Food Research International 39 (2006) 807815

www.elsevier.com/locate/foodres

Physicochemical characterization and oxidative stability of Wsh oil

encapsulated in an amorphous matrix containing trehalose
a,
Stephan Drusch , Yvonne Serfert a, Annick Van Den Heuvel b, Karin Schwarz a

a
Institute for Human Nutrition and Food Science, Department of Food Technology, University of Kiel, Heinrich-Hecht-Platz 10, 24118 Kiel, Germany
b
Cerestar Vilvoorde R&D Centre, Havenstraat 84, 1800 Vilvoorde, Belgium

Received 23 December 2005; accepted 11 March 2006

Abstract

Fish oil with 33% omega-3 fatty acids was microencapsulated by spray-drying in a matrix of n-octenylsuccinate-derivatized starch and
either glucose syrup or trehalose. Samples showed no diVerence in physicochemical properties as determined by measurement of particle
size, oil droplet size, true density and BET surface. Upon storage at low relative humidity, lipid oxidation was decreased in trehalose con-
taining samples indicating that in the amorphous state trehalose is a more suitable wall material for microencapsulation than glucose
syrup. The retarded oxidation of trehalose containing samples may be attributed to the unique binding properties of trehalose to dienes.
At 54% relative humidity, a rapid oxidation of the microencapsulated oil was observed upon crystallization of trehalose, which limits the
range of applications to products to be stored at low humidity.
2006 Elsevier Ltd. All rights reserved.

Keywords: Lipid oxidation; Long chain polyunsaturated fatty acids; Docosahexanoic acid; Propanal; Hydroperoxides; Storage; Relative humidity; Octe-
nylsuccinate-derivatized starch; Trehalose; Crystallization

1. Introduction conditions on microcapsules characteristics have been

For several decades, microencapsulation by spray-dry-
ing has been applied in the food industry and is still the pre-
dominating technology as it is rather inexpensive and
straightforward (Gouin, 2004; R, 1998). Typical wall
materials for microencapsulation by spray-drying are low
molecular weight carbohydrates like maltodextrins or sac-
charose, milk or soy proteins, gelatine and hydrocolloids
like gum arabic or mesquite gum (Fldt & Bergensthl,
1995; Hogan, McNamee, ORiordan, & OSullivan, 2001a,
Hogan, McNamee, ORiordan, & OSullivan, 2001b, 2001c;
Keogh et al., 2001; Kim & Morr, 1996; Lin, Lin, & Hwang,
1995). Recently, the suitability of n-octenylsuccinate-deriv-
atized starch (n-OSA starch) for microencapsulation of Wsh
oil and the inXuence of type of n-OSA starch and drying
*
Corresponding author. Tel.: +49 431 8802370; fax: +49 431 8805544.
E-mail address: sdrusch@foodtech.uni-kiel.de (S. Drusch).
described (Drusch & Schwarz, 2006).
Problems associated with the use of low molecular weight
carbohydrates in microencapsulation are caking and struc-
tural collapse as well as re-crystallization of the amorphous
carbohydrate matrix upon storage. Le Meste, Champion,
Roudat, Blond, and Simatos (2002) concluded that caking
can be explained by the formation of inter-particle bridges
between adjacent particles when surface viscosity reaches a
critical value. Caking and collapse at high relative humidity
were described for microencapsulated sea buckthorn oil,
orange peel oil or linoleic acid (Beristain, Azuara, &
Vernon-Carter, 2002; Partanen, Hakala, Sjvall, Kallio, &
Forssell, 2005; Ponginebbi, Nawar, & Chinachoti, 1999) and
dairy powders (Roos, 2002). Crystallization is a two step
process with the phase of initial nucleation and subsequent
crystal growth. Crystallization of lactose in dairy-based
powders has intensively been studied (Joupilla, Kansikas, &
Roos, 1997, 1998; Knudsen, Antanuse, Risbo, & Skibsted,
2002; Thomsen, Lauridsen, Skibsted, & Risbo, 2005). Apart

0963-9969/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodres.2006.03.003
808 S. Drusch et al. / Food Research International 39 (2006) 807815
from a negative impact on handling properties, both, caking
or collapse and crystallization may lead to a release of the
encapsulated substance from the matrix.
In this context, physicochemical properties of trehalose
appear to be very promising concerning its use in microen-
capsulation. Trehalose possesses a uniquely high glass tran-
sition temperature. Data on the glass transition
temperature range from 79 C to 115 C and are attributed
to polymorphism in the crystallization pattern (Willart
et al., 2002). If trehalose crystallizes, the predominant form
is the trehalose dihydrate, thus immobilizing water and
keeping the water activity at a low level. For these reasons,
trehalose remains in the glassy state at temperatures higher
than other sugars and has a greater capability of stabilizing
proteins, lipids or carbohydrates embedded in trehalose
glasses (Richards & Dexter, 2001).
Aim of the present study was to investigate the physico-
chemical properties of microcapsules with trehalose vs. glu-
cose and whether substitution of glucose syrup by trehalose
leads to an increase in oxidative stability of microencapsu-
lated Wsh oil.
2. Materials and methods
ReWned cold-pressed Wsh oil was provided by Henry
Lamotte GmbH, Bremen, Germany. The Wsh oil contained
approximately 33% omega-3 fatty acids. The concentration
of the long chain polyunsaturated fatty acids eicosapent-
anoeic acid and docosahexanoeic acid amounted to 18.0%
and 12.3%, respectively. Naturally occurring antioxidants,
free fatty acids, pigments and mono- or diglycerides in the
oil were removed by column chromatography as described
by Lampi and Kamal-Eldin (1998).
2.1. Microencapsulation of Wsh oil
For microencapsulation, an emulsion with 45% total sol-
ids was prepared. Oil content was set at 40% of the total
solids. The emulsion was prepared using n-octenylsucci-
nate-derivatized starch (CEmCap 12634, Cerestar Deu-
tschland GmbH, Krefeld, Germany) as emulsiWer at a
concentration of 10%, total solids were made up to 100%
using a glucose syrup with a DE value of 38 (CDry GL
01934, Cerestar Deutschland GmbH, Krefeld, Germany) or
trehalose (CAscend, Cerestar Deutschland GmbH, Kre-
feld, Germany). All water-soluble ingredients were dis-
solved in water prior to emulsiWcation and pH was adjusted
to pH 4.5. Afterwards the oil was dispersed in the aqueous
phase using a hand blender. A coarse emulsion was pre-
pared by homogenisation at 50 bar in a high pressure
homogeniser (Panda 2K, Niro Soavi Deutschland, Lbeck,
Germany) followed by a Wnal two-step homogenisation at
200/50 bar with two passes. Spray drying of the emulsion
was performed on a laboratory scale spray dryer (17 kg/h
water evaporative capacity, Mobile Minor, Niro A/S,
Denmark) equipped with a rotating disk for atomisation.
An air inlet temperature of 170 C and an outlet air temper-
ature of 70 C were chosen, disk rotation was approxi-
mately 30,000 rpm.
2.2. Physicochemical characterization
Scanning electron microscopy using a LEO S420
(Oberkochen, Germany) was applied to view and describe
the characteristics of the microcapsules. A laser-diVraction
sensor (Helos, Sympatec GmbH, Clausthal-Zellerfeld,
Germany) equipped with a cuvette was used for determina-
tion of the particle size and oil droplet size of the microcap-
sules. Particle size analysis of the microcapsules was
performed after dispersing an aliquot of the powder in an
inert oil (Miglyol 812, Sasol Germany, Hamburg,
Germany), for determination of the oil droplet size an ali-
quot of the sample was dissolved in water. All analyses were
performed with four replicates. BET surface analyses were
performed using a Gemini 2360 (Micromeritics, Mnchen-
gladbach, Germany). True density of the powder particles
was determined using a Pycnomatic helium pycnometer
(Thermo Electron Corporation, Dreiech, Germany).
Water activity was measured using a TH500 AW Sprint
(Novasina, PfYkon, Switzerland), moisture content was
analysed using an electronic moisture analyser MA30
(Sartorius, Gttingen, Germany). For moisture sorption
analysis a moisture sorption analyser (CI Electronics, Salis-
bury, United Kingdom) was used. The amount of non-
encapsulated fat in the microcapsules was determined using
a reference method for determination of free fat in dried
milk products including extraction of the fat in a Soxhlet
apparatus with petrol ether and gravimetric determination
of the extracted fat (Verband Deutscher Landwirtschaftli-
cher Untersuchungs- und Forschungsanstalten, 1985). Col-
our measurements were based on the CIE Lab colour
model. Measurements were performed using a sphere spec-
trophotometer (model SP62, X-Rite Inc., Grandville, MI,
USA) equipped with a standard 10 observer. Illuminant
type was D65.
2.3. Analysis of lipid oxidation parameters
To evaluate oxidative stability, samples of microencap-
sulated Wsh oil were stored under controlled relative humid-
ity at 20 C for up to eight weeks. Samples were weighed in
open beakers and placed in glasses sealed with press-on lids
over silica (0% relative humidity) or a saturated solution of
MgNO3 (54.4% relative humidity). Oxidative changes in the
Wsh oil during storage were monitored by analysing three
diVerent parameters. To determine conjugated dienes and
the peroxide values, oil was isolated from the microcapsules
as described by Satu-Gracia, Frankel, Rangavajhyala, and
German (2000). Conjugated dienes were photometrically
determined after dilution of the oil with 2-propanol at
234 nm. For calculation of the concentration, the results
were expressed as millimoles of hydroperoxide per kg oil
using a molar coeYcient of 26,000 for methyl linoleate
hydroperoxides (Chan & Levett, 1976). Hydroperoxide
 S. Drusch et al. / Food Research International 39 (2006) 807815 809

concentration was determined using the IDF standard observed by Elizalde, Herrera, and Buera (2002) as an
method 74A:1991 for the determination of the peroxide endothermal peak in the DSC thermogramm.
value in anhydrous milk fat with slight modiWcations True density, particle size, BET surface and oil droplet
(International Dairy Federation, 1991). All analyses of con- size of the reconstituted emulsion are in agreement with
jugated dienes and hydroperoxides were performed with previous data on microencapsulated Wsh oil with this type
three replicates. of n-OSA starch and glucose syrup (Drusch & Schwarz,
The major volatile aldehyde resulting from the degrada- 2006). Since no diVerence in particle size was observed, but
tion of omega-3 fatty acids is propanal. In several studies, BET surface was increased in the glucose syrup samples
propanal proved to a suitable marker for the evaluation of with 10% oil load, these samples consequently were more
the oxidative status of Wsh oil (Faraji & Lindsay, 2005; porous than the samples with 40% oil load. As the total
Frankel, Satu-Gracia, Meyer, & German, 2002; Horiuchi, amount of non-encapsulated fat was increased in the 40%
Umano, & Shibamoto, 1998; Shahidi, 1998). Therefore, oil glucose syrup samples, pores were probably covered by
propanal was analysed via static headspace gas chromatog- lipids. Comparing the 10% oil load samples, the use of tre-
raphy with Xame ionization detection according to Frankel halose resulted in lower BET values than glucose syrup.
(1993) with modiWcations. BrieXy, 1 g of sample was Spray-drying of the Wsh oil emulsion generally resulted in
weighed into a 20 ml headspace vial, resolved with 2 ml of particles of approximately 20 m (Table 1). However, sam-
0.5% w/w ethylenediaminetetraacetic acid, sealed and incu- ples containing glucose syrup showed a more wrinkled sur-
bated at 70 C for 15 min. An aliquot of the headspace face than trehalose-containing samples (Fig. 1).
(1 ml) was injected into a HP 6890A gas chromatograph
equipped with a DB-1 column (30 m 0.32 mm 3 m). 3.2. Development of lipid oxidation products upon storage
Injector and detector temperature were set at 180 C and over silica
220 C, respectively. Oven temperature was initially set at
40 C and increased after 5 min to 94 C within 10 min. The formation of oxidation products during the early
period of storage (21 days) is shown in Fig. 2. Storage at
2.4. Statistical analysis 20 C over silica was considered to be a protective environ-
ment in terms of structural changes within the microcap-
All experiments were planned and analysed using Design sule. Surana, Pyne, and Suryanarayanan (2004) showed
Expert, Version 6.0.10 (Stat Ease Inc., Minneapolis, USA). that upon storage over anhydrous calcium sulfate (0%
relative humidity) nucleation occurs in spray-dried amor-
3. Results and discussion phous trehalose, but not crystallization. Stored over silica,
formation of conjugated dienes and hydroperoxides was
3.1. Physicochemical characterization of the lower in the trehalose containing samples than in the glu-
microencapsulated Wsh oil cose syrup containing samples in the present study (Fig. 2).
Within 21 days, conjugated dienes increased up to 39 mmol/
Table 1 shows the physicochemical characteristics of the kg oil in the glucose syrup containing samples with no fur-
diVerent microencapsulated Wsh oil products. Moisture ther increase within the next 5 weeks. Trehalose containing
content and water activity of the samples containing glu- samples contained less than 35 mmol conjugated dienes/kg
cose syrup were higher than in the corresponding samples oil after 21 days of storage with no change thereafter in the
containing trehalose. These results may be explained by a 40% oil sample and an increase up to 39 mmol/kg oil in the
partial crystallization of the trehalose during sample prepa- 10% oil containing sample after 8 weeks of storage.
ration. Crystallization leads to binding of water in the dihy- The concentration of hydroperoxides strongly
drate without inducing structural changes in the increased within the Wrst seven days and reached a maxi-
microcapsules. A partial crystallization of trehalose during mum concentration of approximately 90 mmol/kg. In
encapsulation of beta-carotene by freeze drying was samples containing 10% oil the hydroperoxide concentra-
tion decreased again, followed by a moderate increase
over the storage period of eight weeks. By contrast, sam-
Table 1
ples containing 40% oil displayed a nearly constant
Physicochemical characterization of the diVerent microcapsules hydroperoxide concentration until week eight. In both
Wall material: Trehalose Glucose syrup
cases (10% and 40% oil) the hydroperoxide concentration
was on a higher level in glucose syrup containing samples
Oil content (%): 40 10 40 10
(71.5 3.1 and 90.7 1.8 mmol/kg oil) than in trehalose
aw-value 0.093 0.12 0.119 0.151 containing samples (33.6 0.9 and 40.6 2.3 mmol/kg oil).
Moisture content (%) 2.03 3.03 2.39 3.65
Extractable fat (% fat) 4.1 3.4 7.9 3.5
Fig. 2 shows the development of the propanal concentra-
BET surface (m2/g) 0.165 0.178 0.157 0.200 tion in the diVerent samples. Samples stored over silica
True density (g/cm3) 1.178 1.366 1.188 1.379 reached a propanal concentration of 59 mmol/kg oil
Particle size, x50 (m) 21.1 20.3 22.7 19.0 within one week, which remained fairly constant over the
Oil droplet size, x50 (m) 0.99 1.00 1.16 1.17 whole eight weeks of storage.
810 S. Drusch et al. / Food Research International 39 (2006) 807815
Fig. 1. Scanning electron microscopy of spray-dried microcapsules with either 10% oil (A, B) or 40% oil (C/D) and glucose syrup (A/C) or trehalose (B/D)
as carbohydrate source.
The course of oxidation (strong initial increase followed
by a moderate increase or even constant value for the oxi-
dation products) can be explained by diVerent oxidation
behaviour of the extractable fat (non-encapsulated fat) and
the encapsulated fat (Baik et al., 2004). The strong increase
within the Wrst seven days (Fig. 2) is caused by oxidation of
the extractable fat, which is almost completely oxidized
within the Wrst week (own data, not published) whereas the
succeeding slight increase indicates the slow oxidation of
the encapsulated fat, i.e., the oxidation stability of micro-
capsules in the early storage period is almost exclusively
determined by the extractable fat. These Wndings are in con-
trast to other studies, i.e., the surface fat, which is a major
proportion of the extractable fat, is not considered to have
a signiWcant inXuence on lipid oxidation in microcapsules
(Keogh et al., 2001; Minemoto, Hakamata, Adachi, &
Matsuno, 2002; Partanen, Yoshii, Kallio, Yang, & Forssell,
2002).
The reduced rate of lipid oxidation of trehalose contain-
ing samples may be attributed to the unique binding prop-
erties of trehalose to cis-unsaturated double bonds of the
unsaturated fatty acids. Oku et al. (2003) demonstrated that
one molecule trehalose interacts through formation of
OH, and CH,O hydrogen bonds with one cis-oleWn
double bound of unsaturated fatty acids (oleic, linoleic and
linolenic acid). In the present study, the molar ratio of tre-
halose to cis-oleWn double bounds is approximately 2:1, i.e.,
the amount of trehalose is suYcient to interact on a stoichi-
ometric basis with the polyunsaturated fatty acids. A pre-
requisite for an interaction is a transition of trehalose from
the aqueous phase into the oil phase. Disalvo, Lairion,
Martini, and Diaz (2002) reviewed that trehalose can insert
into the lipid phase of membranes upon dehydration and a
similar mechanism may have occurred during dehydration
of the spray-dried emulsion.
3.3. Development of lipid oxidation parameters upon storage
at 54% relative humidity
Samples were stored at 54% relative humidity to investi-
gate lipid oxidation under stress. The glass transition tem-
perature (Tg) of trehalose at 44% relative humidity is 14 C
(Iglesias, Chirife, & Buera, 1997). Addition of other poly-
meric compounds increases Tg of a mixture of compounds,
e.g., Roos and Karel (1991) have shown an increase of Tg
for maltodextrins with decreasing DE value. Due to the
higher average molecular weight Tg of the n-OSA starch
was probably higher than the Tg reported for trehalose,
 S. Drusch et al. / Food Research International 39 (2006) 807815 811

conjugated dienes [mmol/kg oil] 50 50

conjugated dienes [mmol/kg oil]

45 45

40 40

35 35

30 30
G10 G40
25 25
T10 T40
20 20
0 5 10 15 20 25 0 5 10 15 20 25
[days stored over silica] [days stored over silica]

120 120

hydroperoxide concentration
hydroperoxide concentration

G10
100 100
T10
80

[mmol/kg oil]
80
[mmol/kg oil]

60 60

40 40

G40
20 20
T40
0 0
0 5 10 15 20 25 0 5 10 15 20 25
[days stored over silica] [days stored over silica]

12.0 12.0

10.0 10.0
propanal [mmol/kg oil]

propanal [mmol/kg oil]

8.0 8.0

6.0 6.0

4.0 4.0
G10 G40
2.0 2.0
T10 T40
0.0 0.0
0 5 10 15 20 25 0 5 10 15 20 25
[days stored over silica] [days stored over silica]

Fig. 2. Development of lipid oxidation products in microencapsulated Wsh oil stored over silica for 21 days (G: glucose syrup; T: trehalose; 10: 10% oil
load; 40: 40% oil load).

nevertheless, at 20 C and 54% relative humidity, crystalli- Chirife (1997), who reported a complete crystallization of
zation of the matrix with release of the oil and subsequent trehalose as dihydrate at high relative humidity, Miao and
fast oxidation was expected to occur. Roos (2005) recently showed, that trehalose crystallizes as a
Data on moisture sorption from the dynamic vapour mixture of trehalose dihydrate and anhydrate. The high
sorption showed, that at 54% relative humidity with 5.1% level of water sorbed upon storage at relative humidity at
moisture uptake for the 40% oil sample and 8.2% moisture 54% and above must be attributed to both, dihydrate crys-
uptake for the 10% oil sample sorption is close to the tal formation and incomplete crystallization retaining
expected value for complete dihydrate formation of the tre- sorbed water in the amorphous phase (Miao & Roos, 2005).
halose of 5.3% and 8.4%, respectively, calculated from the Conjugated dienes in the 10% oil samples reached
proportion of trehalose in the sample and a moisture con- approximately 40 mmol/kg oil in both samples at day 21
tent of approximately 10.5% in the trehalose dihydrate. (Fig. 3). The trehalose containing sample had lower values
However, these data do not necessarily mean, that water compared to the glucose syrup sample the days before and
sorbed at 54% is completely bound in the trehalose dihy- started to cake thereafter. After Wve weeks it was not
drate. In contrast to Cardona, Schebor, Buera, Karel, and longer possible to analyse the trehalose sample with 10%
812 S. Drusch et al. / Food Research International 39 (2006) 807815

80 80

conjugated dienes [mmol/kg oil]

conjugated dienes [mmol/kg oil]

70 70

60 60

50 50

40 40

G10 G40
30 30
T10 T40
20 20
0 5 10 15 20 25 0 5 10 15 20 25
[days stored at 54 % relative humidity] [days stored at 54 % relative humidity]

180 500
450

hydroperoxide concentration
hydroperoxide concentration

160
140 400
350

[mmol/kg oil]
120
[mmol/kg oil]

300
100
250
80
200
60 150
40 G10 100 G40
20 T10 50 T40
0 0
0 5 10 15 20 25 0 5 10 15 20 25
[days stored at 54 % relative humidity] [days stored at 54 % relative humidity]

10.0 25.0
G10 G40
propanal [mmol/kg oil]
propanal [mmol/kg oil]

8.0 T10 20.0 T40

6.0 15.0

4.0 10.0

2.0 5.0

0.0 0.0
0 5 10 15 20 25 0 5 10 15 20 25
[days stored at 54 % relative humidity] [days stored at 54 % relative humidity]

Fig. 3. Development of lipid oxidation products in microencapsulated Wsh oil stored at 54% relative humidity for 21 days (G: glucose syrup; T: trehalose;
10: 10% oil load; 40: 40% oil load).

oil load. At 40% oil load the trehalose sample showed Development of the hydroperoxide concentration
lower levels of conjugated dienes until day 14 compared to showed a similar course. After 21 days of storage, hydro-
the glucose syrup containing sample and higher levels peroxide concentration in the trehalose containing sample
thereafter. At day 21 the concentration of conjugated with 10% oil load amounted to 130 8.0 mmol/kg oil com-
dienes in the trehalose containing sample amounted to pared to 158 6.5 mmol/kg oil in the glucose syrup contain-
69.6 2.6 mmol/kg oil. The concentration reached its max- ing sample (Fig. 3). At a high oil load of 40%,
imum at day 49 with 133 9.8 mmol/kg oil and decreased hydroperoxide concentration after 21 days of storage was
to 87.9 27.4 thereafter. The unusual high standard devia- noticeably higher than in the 10% oil samples. Hydroperox-
tion can be explained by caking of the matrix, which was ide concentration in the glucose syrup containing sample
observed in this sample and leads to diVerences in the constantly increased over time and amounted to
microstructure of the individually aggregates and may sig- 313 4.9 mmol/kg oil. In contrast, in the trehalose contain-
niWcantly inXuence development of lipid oxidation. In ing sample hydroperoxide concentration moderately
comparison, the glucose syrup containing sample with 40% increased until day 11 up to approximately 50 mmol/kg oil
oil reached a maximum concentration of 74.3 5.8 mmol and sharply increased thereafter up to a Wnal concentration
conjugated dienes/kg oil. of 445 7.3 mmol/kg oil after 21 days of storage.
 S. Drusch et al. / Food Research International 39 (2006) 807815
Fig. 4. Structural changes in trehalose-containing samples stored for six weeks at 54% relative humidity (A: trehalose crystallization; B: fat).
The course of propanal formation is in line with the
hydroperoxide formation (Fig. 3). Samples stored at 54%
relative humidity reached approximately 7 mmol propanal/
kg oil within one week. The glucose syrup containing sam-
ples showed a moderate increase thereafter with a Wnal con-
centration of 33.1 0.0 and 50.3 1.6 mg/kg oil for the 10%
and 40% oil sample, respectively. Propanal concentration in
the trehalose containing sample with 40% oil sharply
increased and amounted to 167 1.5 mmol/kg oil after
eight weeks of storage.
In the sample with 10% oil load, after complete crystalli-
zation in the surface region of the microcapsules, matrix
plasticized through additional water uptake and eVectively
encapsulated the oil in the particle. Therefore, lipid oxida-
tion parameters in the trehalose containing samples were
lower than in the glucose syrup containing samples. Whor-
ton and Reineccius (1995) described a re-encapsulation of
volatiles through collapse of the amorphous microcapsule
matrix. As to be seen from Fig. 4 in the trehalose containing
sample aggregation with structural collapse and a partial
melting of the particle surface resulting in compact aggre-
gates was observed, which supports the hypothesis of re-
encapsulation. Trehalose crystals were observed (Fig. 4A),
which appear to be very similar to lactose crystallization in
microencapsulated milk fat as it was shown by Hardy,
Scher, and Banon (2002). Furthermore partially surface oil
was visible, which was released from the microcapsule due
to structural changes in the inner part of the powder aggre-
gate (Fig. 4B).
Lipid oxidation parameters in the trehalose containing
sample with 40% oil was lower until day 14 and increased
very fast thereafter. These data clearly show, that encapsu-
lation in a trehalose matrix oVers protection for the micro-
encapsulated oil for a certain period of time. It is possible,
that onset of trehalose crystallization was retarded in the
microcapsules. A delay in crystallization has been observed
for sucrose upon humidiWcation in the presence polymers
like carboxymethylcellulose, guar gum or sodium alginate
(Islesias & Chirife, 1978) and for trehalose in the presence
813
of maltodextrin (Iglesias et al., 1997; Mazzobre, del Pilar
Buera, & Chirife, 1997) or lactose (Miao & Roos, 2005). As
mentioned above, upon humidiWcation water is partly
bound in the amorphous phase of the microcapsule.
Elizalde et al. (2002) describe, that water can disrupt the
hydrogen bonded network formed by the non-crystalline
carbohydrate matrix, allowing the entrapped components
to escape from micro-regions of the dried matrix. Naesens
and Tobback (1984) describe a Xotation of lipids on the
water Wlm of a re-hydrated carbohydrate matrix to the sur-
face. These studies may explain, which changes led to the
present data on rapid oxidation of the microencapsulated
oil at a level of 40% upon storage at 54% relative humidity.
Further proof is provided by a study of Elofsson and Millq-
vist-Fureby (2003), who studied the stability of spray-dried
protein stabilized emulsions with trehalose. After storage at
75% relative humidity for Wve days, the authors observed a
broad endothermal peak in the DSC thermogramm, indi-
cating that trehalose crystallization had occurred. Further-
more, surface fat content was increased and, with 1.56 m,
oil droplet size of the reconstituted emulsion was consider-
ably higher than oil droplet size of the reconstituted pow-
der immediately after drying with 0.49 m (Elofsson &
Millqvist-Fureby, 2003). In the present study, a change in
colour in the trehalose containing sample with 40% oil sup-
ports the hypothesis of a release of oil from the microcap-
sule (Table 2). The b-value of the sample increased from 5.1
to 17, reXecting the development of a yellow-brownish col-
our upon storage. Since trehalose is a non-reducing sugar,
the change in colour cannot be attributed to the Maillard
reaction.
Data from the present study show, that in the glassy state
trehalose decreases lipid oxidation and is therefore a suitable
wall material for microencapsulation purposes. Future
research should aim on a microstructural characterization of
the oilwater interface and its physicochemical characteriza-
tion after drying to investigate the mechanisms responsible
for the improved oxidative stability. A rapid oxidation of the
microencapsulated oil was observed upon crystallization of
814 S. Drusch et al. / Food Research International 39 (2006) 807815
Table 2
Results from the colour measurement for microencapsulated Wsh oil using the CIELAB Lab system
Wall material Oil content (%) L a
Initial value After storage at
0% rh 54% rh
Trehalose 40 95.6 94.8 92.8
Trehalose 10 94 94 89
Glucose syrup 40 93.4 94 94.2
Glucose syrup 10 94.4 94.7 95.1
trehalose, which limits the range of applications to products
to be stored at low humidity. Buera, Schebor, and Elizalde
(2005) recently reviewed, that crystallization is a general phe-
nomenon in carbohydrate chemistry leading to decreased
stability of dehydrated foods and ingredient applications.
Apart from lipid oxidation upon crystallization, non-enzy-
matic browning, enzyme activity loss, protein denaturation,
loss of membrane integrity and release of encapsulated com-
pounds from amorphous matrices are accelerated (Buera
et al., 2005). Commercially available microencapsulated
products show a similar behaviour compared to microcap-
sules from the present study, since all products contain
amorphous carbohydrates like dextrins, sucrose or lactose.
However, microencapsulated products are usually stored
under a protective atmosphere like nitrogen and typical food
applications are low moisture foods like instant beverages,
infant formula or bread mix. Nevertheless, to increase the
range of applications, improved stability at higher relative
humidity would be highly desirable. It is well known, that
polymers, mixtures of carbohydrates and salts modify the
kinetics of sugar crystallization, and future research should
investigate the beneWcial eVect of these modiWcations on the
stability of microencapsulated oils.
Acknowledgements
This work is part of the research of the Working Group
on Food Quality and Safety at the University of Kiel, which
is funded by the State government of Schleswig-Holstein.
The study was Wnancially supported by the Stiftung Schle-
swig-Holsteinische Landschaft. We thank Cerestar Deutsch-
land GmbH for technical advise, Linie Geertrui Haest at
Cerestar Vilvoorde R&D Centre for DVS analyses, PD Dr.
H. Steckel from the Department of Pharmaceutics and Bio-
pharmaceutics for providing the analytical equipment for
powder characterization as well as L. Pichert, T. Hartmann
and J. Knipp for skilful technical assistance.
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