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Preparation and characterization of cellulose nanocrystal extracted from Calotropis procera biomass

Preparation and characterization of cellulose nanocrystal extracted from Calotropis procera biomass Calotropis procera fiber (CPF) is the fruit fiber of C. procera and belongs to a typical cellulosic fiber. In this study, Calotro - pis procera fiber (CPF) was first purified in the pretreatment process including delignification and bleaching before the isolation of cellulose nanocrystal. Chemical composition of Calotropis procera fiber was determined according to TAPPI standard method. It was composed of 64.0 wt% cellulose, 19.5 wt% hemicelluloses, and 9.7 wt% of lignin. The morphology of the Calotropis procera fiber and fiber after each pretreatment process was also investigated. Cellu- lose nanocrystal was extracted by classical sulfuric acid hydrolysis of the pretreated Calotropis procera fiber. TEM and SEM were used to analyze the morphologies of the obtained CNC. The crystallinity, thermal stability and suspension stability of the CNC were also investigated. The interesting results proved that this under-utilized biomass could be exploited as a new source of cellulose raw material for the production of cellulose nanocrystal. Keywords: Cellulose nanocrystals, Calotropis procera fiber, Agriculture residue, Acid hydrolysis Introduction material to produce cellulose nanocrystal (Kanchan and Calotropis procera fiber (CPF) is the fruit fiber of C. pro - Atreya 2016). cera that can be collected from its mature fruits with Cellulose nanocrystal (CNC), a kind of nanomaterial 3–4.5 in. long and 2–2.5 in. wide. This fruit fiber belongs derived from cellulose, possessed lots of desirable prop- to a typical cellulosic fiber but has been overlooked for erty, like extremely outstanding mechanical strength, centuries (Kanchan and Atreya 2016; Tarabi et  al. 2016; biocompatible and biodegradable, high specific surface Zheng et al. 2016). Recently, Calotropis procera fiber has area and so on (Yu et  al. 2013; Li et  al. 2016). The dis - received more attention in the textile industry and for tinctive property of cellulose nanocrystals make it use- potential application in fiber-reinforced composites. The ful building block in various applications, for instance as fiber possesses thin cell wall, large lumen and low den - reinforcing agents (Ye et al. 2015; Song et al. 2017, 2020), sity; thus, it exhibits excellent insulation property against biomedical implant (Rueda et al. 2013), rheological modi- sound and heat. In addition, this fiber could be used in fier (Li et  al. 2015), nanocomposites (Yu et  al. 2014) as making ropes, carpets, or sewing threads. It has been well as electronic components (Eyley et al. 2012). reported that the cellulose content of this fiber was in the Currently, cellulose nanocrystal can be obtained from range of 60–75%; thus, it could be a potential cellulosic wood, non-wood fibers, algae, tunicates, and agro-indus - trial residue or biomass. However, cellulosic agro-indus- trial residue or biomass are the most promising sources because of their low cost and availability (Reddy and Yang *Correspondence: kailisong12@163.com; xiaoyanli89@hebust.edu.cn 2011; Zhang et  al. 2012; Chen et  al. 2013). During the Engineering Research Center for Eco-Dyeing and Finishing of Textiles, pursuit of naturally abundant, renewable and sustainable College of Materials and Textiles, Zhejiang Sci-Tech University, Hangzhou 310018, Zhejiang, China cellulosic raw materials, lots of researches have already College of Textile and Garment, Hebei University of Science been focused on the utilization of agricultural residues and Technology, Hebei 050018, China or biomass for the extraction of cellulose nanocrystal, Full list of author information is available at the end of the article © The Author(s) 2019. This article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creat iveco mmons .org/licen ses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. Song et al. Bioresour. Bioprocess. (2019) 6:45 Page 2 of 8 such as rice straw (Johar et  al. 2012; Hsieh 2013), grape Hemicellulose content was determined according to skins (Lu and Hsieh 2012), pineapple leaf (Dos  Santos the TAPPI T257 om-09. Holocellulose content was quan- et  al. 2013), sugarcane bagasse (De Morais Teixeira et al. tified with sodium chlorite treatment according to the 2011), banana rachis (Elanthikkal et  al. 2010) and so on. reported procedure (dos Santos et  al. 2013). Fiber, 1  g, Calotropis procera fiber could be exploited as a suitable was added into the solution, 30  mL, containing acetic new cellulosic material for the production of cellulose acid 0.25 mL, sodium chlorite 0.3 g and kept at 75 °C for nanocrystal. 1  h. The mixture is then cooled down and the residue is This study was to isolate cellulose from Calotropis pro - filtered and washed thoroughly with water. The residue cera fiber and investigate the effect of treatment on the was finally dried and weighted. The holocellulose content properties of the obtained  cellulose nanocrystal. The was calculated using Eq. (2). pretreatment process was carried out to remove those impurities on Calotropis procera fiber, such as the wax, Holocellulose (%) = × 100, (2) lignin and make cellulose more accessible to chemicals. It is the first time that systematical study of pretreatment where M was the obtained residue mass, M was the ini- and acid hydrolysis of Calotropis procera fiber for cellu - tial sample mass. lose nanocrystal extraction was conducted. The influence Cellulose content was determined by extracting holo- of pretreatment on the chemical composition and mor- cellulose with the aqueous sodium hydroxide (17.5%) for phology of Calotropis procera fiber was investigated and 5 h before quenching the reaction with ice. The obtained characterized. The morphology, crystallinity and thermal white powder was washed with copious amount of water stability of the obtained cellulose nanocrystal were also until filtrate becoming neutral (Xu and Hanna 2010). The investigated. cellulose content was calculated using Eq. (3). Materials and methods Cellulose (%) = × 100, Materials Calotropis procera fiber as raw cellulose materials was where M was the obtained white powder mass, M was kindly supplied by World Agroforestry Centre, Kunming the initial sample mass. institute of Botany, CAS. Acetic acid and hydrochloride acid were purchased from Sinopharm Chemical Reagent Pretreatment of Calotropis procera fiber Co., Ltd. (Beijing, China). Sulfuric acid was purchased Calotropis procera fiber (CPF) was first washed and from Pinghu Chemical Reagent Co., Ltd (Pinghu, China). dried. The pretreatment process of CPF included alkali All the chemicals used in this research were of analytical treatment, delignification and bleaching treatment (Ray grade and applied without further purification. et  al. 2001; Neto et  al. 2013). Firstly, the cleaned CPF, 1 g, was immersed in NaOH solution (2 wt%), 100 mL, at Determination of the chemical composition of Calotropis room temperature and stirred for 3  h to finish the alkali procera fiber treatment to remove the impurities including pectin, The chemical compositions of Calotropis procera fiber wax. The alkali-treated fiber was washed thoroughly till (CPF) and the fiber after each treatment were determined neutral. The delignification process was carried out with according to Technical Association of the Pulp and Paper dewaxed CPF, 1  g, suspended in acetic acid (93% v/v), Industry (TAPPI) standard. The lignin content was deter - 50 mL, and hydrochloride acid solution (0.3% v/v) under mined according to the TAPPI norm T222 om-88 (de strong stirring for 3 h at 90 °C and then washed till neu- Oliveira et al. 2016; Espino et al. 2014). Briefly, 1 g of CPF tral pH value. The bleaching procedure was performed was added into the 15-mL H SO solution (72 wt%), and 2 4 by adding the obtained delignined CPF into the mixture maintained at room temperature for 2  h. Then, the dis - of H O (5  wt%) and NaOH (3.8  wt%) at a ratio of 1:50 2 2 tilled water, 560  mL, was added and boiled the mixture and stirred at room temperature for 3  h before washing for 4  h before the centrifuge to get the insoluble lignin. thoroughly. The obtained lignin was oven-dried and weighted. The lignin quantity was determined using Eq. (1). Extraction of cellulose nanocrystal Cellulose nanocrystal (CNC) was obtained by sulfuric Lingin (%) = × 100, (1) acid hydrolysis according to the reported method (Lin et  al. 2012). The pretreated CPF powder, 1  g, was slowly where M was the obtained lignin mass, M was the initial added into H SO solution (63 wt%), 30 mL, under vigor- 1 2 4 sample mass. ously stirring at room temperature for 1 h. After that, the hydrolysis was quenching by adding iced water, 300 mL, Song et al. Bioresour. Bioprocess. (2019) 6:45 Page 3 of 8 into the mixture. The resultant mixture was first centri - deposited into copper grid. TEM analysis was carried fuged at 1000  rpm for 10  min to remove large particles, out at 100  kV. The diameter and length distribution of and then centrifuged at 11,000 rpm for 15 min to obtain the obtained CNC was analysis using Image J software cellulose nanocrystal. The obtained cellulose nanocrystal (National Institutes of Health Co., Ltd., USA). was washed and centrifuged repeatedly for 3 times before dialysis against distilled water for 2  days. The obtained Characterization of the obtained cellulose nanocrystal CNC was processed by ultrasonic processor (VCX FTIR analysis of the obtained CNC was performed by 500:500 W, Sonics & Materials, Newton, CT) to suspen- Nicolet 6700 spectrometer (Thermo Fisher Scientific, sion better before further application. USA) using KBr pellet methods. TG analysis of CNC was performed by TGA-50 thermal stability analyzer at a heating rate of 15  °C/min form room temperature to Particle size and zeta potential measurement 600  °C using N atmosphere. The crystallinity index of of the obtained cellulose nanocrystal the obtained CNC was analyzed by Bruker D4 X-ray dif- The particle size and zeta potential of the obtained CNC fractometer. The measurement was carried out at 40  kV were measured by Nano-Z5 Analyzer (Malvern Instru- under Cu Kα radiation. CrI of the samples was calculated ments Co., Ltd., UK). The obtained CNC suspension was by Eq. (3) (Mariano et al. 2016). diluted to 0.1–0.6  wt% concentration firstly. Then, the suspension was put into a container for measurement. I − I 002 am CrI = × 100, (3) Morphology analysis Morphologies of the obtained CNC were measured by where I was the intensity of 200 peak (I ) between 002 200 Hitachi S-4800 field emission scanning electron micro - 2θ = 22–23° and I was the minimum intensity between am scope (Hitachi Co., Ltd., Japan). CNC powder was the peaks at 200 and 110 (I ) 2θ = 18–19°. am obtained by freeze drying of CNC suspension and the powder was sputter coating with a layer of gold firstly Results and discussion before SEM analysis. Also, TEM analysis was carried out Pretreatment of Calotropis procera fiber for morphology measurement. The obtained CNC sus - The preparation process to isolate CNC from Calotropis pension was diluted to 1–4 mg/mL concentration before procera fiber (CPF) is illustrated in Fig.  1. The first step Fig. 1 Schematic illustration for the process of extraction CNC from Calotropis procera fiber Song et al. Bioresour. Bioprocess. (2019) 6:45 Page 4 of 8 was to isolate cellulose from the obtained natural plant the chromophore of lignin (Lee et  al. 2009), and further fiber by removing lignin, hemicellulose and other impuri - resulted the degradation of lignin and hemicelluloses. ties. As shown in Table 1, the original Calotropis procera The morphology of the original Calotropis procera fiber fiber consisted of 64.1  wt% cellulose, 19.5  wt% hemicel - after treatment is shown in Fig.  2. From Fig.  2a, b, it can lulose, 9.7 wt% lignin. The cellulose content of Calotropis be seen that the original CPF exhibited smooth surface. procera fiber is much higher than other reported agri - There is no obvious difference in the appearance of the cultural biomass, such as 50.7  wt% for kenaf, 61.0  wt% fiber surface except that lots of tiny wrinkles formed after for fiber flax, 41.1 wt% for onion skin (Rhim et al. 2015), the removal of wax and other extractives. After the del- which proved that Calotropis procera fiber could be pro - ignification (Fig.  2e, f ), the surface of the treated fiber posed as a novel and abundant feedstock for nanocellu- became rough and lots of wrinkles were formed. The lose production. After alkali treatment, the extractives bleaching process could further promote the removal of such as pectin and wax were removed without significant the lignin and hemicelluloses from CPF and resulted in a affect the lignin, hemicellulose and cellulose content of rough and coarse fiber morphology as shown in Fig.  2g, the fiber. Almost 83% of lignin was removed after delig - h. nification as shown in Table  1. The cellulose content was Figure  3 shows the FTIR spectra of the original and found to be 91.3 wt% after bleaching treatment. In addi- pretreated Calotropis procera fibers. The peaks around −1 −1 tion, the content of lignin and hemicellulose was also 3340  cm and 2907  cm were assigned to O–H partly reduced as the result of bleaching. Various radi- stretch and C–H stretch stretching of aliphatic moieties cals (HO·, O , and perhydroxyl anions H OO ) were pro- in polysaccharides. In the spectra of CPF, the band at −1 duced during bleaching and those radicals could destroy 1732  cm was assigned to the ester linkage of carbox- ylic group of ferulic and p-coumaric acids of lignin; the −1 peak at 1502  cm was assigned to the C=C stretching of aromatic rings of lignin. The sharp peak appearing Table 1 Chemical composition of  Calotropis procera fiber −1 at 1640  cm in all samples was attributed to the bend- and selected common natural fibers ing mode of absorbed water in cellulose. The peaks Constituent (%) Lignin Cellulose Hemicellulose −1 −1 at 1163  cm and 899  cm were associated with the C–O stretching and C–H vibrations of hemicellulose. Original fiber 9.7 ± 1.2 64.1 ± 1.6 19.5 ± 1.2 The presence of those peaks confirmed the existence of Alkali treated fiber 9.5 ± 1.3 64.1 ± 1.4 20.1 ± 0.8 lignin and hemicellulose in CPF. However, the absorp- Delignined fiber 1.7 ± 0.9 74.5 ± 0.5 24.1 ± 1.1 −1 −1 tion band at 1732  cm and 1502  cm disappeared in Bleached fiber 0.4 ± 0.1 91.3 ± 1.1 8.2 ± 0.9 the delignined fiber, suggesting that lignin was success - Kenaf 15.8 ± 1.9 50.7 ± 1.1 21.5 ± 1.5 fully removed during this process. Additionally, in the Fiber flax 2.2 ± 0.5 61.0 ± 0.9 18.6 ± 1.5 Onion skin 38.9 ± 1.3 41.1 ± 1.1 16.2 ± 0.6 Fig. 2 Morphology of a, b the Calotropis procera fiber; c, d dewaxed Calotropis procera fiber; e, f Calotropis procera fiber after the delignification; g, h Calotropis procera fiber after bleaching Song et al. Bioresour. Bioprocess. (2019) 6:45 Page 5 of 8 Table 2 Onset temperature (T ), degradation temperature on  maximum weight-loss rate (T ), weight loss (W ) onset max L for CPF and the obtained CNC Samples Cellulose thermal degradation Carbonic residue degradation T (°C) T (°C) W (%) T (°C) T (°C) W (%) onset max L onset max L Calotropis procera fiber 277 330 79 420 510 31 Obtained CNC 180 205 57 367 406 43 dispersed in water, ethanol and acetone at a concentra- tion of 10  mg/mL to compare its colloidal stability. As shown in Fig.  4f, the nanocrystal dispersed in water and ethanol stay stable even after 96 h, which showed that the obtained CNC was completely dispersed. After hydroly- sis, negatively charged sulfate group was introduced onto CNC, which contributed to the stabilization of CNC sus- pension by repulsive forces. However, CNC dispersed in acetone solvent started to separate after 24  h due to the fact that CNC tends to highly agglomerate in acetone solvent. Thermal analysis Thermal stability of CPF and the obtained CNC was investigated. Their corresponding thermogram is pre - Fig. 3 FTIR spectrum of the Calotropis procera fiber, alkali treated sented in Fig.  5 and the corresponding degradation tem- Calotropis procera fiber, delignined Calotropis procera fiber and perature is summarized in Table  2. From Fig.  5, we can bleached Calotropis procera fiber see that CPF showed a weight loss from 300 to 400  °C, which could be due to the decomposition of the glycosyl units in cellulose fiber (Chen et  al. 2012; Vinayaka et  al. −1 bleached fiber, the disappearance of the band at 899 cm 2017). As for the obtained CNC, it showed a lower deg- confirmed the removal of hemicellulose. radation temperature which could be attributed to the introduced sulfate groups on the nanocrystal surface. The Extraction of cellulose nanocrystal first degradation step basically corresponding to the cel - TEM graphs of the obtained CNC are shown in Fig.  4a. lulose degradation process was between 160 and 250  °C As can be seen, CNC showed uniform needle-like shape and the second degradation step was attributed to the with 250-nm length and 12-nm diameter, which was oxidation and breakdown of the charred residue to lower similar with the reported works (dos Santos et  al. 2013; molecular weight gaseous products. The introduction of Rhim et  al. 2015; An et  al. 2016). From Fig.  4d, e, we sulfate groups at cellulose nanocrystal could accelerate could also see the needle-like cellulose nanocrystal. Fig - the depolymerization of cellulose (Camarero Espinosa ure  4b, c show the diameter and length distributions of et  al. 2013). Also, the reported degradation temperature the obtained CNC. It could be seen that the length of of CNC from Soy hulls and Flax was 170  °C and 186  °C the obtained CNC was ranging from 100 to 400 nm and (Neto et al. 2013). diameter between 4 and 12  nm. Polydispersity of the obtained CNC was 0.39 (measured by dynamic light scat - XRD and FTIR analysis tering), which was lower than the reported literature (4.1 XRD analysis of the obtained CNC is shown in Fig.  6a. for CNC obtained from filter paper and 0.49 for spherical The XRD diagrams of Calotropis procera fiber and the cellulose nanocrystals). obtained CNC showed peaks at 2θ = 16.0°, and 22.1°, The dispersion stability of the nanocrystal in differ - which could be attributed to the cellulose I character- ent polar solvent is an important parameter to evaluate istic peaks. Crystallinity index (CrI) of the materials is dispersity of CNC as nanofillers in manufacturing nano - summarized in Table  3. The Crystallinity index of the composites. The dispersibility of CNC strongly depends obtained CNC showed a significant increase compared on their surface functionalization, aspect ratio, and sur- with Calotropis procera fiber, indicating that the acid face charges. The obtained CNC was ultrasonicated and digested the amorphous hemicelluloses and the defective Song et al. Bioresour. Bioprocess. (2019) 6:45 Page 6 of 8 Fig. 4 a TEM micrograph of the obtained CNC; b, c diameter and length distribution of the obtained CNC; d, e SEM micrographs of the obtained CNC; f stability of the CNC dispersed in water, ethanol and acetone (from left to right in each picture) Fig. 5 a TG and b DTG analysis of Calotropis procera fiber and the obtained cellulose nanocrystal regions in Calotropis procera fiber. The crystallinity of The FTIR spectra of the original Calotropis procera the obtained CNC was similar with the reported litera- fiber and the obtained cellulose nanocrystal are shown −1 ture as listed in Table 3 (Zhao et al. 2015, 2016; Neto et al. in Fig.  6b. The absence of peaks around 1742  cm −1 2013; Johar et al. 2012). and 1522  cm at cellulose nanocrystal was due to the removal of lignin after the pretreatment of Calotropis −1 procera fiber. The new peak at 1205  cm was resulted Song et al. Bioresour. Bioprocess. (2019) 6:45 Page 7 of 8 Fig. 6 XRD and FTIR analyses of Calotropis procera fiber and the obtained cellulose nanocrystal nanocomposites due to their relatively high aspect ratio Table 3 The crystallinity index (CrI) of  the  obtained CNC in this study and comparing with the reported literature and high crystallinity. Materials Extraction method CrI (%) References Abbreviation CNC from this study Acid hydrolysis 68.7 This study CNC: cellulose nanocrystals. Calotropis procera fiber – 30.1 This study Acknowledgements CNC from Soy hulls Acid hydrolysis 71.5 Neto et al. (2013) Not applicable. CNC from Pine Acid hydrolysis 56.0 Zhao et al. (2015) CNC from corn husk Acid hydrolysis 70.7 Zhao et al. (2015) Authors’ contributions KS is involved in collecting, reviewing the literature and performing the CNC from rice husk Acid hydrolysis 59.0 Johar et al. (2012) preparation of the CNC. WZ is involved in the characterization of the materials. XL is involved in guiding the analysis, improving and revising the manuscript. Both the authors are involved in writing the manuscript. All authors read and approved the final manuscript. from the introduced sulfate groups by sulfuric acid Funding hydrolysis. This work was financially supported by the public projects of Zhejiang Prov- ince (LGF20E030005, LGF20E030006), Zhejiang Provincial Top Key Academic Conclusion Discipline of Chemical Engineering and Technology of Zhejiang Sci-Tech University (CETT 2017003), the Opening Project of Key Laboratory of Clean Cellulose nanocrystal can be isolated from Calotropis Dyeing and Finishing Technology of Zhejiang Province (Project Number: 1808) procera fiber, an under-utilized agriculture biomass. and Scientific Research Foundation of Zhejiang Sci-Tech University (Grant The cellulose content of the Calotropis procera fiber Number 18012211-Y ). was 64.1%. The chemical pretreatment which removed Ethics approval and consent to participate the non-cellulosic constituents of Calotropis procera Not applicable. fiber was found to be an essential and fundamental Consent for publication procedure for the isolation  of cellulose nanocrystal. Not applicable. The obtained CNC exhibited a needle-like shape with an average diameter and length of 12  nm and 250  nm, Competing interests The authors declare that they have no competing interests. leading to an aspect ratio of approximately 30. The crystallinity index of the obtained CNC was 68.7%. Author details Furthermore, the obtained CNC showed good thermal Engineering Research Center for Eco-Dyeing and Finishing of Textiles, Col- lege of Materials and Textiles, Zhejiang Sci-Tech University, Hangzhou 310018, stability. The CNC obtained from the biomass, Calotro - Zhejiang, China. Key Laboratory of Clean Dyeing and Finishing Technology pis procera fiber, showed great potential as reinforce - of Zhejiang Province, Shaoxing University, Shaoxing 312000, Zhejiang, China. ment agents during the manufacturing of renewable Key Laboratory of Advanced Textile Materials and Manufacturing Technology, Song et al. Bioresour. Bioprocess. (2019) 6:45 Page 8 of 8 Ministry of Education, Zhejiang Sci-Tech University, Hangzhou 310018, Mariano M, Cercená R, Soldi V (2016) Thermal characterization of cellulose Zhejiang, China. College of Textile and Garment, Hebei University of Science nanocrystals isolated from sisal fibers using acid hydrolysis. Ind Crops and Technology, Hebei 050018, China. Prod 94:454–462. https ://doi.org/10.1016/j.indcr op.2016.09.011 Neto WPF, Silvério HA, Dantas NO, Pasquini D (2013) Extraction and characteri- Received: 6 September 2019 Accepted: 15 November 2019 zation of cellulose nanocrystals from agro-industrial residue—Soy hulls. Ind Crops Prod 42:480–488. https ://doi.org/10.1016/j.indcr op.2012.06.041 Ray D, Sarkar BK, Rana AK, Bose NR (2001) Mechanical properties of vinylester resin matrix composites reinforced with alkali-treated jute fibres. Compos Part A Appl Sci Manuf 32:119–127. https ://doi.org/10.1016/S1359 -835X(00)00101 -9 References Reddy N, Yang Y (2011) Completely biodegradable soyprotein-jute biocom- An X, Wen Y, Cheng D (2016) Preparation of cellulose nano-crystals through posites developed using water without any chemicals as plasticizer. Ind a sequential process of cellulase pretreatment and acid hydrolysis. Cel- Crops Prod 33:35–41. https ://doi.org/10.1016/j.indcr op.2010.08.007 lulose 23:2409–2420. https ://doi.org/10.1007/s1057 0-016-0964-4 Rhim JW, Reddy JP, Luo X (2015) Isolation of cellulose nanocrystals from onion Camarero Espinosa S, Kuhnt T, Foster EJ, Weder C (2013) Isolation of thermally skin and their utilization for the preparation of agar-based bio-nano- stable cellulose nanocrystals by phosphoric acid hydrolysis. Biomacro- composites films. Cellulose 22:407–420. https ://doi.org/10.1007/s1057 molecules 14:1223–1230. https ://doi.org/10.1021/bm400 219u 0-014-0517-7 Chen L, Reddy N, Wu X, Yang Y (2012) Thermoplastic films from wheat proteins. Rueda L, Saralegi A, Fernández-d’Arlas B (2013) In situ polymerization and Ind Crops Prod 35:70–76. https ://doi.org/10.1016/j.indcr op.2011.06.009 characterization of elastomeric polyurethane-cellulose nanocrystal Chen L, Reddy N, Yang Y (2013) Remediation of environmental pollution by nanocomposites. Cell response evaluation. Cellulose 20:1819–1828. https substituting poly(vinyl alcohol) with biodegradable warp size from wheat ://doi.org/10.1007/s1057 0-013-9960-0 gluten. Environ Sci Technol 47:4505–4511. https ://doi.org/10.1021/es304 Song K, Xu H, Xu L (2017) Preparation of cellulose nanocrystal-reinforced 429s keratin bioadsorbent for highly effective and recyclable removal of dyes de Morais Teixeira E, Bondancia TJ, Teodoro KBR (2011) Sugarcane bagasse from aqueous solution. Bioresour Technol 232:254–262. https ://doi. whiskers: extraction and characterizations. Ind Crops Prod 33:63–66. https org/10.1016/j.biort ech.2017.01.070 ://doi.org/10.1016/j.indcr op.2010.08.009 Song K, Zhu W, Li X, Yu Z (2020) A novel mechanical robust, self-healing and de Oliveira FB, Bras J, Pimenta MTB (2016) Production of cellulose nanocrystals shape memory hydrogel based on PVA reinforced by cellulose nanocrys- from sugarcane bagasse fibers and pith. Ind Crops Prod 93:48–57. https :// tal. Mater Lett 260:126884 doi.org/10.1016/j.indcr op.2016.04.064 Tarabi N, Mousazadeh H, Jafari A, Taghizadeh-Tameh J (2016) Evaluation of dos Santos RM, Neto WPF, Silvério HA (2013) Cellulose nanocrystals from pine- properties of bast fiber extracted from Calotropis (Millkweed) by a new apple leaf, a new approach for the reuse of this agro-waste. Ind Crops decorticator machine and manual methods. Ind Crops Prod 83:545–550. Prod 50:707–714. https ://doi.org/10.1016/j.indcr op.2013.08.049 https ://doi.org/10.1016/j.indcr op.2015.12.071 Elanthikkal S, Gopalakrishnapanicker U, Varghese S, Guthrie JT (2010) Cellulose Vinayaka DL, Guna V, Madhavi D, Arpitha M, Reddy N (2017) Ricinus communis microfibres produced from banana plant wastes: isolation and charac- plant residues as a source for natural cellulose fibers potentially exploit - terization. Carbohydr Polym 80:852–859. https ://doi.org/10.1016/j.carbp able in polymer composites. Ind Crops Prod 100:126–131. https ://doi. ol.2009.12.043 org/10.1016/j.indcr op.2017.02.019 Espino E, Cakir M, Domenek S (2014) Isolation and characterization of cellulose Xu Y, Hanna MA (2010) Optimum conditions for dilute acid hydrolysis of nanocrystals from industrial by-products of Agave tequilana and barley. hemicellulose in dried distillers grains with solubles. Ind Crops Prod Ind Crops Prod 62:552–559. https ://doi.org/10.1016/j.indcr op.2014.09.017 32:511–517. https ://doi.org/10.1016/j.indcr op.2010.06.024 Eyley S, Shariki S, Dale SEC (2012) Ferrocene-decorated nanocrystalline cel- Ye C, Malak ST, Hu K (2015) Cellulose nanocrystal microcapsules as tunable lulose with charge carrier mobility. Langmuir 28:6514–6519. https ://doi. cages for nano- and microparticles. ACS Nano 9:10887–10895. https :// org/10.1021/la300 1224 doi.org/10.1021/acsna no.5b039 05 Hsieh YL (2013) Cellulose nanocrystals and self-assembled nanostructures Yu H, Qin Z, Liang B (2013) Facile extraction of thermally stable cellulose from cotton, rice straw and grape skin: a source perspective. J Mater Sci nanocrystals with a high yield of 93% through hydrochloric acid hydroly- 48:7837–7846. https ://doi.org/10.1007/s1085 3-013-7512-5 sis under hydrothermal conditions. J Mater Chem A 1:3938–3944. https :// Johar N, Ahmad I, Dufresne A (2012) Extraction, preparation and characteriza- doi.org/10.1039/c3ta0 1150j tion of cellulose fibres and nanocrystals from rice husk. Ind Crops Prod Yu H-Y, Qin Z-Y, Yan C-F, Yao J-M (2014) Green nanocomposites based on func- 37:93–99. https ://doi.org/10.1016/j.indcr op.2011.12.016 tionalized cellulose nanocrystals: a study on the relationship between Kanchan T, Atreya A (2016) Calotropis gigantea. Wilderness Environ Med interfacial interaction and property enhancement. ACS Sustain Chem 27:350–351. https ://doi.org/10.1016/j.wem.2015.12.011 Eng 2:875–886. https ://doi.org/10.1021/sc400 499g Lee YJ, Chung CH, Day DF (2009) Sugarcane bagasse oxidation using a com- Zhang S, Keshwani DR, Xu Y, Hanna MA (2012) Alkali combined extrusion pre- bination of hypochlorite and peroxide. Bioresour Technol 100:935–941. treatment of corn stover to enhance enzyme saccharification. Ind Crops https ://doi.org/10.1016/j.biort ech.2008.06.043 Prod 37:352–357. https ://doi.org/10.1016/j.indcr op.2011.12.001 Li MC, Wu Q, Song K (2015) Cellulose nanoparticles as modifiers for rheology Zhao Y, Zhao Y, Yang Y (2015) Modified soy protein to substitute non-degra- and fluid loss in bentonite water-based fluids. ACS Appl Mater Interfaces dable petrochemicals for slashing industry. Ind Crops Prod 67:466–474. 7:5009–5016. https ://doi.org/10.1021/acsam i.5b004 98 https ://doi.org/10.1016/j.indcr op.2015.01.058 Li Y, Liu Y, Chen W (2016) Facile extraction of cellulose nanocrystals from Zheng Y, Cao E, Zhu Y (2016) Perfluorosilane treated Calotropis gigantea fiber: wood using ethanol and peroxide solvothermal pretreatment followed instant hydrophobic-oleophilic surface with efficient oil-absorbing by ultrasonic nanofibrillation. Green Chem 18:1010–1018. https ://doi. performance. Chem Eng J 295:477–483. https ://doi.org/10.1016/j. org/10.1039/C5GC0 2576A cej.2016.03.074 Lin N, Bruzzese C, Dufresne A (2012) TEMPO-oxidized nanocellulose partici- pating as crosslinking aid for alginate-based sponges. ACS Appl Mater Interfaces 4:4948–4959. https ://doi.org/10.1021/am301 325r Publisher’s Note Lu P, Hsieh YL (2012) Cellulose isolation and core-shell nanostructures of Springer Nature remains neutral with regard to jurisdictional claims in pub- cellulose nanocrystals from chardonnay grape skins. Carbohydr Polym lished maps and institutional affiliations. 87:2546–2553. https ://doi.org/10.1016/j.carbp ol.2011.11.023 http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Bioresources and Bioprocessing Springer Journals

Preparation and characterization of cellulose nanocrystal extracted from Calotropis procera biomass

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Chemistry; Biochemical Engineering; Environmental Engineering/Biotechnology; Industrial and Production Engineering
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Abstract

Calotropis procera fiber (CPF) is the fruit fiber of C. procera and belongs to a typical cellulosic fiber. In this study, Calotro - pis procera fiber (CPF) was first purified in the pretreatment process including delignification and bleaching before the isolation of cellulose nanocrystal. Chemical composition of Calotropis procera fiber was determined according to TAPPI standard method. It was composed of 64.0 wt% cellulose, 19.5 wt% hemicelluloses, and 9.7 wt% of lignin. The morphology of the Calotropis procera fiber and fiber after each pretreatment process was also investigated. Cellu- lose nanocrystal was extracted by classical sulfuric acid hydrolysis of the pretreated Calotropis procera fiber. TEM and SEM were used to analyze the morphologies of the obtained CNC. The crystallinity, thermal stability and suspension stability of the CNC were also investigated. The interesting results proved that this under-utilized biomass could be exploited as a new source of cellulose raw material for the production of cellulose nanocrystal. Keywords: Cellulose nanocrystals, Calotropis procera fiber, Agriculture residue, Acid hydrolysis Introduction material to produce cellulose nanocrystal (Kanchan and Calotropis procera fiber (CPF) is the fruit fiber of C. pro - Atreya 2016). cera that can be collected from its mature fruits with Cellulose nanocrystal (CNC), a kind of nanomaterial 3–4.5 in. long and 2–2.5 in. wide. This fruit fiber belongs derived from cellulose, possessed lots of desirable prop- to a typical cellulosic fiber but has been overlooked for erty, like extremely outstanding mechanical strength, centuries (Kanchan and Atreya 2016; Tarabi et  al. 2016; biocompatible and biodegradable, high specific surface Zheng et al. 2016). Recently, Calotropis procera fiber has area and so on (Yu et  al. 2013; Li et  al. 2016). The dis - received more attention in the textile industry and for tinctive property of cellulose nanocrystals make it use- potential application in fiber-reinforced composites. The ful building block in various applications, for instance as fiber possesses thin cell wall, large lumen and low den - reinforcing agents (Ye et al. 2015; Song et al. 2017, 2020), sity; thus, it exhibits excellent insulation property against biomedical implant (Rueda et al. 2013), rheological modi- sound and heat. In addition, this fiber could be used in fier (Li et  al. 2015), nanocomposites (Yu et  al. 2014) as making ropes, carpets, or sewing threads. It has been well as electronic components (Eyley et al. 2012). reported that the cellulose content of this fiber was in the Currently, cellulose nanocrystal can be obtained from range of 60–75%; thus, it could be a potential cellulosic wood, non-wood fibers, algae, tunicates, and agro-indus - trial residue or biomass. However, cellulosic agro-indus- trial residue or biomass are the most promising sources because of their low cost and availability (Reddy and Yang *Correspondence: kailisong12@163.com; xiaoyanli89@hebust.edu.cn 2011; Zhang et  al. 2012; Chen et  al. 2013). During the Engineering Research Center for Eco-Dyeing and Finishing of Textiles, pursuit of naturally abundant, renewable and sustainable College of Materials and Textiles, Zhejiang Sci-Tech University, Hangzhou 310018, Zhejiang, China cellulosic raw materials, lots of researches have already College of Textile and Garment, Hebei University of Science been focused on the utilization of agricultural residues and Technology, Hebei 050018, China or biomass for the extraction of cellulose nanocrystal, Full list of author information is available at the end of the article © The Author(s) 2019. This article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creat iveco mmons .org/licen ses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. Song et al. Bioresour. Bioprocess. (2019) 6:45 Page 2 of 8 such as rice straw (Johar et  al. 2012; Hsieh 2013), grape Hemicellulose content was determined according to skins (Lu and Hsieh 2012), pineapple leaf (Dos  Santos the TAPPI T257 om-09. Holocellulose content was quan- et  al. 2013), sugarcane bagasse (De Morais Teixeira et al. tified with sodium chlorite treatment according to the 2011), banana rachis (Elanthikkal et  al. 2010) and so on. reported procedure (dos Santos et  al. 2013). Fiber, 1  g, Calotropis procera fiber could be exploited as a suitable was added into the solution, 30  mL, containing acetic new cellulosic material for the production of cellulose acid 0.25 mL, sodium chlorite 0.3 g and kept at 75 °C for nanocrystal. 1  h. The mixture is then cooled down and the residue is This study was to isolate cellulose from Calotropis pro - filtered and washed thoroughly with water. The residue cera fiber and investigate the effect of treatment on the was finally dried and weighted. The holocellulose content properties of the obtained  cellulose nanocrystal. The was calculated using Eq. (2). pretreatment process was carried out to remove those impurities on Calotropis procera fiber, such as the wax, Holocellulose (%) = × 100, (2) lignin and make cellulose more accessible to chemicals. It is the first time that systematical study of pretreatment where M was the obtained residue mass, M was the ini- and acid hydrolysis of Calotropis procera fiber for cellu - tial sample mass. lose nanocrystal extraction was conducted. The influence Cellulose content was determined by extracting holo- of pretreatment on the chemical composition and mor- cellulose with the aqueous sodium hydroxide (17.5%) for phology of Calotropis procera fiber was investigated and 5 h before quenching the reaction with ice. The obtained characterized. The morphology, crystallinity and thermal white powder was washed with copious amount of water stability of the obtained cellulose nanocrystal were also until filtrate becoming neutral (Xu and Hanna 2010). The investigated. cellulose content was calculated using Eq. (3). Materials and methods Cellulose (%) = × 100, Materials Calotropis procera fiber as raw cellulose materials was where M was the obtained white powder mass, M was kindly supplied by World Agroforestry Centre, Kunming the initial sample mass. institute of Botany, CAS. Acetic acid and hydrochloride acid were purchased from Sinopharm Chemical Reagent Pretreatment of Calotropis procera fiber Co., Ltd. (Beijing, China). Sulfuric acid was purchased Calotropis procera fiber (CPF) was first washed and from Pinghu Chemical Reagent Co., Ltd (Pinghu, China). dried. The pretreatment process of CPF included alkali All the chemicals used in this research were of analytical treatment, delignification and bleaching treatment (Ray grade and applied without further purification. et  al. 2001; Neto et  al. 2013). Firstly, the cleaned CPF, 1 g, was immersed in NaOH solution (2 wt%), 100 mL, at Determination of the chemical composition of Calotropis room temperature and stirred for 3  h to finish the alkali procera fiber treatment to remove the impurities including pectin, The chemical compositions of Calotropis procera fiber wax. The alkali-treated fiber was washed thoroughly till (CPF) and the fiber after each treatment were determined neutral. The delignification process was carried out with according to Technical Association of the Pulp and Paper dewaxed CPF, 1  g, suspended in acetic acid (93% v/v), Industry (TAPPI) standard. The lignin content was deter - 50 mL, and hydrochloride acid solution (0.3% v/v) under mined according to the TAPPI norm T222 om-88 (de strong stirring for 3 h at 90 °C and then washed till neu- Oliveira et al. 2016; Espino et al. 2014). Briefly, 1 g of CPF tral pH value. The bleaching procedure was performed was added into the 15-mL H SO solution (72 wt%), and 2 4 by adding the obtained delignined CPF into the mixture maintained at room temperature for 2  h. Then, the dis - of H O (5  wt%) and NaOH (3.8  wt%) at a ratio of 1:50 2 2 tilled water, 560  mL, was added and boiled the mixture and stirred at room temperature for 3  h before washing for 4  h before the centrifuge to get the insoluble lignin. thoroughly. The obtained lignin was oven-dried and weighted. The lignin quantity was determined using Eq. (1). Extraction of cellulose nanocrystal Cellulose nanocrystal (CNC) was obtained by sulfuric Lingin (%) = × 100, (1) acid hydrolysis according to the reported method (Lin et  al. 2012). The pretreated CPF powder, 1  g, was slowly where M was the obtained lignin mass, M was the initial added into H SO solution (63 wt%), 30 mL, under vigor- 1 2 4 sample mass. ously stirring at room temperature for 1 h. After that, the hydrolysis was quenching by adding iced water, 300 mL, Song et al. Bioresour. Bioprocess. (2019) 6:45 Page 3 of 8 into the mixture. The resultant mixture was first centri - deposited into copper grid. TEM analysis was carried fuged at 1000  rpm for 10  min to remove large particles, out at 100  kV. The diameter and length distribution of and then centrifuged at 11,000 rpm for 15 min to obtain the obtained CNC was analysis using Image J software cellulose nanocrystal. The obtained cellulose nanocrystal (National Institutes of Health Co., Ltd., USA). was washed and centrifuged repeatedly for 3 times before dialysis against distilled water for 2  days. The obtained Characterization of the obtained cellulose nanocrystal CNC was processed by ultrasonic processor (VCX FTIR analysis of the obtained CNC was performed by 500:500 W, Sonics & Materials, Newton, CT) to suspen- Nicolet 6700 spectrometer (Thermo Fisher Scientific, sion better before further application. USA) using KBr pellet methods. TG analysis of CNC was performed by TGA-50 thermal stability analyzer at a heating rate of 15  °C/min form room temperature to Particle size and zeta potential measurement 600  °C using N atmosphere. The crystallinity index of of the obtained cellulose nanocrystal the obtained CNC was analyzed by Bruker D4 X-ray dif- The particle size and zeta potential of the obtained CNC fractometer. The measurement was carried out at 40  kV were measured by Nano-Z5 Analyzer (Malvern Instru- under Cu Kα radiation. CrI of the samples was calculated ments Co., Ltd., UK). The obtained CNC suspension was by Eq. (3) (Mariano et al. 2016). diluted to 0.1–0.6  wt% concentration firstly. Then, the suspension was put into a container for measurement. I − I 002 am CrI = × 100, (3) Morphology analysis Morphologies of the obtained CNC were measured by where I was the intensity of 200 peak (I ) between 002 200 Hitachi S-4800 field emission scanning electron micro - 2θ = 22–23° and I was the minimum intensity between am scope (Hitachi Co., Ltd., Japan). CNC powder was the peaks at 200 and 110 (I ) 2θ = 18–19°. am obtained by freeze drying of CNC suspension and the powder was sputter coating with a layer of gold firstly Results and discussion before SEM analysis. Also, TEM analysis was carried out Pretreatment of Calotropis procera fiber for morphology measurement. The obtained CNC sus - The preparation process to isolate CNC from Calotropis pension was diluted to 1–4 mg/mL concentration before procera fiber (CPF) is illustrated in Fig.  1. The first step Fig. 1 Schematic illustration for the process of extraction CNC from Calotropis procera fiber Song et al. Bioresour. Bioprocess. (2019) 6:45 Page 4 of 8 was to isolate cellulose from the obtained natural plant the chromophore of lignin (Lee et  al. 2009), and further fiber by removing lignin, hemicellulose and other impuri - resulted the degradation of lignin and hemicelluloses. ties. As shown in Table 1, the original Calotropis procera The morphology of the original Calotropis procera fiber fiber consisted of 64.1  wt% cellulose, 19.5  wt% hemicel - after treatment is shown in Fig.  2. From Fig.  2a, b, it can lulose, 9.7 wt% lignin. The cellulose content of Calotropis be seen that the original CPF exhibited smooth surface. procera fiber is much higher than other reported agri - There is no obvious difference in the appearance of the cultural biomass, such as 50.7  wt% for kenaf, 61.0  wt% fiber surface except that lots of tiny wrinkles formed after for fiber flax, 41.1 wt% for onion skin (Rhim et al. 2015), the removal of wax and other extractives. After the del- which proved that Calotropis procera fiber could be pro - ignification (Fig.  2e, f ), the surface of the treated fiber posed as a novel and abundant feedstock for nanocellu- became rough and lots of wrinkles were formed. The lose production. After alkali treatment, the extractives bleaching process could further promote the removal of such as pectin and wax were removed without significant the lignin and hemicelluloses from CPF and resulted in a affect the lignin, hemicellulose and cellulose content of rough and coarse fiber morphology as shown in Fig.  2g, the fiber. Almost 83% of lignin was removed after delig - h. nification as shown in Table  1. The cellulose content was Figure  3 shows the FTIR spectra of the original and found to be 91.3 wt% after bleaching treatment. In addi- pretreated Calotropis procera fibers. The peaks around −1 −1 tion, the content of lignin and hemicellulose was also 3340  cm and 2907  cm were assigned to O–H partly reduced as the result of bleaching. Various radi- stretch and C–H stretch stretching of aliphatic moieties cals (HO·, O , and perhydroxyl anions H OO ) were pro- in polysaccharides. In the spectra of CPF, the band at −1 duced during bleaching and those radicals could destroy 1732  cm was assigned to the ester linkage of carbox- ylic group of ferulic and p-coumaric acids of lignin; the −1 peak at 1502  cm was assigned to the C=C stretching of aromatic rings of lignin. The sharp peak appearing Table 1 Chemical composition of  Calotropis procera fiber −1 at 1640  cm in all samples was attributed to the bend- and selected common natural fibers ing mode of absorbed water in cellulose. The peaks Constituent (%) Lignin Cellulose Hemicellulose −1 −1 at 1163  cm and 899  cm were associated with the C–O stretching and C–H vibrations of hemicellulose. Original fiber 9.7 ± 1.2 64.1 ± 1.6 19.5 ± 1.2 The presence of those peaks confirmed the existence of Alkali treated fiber 9.5 ± 1.3 64.1 ± 1.4 20.1 ± 0.8 lignin and hemicellulose in CPF. However, the absorp- Delignined fiber 1.7 ± 0.9 74.5 ± 0.5 24.1 ± 1.1 −1 −1 tion band at 1732  cm and 1502  cm disappeared in Bleached fiber 0.4 ± 0.1 91.3 ± 1.1 8.2 ± 0.9 the delignined fiber, suggesting that lignin was success - Kenaf 15.8 ± 1.9 50.7 ± 1.1 21.5 ± 1.5 fully removed during this process. Additionally, in the Fiber flax 2.2 ± 0.5 61.0 ± 0.9 18.6 ± 1.5 Onion skin 38.9 ± 1.3 41.1 ± 1.1 16.2 ± 0.6 Fig. 2 Morphology of a, b the Calotropis procera fiber; c, d dewaxed Calotropis procera fiber; e, f Calotropis procera fiber after the delignification; g, h Calotropis procera fiber after bleaching Song et al. Bioresour. Bioprocess. (2019) 6:45 Page 5 of 8 Table 2 Onset temperature (T ), degradation temperature on  maximum weight-loss rate (T ), weight loss (W ) onset max L for CPF and the obtained CNC Samples Cellulose thermal degradation Carbonic residue degradation T (°C) T (°C) W (%) T (°C) T (°C) W (%) onset max L onset max L Calotropis procera fiber 277 330 79 420 510 31 Obtained CNC 180 205 57 367 406 43 dispersed in water, ethanol and acetone at a concentra- tion of 10  mg/mL to compare its colloidal stability. As shown in Fig.  4f, the nanocrystal dispersed in water and ethanol stay stable even after 96 h, which showed that the obtained CNC was completely dispersed. After hydroly- sis, negatively charged sulfate group was introduced onto CNC, which contributed to the stabilization of CNC sus- pension by repulsive forces. However, CNC dispersed in acetone solvent started to separate after 24  h due to the fact that CNC tends to highly agglomerate in acetone solvent. Thermal analysis Thermal stability of CPF and the obtained CNC was investigated. Their corresponding thermogram is pre - Fig. 3 FTIR spectrum of the Calotropis procera fiber, alkali treated sented in Fig.  5 and the corresponding degradation tem- Calotropis procera fiber, delignined Calotropis procera fiber and perature is summarized in Table  2. From Fig.  5, we can bleached Calotropis procera fiber see that CPF showed a weight loss from 300 to 400  °C, which could be due to the decomposition of the glycosyl units in cellulose fiber (Chen et  al. 2012; Vinayaka et  al. −1 bleached fiber, the disappearance of the band at 899 cm 2017). As for the obtained CNC, it showed a lower deg- confirmed the removal of hemicellulose. radation temperature which could be attributed to the introduced sulfate groups on the nanocrystal surface. The Extraction of cellulose nanocrystal first degradation step basically corresponding to the cel - TEM graphs of the obtained CNC are shown in Fig.  4a. lulose degradation process was between 160 and 250  °C As can be seen, CNC showed uniform needle-like shape and the second degradation step was attributed to the with 250-nm length and 12-nm diameter, which was oxidation and breakdown of the charred residue to lower similar with the reported works (dos Santos et  al. 2013; molecular weight gaseous products. The introduction of Rhim et  al. 2015; An et  al. 2016). From Fig.  4d, e, we sulfate groups at cellulose nanocrystal could accelerate could also see the needle-like cellulose nanocrystal. Fig - the depolymerization of cellulose (Camarero Espinosa ure  4b, c show the diameter and length distributions of et  al. 2013). Also, the reported degradation temperature the obtained CNC. It could be seen that the length of of CNC from Soy hulls and Flax was 170  °C and 186  °C the obtained CNC was ranging from 100 to 400 nm and (Neto et al. 2013). diameter between 4 and 12  nm. Polydispersity of the obtained CNC was 0.39 (measured by dynamic light scat - XRD and FTIR analysis tering), which was lower than the reported literature (4.1 XRD analysis of the obtained CNC is shown in Fig.  6a. for CNC obtained from filter paper and 0.49 for spherical The XRD diagrams of Calotropis procera fiber and the cellulose nanocrystals). obtained CNC showed peaks at 2θ = 16.0°, and 22.1°, The dispersion stability of the nanocrystal in differ - which could be attributed to the cellulose I character- ent polar solvent is an important parameter to evaluate istic peaks. Crystallinity index (CrI) of the materials is dispersity of CNC as nanofillers in manufacturing nano - summarized in Table  3. The Crystallinity index of the composites. The dispersibility of CNC strongly depends obtained CNC showed a significant increase compared on their surface functionalization, aspect ratio, and sur- with Calotropis procera fiber, indicating that the acid face charges. The obtained CNC was ultrasonicated and digested the amorphous hemicelluloses and the defective Song et al. Bioresour. Bioprocess. (2019) 6:45 Page 6 of 8 Fig. 4 a TEM micrograph of the obtained CNC; b, c diameter and length distribution of the obtained CNC; d, e SEM micrographs of the obtained CNC; f stability of the CNC dispersed in water, ethanol and acetone (from left to right in each picture) Fig. 5 a TG and b DTG analysis of Calotropis procera fiber and the obtained cellulose nanocrystal regions in Calotropis procera fiber. The crystallinity of The FTIR spectra of the original Calotropis procera the obtained CNC was similar with the reported litera- fiber and the obtained cellulose nanocrystal are shown −1 ture as listed in Table 3 (Zhao et al. 2015, 2016; Neto et al. in Fig.  6b. The absence of peaks around 1742  cm −1 2013; Johar et al. 2012). and 1522  cm at cellulose nanocrystal was due to the removal of lignin after the pretreatment of Calotropis −1 procera fiber. The new peak at 1205  cm was resulted Song et al. Bioresour. Bioprocess. (2019) 6:45 Page 7 of 8 Fig. 6 XRD and FTIR analyses of Calotropis procera fiber and the obtained cellulose nanocrystal nanocomposites due to their relatively high aspect ratio Table 3 The crystallinity index (CrI) of  the  obtained CNC in this study and comparing with the reported literature and high crystallinity. Materials Extraction method CrI (%) References Abbreviation CNC from this study Acid hydrolysis 68.7 This study CNC: cellulose nanocrystals. Calotropis procera fiber – 30.1 This study Acknowledgements CNC from Soy hulls Acid hydrolysis 71.5 Neto et al. (2013) Not applicable. CNC from Pine Acid hydrolysis 56.0 Zhao et al. (2015) CNC from corn husk Acid hydrolysis 70.7 Zhao et al. (2015) Authors’ contributions KS is involved in collecting, reviewing the literature and performing the CNC from rice husk Acid hydrolysis 59.0 Johar et al. (2012) preparation of the CNC. WZ is involved in the characterization of the materials. XL is involved in guiding the analysis, improving and revising the manuscript. Both the authors are involved in writing the manuscript. All authors read and approved the final manuscript. from the introduced sulfate groups by sulfuric acid Funding hydrolysis. This work was financially supported by the public projects of Zhejiang Prov- ince (LGF20E030005, LGF20E030006), Zhejiang Provincial Top Key Academic Conclusion Discipline of Chemical Engineering and Technology of Zhejiang Sci-Tech University (CETT 2017003), the Opening Project of Key Laboratory of Clean Cellulose nanocrystal can be isolated from Calotropis Dyeing and Finishing Technology of Zhejiang Province (Project Number: 1808) procera fiber, an under-utilized agriculture biomass. and Scientific Research Foundation of Zhejiang Sci-Tech University (Grant The cellulose content of the Calotropis procera fiber Number 18012211-Y ). was 64.1%. The chemical pretreatment which removed Ethics approval and consent to participate the non-cellulosic constituents of Calotropis procera Not applicable. fiber was found to be an essential and fundamental Consent for publication procedure for the isolation  of cellulose nanocrystal. Not applicable. The obtained CNC exhibited a needle-like shape with an average diameter and length of 12  nm and 250  nm, Competing interests The authors declare that they have no competing interests. leading to an aspect ratio of approximately 30. The crystallinity index of the obtained CNC was 68.7%. Author details Furthermore, the obtained CNC showed good thermal Engineering Research Center for Eco-Dyeing and Finishing of Textiles, Col- lege of Materials and Textiles, Zhejiang Sci-Tech University, Hangzhou 310018, stability. The CNC obtained from the biomass, Calotro - Zhejiang, China. Key Laboratory of Clean Dyeing and Finishing Technology pis procera fiber, showed great potential as reinforce - of Zhejiang Province, Shaoxing University, Shaoxing 312000, Zhejiang, China. ment agents during the manufacturing of renewable Key Laboratory of Advanced Textile Materials and Manufacturing Technology, Song et al. Bioresour. Bioprocess. (2019) 6:45 Page 8 of 8 Ministry of Education, Zhejiang Sci-Tech University, Hangzhou 310018, Mariano M, Cercená R, Soldi V (2016) Thermal characterization of cellulose Zhejiang, China. College of Textile and Garment, Hebei University of Science nanocrystals isolated from sisal fibers using acid hydrolysis. Ind Crops and Technology, Hebei 050018, China. Prod 94:454–462. https ://doi.org/10.1016/j.indcr op.2016.09.011 Neto WPF, Silvério HA, Dantas NO, Pasquini D (2013) Extraction and characteri- Received: 6 September 2019 Accepted: 15 November 2019 zation of cellulose nanocrystals from agro-industrial residue—Soy hulls. Ind Crops Prod 42:480–488. https ://doi.org/10.1016/j.indcr op.2012.06.041 Ray D, Sarkar BK, Rana AK, Bose NR (2001) Mechanical properties of vinylester resin matrix composites reinforced with alkali-treated jute fibres. Compos Part A Appl Sci Manuf 32:119–127. https ://doi.org/10.1016/S1359 -835X(00)00101 -9 References Reddy N, Yang Y (2011) Completely biodegradable soyprotein-jute biocom- An X, Wen Y, Cheng D (2016) Preparation of cellulose nano-crystals through posites developed using water without any chemicals as plasticizer. Ind a sequential process of cellulase pretreatment and acid hydrolysis. Cel- Crops Prod 33:35–41. https ://doi.org/10.1016/j.indcr op.2010.08.007 lulose 23:2409–2420. https ://doi.org/10.1007/s1057 0-016-0964-4 Rhim JW, Reddy JP, Luo X (2015) Isolation of cellulose nanocrystals from onion Camarero Espinosa S, Kuhnt T, Foster EJ, Weder C (2013) Isolation of thermally skin and their utilization for the preparation of agar-based bio-nano- stable cellulose nanocrystals by phosphoric acid hydrolysis. Biomacro- composites films. Cellulose 22:407–420. https ://doi.org/10.1007/s1057 molecules 14:1223–1230. https ://doi.org/10.1021/bm400 219u 0-014-0517-7 Chen L, Reddy N, Wu X, Yang Y (2012) Thermoplastic films from wheat proteins. Rueda L, Saralegi A, Fernández-d’Arlas B (2013) In situ polymerization and Ind Crops Prod 35:70–76. https ://doi.org/10.1016/j.indcr op.2011.06.009 characterization of elastomeric polyurethane-cellulose nanocrystal Chen L, Reddy N, Yang Y (2013) Remediation of environmental pollution by nanocomposites. Cell response evaluation. Cellulose 20:1819–1828. https substituting poly(vinyl alcohol) with biodegradable warp size from wheat ://doi.org/10.1007/s1057 0-013-9960-0 gluten. Environ Sci Technol 47:4505–4511. https ://doi.org/10.1021/es304 Song K, Xu H, Xu L (2017) Preparation of cellulose nanocrystal-reinforced 429s keratin bioadsorbent for highly effective and recyclable removal of dyes de Morais Teixeira E, Bondancia TJ, Teodoro KBR (2011) Sugarcane bagasse from aqueous solution. Bioresour Technol 232:254–262. https ://doi. whiskers: extraction and characterizations. Ind Crops Prod 33:63–66. https org/10.1016/j.biort ech.2017.01.070 ://doi.org/10.1016/j.indcr op.2010.08.009 Song K, Zhu W, Li X, Yu Z (2020) A novel mechanical robust, self-healing and de Oliveira FB, Bras J, Pimenta MTB (2016) Production of cellulose nanocrystals shape memory hydrogel based on PVA reinforced by cellulose nanocrys- from sugarcane bagasse fibers and pith. Ind Crops Prod 93:48–57. https :// tal. Mater Lett 260:126884 doi.org/10.1016/j.indcr op.2016.04.064 Tarabi N, Mousazadeh H, Jafari A, Taghizadeh-Tameh J (2016) Evaluation of dos Santos RM, Neto WPF, Silvério HA (2013) Cellulose nanocrystals from pine- properties of bast fiber extracted from Calotropis (Millkweed) by a new apple leaf, a new approach for the reuse of this agro-waste. Ind Crops decorticator machine and manual methods. Ind Crops Prod 83:545–550. Prod 50:707–714. https ://doi.org/10.1016/j.indcr op.2013.08.049 https ://doi.org/10.1016/j.indcr op.2015.12.071 Elanthikkal S, Gopalakrishnapanicker U, Varghese S, Guthrie JT (2010) Cellulose Vinayaka DL, Guna V, Madhavi D, Arpitha M, Reddy N (2017) Ricinus communis microfibres produced from banana plant wastes: isolation and charac- plant residues as a source for natural cellulose fibers potentially exploit - terization. Carbohydr Polym 80:852–859. https ://doi.org/10.1016/j.carbp able in polymer composites. Ind Crops Prod 100:126–131. https ://doi. ol.2009.12.043 org/10.1016/j.indcr op.2017.02.019 Espino E, Cakir M, Domenek S (2014) Isolation and characterization of cellulose Xu Y, Hanna MA (2010) Optimum conditions for dilute acid hydrolysis of nanocrystals from industrial by-products of Agave tequilana and barley. hemicellulose in dried distillers grains with solubles. Ind Crops Prod Ind Crops Prod 62:552–559. https ://doi.org/10.1016/j.indcr op.2014.09.017 32:511–517. https ://doi.org/10.1016/j.indcr op.2010.06.024 Eyley S, Shariki S, Dale SEC (2012) Ferrocene-decorated nanocrystalline cel- Ye C, Malak ST, Hu K (2015) Cellulose nanocrystal microcapsules as tunable lulose with charge carrier mobility. Langmuir 28:6514–6519. https ://doi. cages for nano- and microparticles. ACS Nano 9:10887–10895. https :// org/10.1021/la300 1224 doi.org/10.1021/acsna no.5b039 05 Hsieh YL (2013) Cellulose nanocrystals and self-assembled nanostructures Yu H, Qin Z, Liang B (2013) Facile extraction of thermally stable cellulose from cotton, rice straw and grape skin: a source perspective. J Mater Sci nanocrystals with a high yield of 93% through hydrochloric acid hydroly- 48:7837–7846. https ://doi.org/10.1007/s1085 3-013-7512-5 sis under hydrothermal conditions. J Mater Chem A 1:3938–3944. https :// Johar N, Ahmad I, Dufresne A (2012) Extraction, preparation and characteriza- doi.org/10.1039/c3ta0 1150j tion of cellulose fibres and nanocrystals from rice husk. Ind Crops Prod Yu H-Y, Qin Z-Y, Yan C-F, Yao J-M (2014) Green nanocomposites based on func- 37:93–99. https ://doi.org/10.1016/j.indcr op.2011.12.016 tionalized cellulose nanocrystals: a study on the relationship between Kanchan T, Atreya A (2016) Calotropis gigantea. Wilderness Environ Med interfacial interaction and property enhancement. ACS Sustain Chem 27:350–351. https ://doi.org/10.1016/j.wem.2015.12.011 Eng 2:875–886. https ://doi.org/10.1021/sc400 499g Lee YJ, Chung CH, Day DF (2009) Sugarcane bagasse oxidation using a com- Zhang S, Keshwani DR, Xu Y, Hanna MA (2012) Alkali combined extrusion pre- bination of hypochlorite and peroxide. Bioresour Technol 100:935–941. treatment of corn stover to enhance enzyme saccharification. Ind Crops https ://doi.org/10.1016/j.biort ech.2008.06.043 Prod 37:352–357. https ://doi.org/10.1016/j.indcr op.2011.12.001 Li MC, Wu Q, Song K (2015) Cellulose nanoparticles as modifiers for rheology Zhao Y, Zhao Y, Yang Y (2015) Modified soy protein to substitute non-degra- and fluid loss in bentonite water-based fluids. ACS Appl Mater Interfaces dable petrochemicals for slashing industry. Ind Crops Prod 67:466–474. 7:5009–5016. https ://doi.org/10.1021/acsam i.5b004 98 https ://doi.org/10.1016/j.indcr op.2015.01.058 Li Y, Liu Y, Chen W (2016) Facile extraction of cellulose nanocrystals from Zheng Y, Cao E, Zhu Y (2016) Perfluorosilane treated Calotropis gigantea fiber: wood using ethanol and peroxide solvothermal pretreatment followed instant hydrophobic-oleophilic surface with efficient oil-absorbing by ultrasonic nanofibrillation. Green Chem 18:1010–1018. https ://doi. performance. Chem Eng J 295:477–483. https ://doi.org/10.1016/j. org/10.1039/C5GC0 2576A cej.2016.03.074 Lin N, Bruzzese C, Dufresne A (2012) TEMPO-oxidized nanocellulose partici- pating as crosslinking aid for alginate-based sponges. ACS Appl Mater Interfaces 4:4948–4959. https ://doi.org/10.1021/am301 325r Publisher’s Note Lu P, Hsieh YL (2012) Cellulose isolation and core-shell nanostructures of Springer Nature remains neutral with regard to jurisdictional claims in pub- cellulose nanocrystals from chardonnay grape skins. Carbohydr Polym lished maps and institutional affiliations. 87:2546–2553. https ://doi.org/10.1016/j.carbp ol.2011.11.023

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