Accepted Manuscript

Title: Production of high-purity cellulose, cellulose acetate

and cellulose-silica composite from babassu coconut shells

Authors: Heliane R. Amaral, Daniel F. Cipriano, Mayara S.

Santos, Miguel A. Schettino Jr., João V.T. Ferreti, Carla S.
Meirelles, Vanessa S. Pereira, Alfredo G. Cunha, Francisco G.
Emmerich, Jair C.C. Freitas

PII: S0144-8617(19)30081-5
DOI: https://doi.org/10.1016/j.carbpol.2019.01.061
Reference: CARP 14519

To appear in:

Received date: 5 October 2018

Revised date: 9 January 2019
Accepted date: 21 January 2019

Please cite this article as: Amaral HR, Cipriano DF, Santos MS, Schettino
MA, Ferreti JVT, Meirelles CS, Pereira VS, Cunha AG, Emmerich FG,
Freitas JCC, Production of high-purity cellulose, cellulose acetate and cellulose-
silica composite from babassu coconut shells, Carbohydrate Polymers (2019),
https://doi.org/10.1016/j.carbpol.2019.01.061

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Production of high-purity cellulose, cellulose acetate and cellulose-silica composite from

babassu coconut shells

Heliane R. Amaral a*heliane.amaral@aluno.ufes.br), Daniel F. Cipriano a

(daniel.cipriano@ufes.br), Mayara S. Santos a (mayara.s.santos@aluno.ufes.br), Miguel A.

Schettino Jr. a (miguel.schettino@ufes.br), João V. T. Ferreti b (jvitor.tf10@gmail.com), Carla S.

Meirelles b (carla.meireles@ufes.br), Vanessa S. Pereira c (vanessa.sanches@marinha.mil.br),

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Alfredo G. Cunha a (alfredo.cunha@ufes.br), Francisco G. Emmerich a

(fgemmerich@terra.com.br), Jair C. C. Freitas a (jairccfreitas@yahoo.com.br)

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a Laboratory of Carbon and Ceramic Materials, Department of Physics, Federal University of
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Espírito Santo, 29075-910 Vitória - ES, Brazil.
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b Department of Natural Sciences, Federal University of Espírito Santo, 29932-540 São Mateus -
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ES Brazil.

c Laboratory of Materials Degradation, Nuclear Industrial Center of Aramar, 18560-000 Iperó -

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SP, Brazil.
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*
Corresponding author. Phone: ++ 55 (27) 4009-2487. E-mail address: heliane.amaral@aluno.ufes.br
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Highlights:

 Organosolv cellulose with high-purity was extracted from babassu coconut shells

 Solid-state 13C NMR and SEM were used as the main characterization tools

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 Cellulose-silica composites with fibrous texture were obtained

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 The possibility of synthesis of cellulose acetate was also demonstrated

 The results illustrate the potential applications of this abundant agro-waste

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1. Introduction

The generation of lignocellulosic residues as part of urban wastes or as agroindustry

byproducts constitutes a serious challenge from the environmental point of view. Recent estimates

put Brazil in the second position in the ranking of pulp producing countries (IBA, 2016); furthermore,

Brazil produced in 2016 more than 409 million tons of lignocellulosic residues, which have a large

potential to be converted into fuels and chemicals (IBGE, 2016). These figures illustrate the

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country’s potential for the production of biomass-based materials in a sustainable way. In this

context, the fractionation of a lignocellulosic material in its main constituents – cellulose,

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hemicellulose and lignin – is of great importance for the development of a sustainable economy

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with "green" chemicals (Isikgor & Becer, 2015). A large number of procedures of cellulose

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extraction have been proposed and successfully followed, involving physical, chemical and
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biological methods of pretreatment and treatment of lignocellulosic biomass. The method known
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as organosolv is a promising approach for pretreatment of biomass precursors since the
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lignocellulosic structure can be fragmented and its main components (cellulose, hemicelluloses

and lignin) can be obtained with high-purity. Moreover, the reaction stages involved in this process
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are less harmful to the environment in comparison to conventional pulping methods such as sulfite

and Kraft processes (Zhang, Pei, & Wang, 2016).

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Besides the main lignocellulosic components, many different types of inorganic

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compounds can be present as part of the mineral matter in natural biomass materials. Among
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these, silica (SiO2) is one of the inorganic compounds whose occurrence in plant cell walls has

been best documented (Currie & Perry, 2007). Biogenic silica can be found, for example, in
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pineapple peels (Corrales-Ureña et al., 2018), rice hulls and babassu coconut shells (Freitas,

Emmerich, & Bonagamba, 2000). Considering the widespread applications of silica-based

materials in nanocomposites (Cai et al., 2012), drug delivery (Chen et al., 2017), biosensors

(Mishra, Arukha, Bashir, Yadav, & Prasad, 2017) and optical films (Abdullah et al., 2018), among

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others, there is large interest in the development of efficient methods to extract and take advantage

of the silica occurrence in biomass materials.

According to Wu et al. (2015), in general, most protocols for the synthesis of silicon

nanoparticles are toxic, expensive or use flammable silicon precursors, which may cause

environmental contamination. Then, these authors proposed a low-cost and environmentally-

friendly route to obtain silicon nanoparticles from diatoms. Still in this context, the natural

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occurrence of silicon in the endocarp of babassu coconut (as amorphous hydrated silica and

organically bound silicon species), as evidenced by solid-state 29Si nuclear magnetic resonance

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(NMR) spectroscopy (Freitas et al., 2000), suggests that this precursor can also be used for the

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production of silicon-containing materials for applications as environmentally-friendly biomaterials.

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The babassu palm (Attalea speciosa, also known as Orbignya speciosa, O. phalerata, O.
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martiana, or O. oleifera) is native to the Northeast, North and Midwest regions of Brazil. The palms
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can grow until 20 m in height. The babassu coconut (fruit) grows in bunches with up to 400 drupes,
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four times a year, with a mass of 90-280 g each. This natural resource is extremely important to

the economy of some regions (Carrazza & Avila, 2010), being used primarily for the extraction of
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lauric oil from its nuts, which can be used for the production of cosmetics, soap and lubricants
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(Staufenberg, Graupner, & Müssig, 2015), in addition to biofuels (Emmerich & Luengo, 1996;

Moura et al., 2016). Apart from the nuts, the babassu coconut is composed of three main parts: the
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epicarp as the thin outer layer (11 wt. % of the drupes), the starch-containing mesocarp (23 wt. %)
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and the hard lignified inner layer called endocarp (59% wt. %) (Carrazza & Avila, 2010).
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In this scenario, it is worthwhile to pursue a detailed investigation on the methods to extract

cellulose from babassu coconut (endocarp and epicarp) and to study the development of new

products, which can add value to this abundant agricultural waste in Brazil. This work thus aims at

exploiting the potential of the babassu coconut shells to produce cellulose-based materials such

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as high-purity cellulose (i.e., cellulose free of lignin and hemicellulose), cellulose-silica composite

with fibrous texture and cellulose acetate. The chemical, structural and microstructural

characteristics of the products were investigated, revealing features that make these products

promising for applications as environmentally-friendly biomaterials.

2. Material and Methods

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2.1 Materials

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All the chemicals used were purchased from local suppliers: HNO3 (65%, Neon); ethanol

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(99.5%, Synth); distilled water; H2SO4 (98%, Êxodo); NaOH (99%, Vetec); Na2CO3 (99.5 %, Synth);

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acetic acid (99.8%, Neon); acetic anhydride (97%, Dinâmica). Babassu coconut samples were

provided by local producers from the municipality of Açailândia (Maranhão State, Northeast of
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Brazil). All the chemicals were of analytical grade and were used as received.
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2.2 Precursors and mechanical pretreatments
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Two parts of the babassu coconut were used in this work – the epicarp (here named EpB)

and the endocarp (named EB), which are illustrated in Figure S1 in the Supplementary Material.
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The chemical composition of these precursors (determined according to the methods described by

Morais, Rosa, & Marconcini, 2010), is also informed in the Supplementary Material (Table S1). The
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EB samples were submitted to mechanical pretreatments, as summarized in Table 1 and detailed

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in the Supplementary Material.

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2.3 Organosolv extraction

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2.3.1 Extraction of cellulose from the endocarp of babassu coconut (EB)

Cellulose was extracted from each pre-treated EB sample according to the procedure

described by Rodrigues Filho et al. (2011). The extraction process was carried out in two steps.

Firstly, 5.00 g of the raw material reacted with 50 mL of the mixture ethanol / 20 % HNO3 v/v for 3

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h under reflux (at ca. 100°C). After this, the solution was removed by filtration and the resultant

solid material reacted with 50 mL of 1 mol L-1 NaOH solution during 1 h at room temperature. Then,

the samples were washed with distilled water until pH 7. The cellulose samples were named as

C_EB_1, C_EB_2, C_EB_3, C_EB_4 and C_EB_5, depending on the pre-treated EB precursor

used in the synthesis (see Table 1); pictures of these samples are shown in Figure S2 (B) of the

Supplementary Material.

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2.3.2 Obtention of cellulose-silica composite from the epicarp of babassu coconut (EpB)

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Cellulose was extracted from the raw EpB sample using a similar procedure to the one

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described above for the EB samples, with the exception of the last step (reaction with NaOH

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solution), so as to avoid the removal of silica from the precursor. The obtained product (which is

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actually a cellulose-silica composite material) was named C_SiO2_EpB; its picture is also shown
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in Figure S2 (B) of the Supplementary Material.
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2.4 Acetylation of cellulose
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Cellulose acetate (CA) was obtained from the EB_5 sample, following the procedure

described by Meireles et al. (2010). First, cellulose obtained by the procedure described in Section
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2.3.1 was added to acetic acid (using 1.0 g of cellulose and 35 mL of acetic acid) and the resulting

mixture was stirred for 30 min at room temperature. Then, a catalytic amount of 0.02 g/mL H2SO4
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in acetic acid was added to the system, which was stirred again for 25 min. After that, 64 mL of
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acetic anhydride were added to the system and stirred again for 30 min. After this, the mixture
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stood for 24 h at room temperature. Then, a total of ca. 300 mL water was continuously added to

the filtrate to stop the reaction and until the precipitation of all cellulose acetate, which was filtered
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and washed with distilled water to remove the excess of acetic acid. Finally, the product was

neutralized with 10% Na2CO3 until pH 7. Then, we washed the cellulose acetate during 2 days

using dialysis tubing (with water replaced each ~6 h) and dried at 90 °C for 4 h. The determination

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of the degree of substitution (DS) of the CA samples was conducted using the titration method, as

described in the Supplementary Material (Puleo, Paul, & Kelley, 1989).

2.5 Characterization

Scanning electron microscopy (SEM) images were recorded in a Shimadzu SSX-550

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instrument equipped with an accessory for energy dispersive X-ray spectroscopy (EDS) analyses.

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The samples were coated with gold using a vacuum sputter coating system to improve their

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electrical conductivity and thus the quality of the images, which were recorded using secondary

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electrons. Thermogravimetry (TG) curves were recorded using a TGA-50H Shimadzu instrument,

heating the samples in an O2 flow (50 ml/min) at a rate of 5 °C/min up to 600 °C; derivative TG

(DTG) curves were computationally calculated from the TG data. U

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Solid-state 13C and 29Si NMR experiments were performed at room temperature in a
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Varian/Agilent VNMR 400 MHz spectrometer operating at a magnetic field of 9.4 T, which

corresponds to NMR frequencies of 100.52 and 79.41 MHz for 13C and 29Si nuclei, respectively.
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The powdered samples were packed into 4 mm diameter zirconia rotors for magic angle spinning

(MAS) experiments at the spinning rate of 10 and 14 kHz for 13C and 29Si NMR experiments,
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respectively. The 13C NMR experiments were conducted using 1H-13C cross polarization (CP) with
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variable amplitude radiofrequency (RF) fields during the contact period and high-power 1H
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decoupling (SPINAL sequence) during the acquisition time. In the CP sequence, a /2 1H excitation

pulse of 3.6 s was used, with a recycle delay of 5 s, a contact time of 1 ms, an acquisition time of
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20.48 ms. In the case of 29Si NMR experiments, single pulse excitation (SPE) was employed, with

a /2 29Si excitation pulse of 5.25 s, a recycle delay of 30 s, an acquisition time

of 32 ms. Chemical shifts, given in parts per million (ppm), were externally referred to

tetramethylsilane (TMS), using the methyl peak (at 17.3 ppm) in the 13C NMR spectrum of

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hexamethylbenzene (HMB) or the peak at -91.5 ppm in the 29Si NMR spectrum of kaolin to set the

shift scale.

3. Results and Discussion

3.1 Cellulosic products

Figure 1 shows a number of SEM images recorded for untreated EB samples in several

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areas and under various magnifications. These images show that the surface of EB is composed

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of structures of different shapes and sizes. Figures 1A, 1B and 1C clearly evidence the presence

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of macrofibers (with diameters ~100 m or larger) formed by bundles of microfibers (with diameters

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~10 m); these microfibers are aligned more or less parallel to each other, although exhibiting

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some degree of misalignment and twisting (see Figs. 1D and 1F, for example). The lateral part of
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the macrofibers is covered by several SiO2 phytoliths with a typical “rosette” shape (seen in more
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detail in the images shown in Fig. 1B and Fig. 1F), similarly to what has been found previously in
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EB and in other plant materials (Corrales-Ureña et al., 2018; Neethirajan et al., 2018). The presence

of the elements Si and O was confirmed by EDS analyses performed locally in these regions (Fig.
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1G and 1H).
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 The physical appearance and the color of the cellulose samples obtained after the

organosolv extraction were found to be dependent on the granulometry of the starting material

(which, as described before, was determined by the mechanical pretreatment). All samples

appeared yellowish, but the thinner precursor gave rise to a more agglomerated powder (sample

C_EB_1) after extraction; on the other hand, the cellulosic product obtained from the EpB precursor

(sample C_SiO2_EpB) preserved its fibrous texture; pictures of all extracted samples are shown in

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in Figure S2 (B) of the Supplementary Material.

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The yield of the organosolv extraction process, calculated taking into account the cellulose

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contents of the EB and EpB precursors (given in Table S1 in the Supplementary Material) was in

the range 70 - 95 %, depending on the particle size of the precursor used in each case. These

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values are somewhat above the 66 % yield reported by Ziaie-Shirkolaee, Mohammadi-
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Rovshandeh, Rezayati-Charani, & Khajeheian (2007), who used the organosolv extraction process
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(with dimethylformamide) to extract cellulose from wheat straw. Regarding other common
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processes of cellulose extraction, such as the Kraft process, some typical yields are 53 %

(Courchene, 1998) and 68 % (Ma et al., 2018). This comparison shows that the organosolv process
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is considerably more efficient than the Kraft process. The main reason for the high yield of

organosolv extraction is the protective action of the alcohol addition against carbohydrate
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degradation (Shatalov & Pereira, 2002). Although, to the best of our knowledge, currently there is
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no commercial large-scale application of cellulose extraction using the organosolv process, the
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great potential of this approach motivates many companies to conduct pilot scale studies, as

described by Zhang et al. (2016). A rough estimate of the costs of the organosolv extraction was
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performed for the processing of 1 kg of cellulose and by considering current prices of the chemicals

used in the process, as described in the Supplementary Material. The estimated costs are around

0.3 € for the production of 1 g of cellulose – which is not a prohibitive value, considering the

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environmental benefits of the organosolv process, especially when starting from lignocellulosic

waste materials.

The thermal behavior of the cellulosic products was studied by TG/DTG, as shown in Fig.

2 for a number of representative samples. The TG curves of all obtained samples exhibited the

typical profile expected for cellulosic materials (Benítez-Guerrero, López-Beceiro, Sánchez-

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Jiménez, & Pascual-Cosp, 2014), with consecutive weight losses attributed to the release of water,

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to the decomposition of the lignocellulosic matrix and to the combustion of the remaining char. A

discussion of these processes and of the details of the TG and DTG curves is presented in the

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Supplementary Material. The residual weight observed after complete combustion varied from 4 to

7% for all cellulose samples, with the exception of sample C_SiO2_EpB, which, as described

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before, corresponds to a cellulose-silica composite. The SiO2 content in this composite was
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estimated at 25 wt. %, considering the residual weight (on a dry basis) observed after the complete
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combustion of the material.
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The SEM images of the cellulosic products obtained by organosolv extraction are shown

in Fig. 3. First, it is interesting to note the distinct morphology of the C_EB_1 sample (the one
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obtained from the thinnest EB precursor particles, according to Table 1), which is composed of
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small fragments of irregular shapes and with no evident indication of a fibrillar structure. This feature
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is in contrast with the results obtained for the other milled samples; the SEM images of the C_EB_5

sample displayed in Fig. 3 show the presence of individual microfibers with diameters ~10 m, in
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addition to small irregular fragments; similar images (not shown) were also obtained for the

cellulosic products derived from the EB_2, EB_3 and EB_4 precursors, showing that the

mechanical pretreatment did not cause significant changes in the microstructure of the extracted

cellulose in the case of these samples. The image recorded with enhanced magnification for the

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C_EB_5 sample (Fig. 3) indicates the presence of a number of features (such as terraces and

steps) that are typical of the surface of cellulose fibrils after the removal of amorphous cellulose in

the first stages of acid hydrolysis, as observed by Zhao et al. (2007). On the other hand, in the

case of the C_EB_1 sample, the enlarged view shows the occurrence of small dots, which can

indicate the formation of nanometric bundles of individual cellulose microfibrils, as also discussed

by Zhao et al. (2007).

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Figure 3 also shows that the sample C_SiO2_EpB (obtained from the epicarp of babassu

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coconut without NaOH treatment) has a distinct feature, with the occurrence of macrofibers (with

diameters ~200 m) exhibiting plenty of rosette-like SiO2 phytoliths located around the lateral part

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of the fibers. This result shows then that it is possible to obtain a cellulose-silica composite with
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fibrillar structure using a single step organosolv extraction. The production of similar cellulose-silica
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composites from natural lignocellulosic precursors (e.g., rice husk) has been reported previously
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by Rahman, Ismail, & Osman (1997), but using a much more severe process with nitric acid
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digestion for ca. 12 h. Also, the preparation of cellulose-silica hybrids with promising mechanical

properties has been the subject of many recent investigations, with most of them starting from
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synthetic silicon-containing precursors (Cai et al., 2012; Demilecamps, Reichenauer, Rigacci, &

Budtova, 2014). The main advantage of the method described here is the possibility of obtaining
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fibrous cellulose-silica composites by using a single organosolv extraction with an acid catalyst and
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starting from lignocellulosic waste material (the shells of babassu coconut) naturally containing

silica in its structure.

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Solid-state 13C CP/MAS NMR spectroscopy has been extensively used to characterize

cellulosic products, yielding information on purity, crystallinity, polymorphism and other structural

aspects of these materials (Brinkmann et al., 2016; S. Park, Baker, Himmel, Parilla, & Johnson,

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2010). The 13C CP/MAS NMR spectra recorded for EB, EpB and the cellulosic products are shown

in Fig. 4. The signals present in the 13C NMR spectra of celluloses can be assigned to the six

carbon atoms in the anhydroglucose repeating unit in terms of the following typical chemical shift

ranges (see Fig. 4 for the definition of carbon numbers) C1: 102-108 ppm; C2, C3, C5: 70-81 ppm;

C4: 80-93 ppm; C6: 60-70 ppm. The exact chemical shift values depend on the polymorph type

and the cellulose source. Besides these cellulose signals, the NMR spectra obtained for EB and

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EpB exhibit further signals associated with lignin (a well-defined peak at 56.1 ppm due to methoxyl

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groups, besides the broad peaks due to aromatic carbons in the range 115-160 ppm) and with

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hemicelluloses (peaks at 20.9 and 172.6 ppm due to acetate groups, besides the signals

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superimposed to the cellulose signals) (Freitas et al., 2000; Haghighi Mood et al., 2013).

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The most remarkable difference between the spectra obtained for the raw precursors (EB
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and EpB) and the other ones shown in Fig. 4A is the complete absence of the signals due to lignin
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and hemicelluloses in the spectra corresponding to the cellulosic products obtained by the
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organosolv process. This finding evidences the effectiveness of the method used in the present

work for the achievement of high-purity cellulose samples (i.e., free of lignin and hemicellulose)
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from both the endocarp and the epicarp of babassu coconut.

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It is important to observe that the solid-state 13C NMR spectrum (shown in Fig. 4A) obtained

for the C_SiO2_EpB sample after the first extraction step (reaction with ethanol and HNO3) did not
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indicate the presence of any lignin signal. Then, in the case of the epicarp of babassu coconut, it
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was not necessary to follow the second step (NaOH leaching) in order to obtain lignin-free cellulose;

in that way, it was then possible to achieve a cellulose-silica composite. On the other hand, the
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solid-state 13C NMR spectra (not shown here) obtained for C_EB_1 to C_EB_5 samples after the

first extraction step indicated the presence of significant amounts of lignin; in these cases, the goal

of the second step (NaOH leaching) was to dissolve any residual lignin, leading also to the removal

of most of the silica naturally present in the EB precursor. However, the silica particles were not

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completely removed from these samples, as revealed by the non-vanishing final residual weight

values observed by TG (Fig. 2) and also by the results of EDS analyses of a typical cellulose sample

obtained after NaOH leaching, shown in Fig. S3 of the Supplementary Material.

The signals due to the C4 carbon in the 13C NMR spectra shown in Fig. 4A can be used

for the study of cellulose crystallinity and to estimate lateral crystallite sizes, as there is a splitting

of this resonance into a narrow signal at ca. 89 ppm due to groups in the interior of the cellulose

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crystals and a broad signal (sometimes seen as just a shoulder) at ca. 84 ppm associated with the

crystal surface and amorphous regions (Brinkmann et al., 2016). The spectra corresponding to the

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cellulose samples and the cellulose-silica composite exhibit narrower cellulose peaks in

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comparison to the spectra of EB and EpB, besides an increased relative intensity of the signal at

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ca. 89 ppm (C4 in crystalline regions) in comparison to the band at ca. 84 ppm (C4 in crystallite
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surfaces and amorphous regions). These results are a consequence of the removal of
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hemicelluloses and amorphous cellulose during the organosolv extraction (Park et al., 2010b;
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Wildschut et al., 2013) and, thus, indicate that this methodology was efficient for the achievement

of a material richer in crystalline cellulose; this finding was also supported by the analysis of X-ray
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diffraction (XRD) results, as described in the Supplementary Material (Fig. S4). Using the method

described by Brinkmann et al. (2016) and detailed in the Supplementary Material, the crystallinity
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index (CI) and the average lateral fibril dimension of an elementary cellulose crystallite (<a>) were
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estimated from the relative intensities of the signals due to C4 in the 13C NMR spectra of the
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extracted cellulose samples; the obtained values were CI ~ 0.6 and <a> ~ 4 nm for all analyzed

samples, which are comparable to the ones determined by Brinkmann et al. (2016) for cellulose
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nanocrystals obtained from bleached soft wood Kraft pulp. As expected, the CI value obtained by

solid-state NMR (0.6) was slightly lower than the one obtained by XRD (0.7, as described in the

Supplementary Material); this finding is in agreement with previous reports dealing with similar

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cellulosic materials, which showed the trend of overestimation of the CI values calculated using

XRD-based methods (Park et al., 2010).

The 29Si SPE/MAS NMR spectra obtained for the EpB precursor and the C_SiO2_EpB

composite are shown in Fig. 4B. Both spectra are dominated by broad resonances in the region

between −90 and −130 ppm, with peaks at −109 ppm. Chemical shifts in this spectral range are

typical of silicate groups (Freitas et al., 2000), where silicon atoms are surrounded in a tetrahedral

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arrangement by four oxygen atoms in the first coordination sphere; the chemical shift around

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−110 ppm is usually due to Si(OSi)4 groups. Other weak signals can be observed in these spectra

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(especially in the case of the EpB sample), which could be associated with other types of Si-

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containing groups also involving Si-O bonds (Freitas et al., 2000), but the poor signal to noise ratio

of the recorded spectra precludes a more definitive assignment. The results presented in Fig. 4B
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are thus useful to corroborate the occurrence of SiO2 in both the raw EpB and in the product
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obtained after the organosolv extraction (C_SiO2_EpB composite).
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3.2 Cellulose acetate (CA)

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As mentioned before, CA was also synthesized from the cellulose extracted from EB by
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the organosolv process (C_EB_5 sample). The yield of the acetylation reaction was estimated in

76% (as described in the Supplementary Material). This value is higher than the yield of 66%
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reported by Das, Ali, & Hazarika, (2014), who used acetic anhydride and iodine as catalysts to

obtain cellulose acetate from rice husk. The costs of the cellulose acetate production were
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estimated for the processing of 1 kg of cellulose acetate and by considering the current prices of

the chemicals used in the process, as described in the Supplementary Material. The estimated

costs are around € 1.9 for the production of 1 g of cellulose acetate with DS = 2.63. It is important

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to remark here that this estimated cost corresponds to a laboratory scale process, which can be

significantly reduced with scaling up to the pilot or commercial scale.

The SEM image of the CA sample (Fig. 5A) is quite distinct from the images obtained for

the cellulose samples (Fig. 3), with the CA image not showing the occurrence of terraces and steps

that are typical of the surface of cellulose fibrils (Zhao et al., 2007). The solid state 13C CP/MAS

NMR spectrum recorded for the CA sample (shown in Fig. 5B) confirms the success of the cellulose

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acetylation. The two signals detected at 170.6 ppm and 20.9 ppm are associated with carboxyl and

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methyl carbons in acetate groups, respectively, which are introduced into the material by the

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acetylation reaction; the other signals in the spectrum are ascribed to the carbon atoms in the

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repeating unit of cellulose acetate (Kono et al., 2002; Yamamoto et al., 2006; Kono et al., 2015).

The acetylation can be also verified by the analysis of the Fourier-transform infrared (FTIR) spectra
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of the materials before and after acetylation, as discussed in the Supplementary Material. The
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degree of substitution of the CA sample, obtained by the method described in the Supplementary
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Material, was DS = 2.63 ± 0.01, a value that is consistent with the relative intensities observed for
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the signals associated with carboxyl and methyl groups in the 13C NMR spectrum of CA sample
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(Fig. 5B).
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4. Conclusions
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The organosolv extraction process was followed in this work as a rapid, effective (with

yields in the range 70 - 95%) and eco-friendly approach for the extraction of high-purity cellulose
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(i.e., free of lignin and hemicellulose) from the shells of the babassu coconut, which constitute an

important lignocellulosic residue produced in large amounts in Brazil. In addition, this work has

shown that it is possible to obtain cellulose-silica composites with a fibrous texture by the same

organosolv extraction, taking advantage of the silica content naturally present in the babassu

15
coconut. Cellulose acetate was also produced, illustrating the potential applications of this

renewable precursor in the field of cellulose-based biomaterials.

E-supplementary data of this work can be found in the online version of the paper.

5. Acknowledgements

This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de

T
Nível Superior - Brasil (CAPES) - Finance Code 001. The financial support from the Brazilian

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agencies CNPq (grant 408001/2016-0) and FAPES (grant 73296872, TO 21/2016) is also gratefully

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acknowledged. The authors are also grateful to the Laboratory for Research and Development of

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Methodologies for Crude Oil Analysis (LabPetro), Federal University of Espírito Santo (UFES), for

the use of experimental facilities.

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Table 1: Summary of the preparation conditions and labels corresponding to the samples

described in this work.

Mechanical Mesh size Final

Sample a Sample b

pretreatment range products

60 min –

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EB EB_1 ɸ < 0.297 mm Cellulose d (C_EB_1)
high energy milling

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EB 6 min – knife mill EB_2 ɸ < 0.595 mm Cellulose d (C_EB_2)

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EB 6 min – knife mill EB_3 ɸ < 0.841 mm Cellulose d (C_EB_3)

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0.595 < ɸ <
EB 6 min – knife mill EB_4 Cellulose d (C_EB_4)
0.841mm

U Cellulose d (C_EB_5)
N
EB 3 min – knife mill EB_5 ɸ < 1.68 mm
Cellulose acetate e (CA)
A

Cellulose-silica
M

EpB None EpB n.d.c composite f

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(C_SiO2_EpB)
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a Before mechanical pretreatment.

b After mechanical pretreatment.

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c n.d. = not determined.

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d Organosolv extraction; NaOH leaching.

e Esterification reaction.
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f Organosolv extraction; no NaOH leaching.

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 A
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EPT
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A
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Fig. 1: SEM / EDS results obtained for the raw EB samples. (A) – (F): SEM images recorded

with various magnifications. (G), (H): SEM images and the corresponding EDS maps (for the

elements O, C and Si) of selected regions.

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R IP
SC
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N
A
M
ED
E PT
CC
A

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A
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E PT
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A

Fig. 2: TG (A) and DTG (B) curves recorded under oxidizing atmosphere for representative

cellulosic products obtained by organosolv extraction.

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E PT

Fig. 3: SEM images of the cellulosic products obtained by organosolv extraction, recorded
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with low (C_EB_1: 500×; C_EB_5: 150×; C_SiO2_EpB: 100×) or high (C_EB_1: 6000×;

C_EB_5: 1000×; C_SiO2_EpB: 1800×) magnification.

A

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A
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Fig. 4: (A) 13C CP/MAS NMR spectra recorded for EB and EpB precursors, along with some
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representative cellulosic products obtained by organosolv extraction. The inset shows the
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anhydroglucose repeating unit of cellulose, with the corresponding carbon atom

CC

numbering, used to identify the main signals due do cellulose and hemicellulose in the 13C

NMR spectra. (B) 29Si SPE/MAS NMR spectra recorded for EpB and the cellulose-silica
A

composite (C_SiO2_EpB).

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 T
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Fig. 5: SEM image (A) and 13C CP/MAS NMR spectrum (B) of the CA sample. The inset in (B)

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shows the repeating unit with the corresponding carbon atom numbering used to identify

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the main signals the 13C NMR spectrum of CA.

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A
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A

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