Eur Food Res Technol (2002) 214:242247

DOI 10.1007/s00217-001-0446-1

O R I G I N A L PA P E R

Riitta Partanen Mikko Ahro Mari Hakala

Heikki Kallio Pirkko Forssell

Microencapsulation of caraway extract in -cyclodextrin

and modified starches
Received: 10 July 2001 Revised version: 12 October 2001 / Published online: 24 November 2001
Springer-Verlag 2001

Abstract Microencapsulation of supercritical CO2 extracted caraway fruit oil was investigated. Encapsulation
was carried out by molecular inclusion with -cyclodextrin, by spray-drying with maltodextrin and by spraydrying with a starch derivative. Carvone, one of the two
main constituents of caraway essential oil, was efficiently complexed with -cyclodextrin. Only half of the other
major constituent, limonene, was complexed. The inclusion complex seemed to protect volatile substances more
efficiently during storage, whereas microcapsules with
modified starches as wall material were more heat tolerant. During rapid heating, the -cyclodextrin microcapsules protected the volatile substances from evaporation
up to 100 C and HiCap microcapsules protected them
up to 140 C, while the protection properties of the maltodextrin microcapsules seemed to depend on the encapsulated molecules (160 C for limonene and 120 C for
carvone).
Keywords Caraway Microencapsulation
Cyclodextrin Starch derivatives

Introduction
Encapsulation of flavours can be used to protect volatile
compounds from evaporation as well as from off-flavour
development during storage [1]. Encapsulation can either
be based on wall formation or on molecular inclusion by
complexation with, e.g. cyclodextrins. Typical wall polyR. Partanen () P. Forssell
VTT Biotechnology, Tietotie2, P.O. Box 1500,
FIN-02044 VTT, Espoo, Finland
e-mail: Riitta.Partanen@vtt.fi
M. Ahro
Department of Applied Physics,
FIN-20014 University of Turku, Finland
M. Hakala H. Kallio
Department of Biochemistry and Food Chemistry,
FIN-20014 University of Turku, Finland

mers are hydrolysed starches with emulsifiers, and starch

derivatives with hydrophobic substituents. Recently, cyclodextrin was approved for use in food by the FDA
[2], which has increased the interest in its food-related
applications.
As the mechanism of encapsulation is different in cyclodextrins and in starch-based wall materials, it is expected that protection and release of the encapsulated
compounds would also differ. In complexation, the flavour load is limited by stoichiometry to around 10%,
whereas spray-dried powders may contain more than
20% flavour compounds [1]. -Cyclodextrin is reported
to be superior to starches in humid conditions and, also,
to be more thermo-stable [2].
The encapsulation of limonene has been extensively
studied. The stability of limonene has been used to estimate the level of protection against oxidation in the
spray-drying of orange oil [3, 4, 5]. Yoshii et al. [6, 7, 8]
and Furuta et al. [9, 10, 11, 12] have investigated complex formation between limonene and cyclodextrins by
kneading at low water content. The other major compound of caraway essential oil, carvone, is a biologically
active sprout-inhibitor [13, 14]. Thus, caraway essential
oil is also used in addition to food ingredients in potato
stores to retard sprouting.
The aim of this study was to protect volatile compounds of supercritical CO2 extracted caraway fruit oil
from evaporation by microencapsulation. The properties
of microcapsules achieved by different procedures and
wall materials are compared and the role of molecular
inclusion will be discussed.

Materials and methods

Materials. Caraway fruit oil (type 5737.090) extracted by supercritical CO2 was a mixture of essential oils and triacylglycerol
(9:1) purchased from Flavex Naturextrakte GmbH (Rehlingen,
Germany). Kleptose -cyclodextrin was purchased from Roquette
(Lestrem, France). Limonene and carvone were obtained from
Fluka Chemie AG (Buchs, Switzerland). Maltodextrin with dextrose equivalent 18.5 was purchased from Cerestar (Neuilly-sur-

243
Seine, France). As an emulsifying starch, sodium octenyl succinate derivative HiCap 100 from National Starch & Chemical
(Manchester, United Kingdom) was used. The dextrose equivalent
of the emulsifying starch was between 32 and 37. Gum arabic
(26,0770) was purchased from Aldrich (Milwaukee, USA) and
other chemicals of analytical grade were obtained from various
sources.
Complex formation of -cyclodextrin with limonene, carvone and
caraway fruit extract. -Cyclodextrin (10 wt%) was solubilised in
water at 65 C. Carvone, limonene or the caraway extract were
added at the level of 12% volatile substances per dry weight. The
solutions were allowed to cool at room temperature with magnetic
stirring and kept at +6 C overnight for complete precipitation.
The solutions were filtered or centrifuged at 10 000 g for 10 min
and the precipitate was air dried. Complexation efficiency was determined by measuring, by headspace GC, the contents of volatiles
stored for one week at 70 C.
Emulsification of caraway extract. The maltodextrin emulsion was
made by dissolving gum arabic (20 wt%) in water and homogenising with maltodextrin solution (40 wt%) and caraway fruit extract
with a Heidolph DIAX 600 (Kelheim, Germany) homogeniser at
24,000 rpm three times for a duration of 1 min each time. The HiCap emulsion was made, using a similar procedure, from dissolved HiCap (40 wt%) without any additional emulsifier. The
procedure guaranteed the formation of an emulsion of caraway extract that remained stable for the duration of the spray-drying. The
dry weight composition of the maltodextrin emulsion was 12%
caraway extract, 5% gum arabic and 83% maltodextrin, and that of
the HiCap emulsion was 12% caraway extract and 88% HiCap.
Spray-drying of caraway extract emulsions. Both maltodextrin and
HiCap emulsions were spray-dried in a Niro (Soeborg, Denmark)
Mobile Minor laboratory spray dryer with a rotating atomiser. The
temperature of the inlet air was adjusted to 200 C and that of the
outlet air was kept at 802 C by controlling the flow rate. The
atomiser rotation speed was 25,000 rpm. Powder was collected in
chamber and cyclone collection vessels, but only powder from the
chamber collection vessel was used in the study.
Thermal analysis of complexes. Thermal analysis was carried out
with a Mettler (Dietikon, Switzerland) DSC820 differential scanning calorimeter equipped with a liquid nitrogen cooling system.
A sample of 10 mg was weighed on an aluminium pan, which was
sealed. Heating and cooling were performed at a rate of 10 C/min
between 0 C and 200 C.
Sorption isotherms. Initial water contents were determined by Karl
Fischer titration. The residual water was extracted in methanol for
2 h with continuous stirring. The amount of solvent injected into
the titrator was determined gravimetrically. Samples with initial
moisture content were weighed (100 mg) and placed in humidity
chambers with different salt solutions: LiCl (RH 12%), MgCl2
(RH 33%), Mg(NO3)2 (RH 54%), NaCl (RH 75%) and (NH4)2SO4
(RH 81%). After one week of equilibration, the samples were
weighed again and the water sorption isotherms at room temperature (232 C) were determined.
GC-analysis of carvone and limonene contents in the capsules. All
the five microcapsule species were extracted overnight with methanol at room temperature. The samples were diluted in water, residual methanol content being 5%. The gas phase of the samples
was analysed by headspace-GC using n-butanol as an internal
standard. Equilibration was carried out at 60 C for 20 min. Limonene, carvone and n-butanol standard solutions in 5% methanol
were used for calibration. The gas chromatograph was a Perkin
Elmer Autosystem XL, with a flame ionisation detector (FID)
(Perkin Elmer Corporation, Norwalk, CT, USA) and the headspace
sampler was a Perkin Elmer HS-40 (Perkin Elmer Corporation,
Norwalk, CT, USA). Quantitation was done with PE Nelson
Turbochrom software (version 4,1., Perkin Elmer Corporation,

Norwalk, CT, USA). The column used was PE-5 50 m, i.d.

0.32 mm, df 1.0 m (Perkin Elmer Corporation, Norwalk, CT,
USA). Helium was the carrier gas as well as the make-up gas. The
temperature profile was as follows: 40 C, 1 min; 150 C, 20 min;
200 C, 5 min. The heating rate was 12 C/min.
Evaporation of carvone and limonene from the capsules. Evaporation of carvone and limonene from all the produced microcapsules
was studied by gas-phase FT-IR spectroscopy. Experimental design was divided into two parts: a) the effect of storage at room
temperature on limonene and carvone release, and b) the stability
of the microcapsules against rapid heating. Around 2 g of capsules
were smoothly spread on the bottom of a 100-ml beaker. A total of
167 beakers representing 167 analyses and 5 sample sets were
transferred to a fume hood and stored at 20.80.5 C and
RH<41%. One beaker at a time was taken out for FT-IR analysis.
The overall storage time was 45 days for HiCap and maltodextrin,
and 26 days for -cyclodextrin microcapsules. The stability of the
caraway extract products against rapid heating was measured after
41 days of storage for maltodextrin capsules, after 42 days for HiCap capsules and after 6 days for -cyclodextrin capsules. -Cyclodextrin complexed with pure carvone and limonene were investigated after six days and seven days storage, respectively.
FT-IR analysis. The FT-IR spectrometer, sampling unit and spectral analysis procedure were those described earlier [15]. The calibration principle of the FT-IR is explained in [16, 17]. A glass test
tube of approximately 9 ml volume was used as a sample container. A sample of 0.5 g of capsules was weighed into the test tube,
which was mounted onto the sampling line with a hose connector.
The test tube was cooled with liquid nitrogen and evacuated. The
valve between the test tube and the sampling line was closed and
the test tube was heated for 15 min. The temperature of the tube
was 40 C in the storage time study and ranged between 60 and
200 C in the stability test. The maximum temperature was selected according to the results and properties of the measurement
system: when the concentrations started to exceed the upper limit
of FT-IR spectrometer, the higher temperatures were not used. On
the other hand 200 C was the maximum temperature for the sampling system. The valve was opened again and the volatiles were
allowed to flow into the sample cell of the spectrometer. The sample cell was closed and the spectrum was measured. The measurement time was 60 s for the sample and 120 s for the background.
FT-IR measurements were meant to describe the leak of limonene
and carvone from microcapsules in constant time. The results obtained are given in mg/m3 in gas phase. These results are not
linked in any simple way to the total content of the capsules. The
results should be considered representing the leak speed from the
microcapsules.

Results and discussion

Complexation of pure limonene and carvone
with -cyclodextrin
Based on stoichiometry, the maximum theoretical load of
limonene in a -cyclodextrin complex is 11% and that of
carvone is 12%. Flavour loads in the complexes of pure
carvone and pure limonene were as shown in Table 1. After one week at 70 C, only half of the limonene (5.5%)
was left. In reference samples (dry mixtures of limonene
or carvone with -cyclodextrin) there was practically no
limonene or carvone left after one week of storage at
70 C. Carvone seemed to be complexed efficiently since
no loss by evaporation occurred during the storage.
X-ray diffraction is typically used to verify complexation with -cyclodextrin [8, 10, 12]. Thermal analy-

244
Table 1 Amounts of limonene
and carvone in freshly prepared
and stored -cyclodextrin complexes and reference mixtures
=not detected

Fresh sample
One week at 70 C

Limonene (%)
in complex

Limonene (%)
in reference

Carvone (%)
in complex

Carvone (%)
in reference

10.9
5.5

12.0
0.1

11.3
11.2

12.6

Fig. 1 DSC thermogram of dry

-cyclodextrin

Fig. 2 DSC thermograms of limonene and carvone complexed with -cyclodextrin

sis on complexation has been performed by differential

scanning calorimetry (DSC) [18] which was also applied in our study. No enthalpy changes were observed
in dry -cyclodextrin below 210 C (Fig. 1) where
melting of the crystals occurred [2]. The boiling point
of carvone is 230 C and that of limonene is 177 C.
The DSC thermograms of the dry -cyclodextrin complexes of limonene and carvone are shown in Fig. 2.
There was a clear endothermic peak in both thermograms, which was interpreted as degradation of the
complex. Both complexes showed relatively high heat

stability; limonene was released above 130 C and carvone above 170 C. Compared to the thermograms
measured by Chang and Reineccius [18], ours were
easier to interpret due to the more stable baselines.
Chang and Reineccius observed degradation of the limonene complex at 130 C, which was in good agreement with our results. As for the carvone complex, they
observed degradation as early as 140 C. The differences in thermograms and temperature of carvone release could be because of some residual moisture as
suggested by the authors themselves.

245

Fig. 3 Water vapour sorption isotherms of -cyclodextrin, the cyclodextrin-carvone complex, HiCap and maltodextrin

Fig. 4 Changes in carvone content of caraway fruit extract microcapsules and reference mixture with -cyclodextrin at room temperature

Sorption isotherms of the capsule materials

Water vapour sorption isotherms were determined for
pure -cyclodextrin and -cyclodextrin complexed with
carvone. Maltodextrin with DE 18.5 and chemically
modified starch (HiCap 100) were also studied with regard to the environmental humidity. Sorption isotherms
are shown in Fig. 3. Maltodextrin and HiCap sorbed
more water vapour at high humidity than -cyclodextrin.
Sorption of water in -cyclodextrin was dependent on
complexation, as the carvone guest was bound to possible hydration sites. At higher relative humidities, both
maltodextrin and HiCap started to dissolve.
Retention of caraway limonene and carvone
in the microcapsules
Caraway fruit extract contained 90% essential oil, of
which 37% was limonene and 59% carvone. In order to

Fig. 5 Changes in carvone content of caraway fruit extract microcapsules and reference mixture with -cyclodextrin at 70 C

compare the efficiency of -cyclodextrin complexation

with the efficacy of encapsulation in maltodextrin and
HiCap, caraway extract was used at the same level in all
microcapsules. The reference sample for the -cyclodextrin inclusion complex contained caraway extract mixed
with dry -cyclodextrin and had not undergone the complex formation procedure. Storage stability tests were
carried out at room temperature and at 70 C for 56 days
and carvone content was analysed by headspace GC
(Figs. 4 and 5). There appeared to be essentially no carvone loss from microcapsules during storage at either of
the temperatures. Carvone was completely evaporated
from the reference sample in 28 days at room temperature and in 14 days at the elevated temperature. Thus, all
the wall materials gave good protection against evaporation.
Effect of storage at room temperature on the vaporisable
limonene and carvone
The aim was to measure the amount of vaporisable limonene and carvone from microcapsules at a constant time,
i.e. the leak. Therefore, a short evaporation time and a
small sample amount were selected. The results do not
represent the total content of volatile substances in microcapsules but rather evaporation of the free compounds. The storage experiment lasted 45 days for the
HiCap and maltodextrin microcapsules and 26 days for
the -cyclodextrin microcapsules.
The FT-IR results are presented in Figs. 6 and 7. It
should be noted that the sampling method applied was
not an equilibrium headspace method. The results for cyclodextrin were obtained from pure carvone and pure
limonene microcapsules without the caraway oil matrix.
Taking the relatively high variation into account, it
can be concluded that the release of volatiles from maltodextrin and HiCap microcapsules did not show a clear
trend in 45 days. Figures 6 and 7 indicate a rather con-

246

Fig. 6 Changes in evaporated carvone from caraway fruit extract

(HiCap, maltodextrin) and pure carvone (-cyclodextrin) microcapsules during storage

Fig. 8 Volatile carvone concentration as a function of temperature

in -cyclodextrin, HiCap and maltodextrin microcapsules

Fig. 7 Changes in evaporated limonene from caraway fruit extract

(HiCap, maltodextrin) and pure limonene (-cyclodextrin) microcapsules during storage

Fig. 9 Volatile limonene concentration as a function of temperature in -cyclodextrin, HiCap and maltodextrin microcapsules

stant leak from the HiCap and maltodextrin capsules. If

the release observed had mostly been from the surface of
the capsules, a decreasing trend would have been observed. Compared to the maltodextrin and HiCap microcapsules, the evaporation of carvone and limonene from
-cyclodextrin microcapsules decreased rapidly. The fast
decrease in the concentrations for -cyclodextrin indicates that the higher concentrations observed in the beginning were due to residues on the surface of the microcapsules. When carvone and limonene had vanished
from the surface, no significant amounts were observed.
Thus, vapour release and the shelf-life behaviour of cyclodextrin is different from maltodextrin and HiCap.

Effect of heating on the capsule stability

Release of carvone and limonene from the microcapsules
as a function of temperature was analysed with gas phase
FT-IR, and the results are shown in Figs. 8 and 9. Measurements were made after residues of the volatiles from
the surfaces of microcapsules had vanished. Temperature
was increased step by step and intense rises of volatiles
were noticed at product-specific temperature ranges. Release of carvone from different capsules as a function of
temperature is shown in Fig. 8. Evaporation was released
at higher temperatures from the caraway oil complexed
in -cyclodextrin than from the pure carvone-cyclodextrin inclusion complex. Analogous results of limonene of
-cyclodextrin microcapsules containing pure limonene
vs caraway extract are shown in Fig. 9.

247

In the case of maltodextrin, carvone concentration

was kept constant up to 120 C and increased slowly to
200 C. Release of carvone from HiCap capsules, again,
remained at almost zero level up to about 140 C, at
which range of temperature the degradation of microcapsules was already visible (the capsule material turned
brown). For the caraway oil--cyclodextrin complex,
evaporation of carvone started to increase at 120 C, after which the increase was almost linear.
The maltodextrin capsules did not start to leak limonene significantly until quite high temperatures, above
160 C, were reached (Fig. 9). For HiCap the corresponding temperature was about 20 C lower, at 140 C.
For the caraway oil--cyclodextrin complexes the leakage of limonene started to increase at a temperature of
120 C. -Cyclodextrin complexes with pure carvone
and limonene started to release volatiles above 100 C
(Figs. 8 and 9), which was at a considerably lower temperature than that at which the degradation of the complex was observed by DSC (Fig. 2). This could probably
be explained by the difference in conditions of the two
measurements. The results indicate that despite some
leak of carvone, maltodextrin is the most heat-stable matrix for encapsulated volatiles in dry conditions.

Conclusions
Carvone could be efficiently complexed with -cyclodextrin, whereas only half of the limonene was complexed. Equal amounts of caraway extract encapsulated in
maltodextrin, emulsifying starch and in -cyclodextrin
were relatively stable during storage. As the inclusion
complex protected bound volatiles from evaporation in
-cyclodextrin, some evaporation occurred from both
HiCap and maltodextrin capsules. As for thermal stability, modified starches gave better protection than -cyclodextrin, maltodextrin microcapsules being the most heat
resistant. It can also be concluded that the FT-IR method
proved to be suitable for samples in powder form.
Acknowledgements The authors gratefully acknowledge financial support from the National Technology Agency (Tekes, Finland) and Hannele Virtanen for the HS-GC analyses. Ms. Teija
Jokila is acknowledged for her skilful technical assistance and Ms.
Anja Pirinen for performing the FT-IR analyses. Aromtech Ltd is
acknowledged for supporting the caraway extract.

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