Industrial Crops & Products 171 (2021) 113847

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Industrial Crops & Products

journal homepage: www.elsevier.com/locate/indcrop

Bulgur bran as a biopolymer source: Production and characterization of

nanocellulose-reinforced hemicellulose-based biodegradable films with
decreased water solubility
Didem Sutay Kocabaş a, *, Merve Erkoç Akçelik a, Erinç Bahçegül b, Hatice Neval Özbek c
a
Karamanoğlu Mehmetbey University Department of Food Engineering, 70100, Karaman, Turkey
b
Konya Food and Agriculture University Department of Bioengineering, 42080, Konya, Turkey
c
Gaziantep University Department of Food Engineering, 27310, Gaziantep, Turkey

A R T I C L E I N F O A B S T R A C T

Keywords: Bulgur bran is a lignocellulosic side-stream of bulgur production factories. Separation of bulgur bran into cel­
Bulgur bran lulose- and hemicellulose-rich fractions paved the way of utilization of this under-exploited agro-industrial
Hemicellulose biomass. Although hemicellulose-based biodegradable food packaging films provide significant advantages, their
Cellulose nanocrystal
high water solubility and low mechanical strength are obstacles to their commercialization. To overcome these
Cellulose nanofiber
Biodegradable film
bottlenecks, commercial cellulose nanocrystal (CNC) and cellulose nanofiber (CNF) were incorporated into the
Water solubility hemicellulose matrix. Besides, addition of citric acid (CA) was investigated for its plasticizing effect. To minimize
the film water solubility (FWS) statistical optimization by Box-Behnken design (BBD) and response surface
methodology (RSM) was employed. The proposed full-quadratic model was found to have high accuracy (R2 =
0.9877) within 95 % confidence interval. The results revealed that 10 % (w/w) CNC- and 10 % (w/w) CNF-
incorporated films exhibited 21.3 % reduction in FWS compared to neat films. CNC- and CNF-reinforced films
showed a compact structure in SEM analysis. CNC and CNF as fillers in the hemicellulose network markedly
improved the tensile strength of the films. Nanocellulose incorporation caused a decrease in water vapor
permeability (WVP), light transmittance, total color difference and biodegradability of the films. The properties
of nanocellulose-reinforced and neat films were also compared using thermogravimetric analysis (TGA), dif­
ferential scanning calorimetry (DSC), and Fourier transform infrared spectroscopy (FTIR). Presence of nano­
celluloses in the films increased the glass transition temperature (Tg) by around 15 ◦ C as shown by DSC analysis.

1. Introduction
Bulgur has been a traditional food in Central Asia, Middle East,
Balkans and it is deeply rooted in some areas of Turkey since ages (Erbaş
et al., 2016). Bulgur is a whole wheat product and it is manufactured
from durum wheat (Triticum durum ssp.). The production process of
bulgur consists of cleaning, washing, cooking in water until the whole
grain gelatinises, drying (under sunlight or in drying towers until 12 %
moisture content is reached), tempering, debranning, milling, classi­
fying and polishing (optional) (Bayram and Öner, 2007; Balcı and
Bayram, 2020). Its low price, long shelf life, ease of preparation and high
nutritional value makes bulgur an important ingredient in different
cuisines around the world (Giambanelli et al., 2020). After its recogni­
tion as a whole grain by the WGC (Whole Grain Council), access to
bulgur became easier in USA and European countries. Based on its
increasing global availability and the increasing interest of people to­
wards traditional and ethnic foods, its consumption is increasing in
Western countries (Erbaş et al., 2016). Annual consumption of bulgur in
Turkey is about 15 kg per person which is about 2.5 and 2.0 times higher
than the consumption of pasta and rice, respectively (Savas and Basman,

Abbreviations: ANOVA, Analysis of variance; AOAC, Association of Official Analytical Chemists; BBD, Box-Behnken design; CA, Citric acid; CAGR, Compound
annual growth rate; CNC, Cellulose nanocrystal; CNF, Cellulose nanofiber; DSC, Differential scanning calorimetry; E, Young’s modulus; EB, Elongation at break; FTIR,
Fourier transform infrared spectroscopy; FWS, Film water solubility; HPLC, High performance liquid chromatography; LDPE, Low density polyethylene; R2,
Determination coefficient; RH, Relative humidity; RSM, Response surface methodology; SEM, Scanning electron microscopy; Tg, Glass transition temperature; TGA,
Thermogravimetric analysis; TS, Tensile strength; WGC, Whole Grain Council; WVP, Water vapor permeability; WVTR, Water vapor transmission rate.
* Corresponding author.
E-mail address: didemkocabas@kmu.edu.tr (D. Sutay Kocabaş).

https://doi.org/10.1016/j.indcrop.2021.113847
Received 20 January 2021; Received in revised form 14 July 2021; Accepted 16 July 2021
Available online 24 July 2021
0926-6690/© 2021 Elsevier B.V. All rights reserved.
D. Sutay Kocabaş et al.
2016). The annual commercial production amount of bulgur is over 1
million tons in Turkey, excluding the bulgur production at home level in
rural areas (Caba et al., 2012). Turkey exports bulgur to Iraq, Syria,
Lebanon, Belgium, Germany, Saudi Arabia, Jordan, Israel, England, the
United States, Sweden, the United Arab Emirates, and the Netherlands
which are major importers of bulgur from Turkey (Köksel and Çetiner,
2015).
Bulgur bran is a side-stream of bulgur production factories. Bulgur
bran is separated during the partial dehulling (debranning) stage of the
bulgur production process (Saka et al., 2020) and sold as animal feed at
very low prices. Bulgur bran is a type of agro-industrial residue with
lignocellulosic structure having a great potential as a renewable feed­
stock for chemicals, materials and biofuel production. In addition, like
several other agricultural crop residues, it is a promising source for fi­
bers suitable for uses in industrial products such as composites, textiles,
pulp, and paper production chemicals (Boufi, 2017). Considering the
environmental problems associated with the non-renewable and also
practically non-biodegradable nature of current fossil fuel-based food
packaging materials, bio-based alternatives are getting increasing
attention. In recent years, intensive efforts have been made to develop
bio-based materials from renewable sources in order to reduce the
amount of packaging waste while maintaining food stability and quality
(Azeredo et al., 2015). In parallel to scientific endeavors, industrial use
of bio-based plastics is also increasing. The global biodegradable plastic
market size was estimated as USD 3.27 billion in 2019 and is foreseen to
expand at a CAGR (compound annual growth rate) of 9.4 % to reach USD
7.6 billion in 2027 (Grand View Research, 2019). In 2019, more than
half of the bioplastic market accounted for the packaging industry, both
in rigid and flexible forms of packaging.
Among the renewable sources of bio-based packaging materials,
polysaccharides are an important group. They are naturally occurring
polymers including starch, cellulose, pectin, pullulan, alginates and
chitosan, and are widely used to prepare edible films or coatings (Hassan
et al., 2018). Hemicellulose is the most abundant plant polysaccharide
other than cellulose. Hemicellulose has been formerly accepted as a
collective term, which was ambiguously defined as "those poly­
saccharides soluble in alkali that are associated with cellulose of the
plant cell wall" (Dekker, 1985). Today, the most common hemicelluloses
are known to be xylans, constituting approximately 25–35 % of the dry
biomass, and up to 50 % of some tissues in cereal grains (Mikkonen,
2013). Hemicellulose is composed of linear and branched hetero­
polymers of l-arabinose, d-galactose, d-glucose, d-mannose, and
d-xylose, with methyl or acetyl groups attached to the carbon chain
(Boufi, 2017). Similar to other polysaccharide-based films,
hemicellulose-based films are efficient oxygen blockers due to their
well-ordered hydrogen bonded network shape. However, hemicellulose
films possess poor water vapor barrier properties because of their hy­
drophilic nature (Hassan et al., 2018). Concurrently, these films have
high water solubility properties due to their hydrophilicity, which hin­
ders their utilization in industrial applications. By adding different ad­
ditives (i.e. plasticizers, reinforcing agents and modifiers) to
hemicellulose films, it is possible to increase the mechanical strength
and heat resistance of the films and decrease their hydrophilicity (Xu
et al., 2020). Incorporation of reinforcing agents into the hemicellulose
matrix could change the group distribution and structure by hydrogen
bonding with the hydroxyl group in hemicellulose, yielding a film with
enhanced properties (Zhao et al., 2020).
Incorporation of biodegradable nano-reinforcements into hemicel­
lulose is an important strategy for the development of novel
hemicellulose-based nanocomposite materials which mimic natural
plant cell wall structures (Mikkonen, 2013). An important class of the
nano-reinforcements is nanocellulose which is produced from plant re­
sources via mechanical and chemical processes. Nanocelluloses are
therefore abundant, renewable, nontoxic, and biodegradable materials.
The use of nanocelluloses for bio-based food packaging is the subject of
intense research today, from the perspective of efficiency, food safety,
2
Industrial Crops & Products 171 (2021) 113847
sustainability, end-of-life disposal concerns and environmental aware­
ness (Nair et al., 2014; Thomas et al., 2018). Nanocellulose is generally
divided into two groups as cellulose nanocrystal (CNC) with a highly
crystalline structure and cellulose nanofiber (CNF) with a longer and a
semi-crystalline fibrillar structure (Tan et al., 2019). Nanocelluloses
with nano-scale diameters, large surface area and the ability to form
hydrogen bonds create a strong network which obstructs the passage of
molecules. This superior property of CNC and CNF makes them excellent
candidates for barrier applications required in packaging industry (Nair
et al., 2014). In addition, CNC- and CNF-reinforced composite materials
were shown to have better mechanical properties compared to the ma­
terials with the same matrix but without any CNC- and CNF- addition
(Peng et al., 2011). Considering the commercial production of CNCs and
CNFs, a wide range of possibilities exist for the use of cellulose-based
materials in packaging applications (Nair et al., 2014).
The aim of this study was to utilize bulgur bran, which is a low-cost
lignocellulosic residue, as the raw material for the production of
hemicellulose-based composite films. To the best of our knowledge,
fractionation of bulgur bran to obtain value-added products has not been
reported before. Hemicellulose-rich fraction was separated from bulgur
bran via alkaline extraction. In order to prepare reinforced
hemicellulose-based food packaging films with improved properties,
CNC and CNF were added into the hemicellulose matrix to obtain
composites. Incorporation of citric acid (CA) was also studied in the
present study for its non-toxic nature and on the basis of the previously
reported results by Pereira et al. (2017), in which CA was investigated
for its plasticizing and crosslinking action in wheat straw hemicellulose
films together with glycerol blending. A decrease in the film solubility in
water (FSW) was aimed in order to meet the requirements relevant to
food packaging applications. With the aid of response surface method­
ology (RSM) and Box-Behnken design (BBD), the optimum concentra­
tions of CNC, CNF and CA were statistically determined. Films prepared
at optimum conditions were characterized in terms of film thickness,
water content, optical and mechanical properties, water vapor perme­
ability (WVP), scanning electron microscopy (SEM), thermogravimetric
analysis (TGA), differential scanning calorimetry (DSC) and Fourier
transform infrared spectroscopy (FTIR). Furthermore, film biodegrad­
ability in soil was investigated and compared to conventional food
packaging materials.
2. Materials and methods
2.1. Materials
Bulgur bran was obtained from a local bulgur factory (Karaman,
Turkey) and used as received. CNC (cellulose nanocrystal) and CNF
(cellulose nanofibril) were purchased from Nanografi (Turkey). Ac­
cording to technical data obtained from the manufacturer; CNC (re-
dispersible dry powder) was produced by sulfuric acid hydrolysis of
cellulose and has 1–50 μm powder particle size, <150 nm dispersed
powder particle size, 92 % cellulose crystallinity and (− OH) as the main
functional group; CNF (re-dispersible dry powder) was produced from
cotton and has an average particle size of 10–20 nm in width and 2–3 μm
in length, 92 % cellulose crystallinity and (− OH) as the main functional
group.
2.2. Compositional analysis of bulgur bran
The moisture, ash, protein, fat, glucose, hemicellulose, lignin and
crude fiber compositions of bulgur bran were evaluated. Moisture, ash,
protein and fat analysis of bulgur bran was carried out using standard
procedures outlined by the Association of Official Analytical Chemists
(AOAC, 2005). Glucose (released by acid hydrolysis of cellulose and
starch), hemicellulose (xylan and arabinan) and total lignin (acid solu­
ble and acid insoluble lignin) contents of bulgur bran were analyzed
according to NREL/TP-510− 42618 (Sluiter et al., 2008). 0.3 g of sample
D. Sutay Kocabaş et al.
was suspended in 3 mL of 72 % (w/w) H2SO4 and incubated in a water
bath at 30 ◦ C for 1 h. Then the acid content of samples was diluted to 4%
(w/w) and the samples were autoclaved at 121 ◦ C for 1 h. Hydrolysis
solutions were vacuum filtered through a filtering crucible (pore size:3).
Acid-insoluble lignin content of the samples was measured gravimetri­
cally by ashing in a muffle furnace at 550 ◦ C for 5 h. Acid-soluble lignin
was determined in acid hydrolysates at 320 nm using a UV–vis spec­
trophotometer (Optima SP 3000 Nano, Japan). Acid hydrolysates were
filtered through 0.45 μm syringe filters and the monosaccharides
(glucose, xylose, arabinose) present in hydrolysates were analyzed using
high performance liquid chromatography (HPLC) (Shimadzu SCL-10A
vp, Japan) equipped with a Bio-Rad Aminex HPX-87H column (Hercu­
les, USA) and a refractive index detector (Shimadzu RID-10A). The
column temperature was 65 ◦ C and the mobile phase was 5 mM H2SO4
with a flow rate of 0.6 mL min− 1. Using the measured moisture content,
all analyses were corrected to dry basis and expressed as the mean ±
standard deviation (SD) of three replicates.
Crude fiber content of bulgur bran was determined using
ANKOM2000 Fiber Analyzer (ANKOM Technology, USA). The filter bags
were weighed and approximately 1 g of bulgur bran sample was added
to each bag. Samples were first washed for 40 min with 0.313 N NaOH
followed by another 40 min wash with 0.255 N H2SO4. After the
washing process was completed, the cartridges were kept in acetone and
dried in the oven at 105 ◦ C for 2 h. Following the determination of ash
content in a furnace by heating the samples to 650 ◦ C for 5 h the amount
of raw fiber in the samples were calculated according to Eq. 1.
m2 − (m0 xc1 )
Fibercontent(%) = x 100
m1
Where m0: mass of filter paper (g) on which the sample is placed, m1:
mass of sample weighed (g), m2: ash content (%), c1: empty bag factor
(the ratio of the remaining mass to the initial mass of the empty bag after
burning). Experiments were performed in triplicate.
2.3. Extraction of bulgur bran hemicelluloses
Hemicellulose extraction from bulgur bran was mainly derived from
the previously reported procedure by Zilliox and Debeire (1998). 10 g of
bulgur bran was swolled in 200 mL of water for 1 h at room temperature
on a magnetic stirrer. The suspension was filtered and the liquid was
discarded. The remaining solid phase was mixed with 80 mL of KOH
solution (24 %, w/v) for 24 h at 25 ◦ C in a shaking incubator (IKA KS
4000, Germany). At the end of the extraction, the sample was filtered
and the insoluble solid phase (cellulose-rich fraction) was separated. The
supernatant was centrifuged at 10,000 g for 10 min to remove any
insoluble particles. Following the centrifugation, the volume of the su­
pernatant was measured and an ethanol:acetic acid solution (10:1, v/v)
(with a volume of 2.5 times the volume of the supernatant) was added to
the filtrate to enable hemicellulose precipitation. After 10 min, the
precipitate was separated by centrifugation at 10,000 g for 10 min. The
precipitated hemicellulose portion was dried in an incubator (Nüve EN
400, Turkey) at 45 ◦ C until constant weight and used in biodegradable
film production. The yield of the precipitated hemicellulose fraction was
calculated by Eq. 2. Lignin composition of hemicellulose fraction was
evaluated according to analytical method described in Section 2.2.
Dry weight of extracted hemicellulose
Hemicellulose yield (%) =
Weight of hemicellulose in dry bulgur bran
2.4. Experimental design
Box-Behnken design (BBD) and response surface methodology (RSM)
was used to investigate the effects of three independent variables; CA
concentration (%, w/w) (X1), CNC concentration (%, w/w) (X2) and CNF
concentration (%, w/w) (X3) on the film solubility in water (FWS); the
Industrial Crops & Products 171 (2021) 113847
response of the experimental design. The codes and levels (− 1, 0, +1) of
each independent variable were given in Table 1. A total of 15 sets of
experiments, each with triplicate were performed.
2.5. Preparation of films
A stock aqueous solution of hemicellulose (1 g of hemicellulose in 20
mL) was prepared in distilled water. Before preparation of the stock
solution, it was determined that 81 % (w/w) of the hemicellulose was
soluble in water and the rest 19 % (w/w), presumably containing im­
purities and high molecular weight hemicelluloses, was insoluble.
Therefore, to reach the final desired stock concentration (1 g of hemi­
cellulose in 20 mL solution), 1.235 g of hemicellulose was dissolved in
water to reach 20 mL total volume, by stirring for 1 h at 90 ◦ C. Then the
stirring was continued for 24 h at room temperature without heating.
The solution was centrifuged at 10,000 g for 10 min to remove the
insoluble fraction. CA, CNC and CNF were added to the film forming
solution as specified in the experimental design. The solution was stirred
for 3 h for complete mixing of the additives and it was poured into 9 cm
plastic Petri dish, dried at ambient conditions and used in further
characterizations. The films were conditioned for 24 h in a climatic test
chamber (Nüve TK120, Turkey) at 23 ◦ C and 50 % relative humidity
(RH), before further studies.
2.6. Film solubility in water (FWS)
For water solubility analysis, the method published by Sabiha-Hanim
(1) and Siti-Norsafurah (2012) was used with slight modification. Condi­
tioned films (23 ◦ C and 50 % RH for 24 h) were cut in 3cm × 3cm size
and brought to constant weight (m1) at 70 ◦ C. The samples were
immersed in 10 mL distilled water for 1 h in a shaking incubator (IKA KS
4000, Germany) at 150 rpm. At the end of 1 h, the remaining solid parts
of the films were separated from the solution by filtration and were dried
in an incubator at 70 ◦ C to constant weight (m2). FWS of the film samples
were calculated according to Eq. 3.
(m1 − m2 )
FWS(%) = x 100 (3)
m1
2.7. Statistical analysis and optimization of the composition of film
forming solution
The experimental data were evaluated using Minitab 17 software
(USA). The full-quadratic model was used for the analysis of the
experimental data (as presented in Eq. 4) with RSM at significance level
of p < 0.05.
Y = b0 + Σbi Xi + Σbii Xii + Σbij Xi Xj (4)
Where Y is the dependent variable (predicted response; FWS, %), b0 is
the intercept (model constant), bi, bii, and bij are linear, squared and
interaction coefficients, sequentially. X is the coded level of the inde­
pendent variable. The goodness-of-fit of the model was evaluated using
the determination coefficient (R2), adjusted determination coefficient
(adjusted R2; R2-adj), predicted determination coefficient (predicted R2;
R2-pred) and the F-test value. The lack of fit and the statistical signifi­
cance of the terms (linear, quadratic and interaction) were examined by
x 100
Table 1
(2) The levels of independent variables.
Levels
Code Independent variable
− 1 0 +1
X1 CA concentration (%, w/w) 0 5 10
X2 CNC concentration (%, w/w) 0 5 10
X3 CNF concentration (%, w/w) 0 5 10
CA: citric acid, CNC: cellulose nanocrystal, CNF: cellulose nanofiber.
3
D. Sutay Kocabaş et al.
analysis of variance (ANOVA). For the experimental verification of the
model; films were prepared in two replications according to optimum
film forming solution formulation. The experimental FWS values were
compared with predicted values to determine the validity of the model.
2.8. Characterization of the biodegradable films
2.8.1. Film thickness
Film thickness was measured using a digital micrometer (0.001 mm
accuracy) (Mitutoyo, Japan) and calculated by averaging of five mea­
surements on between the edge and the center of each sample film.
2.8.2. Film solubility in water (FSW)
Water solubility analysis of the biofilms prepared at optimum con­
ditions in compare to neat films was performed as described in Section
2.6.
2.8.3. Color and optical properties
The color of the films was measured using HunterLab device
(HunterLab Color Flex, USA) at three different points after calibrating
with a standard white plate and the results; L* (lightness), a* (green­
ness/redness) and b* (blueness/yellowness) are expressed as mean ±
SD. The total color difference (Δ E*) was calculated according to Eq. 5.
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
ΔE∗ = (ΔL∗ )2 + (Δa∗ )2 + (Δb∗ )
2
(5)
Where ΔL*, Δa* and Δb* are the difference between each color
parameter of the film samples and of the white calibration plate.
The transparency properties of the films were measured with UV-
3600 UV–vis-NIR spectrophotometer (Shimadzu, Japan). The sample
films were placed in the test cell of the spectrophotometer and a scan
was performed between 190–700 nm wavelengths with two replicates.
2.8.4. Water content
Water content analysis of the films was carried out in a rapid mois­
ture analyzer (Ohaus MB 45, China) with 0.5 g sample at 105 ◦ C with
three replicates. The results are expressed as mean ± SD.
2.8.5. Mechanical properties
Specimens (2 cm × 6 cm) were cut from the conditioned films and
tested for their mechanical properties. The tensile testing equipment
(TA-XT Plus, Stable Micro Systems, UK) equipped with a 5 kg load cell
and mini tensile grips A/MTG (Stable Micro Systems, UK) was used. The
test was conducted at a crosshead speed of 10 mm/min in an environ­
ment with 23 ± 1 ◦ C and 40 ± 2% humidity. Three samples were ob­
tained from each of three separate films, corresponding to nine
replicates for each type of film. The results for the tensile strength (TS),
elongation at break (EB), and Young’s modulus (E) were obtained from
the software of the testing device.
2.8.6. Water vapor permeability (WVP)
The method described in ASTM E96/E96M-16 was used with slight
modification to determine the WVP of the films. A cylindrical glass
container (100 mL volume, 5.4 cm diameter) containing 30 mL of
distilled water was sealed with the film sample by using epoxy glue
(Pattex). Film-sealed containers were weighed and their initial masses
were determined. The containers were then placed in a test cabinet at 23
◦
C and 50 % RH. The containers were weighed regularly at 24 h intervals
for 7 days and the change in weight against time was plotted. The water
vapor transmission rate (WVTR) was calculated from the slope of the
straight line (g/h) divided by water permeation area (m2). Eq. 6 was
used to calculate the WVP.
( )
WVTRxl
Water vapor permeability WVP = (6)
ΔP
4
Industrial Crops & Products 171 (2021) 113847
Where; WVP: water vapor permeability (g mm m− 2 h− 1 kPa− 1), WVTR:
water vapor transmission rate (g m− 2 h− 1), ℓ: film thickness (mm), ΔP:
the difference between the partial pressure (P0) of the water vapor on
the surface of the film outside the container (50 % RH) and the partial
vapor pressure (Pi) of the water inside the container (100 % RH) at test
temperature (23 ◦ C) (kPa).
2.8.7. Scanning electron microscopy (SEM)
Hitachi SU 5000 FE-SEM (Japan) scanning electron microscope was
used to determine the cross-sectional morphology of the films to observe
the changes in the film structure caused by the addition of nano­
celluloses. Prior to the SEM analysis samples were coated with gold
palladium alloy for 20 s using a vacuum coater (LEICA EM ACE200,
Germany). The samples were analyzed at 2–5 kV voltage with
500–20,000x magnification.
2.8.8. Thermogravimetric analysis (TGA)
TGA was carried out using the Exstar SII TG/DTA 6300 (Seiko In­
struments, Japan) thermogravimetric analyzer. Samples were weighed
(approximately 4–5 mg) and the experiments were conducted under
inert N2 atmosphere at N2 flow rate of 10 mL/min. The heating rate was
10 ◦ C/min over a temperature range of 20–600 ◦ C. The analysis was
performed with two parallel measurements.
2.8.9. Differential scanning calorimetry (DSC)
DSC was carried out with DSC6220 (SII Nanotechnology Inc., USA)
differential scanning calorimeter to determine the glass transition tem­
peratures (Tg) of the film samples. For each measurement, approxi­
mately 20 mg of sample was first heated from 25 ◦ C to 105 ◦ C at a
heating rate of 5 ◦ C/min and kept at that temperature for 10 min to
remove interferences related to moisture. After cooling back to 25 ◦ C, a
second heating cycle was applied by heating the sample to 225 ◦ C with a
heating rate of 5 ◦ C/min. All the scans were performed at a constant N2
gas flow rate of 10 mL/min.
2.8.10. Fourier transform infrared spectroscopy (FTIR)
FTIR analysis of the films was performed using Vertex 70 ATR-FTIR
spectrometer (Bruker, UK). The spectra of the samples were obtained
from 4000 to 400 cm− 1 with a resolution of 4 cm− 1.
2.8.11. Film biodegradability in soil
Biodegradability of the films was evaluated using the method
described by Jaramillo et al. (2016). A plastic tray (10 cm × 25 cm × 5
cm) was filled with soil to a height of 40 mm. Samples (3 cm × 3 cm)
were cut from films and buried in the soil with a supporting aluminum
net (5 cm × 10 cm) to a depth of approximately 10 mm. The tray was
kept at room temperature. In order to sustain the moisture, the soil was
water-sprayed on daily basis. The images of the films were recorded
regularly once in every 2 days for a period of 10 days.
2.9. Statistical analysis of the data of characterization tests
Unless otherwise stated, results reported are the mean ± SD of three
replicates. One-way ANOVA was used to evaluate differences between
means of a testing parameter. Tukey’s multiple range test at a level of p
< 0.05 was used. All statistical analyses were performed using Minitab
17 software (USA).
3. Results and discussion
3.1. Chemical composition of bulgur bran
The chemical composition of bulgur bran was evaluated according to
standard procedures of AOAC (2005). The moisture content of bulgur
bran was determined as 10.51 ± 0.18 % (w/w). Using this moisture
D. Sutay Kocabaş et al. Industrial Crops & Products 171 (2021) 113847

content data, the chemical composition of bulgur bran on dry weight 2015). Experimental design and FWS results (response) are shown in
basis is given in Table 2. The ash content of bulgur bran was found as Table 3. The experimental FSW values ranged from 50.80 % to 61.49 %.
2.45 ± 0.03 %, which was higher than the ash composition reported as The lowest FSW (50.80 %) was observed in run no.3 (5% CA, 10 % CNC,
1.89–1.92 % for bulgur bran (Saka et al., 2020). Compared with the 10 % CNF) and the highest FSW (61.49 %) was observed in run no.4 (5%
protein content of wheat bran which was reported as 16.50 ± 0.52 % CA, 0% CNC, 0% CNF). The results were modeled, analyzed and statis­
(Yan et al., 2015) and 18.1–23.5 % (Navrotskyi et al., 2019), the protein tically interpreted with the full-quadratic model in Minitab 17 software
content of bulgur bran (14.87 ± 0.66 %) was lower in this study. Saka (USA).
et al. (2020) reported a lower protein composition (5.0–5.6 %) for ANOVA was used for the statistical testing of the model (Table 4). p-
bulgur bran. The result obtained in this study for fat composition of values were examined to determine the significance of the coefficients
bulgur bran (5.07 ± 0.03 %) was similar to that previously reported by and their interactions. The importance of the coefficient is considered to
Yan et al. (2015) for wheat bran as 4.95 ± 0.14 %. be high if its corresponding p-value is less than 0.05. The smaller is the p-
Commercial wheat bran has been the subject of scientific studies due value more significant is the corresponding coefficient. It is evident that
to its high fiber content. However, since all outer layers (outer and inner two linear model terms X2 and X3 were significant (p < 0.05) for the
pericarp, testa, hyaline layer and aleurone layer) of wheat grain are desired response (FWS), meaning that the variables CNC and CNF ex­
removed in commercial wheat bran production, there is also starch in hibits significant effects on FWS while CA shows less effect since its p-
the range of 9.10–38.9 % (on dry basis) in the composition of wheat bran value is >0.05. The FWS was evidently affected by the incorporation of
(Onipe et al., 2015). Bulgur bran is also obtained from the outer layers of nanocelluloses (CNC and CNF). It was noticed that significant quadratic
the wheat grain, and despite the cleaning/debranning stage, the aleu­ effect of variables was shown by X1*X1 and X2*X2 with low p-values
rone layer remains within bulgur product. Therefore, in contrast to (<0.05). In addition, among the interactive effects between variables,
wheat bran, bulgur bran does not contain the aleurone layer, which is only X1*X3 exhibited significant effect on FWS (p < 0.05). The insig­
rich in macro and trace elements, contributing to the nutritional value of nificant terms were eliminated from the second-order polynomial model
bulgur product (Hendek Ertop, 2019; Saka et al., 2020). Due to the equation to simplify the model and ensure the accurate response (Eq. 7).
absence of aleurone layer in bulgur bran, its composition is more Although X1 was found to be insignificant, it was not eliminated in order
fiber-rich compared to commercial wheat bran. In accordance, Saka follow the hierarchy principle of RSM.
et al. (2020) predicted the total dietary fiber content of bulgur bran as
FWS (%) = 60.812 + 0.667 X1
72.67–83.04 %, higher than that of wheat, rice, barley, and oat
(14.0–38.9 %) (Kaur and Sharma, 2011; Saka et al., 2020). In this study, + 0.281X2 –1.039X3 –0.0985X1 ∗X1 –0.0585X2 ∗X2
the crude fiber content of the bulgur bran was found as 58.7 ± 0.39 % + 0.0397X1 ∗X3 (7)
indicating the high potential of bulgur bran as a starting material for
fiber-based (including hemicellullose-based) products. Hemicellulose ANOVA analysis indicated that the model is statistically significant
content of bulgur bran (16.20 ± 0.88 % xylan and 4.95 ± 0.42 % ara­ with a high F-value (44.53) and low p-value (<0.001). Lack of fit was
binan; 21.15 % in total) was in agreement with that reported in the found to be insignificant with a high p-value of 0.953. Another indica­
literature by Cantero et al. (2015) for wheat bran as 22.1 % on dry basis. tion of the fitness of the model is the coefficient of determination (R2)
However, lignin content of bulgur bran (2.60 ± 0.01 % acid soluble and adjusted coefficient of determination (R2-adj). The values of R2 and
lignin and 6.08 ± 1.20 % acid insoluble lignin; 8.68 % in total) in the R2-adj for the model were found as 0.9877 and 0.9655, respectively.
present study was significantly lower than that of the wheat bran which Both coefficient of determination approaches to 1.0 showing a high
was reported as 24.3 %, on dry basis (Cantero et al., 2015). It is known accuracy of the proposed model and a strong correlation between
that the bran composition depends on the wheat variaties, growing experimental and predicted responses. This result indicates the signifi­
environments, and milling performance (Navrotskyi et al., 2019). cance of the model.
Although bulgur is produced from wheat, bulgur bran and wheat bran Fig. 1 shows the response surface (contour) plots of developed model
have shown different properties. equation, which are used to investigate the interactions between vari­
ables (CA, CNC and CNF) and their optimum concentration to achieve
the lowest FWS. Contour plots of three independent variables showed
3.2. Optimization of the composition of film forming solution that FWS decreases with increasing CNC and CNF concentration (Fig. 1.
a,b,c). The positive effect of CNC and CNF incorporation on FWS could
The optimum levels (compositions) of independent variables and the
effect of their interactions on the water solubility of bulgur bran hemi­
cellulose films were determined by RSM using BBD. The optimization Table 3
was carried out with the aim of decreasing the film solubility in water Experimental design and results of RSM of three independent variables for FWS.
(FSW). In this context, hemicellulose films were reinforced with nano­ Run CA (%, w/ CNC (%, w/ CNF (%, w/ FWS (%)
celluloses having crystalline (CNC) and fibrilated (CNF) structures. The no. w) (X1) w) (X2) w) (X3) Experimental Predicted
effect CA was investigated regarding its potential action both as a
1 0 5 0 60.97 60.75
crosslinker and a plasticizer to hemicellulose films (Azeredo et al.,
2 5 5 5 58.84 57.73
3 5 10 10 50.80 50.61
Table 2 4 5 0 0 61.49 61.68
Chemical composition of bulgur bran. 5 5 0 0 55.89 55.71
6 5 10 0 59.31 59.49
Composition (%, w/w, dry weight) 7 0 0 5 56.20 56.23
Ash 2.45 ± 0.03 8 0 10 5 51.68 51.72
Protein 14.87 ± 0.66 9 10 5 0 58.57 58.42
Fat 5.07 ± 0.03 10 10 10 5 52.25 52.23
Glucose 40.36 ± 0.70 11 5 5 5 57.02 57.73
Hemicellulose 12 0 5 10 51.19 51.34
Xylan 16.20 ± 0.88 13 10 0 5 55.07 55.03
Arabinan 4.95 ± 0.42 14 5 5 5 57.32 57.73
Lignin 15 10 5 10 52.76 52.98
Acid soluble 2.60 ± 0.01
CA: citric acid, CNC: cellulose nanocrystal, CNF: cellulose nanofiber, FWS: Film
Acid insoluble 6.08 ± 1.20
water solubility.

5
D. Sutay Kocabaş et al. Industrial Crops & Products 171 (2021) 113847

Table 4
ANOVA of quadratic model for the response (FWS).
Source Seq SS DF Adj SS Adj MS F p

Model 175.351 9 175.351 19.483 44.53 <0.001 Significant

CA(X1) 0.242 1 0.242 0.242 0.5 0.491
CNC (X2) 26.682 1 26.682 26.682 60.98 0.001
CNF (X3) 110.261 1 110.261 110.261 251.99 <0.001
CA*CA (X1*X1) 21.546 1 22.405 22.405 51.20 0.001
CNC*CNC (X2*X2) 8.471 1 7.907 7.907 18.07 0.008
CNF*CNF (X3*X3) 1.370 1 1.370 1.370 3.13 0.137
CA*CNC (X1*X2) 0.723 1 0.723 0.723 1.65 0.255
CA*CNF (X1*X3) 3.940 1 3.940 3.940 9.01 0.03
CNC*CNF (X2*X3) 2.117 1 2.117 2.117 4.84 0.079
Lack of fit 0.284 3 0.284 0.095 0.10 0.953 Not significant
Pure error 1.904 2 1.904 0.952
Total 177.539 14
R2 = 0.9877, R2-adj = 0.9655, R2-pred = 0.9503

CA: citric acid, CNC: cellulose nanocrystal, CNF: cellulose nanofiber, FWS: Film water solubility.

Fig. 1. Contour plots showing the interactive

effects of the independent variables (CA, CNC,
CNF) on FWS. (a) contour plot of CNC and CA
concentrations (%, w/w) (CNF concentration
kept constant at 5%, w/w), (b) contour plot of
CNF and CA concentrations (%, w/w) (CNC
concentration kept constant at 5%, w/w), (c)
contour plot of CNF and CNC concentrations
(%, w/w) (CA concentration kept constant at
5%, w/w). CA: citric acid, CNC: cellulose
nanocrystal, CNF: cellulose nanofibril, FWS:
film water solubility.

be explained by the compatibility of nanocelluloses with hemicellulose.
The hydrophilic character of hemicelluose enables the formation of
multiple and strong hydrogen bonding with nanocelluloses, which is
believed to physically span the gap between the molecules (Mikkonen,
2013; Boufi, 2017). The resulting homogeneous structure of
nanocellulose-incorporated hemicellulose and the coherence between
hemicellulose and nanocelluloses are thought to ensure the lower FWS
of the composites.
The increase in CA increased FWS up to the center point (5% CA, w/
w). Then, FWS decreased when the CA concentration reached 10 % (w/
w) (Fig. 1.a,b). This result showed two options for optimum points;
without CA reinforcement (− 1, +1, +1) and with 10 % (w/w) CA
reinforcement (+1, +1, +1). The suggested mechanism of interaction
between polysaccharide chains and CA was the di-ester linkages
between hydroxyl groups of polysaccharide and carboxyl groups of CA
(Pereira et al., 2017). Pereira et al. (2017) concluded that glycerol may
act as a crosslinking extender to citric acid providing flexibility to the
crosslinking. However, in the present study, bulgur bran
hemicellulose-based films reinforced with 10 % (w/w) CNC and CNF
with additional 10 % (w/w) CA (without glycerol) incorporation were
brittle, which had a negative effect on the flexibility and processibility of
the films. A possible explanation for this result could be the absence of
the glycerol-extended flexible citric acid crosslinking. In addition, as
reported by Azeredo et al. (2015) and Wang et al. (2014), high pro­
cessing temperatures (>100 ◦ C) are required to observe the crosslinking
of CA. Since the biofilms were not cured at high temperatures, the
crosslinking effect was not observed in this study.
Li et al. (2020a) reported that the excessive incorporation of CA into

6
D. Sutay Kocabaş et al.
the composite hemicellulose films reduces the compatibility of the films
and has a negative impact on their performance, which was also the case
in the present study. In literature, many other studies on hemicelluloses
report addition of co-polymers (i.e. PVA, carboxymethyl cellulose) to
improve film formation and different types of plasticizers (i.e. glycerol,
sorbitol) to obtain a continous and self-supporting hemicellulose film
matrix (Shao et al., 2019). However, in the present study, in contrast to
many previous studies, the optimum composition of the film forming
solution does not contain CA, meaning that no external plasticizer was
required in order to prepare standalone flexible hemicellulose films. It is
thought that this result would create a great advantage at industrial
scale, from economical and environmental point of view.
Based on the proposed model, the optimum conditions were deter­
mined as 10 % (w/w) CNC and 10 % (w/w) CNF incorporation to the
hemicellulose matrix without any CA addition. At the optimum condi­
tions, the predicted water solubility value (FWS) by response surface
analysis was predicted as 47.38 %. As a result of triplicate verification
runs, the experimental FWS of the films prepared at optimum conditions
of 10 % (w/w) CNC, 10 % (w/w) CNF, without CA was found to be 49.30
± 0.42 %. As the experimental FWS deviates 3.9 % from the predicted
(theoretical) FWS and is within 95 % confidence interval, the proposed
model is concluded to have a high accuracy and suitability for deter­
mination of CA, CNC and CNF reinforcement concentrations for
achieving the lowest FWS. This result indicates a 21.3 % reduction in
FWS after CNC- and CNF-incorporation compared to neat films having a
FWS of 62.6 %.
In order to determine the individual roles of CNC and CNF in the film
by comparative analysis, composites were prepared by adding only CNC
or CNF and tested for their FWS properties. The addition of 10 % (w/w)
CNC decreased the FWS of the film from 62.6% to 58.29%. Films pre­
pared with only 10 % (w/w) CNF incorporation showed a FWS of 51.23
%, indicating that the addition of CNF caused a greater enhancement in
FWS of the films. The impact of CNF on FWS can be explained by the
placement of CNF into the film network structure, thereby reducing the
accessible space for water molecules in the film matrix (Zhang et al.,
2021).
3.3. Optical properties
The color of the films used in food packaging applications is very
important because the appearance of the films directly affects the
acceptability of the packaged product by consumers (Li et al., 2020b). As
shown in Table 5, both film samples exhibited similar color difference
(ΔE*) values (77.00 and 75.48). The incorporation of CNC and CNF
caused a slight increase in L*, a* and b*, meaning that the
nanocellulose-reinforced hemicellulose films were lighter in color, and
to some extend, more red and yellow in compare to neat hemicellulose
films. Similar to previous studies, incorporation of nanocelluloses
caused minimal changes in the visual aspect of the films (Resende et al.,
2018).
Table 5
Color of the films.
CA (%, CNC (%, CNF (%, L* a* b* ΔE*
w/w) w/w) w/w)
0 0 0 17.41 ± 0.79 ± 8.70 ± 77.00
0.40a 0.01a 0.25a
0 10 10 19.42 ± 2.15 ± 11.96 ± 75.48
0.39b 0.17b 0.21b
L*, a*, b* are Hunter’s Lab color parameters. CA: citric acid, CNC: cellulose
nanocrystal, CNF: cellulose nanofiber, FWS: Film water solubility. White cali­
bration plate (L* = 93.92, a* = − 1.02, b* = 0.26) was used as film background.
Values reported are the mean ± SD of three times testing of three replicates (9
data points in total). Lowercase letters show grouping information using the
Tukey’s test and 95 % confidence. Means that do not share a letter are signifi­
cantly different.
7
Industrial Crops & Products 171 (2021) 113847
The optical transparencies (light transmittance) of the films are
presented in Fig. 2. The transmittance of the films (100 ± 2 μm thick­
ness) increased gradually from the UV region (190–400 nm) to visible
region (400–700 nm). With the addition of CNC and CNF, the light
transmission behaviour of the films in UV region did not change. The
transmittance at 400 nm was only 2%. In the visible region, CNC and
CNF incorporation caused a major decrease in transmittance. For
example, at 600 nm, tranmittance declined from 9.2% to 6.6% by the
addition of CNC and CNF, which corresponds to a decrease of 28 %.
Films prepared by using hemicelluloses, which were obtained by alka­
line extraction conditions are known to block the light transmission
mostly in UV region and show low transmittance in visible region
(Chadni et al., 2020). The incorporation of CNC (at 5–15 % concentra­
tion) and CNF commonly provides lower light transmittance to film
matrices compared to control films (Zhang et al., 2021). The reason of
this effect is attributed to the scattering of light caused by the incorpo­
ration of nanocellulose, which improves the light screening performance
of the film (Zhang et al., 2021). Based on its larger size, the addition of
CNF has a greater effect on the transmittance of edible food packaging
films, compared to CNC. The final light tranmittance level is still high
enough not to adversely affect the visual judgment of food of consumers
(Zhang et al., 2021). In accordance with these results, the CNC- and
CNF-reinforced hemicellulose films prepared in the present study
showed high light barrier property both in the UV and visible region.
Specifically, the remarkable barrier performance of the films in UV re­
gion (≤2%) could make them a very suitable candidate for food pack­
aging applications, because the UV light-exposure leads to loss of
nutritional and organoleptic properties, reducing the shelf life and
quality of food products due to free radical formation (Ahankari et al.,
2020).
3.4. Moisture content of the films
The moisture content of the films decreased from 11.19 % (w/w) to
9.07 % (w/w) with the incorporation of CNC and CNF (Table 6). The
decrease could be associated with the hydrogen bonds between nano­
celluloses and hemicellulose matrices which forbid the water to inter­
face with the hemicellulose matrix. In addition, hemicelluloses are
known to be randomly branched molecules, which create disordered
regions in the matrix. As cellulose is unbranched, they are likely the
preferred sorption sites. Therefore, incorporation of nanocelluloses into
the hemicellulose films may lead to a decrease in their moisture content
Fig. 2. Transmittance (%) curves for hemicellulose films (a) without rein­
forcement (b) with 10 % (w/w) CNC and 10 % (w/w) CNF reinforcement. CNC:
cellulose nanocrystal, CNF: cellulose nanofibril.
D. Sutay Kocabaş et al.
Table 6
Mechanical properties, water content and water vapor permeability (WVP) of the films.
CA (%, w/ CNC (%, w/ CNF (%, w/ Tensile strength (TS) Elongation at break (EB)
w) w) w) (MPa) (%)
0 0 0 4.87 ± 0.89a 29.70 ± 5.41a
0 10 10 20.56 ± 1.21b 14.71 ± 3.11b
CA: citric acid, CNC: cellulose nanocrystal, CNF: cellulose nanofiber, FWS: Film water solubility. Values reported are the mean ± SD of five replicates for TS, EB and
Young’s modulus, and triplicate analysis for water content and WVP. Lowercase letters show grouping information using the Tukey’s test and 95 % confidence. Means
that do not share the same letter in the same column are significantly different.
(Peng et al., 2011).
3.5. Mechanical properties
Food packaging materials are exposed to different mechanical loads.
Therefore, tensile strength (TS) and elongation at break (EB) are among
the key parameters for determining the performance of the packaging
materials (Hassan et al., 2018; Zhang et al., 2021). As can be seen in
Table 6, the TS increased by 4.2 times (from 4.87 ± 0.89 MPa to 20.56 ±
1.21 MPa) with the addition of CNC and CNF. The only conventional
standard found in the literature related to the mechanical properties of
packaging film is linked to the tensile strength (>3.5 MPa) (Azeredo
et al., 2015). CNC- and CNF-reinforced hemicellulose films in this study
met this requirement with TS of 20.56 ± 1.21 MPa. The increase in
Young’s modulus (E) upon CNC- and CNF- addition is found to be
3.8-fold, which also caused approximately 50 % decrease in EB. Chadni
et al. (2020) reported that TS and EB of starch films were 23.1 MPa and
8.5 %, respectively. Based on these results, nanocellulose-incorporated
hemicellulose films showed similar TS and EB values compared to
starch films. Wheat bran is known to contain starch in the range of
9.10–38.9 % (on dry basis) (Onipe et al., 2015). Ghodrat et al. (2017)
reported the content of cellulose in wheat bran as 9.60 ± 0.48 %. As
shown in Table 2, total glucose content of bulgur bran (obtained by acid
hydrolysis of cellulose and starch) was found as 40.36 ± 0.70 %, in this
study. This result showed the potential presence of starch in bulgur bran.
Based on that, one of the possible reasons of high EB value of biofilms
could be the existence of starch residues in hemicellulose fraction. The
high yield value of the precipitated hemicellulose fraction following the
alkaline extraction (52.60 %, on dry basis) also supported this possi­
bility. In addition, total lignin content of hemicellulose fraction was
determined as 6.70 % (1.34 ± 0.22 % acid soluble lignin and 5.36 ± 1.52
% acid insoluble lignin). As reported by Goksu et al. (2007) and Hu et al.
(2016), pure hemicelluloses from various plant sources could not form
self-supporting films. By the help of the plasticizing effect of lignin, it is
possible to prepare continuous films (Goksu et al., 2007; Hu et al.,
2016). Egüés et al. (2013) observed that lignin content in hemicellulose
fraction is the most important characteristic for the film forming ca­
pacity and enhanced film forming properties. In accordance, delignifi­
cation of bulgur bran has been performed in the present study, however,
it was not possible to produce self-supporting continuous films using
lignin-free hemicellulose fraction (data not shown). This result showed
the possible contribution of lignin to tensile properties of hemicellulose
composite films obtained in this study.
It is known that adding CNF to hydrophilic xylan film matrices en­
hances the mechanical properties, in particular the TS, due to the high
aspect ratio, surface area, and flexibility of CNF (Hansen et al., 2012; Xu
et al., 2019). Similarly, addition of CNF had a greater impact on the TS
and E of the films in this study. The incorporation of 10 % (w/w) CNF to
the neat film increased the TS from 4.87 ± 0.89 to 11.7 ± 1.04 MPa and
E from 4 ± 0.66 to 8.44 ± 0.74 MPa. Whereas, addition of 10 % (w/w)
CNC to the neat film increased the TS and E of the films to 8.6 ± 0.53
MPa and 6.4 ± 0.42 MPa, respectively. Xu et al. (2019) reported that the
TS of the plasticized hemicelluloses/chitosan-based edible films
increased by 2.3 times with the addition of 5% (w/w) CNF. Peng et al.
(2011) showed that the incorporation of 5% (w/w) CNF increased both
8
Industrial Crops & Products 171 (2021) 113847
2 1
Young’s modulus (E) Water content (%, WVP (g mm m− h−
(MPa) w/w) kPa− 1)
4.00 ± 0.66a 11.19 ± 1.28a 2.12 ± 0.02a
15.19 ± 0.56b 9.07 ± 0.72a 2.02 ± 0.03b
the TS and E of xylan-rich hemicellulose film by 30 and 80 %. Pereira
et al. (2017) prepared wheat straw hemicellulose-based film with CNC
incorporation. When 4% (w/w) CNC was added, TS, EB and Young’s
modulus were determined as 11.25 MPa, 3.13 % and 864.6 MPa,
sequentially. The results of the present study showed that the incorpo­
ration of CNC and CNF acted synergically to achieve a high TS and high
EB showing the capability of the composite films to resist mechanical
loads to a certain extent without crack formation. In bio­
macromolecules, the mechanical strength is generally associated with
the hydrogen bonds within the matrix (da Silva Braga and Poletto,
2020). Owing to hydrogen bonds between nanocelluloses (CNC and
CNF) and the hydroxyl group of hemicellulose, higher mechanical
strength compared to neat hemicellulose films was obtained. Similar to
CNF, the incorporation of CNC into edible food packaging films have
revealed diverse effects on TS in several studies in the literature (Hu
et al., 2016). These different effects are associated with the concentra­
tions of CNC and CNF in the composite films. In general, when the op­
timum concentration is exceeded, adverse effects of CNC and CNF
incorporation could be observed due to the aggregation of these addi­
tives. The optimum CNC concentration in polysaccharide film matrices
is generally given as 5–10 % (Zhang et al., 2021). In conclusion, the
concentration of CNC and CNF in the present study was 10 % (w/w)
each, which is within the suggested optimum concentration range. As a
result, incorporation of CNC and CNF into hemicellulose film matrix
resulted in positive effects on the mechanical properties of the films.
3.6. WVP
In food packaging applications, the packaging material used is ex­
pected to avoid or at least reduce moisture transfer between the food
material and the exterior atmosphere of the package in order to prevent
the loss of water content of the food inside the package. For this purpose,
WVP is aimed to be as low as possible (El Miri et al., 2015). The rein­
forcement with CNC and CNF was found to reduce WVP of the hemi­
cellulose films in the present study. The incorporation of 10 % (w/w)
CNC and 10 % (w/w) CNF into the film decreased WVP from 2.12 ± 0.02
g mm m− 2 h− 1 kPa− 1 for the neat films to 2.02 ± 0.03 g mm m− 2 h− 1
kPa− 1 for CNC- and CNF-reinforced films (Table 6). This result is in
agreement with the study of Pereira et al. (2017), who reported that the
reinforcement of wheat stalk hemicellulose-based film with CNC
decreased WVP from 4.61 to 3.01 g mm m− 2 h− 1 kPa− 1. Overall, a 4.7 %
decrease in WVP was observed in the present study. The positive effect
of nanocellulose-incorporation could be explained by the compact
microstructure of CNC and CNF, and the ability to form hydrogen bonds
resulting in a strong network, which hampered the transfer (diffusion) of
the water vapor through the film matrix, and occasionally on the filling
of biopolymer film void spaces, leading to the lower permeability and
decrease on WVP (Nair et al., 2014; Fang et al., 2017; Xu et al., 2019;
Zhang et al., 2021). Many CNC (Atef et al., 2014; Yadav and Chiu, 2019)
and CNF (Li et al., 2018; Xu et al., 2019) incorporated biopolymer films
showed better water barrier properties compared to neat films. How­
ever, opposite results have also been reported, where the increase of
WVP after nanocellulose incorporation was observed possibly due to
agglomeration caused by the electrostatic interactions (Zhang et al.,
2021). This phenomenon is in a way similar to the decreased mechanical
D. Sutay Kocabaş et al. Industrial Crops & Products 171 (2021) 113847

properties caused by excessive incorporation of CNC and CNF to the

films.

3.7. SEM

Morphological properties of composite films were evaluated at the

cross-sectional surfaces (Fig. 3.a–d). The neat hemicellulose films
(Fig. 3.a and c) and nanocellulose-incorporated hemicellulose films
(Fig. 3.b and d) films displayed similar cross-sectional morphologies,
both having continuous and homogenous appearance. As can be seen in
Fig. 3.c and 3.d at 20k-magnification, addition of CNC and CNC caused
filling of hemicellulose film void spaces. In conclusion, CNC and CNF
incorporation at a concentration of 10 % (w/w) each was compatible
with bulgur bran hemicellulose since no agglomeration was observed in
the films. This result visually explains the improvement of the me­
chanical properties and the decrease of WVP for the CNC and CNF-
reinforced films.

3.8. TGA

In order to understand the effect of nanocelluloses on the thermal

stability of the films, TGA was performed under N2 atmosphere to pre­
Fig. 4. Thermogravimetric analysis (TGA) curves for hemicellulose films (a)
vent thermoxidative degradation. The neat hemicellulose film was
without reinforcement (b) with 10 % (w/w) CNC and 10 % (w/w) CNF rein­
compared with the film containing 10 % (w/w) CNC and 10 % (w/w)
forcement. CNC: cellulose nanocrystal, CNF: cellulose nanofibril.
CNF since these were the optimal conditions that resulted to the lowest
FWS. As shown in Fig. 4, both films displayed similar patterns with each
increased to 250 ◦ C when CNC and CNF were present in the films. In a
other regarding their response to increasing temperature, similar to
similar trend, presence of nanocelluloses in the films also increased the
previous reports (Gordobil et al., 2014; Hansen et al., 2012) where the
temperature in which the maximum weight loss rate took place from to
inclusion of nanocelluloses to the films appears to enable the films to
275 ◦ C to 289 ◦ C, where such an increase was also observed for
retain more of their original water content since slightly higher %
xylan-rich hemicellulose based nanocomposite films containing CNF
original weight values were obtained at temperatures ≤100 ◦ C. At 600
(Peng et al., 2011).
◦
C, both neat and nanocellulose-reinforced film samples had a residual
mass of app. 35 wt %, which is in agreement with the solid residue data
reported by Egüés et al. (2013) as 35 wt % at 600 ◦ C for the 3.9. DSC
lignin-hemicelluloses obtained from corn cob. For the neat hemicellu­
lose film, the onset of degradation was determined as 236 ◦ C, which was DSC was used in order to determine the changes that took place in

Fig. 3. Cross-sectional images of hemicellulose-based films obtained via scanning electron microscopy (SEM). (a and c) without reinforcement, (b and d) with 10 %
(w/w) CNC and 10 % (w/w) CNF reinforcement.

9
D. Sutay Kocabaş et al.
the glass transition temperatures (Tg) of the films upon the addition of 10
% (w/w) CNC and 10 % (w/w) CNF. Determination of Tg for hemi­
celluloses is quite difficult since unlike the conventional synthetic
polymers, it might not be possible to obtain a clear peak particularly
when unmodified (hydrophilic) hemicelluloses are used since the pres­
ence of hydroxyl groups causes peak overlap (Hartman et al., 2006). The
approach with such hemicelluloses is thus checking the DSC thermo­
gram for “an increase of the heat flow to a higher level” (Gröndahl et al.,
2004) or looking for a discontinuity (Chen et al., 2003) as demonstrated
previously for determining the Tg of galactoglucomannan type hemi­
celluloses (Hartman et al., 2006). When the DSC thermogram shown in
Fig. 5 is examined, the onset of this discontinuity appears to occur at
around 120 ◦ C for the neat hemicellulose film while the onset shifts to
around 135 ◦ C for the film containing CNC together with CNF indicating
that the inclusion of nanocelluloses into the films increased the Tg by
approximately 15 ◦ C.
3.10. FTIR
In order to understand the changes that took place in the films upon
the addition of nanocelluloses, FTIR spectrums of the films with and
without nanocellulose incorporation were obtained together with the
FTIR spectrums of CNC and CNF. As shown in Fig. 6, the spectrum of the
neat hemicellulose film changes at various wavenumbers upon the
addition of CNC and CNF to the film formulation. The broad absorption
band at 3350 cm− 1, which is assigned to O–H stretch in cellulose
(Pandey, 1999), has an increased intensity for the CNC and
CNF-incorporated film compared to the neat hemicellulose film due to
the presence of cellulose. The absorption band at 2900 cm− 1, which is
assigned to C–H stretching in cellulose (Pandey, 1999) is also amplified
for the CNC and CNF-reinforced film compared to neat hemicellulose
film. Presence of various absorption bands found between 1000 cm− 1
and 1200 cm− 1, which were assigned to C–O stretch, asymmetric
glucose ring stretch and C–OC– asymmetric vibration in cellulose
(Pandey, 1999) also leads to the amplification of the intensities in this
region for the film incorporated with CNC and CNF compared to the film
without any nanocellulose. Similar increases in the intensities were also
previously reported by Saxena et al. (2011) related to the inclusion of
CNC to xylan based films and the increase in the intensities of O–H
Fig. 5. Second scan thermograms of hemicellulose films (a) without rein­
forcement (b) with 10 % (w/w) CNC and 10 % (w/w) CNF reinforcement ob­
tained via DSC. The thermograms were displaced in y-direction. CNC: cellulose
nanocrystal, CNF: cellulose nanofibril.
10
Industrial Crops & Products 171 (2021) 113847
Fig. 6. FT-IR spectrums of films with and without nanocellulose addition
together with the spectrums of CNC and CNF; (a) without reinforcement, (b)
with 10 % (w/w) CNC and 10 % (w/w) CNF reinforcement, (c) CNC, (d) CNF.
CNC: cellulose nanocrystal, CNF: cellulose nanofibril.
related bands were regarded as an indicator for the strong CNC-xylan
interactions.
3.11. Biodegradability
Biodegrability is an important property of bio-based packaging ma­
terials over fossil-based synthetic plastics, from environmental point of
view. The most important biological degradation processes for bio­
polymers are hydrolysis reactions catalyzed by extracellular enzymes
produced by microorganisms, called biotic process. In parallel, abiotic
processes occur, which includes chemical and physical break down of
the biopolymers (Polman et al., 2021). The biodegradative pathways by
which microbial enzymes attack the hemicelluloses include the action of
exo- and endo-hemicellulases (i.e. xylanases) (Dekker, 1985). In addi­
tion to enzymatic degradation, the moisture in soil also causes hemi­
cellulose degradation since hemicelluloses are water-soluble in nature.
A comparative and qualitative analysis of the biodegradability of neat
and nanocellulose-reinforced hemicellulose-based films as a function of
time was performed. As a control, conventional packaging paper and
freezer bag (low density polyethylene; LDPE) were also tested. Since the
samples were burried in moist soil, weight measurements were not
possible due to the residual soil on the film samples.
As can be seen in Fig. 7, the visible degradation of the neat hemi­
cellulose film started on the 6th day of burial of the samples while the
decomposition of the CNC and CNF-reinforced films began on 8th day of
the study. Due to the interaction between hemicellulose matrix and
nanocelluloses (CNC and CNF), the film structure became more
compact, which most likely hindered the action of hydrolytic enzymes.
As a result, the degradation of the films was difficult since the break
down of the bonds in the film matrix became more challenging in the
presence of CNC and CNF. Besides, incorporation of nanocelluloses de­
creases the hydrophilicity and increases the crystallinity of the films.
Based on this, it was concluded that the incorporation of CNC and CNF
into the hemicellulose matrix decreased the biodegradability of the
films. This result is in accordance with the decreased water solubility
and enhanced mechanical properties of the films after CNC and CNF
incorporation. In addition, it was determined that the packaging paper
(cellulose) and the freezer bag (LDPE) tested as control samples did not
show any signs of degradation during the test period. The results ob­
tained in this study showed that bulgur bran hemicellulose-based films
are more biodegradable compared to commercial cellulose and LDPE
films. Although the biodegradability of CNC- and CNF-reinforced
hemicellulose films were found to be slightly lower, this study
revealed the promising potential of the CNC- and CNF-reinforced bulgur
bran hemicellulose films for sustainable packaging applications
D. Sutay Kocabaş et al.
Fig. 7. Biodegradability of the films in soil. CNC: cellulose nanocrystal, CNF: cellulose nanofibril, LDPE: low density polyethylene.
considering the rapid degradation of the films.
4. Conclusions
Unlike cereal hemicelluloses and, starch, bulgur bran hemicellulose-
based packaging films do not compete with food production and they
contribute to the utilization of agro-industrial side streams. Therefore,
these films are advantegous for sustainable packaging applications.
However, the high water solubility and high water vapor permeability of
hemicelluloses due to their hydrophilic nature are important obstacles
for the use of hemicellulose-based materials in the packaging of com­
mercial products with high moisture content. In addition, the lower
mechanical strength of hemicellulose-based films compared to their
synthetic alternatives is a negative aspect for the commercialization of
these films. It is known that certain properties of biopolymer films can
be improved by nanocellulose reinforcement. In the present study,
bulgur bran showed promising results as a new resource of hemi­
celluloses and bulgur bran hemicelluloses were found to be compatible
with CNC and CNF. Nanocellulose-incorporated bulgur bran hemicel­
lulose films showed solid potential as a new nanocomposite biomaterial
for application in food packaging due to their decreased water solubility
and enhanced mechanical properties. The biodegradation of the films
took place in a much more rapid manner compared to conventional
packaging materials. In addition, nanocellulose-incorporated films
maintained their intact form after a long-term storage at room condi­
tions. Therefore, the films have a promising potential for sustainable
food packaging. The next step should focus on purification and in depth
characterization of bulgur bran hemicelluloses since the hemicellulose
precipitate contains lignin (6.70 %) and potentially starch, salt (potas­
sium acetate) and other impurities. The performance, stability and
migration tests of the films in contact with different food matrices during
the shelf-life can also be performed. In addition, the cellulose-rich
fraction obtained after hemicellulose isolation from bulgur bran by
alkaline extraction has a potential to be used for second generation
bioethanol production. The cellulose-rich fraction can also be studied
further for the production of nanocelluloses from bulgur bran which
could open a possibility of utilizing bulgur bran as a whole within a
second generation biorefinery process.
11
Industrial Crops & Products 171 (2021) 113847
CRediT authorship contribution statement
Didem Sutay Kocabaş: Conceptualization; Methodology; Investi­
gation; Supervision; Writing - original draft. Merve Erkoç: Investiga­
tion. Erinç Bahçegül: Data analysis, Writing - original draft. Hatice
Neval Özbek: Investigation.
Declaration of Competing Interest
The authors report no declarations of interest.
Acknowledgements
The authors would like to thank Karamanoğlu Mehmetbey Univer­
sity Scientific and Technological Research Application and Research
Center (BİLTEM) for DSC, TGA, UV–vis spectroscopy and SEM analysis.
The authors also thank to Karamanoğlu Mehmetbey University
Department of Bioengineering for FTIR analysis. The authors acknowl­
edge the M.Sc. programme of Department of Food Engineering at Kar­
amanoğlu Mehmetbey University. This work is funded by Karamanoğlu
Mehmetbey University.
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