Article

pubs.acs.org/JAFC

Properties of Chitosan-Microencapsulated Orange Oil Prepared by

Spray-Drying and Its Stability to Detergents
Yue Li,†,§ Lianzhong Ai,† Wallace Yokoyama,# Charles F. Shoemaker,⊥ Dong Wei,§ Jianguo Ma,§
and Fang Zhong*,§
†
State Key Laboratory of Dairy Biotechnology, Technology Center of Bright Dairy and Food Company Ltd., Shanghai 200436,
People’s Republic of China
§
Key Laboratory of Food Colloids and Biotechnology, Ministry of Education, School of Food Science and Technology, Jiangnan
University, Wuxi 214122, People’s Republic of China
#
Processed Food Research, Agricultural Research Service, U.S. Department of Agriculture, Albany, California 94710, United States
⊥
Department of Food Science and Technology, University of California, Davis, California 95616, United States

ABSTRACT: Fragrance encapsulated in small particles of <20 μm diameter is preferred for use in textiles. This study
demonstrated that the proper combination of surfactants could produce small and heat-stable emulsion droplets with chitosan
that could be spray-dried to produce microcapsules. The microcapsules were able to be deposited onto cotton using water or
detergents. It was found that stable emulsion was obtained when Tween 40 and Span 20 were used as compound emulsifiers with
the ratio of 4:1 (w/w). The optimum conditions were 1% (w/w) chitosan in acetic acid with the compound emulsifiers of 3−7%
(w/w) in the oil, and the inlet temperature for spray-drying was 150 °C. The encapsulation efficiency for orange oil was >90%
with a 1:2 (w/w) ratio of oil to chitosan. Microcapsules had a mean diameter of <20 μm and regular particle morphology. The
orange oil in the microcapsules was well retained in cotton fabrics after washing in normal detergent solution. The process and
products are low in cost, nontoxic, biocompatible, and biodegradable.
KEYWORDS: microencapsulation, chitosan, orange oil, emulsion, encapsulation efficiency, retention properties

■ INTRODUCTION
The adsorption of perfumes and other fragrances onto solid
Some small microparticles have been reported recently.
Gordon prepared 5−10 μm microcapsules containing volatile
carrier materials has been of interest in textile manufacturers mint flavor core material;5 however, melamine formalin
because they can be more conveniently incorporated into polymerization was used. Interfacial polymerization was used
textiles. However, volatile fragrances bound to solid carriers by to produce polyurethane/urea (PUU) microcapsules with a
adsorption are easily removed during ordinary washing perfume-containing core for industrial application on a textile
processes by laundry detergents. To increase the persistence substrate for men’s suits.6 The mean particle size of those
of fragrance on textiles, the microencapsulation technology microcapsules was 10 μm. Ethylcellulose has also been used as
widely used by the food and pharmaceutical industries was the wall material to produce microcapsules that were grafted to
adapted by the detergent and fabric softener industries. textiles with particle size range of 10−90 μm.7 Gelatin and
Presently, the microencapsulated particles used in detergents polysaccharides have been used to produce microcapsules by
have an average particle size of ≤100 μm. It was reported that coacervation with particle size ranging from 50 to 100 μm for
microencapsulated particles of ≤20 μm are more easily use in fabric softeners or detergents.8
incorporated into textiles during the final washing step.1 Chitosan, a natural polysaccharide of glucosamine, and N-
Materials used for microencapsulation intended for wearable acetylglucosamine, prepared by partial deacetylation of chitin,9
textiles should be nontoxic, biocompatible, biodegradable, and have been used by the pharmaceutical industry for controlled
low in cost. Currently, the preferred encapsulating polymers are drug delivery systems of conventional drugs, protein drugs, and
prepared from melamine−formaldehyde or urea−formaldehyde DNA and may have potential for wearable textile applications.
condensates and other similar aminoplastics. Formaldehyde is a Chitosan microparticles have attracted increasing attention in
toxic chemical and probably should not be used in textiles that the past decade due to their unique properties including
come in close contact with the body. Capsule-coating materials nontoxicity, biocompatibility, and biodegradation.10,11 Numer-
made with gelatin via simple or complex coacervation may also ous controlled-release delivery systems of chitosan for either
be preferred. Capsules microencapsulated by shell wall implantation or oral delivery have been described in the
materials composed of polyurethane, polyamide, polyolefin, literature.12−14
polysaccharide, protein, silicone, lipid, modified cellulose, gums,
polyacrylate, polystyrene, and polyesters or combinations of Received: November 28, 2012
these materials are also known.2−4 The size of the micro- Revised: March 7, 2013
capsules prepared by these polymers is often too large for Accepted: March 8, 2013
textile applications. Published: March 8, 2013

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Journal of Agricultural and Food Chemistry Article

In addition to its nontoxicity, chitosan is an attractive Spray-Drying. A high-speed centrifugal spray-dryer (model QZ-5,
candidate for textiles because many processing techniques for Lizhou Co., Wuxi, China) was used to convert the emulsions into
the preparation of microcapsules have been developed since the encapsulated powders, as described by Jafari.22 The operational
conditions were as follows: air inlet temperature of 130, 150, or 170
1980s. Some of the principal approaches are ionotropic gelation °C; air outlet temperature of 80 °C; and sampling rate of material at
by oppositely charged, simple or complex coacervation; 1.2 L/h. The dry powder was collected and stored in hermetically
emulsification/solvent evaporation; and more recently, emulsi- sealed packages in a desiccator at room temperature until analysis.
fication/spray-drying.15 The latter process seems best suited for Emulsion Droplet Size and Powder Particle Size Analysis.
the development of controlled release volatile fragrances Laser light scattering with the Mastersizer 2000 (Malvern Instruments,
microcapsules based on the known properties of chitosan Worcestershire, UK) was used to determine the size distribution of oil
microparticles. Spray-dried chitosan microparticles are charac- droplets in the emulsions. Droplet size of the emulsion before and
terized by highly spheroid shape and high specific surface area, after thermal treatment was determined in triplicate. Analyses of
powder particle size and specific surface area of the powder particles
as well as small particle size. Fragrance encapsulated by chitosan were performed in triplicate using the laser light scattering method by
may be controlled or slowly released in water and alkali an analyzer with a batch cell unit (Mastersizer 2000). Encapsulated
conditions present in detergent solutions. In addition to useful powders were dispersed in water for all of the analyses. In all cases,
performance characteristics of spray-dried microparticles, the volume mean diameter or d43 was reported as the emulsion size or
spray-drying process can be applied on a large scale and is low powder particle size.
in cost. Viscosity Measurement. The viscosity of emulsions and chitosan
One of the research challenges to spray-drying encapsulation solutions (chitosan in aqueous acetic acid) was measured at 25 °C
over a shear rate range of 4−400 s−1 using a dynamic rheometer (AR-
is to minimize the amount of free or unencapsulated oil at the
1000, TA Co., Elstree, UK) equipped with flat-plate geometry (CP
surface of powder particles.16−18 Factors that affect the 40). All measurements were performed in triplicate within 24 h after
encapsulation efficiency of flavors and oils include the the emulsions were prepared.
properties of wall and core materials and the spray-drying Scanning Electron Microscopy (SEM) Measurement. Scanning
parameters, as well as the emulsifier characteristics.19−23 electron micrographs of spray-dried samples were recorded with a
Emulsification and the emulsifying ingredients play a key role Quanta-200 scanning electron microscope (FEI Co., Eindhoven, The
in this regard. There are some reports that smaller oil droplets Netherlands) at an accelerating voltage of 5 kV.28 The powders were
are more efficiently retained in the encapsulated product so that sprinkled onto double-backed cellophane tape attached to an
aluminum stub before coating with gold−palladium in an argon
the resulting microcapsules will have less free oil on the atmosphere.
surface.24,25 The application of small molecule surfactants for Encapsulation Efficiency and Retention Determination. The
microencapsulation development is an area that has not been encapsulation efficiency (EE) during the process was determined as
studied extensively because these surfactants do not have the amount of core material encapsulated inside the powder particles,
desirable encapsulation properties such as film-forming abilities. which can be obtained from the following formula:
The objective of this study is to determine the influence of
total oil content − surface oil content
different surfactants and their combinations on emulsifying EE (%) = × 100%
total oil content
effectiveness at high temperatures and the encapsulation
efficiency of spray-dried microencapsulated orange oil. The Total oil is the internal and surface oil content of the powder,
retention of the orange oil in fabrics after washing in normal whereas surface oil is only the unencapsulated oil at the surface of the
detergent solution was evaluated as well. particles. The surface oil, or free or extractable oil, is determined by

■
solvent extraction.
Due to the loss of volatiles during microcapsule preparation, the
MATERIALS AND METHODS term “retention” has been proposed, which was calculated as
Materials. Chitosan (DE = 50000) was provided by Anhui total oil content
Cigarette Factory (Hefei, China). Orange oil (Hua Bao Food Flavor retention (%) = × 100%
and Fragrance Co. Ltd., Shanghai, China) was used as the core original oil content
material. Nonionic surfactants, that is, Tween 20, 40, 60, and 80, Span Total Oil Measurement. Total oil was determined by solvent
20, monoglyceride, and sucrose polyesters SE-11 and SE-15, were extraction.29 Spray-dried powder (0.1 g) was combined with 10 g of
purchased from the National Chemical Co. (Shanghai, China). 1% acetic acid in a 50 mL centrifuge tube and stirred until the powder
Analytical grade hexane and anhydrous ether were from Sinopharm was completely dissolved. The orange oil released from the
Chemical Reagent Co., Ltd. (Shanghai, China). Distilled water was microcapsules was extracted with 50 mL of n-hexane for 10 min
used for the preparation of all solutions. All other chemicals used in three times. The extracts were collected in a 25 mL volumetric flask.
this study were of analytical grade. The content of orange oil in the extract was then determined by
Preparation of Emulsions. Chitosan (wall material) solution was measuring the absorbance at 202 nm (the maximum absorbance for
prepared by adding chitosan to 1% (w/w) aqueous acetic acid and orange oil in n-hexane by full wave scanning) in triplicate by a UV
stirring in a 45 °C water bath until completely dissolved. The core spectrophotometer (2802H, Unic Instruments Co., Ltd., Shanghai,
material, orange oil containing 3, 5, 7, or 10% surfactant by weight (in China).
oil), was progressively added to the continuous phase (chitosan Surface Oil Measurement. Spray-dried microcapsules (0.1 g
solution) during pre-emulsion preparation, and stirred for 1 min at each) were suspended in a known volume of anhydrous ether and
12500 rpm (T25, IKA Labortechnik, Germany). The surfactants used extracted for 10 min three times. The total extracts were collected by
for the pre-emulsion preparations were Tween 20, 40, 60, or 80 as centrifugation. The content of orange oil in the extract was determined
single emulsifier and Tween 40 with Span 20, monoglyceride, or by measuring the absorbance at 219 nm (the maximum absorbance for
sucrose polyesters SE-11 and SE-15 as compound emulsifiers at the orange oil in anhydrous ether by full wave scanning) in triplicate.29
ratio of 1:1, 7:3, 8:2, or 9:1. The coarse emulsions were then further Storage Stability. Spray-dried microcapsules (3 g each) or free
homogenized at 40 MPa (APV-1000, SPX Corp., Charlotte, NC, orange oil were placed in open glass beakers, and the beakers were
USA) for two cycles. Thermal treatment was carried out by boiling the placed in desiccators with relative humidity (RH) of 33 or 52%
emulsions for 3 min and then incubating in a water bath for 30 min at maintained by saturated MgCl2 or Mg(NO3)2 solutions, respectively.
60 °C before cooling in an ice water bath.26,27 The desiccators were then incubated at 25 and 45 °C. For the free

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Table 1. Droplet Size of Emulsions Formed with Different Emulsifiers before and after Heatinga
size of original size of heated size of original size of heated
single emulsifer emulsion emulsion compound emulsifers emulsion emulsion
10% (w/w) in oil (d43, μm) (d43, μm) Δμ (d43, μm)
b
(10% in oil, ratio 1:1) (d43, μm) (d43, μm) Δμb (d43, μm)
Tween 20 0.410 ± 0.009 2.277 ± 0.020 1.867 ± 0.030 Tween 40 + Span 20 0.178 ± 0.015 0.218 ± 0.005 0.040 ± 0.020
Tween 40 0.196 ± 0.003 0.988 ± 0.011 0.792 ± 0.015 Tween 40 + Span 40 0.244 ± 0.009 0.381 ± 0.008 0.137 ± 0.015
Tween 60 0.794 ± 0.015 2.106 ± 0.089 1.312 ± 0.020 Tween 40 + Span 60 0.185 ± 0.008 0.304 ± 0.009 0.119 ± 0.015
Tween 80 0.261 ± 0.019 2.542 ± 0.075 2.281 ± 0.020 Tween 40 + Span 80 0.198 ± 0.011 0.274 ± 0.013 0.076 ± 0.020
Tween 40 + 0.211 ± 0.021 0.781 ± 0.025 0.570 ± 0.045
monoglyceride
Tween 40 + SE-11 0.196 ± 0.025 0.325 ± 0.036 0.129 ± 0.055
Tween 40 + SE-15 0.191 ± 0.019 0.234 ± 0.031 0.043 ± 0.050
a
Values are the mean of triplicate measurements. Core material was orange oil, and 1 wt % chitosan in 1% acetic acid solution was wall material. The
weight ratio of oil to chitosan was 1:1. bΔμ = size of heated emulsion − size of original emulsion.

Table 2. Droplet Size of Emulsions Formed with Compound Emulsifers before and after Heatinga
ratio of compound size of original size of heated ratio of compound size of original size of heated
emulsiferc emulsion emulsion emulsiferc emulsion emulsion
Tween 40/Span 20 (d43, μm) (d43, μm) Δμ (d43, μm)
b
Tween 40/SE-15 (d43, μm) (d43, μm) Δμb (d43, μm)
1:1 0.178 ± 0.015 0.218 ± 0.005 0.040 ± 0.020 1:1 0.191 ± 0.005 0.234 ± 0.010 0.043 ± 0.015
7:3 0.211 ± 0.001 0.220 ± 0.002 0.009 ± 0.003 7:3 0.194 ± 0.009 0.240 ± 0.010 0.046 ± 0.020
8:2 0.224 ± 0.001 0.225 ± 0.001 0.001 ± 0.002 8:2 0.205 ± 0.006 0.225 ± 0.007 0.020 ± 0.015
9:1 0.200 ± 0.003 0.216 ± 0.005 0.016 ± 0.008 9:1 0.229 ± 0.010 0.253 ± 0.015 0.024 ± 0.025
a
Values are the mean of triplicate measurements. Core material was orange oil, and 1% chitosan in 1% acetic acid solution was wall material. The
weight ratio of oil to chitosan was 1:1. bΔμ = size of heated emulsion − size of original emulsion. cCompound emulsifer was 10% in oil.

orange oils, samples were withdrawn every 2 h and analyzed using

ultraviolet spectrophotometry at 202 nm. For the microencapsulated
orange oils, samples were withdrawn every 2 days and completely
dissolved in 1% aqueous acetic acid. Then the orange oil was extracted
with n-hexane and analyzed using ultraviolet spectrophotometry at 202
nm. The retention of orange oil was defined as the ratio of the amount
of orange oil remaining to the amount at the start. The analysis was
carried out in triplicate.
Retention of Orange Oil in Fabrics. Orange oil or micro-
encapsuled products (1 g each) were added to 800 g of water
containing 8 g of a common household laundry detergent. Small
swatches, 3 cm × 3 cm, of cotton fabric or terylene fabric were placed
into the orange oil or microencapsulated oil laundry detergent
solutions, stirred for 2 h, and rinsed in water three times (10 min
each). The washed fabrics were air-dried at room temperature for 12 h.
After drying, the fabrics were stored at room temperature and taken
out for oil measurement every day. The fabrics were immersed in 1%
(w/w) acetic acid and stirred for 2 h. The orange oil was then
exhaustively extracted with n-hexane. The oil content was determined
using UV spectrophotometry at 202 nm. The retention of orange oil
Figure 1. Flow curves of 1 and 2% (w/w) chitosan in 1% acetic acid
was defined as the ratio of the amount of orange oil remaining after
solution.
washing during storage to the amount before washing. The analysis
was carried out in triplicate.
Statistical Analysis. All of the data were analyzed by SPSS 13.0 examined in this study. We found that there was an increase in
(SPSS Institute Inc., Cary, NC, USA) and expressed as the mean ±
standard deviation (SD). The calculations and graphs were made using
emulsion droplet volume after heating briefly at 100 °C and
the computer program Microcal Origin 7.5 (Microcal Software Inc., holding at 60 °C (Table 1). The droplet diameter of all
Northampton, MA, USA). emulsions prepared with single emulsifiers increased by nearly 2
μm after heating except for Tween 40. This is presumably

■ RESULTS AND DISCUSSION

Effect of Emulsifiers on Emulsion Size and Stability.
because the molecular geometry of surfactants changed
differently in response to raised temperature. It is now widely
recognized that the molecular geometry of a surfactant plays a
The chitosan molecules have both hydrophobic and hydrophilic major role in determining its functional performance in
groups, and it is possible that they may exist in the interface of colloidal systems.30 The molecular geometry is characterized
the emulsion by acting as coemulsifiers. The emulsifying by a packing parameter (p), which is the ratio between the
properties of Tween and Span on the size and stability of effective cross-sectional areas of the tail group and the head
emulsions at conventional temperatures are well-known, but group of the surfactant. The packing parameter determines the
the effects of high temperatures have not been well studied. optimum curvature of a monolayer that a particular surfactant
Because the emulsions would be subject to thermal processes tends to form. The optimum curvature influences parameters
during spray-drying, their stability to high temperatures were such as the interfacial tension and rheology, which may then
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Figure 2. Flow curves of emulsions with 1:1 and 1:2 ratios of orange oil to chitosan at 3, 5, and 7% emulsifier concentrations. (Core material was
orange oil, and 1% chitosan in acetic acid solution was wall material. The emulsifiers were Tween 40 and Span 20 with ratio of 4:1.)

Table 3. Influence of Inlet Temperature on Encapsulation Efficiency and Retention of Orange Oila
emulsifier inlet temperature (°C) (outlet size of original size of heated encapsulation
(10% in oil) temperature was 80 °C) emulsion (d43, μm) emulsion (d43, μm) Δμb (d43, μm) efficiency (%) retention (%)
Tween 40 130 0.410 ± 0.010 2.277 ± 0.190 1.867 ± 0.2 88.1 ± 0.04 5.9 ± 0.04
Tween 40/Span 130 0.224 ± 0.001 0.225 ± 0.001 0.001 ± 0.002 91.5 ± 0.02 56.4 ± 0.06
20 = 4:1
Tween 40/Span 150 0.224 ± 0.001 0.225 ± 0.001 0.001 ± 0.001 90.7 ± 0.03 45.7 ± 0.03
20 = 4:1
Tween 40/Span 170 0.224 ± 0.001 0.225 ± 0.001 0.001 ± 0.002 89.3 ± 0.03 43.9 ± 0.03
20 = 4:1
a
Values are the mean of triplicate measurements. Core material was orange oil, and 1% chitosan in 1% acetic acid solution was wall material. The
weight ratio of oil to chitosan was 1:1. bΔμ = size of heated emulsion − size of original emulsion.

affect the stabilities of emulsions formed. As the temperature effects of weight ratio of the compound emulsifiers to chitosan
rises, the headgroup becomes progressively dehydrated, wall material and thermal treatment on droplet size. As from
resulting in altered packing parameter. The single surfactants Table 2, the combination of Tween 40 with Span 20 was
used in this study (Tween 20, 40, 60, and 80) all have similar superior to Tween 40 with SE-15 (value of Δμ was small
polar head groups, but have different nonpolar tail groups. It overall), although all combinations of Tween 40 with either
was hypothesized that the packing parameter changed differ- Span 20 or SE-15 resulted in small particles after heating. SE-15
ently during heating because of the various tail groups of these may not be as good an emulsifying agent in this application
surfactants, which may be responsible for the different heating because it is a solid, and its solubility in water may not be as
stabilities of the emulsions. The emulsions prepared with good as that of liquid emulsifier Span 20 or the stronger
compound emulsifiers were found to be more stable to heat interactions between SE-15 molecules that make it a solid do
treatment, especially for the two combinations, Tween 40 with not allow it to interact as much with the oil core as Span 20.
Span 20 and Tween 40 with SE-15 (Table 1). Because chitosan The droplet sizes of all the ratios of Tween 40 to Span 20 were
has little emulsifying properties, the nonionic surfactants are relatively similar after heating. Although the cold emulsion
responsible for the emulsification of orange oil in chitosan prepared with 80% Tween 40 and 20% Span 20 had the
solution to form O/W emulsion. Others have also found that relatively largest droplet size, the droplets were stable to heat
the emulsifying ability of a single emulsifier is usually inferior to treatment (Δμ = 0.001). Thus, 80% Tween 40 and 20% Span
that of compound emulsifiers.31 Two different surfactants in 20 was the best combination for the preparation of small, stable
combination can not only emulsify water and oil more emulsions in our experiments.
effectively but also interact to form more stable emulsions Emulsion Viscosity Determination. Viscosity is an
that prevent the droplets from agglomeration or flocculation. important property of fluids in processing because it can affect
The combinations of Tween 40 with Span 20 and Tween 40 the selection of equipment and the processing conditions. A
with SE-15 gave the lowest Δμ values (Table 1), so these two lower viscosity is desirable for spray-drying. At the concen-
best combinations were chosen for further investigation of the trations of chitosan we used as the continuous phase of our
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Figure 3. SEM photograph of encapsulated powders produced from emulsions by different spray-drying conditions (×2400): (a) inlet temperature =
130 °C; (b) inlet temperature = 150 °C; (c) inlet temperature = 170 °C. Wall material was 1% chitosan in 1% acetic acid solution. The weight ratio
of oil (core material) to chitosan was 1:1. The emulsifiers (10% in oil) were Tween 40 and Span 20 with a ratio of 4:1.

Table 4. Influence of Different Concentrations of Compound Emulsifiers and the Weight Ratios of Core Material to Wall
Material on Encapsulation Efficiency and Retention of Orange Oila
compound wt ratio of
emulsifier orange oil to size of original size of heated X (powder size −
concentration chitosan emulsion emulsion size of powder original emulsion encapsulation
(wt % in oil) (w/w) (d43, μm) (d43, μm) Δμ (d43, μm)
b
particle (d43, μm) size)/powder size efficiency (%) retention (%)
3 1:1 0.573 ± 0.003 0.670 ± 0.009 0.097 ± 0.012 20.981 ± 0.020 0.973 ± 0.020 85.5 ± 0.02 41.7 ± 0.03
5 1:1 0.298 ± 0.002 0.387 ± 0.008 0.089 ± 0.010 16.857 ± 0.015 0.982 ± 0.015 80.5 ± 0.03 52.5 ± 0.02
7 1:1 0.243 ± 0.002 0.273 ± 0.010 0.03 ± 0.010 17.132 ± 0.010 0.986 ± 0.01 80.5 ± 0.02 72 ± 0.03

3 1:2 0.476 ± 0.003 0.499 ± 0.009 0.023 ± 0.012 24.522 ± 0.019 0.980 ± 0.02 93.7 ± 0.02 80.3 ± 0.02
5 1:2 0.332 ± 0.001 0.334 ± 0.007 0.002 ± 0.007 22.610 ± 0.010 0.985 ± 0.01 92.9 ± 0.02 86.8 ± 0.02
7 1:2 0.214 ± 0.001 0.229 ± 0.007 0.015 ± 0.007 21.091 ± 0.010 0.910 ± 0.01 90.1 ± 0.01 86.9 ± 0.01
a
Values are the mean of triplicate measurements. Core material was orange oil, and 1% chitosan in 1% acetic acid solution was wall material. The
weight ratio of oil to chitosan was 1:1 or 1:2. Tween 40 and Span 20 were used as compound emulsifier with the ratio of 4:1. Spray-drying inlet
temperature was 150 °C, and outlet temperature was 80 °C. bΔμ = size of heated emulsion − size of original emulsion.

emulsified mixtures, the flow curves of chitosan in acetic acid form aggregates and these associations were broken down by
solution showed that at 1% (w/w) concentration, chitosan shear (Figure 2). The emulsion viscosity also decreased with
behaved like a Newtonian fluid, but at 2%, it exhibited shear- increasing concentration of emulsifier in oil. The viscosity
thinning behavior (Figure 1). Interestingly, the viscosity of the reached a minimum when 5 or 7% surfactant in oil was
emulsion in 1% chitosan was lower than 1% chitosan alone incorporated. All viscosity curves had the same shear-thinning
(Figures 1 and 2) suggesting that the emulsion droplets may behavior. The shear -thinning behavior is explained by the
interact with chitosan effectively lowering the concentration in increased shear rate overcoming Brownian motion, resulting in
the aqueous phase. The viscosity was increased when the ratio the emulsion droplets becoming more ordered along the flow
of oil to chitosan was decreased from 1:1 to 1:2. The increasing field and offering less resistance to flow and hence the lower
concentration of chitosan in the aqueous phase would be viscosity.32 The viscosity leveled out with further increases in
responsible for the raised viscosity. shear rate above 10 s−1.
Emulsification of orange oil by surfactants in 1% chitosan Effect of Spray-Drying Conditions and Emulsifiers on
resulted in shear-thinning behavior that was not observed in 1% Microencapsulation. A high amount of encapsulated oil is
chitosan alone, suggesting that the emulsified droplets may desirable, and retention is one of the most important
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Figure 4. Emulsion droplet size distribution before and after thermal treatment as well as the microencapsulated powder size after spray-drying: (a)
weight ratio of oil and chitosan was 1:1; (b) weight ratio of oil and chitosan was 1:2. The emulsifiers (3% in oil) were Tween 40 and Span 20 with a
ratio of 4:1. Thermal treatment was carried out by boiling the emulsions for 3 min and then incubating in a water bath for 30 min at 60 °C.

parameters of spray-dried microencapsulated powders. The use The retention of orange oil was found to be negatively
of compound surfactants did not improve encapsulation correlated to emulsion size when the weight ratio of orange oil
efficiency (EE) significantly, but improved oil retention almost to chitosan was kept constant (Table 4). Because higher
10-fold and resulted in smaller droplet size compared to the use retention was desirable, this suggested that a fine emulsion was
of a single surfactant (Table 3). Emulsions with little change of advantageous and could be stable during both atomization and
the droplet size after thermal treatment also produced spray- spray-drying. In a previous study it was observed that
dried product with higher EE and retention. As expected, the decreasing surface oil is related to the difference between
EE value was reduced when the inlet temperature increased emulsion size and particle size of the spray-dried microcapsules.
(Table 3). However, low inlet temperatures (130 °C) resulted Re and Liu defined a parameter X = (powder size − emulsion
in insufficient water volatility and adhesion of the particles size)/powder size, to relate retention to powder and emulsion
(Figure 3a). Too high inlet temperatures (170 °C) resulted in size.33 They showed that by increasing X from 0.2 to 0.8,
more drapes and microgaps at the surface of the micro- retention of volatiles increased significantly, so it could be
encapsulated particles (Figure 3c). Total retention of orange oil possible to improve the retention by increasing the difference
in spray-dried powders decreased from 56.4 to 43.9% when the between emulsion and powder particle size. Although X was
inlet temperature was increased from 130 to 170 °C (Table 3). greater than 0.8 in this study (Table 4), the results were
Thus, 150 °C was selected as the optimal inlet temperature, at consistent with the previous paper. It was also found that EE
which the microcapsules had regular particle morphology was positively correlated to the powder particle size. The larger
(Figure 3b), although it had slightly lower retention and powder particle size of microencapsules was related to higher
encapsulation efficiency than at 130 °C. values of EE. The explanation is that emulsion droplets are
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Figure 6. Retentions of free orange oil and microencapsulated oil in

fabrics: (a) free orange oil retention in cotton and terylene polyester
after washing; (b) free orange oil and microencapsulated oil retention
in cotton after washing. The weight ratio of oil to chitosan was 1:2.
The emulsifiers (3% in oil) were Tween 40 and Span 20 with a ratio of
Figure 5. Retention of orange oil at 25 °C and 33% humidity or at 45 4:1.
°C and 52% humidity: (a) free orange oil; (b) microencapsulated
orange oil. The weight ratio of oil to chitosan was 1:2. The emulsifiers
(3% in oil) were Tween 40 and Span 20 with a ratio of 4:1. aggregation of emulsion droplets. The emulsion size of oil to
chitosan ratio at 1:2 had similar diameters after heating (Figure
4b) and had higher stability to spray-drying and higher
more likely to adhere to the surface of smaller particles than to retention and EE (Table 4). This confirmed the observation
the surface of larger ones. In other words, fine oil droplets will that a higher proportion of wall material components in
be covered by the wall material more efficiently in bigger emulsion resulted in particles that were more stable during
particles than in smaller ones. The ratio of wall material to core thermal treatment and spray-drying. However, with the
material also had an effect on the spray-dried particle size, EE, increased proportion of wall material, the distribution range
and the total oil retention (Table 4). The EE was >90% at the of powder particle size after spray-drying was expanded and the
ratio of orange oil to chitosan of 1:2. Increasing the wall mean particle size was increased. The microcapsules had a
material weight resulted in more encapsulated oil but increasing mean diameter below 20 μm (Figure 4). It was also shown that
powder particle size. The retention of orange oil was also emulsions with less stability resulted in encapsulated powders
markedly increased when the ratio of orange oil to chitosan with higher surface oil content and lower retention of volatiles
decreased from 1:1 to 1:2. The optimum ratio of wall materials (Table 4), which was consistent with previous studies.34−37
to oil and the emulsion droplet size were found to be the most Storage Stability of Orange Oil Microcapsules. The
important for the retention of orange oil. This observation is in storage stability of orange oil by encapsulation in chitosan was
agreement with Risch and Reineccius, who reported in a similar markedly improved compared to free orange oil. Free orange
study that smaller emulsion size yields a higher retention of oil was extremely volatile and was almost completely volatilized
orange oil.24 in 8 h at 45 °C and 52% relative humidity as seen in Figure 5a.
Emulsion droplet size distributions before and after thermal Orange oil encapsulated in chitosan under the same conditions
treatment as well as microencapsulated powder size distribu- volatilized over a period of months (Figure 5b). Temperature
tions were determined. A new peak about 6 μm in diameter and relative humidity also had a significant effect on volatility.
after heating was observed for the emulsion with the oil to Retention was lower when microcapsules were stored at 45 °C
chitosan ratio of 1:1 (Figure 4a), which was interpreted as the and 52% humidity than when stored at 25 °C and 33%
3317 dx.doi.org/10.1021/jf305074q | J. Agric. Food Chem. 2013, 61, 3311−3319
Journal of Agricultural and Food Chemistry Article

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■
12056−12063.
(20) Desai, K. G. H.; Park, H. J. Recent developments in
AUTHOR INFORMATION microencapsulation of food ingredients. Drying Technol. 2005, 23,
Corresponding Author 1361−1394.
*Phone: 86-138-12536912. Fax: 86-510-85197876. E-mail: (21) Ziani, K.; Chang, Y. H.; McLandsborough, L.; McClements, D.
[email protected] or [email protected]. J. Influence of surfactant charge on antimicrobial efficacy of surfactant-
stabilized thyme oil nanoemulsions. J. Agric. Food Chem. 2011, 59 (11),
Funding 6247−6255.
We gratefully acknowledge the financial support of the National (22) Jafari, S. M.; He, Y. H.; Bhandari, B. Role of powder particle size
Natural Science Foundation of China (30901000 and on the encapsulation efficiency of oils during spray drying. Drying
31171686), BK2012556, and 2011BAD23B02. This work was Technol. 2007, 25, 1081−1089.
also supported by National Basic Research Program of China (23) Madene, A.; Jacquot, M.; Scher, J.; Desobry, S. Flavour
(2010CB735705) and SKLDB2012-004. encapsulation and controlled release − a review. Int. J. Food Sci.
Technol. 2006, 41, 1−21.
Notes (24) Risch, S. J.; Reineccius, G. A. Spray-dried orange oil: effect of
The authors declare no competing financial interest. emulsion size on flavor retention and shelf life. In Flavor Encapsulation;

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