International Journal of Food Science and Technology 2016, 51, 1647–1654 1647

Original article
Effect of citric acid esterification conditions on the properties of
the obtained resistant starch

_
Małgorzata Kapelko-Zeberska,* Tomasz Ziez ba, Witold Pietrzak & Artur Gryszkin
nskiego 37/41, 51 – 630, Wroclaw, Poland
The Faculty of Food Science, Wroclaw University of Environmental and Life Sciences, Chełmo

(Received 14 January 2016; Accepted in revised form 5 April 2016)

Summary This study was aimed at comparing selected properties of starch citrate obtained from native or retro-
grades of potato starch at various temperatures (100, 130 or 160 °C) and at various doses of reactant (10,
20 or 40 g per 100 g). Higher susceptibility to esterification was demonstrated for retrograded starch,
whereas the degree of esterification of the produced esters varied considerably (1.4 to 10.0 g per 100 g
preparation) and was increasing along with increasing roasting temperature and dose of citric acid. The
process of pasting occurred only in the esters obtained at a temperature of 100 °C, which resulted in a
significant decrease in swelling power and solubility in water of the citrates produced at higher tempera-
tures. The resultant starch citrates were characterised by significant resistance to amylolysis (ranging from
22 to 100 g per 100 g). There was observed an increase in starch resistance along with the increase in the
acid dose and roasting temperature. All analysed properties of starch citrates were not correlated with the
degree of esterification, but appeared to depend on the roasting, which may point to a significant effect of
this factor on the mechanism of starch cross-linking with citric acid.
Keywords Amyloglucosidase, functional properties, resistant starch, starch, starch citrate.

starch reduced the energy value of a meal and causes a

Introduction
Resistant starch is referred to as the sum of starch and
products of its degradation that are not absorbed in the
small intestine of a healthy person and is known to
occur in several forms: RS1 – starch physically unavail-
able to digestive enzymes (e.g. starch in partially ground
grains of cereals), RS 2 – nonpasted starch of some
plant species (e.g. potato starch), RS 3 – retrograded
starch (e.g. from cooled cooked starch products), RS
4 – chemically or physically modified starch and RS
5 – amylose–lipid complexes (Cheyne et al., 2005). Fer-
mentation of resistant starch by bacteria colonising the
colon has a beneficial effect on digestion by decreasing
medium pH (Wronkowska et al., 2002), which results in
a decrease in pathogenic microorganism count (Silvi
et al., 1999). Short-chain fatty acids produced in the

colon (Soral-Smietana & Wronkowska, 2004) have been
shown to affect the synthesis of cholesterol and triglyc-
erides (Hara et al., 1999) by decreasing their blood
levels, whereas the butyric acid formed has been claimed
to prevent colon and anal cancer (Leszczy nski, 2004).
The consumption of food products rich in resistant
*Correspondent: Fax: +48 71 320 77 67;
e-mail: malgorzata.kapelko@wnoz.up.wroc.pl
slow release of glucose to blood, which induces the insu-
lin response (Nugent, 2005). The health-promoting sig-
nificance of resistant starch becomes an inspiration for
the search for novel methods of producing preparations
of this type that could be used as food additives. Con-
sidering that it is important that these preparations be
characterised, apart from significant resistance, by prop-
erties tailored to their potential applications. Common
are methods that allow producing resistant starch with
high solubility in water (Masłyk et al., 2003; Shukri
_
et al., 2015), forming viscous pastas (Kapelko-Zeberska
et al., 2015) or characterised by high thermal stability
(Xie & Liu, 2004; Tharanathan, 2005). In recent years,
authors of this manuscript have conducted investiga-
tions on chemically modified (acetylated, cross-linking
with adipic acid) retrograded potato starch. These inves-
tigations resulted in the elaboration of a method for the
production of RS ¾ type resistant starch with texture-
forming properties (Kapelko et al., 2012b). The under-
taken research issues have been continued in studies on
the esterification of retrograded starch with citric acid,
characterised by high reactivity compared to starch
(Gaffar, 2002). The cross-linking with this organic acid
causes reduction of starch susceptibility to amylosis
(Xie & Liu, 2004; Shin et al., 2007) and, simultaneously,

doi:10.1111/ijfs.13136
© 2016 Institute of Food Science and Technology
1648 Starch citrate as resistant starch M. Kapelko-Z_ eberska et al.
lowers its solubility in water (Olsson et al., 2013). No
pasting occurs, however, in this modified preparation at
a higher degree of substitution (Xie & Liu, 2004).
The objective of this study was to compare selected
properties of starch citrate obtained from native or ret-
rograded potato starch under various conditions.
Materials and methods
Materials
The initial experimental material included Superior
Standard potato starch produced by PEPEES Łom_za
and citric acid purchased at POCH SA Gliwice.
Production of retrograded starch preparation
Retrograded starch was prepared according to the
methodology described by the authors of this manu-
script in their earlier works (Kapelko et al., 2012a). To
this end, a five-kilogram portion of paste (with the
concentration of 10 g of starch per 100 g of solution)
was prepared from native potato starch. For complete
pasting of starch, the paste was left for 6 h in a water
bath (Memmert, Germany) at 94 °C, cooled, frozen
for 3 days at 20 °C and defrosted for 2 days at
20 °C. The precipitated starch with a spongy structure
was rinsed with distilled water, dried in an air dryer
(Memmert, Germany) at 35 °C for 24 h, ground and
sieved through a screen with mesh size of 400 lm.
Production of citric acid esterified starch samples
The cross-linking with citric acid was conducted
according to the methodology developed by Klausho-
fer et al. (1978), with modified reagent doses and
roasting temperatures. Native starch (NS) or retro-
graded starch (R) was esterified with citric acid using
three doses of the reagent. Appropriate quantities of
the acid (10, 20 or 40 g per 100 g of starch dry matter)
were dissolved in 70 mL of water, and pH of the resul-
tant solution was adjusted to pH = 3.5 using
10 mol L 1 NaOH; afterwards, the solution was filled
up with water to the volume of 100 mL. Native or ret-
rograded starch was thoroughly mixed with a respec-
tive solution of citric acid, so as to obtain mixtures of
10, 20 or 40 g citric acid per 100 g d.m. starch after
drying. The resultant starch paste was left for 12 h at
a room temperature and afterwards dried in an air
dryer (Memmert, Germany) at 50 °C for 12 h. Each of
the dried modified preparations was divided into three
portions that were next roasted at three temperatures
(100 °C, 130 °C and 160 °C) for 3 h. Each roasted
sample was rinsed three times with ethyl alcohol with
the concentration of 95 mL ethanol per 100 mL solu-
tion (each time, in the volume being three times higher
International Journal of Food Science and Technology 2016
than starch content), and each time the solution was
decanted from above the precipitate. The rinsed pre-
cipitate was dried in an air dryer at a temperature of
30 °C for 12 h, ground in a laboratory mill and sieved
through a screen with mesh size of 400 lm.
Determination of the degree of substitution
The analysed preparation (2 g) was weighed with the
accuracy of 0.001 g (Menzel et al., 2013). Then, 2 mL
of distilled water and 50 mL of 1 mol L 1 KOH solu-
tion were added. The whole sample was heated for
10 min in a boiling water bath. After cooling, the mix-
ture was neutralised to pH=8.5 using a 5 mol L 1
acetic acid solution. Afterwards, 25 mL of borate buf-
fer with pH=8.5 and 0.3 g of an indicator (a mixture
of murexide and Na2SO4 at a ratio of 1:500) were
added. The mixture was filled up with distilled water
to the volume of 300 mL and titrated with a
0.05 mol L 1 solution of CuSO4 till the red-violet
colour disappeared. The degree of starch esterification
with the acid was expressed by the quantity of citric
acid residues in 100 g of the preparation.
Determination of swelling power and solubility in water
with a temperature of 80 °C
A water suspension was prepared from a preparation
of cross-linked retrograded starch that contained 1 g
of starch per 100 g of the solution (Richter et al.,
1968). The suspension was shaken at a temperature of
80 °C for 30 min. Afterwards, the sample was cooled
to 20 °C and centrifuged for 30 min using a Biofuge
28RS centrifuge (Heraeus Sepatech, Germany) with
acceleration of 22 500 g. The separated supernatant
was determined for dry matter content with the gravi-
metric method, and the precipitate left in centrifuge
tubes was weighed.
Determination of thermal characteristics with the DSC
technique
Thermal properties were determined with a differential
scanning calorimeter DSC 822E by MettlerToledo
(Germany), following methodology provided by Ziez ba
et al. (2011), with modification regarding measurement
temperature range. Before the measurement, the
calorimeter was calibrated using a sample of indium
and a sample of zinc. The starch preparation (10 mg
on dry matter basis) was weighed into ME-51119871
medium-pressure crucibles, and bidistilled water was
added at a ratio of 3:1 (water: starch). Afterwards, the
crucible was sealed and conditioned at a temperature
of 25 °C for 30 min. The analysis was carried out in a
temperature range of 25 °C–100 °C at a heating rate
of 4 °C min 1.
© 2016 Institute of Food Science and Technology

Determination of resistance to the action of
amyloglucosidase
Suspensions were prepared that contained 0.36 g of
starch per 100 g of the solution (Kapelko et al.,
2012a). They were heated to the boiling point under
continuous stirring and then cooled to a temperature
of 37 °C at which hydrolysis with amyloglucosidase
was conducted (Amigase by Genecor, Danisco A/S,
Denmark). The enzyme’s concentration was adjusted
so as to induce complete saccharification of pasted
native starch after 120 min of the process. The amount
of free glucose was determined colorimetrically using a
CECIL CE 2010 colorimeter (Cecil Instruments, Eng-
land) at the wavelength of k = 500 nm, using the
GLUCOSE reagent for glucose concentration assay by
Biosystem (Spain) which contains glucose oxidase and
peroxidase. Each time, the process of citrates sacchari-
fication was continued until there was no change in
saccharification degree.
Statistical analysis
Results were statistically analysed using Statistica 10.0
PL software package. Based on statistical computa-
tions (from at least three parallel replications), values
of the least significant differences and standard
10
0 10 20 40
9
LSD = 0.02
6
DS [g 100 g–1]
0
100 130
Native starch
Figure 1 Citric acid level incorporated in starch vs roasting conditions.
© 2016 Institute of Food Science and Technology
Starch citrate as resistant starch M. Kapelko-Z_ eberska et al. 1649
deviation were calculated. For statistical evaluation,
the results were subjected to one-way analysis (in the
case of roasting temperature, calculations were made
of native and retrograded starch) of variance at a sig-
nificance level of 0.05. Values of the least significant
difference (LSD) between the means were computed
using the Duncan’s test at a significance level of 0.05.
Discussion of results
All factors applied in the experiment had a significant
effect on the degree of substitution of the produced
starch citrates (Fig 1). The quantity of bound citric
acid was increasing along with reagent dose and roast-
ing temperature, which is consistent with results of
other studies (Jyothi et al., 2007; Olsson et al., 2013).
At a temperature of 100 °C, the effectiveness of esteri-
fication with the lowest dose of the reagent was on
average three times lower and at a temperature of
160 °C only two times lower than at the highest
applied dose of the acid. These differences result from
the effect of temperature on the mechanism of reac-
tion. Slight esterification of starch with citric acid
proceeds already at 70 °C (Menzel et al., 2013). Tem-
perature increase above 100 °C causes that citric acid
easily releases a water molecule, thus forming an anhy-
dride which reacts with hydroxyl groups of starch
160 100 130 160
Retrograded starch
Temperature [°C]
International Journal of Food Science and Technology 2016
1650 Starch citrate as resistant starch M. Kapelko-Z_ eberska et al.
(Wing, 1996). The long-term roasting of starch at a
high temperature may, however, lead to lower dynam-
ics of the reaction owing to decarboxylation and dehy-
dration of citric acid to itaconic acid and aconitic acid
and their anhydrides (Gaffar, 2002). Also, the type of
potato starch used in the experiment significantly
affected the outcome of the conducted esterification.
The degree of esterification of native starch charac-
terised by a compact granular structure was lower (by
22% on average) than that of retrograded starch with
the porous structure. The susceptibility of retrograded
starch to chemical modifications is determined by the
method of its production (Kapelko et al., 2013;
_
Kapelko-Zeberska et al., 2015), which affects porosity
of the resultant retrograded starch (Kapelko et al.,
2012a). In the case of retrograded starch produced
under the same conditions as in the presented experi-
ment, a similar tendency may be observed during
esterification of the two described forms of starch with
acetic acid (Ziez ba et al., 2011) or adipic acid (Ziez ba
et al., 2014).
The roasting of starch induces processes of depoly-
merisation, transglucosidation and repolymerisation
inside a starch molecule (Leszczy nski, 2004). A well-
known effect of these transformations is an increase in
starch solubility in water and a decrease in its swelling
power, both being the greater the higher is the roasting
temperature (Ueno et al., 1976). Analogous tendency
100
0 10 20 40
90
80
70
Solubility [g 100 g–1]
60
50
40
30
20
10
0
100 130
Native starch
Figure 2 Solubility of starch citrates in water.
International Journal of Food Science and Technology 2016
was observed in the case of roasting potato starch
without acid addition (native or retrograded) (Fig. 2,
Fig. 3). The addition of citric acid to starch during its
roasting at 130 and 160 °C caused a significant
decrease in its solubility in water (to a few per cents)
and its swelling power (to a few g per g). These
changes result from modification in starch structure
proceeding as a result of esterification with citric acid,
which makes water penetration to the interior of
starch molecules impossible (Xie & Liu, Mei et al.,
2015), and from the re-attachment of dextrins formed
as a result of thermolysis of starch chains (Leszc-
zynski, 2004). The least changes of the discussed traits
occurred in the citrates produced at a temperature of
100 °C. The cause of these changes cannot, however,
be sought only in a low esterification degree of these
preparations with citric acid. The preparations roasted
at 100 °C with the highest dose of the acid were char-
acterised by a similar degree of substitution with citric
acid to the preparations roasted at 130 °C with the
addition of 20 or 40 g of citric acid or to those roasted
at 160 °C with 10 g of citric acid, whereas their swel-
ling power and solubility in water differed significantly.
This result may be explained not by the quantitative
but by the qualitative aspect of starch esterification
with citric acid. Many theoretical works point to the
possibility of the formation of mono- or diesters of
starch. However, our earlier studies (Kapelko-Z_
LSD = 0.89
160 100 130 160
Retrograded starch
Temperature [°C]
© 2016 Institute of Food Science and Technology

100
0 10 20 40
90
80
70
Swelling power [g g–1]
60
50
40
30
20
10
0
100 130
Native starch
Figure 3 Swelling power of starch citrates.
eberska et al., 2016) and that of Menzel et al. (2013)
explicitly exclude the formation of monoesters under
conditions of the described experiment. It is likely,
however, that at various temperatures of esterification,
the degree of cross-linking inside an amylopectin mole-
cule differs from that observed between molecular
structures of starch (such as amylose or dextrins
formed as a result of thermolysis). A low degree of
amylopectin cross-linking may even cause an increase
in its swelling power, whereas a higher degree of cross-
linking impairs the possibility of macromolecule
expansion in water. A similar dependency occurs in
the case of starch diphosphates that are characterised
by high swelling power and viscosity of formed pastes
at a low degree of substitution and by insolubility in
water at a high degree of substitution (Tester & Mor-
rison, 1990; Shukri & Shi, 2015). In the present experi-
ment, at a temperature of 100 °C, the cross-linking of
lower molecular fractions of starch was more likely
than the intramolecular cross-linking of amylopectin,
whereas at the higher temperatures (130, 160 °C), this
tendency was, probably, opposite.
The thermal characteristics of roasted starch gelatin-
isation are determined by both the temperature of
heating as well as by starch type or moisture content
(Sekine et al., 2000). The roasting of native potato
starch at various temperatures caused insignificant
© 2016 Institute of Food Science and Technology
Starch citrate as resistant starch M. Kapelko-Z_ eberska et al. 1651
LSD = 1.12
160 100 130 160
Retrograded starch
Temperature [°C]
changes in the thermal characteristics of gelatinisation
(Table 1). The increase in roasting temperature
resulted in a slight decrease in gelatinisation tempera-
ture and phase transition temperature. A similar ten-
dency was observed in the case of retrograded starch;
however, the changes of the discussed parameters were
greater. Starch roasting with citric acid had a signifi-
cant effect on its thermal stability. Regardless of the
type of raw material, all citrates produced at 130 °C
(except for the preparation produced from native
starch with the lowest analysed dose of citric acid) and
at 160 °C were incapable of gelatinisation. This was,
probably, due to high cross-linking of amylopectin
chains that inhibited macromolecular mobility in water
into molecule’s interior. Similar results were reported
for citrates obtained through the roasting with citric
acid of maize starch (Xie & Liu, 2004), rice or pea
starch (Ma et al., 2009) as well as for citrates prepared
through homogenisation of an aqueous suspension of
maize starch saturated with citric acid (Shin et al.,
2007). Esterification conducted at a temperature of
100 °C led to starch citrates that showed the capability
of gelatinisation, with a relatively high heat of phase
transition compared to reference samples. It needs to
be emphasised that this capability did not depend on
the degree of substitution but on the temperature of
roasting. Preparations with a similar degree of
International Journal of Food Science and Technology 2016
1652 Starch citrate as resistant starch M. Kapelko-Z_ eberska et al.

Table 1 Thermal properties of starch citrates determined based on DSC characteristics

Peak temperature [°C] Heat of phase transition [J g 1]

Temperature of roasting [°C] Temperature of roasting [°C]

Addition of
Type of starch citric acid [g per 100 g] 100 130 160 100 130 160

NS 0 61.33  0.01 61.27  0.01 59.23  0.04 13.06  0.02 12.82  0.01 12.65  0.01
10 55.64  0.03 51.96  0.01 – 12.36  0.02 2.57  0.01 –
20 54.89  0.01 – – 12.95  0.01 – –
40 59.16  0.01 – – 11.13  0.02 – –
R 0 52.69  0.02 52.32  0.01 48.93  0.01 5.13  0.01 5.08  0.01 3.83  0.01
10 54.42  0.01 – – 5.21  0.03 – –
20 54.91  0.01 – – 6.95  0.01 – –
40 55.02  0.02 – – 4.74  0.01 – –
LSD = 0.05 LSD = 0.04

substitution roasted at various temperatures were char- occurred in the preparations with a similar degree of
acterised by extremely different thermal properties. substitution and roasted at 130 or 160 °C. As in the
The preparation produced from native starch with the case of the above-described changes in swelling power
use of 20 g of acid per 100 g of starch, roasted at and solubility in water, this should be explained not
100 °C, was characterised by fivefold higher heat of by the quantitative but by the qualitative esterification
transition and by ca. 8 °C higher temperature of gela- of starch with citric acid.
tinisation compared to the sample prepared at 130 °C The roasted starch (regardless of its type and roasting
using a smaller dose of citric acid. In turn, the prepa- temperature) was characterised by ca. 10% resistance to
rations obtained from retrograded starch using 20 or amylolysis (Fig. 4). In the case of native starch, this
40 g of acid per 100 g of starch and roasted at 100 °C could be due to the unnatural bonds formed as a result
were capable of gelatinisation, whereas no pasting of repolymerisation at the position 2 or 3 of glucose

100
0 10 20 40
Resistance to amyloglucosidase activity [g 100 g–1]

90
LSD = 0.71
80

70

60

50

40

30

20

10

0
100 130 160 100 130 160
Native starch Retrograded starch
Temperature [°C]

Figure 4 Resistance of starch citrates to amylolysis.

International Journal of Food Science and Technology 2016 © 2016 Institute of Food Science and Technology

that are left untouched in the process of enzymatic
hydrolysis (Leszczy nski, 2004). Nonroasted retrograded
starch displays ca. 10% resistance to amylases (Ziez ba
et al., 2011). The roasting of this starch is expected to
increase its resistance. Presumably, however, the roast-
ing simultaneously reduced the resistance gained by the
formed retrograded starch and increased it as a result of
repolymerisation. The roasting of starch with the addi-
tion of citric acid caused an increase in its resistance,
which was increasing along with an increasing acid dose
and roasting temperature. Resistance which fluctuated
in a wide range (from ca. 20% to 100%) was not signifi-
cantly influenced by the type of starch used for esterifi-
cation. As in the case of other above-described
properties of starch citrates, starch resistance did not
depend on the degree of esterification but depended on
the conditions of the esterification process. Resistance
of the preparations with a similar degree of substitution
(4.4–5.3 g per 100 g) roasted at various temperatures
ranged from ca. 25 to 100%. It confirms an earlier for-
mulated thesis that at different temperatures, the mech-
anism of starch esterification with citric acid differs. Our
previous studies with the use of the NMR technique
and a Bruker Avance II 600 MHz apparatus proved the
effect of the site of substitution in anhydroglucose with
a residue of citric acid on starch resistance (Kapelko-Z_
eberska et al., 2016). It was, however, impossible to
conduct such assays in the present study, because the
sample to be analysed needs to be in the solubilised
form, whereas the produced starch citrates with a high
degree of substitution were insoluble in all solvents
known in starch analytics.
Conclusions
Starch esterification with citric acid induced changes in
its properties, with tendency and extent of these
changes being dependent on the type of raw material
and reaction conditions. Native starch was esterified to
a lesser extent than the retrograded starch did. The
increase in roasting temperature and reagent dose
resulted in an increasing degree of starch esterification
as well as in lower solubility in water and swelling
power, higher resistance to amylolysis and lost capabil-
ity for gelatinisation of the produced citrate. All anal-
ysed properties of starch citrates were not influenced
by the degree of esterification but mainly by roasting
temperature, which may be indicative of a significant
impact of this factor on the mechanism of starch
cross-linking with citric acid.
Acknowledgments
This study was supported by Wroclaw Centre of
Biotechnology programme, The Leading National
Research Centre (KNOW) for years 2014–2018.
© 2016 Institute of Food Science and Technology
Starch citrate as resistant starch M. Kapelko-Z_ eberska et al. 1653
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