J Food Sci Technol

https://doi.org/10.1007/s13197-019-03901-8

ORIGINAL ARTICLE

Sensory and physicochemical characteristics of dark chocolate bar

with addition of cinnamon (Cinnamomum burmannii) bark
oleoresin microcapsule
Danar Praseptiangga1 • Syuga Eugenia Invicta1 • Lia Umi Khasanah1

Revised: 20 March 2019 / Accepted: 24 June 2019

Ó Association of Food Scientists & Technologists (India) 2019

Abstract Indonesia is one of the world’s most prominent Introduction

producers of cocoa and cinnamon. Dark chocolate bars and
Cinnamomum burmannii are rich in antioxidants. The Indonesia is the third largest cocoa producer in the world
addition of a cinnamon oleoresin to a dark chocolate bar after the Ivory Coast and Ghana (Dwijatmoko et al. 2016).
has not been previously studied due to its strong consis- In 2016, cocoa bean production in Indonesia yielded
tency and sticky texture. Microencapsulation was used to 656,817 tons. The export volume of dry beans and semi-
cover the undesirable properties of oleoresin, and the finished products high ([ 50%) (Direktorat Jenderal
addition of cinnamon bark oleoresin microcapsules was Perkebunan Indonesia 2016) but was relatively low for the
expected to improve the functional properties and influence chocolate products (finished products). Chocolate indus-
the characteristics of dark chocolate bars. This study aimed tries are mostly found in developing countries that do not
to determine the effects of adding various concentrations of have cacao trees (International Cocoa Organization 2017).
cinnamon bark oleoresin microcapsules (4%/F1, 6%/F2, The production of chocolate products, including dark
and 8%/F3) to dark chocolates bars on their sensory, chocolate bars, grows rapidly with the presence of a
physical, and chemical characteristics and to define the best stable market throughout the world (Dwijatmoko et al.
formula of a dark chocolate bar. The results showed that 2016). The world’s fondness for dark chocolate bars is
various concentrations of cinnamon bark oleoresin micro- caused by their taste and functional effects. A dark
capsules led different trends for each evaluation, and the chocolate bar is mainly made from cocoa nibs, cocoa
best formula resulted from the addition of cinnamon bark butter, cocoa liquor/cocoa mass, sugar, and/or lecithin,
oleoresin microcapsules to a dark chocolate bar (8%) that is which is used as an emulsifier. The total phenolic and
accepted by the panellists. This bar had the hardest texture, flavonoid contents in dark chocolate are two to three times
the highest total phenol and antioxidant activities, and the higher than in milk chocolate and white chocolate. The
lowest moisture content, and it was classified as having a content of theobromine in a commercial dark chocolate bar
high potency of vitamin E (tocopherol). is 883.11 ± 3.54 mg/100 g, while in milk chocolate, it is
125.154 ± 0.98 g/100 g (Beckett 2008).
Keywords Dark chocolate bar
Cinnamon bark oleoresin Enhancement of the flavour and functionality of
microcapsule
Sensory characteristics
Physicochemical chocolate bars involves adding other ingredients. Cinna-
characteristics mon is a widely used spice that is often added to chocolate
bars (Dwijatmoko et al. 2016). Exporting 48,900 tons of
cinnamon has made Indonesia the largest cinnamon
exporter in the world (FAOSTAT 2016). Cinnamomum
& Danar Praseptiangga burmannii, which is known as Indonesian cinnamon, is
[email protected] classified as a notable species in the global market (Kha-
1 sanah et al. 2014).
Department of Food Science and Technology, Faculty of
Agriculture, Universitas Sebelas Maret (UNS), Jl. Ir Sutami Based on characterisation by the flow injection mass
36 A Kentingan, Surakarta, Central Java 57126, Indonesia spectrometric (FIMS) fingerprinting method, C. burmannii

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has been shown to contain more type-A proanthocyanidins cinnamon bark oleoresin microcapsules to dark chocolate
than Cinnamomum verum, Cinnamomum cassia, and Cin- bars. Cinnamon is expected to increase the concentration of
namomum loureiroi (Chen et al. 2014). Cinnamomum functional compounds, especially antioxidants, and also
burmannii contains functional compounds used to over- give the signature flavour of Indonesian spices to the dark
come digestive problems, diabetes, inflammation, and chocolate bar. Therefore, the effects of cinnamon bark
microbial activity (Muhammad and Dewettinck 2017). Gas oleoresin microcapsule addition on the properties of dark
chromatography–mass spectrometry showed that cin- chocolate bars were evaluated.
namaldehyde is the main component of cinnamon bark
oleoresin (Khasanah et al. 2017). Cinnamaldehyde per-
forms anti-inflammatory activity by decreasing nitric oxide Materials and methods
(NO) production in lipopolysaccharide-stimulated macro-
phages. Cinnamaldehyde also activates the peroxisome Materials
proliferator-activated receptor to weaken NF-jB, which
leads to cancer (Muhammad and Dewettinck 2017). Etha- The primary material used into make dark chocolates bar
nol extraction of cinnamon bark oleoresin has the antiox- was TULIP Easy Melts Dark Chocolate Couverture (65%
idant activity with an IC50 value of 8.36 lg/ml (Ervina cocoa). The cinnamon bark used for oleoresin microen-
et al. 2016). capsulation was from Girimarto, Wonogiri, Indonesia.
The addition of cinnamon oil and powder to dark Other materials used included 96% ethanol, maltodextrin
chocolate and milk chocolate bars has been observed (Al- DE 10, and arabic gum from Agung Jaya, Surakarta,
bak and Tekin 2015; Dwijatmoko et al. 2016; Ilmi et al. Central Java, Indonesia.
2016; Praseptiangga et al. 2018), while the addition of a
cinnamon oleoresin has not been previously performed. Preparation of cinnamon bark oleoresin
Oleoresin has a strong consistency and sticky texture. microcapsules
Oleoresin contains volatile bioactive components that may
vanish during storage and processing (Irfiana et al. 2017). Preparation of the one-stage cinnamon bark oleoresin was
Cinnamon also has a spicy aroma and taste (Ilmi et al. conducted according to previous studies (Irfiana et al.
2016) that can affect panellist perception. A lower con- 2017; Murti 2012) with slight modifications. Dried cinna-
centration of added cinnamon oleoresin will give a lighter mon bark with an 11–15% moisture content was milled.
taste but will also give less functional effects. Cinnamon powder with a size of 30–50 mesh was then
The undesirable properties of cinnamon oleoresin can be extracted using 96% ethanol (1:6) for 4 h at 70–75 °C. The
masked by microencapsulation. Microencapsulation pro- extraction filtrate was evaporated using a rotary vacuum
tects the active compound in oleoresin by entrapping the evaporator at a temperature of 80 °C. The essential oil was
compound in shell materials and transforming it into a free- prepared according to Irfiana et al. (2017) with modifica-
flowing powder that is easier to handle (Irfiana et al. 2017; tions. The oil was obtained from 8 h of steam distillation.
Muhammad and Dewettinck 2017). The release of the One-stage oleoresin and essential oil were then blended,
active compound can be controlled by controlling the and calculations were performed to meet the essential oil
microcapsule dissolution. One of the factors that influences content standard based on Khasanah et al. (2017).
the dissolution of microcapsules is the solubility of the Oleoresin microcapsules were prepared according to
shell materials (Khasanah et al. 2015). Irfiana et al. (2017) and Murti (2012) with several modi-
The shell materials that are usually used include a fications. An emulsion was made by homogenizing oleo-
mixture of arabic gum and maltodextrin. Arabic gum has a resin. For the shell materials, Aqua Dest (1:10:40) was
good flavour, good oil stabilisation ability and high solu- used and mixed at a speed of 7600 rpm. The shell materials
bility. Arabic gum needs to be combined with maltodex- were a mixture of arabic gum and maltodextrin with a
trin, which is less hygroscopic, to prevent rapid dilution composition of 3:1. The emulsion particle size was then
when in contact with saliva. Thus, the release process can observed with a light microscope. If the particle was uni-
be controlled more slowly, and cinnamon’s strong flavour form and already achieved a micro-size, the homogenisa-
can be momentarily covered (Kania et al. 2015). tion process was stopped (± 15 min). The emulsion
Microencapsulation of cinnamon bark oleoresin with solvent was vaporised using a spray dryer with a feed rate
arabic gum and maltodextrin (3:1) performed by Murti of 15–20 ml/min, an inlet temperature of 100.2 °C, and an
(2012) showed that the water solubility was 94.652% and exhaust temperature of 74 °C. The size of the microcapsule
the aldehyde content was 60.50%; it also had a good uni- obtained was then observed.
form wall, and texture ballooning did not occur. To the best
of our knowledge, there is no study on the addition of

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Preparation of dark chocolate bars maceration extraction of dark chocolate bars. Two types of
solvents were used: methanol and acetone:aquades:acetic
Dark chocolate bars with the addition of cinnamon bark acid. For the methanolic extract, extraction was performed
oleoresin microcapsules were prepared based on previous according to Muhammad et al. (2017) with modifications.
studies (Praseptiangga et al. 2018; Rasuluntari et al. 2016) One gram of a shredded chocolate bar was dissolved in
with several modifications. Cinnamon bark oleoresin 20 ml methanol at 80%. The extract was stirred while it
microcapsules were added to the melted dark chocolate was heated at 48–50 °C for 1 h and then filtered. For the
couverture at the following amounts: 0% (Control/C), 4% acetone:aquades:acetic acid extract, extraction was per-
(Formula 1/F1), 6% (Formula 2/F2), and 8% (Formula 3/ formed based on Muhammad et al. (2017).
F3). The dark chocolate couverture was used, and cinna- Total phenol evaluation was performed using the Folin
mon oleoresin microcapsules were added during the Ciocalteu method according to a previous study (Muham-
refining-conching process in a ball mill. The ball mill was mad et al. 2017). Modifications to this study were made
set to a speed of 90 rpm and stopped if the chocolate and included the addition of 2% Na2CO3 that was incu-
particles were micro-sized and uniform (observed every bated for 10 min and 0.5 ml Folin–Ciocalteau reagent (1:1)
15 min). Ball milling resulted in a homogenous mixture incubated for 30 min. The absorbance was measured with a
with particle sizes of 1.71–9.36 lm. The mixture was then UV–Vis spectrophotometer at k = 750 nm. The antioxi-
hand-tempered using scrapers and knives on a marble table. dant activity was determined by the IC50 method based on
a previous study (Muhammad et al. 2017) with modifica-
Sensory characterisation tions. The chocolate extract concentration was 103 ppm,
while the DPPH concentration was 102 ppm.
The chocolates samples F1, F2, and F3 were evaluated
using the hedonic method according to previous studies GC–MS
(Dwijatmoko et al. 2016; Praseptiangga et al. 2018). The
sensory attributes were presented on 5-hedonic scales, Chocolate extraction for GC–MS also used two solvents.
which were: (1) dislike, (2) rather dislike, (3) neither like The extraction method for the methanolic extract was
nor dislike, (4) rather like, and (5) like. according to Brunetto et al. (2009) with modifications. One
block of the chocolate bar was shredded, added to 13 ml
Physicochemical characterisation methanol, heated at 110 °C for 2 min, and vortexed for
5 min. The mixture was centrifuged at 5000 rpm for 5 min.
Colour attributes For the acetone:aquades:acetic acid extract, extraction was
performed based on Muhammad et al. (2017) with slight
The colour attributes of the dark chocolate bars with the modifications.
addition of cinnamon bark oleoresin microcapsules were The GC–MS injection method was based on the work of
evaluated using a chroma meter Konika Minolta CR-400 Proestos and Komaitis (2013) with modifications. The
with the CIE L*a*b* method based on previous studies methanolic extract (1 ll) was injected with a split ratio of
(Dwijatmoko et al. 2016). The L*, a*, and b* values were 1/10. The inlet temperature was 290 °C, the MS quad
then used to calculate the hue angle and the total colour temperature was 150 °C, and the MS source temperature
difference (TCD). The texture was evaluated using a uni- was 230 °C. The oven temperature was kept at 50 °C for
versal testing machine (UTM) based on Beckett (2008). 5 min, increased 10 °C/min until 280 °C, and held for
The room used to evaluate these attributes was set to a 5 min. The acetone:aquades:acetic acid extract (1 ll) was
temperature of 26–28 °C. injected at a split ratio of 5:1 and inlet temperature of
250 °C. The oven temperature was kept at 50 °C for 5 min,
Moisture content increased by 10 °C/min until 315 °C, and held for 20 min.

The moisture content was evaluated using the Karl Fischer Data analysis
method and a Moisture Meter CA-200 Mitsubishi Chemi-
cal Analytech. The results are presented as the percentage Data were analysed using one-way ANOVA with a sig-
(%) of water in the sample (w/w). nificance level of a = 5%. If there was a significant dif-
ference in the results, the analysis continued using the
Total phenol and antioxidant activity Duncan multiple range test.

The total phenol, antioxidant activity, and 2,2-Diphenyl-1-

picrylhydrazyl (DPPH) IC50 evaluations began with

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Results and discussion Colour measurement

Oleoresin is a mixture of a resin, which is used as a taste The L* value is defined as lightness, which ranges from
carrier, and a volatile essential oil, which is used as an black (0) to white (100) (Renard and Maingonnat 2012).
aroma carrier (Khasanah et al. 2017). At one stage in this Samples with cinnamon bark oleoresin microcapsules
research, oleoresin was blended with an additional essential added had a significantly different lightness than the con-
oil to increase the essential oil content to an amount trol. Thus, cinnamon bark oleoresin microcapsule addition
deemed suitable by the Food and Drug Administration increased the lightness of a dark chocolate bar. The value
(FDA) and Essential Oil Association of America (EOA) of a* describes the chromatic colour of red (a* positive,
standards. According to the Food and Drug Administration ? 60) to green (a* negative, - 60), while b* describes the
(FDA), the minimum EO content is 25% (Khasanah et al. chromatic colour of yellow (b* positive, ? 60) to blue (b*
2014), while the standard is 18–35% for the Essential Oil negative, - 60) (Renard and Maingonnat 2012). All sam-
Association of America (EOA) (FAO-AGST 2002). One ples had a positive a* and a positive b*, so the colour of
stage oleoresin is made from the extraction of fresh dark chocolate bars with and without the addition of cin-
materials with a single-use solvent (Khasanah et al. 2017). namon bark oleoresin microcapsules are in the chromatic
The advantages of a one-step oleoresin are time and cost range of red and yellow.
efficiency. The characteristics of the cinnamon oleoresin As shown in Table 3, the hue angle of the dark choco-
used in this research are shown in Table 1. Cinnamon late bars ranged from 18 to 54, which shows that the pro-
oleoresin was then microencapsulated and added to dark duct colour tends to be red (Ilmi et al. 2016). The hue angle
chocolate bars to be evaluated. tended to increase with the increase in the cinnamon bark
oleoresin microcapsule concentration. The colour of dark
Sensory properties chocolate bars with the addition of cinnamon bark oleo-
resin microcapsules became redder because cinnamon
According to Table 2, different concentrations of cinna- oleoresin is originally a reddish colour (Djafar and Redha
mon bark oleoresin addition did not lead to a significant 2012). Oleoresin was encapsulated with arabic gum and
difference in panellist preference for all sensory attributes. maltodextrin, which are coloured white, so the oleoresin
The scoring scale for F1, F2, and F3 was ‘rather like’, so all microcapsule powder had a lighter colour.
the formulas were accepted by the panellists. In previous The highest concentration (8%) was added to the dark
studies (Dwijatmoko et al. 2016; Ilmi et al. 2016; Prasep- chocolate bar F3, so F3 supposedly has a lighter red colour
tiangga et al. 2018; Rasuluntari et al. 2016), the higher the compared to F2. Differences happen because of several
amounts of cinnamon essential oil and powder added, the factors, which include homogenization, tempering, or
lower the panellist acceptance of the dark chocolate and Schiff base formation. Under-tempered chocolate will also
milk chocolate bars. This result indicated that the strong result in a lighter colour (Afoakwa 2010).
flavour of cinnamon could be masked by microencapsula- When the active compound is excessive, cinnamalde-
tion and that the negative perception of the panellists could hyde will react with an amino acid and induce the forma-
be minimised. The largest amount of cinnamon bark ole- tion of a Schiff base. The Schiff base will decrease the
oresin microcapsules (8%) added to dark chocolates bar did intermolecular bond in the polymer chain, so the matrix
not cause panellist rejection and insignificantly preferred and pore will be more open (López-Mata et al. 2015).
overall. Oleoresin, which has a reddish-brown colour, will escape
from the microcapsule and give it a darker colour. Even so,
Table 1 Cinnamon bark oleoresin characteristics the colour tendency showed no difference.
The TCD calculation was performed to determine the
Attributes Result
colour difference between the treatment samples and con-
One stage oleoresin trol samples and to determine whether the difference was
Moisture content of dry cinnamon 12.596% visible or not. The TCD value, based on Renard and
Yield 10.939% Maingonnat (2012), was either \ 0.5 (invisible), 0.5–1.5
Essential oil content 19.333% (slightly noticeable), 1.5–3.0 (noticeable), 3.0–6.0 (well
Color Reddish brown visible), or [ 6.0 (great difference). Meanwhile according
Blended oleoresin to Gao et al. (2008), the threshold necessary for a colour to
Moisture content of dry cinnamon 13.891% be recognisably different by the naked eye is [ 1.5. As
Essential oil content 21.333% shown in Table 3, the addition of cinnamon bark oleoresin
microcapsules had a noticeable effect on the colour dif-
ference of the samples. Since the TCD values of F1, F2,

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Table 2 Sensory characteristics of dark chocolate bar with addition of cinnamon bark oleoresin microcapsule
Sample Colour Appearance (glossiness) Aroma Taste Hardness Melting capability Overall

F1 4.37a ± 0.76 4.37a ± 0.62 4.23a ± 0.87 4.37a ± 0.81 4.27a ± 0.87 4.27a ± 0.78 4.40a ± 0.67
a a a a a a
F2 4.33 ± 0.80 4.30 ± 0.84 4.17 ± 0.95 4.40 ± 0.77 4.10 ± 0.76 4.03 ± 0.96 4.27a ± 0.83
a a a a a a
F3 4.33 ± 0.81 4.23 ± 0.86 4.33 ± 0.84 4.23 ± 0.77 4.33 ± 0.61 4.13 ± 0.83 4.47a ± 0.94
Cinnamon bark oleoresin microcapsule addition F1 = 4%, F2 = 6%, F3 = 8%
Scale 1 = dislike, 2 = rather dislike, 3 = neither like or dislike, 4 = rather like, 5 = like
Within column, mean values marked by different superscript small letters are differ significantly (a = 0.05)

Table 3 Texture and colour measurement of dark chocolate bar with addition of cinnamon bark oleoresin microcapsule
Sample L* a* b* °Hue TCD Effect Hardness (N)

C 25.44a ± 0.15 8.02a ± 0.08 4.38a ± 0.08 28.61a ± 0.34 23.43 ± 1.21a
b bc ab a
F1 27.22 ± 0.12 8.49 ± 0.28 4.83 ± 0.41 29.60 ± 1.38 1.90 Noticeable 32.96 ± 4.13b
b c b b
F2 27.40 ± 0.30 8.63 ± 0.20 5.32 ± 0.26 31.66 ± 0.71 2.26 Noticeable 32.97 ± 3.38b
b b ab a
F3 27.28 ± 0.15 8.32 ± 0.28 4.74 ± 0.23 29.66 ± 0.48 1.90 Noticeable 35.47 ± 3.39b
Cinnamon bark oleoresin microcapsule addition C = 0%, F1 = 4%, F2 = 6%, F3 = 8%
Within column, mean values marked by different superscript small letters are differ significantly (a = 0.05)

and F3 were close to the threshold (1.5), a small difference A high compactness will increase a product’s hardness
was noticeable; thus, during the sensory evaluation, the (Midaryanto and Yuwono 2014). An increase in the pro-
panellists did not find the colour to be significantly duct mass with the same volume will increase the com-
different. pactness. Increasing the cinnamon bark oleoresin
microcapsule concentration, which was added to the
Texture measurement chocolate mould in the same volume, resulted in an
increase in the hardness of chocolate because the micro-
According to Table 3, there was a significant difference capsule evenly filled the spaces and cavities in the
induced by the addition of cinnamon bark oleoresin chocolate.
microcapsules regarding the hardness of dark chocolate
bars. The hardness of the dark chocolate bars increased as Moisture content
the amount of added cinnamon bark oleoresin microcap-
sule increased, even though there was no significant dif- The moisture content of chocolate is affected by a sequence
ference between the treatment samples. The texture of the of processes that uses a thermal treatment, so moisture is
dark chocolate bar was influenced by refining, conching, primarily decreased in the conching process (Goncalves
and tempering. Tempering is a sequence of processes and Lannes 2010). Referring to Table 4, there was no
consisting of cooling, heating, and chocolate inverting to significant difference in the moisture content from adding
form a chocolate fat crystal b2 (V form) that is resistant to cinnamon bark oleoresin microcapsules to dark chocolate
temperature changes (Afoakwa 2010). Under-tempering bars because of the synced controlling and storing used for
causes an increase in chocolate softness, while over-tem- all samples.
pering causes an increase in hardness (Ilmi et al. 2016). The percentage of the moisture content insignificantly
The large particle size of chocolate (greater than 30 lm) decreased with the increasing of the cinnamon bark oleo-
creates a sandy and rough texture (Beckett 2008). In this resin microcapsule content added to dark chocolate bars.
study, the particle size of the materials was controlled in An increase in the cinnamon bark oleoresin microcapsule
the micro-size. A particle size observation was conducted concentration will increase the total shell materials in the
on the emulsion, microcapsule powder, and melting product, so the total solid content also increases (Kania
chocolate during ball milling and tempering. The sizes of et al. 2015). The dark chocolate bar moisture content is the
the emulsion, microcapsule powder, and chocolate fat result of calculating the percentage of moisture in the
particle after tempering were 1.58–3.30 lm, sample (w/w). An increase in total solids will increase the
1.18–3.02 lm, and 1.74–7.26 lm, respectively. weight of the sample. The moisture weight, which is

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Table 4 Moisture content, total

Sample Moisture content (%) Total phenol (%) IC50 (ppm)
phenol content, and antioxidant
activity of dark chocolate bar Met AAA Met AAA
with addition of cinnamon bark
oleoresin microcapsule C 1.78a ± 0.76 5.14a ± 0.07 68.88a ± 4.12 13,368.57b 1573.36b
a b b a
F1 1.68 ± 0.11 5.67 ± 0.07 233.14 ± 2.82 7250.00 243.18a
a b c a
F2 1.62 ± 0.24 5.73 ± 0.05 257.42 ± 1.07 7112.51 242.67a
a c d a
F3 1.55 ± 0.09 6.62 ± 0.11 265.45 ± 1.94 5675.68 209.15a
Met, methanol; AAA, acetone:aquades:acetic acid
Cinnamon bark oleoresin microcapsule addition C = 0%, F1 = 4%, F2 = 6%, F3 = 8%
Within column, mean values marked by different superscript small letters are differ significantly (a = 0.05)

relatively the same for higher sample weights, will result in (2018). The addition of 2% lyophilized colloidal
a lower moisture content. nanoparticles containing cinnamon extract resulted in a
In this research, arabic gum and maltodextrin were used total phenol content that was approximately two times
as shell materials. Maltodextrin has a low molecular weight higher than that of the control chocolate.
and a simple structure, so water evaporates more easily The acetone:aquades:acetic acid solvent gave a higher
during the drying process. Moreover, maltodextrin with total phenol content because acetone and cinnamaldehyde
DE-10 is less hygroscopic and has a rapid drying rate, so it have the same polarity. Based on the PubChem web-
is not easy to reabsorb water (Kania et al. 2015). Beckett database (2018), the topological polar surface area (TPSA)
(2008) stated that the maximum moisture content in of acetone and cinnamaldehyde is 17,1 A^2, while the
chocolate should be 2% to prevent the growth of microbes. TPSA for methanol is 20,2 A^2. Thus, the hydroxyl group
A high moisture content can cause blooming (Afoakwa of cinnamaldehyde, which is a major polyphenol com-
2010) and a soft texture (Goncalves and Lannes 2010). pound found in cinnamon bark (Başer and Buchbauer
2010), bonded to the phenyl ring of the ace-
Total phenolic content tone:aquades:acetic acid solvent during the Folin-Ciocalteu
assay and gave a higher calculation result.
Both cocoa and cinnamon contain polyphenols. The major
polyphenol present in dark chocolate is flavanols, such as Antioxidant activity
epicatechin, catechin, and procyanidin (Beckett 2008). The
phenolic compounds contained in cinnamon are cineole, Antioxidant activity is presented as the DPPH IC50 value,
terpineol, cinnamyl alcohol, cinnamyl acetate, eugenol, which is shown in Table 4. DPPH, along with FRAP and
methyl eugenol, and linalool. Vanillic acid, gallic acid, p- ORAC, is the most common type of antioxidant assay. It is
coumaric acid, p-hydroxybenzoic acid, and p-hydroxy- usually used in chocolate- and cinnamon-related studies
benzaldehyde are polyphenol constituents of cinnamon. If (Ervina et al. 2016; Muhammad and Dewettinck 2017;
cocoa and cinnamon are combined, the total phenol content Muhammad et al. 2017, 2018). DPPH is a rapid assay that
of the final product will be increased (Muhammad and is easy to perform. The Folin-Ciocalteu method is more
Dewettinck 2017). correlated with DPPH and FRAP than electron transfer by
The Folin-Ciocalteu method used to determine the total a hydrogen donor (Boeing et al. 2014; Muhammad et al.
phenol content is easy, rapid, and the most common 2017).
method used in dark chocolate and cinnamon extract The addition of cinnamon bark oleoresin microcapsules
studies (Ervina et al. 2016; Muhammad and Dewettinck led to a significant difference in antioxidant activity com-
2017; Muhammad et al. 2017, 2018). Table 4 shows that pared to the dark chocolate control. The higher the con-
variation of cinnamon bark oleoresin microcapsule addi- centration of added cinnamon bark oleoresin
tion resulted in a significant difference in dark chocolate microcapsules, the lower the concentration of the chocolate
bars’ total phenol content in both solvents. The total phenol bar needed to scavenge the 50% free radicals of DPPH.
content increased with the increase in the cinnamon bark This result is similar to Albak and Tekin (2015), and the
oleoresin microcapsule concentration, and the chocolate active compound in cinnamon play a role in increasing the
bar F3 contained the highest total phenol content. The total antioxidant activity of the dark chocolate bar.
phenol content of the acetone:aquades:acetic acid extract All types of polyphenols are antioxidants, including
increased to four times higher than that of the methanolic flavonoids, flavonols (catechin and epicatechin), pro-
extract. This result is consistent with Muhammad et al. cyanidins, anthocyanidins, flavonol in cocoa (Beckett

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2008), eugenol, linalool, and terpineol in cinnamon (Ervina detected using acetone:aquades:acetic acid, but the per-
et al. 2016; Muhammad and Dewettinck 2017). Methylx- centage was different than the methanolic extract because
anthines, which are theobromine, caffeine, and theo- acetone was probably not the best solvent for methylxan-
phylline in cocoa, are also antioxidants (Franco et al. thine. As previously explained, the topological polar sur-
2013). The major compound of Cinnamomum sp. bark is face area of acetone and cinnamaldehyde is exactly the
the antioxidant cinnamaldehyde, which reaches 70% same (PubChem web-database 2018) and was suspected to
(Başer and Buchbauer 2010). be the main reason for the solvent and compound
The use of different solvents in the extractions gave interaction.
different IC50 values. The IC50 value for the ace- One of the functional food criteria, according to BPOM
tone:aquades:acetic acid extract was lower than the RI Regulation No. HK 00.05.52.0685 (2005), is the
methanolic extract, so its antioxidant activity was higher. antioxidant content of the product. GC–MS detection
Even so, all of the samples were classified as super weak showed that chocolate bars with the addition of the cin-
antioxidants. According to the antioxidant classification by namon bark oleoresin microcapsules contained methylx-
Molyneux (2004), a super potent antioxidant has IC50 \ anthine, vanillin, tocopherol, and cinnamaldehyde as
50 ppm, while strong is 50–100 ppm, middle is antioxidants. Among the detected antioxidants, tocopherol
10–150 ppm, weak is 150–200 ppm, and super weak is the only compound that is already regulated according to
is [ 200 ppm. The IC50 value of the ace- its nutrient label by the FDA (2017).
tone:aquades:acetic acid extract from dark chocolate bars As shown in Table 6, b- and c-tocopherol were con-
with the addition of the cinnamon bark oleoresin micro- verted to a- tocopherol based on EFSA (2008), so it could
capsules was 200 ppm, which is considered weak. The be claimed to be the source of regulation. The vitamin E
antioxidant content in products is not a constant value; it and a- tocopherol contents did not exceed the limit of the
differs depending on many aspects, including the condi- BPOM Regulation No. HK. 00. 05. 23. 3644 in 2004. The
tion, processing, or assay method of the materials (Beckett concentration of a- tocopherol in dark chocolate bars was
2008; Muhammad and Dewettinck 2017). The result of the higher than in the control and exceeded C 100% of the
antioxidant activity IC50 evaluation was linear with the RDI for children (4 years old) and adults (FDA 2017).
total phenol and GC–MS evaluations. Previous studies by Therefore, dark chocolate bars with the addition of the
Muhammad et al. (2017) showed the same result: the cinnamon bark oleoresin microcapsules had a high potency
antioxidant activity that was evaluated was positively of vitamin E and fulfilled the antioxidant need of adults and
correlated with the total phenol content. children.

GC–MS detection Determination of the best formula

According to Table 5, all of the compounds detected The best dark chocolate bar formula was determined by a
contain cacao and its processing products. The compounds model weighting test (Sullivan et al. 2015). The parameters
found in all formulas were vanillin, methylxanthines (caf- used for determining the best dark chocolate bar formula
feine and theobromine), fatty acids (palmitic acid and oleic were the attribute, L* and hue angle, hardness (N),
acid), and tocopherols. Franco et al. (2013) stated that the methylxanthine and tocopherol contents, moisture content
methylxanthines present in cocoa are caffeine, theo- (%), total phenol content (%), and antioxidant activity IC50
bromine, and theophylline. The major methylxanthines in (ppm). Each parameter was given a weight from 0 to 1
cocoa are theobromine and caffeine at lower concentrations according to its effect on sample quality. All parameters
(Beckett 2008; Franco et al. 2013). The cocoa bean pri- had the same effect on dark chocolate bar quality, so all
marily contains cocoa fat, which is composed of palmitic parameters were weighted as 1. F3 had the highest total
acid, stearic acid, and oleic acid (Beckett 2008). score (0.8724), followed by F1(0.3794) and F2 (0.1602).
According to Djafar and Redha (2012) and Boeing et al. Therefore F3, which had an 8% addition of cinnamon bark
(2014), different solvents will give different assay results, oleoresin microcapsules, was the best formula for a dark
and the solvent used strongly determines the solubility of chocolate bar.
the bioactive compound. Cinnamaldehyde was not found in Further research may evaluate the effect of increased
the GC–MS evaluation using the methanolic extract, so microcapsule addition ([ 8%) to dark chocolate or a higher
other solvents, such as acetone:aquades:acetic acid, were oleoresin concentration added to microcapsules for later
used to extract the defatted chocolate. As shown in addition to dark chocolate. A higher concentration of cin-
Table 5, the cinnamaldehyde content of the ace- namon microcapsules increased the total phenolic content
tone:aquades:acetic acid extract was 56.3362%. In addition and antioxidant activity of dark chocolate bars (Albak and
to cinnamaldehyde, theobromine and caffeine were also Tekin 2015; Muhammad and Dewettinck 2017) and also

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Table 5 GC–MS detection of

No. Compounds Content (%)
dark chocolate bar with addition
of cinnamon bark oleoresin Met AAA
microcapsule
C F1 F2 F3 F3

Methylxanthines
1. Theobromine 16.458 25.050 17.342 33.879 11.993
2. Caffeine 6.439 11.272 6.719 10.879 31.671
Aldehyde
3. Cinnamaldehyde – – – – 56.336
4. Benzaldehyde, 4-hydroxy-3-methoxy (vanillin) 2.735 4.748 3.184 2.490 –
Fatty acids
5. Palmitic acid 26.600 26.795 18.237 1.325 –
6. Oleic acid 21.685 11.789 44.40 14.667 –
7. Linoleic acid – – – 31.106 –
8. Lauric acid (dodecanoic acid) – – 0.795 2.280 –
9. Trans-oleic acid (elaidic acid) 5.410 11.017 – – –
Tocopherols
10. b-tocopherol 1.618 3.094 – 3.376 –
11. c- tocopherol – – 2.543 – –
Phytosterols
12. Campesterol – – 3.151 – –
13. b-sitosterol – – 3.632 – –
14. c-sitosterol – 3.808 – – –
Hidrocarbons
15. Pentadecane 3.402 2.426 – – –
16. Heptadecane-8-carbonic acid-1- 0.698 – – – –
Ester
17. Ethyl cinnamate 1.471 – – – –
18. Ethyl p-methoxy cinnamate 5.426 – – – –
Amide
19. Palmitic amide 0.497 – – – –
Met, methanol; AAA, acetone:aquades:acetic acid
Cinnamon bark oleoresin microcapsule addition C = 0%, F1 = 4%, F2 = 6%, F3 = 8%

Table 6 Tocopherol content of dark chocolate bar with addition of cinnamon bark oleoresin microcapsule (F3, Met) and claims based on
regulations (BPOM 2004; FDA 2017)
Formula Tocopherol contenta (%) a-tocopherolb FDA BPOM Maximum intake (IU) Claim
RDI (mg)
b c mg mg IU

C 1.618 113.232 56.616 84.358 15 400 High-potency antioxidantc, not exceed

F1 3.094 216.580 108.290 161.352
F2 2.543 177.989 44.497 66.301
F3 3.376 236.299 118.150 176.043
Met, methanol; AAA, acetone:aquades:acetic acid
a
Content per 1 chocolate block (7 g) which identified in vitro using GC–MS assay
b
1 mg d-a-tocopherol = 1,49 IU, 1 mg d-a-tocopherol = 2 mg d-b-tocopherol = 4 mg d-c- tocopherol
c
Contain C 100% of RDI vitamin E (tocopherol) for adults and children (4 years old)

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led to more compounds in GC–MS detection (Beckett Acknowledgements The authors would like to thank Universitas
2008; Franco et al. 2013; Ervina et al. 2016; Muhammad Sebelas Maret (UNS), Indonesia for funding this research under the
PNBP Research Grant Scheme 2018 (Nomor 543/UN27.21/PP/2018).
and Dewettinck 2017). The texture and colour of dark
chocolate may be affected as well. However, the main
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