Food Packaging and Shelf Life 18 (2018) 37–41

Contents lists available at ScienceDirect

Food Packaging and Shelf Life

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

Coffee-cocoa additives for bio-based antioxidant packaging T

a,⁎ b b b
Pricila Veiga-Santos , Luciana T. Silva , Carolina O. de Souza , Jaff R. da Silva ,
Elaine C.C. Albuquerqueb, Janice I. Druzianb
a
São Paulo State University-UNESP, FCA, 18603-970, Botucatu, Brazil
b
UFBA-Faculty of Pharmacy, Salvador, BA, 40171-970, Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: Coffee and cocoa antioxidant capacity is well known, and besides its health benefits, great acceptance and
Oxidation availability; there is few information about their utilization, especially simultaneously, as antioxidant packaging
Intelligent additives. The antioxidant capacity of a coffee-cocoa-cassava starch polymer was evaluated in-vitro (through
Packaging DPPH scavenging %, flavonoid and total phenolic content) and in-vivo (by packaging palm oil and monitoring its
Eco-friendly
oxidation during a 45-days storage at 63%RH/30 °C). In-vivo investigations indicated a protective effect up to
Biodegradable polymers
6.09 times against peroxide index increase, up to 60.4 times against hexanal production, and up to 6.88 times
against conjugated dienoic acid production, compared to a commercial polymer. Simultaneous utilization of the
additives presented a synergistic antioxidant effect. Additives negatively affected films mechanical properties
and homogeneity, but presented a decreased water vapor permeability and dark pigmentation that could help
avoiding the catalytic oxidationn effect of water and light.

1. Introduction
Oxidation, especially on high fat content foods, is one of the most
important degradation reaction, compromising its quality and shelf life
(Louli, Ragoussis, & Magoulas, 2004; Nerín, Tovar, & Salafranca, 2008)
and developing harmful compounds (Estévez, Li, Soladoye, & Van-
Hecke, 2017). Antioxidant packaging polymers appears as a safe and
efficient alternative (Lin, Abdel-Samie, & Cui, 2018; Tian, Decker, &
Goddard, 2013). Because synthetic antioxidants may have a tox-
icological long-terms effects potential (Louli et al., 2004; Nerín et al.,
2008), there is an attempt of substituting them for natural and re-
newable antioxidants (Adilah, Jamilah, Noranizan, & Hanani, 2018;
Masek, Latos, Piotrowska, & Zaborski, 2018) additives.
Coffee (Coffea arabica L.) and cocoa (Theobroma cocoa L.) are rich
sources of polyphenols and flavonoids, with antioxidant capacity
(Kwak, Ji, & Jeong, 2017; Martín & Ramos, 2016; Żyżelewicz et al.,
2016), potential health benefit; preventing cardiovascular, cancer,
diabetes, obesity, and neurodegenerative diseases (Martín & Ramos,
2017; Martinez-Saez & del Castillo, 2018) and great acceptance among
consumers (Moreira et al., 2018). Recently, Çelik and Gökmen (2018)
have observed that simultaneous use of cocoa and coffee can result in
bound antioxidants instead of free antioxidants, which could result in
an improved synergistic antioxidant effect. Besides all this potential,
great availability and the recognition of being safe for food contact,
only few works have applied coffee and cocoa (Cacciotti, Mori,
Cherubini, & Nanni, 2018; Calatayud et al., 2013) into packaging ma-
terials, and the simultaneous effect of coffee and cocoa in active
packaging is unknown. For this matter, this work have investigated the
simultaneous use of coffee extract and cocoa powder as antioxidant
additives for cassava starch bio-based packaging, following a central
composite experimental design.
Polymers antioxidant capacity were evaluated in-vitro, through
coffee and cocoa 2,2-diphenyl-1-picrylhydrazyl (DPPH) scavenging %,
flavonoid concentration and total phenolic content. Palm oil was
packed with the coffee-cocoa films and the increase in oxidation com-
pounds (peroxide index, hexanal and conjugated dienoic acid) during a
45-days of accelerated storage (63%RH/30 °C), have indicated poly-
mers in-vivo antioxidant capacity. Palm oil packed with cassava starch
films (without the antioxidant compounds) (C1), with low-density
polyethylene-LDPE films (C2), and without any packaging (C3), served
as controls.
2. Material and methods
2.1. Materials
Cassava starch (amylose – 23.5% and amylopectin – 64,2%), de-
fatted ground cocoa beans (donated by Cargill Agrícola SA, Brazil),

⁎
Corresponding author.
E-mail address: priveiga@fca.unesp.br (P. Veiga-Santos).

https://doi.org/10.1016/j.fpsl.2018.08.005
Received 4 January 2018; Received in revised form 3 August 2018; Accepted 9 August 2018
2214-2894/ © 2018 Elsevier Ltd. All rights reserved.
P. Veiga-Santos et al.
medium roasting arabica ground coffee (Mellita®, purchased at
Brazilian local market), industrialized palm oil (donated by Odelsa SA,
Brazil), commercial sucrose and inverted sugar (60% inversion) (do-
nated by Açúcar Guarani SA, Brazil) and low-density polyethylene
(LDPE) films (PolyPlastic®, 0.120 mm thickness-purchased at Brazilian
local market).
2.2. Coffee extract
Coffee powder (0–2.0 %) were extracted with hot deionized water
(90 °C) for optimal extraction and preservation of its antioxidant com-
pounds (Famá et al., 2006) and then filtered through Whatman No.1
filter paper.
2.3. Active packaging film preparation
Cassava starch (4%), plasticizers (0.7% sucrose and 1.4% inverted
sugar) and cocoa powder (0-0.46%) were directly dissolved in the
coffee extract (0–2.0%) in combinations according to a 22 factorial
central composite design.
Dispersions were heated (70 °C), degassed for 30 min. in ultrasonic
bath to remove the bubbles, placed in polystyrene Petri dishes
(150 × 15 mm) and dehydrated at 35 °C (oven, airflow and circulation).
Resulting films were stored in desiccators with a supersaturated solu-
tion of sodium chloride (23 ± 2 °C; 75 ± 2% RH) for 3 days prior
testing (Souza et al., 2011). The same procedure, but without any an-
tioxidant additives, was used to produce control C1.
2.4. In-vitro antioxidation evaluation
Cocoa powder and coffee extract were investigated through their
antioxidant capacity - DPPH scavenging % (Brand-Wiliams, Cuvelier, &
Berset, 1995). Polymer samples and additives (coffee extract and cocoa
powder) were also analyzed for flavonoid concentration and total
phenolic content. For the polymers analysis, 100 mg samples were de-
fatted with petroleum ether, extracted with 10 mL of distilled water and
shaken for five minutes in vortex. Samples were centrifuged in a conical
flask refrigerated centrifuge (5 °C, 4400 rpm, for 3 min), and the su-
pernatant was used as the final sample. For flavonoid concentration (FC)
1 mL of the final sample was added to a 10 mL volumetric flask con-
taining 4 mL of distilled water. 0.3 mL of 5% sodium nitrite solution
was added to the volumetric flask, and after 5 min; 0.3 mL of 10%
aluminum chloride was added. One minute later, 2 mL of 1 M sodium
hydroxide was added, volume completed with distilled water and ab-
sorbance was read at 510 nm A standard curve was prepared with di-
lutions of epicathechin standard (Lee, Kim, Lee, & Lee, 2003). Total
phenolic content (PC) were determined using Folin- Ciocalteu reagent as
describe by Swain and Hillis (1959). 0.5 mL of the final sample was
pipette onto a glass tube, and 2.5 mL with addition of Folin-Ciocalteu
reagent. After 3 min, 2 mL of sodium carbonate (7.5%) were added,
mixture, heated (50 °C/5 min) and immediately frozen to stop the re-
action. A gallic acid standard curve was used and absorbance was read
at 760 nm.
2.5. In-vivo antioxidation evaluation
Rectangle shaped (10 × 4 cm2) cocoa-coffee film samples were
folded as an envelope and sealed (Sealer SULPACK Basic SM BL 350,
Brazil) at the bottom and sides, slightly humidifying the borders before
sealing for a thermoplastic closure (Fig. 1). A 10 mL volumetric pipette
transferred palm oil into this envelope and finally its upper side were
also sealed to simulate samples antioxidation protection during a real
packed product shelf life (0, 7, 15, 30 and 45 days), in accelerated
storage (63%RH, 30 °C) conditions. Storage and analyses were per-
formed in a dark room to avoid interference of light. Controls were
given by packing palm oil with a cassava starch film (without
38
Food Packaging and Shelf Life 18 (2018) 37–41
Fig. 1. Sealed samples packing palm oil for in-vivo shelf life evaluation (F4:
maximum coffee and cocoa, F5: no cocoa, F7: no coffee and F8: maximum
coffee).
antioxidants) (Control 1 - C1), with low density polyethylene films
(Control 2 - C2) and without any packages - placed in a Petri dish -
(Control 3 - C3).
The packed oil oxidation during storage was evaluated through the
resulting peroxide value. Samples with better protective effect on
packed products against peroxid formation were also analyzed for
conjugated dienoic acid and hexanal contents. The peroxide value was
investigated according to the Association of Official Analytical
Chemists, AOAC (2001) titration procedure, for all palm oil packed
samples (0, 7, 15, 30 and 45 days), in triplicate. The conjugated dienoic
acid content was determinate by the AOCS - American Oil Chemists
Society (1993) spectrophotometric procedure. 10 mL palm oil was
dissolved in isooctane and absorbance was measured at 233 nm. Results
were expressed in percent (%), based on reading on day 1 of storage.
They were calculated according to Eq. (1), were K0 is the absorptivity
by acids equal to 0.03; A the observed absorbance at 233 nm; b the
cuvette length in cm, and c, the concentration of sample in g/L of the
sample used for the absorption measurement.
A
Conjugated dienoic acid% = 0.84 ⎛ ⎞−Ko
⎝ bc ⎠ (1)
Hexanal content was measured with heating (140 °C/30 min) 15 mL
headspace vial of the packed palm oil (200 mL), pressurized by 2 min
following a 0.5 min injection time (Amstalden, Leite, & Menezes, 2001).
Separation was performed by gas chromatography (CLARUS 500,
Perkin Elmer gas chromatographer fitted with a mass spectrometer
(MS) coupled with a Turbomatrix Perkin Elmer Headspace) using a
Wax-FFAP column (50 m × 0.20 mm × 0.2 μm) with 1.0 mL/ min he-
lium flow. The operation parameters were as follows: Injector at 180 °C;
Column oven programmed from 35 °C to 160 °C with three ramps (35 °C
for 1 min, heating at 3 °C/min up to 80 °C, and at 7 °C/min up to 160 °C
for 22.57 min). The mass spectrometer had an electron impact ioniza-
tion and ionization energy of 70 eV. Mass spectra were collected over
the mass range of m/z 50-600. Hexanal was identified by comparing the
standard area retention time and mass spectra using an NIST library.
The volatile constituent was quantified using a hexanal external stan-
dard (Sigma Aldrich, Saint Louis, Missouri, USA), at five different
headspace vial concentrations (0.40–32.00 μg/mL) and analyzed as
above. Standards peak area calibration curve was determined and ex-
pressed in μg/mL.
For comparison reasons, palm oil was packed in three different
conditions: with cassava starch films (same process formation, without
cocoa or coffee) (C1), with low density polyethylene LDPE films (C2)
and unpacked, placed in open Petri dishes (C3).
2.6. Samples characterization
Samples total solids content was determined measuring weight loss
of films, upon drying (105 °C) until constant weight. Thickness was
P. Veiga-Santos et al. Food Packaging and Shelf Life 18 (2018) 37–41

evaluated using a flat parallel surface micrometer (Mitutoyo model
103–137, precision 0.002 mm). FTIR Spectrum, mechanical properties
and water vapor permeability were investigated for samples F1 (added
with minimum additives concentration), F4 (added with the highest
concentration of both additives) and F9 (added with intermediate ad-
ditives concentration). FTIR spectroscopy (Perkin Elmer, Spectrum 100,
Waltham, Massachusetts, USA) evaluated materials functional groups
between 4000-400 cm−1 using a single-bounce attenuated total reflec-
tion (ATR) accessory with a Zinc selenide (ZnSe) crystal. Rectangular
(7 × 2.5 cm) and conditioned (50% RH, 23 °C) samples elongation at
break and tensile strain (Emic Universal Testing Instrument -Model
DL2000) evaluated materials mechanical properties (ASTM standard
method D882–01, 2001); with initial position in 50 mm and a separa-
tion speed of 12.5 mm/min. Polymers water vapor permeability (WVP)
was conducted using American Society for Testing and Materials,
method E96 (ASTM, 2001).
2.7. Statistical analysis
A central composite experimental design was used to evaluate the
efficacy of cocoa powder and coffee extract as antioxidant additives for
thermoplastic polymers. Defatted cocoa powder (% w/w; X1) and coffee
extract (% w/w; X2) were chosen as independent variables and their
real and coded values are shown in Table 1.
A 22-factorial design with four axial points (α = 1.41) and three
replications at the center points (totalizing 11 experiments) was em-
ployed (Table 1).
The independent variables significant influence was evaluated by
the Pareto chart of standardized effect, considering ANOVA pure error
and 95% confidence. The software Statistica 5.0 was used to generate
and analyze the experimental data.
3. Results and discussion
Coffee extract and cocoa powder presented an expressive poly-
phenol (1953.2 mg/g and 1558.2 mg/g, respectively) and flavonoid
(1872.6 mg/g and 1506.1 mg/g) concentration, and a DPPH scavenging
of 48.6% and 31.17%; respectively (Table 1).
No significant difference (p < 0.05) between samples thickness
(from 0.113 to 0.143 μm) and total solids content (from 87.81–88.08
%) was observed.
Additives natural pigmentation have performed an interesting dark
pigmentation to the polymers (Fig. 1), desired to minimize, or avoid,
light catalytic effect on the packed product oxidation.
Polyphenols and flavonoids were still present after film formation,
ranging from 35.05 mg/g to 118.66 mg/g, and from 23.24 mg/g to
102.54 mg/g; respectively (Fig. 1; Table 1) at the first day of storage. As
expected, results have indicated a concentration-dependent fashion
with higher polyphenol and flavonoids content as higher the added
cocoa or coffee concentrations.
After 45 days of storage, samples still presented up to 100.03 mg/g
polyphenol and up to 85.43 mg/g flavonoids content, with a little de-
crease on films total polyphenol (up to 34.9%) and flavonoid (up to
32.7%) (Table 1).
The second order polynomial Eqs. (2) and (3), as function of cocoa
powder (%, X1) and coffee powder (%, X2), was obtained to predict the
decrease in packaging total polyphenol (PC, mg/g) and flavonoids
content (FC, mg/g) atr 45 days-storage, with a 0.97 and 0.96 coefficient
of determination (R2), respectively.
PC (Day 45) = 9.71 + 1.30X 1 + 9.07X 2 (2)
FC (Day 45) = 4.79 + 3.41X 1 + 1.95X 2 + 2.61X 22−2.69X 1X 2 (3)
Although a flavonoid and polyphenol migration to the packed
product is a possibility, the protective effect on the packed product
presented ahead lead us to believe that the antioxidant compounds of
the packaging polymer have oxidized preferentially, instead of the
packed product (Grisi, Veiga-Santos, Silva, Cabral-Albuquerque, &
Druzian, 2008; Souza et al., 2011). Results are in agreement with lit-
erature (Jonfia-Essien, West, Alderson, & Tucker, 2008; Farah &
Donangelo, 2006) and can be and indicative of samples in-vitro anti-
oxidant capacity.

Table 1
CCD matrix employed for the independent variables X1 (cocoa powder) and X2 (coffee extract) with their coded and real (%) values formulations. Total polyphenol
and flavonoid content decrease in mg/g (and w/w), for all samples, at 7, 15, 30 and 45 days of storage.
S Cocoa-coffee-starch polymers

Antioxidant coded and (%) Total Polyphenol Content (mg/g) and decrease (w/w) Total Flavonoid Content (mg/g) and decrease (w/w)

X1 X2 0 7 15 30 45 0 7 15 30 45

F1 −1.00 −1.00 35.05 a

30.64a
27.44a
25.58 f
23.87a
23.24a
21.45 a
20.18 a
18.08a
16.62a
(0.30) (0.07) (10.02) (19.40) (24.88) (29.88) (7.70) (13.14) (22.20) (28.48)
F2 −1.00 1.00 97.70b 86.95b 84.185b.c 82.39b.c 80.15b 84.95b 75.38b 72.45b 70.73b 68.20b
(0.30) (0.39) (11.00) (13.84) (15.67) (17.96) (11.26) (14.71) (16.74) (19.72)
F3 1.00 −1.00 71.24c 61.98c 58.77b 56.41b 54.48b 55.35c 48.70c 46.96c 42.12c 41.96c
(1.7) (0.07) (13.00) (17.50) (20.81) (23.53) (12.00) (15.15) (20.29) (24.20)
F4 1.00 1.00 112.38d 99.45d 97.06d 93.86d 92.10c 99.92d 88.23d 85.68d 83.73d 81.67d
(1.7) (0.39) (11.50) (13.63) (16.48) (18.04) (11.70) (14.25) (16.20) (18.27)
F5 −1.41 0.00 57.10e 52.82a 49.19e 46.99a.e 44.49d 47.91e 46.47a 44.64a 42.18a 39.39e
(0.00) (0.23) (7.50) (13.85) (17.71) (22.10) (3.01) (6.81) (11.94) (17.77)
F6 1.41 0.00 94.91b 82.88b.d 80.88c 77.96c.d 75.36c.e 85.59b 75.67b 72.96b 71.07b 69.56b
(2.00) (0.23) (12.66) (14.78) (17.86) (20.60) (11.59) (14.76) (16.96) (18.73)
F7 0.00 −1.41 39.17f 33.47e 30.69e 27.41e.f 24.47f 30.38f 26.54e 23.78e 22.20e 20.43f
(1.00) (0.00) (14.56) (21.65) (30.03) (34.98) (12.64) (21.72) (26.93) (32.76)
F8 0.00 1.41 118.66g 106.52d 104.06c.d 102.59b.c 100.03e 102.54d 92.47b.d 89.23b.d 87.53b.d 85.43b.d
(1.00) (0.46) (10.23) (12.30) (13.55) (15.70) (9.82) (12.98) (14.64) (16.68)
F9(c) 0.00 0.00 75.92h 68.88e.f 65.89f 63.76f 61.64f 66.41g 61.68e.f 58.27c 57.16e.f 55.22f.g
(1.00) (0.23) (9.28) (13.22) (16.00) (18.82) (7.13) (12.26) (13.93) (16.85)
F10(c) 0.00 0.00 76.87h 69.14f 65.08f 64.30f 62.20f 67.16g 61.52c.f 59.11c 56.95c.f 55.09g
(1.00) (0.23) (10.06) (14.04) (16.35) (19.09) (8.39) (11.98) (15.20) (17.96)
F11(c) 0.00 0.00 76.76h 69.42f 66.62f 64.56f 63.37d.f 66.28g 61.49e.f 58.12c 57.24e.f 55.34f
(1.00) (0.23) (9.57) (13.21) (15.90) (17.44) (7.23) (12.32) (13.65) (16.50)

S: Samples, X1 and X2: Cocoa powder and coffee extract concentration on initial bio-based films formulation, respectively, (c): Central Points.
Means with the same letters in the same columns presented no statistical difference (p > 0.05) according to the Tuckey test.

39
P. Veiga-Santos et al. Food Packaging and Shelf Life 18 (2018) 37–41

Fig. 2. (A) Packed oil and controls peroxide content increase at 45 days of storage and (B) Pareto analysis indicating the significant effect of coffee and cocoa on the
packed oil peroxide content.

Table 2
Peroxide value, hexanal content and conjugated dienoic acid (CDA) content
increase, at 7, 15, 30 and 45 days of storage (63%RH/30 °C).
Samples PV increase Hexanal CDA

in meq/kg (%) μg/100 mL mg/100 g

(%) (%)
7 15 30 45 45 45

a,b a a a
C1 7.66 10.81 15.31 21.53 4.38a 31.80a
b b b b
C2 9.14 18.14 62.11 85.10 19.93b 58.70b
c c c c c
C3 28.89 38.28 102.69 150.07 31.54 134.85c
a,e a,d a a,e d
F1 5.96 9.13 11.85 18.11 0.62 13.80d
d d a d
F2 3.89 7.14 7.70 14.35 NA* NA
d,e a,d a d,e
F3 5.21 8.10 10.39 16.15 NA NA
d,e a,d a d
F4 4.00 7.33 8.00 14.50 NA NA
a,d,e a,d a d,e d
F5 5.32 8.20 10.60 16.37 0.36 10.10e,f
d,e a.d a d
F6 4.00 7.24 7.87 14.40 NA NA
a,d,e a,d a
F7 5.69 8.54 11.35 17.01d,e 0.36d 10.10e,f
d d a d Fig. 3. FTIR Spectrum of samples C (control 1; cassava starch with no ad-
F8 3.76 7.01 7.53 14.00 0.33d 9.05e
ditives), F1 (lowest sum of cocoa and coffeE%), F9 (central point) and F4
d,e a a d
F9(c) 4.14 7.16 8.30 14.24 NA NA (higher sum of cocoa and coffeE%).
d a a d
F10(c) 4.10 7.22 8.23 14.34 NA NA
d,e a a d
F11(c) 4.12 7.20 8.27 14.38 NA NA Table 3
Samples C1, F1, F9 and F4 elongation at break (E%), tensile strain (T, mPA),
water vapor permeability (WVP, gH2O.μm/m2.h.mmHg).
Although coffee extract have presented 1.25 times more poly-
Sample E T WVP
phenols, 1.24 times more flavonoids and 1.55 times higher DPPH
scavenging % (p < 0.05) when compared with the cocoa powder ad- C1 14 7,5 9,25 × 10−8
ditives, both additives (Fig. 2B) presented a quadratic and linear sig- F1 57,7 3,4 10,4 × 10−8
nificant effect (p < 0.05) in lowering the peroxide formation on the F9 27,5 3,4 6,96 × 10−8
F4 14,5 4,4 6,50 × 10−8
packed oil samples. The Pareto analysis has indicated that the si-
multaneous use of cocoa and coffee resulted in a synergistic effect
(p < 0.05) in lowering the peroxide content on the packed oil PV (Day 45) = 14.32−0.87X 1 + 0.96X 12−2.53X 2 + 1.63X 22 + 0.50X 1X 2
(Fig. 2B). This indicates that the simultaneous use of cocoa and coffee
(4)
as additives may result in a better oxidation protection effect.
All polymers presented a homogeneous appearance and malleable Although peroxide index decreases at terminal stages of food au-
matrix (in storage conditions) allowing to fold polymers into a rectan- toxidation reactions (Fukumoto & Mazza, 2000; Louli et al., 2004), the
gular shape packaging capable to be hot sealed when slight humidifying analyzed oils peroxide values only increased, indicating that the oxi-
the sealing surface (Fig. 1). dation process was still in the beginning or in the propagation stage and
The second order polynomial Eq. (4) has predicted the protective therefore, could safely be used to monitor oxidation in the studied
effect of the cocoa-coffee packaging against packed oil peroxide in- conditions. No difference was observed (p > 0.05) regarding hexanal
crease (PV, meq/Kg), at 45 days of storage, with a coefficient of de- and conjugated dienoic acid contents (Table 2), reinforcing that the oil
termination (R2) of 0.95. oxidation has not reached the reaction´s final stages.

40
P. Veiga-Santos et al.
At 45 days of storage, polymers have protected (p < 0.05) the palm
oil against peroxide formation, up to 1.54 times, 6.09 times and 10.72
times; when compared with control 1 (cassava starch films with no
additives), control 2 (commercial low density polyethylene-LDPE
polymer) and the control 3 (unpacked oil), respectively. Results in-
dicates an in-vivo antioxidant capacity of the cocoa-coffee materials.
In a lower efficacy (up to 53.75%) as observed for cocoa and coffee
addition, the cassava starch control films also conferred a higher pro-
tective effect against peroxide formation on the packed oils (p < 0.05)
when compared with the LDPE controls (Fig. 2A, Table 2). Such result
may be explored in future works.
Unpacked oil (control 3) presented up to 92.47% higher hexanal
and 71.54% higher conjugated dienoic acid production (Table 2) when
compared with oils packed with the coffee-cocoa packaging. Since
hexanal and conjugated dienoic acid are products of oxidation reaction
final stages, control 3 presented a much faster oxidation rate, as ex-
pected.
FTIR spectrum revealed a large absorption band at 3422 cm−1, OH
hydrogen bounding region, expected for thermoplastic starch materials.
Two peaks around 1125 and 1060 cm−1 are probably attributed to
acetal groups eCeOeCeOeCe, which could be explained by amylose
and amylopectin presence (Guinesi et al., 2006), common on starch
based materials.
Coffee and cocoa addition resulted in larger deformations at region
1710 a 1730 cm−1, characteristic from carbonylic (eC]O, eCOOe) or
nitrogenated (eNeH, eC]N) groups. Region 1800 to 900 cm−1 was
observed, indicating chemical composition modification. At
1060 cm−1, control 1 presented a 1.7% straighter band when compared
to coffee-cocoa samples, indication C–O angular deformation, probably
related to carbohydrate groups (Fig. 3). Results suggests that cocoa-
coffee addition have increased polymer carbonilic or dicarbonilic
groups, modifying its chemical composition. Authors believe this is due
to a lack of dispersion of the additives, once as their concentration in-
creased; it became more difficult to blending them with the film
forming solution.
The possible heterogeneity resulted by coffee-cocoa addition may
explain the effect (p < 0.05) on polymers mechanical and permeability
performance. Higher cocoa-coffee addition has lower polymers tensile
strain up to 2.2 times (p < 0.05) and elongation at break up to 4.12
times (p < 0.05) (Table 3).
The heterogeneity in dispersing higher cocoa and coffee con-
centrations could resulted in small particles among the polymer matrix,
acting as rupture points, and/or as anti-plasticizers, consequently
lowering samples F4 and F9 elongation at break (Table 3).
Water vapor permeability decreased up to 1.42 times, which can
indicate lower water affinity for polymers with higher additives con-
centration. Fortunately, a lower water vapor permeability is a desired
characteristic for antioxidant polymers, since water can have a catalytic
effect on food oxidation.
4. Conclusion
Results have demonstrated that coffee and cocoa can attribute an-
tioxidant ability to eco-friendly packaging materials and that their si-
multaneous use as additives would have a positive symbiotic effect in
protecting the packaged product against oxidation. Their use as ad-
ditive also can lower polymers water vapor permeability and add an
interesting dark pigmentation, ideals characteristics for helping anti-
oxidant polymers to avoid water and light catalytic oxidation effect on
food oxidation.
Acknowledgements
The authors would like to acknowledge Cargill Agrícola SA, Açúcar
Guarani SA and Odelsa S.A. for the ingredients donation and to FAPESB
- APP0091/2016, CNPq and CAPES for the financial support and
41
Food Packaging and Shelf Life 18 (2018) 37–41
scholarships.
References
Adilah, A. N., Jamilah, B., Noranizan, M. A., & Hanani, Z. A. N. (2018). Utilization of
mango peel extracts on the biodegradable films for active packaging. Food Packaging
and Shelf Life, 16, 1–7.
Amstalden, L. C., Leite, F., & Menezes, H. C. (2001). Identificação e Quantificação de
Voláteis de Café através de Cromatografia gasosa de Alta Resolução/Espectrometria
de Massas Empregando um Amostrador Automático de “Headspace”. Ciência e
Tecnologia de Alimentos, 21(1), 123–128.
AOCS - American Oil Chemists Society (1993). Official method of analysis Ti 1a-64.
Spectophotometric determination of conjugated dienoic acid.
Association of Official Analytical Chemists, AOAC (2001). Official methods of analysis.
Arlington. AOCS Cd 8b-90.
ASTM (2001). Standard test method for tensile properties of thin plastic sheeting D882-00.
West Conshohocken, Pennsylvania, USA: American Society for Testing and Materials
(1 CD Room).
Brand-Wiliams, W., Cuvelier, M. E., & Berset, C. (1995). Use of a free radical method to
evaluate antioxidant activity. Food Science and Technology, 28, 25–30.
Cacciotti, I., Mori, S., Cherubini, V., & Nanni, F. (2018). Eco-sustainable systems based on
poly(lactic acid), diatomite and coffee grounds extract for food packaging.
International Journal of Biological Macromolecules, 112, 567–575.
Calatayud, M., López-de-Dicastillo, C., López-Carballo, G., Vélez, D., Muñoz, P. H., &
Gavara, R. (2013). Active films based on cocoa extract with antioxidant, anti-
microbial and biological applications. Food Chemistry, 139(1–4), 51–58.
Çelik, E. E., & Gökmen, V. (2018). A study on interactions between the insoluble fractions
of different coffee infusions and major cocoa free antioxidants and different coffee
infusions and dark chocolate. Food Chemistry, 255, 8–14.
Estévez, M., Li, Z., Soladoye, O. P., & Van-Hecke, T. (2017). Health risks of food oxida-
tion. In Fidel Toldrá (Vol. Ed.), Advances in food and nutrition research: Vol. 82, (pp.
45–81). Academic Press Chapter 2.
Fama, L., Flores, S., Gerschenson, L., & Goyanes, L. (2006). Physical characterization of
cassava starch biofilms with special reference to dynamic mechanical properties at
low temperatures. Carbohydrate Polymers, 66, 8–15.
Farah, A., & Donangelo, C. M. (2006). Phenolic compounds in coffee. Brazilian Journal of
Plant Physiology, 18(1), 23–36.
Fukumoto, L. R., & Mazza, G. (2000). Assessing antioxidant and prooxidant activities of
phenolic compounds. Journal of Agriculture and Food Chemistry, 48, 3597–3604.
Grisi, C. V. B., Veiga-Santos, P., Silva, L. T., Cabral-Albuquerque, E. C. M., & Druzian, J. I.
(2008). Evaluation of the viability of incorporating natural antioxidants in bio-based
packagings. Nova Science Publishers1–11 Food Chemistry Research Developments 1.
Guinesi, l. S., Róz, A. L. da, Corradini, E., Mattoso, L. H. C., Teixeira, E.de M., & Curvelo,
A. A.da S. (2018). Kinetics of thermal degradation applied to starches from different
botanical origins by non-isothermal procedures. Thermochimica Acta, 447(2),
190–196.
Jonfia-Essien, W. A., West, G., Alderson, P. G., & Tucker, G. (2008). Phenolic content and
antioxidant capacity of hybrid variety cocoa beans. Food Chemistry, 108(3),
1155–1159.
Kwak, R. S., Ji, S., & Jeong, Y. (2017). The effect of air flow in coffee roasting for anti-
oxidant activity and total polyphenol content. Food Control, 71, 210–216.
Lee, K. W., Kim, Y. J., Lee, W. J., & Lee, C. Y. (2003). Cocoa has more phenolic phyto-
chemicals and a higher antioxidant capacity than teas and red wine. Journal of
Agricultural and Food Chemistry, 51, 7292–7295.
Lin, L., Abdel-Samie, M. A.-S., & Cui, H. (2018). Novel packaging systems in food.
Reference Module in Food Science. https://doi.org/10.1016/B978-0-08-100596-5.
22291-9.
Louli, V., Ragoussis, N., & Magoulas, K. (2004). Recovery of phenolic antioxidants from
wine industry by-products. Bioresource Technology, 92, 201–208.
Martín, M. A., & Ramos, S. (2016). Cocoa polyphenols in oxidative stress: Potential health
implications. Journal of Functional Foods, 570–588.
Martín, M. A., & Ramos, S. (2017). Health beneficial effects of cocoa phenolic compounds:
A mini-review. Current Opinion in Food Science, 14, 20–25.
Martinez-Saez, N., & del Castillo, M. D. (2018). Development of sustainable novel foods
and beverages based on coffee by-products for chronic diseases. Reference Module in
Food Science. https://doi.org/10.1016/B978-0-08-100596-5.22136-7.
Masek, A., Latos, M., Piotrowska, M., & Zaborski, M. (2018). The potential of quercetin as
an effective natural antioxidant and indicator for packaging materials. Food Packaging
and Shelf Life, 16, 51–58.
Moreira, I. M.da V., Vilela, L., de, F., Santos, C., Lima, N., & Schwan, R. F. (2018). Volatile
compounds and protein profiles analyses of fermented cocoa beans and chocolates
from different hybrids cultivated in Brazil. Food Research International, 109, 196–203.
Nerín, C., Tovar, L., & Salafranca, J. (2008). Behaviour of a new antioxidant active film
versus oxidizable model compounds. Journal of Food Engineering, 84, 313–320.
Souza, C. O., Silva, L. T., Silva, J. R., López, J. A., Veiga-Santos, P., & Druzian, J. I. (2011).
Mango and acerola pulps as antioxidant additives in cassava starch bio-based film.
Journal of Agricultural and Food Chemistry, 59(6), 2248–2254.
Swain, T., & Hillis, W. E. (1959). The phenolic constituents of Prunus domestica: The
quantitative analysis of phenolic constituents. Journal of the Science of Food and
Agriculture, 10, 63–68.
Tian, F., Decker, E. A., & Goddard, J. M. (2013). Controlling lipid oxidation of food by
active packaging technologies. Food & Function, 4, 669–680.
Żyżelewicz, D., Krysiak, W., Oracz, J., Sosnowska, D., Budryn, G., & Nebesny, E. (2016).
The influence of the roasting process conditions on the polyphenol content in cocoa
beans, nibs and chocolates. Food Research International, 89(2), 918–929.