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Microencapsulation of Cinnamon Oleoresin by Spray


Drying Using Different Wall Materials
a a a
Swapnali Vaidya , Rajesh Bhosale & Rekha S. Singhal
a
Food Engineering and Technology Department, Institute of Chemical Technology, University
of Mumbai, Matunga, Mumbai, India
Version of record first published: 06 Feb 2007.

To cite this article: Swapnali Vaidya, Rajesh Bhosale & Rekha S. Singhal (2006): Microencapsulation of Cinnamon Oleoresin by
Spray Drying Using Different Wall Materials, Drying Technology: An International Journal, 24:8, 983-992

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Drying Technology, 24: 983–992, 2006
Copyright # 2006 Taylor & Francis Group, LLC
ISSN: 0737-3937 print/1532-2300 online
DOI: 10.1080/07373930600776159

Microencapsulation of Cinnamon Oleoresin by Spray Drying


Using Different Wall Materials
Swapnali Vaidya, Rajesh Bhosale, and Rekha S. Singhal
Food Engineering and Technology Department, Institute of Chemical Technology, University of
Mumbai, Matunga, Mumbai, India
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it is most cost effective, produces microcapsules in a rela-


Microencapsulation of spice oleoresin is a proven technology to tively simple continuous processing operation, and is most
provide protection against degradation of sensitive components suited for the encapsulation of spice oils and oleoresins.[3,4]
present therein. The present work reports on the microencapsulation More than 90% of the microencapsulated flavors are pro-
of cinnamon oleoresin by spray drying using binary and ternary duced by this method.[5] In spray drying of hydrophobic
blends of gum arabic, maltodextrin, and modified starch as wall
materials. The microcapsules were evaluated for the content and flavors, the first step is its emulsification in the solution
stability of volatiles, entrapped and total cinnamaldehyde content of desired wall material followed by atomization in hot
for six weeks. A 4:1:1 blend of gum arabic:maltodextrin:modified air, evaporation of water, and separation of product.
starch offered a protection, better than gum arabic as seen from Numerous studies have been conducted to evaluate the
the t1/2; i.e., time required for a constituent to reduce to 50% of retention and stability of flavors during spray drying con-
its initial value.
ditions. Microencapsulation protects oleoresin against
destructive changes, converts it into a free-flowing powder,
Keywords Cinnamon oleoresin; Gum arabic; Maltodextrin;
Microencapsulation; Modified starch; Spray drying and protects the flavor from undesirable interaction with
food and flavor-to-flavor interaction.[3] Many studies have
been carried out on the influence of drying conditions and
INTRODUCTION the composition of wall materials, different types of emul-
Spice oleoresins exhibit a flavor profile closely related to sifiers on retention of emulsified flavors during spray dry-
fresh ground spices. They are concentrated and have good ing, and the shelf-life of the encapsulated flavors.[6–12] An
replacement value compared to spice powders. However, area of research of increasing interest is the development
they are susceptible to degradation in the presence of air, of an alternative and inexpensive polymer or polymer
light, moisture, and high temperatures and have short blends, that could encapsulate flavors with the same or
storage life if not stored properly. To resolve this problem, greater efficiency than gum arabic. Gum arabic in combi-
microencapsulation is a useful tool. nation with maltodextrin and modified starch are known
Microencapsulation is process in which particles of an to give a better encapsulation efficiency and stability than
active and sensitive ingredient are formed and covered with gum arabic.[13–16]
a thin layer of another material, thus providing protec- Among the spices, cinnamon is widely used in seasoning
tion.[1,2] The composition of the coating material deter- and condiments. Oleoresin of cinnamon is deep reddish
mines the functional properties of the microcapsules. The brown in color and has cinnamaldehyde (approx. 90%) as
most common materials are hydrocolloids, vegetable gums, its main constituent. Cinnamaldehyde is sensitive to light
modified starches, dextrins, and lipids. Techniques such as and oxygen. Microencapsulation helps to stabilize oleoresin
spray drying, spray cooling, fluidized bed drying, by preventing against volatile losses. There are very few
extrusion, centrifugal extrusion, coacervation, liposome reports on encapsulation of spice oleoresin by spray drying.
entrapment, co-crystallization, rotational suspension sep- Microencapsulation of capsicum oleoresin in a gum mixture
aration and molecular inclusion can be used for microen- composed of carrageenan and maltodextrin at a ratio of
capsulation. Among these, spray drying is attractive since 0.5–3.5:9.5–7.0 was studied.[17] Spray drying has also has
been used to encapsulate paprika oleoresin and several vol-
Correspondence: Rekha S. Singhal, Food Engineering and atile esters in gum arabic.[18] Microencapsulation of red
Technology Department, Institute of Chemical Technology, Uni- pepper oleoresin using gum arabic and modified starch
versity of Mumbai, Matunga, Mumbai 400 019, India; E-mail:
rekha@udct.org has also been tried.[19] Spray-dry microencapsulation has

983
984 VAIDYA, BHOSALE, AND SINGHAL

been used to improve the stability of carotenoids in carrot


pulp and paprika oleoresin.[20] A 4:1:1 blend of gum arabic,
maltodextrin, and modified starch has also shown better
encapsulation efficiency and stability for cardamom oleo-
resin as compared to gum arabic.[21]
Numerous operating parameters, geometric parameters,
and feed properties affect the performance of spray dryers
both in terms of heat and mass transfer as well as the par-
ticle size distribution and morphology of spray-dried pro-
ducts. For scaling up of spray-drying operation, these
parameters are extremely essential. Interested readers are
encouraged to go through process details of spray drying
mentioned recently by few authors.[22,23] Recent reviews
on microencapsulation processes and their applications
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have provided excellent information on microencapsula-


tion with a broader outlook.[24–26] Readers are encouraged
to visit websites mentioned in references.[27] There are very
few reports on encapsulation of cinnamon oleoresin. The
present work investigates microencapsulation of cinnamon
oleoresin using gum arabic, maltodextrin, and modified
starch (Hi-Cap 100) as such and in binary and ternary mix- FIG. 1. Stability of total cinnamaldehyde (TC) in microencapsulated
tures using the well-known and intensively used industrial cinnamon oleoresin prepared from gum arabic–maltodextrin blend.
process of spray drying. The microcapsules were evaluated
for the content and stability of volatiles and entrapped and
total cinnamaldehyde. Scanning electron microscopy was height, 60 cm diameter) equipped with a 0.5-mm-diameter
used to observe the structural characteristics of encapsu- nozzle. The pressure of compressed air for the flow of the
lated powder. spray was adjusted to 3 bars. The inlet and outlet tempera-
ture were maintained at 160  2C and 120  5C, respect-
MATERIALS AND METHODS ively. A peristaltic pump was used to feed the spray dryer
at 300 g=h. The microcapsules prepared were collected from
Materials
Gum arabic was obtained as a gift sample from TIC
Gums, Belcamp, MD. Modified starch (Hi Cap100) was
obtained from National Starch Chemicals Corporation,
Mumbai, India. Maltodextrin (DE –18) was obtained
from Raptokos Brett Co., Ltd, Thane, Mumbai, India.
Cinnamon oleoresin was a gift sample from Plant Lipids
Pvt. Ltd., Cochin, India. Standard cinnamaldehyde was
procured from Quest International, Mumbai, India. All
chemicals were of AR grade.

Preparation of Microcapsules by Spray Drying


A 30% w=v solution of the different blends of gum ara-
bic, maltodextrin, and the commercial modified starch Hi-
Cap 100 were dispersed in distilled water to final volume of
100 mL. It was rehydrated for about 12 h at refrigerated
temperature (10–12C). Three grams (10% based on the
carrier used) of oleoresin was added to the mixture. The
mixture was emulsified in a shear homogenizer (Indofrench
Industries Engineers, Mumbai, India; Model type- SPM-9)
for 5 min at 3000 rpm until complete dispersion of the
oleoresin. Two drops of Tween-80 was added for proper
emulsification. The resulting slurry was spray-dried in a JISL FIG. 2. Stability of entrapped cinnamaldehyde (EC) in microencapsu-
LSD-48 mini spray dryer (inside chamber dimension: 100 cm lated cinnamon oleoresin prepared from gum arabic–maltodextrin blend.
MICROENCAPSULATION OF CINNAMON OLEORESIN 985
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FIG. 3. Stability of total volatiles (TV) in microencapsulated cinnamon oleoresin prepared from gum arabic–maltodextrin blend.

the collecting chamber and filled in airtight, self-sealable analysis for entrapped cinnamaldehyde (EC). Known quan-
polyethylene pouches. These pouches were stored in a dessi- tity of microcapsules was taken in 50-mL standard conical
cator for further study. flask and 10 mL of hexane was added to wash the surface
components.[30] The conical flask was shaken vigorously
Analysis of Spray Dried Microcapsules for 5 min. After 10 min, the microcapsules were filtered;
Analysis of Entrapped Cinnamaldehyde Content (EC) residual hexane was removed partly to estimate entrapped
To evaluate the ability of these carrier materials as a fla- cinnamaldehyde. Microcapsules of 1.2 g were taken in a
vor carrier, the spray-dried microcapsules were subjected to 50 mL standard conical flask and 8 mL of water was added.

TABLE 1
Regression analysis of EC, TC, and TV, in the microcapsules prepared from gum arabic:maltodextrin blend as wall
materials
Constituent in microencapsulated cinnamon oleoresin
EC TC TV
Encapsulating Regression t1=2 Regression t1=2 Regression t1=2
material equation (Weeks) equation (Weeks) equation (Weeks)
GA:MD Y ¼ 0.0119X þ 4.60 58.24 Y ¼ 0.0207X þ 4.60 33.48 Y ¼ 0.0115X þ 4.60 60.26
(0:100) R2 ¼ 0.96 R2 ¼ 0.97 R2 ¼ 0.95
GA:MD Y ¼ 0.0099X þ 4.60 70.00 Y ¼ 0.0180X þ 4.61 38.50 Y ¼ 0.0096X þ 4.59 72.10
(25:75) R2 ¼ 0.96 R2 ¼ 0.96 R2 ¼ 0.93
GA:MD Y ¼ 0.0069X þ 4.59 100.43 Y ¼ 0.0150X þ 4.60 46.20 Y ¼ 0.0066X þ 4.60 105.00
(50:50) R2 ¼ 0.92 R2 ¼ 0.99 R2 ¼ 0.96
GA:MD Y ¼ 0.067X þ 4.60 103.43 Y ¼ 0.0126X þ 4.61 55.00 Y ¼ 0.0060X þ 4.60 115.50
(75:25) R2 ¼ 0.89 R2 ¼ 0.94 R2 ¼ 0.99
GA:MD Y ¼ 0.0046X þ 4.60 150.65 Y ¼ 0.0117X þ 4.60 59.23 Y ¼ 0. 0040X þ 4.60 173.25
(100:0) R2 ¼ 0.97 R2 ¼ 0.97 R2 ¼ 0.98
986 VAIDYA, BHOSALE, AND SINGHAL

TABLE 2
Regression analysis of EC, ETA, and TV in the microcapsules prepared from gum arabic:modified starch
blend as wall materials
Constituent in microencapsulated cinnamon oleoresin
EC TC TV
Encapsulating Regression t1=2 Regression t1=2 Regression t1=2
material equation (Weeks) equation (Weeks) equation (Weeks)
GA:MS Y ¼  0.0140X þ 4.60 49.50 Y ¼  0.0154X þ 4.60 45.00 Y ¼  0.0136X þ 4.59 50.96
(0:100) R2 ¼ 0.96 R2 ¼ 0.96 R2 ¼ 0.95
GA:MS Y ¼  0.0126X þ 4.60 55.00 Y ¼  0.0180X þ 4.61 38.50 Y ¼  0.0111X þ 4.60 62.43
(25:75) R2 ¼ 0.98 R2 ¼ 0.96 R2 ¼ 0.90
GA:MS Y ¼  0.0104X þ 4.60 66.63 Y ¼  0.0150X þ 4.60 46.20 Y ¼  0.0100X þ 4.61 69.30
(50:50) R2 ¼ 0.95 R2 ¼ 0.99 R2 ¼ 0.86
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GA:MS Y ¼  0.0078X þ 4.60 88.85 Y ¼  0.0126X þ 4.61 55.00 Y ¼  0.0075X þ 4.60 92.40
(75:25) R2 ¼ 0.97 R2 ¼ 0.94 R2 ¼ 0.96
GA:MS Y ¼  0.0046X þ 4.60 150.65 Y ¼  0.0117X þ 4.60 59.23 Y ¼  0.0040X þ 4.60 173.25
(100:0) R2 ¼ 0.97 5 R2 ¼ 0.97 R2 ¼ 0.98

The conical flask was shaken vigorously to dissolve in the volume was measured with measuring cylinder. One gram
water. Dichloromethane (12 mL) was added to this while of Na2SO4 was added and the extract was filtered. Ten milli-
shaking. The mixture was transferred to a 125-mL separat- liters of the extract was transferred to a 10-mL standard
ing funnel and 8-mL of ethanol was added. The separating volumetric flask in which 20 mg of hexadecane was added.
funnel was shaken properly and allowed to stand for 5 min One microliter was injected in the column of the GC. The
to separate into layers. The bottom layer (dichloromethane) entrapped cinnamaldehyde content was then estimated
was taken in a 25-mL standard volumetric flask. The using the standard curve. The gas chromatography system

FIG. 4. Stability of total cinnamaldehyde (TC) in microencapsulated cinnamon oleoresin prepared from gum arabic–modified starch blend.
MICROENCAPSULATION OF CINNAMON OLEORESIN 987

used was Chemito GC8610 model, India. Chromatography TABLE 3


was performed using 5% SE 30 on chromosorb W-HP, Design centrum for blending gum arabic, maltodextrin,
80-100 mesh (4 m, 1/8" outer diameter, S.S. column) with and modified starch for effective encapsulation
carrier gas nitrogen (35 ml/min.) and an oven temperature Resulting coordinates of mixture experiment in the
programme comprising of an injector temperature of 240C, sub-region defined by pseudo-components
initial temperature of 100C for 0 min., temperature
increase was from 100–120C at 9C/min., held for 1 min, Coordinates Gum Maltodextrin Modified
then 120–124C at 3.4C/min., held for 4.30 min. Further arabic (%) (%) starch (%)
temperature was increased from 124–138C at 3.2C/min., (1=3, 1=3, 1=3) 49.75 25.12 25.12
and then finally 138–240C at 9C/min. Temperature of (4=6, 1=6, 1=6) 74.50 12.75 12.75
flame ionization detector was maintained at 250C. (1=6, 1=6, 4=6) 36.25 12.75 51.00
(1=6, 4=6, 1=6) 36.25 51.00 12.75
Analysis for Total Cinnamaldehyde Content (TC)
Total retention of this character impact constituent was
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carried out by the same method as adopted for the distilled water was added, sonicated for 1 min. The mixture
estimation of EC, without subjecting the microcapsules to was quantitatively washed with water into a separating
preliminary washing by hexane. funnel and allowed to stand until the layers separated. The
bottom layer was drawn into another separating funnel. To
Analysis for Total Volatiles (TV) and Nonvolatile Ether this fraction, a mixture of 8-mL diethyl ether and 2-mL
Extract (NV) ethyl alcohol was added, shaken well, and the phases were
The method entails organic-solvent extraction of the allowed to separate. The bottom water layer was drained
nonvolatile material from a water solution. The nonvolatile into a weighed flask. The ether extracts were combined
entrapped phase is separated from the encapsulating agent and washed with a 2-mL portion of water to ensure com-
and the amount extracted by the organic solvent can be plete removal of the water-soluble components. These
determined by weighing the evaporation residue.[31] materials were then transferred to the weighed flask to
Two hundred milligrams of the sample was weighed determine the water-soluble fractions. The combined ether
accurately. To this, 10-mL of diethyl ether and 3 mL extract was transferred to another weighed boiling flask,

FIG. 5. Stability of entrapped cinnamaldehyde (EC) in microencapsulated cinnamon oleoresin prepared from gum arabic–modified starch blend.
988 VAIDYA, BHOSALE, AND SINGHAL
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FIG. 6. Stability of total volatiles (TV) in microencapsulated cinnamon oleoresin prepared from gum arabic–modified starch blend.

the solvents evaporated, and the flask was dried for 2–4 h Stability of the EC and TC, Volatiles and Nonvolatiles
in an oven at 105C. The results were reported as non- of the Microcapsules
volatile ether extract (NV) and percent ether extract (EE) The samples were analyzed over a period of 6 weeks for
as follows. entrapped cinnamaldehyde (EC), total (TC), and also for
total volatiles (TV) and nonvolatiles (NV). The percentage
1. % NV ¼ Re=S  100, In which S ¼ weight of sample
retention of all these analytes was calculated by the for-
and Re ¼ weight of ether soluble residue.
mula (analyte at X storage time)  100=(analyte at zero
2. % EE ¼ 100 þ W–(Rw=S  100), in which, S ¼ Weight
of sample, Rew ¼ weight of water-soluble residue, and storage time). A semi-log plot of percentage retention of
all these analytes vs. time was done to obtain the rate con-
W ¼ water content of sample.
stant (k) as the slope of the graph.[32] Half-life (t1=2) for the
3. % Volatiles ¼ % EE -%NV

TABLE 4
Regression analysis of EC, TC, and TV in the microcapsules prepared from the blends of gum arabic, maltodextrin, and
modified starch
GA:MD:MS t1=2 GA:MD:MS t1=2 GA:MD:MS t1=2 GA:MD:MS t1=2
(1=3,1=3,1=3) (Weeks) (4=6,1=6,1=6) (Weeks) (1=6,4=6,1=6) (Weeks) (1=6,1=6,4=6) (Weeks)
EC Y ¼  0.0070X þ 99.00 Y ¼  0.0045X þ 154.00 Y ¼  0.0107X þ 64.77 Y ¼  0.0105X þ 66.00
4.60 4.60 4.60 4.60
R2 ¼ 0.99 R2 ¼ 0.91 R2 ¼ 0.96 R2 ¼ 0.98
TC Y ¼  0.0109X þ 63.58 Y ¼  0.0091 þ 76.15 Y ¼  0.0166X þ 41.75 Y ¼  0.0132X þ 52.50
4.60 4.59 4.60 4.60
R2 ¼ 0.98 R2 ¼ 0.97 R2 ¼ 0.99 R2 ¼ 0.98
TV Y ¼  0.0067X þ 103.43 Y ¼  0.0039X þ 177.69 Y ¼  0.0104X þ 66.63 Y ¼  0.0098X þ 70.71
4.60 4.60 4.60 4.60
R2 ¼ 0.97 R2 ¼ 0.97 R2 ¼ 0.98 R2 ¼ 0.96
MICROENCAPSULATION OF CINNAMON OLEORESIN 989
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FIG. 9. Stability of total volatiles (TV) in microencapsulated cinnamon


oleoresin prepared from gum arabic–maltodextrin–modified starch blends.

retention of cinnamaldehyde was calculated from the rate


FIG. 7. Stability of total cinnamaldehyde (TC) in microencapsulated
cinnamon oleoresin prepared from gum arabic–maltodextrin–modified
constant as 0.693=k.
starch blend.
Scanning Electron Microscopy (SEM)
Particle size and structure of spray-dried microcapsules
were evaluated with scanning electron microscope, Philips
XL 30 (Netherlands). The microcapsules were mounted
on specimen stubs with double-sided adhesive carbon
tapes. The specimen was coated with gold-palladium and
examined at 10 kV.

RESULTS AND DISCUSSION


Analysis and Stability of EC, TC, NV, and TV in Free and
Encapsulated Oleoresin
The cinnamon oleoresin was analyzed for total volatiles
(77.18%) and nonvolatiles (22.82%). It also showed
74.91% of cinnamaldehyde. This oleoresin was evaluated
for six weeks at 25C for percent retention of cinnamalde-
hyde, total volatiles, and nonvolatiles. A semi-log plot of
percent of cinnamaldehyde and percent volatiles vs. storage
time showed a sharp linear decrease in all the cases, indicat-
ing the decrease in these constituents to follow first order
kinetics (data not given). The half life, t1=2, is the time
required for the reduction of a value to 50% of its original
was calculated from the slope k as t1=2 ¼ 0.693=k. The t1=2
of cinnamaldehyde and volatiles in the cinnamon oleoresin
stored at 25C was 30.80 and 33.48 weeks, respectively, indi-
FIG. 8. Stability of entrapped cinnamaldehyde (EC) in microencapsu- cating they are equally susceptible to storage conditions.
lated cinnamon oleoresin prepared from gum arabic–maltodextrin–modi- Oleoresin at 10% based on carrier material was mixed sep-
fied starch blend. arately with 30% gum arabic, maltodextrin, and modified
990 VAIDYA, BHOSALE, AND SINGHAL
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FIG. 10. SEM of the microcapsules prepared from gum arabic (a), maltodextrin (b), modified starch Hi-Cap100 (c), and the blends of GA:MD:MS
(4=6,1=6,1=6) (d).

starch slurry to prepare microcapsules. Microcapsules were were tried such as 25:75 (GA:MS), 50:50 (GA:MS), and
prepared by spray drying using maltodextrin, gum arabic, 75:25 (GA:MS), and the microcapsules so prepared were
modified starch, and the different blends of these three. studied for cinnamaldehyde and volatiles for a period of
Different proportions of gum arabic and maltodextrins six weeks (Figs. 4, 5, and 6). In this case also, a combination
were tried such as 25:75 (GA:MD), 50:50 (GA:MD), containing higher proportions of gum arabic provided better
75:25 (GA:MD) as wall materials and microcapsules entrapment of the constituents. The half-life of retention
obtained were compared to those prepared with the indi- in the said microcapsules is given in Table 2. As the
vidual wall material. Figures 1, 2, and 3 show the results concentration of the gum arabic increased, the half-life of
over six-week storage for TC, EC, and TV, respectively. the constituents increased showing greater stability of cinna-
The half-life of retention in the said microcapsules maldehyde and total volatiles in the microcapsules.
(Table 1) showed blend containing gum arabic to a larger None of the gum arabic–maltodextrin or gum arabic–
content to provide maximum protection. Mixture of gum modified starch blends could provide the protection offered
arabic and maltodextrin was reported effective in microen- by gum arabic. Hence, blends of gum arabic, maltodextrin,
capsulation of cardamom oil using a spray dryer.[12] As the and modified starch were taken for further study. Blends of
concentration of the gum arabic increased, the half-life of gum acacia, maltodextrins, and modified starches may rep-
the constituents increased. resent an encapsulating matrix with improved properties
The same procedure was followed for the modified starch. regarding flavor retention, emulsion stability, and protec-
Different proportions of gum arabic and modified starch tion against oxidation. An augmented simplex-centroid
MICROENCAPSULATION OF CINNAMON OLEORESIN 991

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