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PII: S0141-8130(17)32895-7
DOI: doi:10.1016/j.ijbiomac.2018.03.082
Reference: BIOMAC 9304
To appear in:
Received date: 4 August 2017
Revised date: 21 February 2018
Accepted date: 16 March 2018
Please cite this article as: Hira Arshad, Tahira Mohsin Ali, Abid Hasnain , Native and
modified Sorghum starches as wall materials in microencapsulation of nutmeg oleoresin.
The address for the corresponding author was captured as affiliation for all authors. Please
check if appropriate. Biomac(2017), doi:10.1016/j.ijbiomac.2018.03.082
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oleoresin
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Department of Food Science and Technology, University of Karachi, 75270, Karachi, Pakistan
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Corresponding author email (hira_fst@hotmail.com)
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Abstract
The effect of the partial or total substitution of gum arabic (GA) with native (NA), octenyl
nutmeg oleoresin was studied using spray drying technique. The oleoresin with 10% load is
emulsified by using three different combinations of GA along with native and modified sorghum
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starches. The proportion of GA and sorghum starch was fixed at 75:25, 50:50, and 25:75. Most
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of the feed emulsions were having good emulsion stability and lower emulsion viscosity. The
highest oil retention of 95% with 84.07% encapsulation efficiency was achieved when GA: NA
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starch was used in the fraction of 25:75. The highest encapsulation efficiency of 95.38% was
obtained by GA: OSA in a ratio of 75:25. Results obtained suggested that both NA and OSA
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starches could be considered as a good alternative to gum arabic for microencapsulation.
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Keywords
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1. Introduction
Spices are derivatives of aromatic plants used to enhance the flavor and aroma profile of food
and possess a significant position in the field of food industry. Common spices include clove,
cinnamon, mace, nutmeg, black pepper, cumin etc. Spices could be used directly in the form of
dried powder or in the form of its oleoresin. Spice oleoresin represents the aroma profile similar
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to that of original spice from which it has been extracted [1]. Oleoresins are the solvent extract of
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spices that exhibit volatile as well as non volatile constituents of spices. Rather than ground
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powder, oleoresins are more preferred because of their balanced, reliable and quantifiable nature
[2]. Oleoresins are easily accessible throughout the year with guaranteed storage stability in the
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final product and also free from microbial contamination. As oleoresins are sensitive to light, air,
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moisture and elevated temperature, they can easily degrade [3]. Microencapsulation offers an
alternative method to limit the aroma and flavor loss during storage and processing.
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coating material to give capsules of micron size ranging from one micron to several hundred
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microns [5]. These protected particles remain inert in capsules for specific period of time and
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release when needed for its specific function. Solid, liquid or even gaseous particles can be
encapsulated for uncountable reasons [3].The material within the capsule is often refer to as core
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or fill whereas the wall material refers as coating or shell material [6]. Core material may be in
solid material as an active constituent, diluents, stabilizers, excipients or release rate accelerators
and as a liquid core could include dispersed or dissolved material [7]. Microencapsulation is an
important technique to provide coating of bioactive compounds into food system and their
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successful release to gastrointestinal tract such as essential oils, vitamins, lycopene, minerals,
Numerous methods are reported for microencapsulation of spice oleoresin, but the most accepted
technique employed in the industry is spray drying. Spray drying is an appropriate method for
microencapsulation of oils and oleoresins [8], [9]. Carbohydrates such as hydrolyzed starches
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(SHPs), modified starches, emulsifying starches and gums (especially gum acacia) are the most
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common carrier materials [10]. Gums are also used for secondary effect such as stabilization of
emulsion, encapsulation, and film formation. Being hydrophilic in nature, gum arabic and native
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starches have little affinity for hydrophobic flavor oils. Their hydrophilic nature can be altered
by modifying them with octenyl succinic anhydride (n-OSA). N-OSA treated starch contains
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hydrophobic octenyl side chains, which impart emulsifying ability to the starches. These wall
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materials have excellent emulsification properties [11]. However, emulsifying starches have
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some limitations. In addition, problems associated with the use of gum arabic in
microencapsulation are high cost and limited supply and they exhibit poor flavor protection
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against oxidation and have off flavor [10]. Krishnan [1] studied the effectiveness of succinylated
waxy maize starch, maltodextrin and gum arabic as wall materials for encapsulation of
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White sorghum (Sorghum bicolor) is a non-gluten cereal crop with major storage form of
carbohydrate is starch that ranges from 55.6 to 77% based on kernel weight [12]. Sorghum starch
is very similar to commercially important corn starch in many of its functional properties,
whereas in terms of agronomic properties it is even better than corn. Nevertheless, low cost of
sorghum combined with significant agronomic properties make sorghum an ideal crop for
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isolation of starch especially for a country like Pakistan facing heightened water shortage.
Secondly, with increased use of corn and potato in preparation of breakfast cereals and snacks,
The present work deals with microencapsulation of nutmeg oleoresin by spray drying. The
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objective of this research was to study suitability of native and modified sorghum starches (OSA
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and Succinylated) in combination with gum Arabic in different ratios as wall material. Emulsion
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characteristics, encapsulation efficiency, physiochemical properties of spray dried
microcapsules; retention and stability of the main flavor oil in microcapsules during storage were
studied.
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2. Material and methods
White sorghum grains were provided by Pakistan Agriculture Research Council (PARC) and
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stored at room temperature after fumigation. Nutmeg seeds were purchased from local market in
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Karachi and stored at 4⁰C prior to extraction of oleoresin. Gum Arabic, succinic anhydride, n-
acid and n-hexane were purchased from Merck (Darmstadt, Germany). All chemicals utilized
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Nutmeg oleoresin was obtained from nutmeg seeds (Myristica fragrans houtt) by direct
Isolation of starch from sorghum grains was carried out by using the method described by
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Succinylation of sorghum starch was done by the method of Moin et al. [15].
Molar degree of substitution (DS) is the average number of hydroxyl groups substituted per
glucose unit of starch. The method described by Wurzburg [16] was adopted to calculate the
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degree of substitution for succinylated starch.
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2.2.3. Octenyl succinic anhydride (OSA) modification of sorghum starch
The method of Bhosale and Singhal [17] was used for octenyl succinic anhydride modification of
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sorghum starch with few modifications.
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2.2.4 Degree of substitution of OSA modified starch
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The determination of octenyl succinylation level of modified sorghum starch was done by
For native and modified sorghum starches, the particle size distribution of each sample was
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analyzed by using public domain software Image (J v1.36b). The result was obtained by
measuring the diameter of 100 particles of starch (native and modified) with the help of SEM
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images (1000x) through software. The particle size of starches (native and modified) were
expressed as the mean volumetric size d43 (De Brouckere mean diameter) of sphere having same
volume [20].
The wall material used in the current study was gum arabic, native and modified (succinylated
and octenyl succinylated) sorghum starches and nutmeg oleoresin was used as core material.
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About 30% (w/w) solution of gum Arabic (GA) and sorghum starches (ST) (native and
modified) in the proportion of 75:25, 50:50 and 25:75 on dry weight bases were unified in
500mL distilled water with constant stirring at ambient temperature. While the forth emulsion
comprised of starch only. The blends were kept in refrigerator for rehydration for about 24 hours
at 10⁰C. Nutmeg oleoresin was added slowly in a proportion of 10% (w/v) with respect to wall
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material concentration. The blend was then homogenized at 9000 rpm for 15 min by using T.K
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Homo Mixer 2 (Model A94506X, Osaka, Japan).
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2.3.1. Emulsion stability
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Emulsion stability or creaming stability was estimated using the method of Park et al., [18] based
Emulsion viscosity of emulsion was determined by Haake Visco tester 6 L at 30 rpm (HAAKE,
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The particle droplet size of emulsions was determined by the method described by Frascareli
[19].
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The homogenized emulsion was spray dried in Eyela spray dryer SD-1 (Tokyo Rikakikai Co.,
Ltd Japan) equipped with twin fluid nozzle operating co currently at air pressure of 0.6 kg/cm2
with flow rate of 400 mL/h using the method of Frascareli et al., [19].
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The moisture content of spray dried microcapsules was determined according to the method of
Fernandes et al., [20] by drying 0.5g powdered sample gravimetrically in hot air oven at 103
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2.5.2. Cold Water Solubility
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Cold water solubility of spray dried powder was determined using the method of Singh and
Singh [21].
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2.5.3. Hygroscopicity
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Hygroscopicity of the spray dried powdered samples were analyzed using the method of Cai and
Corke [22] with some modifications. One gram of each sample was placed in a dessicator
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containing saturated brine solution of relative humidity 75.3% for 7 days. The weight of the
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samples was taken after one week and hygroscopicity of samples were determined by the amount
Powder wettability of spray dried microcapsules was determined by the method of Fernandes et
al., [20].
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The bulk densities (ρB) and tapped densities (ρT) were determined in 25ml graduated glass
cylinders described by Xue et al., [23]. About 3g of sample (mo) was poured into graduated
cylinder. The volume of the sample (v0) was read directly from the cylinder and used to calculate
the bulk density (ρB= mo/vo). For tapped density, the cylinder was tapped until a constant volume.
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The flow ability of samples was observed by Carr’s index and the Hausner Ratio by using
Oil retention for nutmeg microcapsules was estimated by calculating the oil concentration before
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2.5.7. Surface oil content on microcapsules
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The amount of oil present on the surface of microcapsules represents the non encapsulated or
free oil and was determined by the method of Tan et al., [24].
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2.5.8. Estimation of total oil in microcapsules
Extraction and measurement of the total oleoresin present in the spray dried powder was
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determined by using soxhlet method illustrated in Wrolstad [25].
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Encapsulation efficiency (EE %) was determined by the fraction of encapsulated oil over the
To determine the oxidative stability of encapsulated oil, the spray dried powder samples as well
as pure nutmeg oleoresin were stored at 7 and 25 in air tight plastic containers for 6 weeks.
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Samples were examined from first week to sixth week with respect to lipid oxidation by
evaluating the peroxide index of samples. To determine the Peroxide value, the oil was extracted
by the method of Partanen et al., [26]. The result was calculated as peroxide value meqv/ kg of
encapsulated oil.
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Peroxide values were determined according to IDF standard method described by Frascareli et
al., [19] with some modifications. The portions of 400µl of extracted sample were incorporated
solution and 50 ml of Fe+2 solutions. The sample was reacted in the dark and absorbance was
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measured at 500nm before 10 min. By using Fe+3 standard curves with iron concentration
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ranging from 1 to 25 µg, the hydroperoxide concentrations were evaluated.
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2.5.12. Powder morphology and Particle size analysis of microcapsules
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Morphological properties of microcapsules were observed by scanning electron microscopy
(JSM, 6380A, Jeol Japan) operating at an accelerating voltage of 10 kv. The powder sample was
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fixed on stub and coated with gold layer in a vacuum evaporator. The images of all
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microcapsules were studied at 2000x magnification. For spray dried microcapsules, the particle
size distribution of each sample was analyzed by using public domain software Image J (v1.36b).
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The particle size of microcapsules were calculated as the mean volumetric size d43 (De
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Brouckere mean diameter) of sphere having same volume by measuring the diameter of 100
particles of microcapsules with the help of SEM images (1000x) through software [20]. The
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All measurements were carried out in triplicate. The results were statistically analyzed using
software statistical package for social sciences (SPSS). Analysis of variance (ANOVA) was
performed using the Duncan’s multiple range tests to compare treatments means (n≥3). Whereas
for comparing significant difference at p<0.05 for two samples (n=2), t-test was used employing
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Starch is a naturally occurring, low cost biopolymer with comprehensive applications in food
characteristics such as gelling property, thickening, film forming, fat mimicking, etc [28]. Native
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starch is hydrophilic in nature and their hydrophilicity is further altered by esterification with
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hydrophobic groups or negatively charged groups. OSA modification gives a specific surface
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activity to starch by incorporating hydrophobic alkenyl groups from OSA into the hydrophilic
starch molecule which disturbed the linearity of amylose chain and ramified portion of
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amylopectin. Therefore, OSA starches are characterized by a decreased in gelatinization
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temperature and increase in paste viscosity. Octenyl succinic starches are used as emulsion
stabilizers, texturizing agents in many food-systems and for flavor encapsulation. Succinylation
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of starch leads to addition of hydrophilic negatively charged succinyl groups which in turn gives
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a hydrophilic character to starch. Succinic groups weaken the internal bonding in starch granules
and facilitate starch solubilization even in cold water [28]. The degrees of substitution for
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modified starches are presented in Table 1. All sorghum starch samples were treated with 3%
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succinic anhydride. The DS of 0.0709 was observed for succinylated sorghum starch. The
difference in chemical substitution between starches of varying botanical sources is due to the
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difference in packaging of amylose in amorphous region together with the packaging of both
amylose and amylopectin within the granule. Degree of substitution of 0.023 was achieved for
OSA sorghum starch. The present result is quite similar to that reported by [17] having a DS of
0.021 for waxy corn starch treated with 3% OSA under the same conditions. In the current study,
the modifications of starches were done at a level of 3% which is the approved limit for
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modification of starches by Food and drug administration (FDA). The mean particle size of
native, OSA modified and succinylated starches are presented in Table 1. The mean particle
diameter for native sorghum starch was observed as 12.56µm, whereas 13.65µm for OSA and
12.41µm for succinylated sorghum starch. There is no significant difference in mean particle size
of native and succinylated starch while OSA starch showed slight increase in particle size as
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compared to both native and succinylated starch.
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3.2. Emulsion stability and emulsion viscosity and oil droplet size
According to kinetic stability, emulsions are thermolabile systems which can be rapidly or
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slowly divided into two immiscible phases [27]. Emulsion stability has been reported to have an
impact on microencapsulation efficiency, stability and properties of spray dried oil powders in
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terms of flocculation, coalescence or phase separation [24]. The emulsion stability and emulsion
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viscosity are presented in Table 2. Most of the samples consisting of high proportion of gum
Arabic with starch had excellent emulsion stability which ranged from 0.80-1.0. Samples
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comprised of 100% starch (native and both OSA and Succinylated modified) showed slight
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phase separation after 24 hours. The emulsion stability for 100% OSA modified sample was
found to be 0.63, 0.73 for 100% native and 0.77 for 100% succinylated starch sample. The
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sample containing the fractions 25:75 (GA:SUC) also resulted in low emulsion stability 0.63, as
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succinylated starches have more hydrophilic characteristic which resulted in low emulsion
stability as compare to both native and OSA modified starches . In current study, spray drying
process took 45-55 minutes for one batch after emulsion preparation. Minor flocculation during
this process had been observed in all samples comprising of 100% starch. Emulsions consisting
of high portion of gum Arabic had high viscosity values as compared to the samples comprising
of high portion of starch either native or modified. The highest value of 48.67m.Pa.s was
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observed for the sample comprising of 75% gum Arabic along with 25% OSA starch.
Additionally, the samples containing OSA modified starch with or without gum arabic had
slightly high values of emulsion viscosities as compare to native and succinylated. This is due to
the fact that hydrophobically modified polymers such as OSA starches are also called associative
thickeners due to interactions with other polymers and surfactants in aqueous solutions. The
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viscosity of OSA starches is generally higher than that of other substituted derivatives. This
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observable fact may be caused by an associative effect of the hydrophobic chains [28]. Due to
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the greater molecular structure of gum Arabic, emulsions comprising of high proportion of gum
arabic led to an increase in high viscosity and vice versa [29]. Whereas, the samples consisting of
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greater proportion of starch had lowest viscosities. Results described by Chanamai and
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McClements [30] proposed that the rheology of concentrated emulsions (viscosity) is fairly
dependent on droplet concentration, size and shear rate, in addition to the electrostatic repulsion
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between droplets.
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The emulsion droplet size is an important factor for retention of encapsulated material in spray
dried process and enhanced by reducing the mean emulsion droplet diameter. The mean diameter
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of the emulsions is presented in Table 2. The lowest mean diameter was observed in the sample
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GA: NAT (25:75) i.e. 2.36µm and highest value was observed in sample GA: SUCCI (0:100)
which is 4.88 µm. The replacement of gum arabic with starch in different samples and the
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modification of starch (both OSA and succi) did not make any remarkable changes in mean oil
Besides microencapsulation efficiency, flowing properties are measured in term of bulk density,
hausner ratio and carr’s index [23]. The bulk density values for the reported spray dried samples
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ranged from 0.30-0.418g/ml. These values were close to those as previously observed for
microencapsulation of rosemary essential oil prepared using gum arabic as the wall material
Carr’s index can influence powder properties during processing and storage conditions.
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According to the categorization (Table 2.) for flowing property of powder, all spray dried
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microcapsules had poor powder flowing property. The different ratios of gum arabic with native
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and modified sorghum starch showed little influence on Hausner and Carr’s index. However, as
compared to native and OSA starch, combinations of gum arabic with succinylated sorghum
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starch showed little improvement in Hausner and Carr’s index. It was observed that
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modification of starch did not affect the flowing ability of microcapsules.
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Moisture content depends on the physical and chemical properties of the wall material and core
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material, method of encapsulation and operating conditions thus affects the shelf life of
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microcapsules [22]. The moisture content of under studied microcapsules ranged from 1.85%-
3.20% as given in the Table 3. There was no significant difference (p<0.05) between the samples
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constituting of native and modified starches along with the gum arabic. . Therefore, the obtained
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results were in accordance with the results reported by B.Cuq et al., [32] who found out that in
spray drying process, higher inlet and outlet temperatures accelerated the drying rate of droplets
3.5. Hygroscopicity
surrounding. In microencapsules, the presence of moisture can affect many parameters such as
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lipid oxidation, flowing property, solubility etc. The results obtained confer an idea about the
hygroscopic nature of gum Arabic and sorghum starch. As mentioned in the Table 3, the
hygroscopicity values of all the samples were in the range of 4.57%-12.80%. These results
showed that the spray dried powders can be handled with ease and feasible for storage. The
highest values were observed for the compositions comprising of high proportion of gum Arabic
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and low proportion of sorghum starch (native and modified) and vice versa. These values of the
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hygroscopicity were observed due to the changes in gum Arabic content [17]. The
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hygroscopicity of samples consisting of native starch is lower than the samples comprising of
modified starches. These changes can be attributed to the different polarities of the wall material
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used, highly branched structure of gum Arabic which makes the polar interactions with water
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easy by hydrogen bonding, amphiphilic nature of OSA and hydrophilic nature of succinylated
starches.
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Water solubility of the nutmeg microcapsules varied from 2.72%-75.20% with the highest values
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observed for the samples having high percentage of gum arabic (Table 3). With the increase in
starch proportion in all samples, the percent water solubility decreases and least value was
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observed for the samples consisting of 100% native, OSA and succinylated starches. Sample A
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constituting of 75% gum Acacia with 25% native and 25% modified starches (OSA and
succinylated) had the highest values for water solubility. This is due to the fact that gum arabic is
a complex hydrocolloid with brilliant water soluble attribute and consists of highly branched
arrangement of the simple sugars galactose, arabinose, rhamnose, and glucuronic acids [7].On
the other hand, native starch granules are insoluble in cold water due to the hydrogen bonds and
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polymer is in low range; consequently, it doesn't influence the overall hydrophilicity of starch
granules that’s why very slight variation in water solubility was observed among native and
The capability of spray dried microcapsules to combine with water is one of the most important
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physical characteristics associated with reconstitution with water. In fact, powder rehydration is a
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quality determining aspect and it is directly affected by the molecular interaction between two
phases [32]. In current study, the time taken for spray dried powders to become fully wet and
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disappearance from the surface was used to evaluate the extent of wettability [20]. Powder
wettability of spray dried microcapsules ranged from 3sec-688sec (Table 3). The powder
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samples comprising of high proportion of gum Arabic took more time to disappear from surface
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while samples consisting of sorghum starch (native or modified) as a whole, settled immediately.
This is due to the fact that starch samples (native and modified) had high density as compared to
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gum Arabic .Powder Wettability depends on powder particle size, type of wall materials, density,
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porosity, surface activity and hydrophilic nature of wall materials [33]. In present study, powder
wettability was affected by difference in proportion of gum Arabic and sorghum starch rather
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Microencapsulation efficiency and oil retention are most important quality parameters for the
encapsulation of essential oil and is mainly determined by the content of oil retained in the dried
capsule and total oil captured inside the matrix. The amount of surface oil and entrapped oil was
first determined to estimate the EE%. The quantity of surface oil in spray dried powder is critical
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for storage stability of microcapsule. This is due to the fact that surface oil can easily be oxidized
resulting in inappropriate off flavors. In obtained results (Table 4), the quantity of surface oil
ranged from 0.24-1.51g/100g of dried powder. These results revealed that the quantity of wall
materials used were sufficient for encapsulation of bulk oil. The mixtures comprising of gum
arabic and native sorghum starch showed high values of surface oil as compare to gum arabic
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with modified starches. On the other hand, the sample containing purely native sorghum starch
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resulted in high surface oil as compared to sample containing of OSA and succinylated sorghum
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starch wholly. The amount of oil retention in obtained results ranged from 33.53-44.40% for the
mixtures containing succinylated sorghum starch, 42.10-71.40% for mixtures of OSA starch and
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58.55-95% for native sorghum starch along with gum arabic. The sample GA: NAT (25:75)
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showed the highest value for oil retention i.e. 95% oil retention as compared to all other samples.
In this study, the substitution of sufficient amount of gum arabic by native and OSA modified
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sorghum starch resulted in better oil retention. The lower values of oil retention were observed in
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sample comprising of 100% succinylated sorghum starch and mixture of gum arabic along with
succinylated starch. This is due to the fact that succinylation of starch leads to addition of
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hydrophilic negatively charged succinyl groups which gives hydrophilic nature to that starch
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[28]. The encapsulation efficiency for all the samples varied from 74.46-95.38%. On other hand,
50.52-83.60% EE was observed by Kausadikar [34] by using gum arabic, modified starch and
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maltodextrin for lemon oil. In current study, the sample containing GA: OSA starch resulted in
higher EE%, good retention of oil and lower surface oil in comparison with the samples
comprising of gum arabic with native sorghum starch that showed a high encapsulation and oil
retention but also resulted in slightly higher values for surface oil then previous samples and
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The oxidative stability of nutmeg oleoresin encapsulated in different combinations of binary wall
system comprising of gum arabic and sorghum starch at 4⁰C and 25⁰C was calculated by their
peroxide values (PV). The results are shown in fig 1, for oxidative stability of microcapsules
correspond to native, OSA and SUC starch as wall material with gum arabic. The peroxide value
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of bulk oil at both temperatures in comparison to encapsulated oil was evaluated for 6 weeks. At
1st day, the bulk oil at both temperature had the starting PV of 0.0766 meqv kg-1 and 0.0805
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meqv kg-1 respectively while all the encapsulated samples showed the PV lower than bulk oil
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ranged from 1.21x10-4 meqv kg-1 for the sample GA: NA (25:75) and 7.5x10-4 meqv kg-1 for the
sample comprising of native starch only. The most elevated value for bulk oil at 4⁰C for PV was
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observed on 3rd week that was 2.3229 meqv kg-1 while for 25⁰C; the elevated value observed
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was 1.992 meqv kg-1 on 4th week. All the encapsulated samples showed that there is no
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significant increase in the PV in all the samples during six weeks of study. The results showed
that encapsulated samples were stable during six weeks of storage at ambient and refrigerated
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temperatures. The peroxide value was slightly decreased in bulk oil sample after 3 rd and 4th week
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at both refrigerated and ambient temperatures. This implies that all the different combinations of
gum arabic with native and modified sorghum starch samples were more stable against oxidation
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than bulk oil. Similar to the present work Frascareli, et al., [19]; Bae and Lee [27] observed that
bulk and encapsulated coffee and avocado oil were stable during storage under refrigeration and
at room temperature as compare to oil samples stored at 60⁰C as peroxide index increased at
higher temperatures. Oxygen is of main concern in the formation of primary oxidation products
and controlling these reactions is important to avoid off flavor formation in foods. In bulk fats
and oils, mechanism of oxidations is well known as compared to the dispersed liquid phase
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which is complicated due to different compositional and structural behavior. There are many
factors which affected the oxygen permeability of the wall matrix and determined the oxidative
stability of the core material. These factors include porosity of wall material, biopolymer
composition, moisture content and glass transition temperature of biopolymers [27], [36]. Pores
were not observed in the morphology of spray dried powders and microcapsules showed low
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moisture content. Therefore, the permeability of oxygen is limited which in turn minimized the
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lipid oxidation. In carbohydrate glasses, such as starch, transportation of oxygen is minimized by
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solubility and diffusion of oxygen which in turn is affected by the amount of water content
present in carbohydrates. Considering all these facts, it can be concluded that the whole
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encapsulating system has reduced the lipid oxidation by interrupting oxygen permeation.
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3.10. Powder morphology
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microencapsulated systems for example flow properties, entrapment of core material and
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protection of core material from the surroundings depends upon their morphology. Fig 2a, 2b and
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combinations of gum arabic and sorghum starch (native and modified). All powder samples
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powder samples showed spherical shape microgranules with various sizes which is the typical
characteristic of spray dried powder [19]. The microgranules have no apparent crack, holes and
fracture on external surfaces which concluded that capsules have lower permeability to gases,
enhanced protection and retention of core material. The samples comprising of 75% gum arabic
along with 25% native and modified starches (OSA and succinylated) showed spherical shape
with extensive dented surfaces while smoothness on the surface of powder samples improved as
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the percentage of starch (native and modified) increased in each sample. Round and smooth
surfaces with no dents was observed in samples consisting of native and modified starches as a
whole. It is suggested that depressions are formed as a result of mechanical stress encouraged by
irregular drying at different parts of the liquid droplets produced during the early stages of spray
drying, to the transfer of moisture during the non saturated surface drying period and as a result
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of surface tension-viscous flow [35]. The particle size distribution of spray dried microcapsules
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is shown in figure 3a, 3b and 3c. Most of the curves showed three distinct peaks while few
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presented bimodal behavior (two peaks). Most of the particles were observed to have first broad
peak corresponding to mean particle diameter of approximately 1-5µm. The samples comprised
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of 100% starch (both native and modified) and showed broad peaks between 5-10µm. Similar
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results were also obtained by Fernandes et al., [20]. The author observed that the particle size
was significantly affected by the type of wall material and resulted in largest particle size when
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starch was used [21].The particle size distribution for the spray dried microcapsules of samples
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GA: NAT (75:25), (50:50), (25:75) and (0:100) ranged from (2.8-14.3) µm, (2.2-19.8) µm, (2.0-
21.9) µm and (3.7-18.5) µm respectively. For the microcapsules comprising of OSA modified
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starch, the particle size for spray dried microcapsules of sample GA: OSA (75:25), (50:50),
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(25:75) and (0:100) ranged from (2.4-11.6) µm, (2.3-18.1) µm, (1.3-19.0) µm and (6.8-21.04)
µm respectively. The particle size distribution for the spray dried microcapsules of samples GA:
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SUCCI (75:25), (50:50), (25:75) and (0:100) ranged from (2.0-23.1) µm, (2.7-22.7) µm, (2.1-
Conclusion
In current study, it was possible to encapsulate nutmeg oleoresin by spray drying method using
gum arabic, native sorghum starch and modified sorghum starch (succinylated and OSA) as wall
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materials. Most of the emulsion formulations showed better stability after 24 h except the blends
comprising of starch as a whole. The spray dried nutmeg microcapsules had poor flowing
properties but contained lower moisture content values. While hygroscopicity, cold water
solubility and powder wettability decreased as the ratio of gum arabic decreased. The spray dried
powder samples showed spherical shaped microgranules with various sizes with no apparent
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crack, holes and fracture on external surfaces. The studied wall matrices comprising of 25%
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OSA sorghum starch with 75% gum arabic and 75% native sorghum starch along with 25% gum
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arabic resulted in high oil retention and encapsulation efficiency. Based on results, it could be
concluded that native sorghum starch and octenyl succinic anhydride (OSA) starch, in different
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combinations with gum arabic, is a suitable wall material for the production of nutmeg capsule
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with functional claims and enhancing the potential of developing novel formulations of
encapsulants.
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References
Evaluation of blends of gum arabic, maltodextrin and a modified starch as wall materials,
CE
drying using different wall materials, Drying Tech. 24(8) (2006) 983-992.
peppermint (Mentha piperita L.) essential oil spray-dried in modified starches during
encapsulation and storage, J. agric & food Chem. 55(8) (2007) 3027-3036.
21
ACCEPTED MANUSCRIPT
drying in microencapsulation of food ingredients: An overview, Food Res. Intl. 40(9) (2007)
1107-1121.
T
[6] H. Umer, H. Nigam, A.M. Tamboli, M.S.M. Nainar, Microencapsulation: Process, techniques
IP
and applications, Intl. J. Res. pharma. and biomed. Sci. 2(2) (2011) 474-481.
CR
[7] S. Bansode, S. Banarjee, D. Gaikwad, S. Jadhav, R. Thorat, Microencapsulation: a review,
US
[8] B. Raghavan, K. Abraham, M. Shankaranarayana, Encapsulation of spice and other flavour
AN
materials, Ind. Perfumer 34(1) (1990) 75-85.
cardamom oil by spray drying technique, J. Food Sci. Tech. 25(6) (1988).
ED
modified tapioca starch, native tapioca starch and maltodextrin, Food hydrocoll. 21(5) (2007)
CE
928-935.
[12] V.G. Reddy, H. Upadhyaya, C. Gowda, Current status of sorghum genetic resources at
AC
ICRISAT: their sharing and impacts, Intl. Sorghum and Millets Newsletter 47 (2006) 9-13.
[13] S. Mehboob, T.M. Ali, F. Alam, A. Hasnain, Dual modification of native white sorghum
(Sorghum bicolor) starch via acid hydrolysis and succinylation, LWT-Food Sci. Tech. 64(1)
(2015) 459-467.
22
ACCEPTED MANUSCRIPT
[15] A. Moin, T.M. Ali, A. Hasnain, Effect of succinylation on functional and morphological
properties of starches from broken kernels of Pakistani Basmati and Irri rice cultivars, Food
T
Chem. 191 (2016) 52-58.
IP
[16] O. Wurzburg, Acetylation, Methods in carbohyd. Chem. 4 (1964) 286-288.
CR
[17] R. Bhosale, R. Singhal, Process optimization for the synthesis of octenyl succinyl derivative
of waxy corn and amaranth starches, Carbohyd. Polym. 66(4) (2006) 521-527.
US
[18] C.I. Park, W.-G. Cho, S.J. Lee, Emulsion stability of cosmetic creams based on water-in-oil
AN
high internal phase emulsions, Korea-Australia Rheology J. 15(3) (2003) 125-130.
microencapsulation of coffee oil by spray drying, Food bioproducts processing 90(3) (2012) 413-
ED
424.
[20] R.V. de Barros Fernandes, S.V. Borges, D.A. Botrel, Gum arabic/starch/maltodextrin/inulin
PT
as wall materials on the microencapsulation of rosemary essential oil, Carbohyd. Polym. 101
CE
(2014) 524-532.
[21] J. Singh, N. Singh, Studies on the morphological and rheological properties of granular cold
AC
water soluble corn and potato starches, Food hydrocoll. 17(1) (2003) 63-72.
[23] F. Xue, C. Li, Y. Liu, X. Zhu, S. Pan, L. Wang, Encapsulation of tomato oleoresin with zein
prepared from corn gluten meal, J. Food Eng. 119(3) (2013) 439-445.
23
ACCEPTED MANUSCRIPT
[24] L. Tan, L. Chan, P. Heng, Effect of oil loading on microspheres produced by spray drying,
humidity on oxidation of flaxseed oil in spray dried whey protein emulsions, J. Agri. Food
T
Chem. 56(14) (2008) 5717-5722.
IP
[27] E. Bae, S. Lee, Microencapsulation of avocado oil by spray drying using whey protein and
CR
maltodextrin, J. Microencapsulation 25(8) (2008) 549-560.
US
Starch modification by organic acids and their derivatives: A Review, Molecules 20(10) (2015)
AN
19554-19570.
[29] C. Chranioti, C. Tzia, Arabic gum mixtures as encapsulating agents of freeze-dried fennel
M
[30] R. Chanamai, D. McClements, Comparison of gum arabic, modified starch, and whey
protein isolate as emulsifiers: influence of pH, CaCl2 and temperature, J. Food Sci. 67(1) (2002)
PT
120-125.
CE
and oxidation resistant superhard coating materials, Surface Coatings Tech. 86 (1996) 394-401.
AC
[32] B. Cuq, E. Rondet, J. Abecassis, Food powders engineering, between knowhow and science:
[33] C. Vega, Y. Roos, Invited review: spray-dried dairy and dairy-like emulsions—
24
ACCEPTED MANUSCRIPT
drying and its application in flavour tea, Adv. Appl. Sci. Res 6 (2015) 69-78.
whey proteins or mixtures of whey proteins and lactose, Food Structure 12(4) (1993) 6.
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Figure caption
Fig. 1. Oxidation stability of bulk and encapsulated nutmeg oil in microcapsules at 4⁰C and
25⁰C. NAT A: gum arabic75% & native sorghum starch 25%; NAT B: gum Arabic 50% &
native sorghum starch 50%; NAT C: gum arabic 25% & native sorghum starch 75%; NAT D:
100% native sorghum starch; OSA A: gum arabic 75% & modified OSA starch 25%; OSA B:
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gum arabic 50% & modified OSA sorghum starch 50%; OSA C: gum arabic 25% & modified
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OSA sorghum starch 75%; OSA D: 100% modified OSA sorghum starch; SUC A: gum
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arabic75% and modified succinylated sorghum starch 25%; SUC B: gum arabic 50% and
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modified succinylated sorghum starch 50%; SUC C: gum Arabic 25% and modified succinylated
sorghum starch 25% , (b) gum arabic 50% & native sorghum starch 50%, (c) gum arabic 25%
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& native sorghum starch 75%, (d) 100% native sorghum starch.
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Fig. 2b. SEM of the microcapsules prepared from a) gum arabic 75% & modified OSA starch
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25%, (b) gum arabic 50% & modified OSA sorghum starch 50%, (c) gum arabic 25% &
modified OSA sorghum starch 75%, (d) 100% modified OSA sorghum starch
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Fig. 2c. SEM of the microcapsules prepared from a) gum arabic 75% & modified succinylated
sorghum starch 25%, (b) gum arabic 50% & modified succinylated sorghum starch 50%, (c) gum
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arabic 25% & modified succinylated sorghum starch 75%, (d) 100% modified succinylated
sorghum starch.
Fig. 3a. Particle size distribution of the nutmeg microcapsules prepared from (a) gum arabic
75% & native sorghum starch 25% , (b) gum arabic 50% & native sorghum starch 50%, (c)
gum arabic 25% & native sorghum starch 75%, (d) 100% native sorghum starch.
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Fig. 3b. Particle size distribution of the microcapsules prepared from a) gum arabic 75% &
modified OSA starch 25%, (b) gum arabic 50% & modified OSA sorghum starch 50%, (c) gum
arabic 25% & modified OSA sorghum starch 75%, (d) 100% modified OSA sorghum starch
Fig. 3c. Particle size distribution of the microcapsules prepared from a) gum arabic 75% &
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modified succinylated sorghum starch 25%, (b) gum arabic 50% & modified succinylated
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sorghum starch 50%, (c) gum arabic 25% & modified succinylated sorghum starch 75%, (d)
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100% modified succinylated sorghum starch
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Table 1
Degree of substitution of chemically modified white Sorghum starches and particle size analysis a
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OSA sorghum starch 0.0232±0.00a 13.65±0.03b
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Succinylated sorghum starch 0.0709±0.08b 12.41±0.04a
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a
Values are the mean of three different replications. Different superscript letters within first column are significantly
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*Not Determined
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Table 2
Mean values and standard deviations for emulsion stability, viscosity, mean droplet size and flowing properties of nutmeg microcapsules a
1.00±0.00d
d3,2(µm)
2.82±0.00d
(mPa.s)
44.67±9.29a,b
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(gm/ml)
S
0.356±0.04d 1.67±0.023d 39.93±1.65d
GA:NAT(75:25)
1.00±0.00d 2.36±0.00a A
32.00±2.00b,c,d 0.418±0.04d 1.65±0.035d 39.39±1.50d
GA:NAT(25:75)
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GA:NAT(0:100) 0.73±0.06b 3.30±0.00h
GA:OSA(75:25) 0.90±0.00c
0.80±0.00b P T
2.62±0.00c
3.63±0.00i
48.67±12.58e
44.00±9.64d,e
0.302±0.04c
0.331±0.04b
1.53±0.036b,c
1.68±0.03b,c
34.09±1.48c
40.78±1.28d
E
GA:OSA(50:50)
GA:OSA(25:75) 0.80±0.00b
GA:OSA(0:100)
GA:SUC(75:25)
A
0.63±0.15a
1.00±0.00d
4.31±0.00k
2.84±0.00e
30.67±5.13a,b,c,d
42.00±3.60c,d,e
0.324±0.04a
0.308±0.04d
1.48±0.046a,b
1.51±0.012b
32.36±2.22a,b,c
33.71±0.66b,c
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GA: gum arabic; NAT: native sorghum starch; OSA: octenyl succinic anhydride sorghum starch; SUC: succinylated sorghum starch
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S C
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Table 3
Mean values and standard deviations for moisture content, hygroscopicity, cold water
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(min)
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GA:NAT(75:25) 1.94±0.6a 11.06±0.82d,e 75.20±2.45f 8.14±0.91e,f
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GA:NAT(25:75) 1.95±0.15a 5.64±1.01a 27.33±6.38b,c 3.48±0.67b
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GA:NAT(0:100) 1.85±0.61a 4.57±0.41a 2.72±0.67a 0.53±0.57a
different at p≤0.05.
GA: gum arabic; NAT: native sorghum starch; OSA: octenyl succinic anhydride sorghum starch; SUC: succinylated
sorghum starch
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Table 4
Mean values for surface oil, total oil, retention of oil and encapsulation efficiency of the
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GA:NAT(75:25) 0.79±0.82d 6.89±0.00b 68.9±0.00d 88.51±0.91c,d
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GA:NAT(50:50) 0.48±0.79a,b,c 5.19±1.27a,b 58.55±7.07b,c,d 91.97±0.95d,e,f
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GA:NAT(25:75) 1.51±0.82f 9.50±0.71c 95±7.07e 84.07±2.07b
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GA:OSA(75:25) 0.24±0.10a 5.21±0.28a,b 52.1±2.80a,b,c,d 95.38±0.00f
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GA:OSA(50:50) 0.29±0.00a 6.22±0.00a,b 62.30±0.02c,d 90.36±0.00c,d,e
microcapsulesa
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a
Values are the mean of three different replications. Different superscript letters within each column are significantly
different at p≤0.05.
GA: gum arabic; NAT: native sorghum starch; OSA: octenyl succinic anhydride sorghum starch; SUC: succinylated
sorghum starch
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Highlights
The combinations of gum arabic and OSA starch resulted in high oil retention.
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The microgranules had no apparent crack, holes and fracture on external surfaces.
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Figure 1
Figure 2a
Figure 2b
Figure 2c
Figure 3