Accepted Manuscript

Title: Analysis of the pasting profile in corn starch: structural,

morphological, and thermal transformations, Part I

Author: Natalia Rincón-Londoño Lineth J. Vega-Rojas

Margarita Contreras-Padilla A.A. Acosta-Osorio Mario E.
Rodrı́guez-Garcı́a

PII: S0141-8130(16)30482-2
DOI: http://dx.doi.org/doi:10.1016/j.ijbiomac.2016.05.070
Reference: BIOMAC 6131

To appear in: International Journal of Biological Macromolecules

Received date: 9-12-2015

Revised date: 12-5-2016
Accepted date: 18-5-2016

Please cite this article as: Natalia Rincón-Londoño, Lineth J.Vega-Rojas, Margarita
Contreras-Padilla, A.A.Acosta-Osorio, Mario E.Rodrı́guez-Garcı́a, Analysis of
the pasting profile in corn starch: structural, morphological, and thermal
transformations, Part I, International Journal of Biological Macromolecules
http://dx.doi.org/10.1016/j.ijbiomac.2016.05.070

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Analysis of the pasting profile in corn starch: structural, morphological, and thermal

transformations, Part I

Natalia Rincón-Londoñoa, LinethJ.Vega-Rojasb, Margarita Contreras-Padillac, A.A.

Acosta-Osoriod, Mario E. Rodríguez-Garcíae,*

a
Posgrado en Ciencias e Ingeniería de Materiales, Centro de Física Aplicada y Tecnología

Avanzada, Universidad Nacional Autónoma de México, Campus Juriquilla, Querétaro,

Qro, C.P 76230, México.

b
Posgrado en Ciencias Químico Biológicas, Facultad de Química, Universidad Autónoma

de Querétaro, Cerro de las Campanas S/N. Centro Universitario C.P 76010 Querétaro,

Qro., México.
c
División de Investigación y Posgrado, Facultad de Ingeniería, Universidad Autónoma de

Querétaro, Centro Universitario, C.P. 76010 Santiago de Querétaro, Qro., México.

d
Universidad Tecnológica Nacional, Veracruz, Vrz., México.
e
Departamento de Nanotecnología, Centro de Física Aplicada y Tecnología Avanzada,

Universidad Nacional Autónoma de México, Campus Juriquilla, Boulevard Juriquilla No.

3001 C.P. 76230, Juriquilla, Querétaro, A.P. 1-1010, México.

Correspondingauthor: Mario Rodríguez, Departamento de Nanotecnología, CFATA,

UNAM, Querétaro, Qro, México. Tel. (+52-442)2381141

Fax: (+52-442)2381165 E-mail:marioga@fata.unam.mx

ABSTRACT

This work is focused on the understanding of the apparent viscosity profile of corn starch,

in terms of the physicochemical and morphological changes that take place during the

thermal profile of starch-water suspension to its respective gel formation. A mathematical

model was used to obtain the experimental operating conditions that satisfy the Froude

number. Freeze drying samples are studied in different stages along the pasting profile.

Changes in the structural properties of the samples are studied using X-ray diffraction, and

the morphological changes are followed using scanning electron microscopy, differential

scanning calorimetry was used to analyze the thermal changes in starch. The changes in the

pasting profile are associated with structural, thermal,and morphological changes of the

system and the analysis of the physicochemical transformation that occur during the pasting

profile are explained. The finding in this work does not show evidence of gel retrogradation

at the end of the cooling process.

Keywords: gelatinization; pasting; starch; retrogradation.

1. Introduction

Starch is possibly the most important carbohydrate in modern human life, with different

applications in industries such as the food, petroleum, pharmaceutical, paint, and cosmetic

industries, among others. Starch is a granule or particle composed of two macromolecules:

amylose and amylopectin [1] and [2]. Amylose has a linear structure of D-glucan units

bonded together by α-(1,4) bonds, in the shape of a helix which consists of six fragments of

glucose per turn [3]. On the other hand, amylopectin is a branched polymer that iscomposed
of linear chains with α-(1-4) bonds and α-(1-6) bonds. Amylopectin structure consists of

short chains forming double helices.

One of the most important aspects to study in the case of starch and its derivative

productsare the rheological and pasting properties. Pasting properties are often obtained by

studying a pasting profile of a starch-water suspension, as a function of the time and

temperature. The importance of characterizing the starchpasting profile is that many foods

containing starch are cooked with water; this process causes great changes in the structure

and morphology of the starch granules [4]. These changes resultin some modified

properties of the final product. Moreover, the swelling of the starch granules during

cooking begins predominantly in amorphous regions [5]; this property is important

becauseit allows the development of gel.The increase of apparent viscosity in starch-water

suspensions occurs mainly due to the exudate products released from the starch granules

forming a network [6]. Therefore, the effects of the thermal profile and the shear rate on the

physicochemical properties of the starch-water suspension were not studied.

Wajiraand David [7] studied the gelatinization process of different native starches, using

SEM, DSC, and X-ray diffraction followed by the micro, thermal, and structural

transformations of starch-water suspension subjected to heating (35-85°C at 5°C intervals).

Their results showed that the gelatinization is not only an order-disorder transition between

the amylose/amylopectin arranged inside the starch granule, but the disordered system can

include the exudation of macromolecules. However, the pasting profiles of different

starches and their morphological and structural changes as a function of the time during a

pasting profile were not studied.

There are usually five sample characteristics, whichare obtained with a pasting profile:

peak viscosity and peak viscosity temperature; the ease of cooking; the paste stability or

resistance to breakdown; setback or cold paste viscosity, and stability of the cooked paste.

Additionally, the setback value may indicate the retrogradation tendency of the starch paste

by part of components leachate [8]. However, these definitions were only

phenomenological and no evidence of the physicochemical changes or the influence of

these changes during a pasting profile, were reported. In the same direction, Karim et al. [9]

defined the setback as the rapid retrogradation of leached amylose in the starch paste, but

no evidence of the recrystallization (retrogradation) of amylose was reported.

The commercial system used to study pasting profiles is based on the principle given by the

Rushton [10] equations, about the use of an impeller to study the rheological properties of a

system. The basic viscometer impeller assumption is that the shear rate is independent of

the rheological properties of the fluid. The experimental system can convert the torque

reading into a shear stress/shear rate relationship.

In all the works above, even in an important number of researches related to the pasting

properties of starches, it is not clear what kind of physicochemical changes take place

during the pasting profile. There does not exist a detailed explanation of the changes in the

morphology of the starch-water system as a result of the temperature and shear rate.

The objective of this work is to explain in detail the pasting profile of corn starch-water

suspensions based on the physicochemical and morphological changes that take place

during the thermal profile at the constant shear rate. For these experiments, corn starch was

used. The Froude number (Fr=1) was used to determine the experimental shear rate to carry
out a pasting profile. Fr=1 avoid precipitation of the starch granules because at this point

gravity and inertia forces are equal. The morphological changes that take place along the

pasting profile were studied using SEM with frozen samples; structural changes and

thermal profiles were studied by means of X-ray diffraction and DSC respectively, for

different points of the pasting profile.

2. Material and methods

2.1. Materials

Corn starch from Newport Scientific Pty Ltd. (part number 102102, Warriewood, Australia)

was used in all experiments (see Fig. 1(A) and (B)). This regular starch contains 66% of

amylopectin and 34% of amylose. Starch is characterized by a polyhedral morphology and

some spherical granules between 4 to 12 µm. The chemical composition of the corn starch

was the follows: the protein content was 0.67±0.05%, fat content was 0.15±0.02%, and

fiber was not detected. The characteristic Tg of this starch was 70.51°C (see Fig. 1(C)) the

beginning of the thermal transformation defined as To was 64.65°C and the end of this

transition was determined at 75.64°C (Te).While the characteristic X-ray pattern (Fig. 1(D))

shows a semi-crystalline phase A-type amylose reported in the Powder Diffraction File

(PDF#43-1858, [11]).

2.2. Measurement of pasting profile

The pasting profiles of the starch aqueous suspensions were determined using a rheometer

model MCR 102(Anton Paar, St Albans, United Kingdom). The starch is adjusted to 12%

moisture content and 3 g of starch and 18 ml of distilled water were used. The thermal

profile shown in Fig. 2(A) was used. Initial temperature of the system was 50 °C, and it

remained constant for 1 min. The sample was then heated for 5.3 min from 50 ºC to 90 ºC,
and then held at a constant temperature of 90 ºC for 5.3 min. The sample was cooled down

to 50 ºC in 5.3 min, then this temperature was kept constant for 1 min, and 193 rpm was

used.

A typical pasting profile was used to study the physicochemical changes that take place

during the thermal profile (see Fig. 2(A)). Critical points for this profile can be determined

by using the first and second derivative criteria (see Fig. 2(B) and (C)). The derivative

gives direct information about the drastic changes between dependent (apparent viscosity)

vs independent variable (time). The pasting profile is divided into three regions: Region I

corresponds to the heating process of the starch-water suspension from 50 to 90°C; Region

II corresponds to the isothermal (90°C), and region III corresponds to the cooling (from 90

to 50°C). In these three regions 9 points along pasting profile were studied.

For region I, 4 points were studied. In order to obtain Point 1, a pasting profile was carried

out from 0 to 200 s; for point 2 pasting, profile was carried out from 0 to 266 s; for point 3

from 0 to 285 s that reveals changes in the first and second derivate; Point 4 from 0 to 339 s

(peak viscosity). Region II corresponds to the isothermal section of the pasting profile. By

direct inspection of the first and second derivative no changes occur in this region. Two

points in this region were studied: points 5 and 6, in which theso-called breakdown is

located. Region III corresponds to the cooling of the pasting profile and no significant

changes in the first and second derivative were observed, also three points in these regions

were studied in order to determine the factors that influence the increase in the viscosity as

result of the cooling process (point 7, 8, and 9) (See Fig.2(A)).

When the sample reaches each point, the rheometer is immediately stopped, and the sample

is cooled in liquid nitrogen and stored in a freezing container to avoid any change in its

physicochemical properties. The samples were immediately freeze-dried using a freeze dry

Freezone 2.5 (Labconco, Kansas City, USA), for 48 h. All samples are dried for the same

time under the same thermal conditions.

2.3. Scanning electron microscopy (SEM)

The changes in the morphology of the samples obtained for point 1 to point 9 of the pasting

profile were analyzed by SEM, Model JSM-6060LV at high vacuum (JEOL, Tokyo-Japan).

The samples were fixed on an aluminum specimen holder with double graphite tape and

gold coated for sputtering. The analysis was performed employing a 5 kV electron

acceleration voltage, to avoid any damage of the sample due to power beam.

2.4. Differential scanning calorimetry (DSC)

The DSC thermograms of the samples obtained for point 1 to point 9 along the pasting

profile were measured using the Differential Scanning Calorimeter DSC 1 (Mettle Toledo,

Greifensee-Switzerland) and data was processed with TA Instrument software. Calibrations

were performed using pure indium. Samples of 2.0 ± 0.1 mg were prepared by adding

deionized water to the samples into the pan until they reach a moisture of 85% (w/w).The

pans were hermetically sealed and kept at room temperature for 6 h. The samples were

scanned from 30°C to 110°C at 7.5°C/min. Each experiment was conducted in triplicates.

2.5. X-ray diffraction

In order to study the structural changes that take place along the pasting profile (9 points),

dry samples werestudiedusing X-ray diffraction. The samples were ground using a coffee

miller (Krups-USA) and then were passed through a 250 µm screen. The X-ray diffraction

patterns were recorded on a diffractometer (RigakuMiniflex, Texas-EE.UU) operating at 35

kV and 15 mA, with a CuKα radiation wavelength of 1.5406 Å. The measurements were

made from 5° to 60° on a 2θ scale with a step size of 0.05.

3. Calculation: Mathematical model for pasting profiles

In order to understand the physicochemical changes that take place during a pasting profile

of corn starch, it is very important to know the mathematical model that allow an

instrument to determine a pasting profile. The viscosity measurements of mycelia

suspensions system must be obtained with an impeller viscometer system, given by:

𝑃
𝜂= (1)
𝑐𝑁2 𝐷3

Where, η is the Viscosity (Pa s-1), Pis Power consumption of the motor (W), c is aconstant

that depend of impeller dimensions, N is the impeller speed (s-1), and D is the impeller

diameter (m).

This viscometer is based on Rushton-turbine model. Rushton et al. [10] developed this

turbine from dimensionless number theory and pi-Buckingham theorem. The result of both

(theory and theorem) can be written:

𝑐
𝑃0 = 𝐹𝑟 (2)
𝑅𝑒
Where Po is power number, Fr is Froude number, and Re is a Reynolds number, given by:

𝑃
𝑃0 = (3)
𝜌𝑁3 𝐷5

𝜌𝑁𝐷2
𝑅𝑒 = (4)
𝜂

Where ρ is a density (kg m-3), by replacing Eqs. (3) and (4) in Eq. (2) is possible to find η

(Eq. 1).

Equation (2) is valid only if the flow isof the laminar regimen and theFroude number (Fr) is

one [10]. The Froude number is given by:

𝑁2 𝐷
𝐹𝑟 = (5)
𝑔

Where g is gravity acceleration (ms-2).

When the Fr number is lower than 1, the gravity forces possess the system and whole

system is not mixed; when the Fr numberis bigger than 1, the centripetal forces dominate

the system and the fluid tends to flow out of thevessel. The final option is when the Fr

number equals 1. In this case, the centripetal and gravitational forces are equal and the

system is mixed homogeneously [12].

A unique impeller velocity to carry out any experiment is set. The pasting profiles were

carried out on the Anton-Paarrheometer with starch cells; this device has a different

geometry and, as a result, it is necessary to calculate the impeller speed. The impeller

diameter (D) is 24 mm, g= 9.81 ms-2, and the Fr = 1, replacing in equation 5 obtain:
 𝐹𝑟 𝑔 1 ∗ 9.81 ∗ 3600
𝑁=√ =√ 2 = 193 𝑟𝑝𝑚
2𝜋𝐷 2 ∗ 𝜋 2 ∗ 0.024

When the impeller velocity is 193 rpm, the entire system is in movement and the energy is

used only for this purpose. It is clear that the system can work at any RPM, but there exists

a unique frequency in which the pasting profile makes sense physically.

4. Some definitions about starch and its changes during a pasting profile

Before studying the physicochemical changes that take place during a pasting profile, it is

necessaryto know the definitions that describe some phenomena that take place during the

thermal process.

Gelatinization: when starch (amylose–amylopectin) is heated in presence of water, it

undergoes an order-disorder phase transition called gelatinization.This transition occurs in a

range of temperature that is characteristic of the starch source and the amount of water [13].

This phase transition is associated with the diffusion of water into the granule; as a result,

there is a loss of optical birefringence and total loss of crystalline order. According to

Hoover et al. [14] there exists an amylose leaching as well as the apparition of a new phase

water-amylose/amylopectin.

Pasting: occurs after of gelatinization processand implicates the granular swelling,

exudation of the granular molecular components, and eventually, total disruption of the

granules; finalizing is the formation of gel.

Retrogradation: is a process which describes the molecular interactions between glucan

molecules (by means hydrogen bonding) in the gelatinized starch, after cooling. It also

involves that amylose and amylopectin form an ordered double-helical structure. These
interactions occur after long time and low temperature. Amylose is responsible for the

short-term retrogradation [15].

Fig.3 shows the conventional parameters used in the analysis of a corn starch pasting

profile (Sigma Aldrich, USA. CAS Number: 9005-25-8), in this case:

Pasting temperature: provides an indication of the minimum temperature required to cook a

given sample [16].

Peak viscosity: indicates the capacity and ability of water “absorption of the starch

granules”, and it is characterized by a cessation of the swelling. At this point, an

equilibrium take place between the swollen granules and the leachate polymers [8], [16]

and [17].

Breakdown:considered a measure of the disintegrationdegree caused by the shear force of

the starch granule or the paste stability [18].

Setback: measure of the retrograde tendency during cooling [19], and the increases in final

viscosity due to the re-association (cross-links) between starch chains (molecules) leached

together allowing formation of additional junction zones [5], [9] and [20].

5. Results and discussion

5.1. Pasting profile

The changes in the pasting profile of the sample are governed by the physical (morphology,

gelatinization) and structural (interaction between macromolecules and the solvent)

transformations promoted by the heat and the “rotation” of the sample during the

experiment.

5.1.1 Morphological changes during a pasting profile

The changes in the morphology were studied in detail for Region I, II, and III using SEM

images taken at 1500x and 3500x. For Region I, Fig. 4(A) and (B) shows the SEM images

of corn starch granules for Point 1 taken at 66.12 ºC. At this temperature, the starch

granules retain the polyhedral morphology. Some granules exhibit the presence of micro

holes; however, all granules remain separated. By direct inspection of Fig. 1(C), this point

is located at the beginning of the thermal transition identified as To. For Point 2 (Fig. 4(C)

and (D)) taken at 74.81ºC, the existence of branches that interconnect granulesis observed.

These branches are formed by some exuded amylose and amylopectin.This point is found

after the gelatinization temperature (see Fig. 1(C)), and SEM images show a morphological

change in the starch granules; however,the apparent viscosity does not exhibit significant

changes. An important fact is that during the swelling of the starch granulesand for the

determination of the gelatinization temperature, the pasting profile is not sensitive.

For point 3 (Fig. 4(E) and (F)) taken at 76.70 °C is noticeable that at this temperature the

starch granules do not retain the original shape, but that “donut” structures appear as a

result of the heating and shear rate of the starch granules. These “donuts” are

interconnected between each other, which causes the system flow to be lower in

comparison with a particle suspension, producing an increment in the apparent viscosity.

The starch gelatinization process took place between point 1 and 3 (see arrows in Fig.

2(A)). It is very important to note that the starch granule (micro particles), under this

condition, does not retain its original shape, and it also means that starch as a

microstructure isnot present in this part of the pasting profile, and that amylose and

amylopectin are outside of the original granules. Point 3, corresponds to the peak of the

first derivative of the pasting profile (see Fig. 2(B)).

It is critical to point out that, according to the SEM images correlated to the strong changes

in the morphology of the sample is related to the starch morphology changes from granules

to “donuts”.

Point 4: the “donuts” break down now forming flakes as seen in Fig. 4(G) and (H). This

point corresponds to the peak viscosity for the corn starch pasting. A more detailed

inspection of this morphology is presented in Fig. 4. H taken at 3500X which shows the

formation of a filamentous network (submicron) which interconnects these flakes. These

filaments cause the increase in the apparent viscosity, whichis governed by the exuded

amylose and amylopectin and by the formation ofthe filamentous network. It is very

important to note that for the peak viscosity, there are no starch granules present. This

result is not in agreement with that reported in the RVA handbook [21], in which he

reported that half of the starch granules remained intact. According to Singh et al. [22] peak

viscosity is the point where the starch granules present the maximum swelling. This result

in the case of corn starch does not agree with their results, because as it is shown in Fig. 4

(G) and (H) when the water-starch suspension reaches the peak viscosity there are not

integer grains of starch which implied that the peak viscosity cannot be related to the

swelling power of the starch granules.

For region I, it is evident that the gelatinization process took place in this temperature range

and that the pasting properties are governed not only by thermal changes, but also by the

morphological changes of the starch granules which plays a very important role in the

pasting profile. For this region the initial system is a starch-water suspension, passed into a

systemwith some integer starch granules that are interconnected by biopolymers; then the

system is transformed by “like-donuts” connected between them, and due to the rotation
and the change in the temperature, themorphology of the system passes a flakes

interconnected network (peak viscosity).

For region II (Fig. 5(A) to (D), isothermal region), a decrease of the apparent viscosity

(point 5 and 6) is evident. The drop in the apparent viscosity is due to the disintegration of

the starch granules at ahigh temperature, but by direct inspection of Fig. 4(A) to (F) the

disintegration of the starch granules occurs during the gelatinization process. Our

explanation for the drop of the apparent viscosity is based on the changes of the

morphology: the system goes from an interconnected filamentous network to an

interconnected flakes layer. These flakes become aligned with the parallel layers

(hydrogel), and this phenomenon in the isothermal region produces a decrease in the

apparent viscosity. SEM studies in this region reveal that in the so called breakdown (point

6) a total alignment of the flakes occurs giving as a result the reduction of the shear stress

and decreases in the apparent viscosity.

For region III (points 7, 8, and 9, cooling process), the sample remains with the same flakes

morphology shown in Fig. 5(E) to (J). The increase in the apparent viscosity can be related

to the reduction of the total internal energy of the system (decrease of temperature) and the

increases of the shear stress between the layers formed by flakes.

5.1.2 Structural changes

The morphological changes of sample asa result of the temperature can be related to the

changes in the starch structures. Fig. 6 shows the X-ray diffraction patterns of the freezing

samples taken for each one of the points described in Fig. 2(A). Point 1, which is located at

the beginning of the endothermic peak (see Fig. 1(C)), the starch is integer (see Fig. 4(A)

and (B)) and the sample exhibits a semi crystalline structure, indicating that no
gelatinization took place even the temperature increases and water becomes to diffuse into

the starch grains (Fig. 6(A)). For point 2, (See Fig. 4(C) and (D)) the pattern (beginning of

the gel formation) still showed a remaining crystallinity, indicating that this sample is still

undergoing the gelatinization process, and that this point is located inside of the

endothermic peak. By detail inspection of the points 3 to 9, it is evident that the X-ray

diffraction patterns show an amorphous system. The SEM images and X-ray diffraction

patterns are conclusive, indicating that the crystalline order of amylose and amylopectin

macromolecules occurs exclusively inside of the micro particle called starch.

5.1.3 Thermal changes:

In order to understand the correlation between thermal changes that occurs during pasting

profiles, the thermograms of freeze dried samples were studied using DSC. Fig. 7(A) to (I)

show the characteristic of thermograms for each one of these points. For point 1, it is

characterized by an endothermic transition, which implies that the amylose and

amylopectin inside starch granules at this point still have the internal order. This result is

confirmed by the X-ray diffraction pattern shown in Fig. 6(A) in which a clear semi

crystalline structure is present and correlated to the SEM images shown in Fig. 4(A) and

(B). The thermogram for point 2 showed a remaining endothermic peak, which is

indicative of some crystalline order inside of the starch granules that can be corroborated by

the analysis of the X-ray diffraction pattern shown in Fig. 6(B), and by the existence of

starch granules shown in Fig. 4(C) and (D). For points 3 to 9 (hydrogel system) in the case

of corn starch, no crystalline structures were found, even for points 8 and 9. This result is

very important in terms of the pasting interpretation because according to the SEM images,

X-ray patterns, and DSC thermograms, no recovery of the crystalline order is evident.
Taking into account the amorphous patterns for points 8 and 9, no molecular reorganization

took place in this region (setback), and SEM, DSC, and X-ray diffraction showed that no

retrogradation. This means that during a pasting profile the retrogradation does not take

place and some misinterpretation in the literature are often reported.

5.2 Analysis about of the phenomena occurred during a pasting profile

The changes in the pasting profile for isolated corn starch are influenced by different

physicochemical changes that take place as result of the temperature, water, and constant

shear rate applied during the test. Taking into account the X-ray diffraction, DSC, and SEM

images results, during the pasting profile for isolated corn starch, some phenomena that

take place during a pasting profile of corn-starch can be analyzed as follows:

Pasting: network formation of a gel and occurs after of gelatinization process. Taking

into account Fig. 1(C) where To and Te are shown, in this range of temperature the

gelatinization of starch occurs. We can conclude that the pasting profile is not able to

determine the range of temperature in which the gelatinization occurs. DSC is a better tool

to determine the beginning and end of the gelatinization.

Pasting temperature: defined as a range of temperature after the gelatinization of starch

in which the system undergoes new hydrogel morphology, it can be defined by the use of

the first derivative of the pasting profile (peak maximum) and begins at the end of the

gelatinization (Te), and finished when the hydrogel is formed.

Peak viscosity: indicates the end for the stable hydrogel formation with characteristic

morphology (interconnected micro fibrils). SEM images shown in Fig. 4(G) and (H)

confirm this event. On the other hand, the temperature at peak viscosity can be defined as
the temperature in which the gel finalizes the formation, and at this point no starch granules

are integer.

Breakdown: the decrease in the apparent viscosity for the isothermal region of the pasting

profile at constant rotation (rpm) is independent of the temperature and it is originated by

the reduction of the internal shear stress between the layers formed due to rotation of the

sample. In the case of corn starch, the planes are formed by flakes. Breakdown can

therefore be understood as the minimum value of the apparent viscosity of the sample at the

end of the isothermal region of the pasting profile. According to our analysis, it is not

caused by the disintegration of the starch structure caused by the shear forces [18], because

at this time and temperature the system is already a hydrogel.

Setback is originated by the reduction of the temperature of the system and it is related to

the changes in the internal shear stress between planes. According to our results, it does not

have any relationship with retrogradation, because as can be seen in the detailed study of

the structural changes shown in Fig. 6(I) (Point 9 for the pasting profile of corn starch) for

the end of the pasting profile of isolated corn starch, no recrystallization took place due to

the cooling process. It is clear that in the case of the micro flakes formed during the pasting

profile of corn starch-water suspension, the reduction in the temperature originated the

increases in the apparent viscosity, increase the shear stress between them. The

retrogradation occurs after gelatinization and it is defined as the transition from an

amorphous state to a crystalline state (more orderly). The changes that occur during

phenomenon can be monitored by X-ray Diffraction [23]. This instrumental technique is

used for determinate and identified the long atomic order of a sample. On the other hand,

the studies performed on retrogradation report a time of storage of the sample and this

condition is not comply in the work. It has been reported the evident of retrogradation in
samples storage by 14 days used DSC from 20 to 120°C, the transition peak is observed

[24]. Therefore, we consider that the final viscosity is not a parameter indicating the

retrogradation of the starch compounds and this was corroborated by X-ray Diffraction.

6. Conclusion

Changes in the viscosity profile of corn starch are influenced by different physicochemical

changes taking place as a result of temperature, and shearing force applied during the

measurement due to the constant rotation of the starch-water suspension and after

gelatinization the hydrogel. Considering the morphological changes of the starch water

suspension along the pasting profile, these changes governed the behavior of the curve of

viscosity profile. Moreover, during the viscosity profile structural and thermal changes in

starch were observed, which ends after that the starch gelatinization occurred. X-ray

Diffraction studies confirm that during the cooling process of the hydrogel, no

retrogradation was observed. An important point in the case of the study of pasting profiles

of starch is that is necessary to determine the region. Dilute, transition, and concentrate, in

which these experiments can be obtained, then is necessary to run experiments with

different starch/water ratios.

Acknowledgements

This work was partially supported by CONACYT (National agreement studentship, No.

293329). We thank Carmen Peza, M. en I.Q. Alicia del Real López, and Dr. Beatriz Millan

(CFATA-UNAM) for their technical support.

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Figure captions

Fig. 1(A) and (B) SEM images of isolated corn starch, Fig. 1(C) shows the DSC

thermogram and Fig. 1(D) the characteristic X-ray diffraction pattern.

Fig. 2 (A),(B) and (C) Characteristic pasting profile of isolated corn starch as well as the

first and second derivative used to determine the critical points.

Fig. 3. Pasting profile and conventional definitions used in the analysis.
Fig. 4. SEM images of the morphological changes for region I (points 1, 2, 3, and 4) for

pasting profile of isolated corn starch.

 d

Fig. 5. SEM images of the morphological changes for region II (Points 5 and 6) and Region

III (points 7, 8, and 9) for pasting profile of isolated corn starch.

Fig. 6. Structural changes of the dry freezing samples obtained for each one of the points

selected in the pasting profile of isolated corn starch.

Fig. 7. Thermal profiles of dry freezing samples obtained for each one of the points selected

in the pasting profile of isolated corn starch.