Articulo de Almidones

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Instituto Nacional de Investigacin y Tecnologa Agraria y Alimentaria (INIA) Spanish Journal of Agricultural Research 2008, 6 (Special issue), 129-137

Available online at www.inia.es/sjar ISSN: 1695-971-X

Partially-gelatinised starches by high hydrostatic pressure


as oligoelement carriers
P. P. Fernndez1, P. D. Sanz1, M. N. Martino2 and A. D. Molina-Garca1*
1
Department of Engineering. Instituto del Fro. CSIC. C/ Jos Antonio Novais, 10. 28040 Madrid. Spain
2
Centro de Investigacin y Desarrollo en Criotecnologa de Alimentos (CIDCA). Facultad de Ciencias Exactas.
Universidad Nacional de La Plata. CONICET, 47 y 116. (CP 1900) La Plata. Argentina

Abstract
Zinc deficiency is a world wide problem, centred on the lower income population, though not restricted to it. Food
supplementation with magnesium is also considered of interest for correcting deficiencies in this oligoelement. High-
pressure partially gelatinised starch is proposed as a vehicle for inclusion of these metals in food products. While high-
pressure levels (and/or temperature) give rise to total gelatinisation, lower pressures, at temperatures close to ambient,
yield partially-gelatinised products, where only a portion of the intramolecular bonds in the amylopectin double helix
has been substituted by intermolecular bonds between the unfolded amylopectin and water, as it can be deduced by
differential scanning calorimetry, while the resultant granular microstructure is strongly altered (observed by low
temperature scanning electron microscopy). Production of this modified starch implies lower energy expense, compared
to thermal gelatinisation, and it guarantees higher homogeneity in the final degree of gelatinisation. The effect of
moderated high-pressure treatments (400 MPa, 25C, 35 min) on potato and corn starches has been studied. The effect
of pressure treatment, after alkaline treatment or the addition of another hydrocolloid (guar gum) has also been
considered. The observed preferential binding of zinc and magnesium salts to these modif ied starches (after
determination of metal content by atomic absorption spectrophotometry) is favourable to the use of these products as
metal carriers.
Additional key words: differential scanning calorimetry, magnesium, metal binding, micronutrients, scanning elec-
tron microscopy, supplementation, zinc.

Resumen
Almidones parcialmente gelatinizados mediante altas presiones como transportadores de oligoelementos
La deficiencia de cinc es una cuestin de alcance mundial, centrada en la poblacin de menores recursos, aunque
no restringido a ella. La suplementacin de alimentos con magnesio tambin se considera de inters para corregir las
carencias de este oligoelemento. Como vehculo para la inclusin de estos metales en productos alimenticios se pro-
pone el almidn parcialmente gelatinizado por alta presin. Mientras que altos niveles de presin (y/o temperatura)
causan gelatinizacin total, menores presiones a temperaturas cercanas a la ambiente rinden productos parcialmente
gelatinizados, en los que slo una proporcin de uniones intramoleculares de la doble hlice de amilopectina han si-
do sustituidas por enlaces intermoleculares entre la amilopectina desenrollada y agua, segn se deriva de datos de ca-
lorimetra diferencial de barrido, mientras que la microestructura del grnulo resulta muy alterada (observada por mi-
croscopa electrnica de barrido de baja temperatura). La produccin de este almidn modificado conlleva menor
gasto energtico, en comparacin con la gelatinizacin trmica, as como garantiza mayor homogeneidad en el grado
de gelatinizacin final. Se ha estudiado el efecto de tratamientos moderados de alta presin (400 MPa, 25C, 35 min)
sobre almidones de patata y de maz. Tambin se ha considerado el efecto de la presurizacin despus de un trata-
miento alcalino o de adicin de otros hidrocoloides (goma guar). La observacin de la unin preferencial de sales de
cinc y de magnesio a estos almidones modificados (tras determinacin del contenido en metales mediante espectro-
fotometra de absorcin atmica) es favorable al empleo de estos productos como portadores de metales.
Palabras clave adicionales: calorimetra diferencial de barrido, cinc, magnesio, micronutrientes, microscopa elec-
trnica de barrido, suplementacin, unin de metales.

* Corresponding author: [email protected]


Received: 05-09-07; Accepted: 29-01-08.
130 Span J Agric Res (2008), 6 (Special issue J. M. Malpica), 129-137

Introduction1 of nutritional value, including minerals, vitamins, and


antioxidants. These substances are often unstable,
Starch, a major food component, is widely employed reactive and difficult to bind or to assimilate from supple-
as an ingredient in many processed foods. Starch granules mented food. Pharmaceutically active compounds can
are complex structures with different proportions and also be introduced into food in this way. The uses of
spatial arrangements of two glucose polymers, linear starch as a food formulations stabilizer reflects the
amylose (with 1-4 bonds) and branched amylopectin interaction of water with the polymer network formed
(with 1-6 bonds). Energy is stored in starch as immo- on gelatinisation. Its binding and gelling properties
bilised sugar units within these two polymers. Starch can be modulated by modification of the native granules
granules are osmotically inactive and not easily accessible or the gelatinised free-chains. High hydrostatic pressure
to degradation. Specif ic plant enzyme systems can processing (HHPP) of food is a novel technology with
process the complex and compact granule structure as an increased presence in food processing. It is most
required during seed germination, fruit ripening and often employed to reduce food microbial load with
other physiological plant events. On the other hand, minimal associated chemical composition change and
human enzymes cannot properly degrade starch. It must without resorting to the addition of chemical preserva-
be previously thermally gelatinised in an irreversible tives. Other HHPP applications include modification
physico-chemical reaction with water, at temperatures of food enzymes, proteins and other macromolecular
between 50 and 90C depending on its botanical source. components. The equilibrium structure of macro-
Gelatinisation involves several sequential physical, molecules (including proteins and starch) is altered by
chemical and mechanical processes (Hoover, 2001). high-pressure in a similar way. In both cases equilibria
The highly ordered granule structure, evidenced by the are displaced towards the smallest volume species (Le
presence of a characteristic feature (Maltese cross) Chatelier), breaking secondary and tertiary structures
observed through polarizers under optical microscopy but leaving covalent bonds intact. Covalent bonds require
is lost during gelatinisation. Additionally, its component much higher energy than that supplied by hydrostatic
molecules escape from the granules, firstly the linear pressure. When there is no pressure-transmitting fluid
amylose and then the branched amylopectin. This leads medium, hydrostatic conditions do not apply and local
to granular binding and a large increase in the suspension pressure can be much higher. The shear forces acting
viscosity, due to formation of long-range interactions. under these conditions can induce covalent bond splitting.
This explains the frequent use of starch as a food The pressure-denatured state of proteins has been re-
thickening and binding agent. One of the main tools ported to be different from thermally or chemically
to investigate starch gelatinisation is differential scanning induced ones (Smeller, 2002; Molina-Garca, 2003).
calorimetry (DSC). The thermograms obtained in Kinetically driven processes are favoured, in a similar
heating scans show a wide transition curve, reflecting way, when the intermediate state volume is smaller
the many associated processes and the heterogeneous than that of the reactant species.
nature of starch granules. It shows a maximum in endo- Starch treated at sufficiently high-pressure becomes
thermic heat exchange between 50 and 90C, but because gelatinised, as its hydrated state has a lower specific
gelatinisation is an irreversible process and, so, scan volume (Katopo et al., 2002). Pressure- and thermally-
rate-dependent, the onset temperature of the process gelatinised starches are reported to be not completely
is most often reported. The associated enthalpy roughly equivalent (Knorr et al., 2006). The former process is
corresponds to the number of sugar monomer-sugar still under study. The lower thermal agitation (a function
monomer hydrogen bonds (within the amylopectin of temperature) could be the cause of differences in
helix) that have been replaced by water-sugar monomer molecular drifting: amylose and amylopectin movement
interactions. Chemical, enzymatic or physical modifi- away from their position in the granule could be reduced
cations of starch structure are reflected both in gelatini- compared with thermally gelatinised starch, and this
sation temperature and enthalpy. could be reflected in rheological behaviour of the
Food formulation requires the introduction of addi- resulting product. At pressures lower than those required
tives as colorants, flavours, aromas and also molecules for complete gelatinisation, about 600 MPa at room

1
Abbreviations used: AA (atomic absorption spectroscopy), cryo-SEM (low temperature scanning electron microcopy),
DSC (differential scanning calorimetry), HHPP (high hydrostatic pressure processing).
High-pressure-treated starch binds oligoelements 131

temperature (Smeller, 2002; Knorr et al., 2006), starch Sample preparation


becomes partially gelatinised. Many of the amylose
chains protrude from the granules, so that interactions Dry potato (analytical grade, Panreac, Castelar del
among them and with other molecules becomes possible. Valls, Spain) and corn (Roquette, Barcelona, Spain)
However, swelling, amylose solubilisation and granule starch, selected for comparison purposes, were obtained
dispersion are restricted in pressure (as compared to (but, with 12 and 15% residual water, respectively).
heat) gelatinisation. Starch gelatinisation under pressure Starch also contains a small amount of tightly bound
also leads to altered gel retrogradation behaviour (Douzals phospholipids, less than 0.1% for potato and around
et al., 1996). Additionally, some intact granule properties 0.8% for corn starch (Buleon et al., 1998; Vasanthan
are maintained, and thus the digestibility of partially- et al., 1999; Debet and Gidley, 2006). The starches
pressure-denatured starch would be lower or slower were used without further purification or defattening
than that of completely gelatinised starch. This property and suspended in deionised water at a concentration
can be exploited to carry and deliver bound molecules of 10% w/w. Although no stirring was available during
further into the digestive track. HHPP acts almost instan- the pressure treatments and starch granules quickly
taneously and independently from sample geometry and sedimented, the overlying water was considered to be
size, not giving rise to pressure gradients. Thus, pressure in equilibrium with the gelatinisation process without
partially gelatinised starch would be more homogeneous the need to resort to the addition of an auxiliary hydro-
and easier to obtain than its thermal equivalent. colloid (as employed by, e.g., Stolt et al., 2001; Kawai
Zinc and magnesium supplementation is, at present, et al., 2007). This procedure, successfully followed by
of high interest, in the case of at risk populations. Mo- many workers (e.g., Bl/ aszczak et al., 2005a; Oh et al.,
dified starch is considered a suitable vehicle for oligo- 2008), was adopted after tests with different water
element transport, due to its multiple uses as food in- contents showed that the overlying water was enough
gredient, low-cost and the versatility of its interactions to guarantee the required water/starch ratio (data not
with foods. In this study, the preferential union of these shown). Milli-Q deionised water was used for all sample
two metals to partially pressure-gelatinised starch was preparation (Millipore Inc Bedford, MA, US).
investigated as a model for the vehiculisation of a wide Guar gum (Sigma-Aldrich, San Louis, MO, USA)
range of food additive molecules, which may show food was solubilised in 50% of the final water volume by
modification properties or have nutritional or medical stirring under moderate heating (under 50C). Then,
interest. Starch alkaline treatment associated with starch previously suspended in the rest of the water,
pressure, to increase and modulate gelatinisation, was was added and mixed, stirred and left for starch hydration
also considered, as well as the addition of gum guar, and equilibration for 12 hours before further treatment.
another hydrocolloid, that could form interaction bridges Just before pressurisation, the suspension was stirred
between starch and the molecules bound to it. DSC, thoroughly. The gum:starch suspensions had a final
low-temperature scanning electron microscopy (cryo- concentration of 0.3% gum and 10% starch.
SEM) and atomic absorption spectroscopy (AA) were Alkaline-treated 10% w/w starch suspensions were
employed to investigate starch state and metal binding. prepared just before pressurisation by adding a 1%
solution of NaOH (Panreac) to the starch suspensions,
to a final concentration of 0.1% w/w, while the suspen-
Material and Methods sion was stirred thoroughly at room temperature. The
alkaline solution was removed when the sample was
Native, alkaline-treated or guar gum-added suspen- decanted, after pressure treatment.
sions of potato or corn starch were treated with high-
pressure (a single condition of pressure, temperature
and treatment duration). Later, the treated starch was Pressure treatment
mixed with zinc or magnesium salts and washed. The
DSC behaviour of the pressure-treated samples was All samples were subjected to pressure treatment
investigated, as well as its aspect by cryo-SEM. The under the same conditions, i.e. 25C initial vessel
metal content in the final samples was determined by temperature, 400 MPa and 35 min treatment time.
atomic absorption spectrometry. All treatments and Briefly, the experimental HHPP set-up employed
determinations were performed, at least, in triplicate. (previously described elsewhere: Otero et al., 2000,
132 Span J Agric Res (2008), 6 (Special issue J. M. Malpica), 129-137

freeze-dried and fresh samples (data not shown). Pressure


treatments were performed in triplicate.
Ambient thermocouple

T
T Metal addition
Liquid water
Metals were added as zinc sulphate and magnesium
2T
acetate (analytical grade, Panreac). Dry, treated and
T untreated starch samples (1 g) were suspended in 0.5 M
zinc sulphate or magnesium acetate aqueous solutions
(10 mL). After overnight agitation at room temperature,
the suspensions were centrifuged at 5,000 g with a table
T centrifuge and the pellet was water-washed (resuspension
plus stirring in 10 mL deionised water followed by cen-
Thermoregulating Thermocouples
bath trifugation) and oven-dried. The metals were quantified
Figure 1. Diagram of the high-pressure vessel used for hydros- by atomic absorption (AA) spectrophotometry, using
tatic pressure treatments. a Model 5100 spectrophotometer, Perkin-Elmer,
Norwalk, Connecticut, USA). AA analyses were per-
2002) was a pilot-scale unit from GEC Alsthom ACB formed in triplicate and are reported as averages. Cross-
(Nantes, France) with vessel temperature controlled determinations (i.e., quantification of magnesium in
by an ethylene glycol mixture circulating through a samples added with zinc and vice versa) were performed,
surrounding jacket (Fig. 1). Pressure was increased by always yielding negative results.
pumping fluid in the vessel, at 100 MPa min-1, and it
was released by opening a valve to the atmosphere,
which could be as quick as 100 MPa s-1. Differential scanning calorimetry studies
The internal vessel volume was 2.35 L. It was equipped
with two flexible inner thermocouples type T and a Differential scanning calorimetry (DSC) determina-
pressure gauge (type PR811, ASCO Instruments, Cha- tions were performed with a TA-1000 instrument (TA
teaufort, France), which was located in the pressure, Instruments, New Castle, DE, USA), at a scanning rate
circuit, at 15 cm from the vessel. Both thermocouples of 10C min-1. To minimize hydration variability, starch
and pressure gauge had been recently calibrated for samples were dispersed in water (10% w/w) 24 h before
use in this equipment and their data were collected by DSC analysis. Then, 15 L of slurry were introduced
a quick data acquisition system (Fluke, Helios I, Fluke in weighted aluminium pans, sealed and re-weighted.
Precision Measurement Ltd, Norwich, United Kingdom) After analysis, pans were punctured and dried at 110C
connected to a computer equipped with Labtech Note- to constant weight, to ensure accurate moisture and
book software (Laboratory Technology Corporation, starch content determinations. Thermograms were ana-
Wilmington, MA, USA). Error in the temperature lysed following standard procedures (Universal Analysis
measurement systems was estimated to be below Program, TA Instruments). Analyses were performed
0.5C, while error in the pressure was under 5%. Both in triplicate.
pressurisation and depressurisation induce changes in
temperature in both sample and the pressure transmitting
medium (Otero et al., 2000). Therefore, the value of Scanning electron microscopy
25C reported here must be considered an average over
time. Low-temperature scanning electron microscopy
Samples were treated in polypropylene flat 125 mL (SEM) was carried out with a Zeiss DSN-960 scanning
cylindrical containers (of 3 cm in height) immersed in microscope equipped with a Cryotrans CT-1500 cold
water as the pressure-transmitting medium. After plate (Oxford, UK). Cryo-SEM allows sample obser-
pressure treatment, starch was decanted and freeze- vation without chemical fixing or drying. The procedure
dried before further studies were carried out. Control consists of sample freezing by immersion in liquid
DSC determinations showed no difference between nitrogen, breaking and etching. Sample holders were
High-pressure-treated starch binds oligoelements 133

f itted into a special bracket on the microscope and from 14.2 1.0 J g-1 to 9.5 1.0 J g-114 in corn starch.
placed in the pre-chamber cold plate (180C), where Cryo-SEM observation of native and treated samples
samples were broken to obtain a suitable observable show that, in spite of minor changes to the gelatinisation
surface. Samples were then inserted in the microscope thermograms caused by the pressure treatment (Fig. 2),
and etching was performed for 3 min at 90C. After starch granule microstructure was partially-disintegrated
etching, samples were gold coated and observed at (Fig. 3). The granular integrity of native starch (Fig. 3A)
150/160C under secondary and backscattering was signif icantly reduced in HHPP-treated starch,
electron modes. A large number of granules (over 1,000) showing a core ghost surrounded by a residual network
corresponding to different regions of the sample on the of polymer chains (Fig. 3C and 3F). Figure 3C and 3F
stage were observed before representative electron show chosen field areas where more semi-intact granules
micrographs were taken. can be seen. Both alkaline treatment and guar gum
addition resulted in the appearance of filaments inter-
connecting the remaining granules, probably due to
Results amylose leaking from them and, in the case of Figure
3C, also to the gum. General microscopic observation
Both potato and corn starch appeared destabilized showed that alkaline treatment and gum addition had
after high-pressure treatment (400 MPa, 25C and 35 little effect, other than the appearance of filaments, on
min) in DSC thermograms. When compared with the aspect of pressurised starch granules. The observed
native potato starch (curve a), the gelatinisation curve effects were similar in both corn and potato starch (data
for the HHPP-treated potato starch (curve b) was not shown).
displaced towards lower temperatures (by 1-2C) and Pressure-treated starch samples tended to bind metals
the enthalpy of the process was partially reduced, by preferentially compared to untreated starch (Fig. 4).
approximately 30% (Fig. 2). In potato samples there Partially gelatinised potato starch, without alkaline
was an average enthalpy decrease from 20.1 0.9 J g-1 treatment or gum addition only, bound significantly
to 16.3 0.8 J g-1. Thermograms for alkaline-treated more magnesium. Alkaline and pressure-treated samples
(curve c) and guar gum added starch (curve d) show of both starch types bound more magnesium and zinc.
that, from a calorimetric point of view, these processes Zinc binding by samples of both starch types containing
had no significant effect on starch gelatinisation. Similar guar gum was increased approximately four-fold. In
results were obtained for corn starch (data not shown). all cases estimated error was less than 5%.
On pressurisation gelatinisation enthalpy was reduced

5.0
Discussion

a
Potato and corn starch samples treated at 400 MPa
5.5
Heat flow (W g1)

(at 25C for 35 min), were studied by DSC and observed


b by cryo-SEM to evaluate structural changes caused by
6.0 c this treatment. The pressure and temperature levels
d used were lower than those reported giving complete
6.5 starch gelatinisation (Smeller, 2002; Knorr et al., 2006;
Kawai et al., 2007). In agreement with published reports,
Exothermic all thermograms presented a thermal gelatinisation
7.0
30 40 50 60 70 80 90 curve, showing that in no case was gelatinisation com-
Temperature (C) plete. The enthalpy reduction observed reflected the
Figure 2. Typical DSC thermograms obtained with potato fraction of amylopectin helix hydrogen bonds that were
starch. Scanning speed was 10C min1 and samples were 10% replaced by bonds with water during pressure treatment
starch aqueous suspensions (thoroughly mixed and incubated suggesting that pressure-treated starch samples retained
for at least 1 hour) containing 1.5 g of starch. a: native starch. approximately 70% of their original intramolecular
b: high-pressure partially-gelatinised starch. c: high-pressure
partially-gelatinised starch after alkaline treatment. d: high- bonds.
pressure partially-gelatinised starch after addition of guar gum. Cryo-SEM enables observation of starch with little
Heat flow units are W/wet sample g. extrinsic manipulation. The branched structure observed,
134 Span J Agric Res (2008), 6 (Special issue J. M. Malpica), 129-137

A B C

D E F

Figure 3. Cryo-SEM micrographs of starch granules after different treatments. A, B, C: potato starch granules; A: native, B: high-
pressure partially-gelatinised, C: high-pressure partially-gelatinised with addition of guar gum. D, E, F: corn starch granules;
D: native, E: high-pressure partially-gelatinised. F: high-pressure partially-gelatinised after alkaline treatment.

A 5 5 B

4 4

3 3

2 2

1 1

0 0
Mg Zn Mg Zn

Native High pressure-treated after alkaline treatment


High pressure-treated High pressure-treated after addition of guar gum

Figure 4. Metal mass bound to starch after different treatments, relative to that bound by native starch A) potato starch, B) corn
starch. Bars above each column are the standard deviation.
High-pressure-treated starch binds oligoelements 135

down to the nanometric scale, is a promising substrate associated starch modif ications: alkali treated and
for food and medical applications. The numerous water samples with added guar gum (Fig. 4). Alkali treated
hydrogen bonds could be replaced by appropriate polar samples showed high but non-specific binding, which
molecules while the large carbohydrate chains could could be a result of actual akalinisation of the starch
offer non-polar substances a harbouring place. Moreover, substrate. Metal species bound may, then, may be in a
the gelatinisation of pressure-treated starch would be different state from ionised salts, forming hydroxides
completed, as shown by the DSC thermogram, at lower or metal oxides. This could have different consequences
temperatures than the corresponding native starch. on the transport, binding stability and assimilation of
The degree of starch gelatinisation and the degradation the metals. Further research into the state of the metal
observed in granules was roughly similar for both potato atoms bound to starch is deemed necessary.
and corn starch. Nevertheless, the literature assigns a Samples with added guar gum showed a significant
higher pressure resistance to potato starch (e.g., Douzals degree of binding of magnesium salts to potato starch
et al., 1996; Katopo et al., 2002; Bauer and Knorr, but not to corn starch. The binding for zinc was higher
2005). A possible explanation may be the higher surface (over 4-fold that of native starch) and was similar for
resistance of potato starch granules to pressure degra- both corn and potato starch. An effect based on structural
dation (Sevenou et al., 2002; Bl/ aszczak et al., 2005b; factors (generation of binding sites of adequate size)
Oh et al., 2008). A higher superficial resistance may or mediated by the role of gum in starch gelatinisation
have the effect of showing intact or only slightly affected must be considered, as guar gum is non-ionic. From
potato granules when studied by optical or room tem- the current data, it is not possible to extract further
perature-electron scanning microscopy, while internal conclusions on the differential behaviour of zinc and
granule degradation may have progressed to a further magnesium. Both form divalent salts have a similar
degree. It must also be considered that most studies ionic size. It may also be of interest to investigate the
have been performed on fully gelatinising pressure role of anions on metal binding, as they might be
treatments, rather than in partial gelatinisation, as in responsible for salt retention (e.g., Ciesielski and
this case. While complete starch gelatinisation is Tomasik, 2003).
reported to take place under harsher conditions (higher With regard to the differences in binding between
pressure and/or temperature) (e.g., Knorr et al., 2006), potato and corn starch, the degree of gelatinisation and
the same authors reported studies where gelatinisation microscopic aspects of the samples being similar, it is
behaviour of both corn and potato starch had been altered again difficult to achieve further insight into the binding
by treatments at 400 MPa (Thevelein et al., 1981; Muhr process, as pressure-treated potato starch bound more
et al., 1982). Specifically for corn, an 18% swelling magnesium salts while gum guar-added (pressure-
degree was found after pressurisation at 400 MPa (Oh treated) corn starch retained more zinc salts. This is
et al., 2008). not easy to explain from facts such as native ionic
Though small, a decrease in the gelatinisation tem- starch behaviour.
perature of pressure-treated starch was found (Fig. 2). The granular structure, although weakened, could
This behaviour is generally observed (Knorr et al., allow formation of chelate-type bonds in which large
2006). A parallel with proteins suggests that the granule molecules or atoms could be attached by freely moving
stability of pressurised samples was reduced. This starch amylopectin branches. These molecules or atoms
could only be strictly true for equilibrium thermal pro- could be trapped or encapsulated in the semi-disinte-
cesses and starch gelatinisation has a significant non- grated granules, and they would be released on the di-
equilibrium aspect. Water access to the inner regions gestion of the remaining starch core. The digestion of
of starch granules may be an important initial step these granules would, consequently, be easier than that
in the whole gelatinisation process. Pressurisation, of native starch but slower than completely gelatinised
at moderate pressure levels, could give better access granules. Therefore, partially pressure-gelatinised
of water molecules to these regions, so that subse- starch could be used to transport and deliver substances
quent thermal gelatinisation can start at lower tempe- for the food and pharmaceutical industry including
ratures. nutrients, oligoelements, vitamins, antioxidants, colo-
Preferential metal binding, in spite of higher bound rants, flavours, aromas and pharmaceuticals. The prefe-
magnesium mass, for high-pressure treated potato rential binding of zinc and magnesium to high-pressure
starch, can be seen as especially high for the two other modified starch (potato and corn), alone or with a small
136 Span J Agric Res (2008), 6 (Special issue J. M. Malpica), 129-137

percentage of added hydrocolloids (e.g., guar gum) Acknowledgements


and the use of alkaline treatment confirms the potential
of these modified starches as metal carriers. The role This work was carried out with financial support
of guar gum in zinc binding and the differences in from the Spanish Plan Nacional de I+D+I (2004-
metal union of the alkaline-treated samples still need 2006) MCYT through the AGL 2003-06862-C02-00
to be investigated. project. P.P Fernndez thanks the CSIC, Spain for his
Thermal processes also yield partially gelatinised grant in the context of the I3P Program, partially
starch, but pressure appears to be an advantageous supported by the European Social Fund.
production procedure, as the lack of pressure gradients
during treatment would give rise to more homogeneous
partially gelatinised granules. Pressure is transmitted References
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