Carbohydrate Polymer Technologies and Applications: Ibrahim O. Mohamed
Carbohydrate Polymer Technologies and Applications: Ibrahim O. Mohamed
Carbohydrate Polymer Technologies and Applications: Ibrahim O. Mohamed
a r t i c l e i n f o a b s t r a c t
Keywords: Starch is an important source of energy in the human diet with a variety of taste, texture, physicochemical, and
Resistant starch organoleptic properties which is greatly influenced by processing methods and additives. Recently, greater atten-
Gelatinization tion is directed towards modifying the physicochemical properties of starch using some processing technologies
Retrogradation
or additives such as sugars, hydrocolloids, proteins, lipids, and other additives with synergistic effects to improve
Digestibility
shelf stability and retard starch digestion through a physical barrier, steric hindrance effects or combination.
Ternary complex
Extrusion process showed greater potential in altering starch physicochemical and digestibility properties, while
high hydrostatic pressure and microwave showed some potential but need further investigation. A ternary com-
plex of starch-lipid-protein produces a supramolecular structure which could accommodate bioactive compounds
and food sensitive ingredients as a guest in the V-amylose helix or embedded in the ternary structure, further
research is needed in this area especially on the digestibility and bioavailability of the embedded compounds.
1. Introduction gen bonds resulting in loss of birefringence of intact granules (Wang, Li,
Copeland, Niu, & Wang, 2015). These physicochemical changes were
Starch is classified as one of the three polysaccharides widely dis- known as starch gelatinization which is accompanied by rapid increases
tributed in nature along with cellulose and chitin, used extensively in in viscosity. The onset temperature corresponding to an increase in vis-
foods such as bakery products, pasta, tortillas, and snacks in which cosity often refers to as the pasting temperature which is generally
starch gives the physicochemical, functional, and digestibility charac- higher than the gelatinization temperature measured by the DSC be-
teristics to those products (Agama-Acevedo, Flores-Silva, & Bello-Perez, cause the increase in viscosity takes place when the starch granules are
2019; Magallanes‐Cruz, Flores‐Silva, & Bello‐Perez, 2017). Native starch completely gelatinization (Balet et al., 2019). However, other results
is organized in discrete particles called granules, the granules of differ- reported that pasting temperature was significantly correlated with the
ent botanical sources show specific shapes, sizes, and surfaces (smooth gelatinization temperature (Bao, 2008). This could be explained by the
or rough) that play an important role in functionality and digestibil- fact that the gelatinization temperature on the DSC consists of; onset,
ity (Magallanes‐Cruz et al., 2017). Starch granules are generally con- peak, and conclusion, therefore when the gelatinization temperature
sidered to be semi-crystalline consisting of a series of alternating crys- correlates with pasting temperature it refers to the conclusion tempera-
talline and amorphous lamellae, the crystalline lamella consists of short ture.
chains of amylopectin forming double helices while the amorphous con- Pasting characteristics of starch were extensively studied using var-
sist of branched amylopectin and amylose (Gallant, Bouchet, & Baldwin, ious types of instruments but the RVA and rotational viscometer fitted
1997). with pasting cells are the most popular. During pasting study starch sus-
The main sources of starch at the global level are maize (82%), wheat pension is subjected to control heating, holding, and cooling processes at
(8%), potatoes (5%), and cassava (5%) (Angellier et al., 2004). In Eu- constant shearing. Fig. 1 show a typical pasting curve obtained using a
rope, the main sources of starch are maize and potato, while wheat rotational viscometer fitted with a pasting cell. From the measurements
starch is produced on a small scale, and in the United States and Canada there are four primary parameters; pasting temperature PT (onset tem-
wheat starch produced may be considered a by-product in the manufac- perature when viscosity start increasing), peak viscosity PV (the highest
ture of wheat gluten (Knight & Olson, 1984) viscosity during pasting), trough viscosity TV (the minimum viscosity
When starch undergoes heating in presence of water such as in batch after the peak viscosity) and final viscosity FV (the viscosity at the end
cooking or extrusion, the starch granules structure will collapse due to of cooling,). Two secondary characteristics can be derived from the pri-
melting of crystallites, unwinding of double helices, breaking of hydro- mary characteristics; break down BD interpreted as the breakdown in
https://doi.org/10.1016/j.carpta.2021.100039
Received 26 August 2020; Received in revised form 27 January 2021; Accepted 27 January 2021
2666-8939/© 2021 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/)
I.O. Mohamed Carbohydrate Polymer Technologies and Applications 2 (2021) 100039
Fig. 1. The pasting curve of corn starch showing pasting parameters (adapted from Mohamed and Babucuur (2015))
viscosity during cooking at 95 C (PV - TV) which is attributed to melt- has been categorized into five types as Type-1 physically inaccessible,
ing of the crystalline region of the starch granules and the alignment Type-2 ungelatinized starch, Type-3 retrograded starch, Type-4 chem-
of leached amylose along the direction of flow (Sharma et al., 2009; ically modified starch, and Type-5 soluble or insoluble resistance mal-
Balet et al., 2019) and setback (PV – TV) interpreted as an increase in todextrins or amylose-lipid complexes starch (Fuentes‐Zaragoza et al.,
viscosity during cooling or retrogradation tendency of the starch paste 2011). The soluble resistance dextrin is an indigestible glucose polysac-
as a result of the re-association of amylose molecules (Kaur et al. 2007) charide (rich in 𝛼-1,2 or 𝛼-1,3 linkages) formed when corn or wheat
some research prefer to use total setback (FV – TV). starch is heated and treated with an enzyme (Mukai, Tsuge, Yamada,
Retrogradation is a process of recrystallization followed by starch Otori, & Atsuda, 2017). This review presents a comprehensive review
gelatinization which takes place during cooling and storage. Starch ret- of the effects of processing and additives on starch physicochemical
rogradation is usually associated with loss in food product quality such and digestibility properties. Special focus will be on extrusion, high hy-
as; bread staling, loss of viscosity, syrenesis, precipitation in soups, and drostatic pressure, microwave processing, and additives include sugars,
sauces (Miles, Morris, Orford, & Ring, 1985). Karim et al. (2000) re- hydrocolloids, proteins, and lipids. The review will highlight some of
ported that long-term storage can promote amylopectin recrystalliza- the mechanisms responsible for the changes in the physicochemical and
tion, thus increasing the rigidity of swollen granules by reinforcing the digestibility properties in attempts to understand the discrepancies in
continuous amylose phase. They also, reported that retrogradation of some published data especially for additives which in some situations
gels from legumes can result in syrenesis making products requiring are contradictory. The ternary complex between starch, proteins, and
low-temperature storage undesirable. It is important to note that gela- fatty acids will be discussed followed by a presentation of a schematic
tinized legumes starches are more susceptible to short-time retrograda- of the speculated interactions between these macromolecules.
tion compared to cereals because normal varieties of cereals contains
about 25% amylose, while that in legumes may be up to 75% on starch
2. Effect of processing on starch physicochemical and
basis (Guilbot & Mercier, 1985). Retrogradation can result in desirable
digestibility properties
characteristics in a starch-based product such as an increased level of
slowly digestible starch (SDS) and resistant starch (RS) in food products
Many processes are used to modify native-starch physicochemical
such as pasta, breakfast cereals, baked products, and others.
and structural properties to improve; digestibility, textural properties,
Resistant starch (RS) can be defined in-vivo basis; as the fraction of
storage stability, and others. Recently, greater attention was directed
dietary starch which escapes digestion in the small intestine of a human
towards the process that is capable of increasing the level of resistant
(Sajilata, Singhal, & Kulkarni, 2006), while SDS can take between 20
starch or slowly digested starch (SDS) to reduce the risks from an in-
to 120 min to be digested (Englyst, Kingman, & Cummings, 1992). RS
creased level of obesity, diabetes, and other diseases associated with the
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I.O. Mohamed Carbohydrate Polymer Technologies and Applications 2 (2021) 100039
Table 1
Shows some of the levels of RS Type-3 achieved using different processes and starch type.
increased level of sugars in the blood. The physical processing methods to the changes in starch crystal polymorph from high digestible form to
commonly used to prepare Type-3 resistant starch based on the mech- low digestible or resistant form.
anism of retrogradation are; hydrothermal treatment, extrusion, high
hydrostatic pressure, microwave treatments, and others.
2.2. Extrusion
2.1. Hydrothermal treatment Extrusion is one of the important processes in the food industry be-
cause of the greater processing capabilities of food extruders to alter
Hydrothermal treatments commonly used to induce recrystallization food physicochemical and structural properties. Processing parameters
of starch molecules without destroying it is granule structure consists in twin extrusion processes such as; temperature, pressure, shear rate,
of; heat moisture treatment (HMT) which involve heating starch at low feed rate, screw speed, moisture content can be manipulated with a great
moisture content < 35% at a temperature higher than the glass tran- degree of freedom allowing the production of foods with desired textu-
sition temperature but lower than the gelatinization temperature for a ral and nutritional properties. Also, the extrusion process allows the ad-
specified period, or annealing (ANN) which is a physical treatment in- dition of other food ingredients such as proteins, lipids, hydrocolloids,
volves incubation of starch granules at moisture content > 40% for a bioactive compounds, fibers, and others for enhancement of the extru-
certain period, at a temperature above the glass transition temperature date properties.
but below gelatinization temperature (Jacobs & Delcour, 1998), after The extrusion process was reported to enhance the formation of
the heating, the starch will be allowed to undergo cooling to facilitate starch lipid complexes, with higher yield obtained using saturated fatty
recrystallization of starch molecules. Another hydrothermal treatment acid compared with monounsaturated fatty acid with the same chain
method used to physically alter starch molecular structure is autoclav- length (Cervantes-Ramírez et al., 2020). De Pilli, Giuliani, Buléon, Pon-
ing; which is based on hydrating and heating the starch at a temperature toire, and Legrand (2016) showed that extruder assisted in the formation
above 100 °C under pressure causing starch molecules to become fully of starch-lipid and lipid-protein complexes. However, research work car-
disrupted and upon cooling, the amylose chains can associate to form ried out using a rapid visco analyzer (RVA) showed the formation of the
hydrogen bond stabilized doubled helices (Dupuis, Liu, & Yada, 2014). ternary complexes between starches, lipids, and proteins (Wang, Zheng,
Starch with a high content of amylose is usually used to achieve Yu, Wang, & Copeland, 2017; Zheng et al., 2018). The ternary com-
a high level of RS Type-3, for starch with low amylose content such as plex was reported to be more resistant to digestive enzyme hydrolysis
waxy starch, chemical or enzymatic modification of the starch molecules compared to starch-lipid complexes (Zheng et al., 2018). Therefore, this
such as debranching is necessary, followed by HMT or annealing process ternary complex could be produced properly using the extrusion process
or combination. because of the greater control of the processing parameters. Future re-
Table 1 show shows some of the levels of RS Type-3 achieved us- search work should focus on the formation of ternary complexes (starch-
ing different processes and starch types. Shin et al. (2005) achieved lipid-protein) because as mentioned previously lipid-protein complex
68% RS with heat treatment of 20% moisture sweet potato starch at was already observed using the extrusion process.
40 °C. Jacobasch et al. (2006) increased the level of RS in Novelose Gelatinization process increases the accessibility of digestive en-
330 a commercial RS from 40.4% to 75 % using HMT. In 1993 the Hi- zymes to starch, especially when fully gelatinized. However, banana
maize company in Australia was the first to successfully achieved 42% starch subjected to high shear extrusion process resulted in fully gela-
RS from a hybrid corn contains more than 80% amylose which gained tinized starch with 36% reduction in the rate of digestion; this reduction
widespread in Australia as an ingredient in bread and other baked prod- is due to shear-induced fragmentation of starch molecules resulted in
ucts (Sajilata et al., 2006). Shi et al. (2018) reported RS of 70.7% from enhanced retrorgradation during storage (Roman, Campanella, & Mar-
enzymatically prepared de-branched waxy maize starch maintained at tinez, 2019). In another study with bread crumb containing 20% ba-
25 °C for 24 h to recrystallize. In another study, Li et al. (2019) treated nana starch high induced-shear from extrusion process resulted in an in-
wheat starch with citric acids followed by HMT achieved 71% resistant creased level of SDS by 85% which was attributed to the increased level
starch. It is important to note that for starch treated with citric acid the of defragmentation of amylopectin (Román, Gómez, Hamaker, & Mar-
resistant starch developed could be a combination of retrogradation ef- tinez, 2019). These results demonstrated that the extrusion process has
fects and steric hindrance effect from anhydrate starches citrate, further great potential for the development of food products with retarded di-
investigation on such dual process is needed. The mechanism for the gestibility without compromising sensory quality. Furthermore, as out-
change in digestibility as a result of the HMT and ANN process is due lined previously successful modification of starch structure to produce
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I.O. Mohamed Carbohydrate Polymer Technologies and Applications 2 (2021) 100039
a high level of RS is usually achieved with high amylose starch or with of starch granules in some cases, untangle the entanglement between
debranched amylopectin. For low amylose starch or waxy starch usually the starch chains (Palav & Seetharaman, 2007; Shah et al., 2016). Be-
debranching is done by use of debranching enzymes such as pullulanase sides, enhanced formation of unpacked helices and disordered ends into
or some chemical treatments. However, induced shear defragmentation a crystalline form (Fan et al., 2014). MW pretreatment of rice starch
of amylopectin with extruder was proven to be an excellent alternative followed by ANN resulted in significant enhancement of lo short-range
to processes that involve chemicals or enzymes, as the whole process is and long-range crystalline structure, increased gelatinization enthalpy,
done physically to alter starch digestibility. peak, and breakdown viscosities (Zhong et al., 2020). MW treated rice
starch compared to conventionally treated counterpart undergoes con-
2.3. High hydrostatic pressure current matrix hydrolysis and molecular reassembly during digestion
resulting in stronger decreases in digestibility (Li, 2020).
High hydrostatic process (HHP) is another physical process that is Research in MW with regards to starch processing is limited but re-
used to alter starch physicochemical properties through the applica- sults reported regarding digestibility are encouraging, furthermore, ad-
tion of pressure in the range 10 – 1200 MPa, resulting in partially or ditives such as; salt, proteins, and lipids could have profound effects
fully gelatinized starch depending on the starch type, concentration, on physicochemical properties especially polar molecules because they
pressure amplitude, temperature and treatment time (Dupuis et al., will alter dielectric properties which influence heating rates and hence
2014; Pei‐Ling, Xiao‐Song, & Qun, 2010; Zhang, Chen, Zhao, & Li, physicochemical changes. Also, MW induces volumetric heating, unlike
2013). HHP was shown to promote starch-lipid complexes, increase the other conventional heating. All these need to be investigated to have a
level of RS and when applied to HMT starches resulted in increased better understanding to assist in the improvement in food processing in
peak viscosity, setback, and final viscosity, transition temperature, and this area.
swelling power (Dupuis, et al., 2014; Zhang, Tong, Zhu, & Ren, 2013;
Zhou et al., 2015). Li et al. (2015) reported that mung bean starch
when subjected to HHP treatment followed by the aging process resulted 3. Influence of additives on starch gelatinization and
in increased starch crystallinity, increased transition temperature, and retrogradation
enthalpy of retrogradation. However, the heat gelatinized mung bean
starch showed no endothermic gelatinization peak indicating the ab- Native starch has a tendency to syneresis, retrogradation, and exhibit
sence of formation of crystallized structure. This clearly showed that breakdown either from extended cooking, high shear or acidic condi-
HHP treatment promoted amylose-amylose and amylose-amylopectin tions producing weak matrix, cohesive, rubbery pastes, and undesirable
chains association from leached amylose and amylopectin for mung gel (BeMiller, 2007). For improvement of starch-based product, quality,
bean, amaranth, quinoa, and wheat starches during storage (Li et al., texture, stability, water retention, and mobility, functional properties,
2015; Linsberger‐Martin, Lukasch, & Berghofer, 2012). different types of ingredients such as sugars, salts, hydrocolloids, pro-
The research pertains to the effect of HHP on starch physiochemi- teins, amino acids, lipids, and others are often added to starch.
cal changes is limited; I speculate that the mechanism of the changes Effects of various types of sugars and sugar alcohols (glucose, fruc-
could be due to several factors. Under HHP the starch granules swelling tose, galactose, mannose, L-arabinose, tagatose, ribose, xylose, sucrose,
is restricted due to the high pressure also, amylose leaching may be en- maltose, trehalose, isomaltulose, raffinose, maltotriose and sugar al-
hanced by the high pressure, and associations involving amylopectin, cohol sorbitol, maltitol, isomalt xylitol) on starch gelatinization and
in particular, may be enhanced due to increased contact between func- retrogradation were extensively investigated (Allan, Rajwa, & Mauer,
tional group leading to increased short-term crystallization. Besides en- 2018; Baek, Yoo, & Lim, 2004; Chang, Lim, & Yoo, 2004; Mohamed &
hanced starch-lipid and starch-protein interaction due to the increased Babucurr, 2015, 2017).
contact between these macromolecules, further research is needed to Effects of various types of gums hydrocolloids (xanthan, pullulan,
elucidate the effect of HPP on starch physicochemical changes. and gum Arabic) on gelatinization and retrogradation were extensively
studied (Chantaro, Pongsawatmanit, & Nishinari, 2013; Chen, Tong,
2.4. Microwave Ren, & Zhu, 2014; Singh, Geveke, & Yadav, 2017) additional infor-
mation on other gums and hydrocolloids can be found in the review
Microwave (MW) heating is one of the important emerging food pro- (BeMiller, 2011). The effect of salt on starch gelatinization and retrogra-
cessing technologies with a diversity of applications in food processing dation is often investigated in a mixture of a salt-starch-hydrocolloids
include pasteurization, sterilization, drying, thawing, tempering, bak- system (Samutsri & Suphantharika, 2012; Viturawong, Achayuthakan,
ing, etc. (Chandrasekaran, Ramanathan, & Basak 2013; Chong et al., & Suphantharika, 2008).
2014; Zhang et al., 2006). MW heating is distinguished from conven- Effects of amino acids, polypeptides, and proteins on gelatinization
tional heating by energy-saving due to volumetric heating, high heating and retrogradation also received greater attention (Jekle, Mühlberger,
rates, reduced processing time, low operational cost, and better reten- & Becker, 2016; Kett et al., 2013; Lian, Zhu, Wen, Li, & Zhao, 2013;
tion of food components (Ekezie et al., 2017; Ştefănoiu et al., 2016). Xijun, Junjie, Danli, Lin, & Jiaran, 2014; Yu, Jiang, & Kopparapu, 2015).
However, MW has some major drawbacks that include uneven heating Fatty acids, monoglycerides, and lipids in addition to starches were stud-
which may lead to overheating resulting in scorching or under heating ied by several researchers (Lu, Liu, & Huang, 2020; Marinopoulou, Pa-
resulting in a food safety concern, in addition to possible textural dam- pastergiadis, Raphaelides, & Kontominas, 2016; Reddy, Lee, Lim, &
age (Zhang et al., 2006; Ekezie et al., 2017). Park, 2019).
The heating during MW treatment is due to internal friction from Other additives such as polysaccharides like soluble soybean polysac-
oscillating ions, charged groups or dipolar molecules such as water in charides or pectin and others received greater attention recently because
an oscillating magnetic field of the microwave resulting in fast volu- they influenced rheological and pasting properties of starches and most
metric heating rates. The heating rate in MW depends on food product importantly their effects in retarding starch digestion through either;
dielectric properties, product geometry and orientation, microwave fre- formation of a physical barrier or alteration of the starch granule crys-
quency, and oven design (Salazar-González et al., 2012; Ekezie et al., tal structure (Liu, Li, Fan, Zhang, & Zhong, 2019; Ma, 2019; Zhang et al.,
2017; Chandrasekaran, Ramanathan, & Basak, 2013). 2018).
Treatment by MW for starches could result in a variety of effects de- Fig. 2 shows some of the desirable characteristics of commonly used
pending on; starch type, concentration, MW intensity, treatment time, additives on starch gelatinization and retrogradation The focus of this
dielectric properties. These effects could result in; lack of starch gran- review will be on sugars, sugar alcohols, hydrocolloids, amino acids,
ules rupture and swelling decreased swelling power and increased size polypeptides, proteins, lipids, and salts with an attempt to highlight
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I.O. Mohamed Carbohydrate Polymer Technologies and Applications 2 (2021) 100039
Baek, et al., 2004; Spies & Hoseney, 1982). However, for trisaccharide
(18-carbon sugar) the Tegel continued to increase on a molar basis but
not on a mass basis (Allan, et al., 2018). 5-carbon sugar alcohol such
as xylitol, 6-carbon sugar alcohol such as sorbitol, mannitol, and 12-
carbon sugar alcohol such as maltitol and isomalt were found to have
higher Tgel compared to their counterpart sugars (Allan, et al., 2018).
The effect of sugars on short term and long term retrogradation
is conflicting; some studies found that sugar accelerates the rate of
retrogradation depending on the type of sugar and starch (Hoover &
Senanayake, 1996; Katsuta, Nishimura, & Miura, 1992; Prokopowich &
Biliaderis, 1995; Slade & Levine, 1987), other studies found sugar to
retard retrogradation (Katsuta, Miura, & Nishimura, 1992; Mohamed &
Babucurr, 2015; Slade & Levine, 1987). Concerning starch and sugar
type; hexoses except galactose were more effective than pentose in
retarding retrogradation of rice starch gel and the disaccharide is
more effective than the monosaccharide in stabilizing rice starch gel
(Katsuta, Nishimura et al., 1992). Other study found that pentose (ri-
bose and xylose) suppressed the rate of retrogradation of wheat starch
gel (Cairns, Miles, & Morris, 1991), and xylose is more effective than
glucose and sucrose in suppressing retrogradation of corn starch gel
(Chang et al., 2004).
For oat starch gel the extent of retrogradation increased in pres-
ence of sugars in the order (glucose > fructose > sucrose) (Hoover &
Senanayake, 1996). These studies demonstrated the complexity of the
starch-sugar-water composite which triggered interest in exploring the
mechanism of how sugars behave in starch-sugar-water composite dur-
ing gelatinization and retrogradation.
Several studies were conducted to explain the behavior of differ-
ent types of sugars in retarding or accelerating starch retrogradation,
Slade and Levine (1987) indicated that sugars act as anti-plasticizers re-
sulting in reduced chain mobility and crystallization rate of starch gel
resulting in increased gelatinization temperature in the order of xylose
> maltose > glucose > galactose > control (no sugar) > fructose, the
anti-plasticizing effect of sugar has been explained by the decrease in
Fig. 2. Desirable characteristics of gelatinized and retrograded starch with ad-
free volume relative to water alone or starch-sugar interaction resulting
ditives
in the reduced plasticizing effect of water (Hoover & Senanayake, 1996;
Spies & Hoseney, 1982). This hypothesis seems not to explain why sug-
some of the mechanisms of the effects of these additives on starch ars with the same molecular weight such as hexose behave differently
physicochemical changes. in retarding retrogradation. Another hypothesis is based on reduction
of water activity as a result of competition between starch and sugar
3.1. Sugars and sugar alcohols for available water and the associated free volume changes (Spies & Ho-
seney, 1982) but this also seems not to explain the variability mentioned
The primary reason for the addition of sugar to food products con- in retrogradation when using different sugars, for example, the water ac-
taining starch is to enhance sweetness taste to be appealing to con- tivity of 2M sorbitol, glucose, fructose, and ribose had the same value
sumers. Also, sugar was found to influence starch gelatinization and (0.957) but the Tgel were all significantly different ranging from 62.0
retrogradation properties leading to some desirable properties such as °C to 71.6 °C (Allan et al., 2018). Spies and Hoseney (1982) indicated
control of gelatinization of the low-moisture baked product leading to that sugar penetrated the starch granules forming a crosslink between
improved spread-ability during baking and final crispy texture (Pareyt & the starch chain in the amorphous region and restrict chain mobility
Delcour, 2008). Different sugars with the same mass concentration pro- and granules swelling resulting in increased Tgel. Large sugar molecules
duce different extents of increased gelatinization temperature (Slade & can bridge longer gaps between chains in the amorphous region com-
Levine, 1987; Spies & Hoseney, 1982). pared to small sugar molecules requiring more energy to pull the starch
Sucrose is the sugar widely used as a sweetener in food prod- crystallites apart resulting in higher gelatinization temperature and en-
ucts, but recently, consumers are becoming more interested in health- thalpy (Baek et al., 2004). Another hypothesis related to the effect of
ier baked products made with sugars and sugar alcohols with lower sugars on retrogradation is that sugar molecules with a large number
glycemic index and prebiotic nutritional benefit which resulted in in- of mean equatorial (OH) were more effective in stabilizing the amor-
tensive investigations on these sucrose alternatives on baked products phous region and the entangled matrix of the starch chain in the gels
quality (Kweon, Slade, & Levine, 2016; Miller, Dann, Oakley, Anger- resulting in reduced retrogradation (Katsuta, Miura, & Nishimura, 1992;
mayer, & Brackebusch, 2017). Sugars were found to have a great in- Katsuta, Nishimura, & Miura, 1992). The average number of equatorial
fluence on starch gelatinization and retrogradation properties, the ex- OH in increasing order as reported by Uedaira and Ishimura (1989) ri-
tent of changes in gelatinization and retrogradation properties depend bose < fructose < mannose < xylose < glucose < sucrose < maltose
on the type and concentration of sugars, botanical origin of starch, this hypothesis seems not to correlate with other studies (Ahmad &
starch concentration, and the ratio of amylose/amylopectin (Ahmad & Williams, 1999; Cairns et al., 1991; Chang, et al., 2004; Prokopowich &
Williams, 1999; Slade & Levine, 1987). Biliaderis, 1995).
Gelatinization temperature (Tgel ) was found to increase with in- Finally, stereochemistry seems to be the key towards explaining the
creased sugar concentration on mass and molar basis for mono and behavior of starch-sugar-water composites during aging, the study on
disaccharide (Ahmad & Williams, 1999; Allan, Rajwa, & Mauer, 2018; corn starch-sugar composite showed that sugar compatible with wa-
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I.O. Mohamed Carbohydrate Polymer Technologies and Applications 2 (2021) 100039
ter structure was found to correlate well with stereochemistry concept showed that MCP inhibited starch swelling resulting in decreased peak,
rather than the equatorial OH group (Chang et al., 2004), also the glyco- trough, and final viscosities compared to control (Allan et al., 2018).
sidic linkage in sweeteners affected how sweeteners interact with starch Several researchers reported that the increase in gelatinization temper-
with those containing an 𝛼-1,6 glycosidic linkage increasing the Tgel ature, reduction in peak, trough or final viscosities compared to con-
the most, regardless of the monomeric units, glucose dimers, isomal- trol for starch-hydrocolloid composite, for both electrolytic and non-
tose linked via 𝛼-1,6 glycosidic linkage has greater molecular flexibility electrolytic hydrocolloids could be due to the formation of a hydra-
and form more intermolecular interactions than maltose linked via 𝛼- tion layer by the polysaccharides around the starch molecules, prevent-
1,4 linkage (Allan et al., 2018). Furthermore, sugar alcohol was found ing starch-water association or due to association of the hydrocolloids
to increase Tgel more than their counterpart sugars because they are with leached out amylose and/or amylopectin in addition to inhibi-
more flexible with an open structure, with less steric hindrance, large tion of starch molecules swelling already mentioned (Allan et al., 2018;
atomic radius, and additional hydroxyl group leading to more H-bonds Chen, et al., 2014). Chen et al. (2014) showed that the dynamic rheo-
with starch and water (Allan et al., 2018). Based on kinetic experimental logical measurements of rice starch gel with pullulan a neutral hydro-
data modification of starch gels structure caused by sugars will be more colloid resulted in increased storage modulus (Gʹ) and the loss modulus
distinct with starch of low amylose content, as high amylose content (Gʹʹ) of the gel with increased pullulan concentration from 0.01% to
will mask the effect of sugars (Biliaderis, 2009), this should be taken into 0.07%, but then both moduli decreased with increases in pullulan con-
consideration when assessing the role of sugars on gelatinization and ret- centration from 0.07% to 0.5% which was attributed by the authors to
rogradation of starch. Recently, van der Sman and Mauer (2019) showed the hydrocolloids film formed around the rice strach granules resulting
that the gelatinization temperature of starch in sugar and polyol solu- in reduced granular swelling and leached amylose. The behavior of the
tions correlate well with the volumetric density of hydrogen bond in the electrolytic hydrocolloids in foods is more complex than the neutral be-
solution based on 19 different sugar and polyol with different concen- cause the presence of counterions and co-ions cause complex behavior
trations. More studies on the effects of volumetric density of hydrogen which may be ion-specific and depends on the concentration of all ionic
bonds are needed to explore the behavior with different starches and solute (Vlachy, 2008). XT gum added to potato starch with different
the effects on starch retrogradation. levels of amylose content showed improvement of both short-term and
long-term retrogradation properties of the starch gel (Dobosz, Sikora,
3.2. Gums and hydrocolloids Krystyjan, Lach, & Borczak, 2020). Zhang et al. (2020) investigated the
effects of XT and guar gum on pasting and gel properties of high amylose
Hydrocolloids and gums are terms used interchangeably to refer to starches NF-CG170 (71 % amylose) and Hylon-V (50% amylose), the re-
non-starch polysaccharides or their derivatives with varying degree of sults showed that guar gum displayed more profound effects on pasting
water solubility, they are known for their thickening and/or gelling properties and gel strength with NF-CG170 starch compared to XT gum.
properties. The only protein that can properly be described as hydro- The authors concluded that guar gum has a stronger molecular associa-
colloids is gelatin which has some of the common characteristics of tion with amylose as an explanation for this phenomenon. However, for
polysaccharides (Dickinson, 2018). Hydrocolloids such as guar gum, lo- example, Hylon-V, XT showed higher final viscosity compared to guar
cust bean gum, and tara gum are not pure polysaccharides, but rather gum contrary to the case with NF-CG170 where the final viscosity is
are the grounded endosperm of their respective seeds and thus contain much higher with guar gum than XT. This clearly showed the complex-
protein, fiber ash, etc. (BeMiller, 2007). Starch-based products made ity of the behavior of hydrocolloids and their association with starch and
with native starch might not meet consumer expectation based on sen- water besides, the electrolytic properties of some hydrocolloids which
sory quality and stability for that reason hydrocolloids are added to require further investigation to have a better understanding of the be-
starch-based products to improve their tolerance to heat, shear, acidic havior of starch with hydrocolloids. Recently, Ma et al. (2019) showed
condition, protect starch granules during cooking against shear, control that konjac glucomannan (KGM) non-electrolytic hydrocolloids raised a
water mobility, and retention, improve the texture of pastes and gels peak viscosity, breakdown, and setback viscosities of corn starch. The
and improve cold storage and freeze-thaw stability (BeMiller, 2011). study also showed that increasing the level of KGM resulted in increased
Some hydrocolloids such as 𝜆-carrageenan could be potentially used viscoelasticity of corn starch gel. KGM was also reported to increase vis-
to sequester pro-oxidant metal ions, thus inhibiting lipid oxidation in coelasticity and the level of resistant starch to 65% with debranched
lipid-containing foods (Gao et al., 2017). Also, various hydrocolloids corn starch as a result of an increased level of crystallinity enhanced by
impart different cryoprotective effects to food products depending upon the gum addition (Ning et al., 2020).
their solubility, water-holding capacity, rheological properties, and syn-
ergistic effect with other ingredients during freezing and frozen storage 3.3. Proteins
(Maity, Saxena, & Raju, 2018).
Most hydrocolloids are neutral with regards to flavor and taste for The macronutrients widely used in human diets are proteins and
that reason they are used in a variety of foods to provide adhesive- starches because they provide the essential nutrients for growth and
ness, as foam and whipping agent, as an emulsifier, for film-forming, nourishment. Both starch and protein can form a gel when hy-
as a stabilizer, as a gelling agent, for flavor encapsulation, as a drying drated and heated, however, the gelling of proteins also is influ-
agent and others. Some hydrocolloids possess electrolytic characteris- enced by several factors such as heating rate, holding time and
tics because it contains some charge groups others are neutral, there- temperature, pH, ionic strength, minerals contents, and presence of
fore this may result in complex interaction with starches and other ad- other hydrocolloids resulting in a complex physicochemical environ-
ditives especially the charged hydrocolloids. Xanthan (XT) gum as an- ment (Nunes, Raymundo, & Sousa, 2006; Yang, Luan, Ashton, Gor-
ionic hydrocolloid showed different pasting behavior compared to guar czyca, & Kasapis, 2014). Gelation of proteins can be induced by
gum (neutral) when added to waxy corn starch at the same level, XT heating or other extrinsic factors, however, the heat-induced gela-
showed better protection for starch granules structure against shearing tion takes place in two steps; denaturation of protein resulting in the
compared to guar gum (Heyman, De Vos, Depypere, Van der Meeren, unfolding of the protein globular structure and exposure of nonpo-
& Dewettinck, 2014). Similar effects were observed for granules pro- lar and sulfhydryl groups followed by aggregation of the polypep-
tection using XT gum with tapioca starch resulting in retardation of tides through covalent disulfide bonds, and/or non-covalent bonds
gelatinization, while guar gum showed no effect in retarding gelatiniza- (hydrogen bonds, hydrophobic interaction and Van der Waals forces)
tion resulting in increased peak viscosity from unrestricted granules (Britten & Giroux, 2001).
swelling (Chaisawang & Suphantharika, 2006). Recently, the study on Several research works were carried out to investigate the interac-
Mesona chinensis an anionic polysaccharide (MCP) with wheat starch tion of proteins-starches gel composite which is a complex physicochem-
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I.O. Mohamed Carbohydrate Polymer Technologies and Applications 2 (2021) 100039
ical process influenced by the thermodynamic compatibility of proteins Mixolab and rheological measurements were used to study the
and polysaccharides as affected by processing conditions, intrinsic and thermo-mechanical and rheological behavior of potato starch with soy
extrinsic factors leading to dynamic competition between phase sepa- protein concentrate, powdered egg protein, or gluten protein, the fun-
ration and gel formation (Nunes et al., 2006). Milk proteins are widely damental rheological measurements showed that potato starch is highly
used with starch for the formation of protein-starch gel composite due influenced by the addition of proteins (Patraşcu, Banu, Vasilean, &
to their availability, nutritional value, diverse functional properties, and Aprodu, 2016). The study showed that powdered egg addition resulted
low cost such as whey protein because it is effluent from the cheese- in the weak structure of the batter with high frequency-dependent, while
making industry. Yang et al. (2014) used 15 % wheat starch with 15 % gluten and soy protein resulted in low frequency-dependent and high
whey protein isolate (WPI)and 5 mM to 192 mM calcium chloride salt cross-linked structure, also, the thermo-mechanical test showed that the
to prepare starch-protein gel that is resistant to enzymatic hydrolysis, starch-protein formulation with soy protein concentrate withstand the
their result showed that the 45 mM calcium chloride level yielded the heating at 90 °C while gluten was found to limit the retrogradation of
best result while the low level and high level of the calcium chloride the potato starch (Patraşcu, et al., 2016). Fish myofibrillar protein and
resulted in a gel structure which is more porous making the starch gran- cassava starch composite were investigated in terms of textural, rheo-
ules more accessible to enzymatic hydrolysis. Another study was carried logical, morphological, and spatial distribution behavior using starch
out to investigate the effect of WPI with chitosan in protecting against fraction from 0 to 1 within a constant total content of 60 mg/mL the
hydrolysis of wheat starch, the result showed that the composite gels, result showed that the starch fraction 0.5 was critical for conversion of
consist of low to medium molecular weight chitosan in combination the protein matrix to the starch matrix and conversion of the gel from
with WPI and wheat starch were effective at enhancing the protective elastic to weak, also at 0.5 and 0.6 starch there is the formation of a semi-
barrier against starch hydrolysis during an in-vitro test (Yang, Ashton, interpenetrating network with more amylose from the melted starch
Gorczyca, & Kasapis, 2017). granules interpenetrated protein molecules, also there is no covalent
Kett et al. (2013) investigate the gelatinization of 5 wt% waxy bonding between protein and starch molecules with an increased starch
maize starch with added 5 wt% 𝛼-lactalbumin, 𝛽-lactoglobulin, 𝛼- fraction (Fan et al., 2017). In another study with myofibrillar protein
caseinate or 𝛽-caseinate their results showed that the caseinates rein- (MP), composite gels were prepared using 2% MP with native potato or
forced the starch-protein gel but not the whey protein (𝛼-lactalbumin, tapioca starch and their modified form (esterified and cross-linked), the
𝛽-lactoglobulin), with 𝛼-caseinate more effective than the 𝛽-caseinate results showed that the esterified form of both starches improved signif-
because of their ability to penetrate the starch granules, unlike the 𝛽- icantly the composite gel strength and water holding capacity compared
caseinate which form large aggregates outside the granules. Other re- to native and cross-linked form, with the cross-link showed better per-
searchers showed a similar result about the ability of the caseinates to formance than the native starches, the microstructural analysis showed
associate more than the whey protein with starch granules for both nor- that the “packing effect” of potato starch on gels was more remarkable
mal and waxy rice starch (Noisuwan, Hemar, Wilkinson, & Bronlund, than tapioca starch because of the large granule size (Wu, Wang, Ge,
2011). Yu, & Xiong, 2018).
Whey protein hydrolysate (WPH) add to rice starch was found to be The effect of acidification on the starch-protein gel was investi-
effective in retarding starch gel retrogradation during storage, by retard- gated using 10 wt% of egg albumin or soy protein isolate (SPI) with
ing hydrogen bonding between starch chains resulting in enhanced gel rice, potato, or tapioca starch combined with a reduction of pH to 4.5
stability and shelf life (Hu et al., 2020). The effect of the addition of a and heating temperature of 90 °C and 120 °C, the result showed that
different type of milk proteins on pasting of normal and rice starch was gel prepared at 120 °C were much weaker and prone to break-down
investigated using whey protein isolate (WPI), skim milk protein (SMP), upon deformation than those formed at 90 °C; with rice starch being
and sodium caseinate (NaCAS), the result showed that NaCAS and SMP the most sensitive to temperature and potato most resistant, the re-
resulted in an increase of onset temperature by 2 °C and 4 °C respectively sults also revealed that acidification weakened the structure of these
as a result of restricted swelling and leaching of polysaccharides for both gels (Villanueva, Ronda, Moschakis, Lazaridou, & Biliaderis, 2018). Re-
starches while WPI did not affect swelling and onset temperature, the cently, Niu et al. (2018) investigated the effect of porcine plasma protein
reason for the restricted swelling and leaching of polysaccharides was hydrolysates (PPPH) on short term retrogradation of corn starch, the re-
postulated to be due to the adsorption of milk proteins to the starch gran- sults showed that PPPH significantly retards short term retrogradation of
ules through hydrophobic interaction which restricts diffusion of water the corn starch. The inhibition is being attributed to the interaction be-
into the starch granules and hence reduces swelling (Noisuwan, Hemar, tween the polypeptide of the PPPH and amylose chains, the authors also
Bronlund, Wilkinson, & Williams, 2007; Noisuwan et al., 2011). Fur- postulated that PPPH might competitively bind with water molecules
thermore, confocal laser scanning microscopy showed that in the case of restricting the mobility of the starch chains to associate with each
NaCAS, for both normal and waxy rice starch 𝛼-casein adsorbed prefer- other. Recently, Zang et al. (2019) showed that rice protein retarded
entially and in a higher amount than the 𝛽-casein and for the case of WPI, retrogradation of rice starch by blocking the cross-linking of starch
although the amount of adsorbed 𝛽-lactoglobulin is higher than that of molecules.
𝛼-lactalbumin no preferential adsorption is observed (Noisuwan et al., Liang et al. (2003) compared the effects of amino acid struc-
2011). ture on the pasting properties and crystallinity of rice starch. The re-
Recently, Villanueva et al. (2018) investigated the effect of mi- sults showed that charged amino acids had more influence on past-
crowave treatment (MWT) on products based on potato and rice starches ing properties than the neutral amino acids. Furthermore, charged
supplemented with 5% calcium caseinate (CaCAS) or soy protein isolate amino acids decreased cooking stability and increased retrogradation
(SPI), the results showed that the effect of MWT depends on the starch tendency which could potentially help in the development of resistant
source and protein type. MWT changed the hydration properties and en- starch (Liang & King, 2003). Glutamic or lysine amino acids added
hanced water absorption index and swelling power in potato samples, to cross-linked potato starch was found to increase the gelatinization
while it decreased in rice starch samples regardless of the type of pro- temperature and decreased both the loss and storage modulus of the
tein. MWT also influenced mainly the pasting properties of rice starch gel (Gałkowska & Juszczak, 2019). Recently Hu et al. (2020) showed
by increasing pasting temperature and setback, and decreasing peak and that the addition of amino acids (Lys, Ser, Ala, Asp) to potato starch
breakdown viscosities, the treatment also significantly increased the vis- followed by hydrothermal treatment (HMT & ANN) resulted in sig-
coelastic moduli and decreased the loss tangent for potato starch gels nificantly increased pasting and gelatinization temperatures, and de-
with and without added proteins (Villanueva, De Lamo, & Harasym, creased swelling power, peak viscosity and enthalpy in addition to
2018). increased resistant starch content. In another study, added soybean
protein hydrolysates (SPH) and XT gum to rice starch showed a syn-
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I.O. Mohamed Carbohydrate Polymer Technologies and Applications 2 (2021) 100039
3.4. Lipids
Indigenous lipids present with starch or added lipids during the heat-
ing and cooling process were found to influence starch viscoelastic prop-
erties by forming an inclusion complex with helical structures of amy-
lose resulting in V-type crystalline structure, the outer surface of the
helices are hydrophilic and the inner core cavity is hydrophobic that
can accommodate compatible ligands (Hibi, Kitamura, & Kuge, 1990;
Wang et al., 2020). Starch lipid complex formation was found to im-
prove the functionality of starchy foods by reducing hydrolysis of starch
and protect volatile and bioactive compounds and other food sensitive
ingredients in addition to improving their delivery and bioavailability
in the human body (Zhang, Huang, Luo, & Fu, 2012). The characteris-
tics of amylose-fatty acid complexes are commonly influenced by the
purity of the starting materials and complexation reaction conditions
(Reddy, Choi, Lee, & Lim, 2018).
The complexes between lipids and starch are predominantly between
lipids and amylose, however, there is some evidence that amylopectin
can also form complexes with lipids (Huang & White, 1993; Reddy, et al.,
2019). Lipid complexes with amylopectin will be weaker compared to
amylose due to the restriction from the amylopectin side branch for
the formation of a single glucan helix confirmation as with amylose.
However, debranching of waxy starch and starch with low amylose con-
tent using debranching enzymes such as pullulanase or isoamylase or Fig. 3. Left-handed single amylose helix (V-amylose) featuring a unique cen-
combination will be an effective method to increase the level of resis- tral hydrophobic channel containing polyiodide (shown as purple color). Atoms
tant starch through retrogradation of debranched starch or enhanced are shown with CPK coloring while blue and green represent hydrophilic and
complexing with lipids or lipid-protein (Cao et al., 2020; Chang et al., hydrophobic surfaces, respectively. (Adapted from, Mottiar et al., 2011, repro-
2020; Wang et al., 2020). The dual retrogradation-annealing process duced by permission from Elsevier)
for rice starch with different amylose content showed that starch-
lipid complexes form the major component of the crystalline struc-
ture and resulted in prominent amylopectin-lipid complexes (Iftikhar amylopectin-lipid complexation is evident from the analysis, further-
& Dutta, 2019). more, the DSC analysis showed that MGs resulted in a significant de-
Starch-lipid complexes were found to be influenced by several fac- crease of onset temperature in the presence of MGs except for mono-
tors such as; amylose chain length, fatty acids chain length and degree of stearin and also the enthalpy for the samples containing MGs is statisti-
saturation, reaction temperature, heating time, substrate concentration cally lower than the control except for samples with mono-myristin.
and ratio, water content, and pH (Gelders, Vanderstukken, Goesaert, & Complexes of lauric fatty acids (LA) with enzymatically de-branched
Delcour, 2004; Wang et al., 2020). The addition of lipids to amylose high amylose maize starch showed changes in the melting temperature
induces spontaneous folding of the amylose chain into helical structure and enthalpy. The starch-lipid complex was enhanced with increased
driven principally by the interaction of the aliphatic lipid-tails with the de-branching time resulting in an increased crystalline structure with a
hydrophobic core of the amylose (López, de Vries, & Marrink, 2012). dense aggregation of helices from the amylose LA complex and the retro-
V-amylose most likely cannot exist without a guest molecule which is graded amylose was suggested to be resistant starch (Zhang et al., 2012).
important for inducing the conformational changes leading to the for- In another study that involves complexation of lauric acid with normal
mation of the amylose inclusion complex (Zobel 1988; López, de Vries, corn starch, the study investigated the method of addition of lauric acid
& Marrink 2012). For illustration Fig. 3 show a V-amylose inclusion to corn starch which showed that the method based on adding LA to
complex with polyiodide as a guest prepared using structural models heated starch suspension is favorable for the formation of V-amylose
(Mottiar & Altosaar, 2011). The V-amylose configuration permits a wide crystalline structure and the in-vitro digestibility test showed that this
range of guest molecules due to the flexibility afforded by rotation of the method produces complexes with the ability to slow the hydrolysis of
hydroxymethyl groups of glucopyranose (Rao et al., 1998). starch (Chang, He, & Huang, 2013).
The type of lipid is reported to be an important factor for com- Meng et al (2014) investigated the effect of homogenization pres-
plex formation with amylose; as fatty acids, mono-acyl and di-acyl glyc- sure (0–120 MPa) on starch-lipid complexes of corn starch with added
erol can form complexes while tri-acyl glycerol cannot form complexes (0.5–8%) palmitic acid based on starch content. The result showed that
(Chao, Yu, Wang, Copeland, & Wang, 2018; Tufvesson, Wahlgren, & the complex index increased to a maximum value of 60% for fatty acid
Eliasson, 2003). content of 4% and homogenization pressure of 100 MPa. Starch-lipid
Other studies reported that di-acyl glycerol cannot form complexes complexes between conjugated linoleic acid (CLA) and high-amylose
with amylose in addition to tri-acyl glycerol and the complex struc- maize starch was obtained with a maximum yield of 67.7% when the
ture from mono-acyl glycerol is less stable compared to fatty acids reaction was performed at 90 °C for 6 h at neutral pH, the complexes
(Chao et al., 2018). formed was found to be shelf-stable at ambient storage temperature for
Numerous studies were carried out to investigate starch-lipid com- 4 weeks (Seo, Kim, & Lim, 2016).
plex structures using various types of starches and lipids. Huang and Marinopoulou et al. (2016) used an aqueous alkaline solution to
White (1993) investigate the effects of different saturated mono-acyl prepare amylose-fatty acid complexes using fatty acids with different
glycerol (MGs) with waxy corn starch as a model system to explore chain lengths and degrees of saturation and amylose extracted from
the complexation of amylopectin with lipids, their result showed that pea. Three reaction temperatures were used 30, 50, and 50 °C, the re-
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I.O. Mohamed Carbohydrate Polymer Technologies and Applications 2 (2021) 100039
sults showed that all complexes formed were semi-crystalline regard- 3.6.1. Process induced macromolecules interactions
less of the temperature used for their preparation and the dissociation Fig. 4 showed that starch-lipid-protein can form a ternary com-
temperature of complexes is dependent on the fatty acids carbon chain plex, the second peak from High-pressure size exclusion chromatogra-
length and degree of unsaturation as well as the temperature of complex phy (HPSEC) represents the ternary complex, while the first is for amy-
preparation. The longer the chain length and the higher the tempera- lopectin and the last for excess protein aggregates. Information about
ture of complex preparation the higher is the dissociation temperature the nature of interactions between protein and the inclusion complex of
(Marinopoulou et al., 2016). starch lipid is rare; an attempt will be made to speculate about the inter-
Recently, Reddy et al. (2018) investigated the effect of de-branching action between these three macromolecules based on published work.
of high amylose corn starch and formation of complexes with stearic Recently, Cornell et al. (2019) reported that positively charged amino
acid, their results showed that starch-stearic acid complexes increased acids bind more strongly to fatty acid polar head in vesicles, this im-
with an increase of de-branching time from 6 to 24 h and the com- plies that the interaction between the fatty acid and the polypeptide is
plexes contain both B-type and V-type crystal structure with the through electrostatic interaction, indicating that fatty acid plays a key
B-type crystal representing retrograded starches. In another study role in this complex.
Lu et al. (2020) showed that lauric acid form complex with high amylose In a study on the interaction of amylose-𝛼-linoleic complex versus
corn starch with increased resistance to digestion besides emulsification amylose alone with water, the V-amylose complex attained more com-
properties during the formation of Pickering emulsions. Treatment of pact conformation through the formation of additional hydrogen bonds
debranched corn starch with lauric acid prepared at high temperature which played a major role in the polymerization and stabilization of
(90 °C) was found to produce starch-lipid complexes with high melt- the complex (Feng et al., 2018). This implies that V-amylose helices
ing temperature, increased stability, and high resistance to amylolytic could form hydrogen bonds between helices or helices and hydrophilic
enzyme hydrolysis (Wang, Liu, Zhang, & Chen, 2020). amino acids because the outer surfaces of the helixes are hydrophilic as
mentioned earlier. Furthermore, polypeptide chains could make intra-
or inter-interaction through disulfide bonds, hydrophobic, or hydrogen
bonds.
3.5. Starch-protein-lipid complex
The interaction between these three macromolecules as outlined is
dominated by hydrogen bonds, hydrophobic, and electrostatic interac-
Plant cells deposit storage resources of carbohydrates, proteins, and
tion leading to conclude that this ternary complex is a supramolecular
neutral lipids in subcellular particles termed starch granules, protein
structure. Because, supramolecular materials have a broad definition
bodies, and oil bodies, respectively (Tzen, 2012). In cereals, legumes,
that covers any material consisting of components connected by non-
and tubers, starch granules are synthesized in the endosperm (cereals),
covalent interactions and experiencing spontaneous assembly or disas-
cotyledon (legumes), or parenchyma (tubers) cells. The proportion of
sembly process (Ma & Zhao, 2015; Rybtchinski, 2011).
these macromolecules differs greatly depending on species genotype
The supramolecular material because they are connected by non-
and climatic conditions. For legumes, there is an inverse relationship
covalent weak and dynamic interactions their structure is reversible,
between oil content and starch content, while tubers generally contain
allowing convenient structural changes at low energy cost by ma-
the least amount of lipids among these macromolecules. The organi-
nipulation of external stimuli (Liu, Kang, Wang, & Zhang, 2013;
zational structure of these macromolecules in-planta greatly influences
Rybtchinski, 2011). The ternary supramolecular complex can be used
digestibility and availability in the human body.
as a carrier for bioactive compounds and drug delivery with the pos-
sibility of control release and enhanced bioavailability in the human
body. Furthermore, recent studies showed that the ternary complexes
3.6. In-Planta macromolecules interactions have a V-type structure and are more stable compared to binary starch-
lipid complexes, with greater resistance to digestive enzymes hydrolysis
The endosperm of cereal (the major source of starch) is sur- (Wang et al., 2017; Zheng et al., 2018).
rounded by an aleurone layer rich in phosphorus, protein, and thiamine Fig. 5 shows the speculated ternary complex which consists of lamel-
(Mlyneková, Chrenková, & Formelová 2014). The starch granules are lae crystalline structure with the V-amylose helices oriented perpendic-
embedded in a continuous matrix of proteins that is surrounded by ular to the plane of the lamellar stacks (Biliaderis & Galloway, 1989).
a cell wall (Echoff & Watson, 2009). Lipid bodies consist of a central During hydrothermal treatment the heating process amylose leaked
core of triglycerides (TAG) molecules that are encapsulated and stabi- from starch granules during the gelatinization form left-handed inclu-
lized by phospholipid monolayer embedded within the protein matrix sion complexes with fatty acids, then during the cooling process the
(Do et al., 2018). Also, lipids are reported to be inside the starch gran- denatured proteins interact with V-amylose helices to form the ternary
ules associated with starch through V-type inclusion complexes as evi- complex (Wang et al., 2017). The amylopectin and aggregated protein
dent from the study on raw rice, corn, and oat starches (Morrison, Law, fractions are shown in Fig. 4 form an amorphous layer with the crys-
& Snape 1993), or association through ionic or hydrogen bonding to talline layer sandwiched between them or randomly linking the crys-
the hydroxyl group of the starch molecules (Dhital, Brennan, & Gid- talline lamellae structure (Biais, Le Bail, Robert, Pontoire, & Buleon,
ley 2019). Edwards et al. (2015) reported that the structural integrity 2006; Biliaderis & Galloway, 1989). Furthermore, the crystalline and
of endosperm is a major factor influencing starch bio-accessibility and amorphous fractions could form a spherulites structure consisting of
absorption in the small intestine. Indeed, several studies showed that in- crystalline lamellae and amorphous fractions spread between them, also
tact cell wall structure acts as a physical barrier restricting digestive en- the spherulites are reported to form aggregates (Bhosale & Ziegler, 2010;
zymes from accessing starch granules. Also, coarse flour was reported to Zabar, Lesmes, Katz, Shimoni, & Bianco-Peled, 2010). It is important to
reduce glucose release more than finely milled flour due to intact starch note that if there is a limitation in fatty acids and excess amylose, the
granules enclosed in the cell wall (Al-Rabadi, Gilbert, & Gidley 2009). excess amylose will form double helices during the cooling process and
Proteins matrix on starch granules surface (particularly in sorghum) pro- form aggregate in the amorphous layer. On the other hand, if there is
mote non-catalytic binding of amylase on cell wall surface limiting the excess in fatty acids it will interact with other macromolecules in the
hydrolysis of starch (Bhattarai et al., 2018). Other studies suggested that amorphous region or could be positioned between V-amylose helices in
the strong protein matrix and starch-protein interactions in sorghum the crystalline lamellae, these scenarios need be investigated.
provide physical restriction for access of 𝛼-amylase to the starch gran- Results from Raman, FTIR, and X-ray diffraction showed that the
ules leading to the lowest digestibility for sorghum starch compared to ternary V-type complex had a greater short-range molecular order and
other cereals (Rooney & Pflugfelder 1986; Zhang & Hamaker 1998). higher relative crystallinity compared with those of the binary starch
9
I.O. Mohamed Carbohydrate Polymer Technologies and Applications 2 (2021) 100039
Fig. 4. High Pressure Size Exclusion Chromatography (HPSEC) results of different materials: (A) starch control, (B) starch + protein, (C) starch + FFA, and (D)
starch + protein + FFA (Shah, Zhang, Hamaker, & Campanella, 2011) (Reproduced by permission from Elsevier).
fatty acid complex (Wang et al., 2017). Furthermore, the DSC study 2008; Samutsri & Suphantharika, 2012) or proteins (Wu et al., 2018;
showed that the ternary complexes have lower enthalpy during the heat- Yang et al., 2014). Gelatinization properties of rice starch (RS) with
ing process compared to binary complexes, also, the ternary complex is Xanthan gum (XT) are pronouncedly affected by the addition of salts,
less sensitive to fatty acids chain length and degree of saturation com- and the changes in pasting gelling characteristics depend on the type of
pared to binary complexes (Zheng et al., 2018). The lower energy of dis- added salt (Viturawong et al., 2008).
sociation of the ternary complex supports the idea that the interaction Samutsri & Suphantharika (2012) investigated the effects of added
between these three macromolecules is by non-covalent bonds namely, salts on pasting, thermal and rheological properties of rice starch with
hydrogen, hydrophobic and electrostatic interaction which also support guar gum (GG) or Xanthan gum (XT). The results showed that the addi-
the speculation that the ternary complex is indeed a supramolecular tion of salts significantly increased peak, breakdown, and final viscosi-
structure which could be easily manipulated by extrinsic parameters ties and pasting temperature of RS/XT blend, whereas those of RS/GG
such as temperature, pH or ionic strength changes. This characteris- was varied depending on the type of added salt (Samutsri & Suphan-
tic will facilitate control release and enhanced bioavailability of bioac- tharika, 2012). The effect of added salt to starch-hydrocolloids compos-
tive compounds, food sensitive ingredients, or drugs embedded in the ite in some situations is due to its synergistic effect. A study on corn
structure. The ternary complex will have greater potential applications starch with iota-carrageenan showed that added salt modifies the coil-
in food and pharmaceuticals as supramolecular Nano-carriers for food helix structure of the hydrocolloids and hence promoting the associa-
bioactive compounds and drugs which need to be explored. tion between starch and the hydrocolloids which affected the gelatiniza-
tion and retrogradation properties of the starch-hydrocolloids composite
3.7. Salts (Funami et al., 2008).
Fig. 6 shows how salts cause conformational changes of anionic
Salt such as sodium chloride is widely used in foods to elicit the kappa and iota carrageenans as a result of ionic strength modulation,
distinct sensory taste of saltiness also; salts are used to improve cer- which influences gelatinization and retrogradation of starches as men-
tain textural attributes and storage stability and in some situations as tioned previously. The addition of NaCl and CaCl2 induced conforma-
a preservative such as in salted meat of fish products. Salts are used tional transition from flexible random coils in absence of other salts.
with various types of starches; alone or in combination with other However, upon addition of KCl, the conformation changes resulted in
additives such as hydrocolloids (Fu & BeMiller, 2017; Funami et al., coil-helix transition with stiff kappa-carrageenan and more flexible iota
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I.O. Mohamed Carbohydrate Polymer Technologies and Applications 2 (2021) 100039
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I.O. Mohamed Carbohydrate Polymer Technologies and Applications 2 (2021) 100039
Changes in starch gelatinization temperature and enthalpy are cer- Angellier, H., Choisnard, L., Molina-Boisseau, S., Ozil, P., & Dufresne, A. (2004). Opti-
tainly affected by salt concentrations. At a given salt concentration, if the mization of the preparation of aqueous suspensions of waxy maize starch nanocrystals
using a response surface methodology. Biomacromolecules, 5, 1545–1551.
driving force of the anion exceeds the repulsing force of the Donnan po- Baek, M. H., Yoo, B., & Lim, S. T. (2004). Effects of sugars and sugar alcohols on thermal
tential, anions will enter the granules and cause rupturing of the hydro- transition and cold stability of corn starch gel. Food Hydrocolloids, 18(1), 133–142.
gen bond between starch molecules and hence influence gelatinization https://doi.org/10.1016/s0268- 005x(03)00058- 4.
Balet, S., Guelpa, A., Fox, G., & Manley, M. (2019). Rapid Visco Analyser (RVA) as a
(Chiotelli, Pilosio, & Le Meste, 2002). This perhaps supports researchers tool for measuring starch-related physiochemical properties in cereals: A review. Food
who showed that it is the anions which influence gelatinization. Don- Analytical Methods, 12(10), 2344–2360.
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Declaration of Competing Interest Chang, R., Xiong, L., Li, M., Wang, Y., Lin, M., Qiu, L., & Sun, Q. (2020). Interactions
between debranched starch and emulsifiers, polyphenols, and fatty acids. International
This research did not receive any specific grant from funding agen- Journal of Biological Macromolecules, 150, 644–653.
Chang, Y. H., Lim, S. T., & Yoo, B. (2004). Dynamic rheology of corn starch–sugar compos-
cies in the public, commercial, or not-for-profit sectors, therefore there ites. Journal of Food Engineering, 64(4), 521–527. https://doi.org/10.1016/j.jfoodeng.
is no conflict of interest 2003.08.017.
Chantaro, P., Pongsawatmanit, R., & Nishinari, K. (2013). Effect of heating–cooling on
rheological properties of tapioca starch paste with and without xanthan gum. Food
Acknowledgment Hydrocolloids, 31(2), 183–194.
Chao, C., Yu, J., Wang, S., Copeland, L., & Wang, S. (2018). Mechanisms underlying the
formation of complexes between maize starch and lipids. Journal of Agricultural and
The author expresses his great thanks and gratitude to Mohamed I. Food Chemistry, 66(1), 272–278.
Omer from Nanyang Technological University, Singapore for his excel- Chen, L., Tong, Q., Ren, F., & Zhu, G. (2014). Pasting and rheological properties of rice
lent job in preparing Fig. 5. starch as affected by pullulan. International Journal of Biological Macromolecules, 66,
325–331.
Chiotelli, E., Pilosio, G., & Le Meste, M. (2002). Effect of sodium chloride on the gela-
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