Abstract
Bacterial cellulose nanocrystals (BCNCs) have hydrophilic surfaces due to hydroxyl groups but are water-insoluble. The carboxymethylation improves the solubility of cellulose in polar media through the insertion of carboxymethyl groups. This study aims to evaluate the use of two different alcoholic solvents in the carboxymethylation reaction of BCNCs: ethanol and isopropanol. BCNCs were obtained under two hydrolysis conditions: sulfuric acid (BCNC-S) and combination of sulfuric and hydrochloric acids (BCNC-S/Cl). Two techniques (NMR and titration) were used to determine the degree of substitution (DS) values. Carboxymethylation of BCNC-S/Cl led to high DS compared to BCNC-S and the use of isopropanol promoted an even greater DS. The thermal properties were not affected after the chemical modification. However, functionalization provided an increase in the negative charge density at the surface of nanostructures and a change in the crystal structure (cellulose type Iα for amorphous), making this material a potential polyanion for the synthesis of polyelectrolyte complexes (PECs). The micrographs showed that the nanocrystals became soluble after carboxymethylation. Carboxymethylated bacterial cellulose nanocrystals hydrolyzed through the mixture of inorganic acids and modified using isopropanol (CBCNC-S/Cl-IPA) was a suitable polyanion to produce PECs with chitosan. The PECs produced had particle size ranging from 276 to 588 nm and zeta potential ranging from − 24.3 to + 39.0 mV.
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Abraham E, Kam D, Nevo Y, Slattegard R, Rivkin A, Lapidot S, Shoseyov O (2016) Highly modified cellulose nanocrystals and formation of epoxy-nanocrystalline cellulose (CNC) nanocomposites. ACS Appl Mater Interfaces 8(41):28086–28095. https://doi.org/10.1021/acsami.6b09852
Ambjörnsson HA, Schenzel K, Germgard U (2013) Carboxymethyl cellulose produced at different mercerization conditions and characterized by NIR FT Raman spectroscopy in combination with multivariate analytical methods. BioResources 8(2):1918–1932
ASTM: D1439-15 (2015) Standard test methods for sodium carboxymethylcellulose. ASTM International, West Conshohocken. https://doi.org/10.1520/D1439-15
Bigucci F, Abruzzo A, Vitali B, Saladini B, Cerchiara T, Gallucci MC, Luppi B (2015) Vaginal inserts based on chitosan and carboxymethylcellulose complexes for local delivery of chlorhexidine: preparation, characterization and antimicrobial activity. Int J Pharm 478:456–463. https://doi.org/10.1016/j.ijpharm.2014.12.008
Boddohi S, Moore N, Johnson PA, Kipper MJ (2009) Polysaccharide-Based Polyelectrolyte Complex Nanoparticles from Chitosan, Heparin, and Hyaluronan. Biomacromolecules 10(6):1402–1409. https://doi.org/10.1021/bm801513e
Campelo CS, Lima LD, Rebêlo LM, Mantovani D, Beppu MM, Vieira RS (2016) In vitro evaluation of anti-calcification and anti-coagulation on sulfonated chitosan and carrageenan surfaces. Mater Sci Eng C Mater 59:241–248. https://doi.org/10.1016/j.msec.2015.10.020
Candido RG, Gonçalves AR (2016) Synthesis of cellulose acetate and carboxymethylcellulose from sugarcane straw. Carbohydr Polym 152:679–686. https://doi.org/10.1016/j.carbpol.2016.07.071
Casaburi A, Montoya Rojo Ú, Cerrutti P, Vázquez A, Foresti ML (2018) Carboxymethyl cellulose with tailored degree of substitution obtained from bacterial cellulose. Food Hydrocoll 75:147–156. https://doi.org/10.1016/j.foodhyd.2017.09.002
Cha R, He ZB, Ni YH (2012) Preparation and characterization of thermal/pH-sensitive hydrogel from carboxylated nanocrystalline cellulose. Carbohydr Polym 88:713–718. https://doi.org/10.1016/j.carbpol.2012.01.026
Chang W, Chen H (2016) Physical properties of bacterial cellulose composites for wound dressings. Food Hydrocoll 53:75–83. https://doi.org/10.1016/j.foodhyd.2014.12.009
Charreau H, Foresti ML, Vázquez A (2013) Nanocellulose patents trends: a comprehensive review on patents on cellulose nanocrystals, microfibrillated, and bacterial cellulose. Recent Pat Nanotechnol 7:56–80. https://doi.org/10.2174/187221013804484854
Chawla PR, Bajaj IB, Survase SA, Singhal RS (2009) Microbial cellulose: fermentative production and applications. Food Technol Biotechnol 47:107–124
Coseri S, Biliuta G, Simionescu BC, Stana-Kleinschek K, Ribitsch V, Harabagiu V (2013) Oxidized cellulose—survey of the most recent achievements. Carbohydr Polym 93:207–215. https://doi.org/10.1016/j.carbpol.2012.03.086
Das AM, Ali AA, Hazarika MP (2014) Synthesis and characterization of cellulose acetate from rice husk: eco-friendly condition. Carbohydr Polym 112:342–349. https://doi.org/10.1016/j.carbpol.2014.06.006
Degen T, Sadki M, Bron E, König U, Nénert G (2014) The high-score suite. Powder Diffr 29:13–18
Dufresne A (2012) Nanocellulose: from nature to high performance tailored materials (chapter 3), 1st edn. Walter de Gruyter, Boston
Dufresne A (2017) Cellulose nanomaterial reinforced polymer nanocomposites. Curr Opin Colloid Interface Sci 29:1–8. https://doi.org/10.1016/j.cocis.2017.01.004
Elomaa M, Asplund T, Soininen P, Laatikainen R, Peltonen S, Hyvarinen S, Urtti A (2004) Determination of the degree of substitution of acetylated starch by hydrolysis, H-1 NMR and TGA/IR. Carbohydr Polym 57:261–267. https://doi.org/10.1016/j.carbpol.2004.05.003
Ferreira FV, Mariano M, Rabelo SC, Gouveia RF, Lona LMF (2018) Isolation and surface modification of cellulose nanocrystals from sugarcane bagasse waste: from a micro- to a nano-scale view. Appl Surf Sci 436:1113–1122. https://doi.org/10.1016/j.apsusc.2017.12.137
French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21(2):885–896. https://doi.org/10.1007/s10570-013-0030-4
French AD, Cintrón MS (2013) Cellulose polymorphy, crystallite size, and the Segal crystallinity index. Cellulose 20(1):583–588. https://doi.org/10.1007/s10570-012-9833-y
Fukuzumi H, Saito T, Iwata T, Kumamoto Y, Isogai A (2008) Transparent and high gas barrier films of cellulose nanofibers prepared by TEMPO-mediated oxidation. Biomacromol 10:162–165. https://doi.org/10.1021/bm801065u
Gama M, Gatenholm P, Klemm D (eds) (2012) Bacterial nanocellulose: a sophisticated multifunctional material (chapter 2). CRC Press, Boca Raton
Ge Y, Li Z (2013) Preparation and evaluation of sodium carboxymethylcellulose from sugarcane bagasse for application in coal-water slurry. J Macromol Sci A 50(7):757–762. https://doi.org/10.1080/10601325.2013.792646
Ghasemi S, Behrooz R, Ghasemi I (2016) Extraction and characterization of nanocellulose structures from linter dissolving pulp using ultrafine grinder. J Nanosci Nanotechnol 16(6):5791–5797. https://doi.org/10.1166/jnn.2016.12416
Grishkewich N, Mohammed N, Tang J, Tam KC (2017) Recent advances in the application of cellulose nanocrystals. Curr Opin Colloid Interface Sci 29:32–45. https://doi.org/10.1016/j.cocis.2017.01.005
Gromovykh TI, Sadykova VS, Lutcenko SV, Dmitrenok AS, Feldman NB, Danilchuk TN, Kashirin VV (2017) Bacterial cellulose synthesized by Gluconacetobacter hansenii for medical applications. Appl Biochem Microbiol 53:60–67. https://doi.org/10.1134/S0003683817010094
Gu J, Catchmark JM, Kaiser EQ, Archibald DD (2013) Quantification of cellulose nanowhiskers sulfate esterification levels. Carbohydr Polym 92:1809–1816. https://doi.org/10.1016/j.carbpol.2012.10.078
Guo J, Catchmark JM (2012) Surface area and porosity of acid hydrolyzed cellulose nanowhiskers and cellulose produced by Gluconacetobacter xylinus. Carbohydr Polym 87:1026–1037. https://doi.org/10.1016/j.carbpol.2011.07.060
Habibi Y (2014) Key advances in the chemical modification of nanocelluloses. Chem Soc Rev 43:1519–1542. https://doi.org/10.1039/C3CS60380F
Haleem N, Arshad M, Shahid M, Tahir MA (2014) Synthesis of carboxymethyl cellulose from waste of cotton ginning industry. Carbohydr Polym 113:249–255. https://doi.org/10.1016/j.carbpol.2014.07.023
Hattori K, Arai A (2016) Preparation and hydrolysis of water-stable amorphous cellulose. ACS Sustain Chem Eng 4(3):1180–1186. https://doi.org/10.1021/acssuschemeng.5b01247
Ho FF, Klosiewicz DW (1980) Proton nuclear magnetic resonance spectrometry for determination of substituents and their distribution in carboxymethylcellulose. Anal Chem 52:913–916. https://doi.org/10.1021/ac50056a032
Horii F, Hirai A, Kitamaru R (1987) CP/MAS carbon-13 NMR spectra of the crystalline components of native celluloses. Macromolecules 20(9):2117–2120. https://doi.org/10.1021/ma00175a012
Ibrahim AA, Adel AM, El-Wahab ZH, Al-Shemy MT (2011) Utilization of carboxymethyl cellulose based on bean hulls as chelating agent synthesis, characterization and biological activity. Carbohydr Polym 83:94–115. https://doi.org/10.1016/j.carbpol.2010.07.026
Kian LK, Jawaid M, Ariffin H, Karim Z (2018) Isolation and characterization of nanocrystalline cellulose from roselle-derived microcrystalline cellulose. Int J Biol Macromol 114:54–63. https://doi.org/10.1016/j.ijbiomac.2018.03.065
Krystynowicz A, Czaja W, Wiktorowska-Jezierska A, Gonçalves-Miskiewicz M, Turkiewicz M, Bielecki S (2002) Factors affecting the yield and properties of bacterial cellulose. J Ind Microbiol Biotechnol 29:189–195. https://doi.org/10.1038/sj.jim.7000303
Lankalapalli S, Kolapalli VRM (2009) Polyelectrolyte complexes: a review of their applicability in drug delivery technology. Indian J Pharm Sci 71:481–487. https://doi.org/10.4103/0250-474X.58165
Leng I, Zhang Y, Peng Y, Gong X, Mao M, Li X, Yu Y (2018) In situ structural changes of crystalline and amorphous cellulose during slow pyrolysis at low temperatures. Fuel 216:313–321. https://doi.org/10.1016/j.fuel.2017.11.083
Lin N, Dufresne A (2014) Surface chemistry, morphological analysis and properties of cellulose nanocrystals with gradient sulfation degrees. Nanoscale 6:5384–5393. https://doi.org/10.1039/C4NR00241E
Liu T, An QF, Wang XS, Zhao Q, Zhu BK, Gao CJ (2014) Preparation and properties of PEC nanocomposite membranes with carboxymethyl cellulose and modified silica. Carbohydr Polym 106:403–409. https://doi.org/10.1016/j.carbpol.2014.01.040
Lu P, Hsieh Y (2010) Preparation and properties of cellulose nanocrystals: rods, spheres, and network. Carbohydr Polym 82(2):329–336. https://doi.org/10.1016/j.carbpol.2010.04.073
Ma X, Cheng Y, Qin X, Guo T, Deng J, Liu X (2017) Hydrophilic modification of cellulose nanocrystals improves the physicochemical properties of cassava starch-based nanocomposite films. LWT Food Sci Technol 86:318–326. https://doi.org/10.1016/j.lwt.2017.08.012
McMurry J (2013) Organic chemistry (chapter 2), 7th edn. Cengage Lernaning, São Paulo
Meng X, Edgar KJ (2015) Synthesis of amide-functionalized cellulose esters by olefin cross-metathesis. Carbohydr Polym 132:565–573. https://doi.org/10.1016/j.carbpol.2015.06.052
Mirhosseini H, Tan CP, Hamid NSA, Yusof S (2008) Effect of arabic gum, xanthan gum and orange oil contents on ζ-potential, conductivity, stability, size index and pH of orange beverage emulsion. Colloids Surf A 315:47–56. https://doi.org/10.1016/j.colsurfa.2007.07.007
Morais JPS, Rosa MF, Souza MSM, Nascimento LD, Nascimento DM, Cassales AR (2013) Extraction and characterization of nanocellulose structures from raw cotton linter. Carbohydr Polym 91(1):229–235. https://doi.org/10.1016/j.carbpol.2012.08.010
Moreira S, Silva NB, Lima JA, Rocha HAO, Medeiros SRB, Alves Junior C, Gama FM (2009) BC nanofibres: in vitro study of genotoxicity and cell proliferation. Toxicol Lett 189:235–241. https://doi.org/10.1016/j.toxlet.2009.06.849
Mukarakate C, Mittal A, Ciesielski PN, Budhi S, Thompson L, Iisa K, Nimlos MR, Donohoe BS (2016) Influence of crystal allomorph and crystallinity on the products and behavior of cellulose during fast pyrolysis. ACS Sustain Chem Eng 4(9):4662–4674. https://doi.org/10.1021/acssuschemeng.6b00812
Ng HM, Sin LT, Tee TT, Bee ST, Hui D, Low CY, Rahmat AR (2015) Extraction of cellulose nanocrystals from plant sources for application as reinforcing agent in polymers. Compos B 75:176–200. https://doi.org/10.1016/j.compositesb.2015.01.008
Nishiyama Y, Sugiyama J, Chanzy H, Langan P (2003) Crystal structure and hydrogen bonding system in cellulose Iα from synchrotron X-ray and neutron fiber diffraction. J Am Chem Soc 125(47):14300–14306. https://doi.org/10.1021/ja037055w
Pecoraro E, Manzani D, Messaddeq Y, Ribeiro SJ (2008) Monomers, polymers and composites from renewable resources. Bacterial cellulose from Glucanacetobacter xylinus: preparation, properties and applications, 1st edn. Elsevier, Oxford, pp 369–384
Pereira ALS, Nascimento DMD, de Souza Filho M, Sá M, Morais JPS, Vasconcelos NF, Feitosa JPA, de Rosa MF (2014) Improvement of polyvinyl alcohol properties by adding nanocrystalline cellulose isolated from banana pseudostems. Carbohydr Polym 112:165–172. https://doi.org/10.1016/j.carbpol.2014.05.090
Petersson L, Kvien I, Oksman K (2007) Structure and thermal properties of poly(lactic acid)/cellulose whiskers nanocomposite materials. Compos Sci Technol 67:2535–2544. https://doi.org/10.1016/j.compscitech.2006.12.012
Picheth GF, Pirich CL, Sierakowski MR, Woehl MA, Sakakibara CN, Souza CF, Martin AA, Silva R, Freitas RA (2017) Bacterial cellulose in biomedical application: a review. Int J Biol Macromol 104:97–106. https://doi.org/10.1016/j.ijbiomac.2017.05.171
Pushpamalar V, Langford SJ, Ahmad M, Lim YY (2006) Optimization of reaction conditions for preparing carboxymethyl cellulose from sago waste. Carbohydr Polym 64:312–318. https://doi.org/10.1016/j.carbpol.2005.12.003
Qi H, Liebert T, Meister F, Heinze T (2009) Homogenous carboxymethylation of cellulose in the NaOH/urea aqueous solution. React Funct Polym 69:779–784. https://doi.org/10.1016/j.reactfunctpolym.2009.06.007
Rachtanapun P, Luangkamin S, Tanprasert K, Suriyatem R (2012) Carboxymethyl cellulose film from durian rind. LWT Food Sci Technol 48:52–58. https://doi.org/10.1016/j.lwt.2012.02.029
Ramírez JAA, Suriano CJ, Cerrutti P, Foresti ML (2014) Surface esterification of cellulose nanofibers by a simple organocatalytic methodology. Carbohydr Polym 114:416–423. https://doi.org/10.1016/j.carbpol.2014.08.020
Roman M, Winter WT (2004) Effect of sulfate groups from sulfuric acid hydrolysis on the thermal degradation behavior of bacterial cellulose. Biomacromol 5:1671–1677. https://doi.org/10.1021/bm034519
Santos DM, Lacerda BA, Ascheri DPR, Signini R, Aquino GLB (2015) Microwave-assisted carboxymethylation of cellulose extracted from Brewer’s spent grain. Carbohydr Polym 131:125–133. https://doi.org/10.1016/j.carbpol.2015.05.051
Schatz C, Lucas JM, Viton C, Domard A, Pichot C, Delair T (2004) Formation and Properties of Positively Charged Colloids Based on Polyelectrolyte Complexes of Biopolymers. Langmuir 20(18):7766–7778. https://doi.org/10.1021/la049460m
Scherrer P (1918) Bestimmung der Größe und der inneren Struktur von Kolloidteilchen mittels Röntgenstrahlen. Nachrichten von der Gesellschaft der Wissenschaften zu Göttingen, Mathematisch-Physikalische Klasse, pp 98–100. http://resolver.sub.uni-goettingen.de/purl?PPN252457811_1918. Accessed 5 Dec 2018.
Seabra AB, Bernardes JS, Fávaro WJ, Paula AJ, Durán N (2018) Cellulose nanocrystals as carriers in medicine and their toxicities: a review. Carbohydr Polym 181:515–527. https://doi.org/10.1016/j.carbpol.2017.12.014
Segal L, Creely J, Martin A, Conrad C (1959) An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer. Text Res J 29:786–794. https://doi.org/10.1177/004051755902901003
Shang Q, Liu C, Hu Y, Jia P, Hu L, Zhou Y (2018) Bio-inspired hydrophobic modification of cellulose nanocrystals with castor oil. Carbohydr Polym 191:168–175. https://doi.org/10.1016/j.carbpol.2018.03.012
Shoda M, Sugano Y (2005) Recent advances in bacterial cellulose production. Biotechnol Bioprocess Eng 10:1–8. https://doi.org/10.1007/BF02931175
Song Y, Chen L (2015) Effect of net surface charge on physical properties of the cellulose nanoparticles and their efficacy for oral protein delivery. Carbohydr Polym 121:10–17. https://doi.org/10.1016/j.carbpol.2014.12.019
Sugiyama J, Persson J, Chanzy H (1991) Combined infrared and electron diffraction study of the polymorphism of native celluloses. Macromolecules 24(9):2461–2466. https://doi.org/10.1021/ma00009a050
Togrul H, Arslan N (2004) Carboxymethyl cellulose from sugar beet pulp cellulose as a hydrophilic polymer in coating of mandarin. J Food Eng 62:271–279. https://doi.org/10.1016/S0260-8774(03)00240-1
Varma CAK, Koley RK, Singh S, Sen AK, Kumar KJ (2016) Homogeneous carboxymethylated orange pulp cellulose: characterization and evaluation in terms of drug delivery. Int J Biol Macromol 93:1141–1146. https://doi.org/10.1016/j.ijbiomac.2016.09.084
Vasconcelos NF, Feitosa JPA, Gama FMP, Morais JPS, Andrade FK, Souza MSM, Rosa MF (2017) Bacterial cellulose nanocrystals produced under different hydrolysis conditions: properties and morphological features. Carbohydr Polym 155:425–431. https://doi.org/10.1016/j.carbpol.2016.08.090
Vehlow D, Schmidt R, Gebert A, Siebert M, Lips KS, Müller M (2016) Polyelectrolyte complex based interfacial drug delivery system with controlled loading and improved release performance for bone therapeutics. Nanomaterials 6(53):1–21. https://doi.org/10.3390/nano6030053
Wan Y, An F, Zhou P, Liu Y, Lu C, Chen H (2017) Effect of the polymorphs of cellulose on its pyrolysis kinetic and char yield. J Anal Appl Pyrolysis 127:223–228. https://doi.org/10.1016/j.jaap.2017.08.002
Wu H, Williams GR, Wu J, Wu J, Niu S, Li H, Zhu L (2018a) Regenerated chitin fibers reinforced with bacterial cellulose nanocrystals as suture biomaterials. Carbohydr Polym 180:304–313. https://doi.org/10.1016/j.carbpol.2017.10.022
Wu Z, Xu J, Gong J, Li J, Mo L (2018b) Preparation, characterization and acetylation of cellulose nanocrystal allomorphs. Cellulose 25:4905–4918. https://doi.org/10.1007/s10570-018-1937-6
Yamada Y, Yukphan P, Vu HTL, Muramatsu Y, Ochaikul D, Tanasupawat S, Nakagawa Y (2012) Description of Komagataeibacter gen. nov., with proposals of new combinations (Acetobacteraceae). J Gen Appl Microbiol 58:397–404. https://doi.org/10.2323/jgam.58.397
Yan H, Chen X, Song H, Li J, Feng Y, Shi Z, Lin Q (2017) Synthesis of bacterial cellulose and bacterial cellulose nanocrystals for their applications in the stabilization of olive oil pickering emulsion. Food Hydrocoll 72:127–135. https://doi.org/10.1016/j.foodhyd.2017.05.044
Yeasmin MS, Mondal MIH (2015) Synthesis of highly substituted carboxymethyl cellulose depending on cellulose particle size. Int J Biol Macromol 80:725–731. https://doi.org/10.1016/j.ijbiomac.2015.07.040
Zhou Y, Sun S, Bei W, Zahi MR, Yuan Q, Liang H (2018) Preparation and antimicrobial activity of oregano essential oil Pickering emulsion stabilized by cellulose nanocrystals. Int J Biol Macromol 112:7–13. https://doi.org/10.1016/j.ijbiomac.2018.01.102
Zugenmaier P (2008) Crystalline cellulose and derivatives: characterization and structure (chapter 5). Springer, Berlin. https://doi.org/10.1007/978-3-540-73934-0
Acknowledgments
The authors wish to acknowledge the financial support provided by the Coordination for the Improvement of Higher Education Personnel (CAPES, Brazil), the National Council of Technological and Scientific Development (CNPq, Brazil), the Foundation for Science and Technology (FCT, Portugal), the Institute for Biotechnology and Bioengineering (IBB, University of Minho, Portugal), Instituto Nacional de Ciência e Tecnologia em Materiais Complexos Funcionais (INOMAT, Brazil), and the Embrapa Agroindústria Tropical. This research was also supported by the international collaboration program FCT/CAPES (No. 99999.008530/2014-09). The authors would like to thank the Fundação Oswaldo Cruz (FIOCRUZ – Instituto Aggeu Magalhães) and the Laboratório de Raios-X (LRX – UFC) for supporting the analysis of TEM and XRD, respectively.
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Vasconcelos, N.F., Feitosa, J.P.A., Andrade, F.K. et al. Chemically modified cellulose nanocrystals as polyanion for preparation of polyelectrolyte complex. Cellulose 26, 1725–1746 (2019). https://doi.org/10.1007/s10570-018-2223-3
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DOI: https://doi.org/10.1007/s10570-018-2223-3