. Pharm. Res. 2002, 19, 391–395. [Google Scholar] [CrossRef]
- Henschen, J.; Illergård, J.; Larsson, P.A.; Ek, M.; Wågberg, L. Contact-active antibacterial aerogels from cellulose nanofibrils. Colloids Surf. B Biointerfaces 2016, 146, 415–422. [Google Scholar] [CrossRef]
- Cai, H.; Sharma, S.; Liu, W.; Mu, W.; Liu, W.; Zhang, X.; Deng, Y. Aerogel microspheres from natural cellulose nanofibrils and their application as cell culture scaffold. Biomacromolecules 2014, 15, 2540–2547. [Google Scholar] [CrossRef]
- Raghuwanshi, V.S.; Cohen, Y.; Garnier, G.; Garvey, C.J.; Russell, R.A.; Darwish, T.; Garnier, G. Cellulose dissolution in ionic liquid: Ion binding revealed by neutron scattering. Macromolecules 2018, 51, 7649–7655. [Google Scholar] [CrossRef]
- Mohd, N.; Draman, S.F.S.; Salleh, M.S.N.; Yusof, N.B. Dissolution of cellulose in ionic liquid: A review. AIP Conf. Proc. 2017, 1809, 020035. [Google Scholar] [CrossRef]
- Rosenau, T.; Potthast, A.; Sixta, H.; Kosma, P. The chemistry of side reactions and byproduct formation in the system NMMO/cellulose (Lyocell process). Prog. Polym. Sci. 2001, 26, 1763–1837. [Google Scholar] [CrossRef]
- Zhang, S.; Wang, W.-C.; Li, F.-X.; Yu, J.-Y. Swelling and dissolution of cellulose in NaOH aqueous solvent systems. Cell. Chem. Technol. 2013, 47, 671–679. [Google Scholar]
- Röhrling, J.; Potthast, A.; Rosenau, T.; Lange, T.; Ebner, G.; Sixta, H.; Kosma, P. A novel method for the determination of carbonyl groups in cellulosics by fluorescence labeling. 1. Method development. Biomacromolecules 2002, 3, 959–968. [Google Scholar] [CrossRef]
- Bohrn, R.; Potthast, A.; Rosenau, T.; Sixta, H.; Kosma, P. Synthesis and testing of a novel fluorescence label for carboxyls in carbohydrates and cellulosics. Synlett 2005, 20, 3087–3090. [Google Scholar] [CrossRef]
- Fischer, S.; Leipner, H.; Thümmler, K.; Brendler, E.; Peters, J. Inorganic molten salts as solvents for cellulose. Cellulose 2003, 10, 227–236. [Google Scholar] [CrossRef]
- Leipner, H.; Fischer, S.; Brendler, E.; Voigt, W. Structural changes of cellulose dissolved in molten salt hydrates. Macromol. Chem. Phys. 2000, 201, 2041–2049. [Google Scholar] [CrossRef]
- Medronho, B.; Lindman, B. Competing forces during cellulose dissolution: From solvents to mechanisms. Curr. Opin. Colloid Interface Sci. 2014, 19, 32–40. [Google Scholar] [CrossRef]
- Pircher, N.; Carbajal, L.; Schimper, C.; Bacher, M.; Rennhofer, H.; Lichtenegger, H.C.; Nedelec, J.-M.; Rosenau, T.; Liebner, F. Impact of selected solvent systems on the pore and solid structure of cellulose aerogels. Cellulose 2016, 23, 1949–1966. [Google Scholar] [CrossRef] [Green Version]
- Lavoine, N.; Bergström, L. Nanocellulose-based foams and aerogels: Processing, properties, and applications. J. Mater. Chem. A 2017, 5, 16105–16117. [Google Scholar] [CrossRef]
- Jeong, M.-J.; Lee, S.; Kang, K.-Y.; Potthast, A. Changes in the structure of cellulose aerogels with depolymerization. J. Korean Phys. Soc. 2015, 67, 742–745. [Google Scholar] [CrossRef]
- Lee, S.; Jeong, M.-J.; Kang, K.-Y. Preparation of cellulose aerogels as a nano-biomaterial from lignocellulosic biomass. J. Korean Phys. Soc. 2015, 67, 738–741. [Google Scholar] [CrossRef]
- Kuga, S. The porous structure of cellulose gel regenerated from calcium thiocyanate solution. J. Colloid Interface Sci. 1980, 77, 413–417. [Google Scholar] [CrossRef]
- Röhrling, J.; Potthast, A.; Rosenau, T.; Lange, T.; Borgards, A.; Sixta, H.; Kosma, P. A novel method for the determination of carbonyl groups in cellulosics by fluorescence labeling. 2. Validation and applications. Biomacromolecules 2002, 3, 969–975. [Google Scholar] [CrossRef] [PubMed]
- Jeong, M.-J.; Kang, K.-Y.; Bacher, M.; Kim, H.-J.; Jo, B.-M.; Potthast, A. Deterioration of ancient cellulose paper, Hanji: Evaluation of paper permanence. Cellulose 2014, 21, 4621–4632. [Google Scholar] [CrossRef]
- Bohrn, R.; Potthast, A.; Schiehser, S.; Rosenau, T.; Sixta, H.; Kosma, P. The FDAM method: Determination of carboxyl profiles in cellulosic materials by combining group-selective fluorescence labeling with GPC. Biomacromolecules 2006, 7, 1743–1750. [Google Scholar] [CrossRef]
- Emsley, A.M.; Heywood, R.J.; Ali, M.; Eley, C.M. On the kinetics of degradation of cellulose. Cellulose 1997, 4, 1–5. [Google Scholar] [CrossRef]
- Hattori, M.; Shimaya, Y.; Saito, M. Solubility and dissolved cellulose in aqueous calcium- and sodium-thiocyanate solution. Polym. J. 1998, 30, 49–55. [Google Scholar] [CrossRef]
- Lee, S.; Jeong, M.-J.; Potthast, A.; Liebner, F.; Kang, K.-Y. Evaluation of supercritical CO2 dried cellulose aerogels as nano-biomaterials. J. Korean Phys. Soc. 2017, 71, 483–486. [Google Scholar] [CrossRef]
- Budtova, T. Cellulose II aerogels: A review. Cellulose 2019, 26, 81–121. [Google Scholar] [CrossRef]
- Zdravkov, B.D.; Čermák, J.; Šefara, M.; Janků, J. Pore classification in the characterization of porous materials: A perspective. Cent. Eur. J. Chem. 2007, 5, 385–395. [Google Scholar] [CrossRef]
- Reichenauer, G. Structural characterization of aerogels. In Aerogels Handbook; Aegerter, M.A., Leventis, N., Koebel, M.M., Eds.; Springer: New York, NY, USA, 2011; pp. 471–482. [Google Scholar] [CrossRef]
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Jeong, M.-J.; Lee, S.; Yang, B.S.; Potthast, A.; Kang, K.-Y. Cellulose Degradation by Calcium Thiocyanate. Polymers 2019, 11, 1494. https://doi.org/10.3390/polym11091494
Jeong M-J, Lee S, Yang BS, Potthast A, Kang K-Y. Cellulose Degradation by Calcium Thiocyanate. Polymers. 2019; 11(9):1494. https://doi.org/10.3390/polym11091494
Chicago/Turabian StyleJeong, Myung-Joon, Sinah Lee, Bong Suk Yang, Antje Potthast, and Kyu-Young Kang. 2019. "Cellulose Degradation by Calcium Thiocyanate" Polymers 11, no. 9: 1494. https://doi.org/10.3390/polym11091494