Carbohydrate Polymers 122 (2015) 456480

Contents lists available at ScienceDirect

Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Review

Composition, structure, physicochemical properties,

and modications of cassava starch
Fan Zhu
School of Chemical Sciences, University of Auckland, Private Bag 92019, Auckland 1142, New Zealand

a r t i c l e i n f o a b s t r a c t

Article history: Cassava is highly tolerant to harsh climatic conditions and has great productivity on marginal lands. The
Received 3 July 2014 supply of cassava starch, the major component of the root, is thus sustainable and cheap. This review
Accepted 23 October 2014 summarizes the current knowledge of the composition, physical and chemical structures, physicochem-
Available online 30 October 2014
ical properties, nutritional quality, and modications of cassava starch. Research opportunities to better
understand this starch are provided.
Keywords:
2014 Elsevier Ltd. All rights reserved.
Cassava starch
Composition
Structure
Property
Modication

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457
2. Starch yield and chemical composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457
2.1. Yield . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457
2.2. Chemical composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 458
3. Granular morphology and polymorphic composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 459
3.1. Granular morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 459
3.2. Crystallinity and polymorphic composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 460
4. Molecular structural characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 461
4.1. Amylose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 461
4.2. Amylopectin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 461
4.2.1. Internal molecular structure of amylopectin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 462
4.2.2. Cluster structure of amylopectin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 462
5. Physical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 463
5.1. Specic heat and thermal diffusivity of starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
5.2. Glass transition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
5.3. Swelling and solubilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
5.4. Gelatinization analyzed by differential scanning calorimetry (DSC) and Koer hot stage microscopy (KHSM) . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
5.5. Rheological properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 465
5.5.1. Pasting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 465
5.5.2. Rheological properties other than pasting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 467
5.6. Retrogradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 468
6. Nutritional properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 468
6.1. In vitro enzyme susceptibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 468
6.2. In vivo digestibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 468
6.3. Health benets of native and modied starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469

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0144-8617/ 2014 Elsevier Ltd. All rights reserved.
 F. Zhu / Carbohydrate Polymers 122 (2015) 456480 457

7. Starch modications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469

7.1. Chemical modications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469
7.1.1. Cross-linking (CL) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469
7.1.2. Alkaline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469
7.1.3. Acid modication in aqueous solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469
7.1.4. Acid modication in methanol/ethanol environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 471
7.1.5. Cationization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 471
7.1.6. Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 471
7.1.7. Substitution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 471
7.2. Physical modications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 472
7.2.1. Electric eld modication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 472
7.2.2. High-pressure-based modications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 472
7.2.3. Extrusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 472
7.2.4. Pre-gelatinization by drum drying . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473
7.2.5. UV-irradiation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473
7.2.6. -Irradiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473
7.2.7. Ball milling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473
7.2.8. Ultrasound . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473
7.2.9. Microwave . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473
7.2.10. Heat-moisture treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473
7.2.11. Annealing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473
7.2.12. Thermal degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473
7.2.13. Blending with other starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 474
7.3. Enzymatic modications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 474
7.4. Combined modications to increase the resistant starch content . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 474
7.5. Sour starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 474
8. Conclusions and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 475
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 475
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 475

1. Introduction a large amount of cassava that would be produced in the near

future. This review summarizes the current knowledge of the
Cassava (Manihot esculenta Crantz), sometimes named tapioca, composition, granular and molecular structures, physicochemical
manioc, or yuca, is a perennial woody shrub with tuberous roots properties, nutritional quality, and modications of cassava starch,
in the family Euphorbiaceae (Alves, 2002). With a South American and makes suggestions of research to better understand and utilize
origin, cassava is now widely cultivated in tropical and subtrop- the starch.
ical regions of Asia, Africa, and Latin America as the third most
important source of calories in the tropics, after rice and maize 2. Starch yield and chemical composition
(FAO, 2014). The world production of cassava in 2012 was esti-
mated as 262,585,741 tonnes with the top producers being Nigeria, 2.1. Yield
Indonesia, Brazil, and Thailand (FAO, 2014). Cassava is highly tol-
erant to drought and harsh climatic conditions, and is admirably Starch isolation from the cassava roots on industrial scale
productive on poor soils and marginal lands (Alves, 2002). It has an has been reviewed previously (Breuninger, Piyachomkwan, &
around-the-year availability due to the exibility of crop planting Sriroth, 2009). Briey, the fresh roots are washed, chopped and
and harvesting. These agronomic traits make cassava a reliable crop grated in sulfur-containing water to separate starch from pulp
for food security and various applications. in the extractor. The starch fraction then is separated from the
Cassava is generally considered a source of carbohydrate, pulp and de-watered before drying. The starch extraction on
riboavin, thiamin, and nicotinic acid, but not protein (Westby, the laboratory level in principle resembles the industrial one.
2002). In Africa, over 80% of cassava produced is for human food The freshly extracted and un-dried starch can be alternatively
as a major calorie source, with more than 50% in various processed stored in sodium metabisulphite solution which inhibits the
forms. In the Americans, about 40% of cassava production is for microbial growth. The starch properties were little affected by
human consumption and 30% is for livestock feed, while Asia as this wet storage (Jyothi, Kiran, Wilson, Moorthy, & Nambisan,
a whole is an exporter of cassava products (Westby, 2002). Apart 2007).
from food and feed consumption, cassava is extensively used for There is a wide range of starch yield from various reports
various industrial applications. For example, using cassava to pro- (Table 1). The starch yield amounted up to 80% of dried weight
duce biofuel and ethanol becomes a focus of research and practice of cassava root (Olomo & Ajibola, 2003). Great genetic variation
during the last decade in the light of the limited fossil oil reserve in starch yield has been observed (Benesi, Labuschagne, Dixon,
(Lu, Ding, & Wu, 2011). Starch is the major component of cas- & Mahungu, 2004; Benesi, Labuschagne, Herselman, Mahungu, &
sava root and can amount up to 80% of dried weight of the root Saka, 2008; Joseph, Yeoh, & Loh, 2004). High starch yield can be
(Olomo & Ajibola, 2003). It is naturally expected that the quality achieved by using suitable varieties with high dry matter con-
of many cassava-based products is to a large extent determined by tent and thin peel thickness (Prez et al., 2011). Various articial
the starch quality. factors affecting the starch yield include the drying conditions of
The world cassava use is expected to reach up to about 290 raw materials (oven-dried chips and our gave higher yield than
million tonnes in 2020 with Africa being the major producer sun-dried ones) (Olomo & Ajibola, 2003), harvesting time and root
accounting over 60% of total production (Westby, 2002). Thus, a storage (root storage decreased starch content) (Benesi et al., 2008;
better understanding of various factors affecting the starch qual- Osunsami, Akingbala, & Oguntimein, 1989), the status of the roots
ity would greatly facilitate a more efcient utilization of such used for extraction (fresh root gave better extraction efciency and
458 F. Zhu / Carbohydrate Polymers 122 (2015) 456480

purer starch than dried chips and pellets) (Meuser, Smolnik, Rajani,
& Giesemann, 1978), and the environmental conditions for grow-
ing the crop (e.g., two growth locations gave signicant difference
in starch yield of the same variety) (Benesi et al., 2004). All these
factors can be controlled, and careful selection of the parameters
would lead to a maximum of starch yield. It should be noted that
a high yield does not necessarily mean the starch would have the
desired quality for any specic application.
2.2. Chemical composition
The resulting starch showed a wide variation in the chemical
composition (Table 1). The ranges of ash, protein, lipid, phospho-
rous, and ber contents are 0.030.29%, 0.060.75%, 0.011.2%,
0.00290.0095%, and 0.111.9%, respectively. The fatty acids in the
starch granules are mostly palmitic, oleic, linoleic, and linolenic
acids (Lehrman, 1932). Compared with cereal starches, cassava

Table 1
Starch yield and chemical composition.

No. Yield (%) Amylose (%) Method for Ash (%) Protein (%) Lipid (%) Phosphorous (%) Fiber (%) Reference
amylose
quantication

1 24.4 0.24 0.49 0.13 0.15 Osunsami et al.

(1989)
4a 1620 SEC-AD 0.120.33 0.050.28 0.040.38 0.0090.021 Asaoka et al. (1991)
1b 20.621 Iodine-S 0.320.66 0.590.63 0.0026 Padmanabhan and
Lonsane (1992)
1 0.15 0.05 Gorinstein and Lii
(1992)
3 2c 17.420 SEC-AD Asaoka et al. (1993)
5 22.626.2 Iodine-S 0.110.22 0.110.15 Moorthy, Wenham,
and Blanshard
(1996)
4 2 5d 17.923.6 SEC-AD Deoor et al.
(1998)
4 4e 19.624.1 SEC-WD 0.080.15 0.150.30 0.01 Sriroth et al. (1999)
3 3f 20.727.8 22.523.8 Iodine-S 0.070.16 0.250.36 0.030.15 0.170.42 Abera and Rakshit
(2003)
1 8g 48.879.9j 0.31.9 Olomo and Ajibola
(2003)
1 23 Iodine-S 0.09 0.1 1.2 Freitas et al. (2004)
23 11.326.0 17.528.9 Iodine-S Joseph et al. (2004)
20 2h 26.2552.19k 0.250.09 Benesi et al. (2004)
42 15.925.3 l SEC-AD and 0.70.9 0.751.1 0.1 0.50.9 Charles et al.
Iodine-A (2004)
10 1.619.2 Iodine-S 0.0080.0095 Raemakers et al.
(2005)
4 17.1419.11 m Iodine-A and Charoenkul et al.
SEC-AD (2006a)
1 16.3 Iodine-S 0.2 0.51 0.51 0.00756 Mishra and Rai
(2006)
40 15.230.2 Iodine-S 0.040.49 0.230.7 Onitilo et al.
(2007a)
39 16.225.1 Iodine-S 0.030.77 0.060.7 Eke et al. (2007)
3 020.4 Iodine-S and Ceballos et al.
DSC (2007)
33i 1628.1 Iodine-S Teerawanichpan
et al. (2008)
4050 15.226.5 Iodine-S Snchez et al.
(2009)
3 14.124.3 Iodine-S 0.110.23 0.150.34 0.160.28 0.00290.0048 Mbougueng,
Dzudie, Scher, and
Clerge (2009)
1 29.3 N.A. 0.29 Nwokocha, Aviara,
Senan, and
Williams (2009)
17 17.121.3 Iodine-S 0.00730.0078n Anggraini et al.
(2009)
2 618.4 Con A Gomand et al.
(2010a)
9 2-24.9 Iodine-S Koehorst-van
Putten et al. (2012)
8 030.3 DSC and Rolland-Sabate
Iodine-A et al. (2012)
8 016.5 DSC and Rolland-Sabate
Iodine-A and et al. (2013)
Iodine-S

No., number of genotypes/samples; the yield was based on wet weight except stated. DSC, differential scanning calorimetry based method for amylose measurement; SEC,
size-exclusion chromatography based method; SEC-AD; size-exclusion chromatography after debranching; SEC-WD, size-exclusion chromatography without debranching;
Iodine-S, iodine-spectrophotometry/colorimetry based method; Iodine-A, iodine-amperometry based method; Con A, concanavalin A based precipitation method; N.A., not
available; a, 34 different month harvest; b, 2 extraction method; c, with/without pruning aerial growth; d, 5 different harvesting month, and two different planting seasons;
e, 4 different harvesting months; f, 3 different extraction ways; g, starches extracted from sun-dried and oven dried chips and our; h, 2 different growth locations; i, 33
samples and genotypes with variations in the layers of roots, harvesting month, and planting season; j, dry base; k, fresh root; l, 2 different measuring methods; m, 3 different
measuring methods, 2 variations for SEC after debranching methods with/without amylopectin isoamylolyzate involvement; n, 7 genotypes.
 F. Zhu / Carbohydrate Polymers 122 (2015) 456480 459

starch contains much less amount of lipids. The phosphorous iodine-binding, chromatography, and so on. Different methods may
in the starch is mainly in the form of phosphate monoester give different result for the same sample (Charoenkul, Uttapap,
(0.0065%) as detected by 13 P nuclear magnetic resonance spec- Pathipanawat, & Takeda, 2006a; Zhu, Yang, Cai, Bertoft, & Corke,
troscopy (Kasemsuwan & Jane, 1996). The amount of C3-phosphate 2011). This has been observed between the following pairwise
is much higher than C6-phosphate (trace amount) (Anggraini, methods: gel permeation chromatography of Sepharose CL-2B and
Sudarmonowati, Hartati, Suurs, & Visser, 2009; Gomand et al., iodine-bindingamperometry method (Charles, Chang, Ko, Sriroth,
2010a). Compared with other starches (potato, wheat, mung bean, & Huang, 2004), two iodine-binding-based methods (spectropho-
normal and high-amylose maize), cassava contains much smaller tometry/colorimetry vs amperometry) (Rolland-Sabate et al.,
amount of phosphorus (Kasemsuwan & Jane, 1996). Apart from 2013), DSC and iodine-bindingamperometry method (Rolland-
the crop genetics, other factors such as planting season and year, Sabate et al., 2012), and iodine-bindingamperometry and
and the form from which the starch is extracted (fresh vs dried) high-performance size-exclusion chromatography after debranch-
may inuence the chemical composition of starch (Abera & Rakshit, ing the starch (Charoenkul et al., 2006a). For example, the
2003; Asaoka, Blanshard, & Rickard, 1991; Eke et al., 2007, 2009). iodine-bindingspectrophotometry based method gave higher val-
For example, starch extracted from fresh roots had lower ber con- ues of amylose content than that measured by DSC method for the
tent than that from dried roots (Abera & Rakshit, 2003). The type same sample (Ceballos et al., 2007). Thus the specic method for
of milling for dried roots (wet or dry milling) had little effect on amylose measurement should be noted when comparing data from
the composition (Abera & Rakshit, 2003). The chemical composi- different studies.
tion of starch (including the amylose content) was not affected by
the planting seasons (Asaoka et al., 1991). In general, the chemi- 3. Granular morphology and polymorphic composition
cal nature of the minor constitutes such as protein, lipid, and ber
remains to the further explored. 3.1. Granular morphology
Starch consists of two major molecular components, amylose
and amylopectin. The amylose content is a major quality attribute The molecular components amylose and amylopectin are nat-
of starch and determines diverse properties of starch and eventu- urally assembled in the form of semi-crystalline granules. The
ally the end-use purposes, which has been subjected to a great deal morphological features of cassava starch including the size and the
of investigation (Srichuwong & Jane, 2007). Wide variation in amy- shape have been summarized (Table 2). The shape of the granules
lose content has been observed (030.3%) (Table 1). Great genetic has been linguistically described as oval, truncated, and rounded as
diversity in amylose content has been documented. For example, observed by various microscopic techniques (e.g., Scanning Elec-
the amylose content ranged from 15.2 to 26.5% in 4050 cassava tron Microscopy and Light Microscopy). The granule surface was
genotypes from a world collection (Snchez et al., 2009). Inuence probed by atomic force microscopy (AFM) in non-contact mode
of agronomic factors on the amylose content has also been observed to reveal the structural details (Juszczak, Fortuna, & Krok, 2003).
(Deoor, Dehing, & Delcour, 1998; Moorthy & Ramanujam, 1986; Blocklets, depressions, and protrusions on the surface of starch
Sriroth et al., 1999). Amylose content remained similar at various granules have been observed as illustrated in Fig. 1. In general, cas-
growth stages up to 6 month (Moorthy & Ramanujam, 1986). From sava starch had smoother surface compared with that of potato
6 to 16 month, the amylose content decreased (Sriroth et al., 1999). (Juszczak et al., 2003).
The harvesting time thus can inuence the amylose content on The granule size has ranged from about 2 to 32 m (Table 2).
which the seasons of planting apparently had little effect (Asaoka The size of 720 m was the most frequent (Rolland-Sabate et al.,
et al., 1991; Deoor et al., 1998). It is also interesting to observe 2012). The average size of granules from normal genotypes dif-
that there was little change in amylose content from outermost to fered greatly between different studies (1018 m) (Deoor et al.,
innermost layers of the root (Teerawanichpan et al., 2008).
Various genetic means (natural selection and articial genetic
modications) have been employed to create greater diversity in
the amylose content of cassava starch. Through natural selection, a
waxy mutant with little amylose and the absence of granule-bound
starch synthase (GBSS) enzyme which is responsible for amylose
biosynthesis in the granules has been reported (Ceballos et al.,
2007). Articial genetic modications can be much more robust
in creating amylose content variations, though it is a subject of
much debating. A cyclic somatic embryogenic system has been used
in vitro to make waxy mutants with reduced starch content in the
root through -irradiation (Joseph et al., 2004). Amylose free starch
was generated by antisense inhibition of granule-bound starch syn-
thase 1 (GBSS1) (Raemakers et al., 2005). Another study reported
novel genotypes with nil or reduced amylose content by suppress-
ing the expression of GBSS1 (Zhao, Dufour, Snchez, Ceballos, &
Zhang, 2011). Genetically modied cassava genotypes with low/nil
amylose content were tested in the eld in Indonesia and showed
promising commercial potential with good root yield and starch
quality (Koehorst-van Putten et al., 2012). Genotypes with higher
amylose content are sometimes desirable for specic applications.
Through -irradiation, starch from mutants with relatively high
amylose (30%) was obtained (Ceballos et al., 2008; Rolland-Sabate
et al., 2012). Genotypes with higher amylose content (e.g., >50%)
remain to be developed.
Fig. 1. Atomic force microscopy (AFM) image of the surface of cassava granule
For the quantication of amylose content in starch, there are obtained in a non-contact mode (scan size 2.5 2.5 m) (Juszczak et al., 2003) (with
diverse methods based on differential scanning calorimetry (DSC), permission from John Wiley and Sons).
460 F. Zhu / Carbohydrate Polymers 122 (2015) 456480

Table 2
Granular morphology and polymorphism.

No. Polymorph Crystallinity (%) Granular size (m) Shape description Reference

4a Ca 15.317.8 2.431.1 Asaoka et al. (1991)

6 6.9611.21 (average) Safokantanka and Owusunipah (1992)
1b Ca Smooth surfaces and Padmanabhan and Lonsane (1992)
partially inward
curvatures; round,
cylindrical and polygonal
1 A Gorinstein and Lii (1992)
3 2c Ca 15.417.8 2.431.1, 1015 (peak) Asaoka et al. (1993)
1 A Francisco et al. (1996)
1 A 15 (average) Garcia et al. (1996)
5 332, 10.320.2 (peak) Moorthy et al. (1996)
4 2 5d A 3.032.0, 9.513.6 (average) Deoor et al. (1998)
4 4e 822, 15 (average) Considerably irregular with Sriroth et al. (1999)
oval, round and truncated
granules; little difference
between genotypes
11 920 Oval, truncated, rounded, Niba, Bokanga, Jackson, Schlimme, and Li (2002)
5 12.917.2 (average) Charles et al. (2005)
40 12.523.8 Onitilo et al. (2007a)
1 16 Tetchi et al. (2007)
4 5.8018.73 (average) Ceballos et al. (2008)
39 12.522.5 Eke et al. (2009)
1 2.8114.03 Nwokocha et al. (2009)
17 7.39.7 (average) Anggraini et al. (2009)
2 A 4049 16.918 Oval to round, a small Gomand et al. (2010a)
population with a
truncated end
12 A 4.623.8, 12.615.0 (average) Round and truncated Charoenkul et al. (2011)
8 Ca 2540 817 (average) Spherical, polyhedral, and Rolland-Sabate et al. (2012)
truncated
8 Ca 3540 12.116.9 (average) Rolland-Sabate et al. (2013)
1 7.125.0, 15 (average) Spherical, truncated Mishra and Rai (2006)

No., number of genotypes/samples; a, 34 different harvesting months; b, 2 extraction methods; c, with/without pruning aerial growth; d, 5 different harvesting month, and
two different planting seasons; e, 4 different harvesting months; peak and average in the parenthesis denote the peak and average size of the granules, respectively.

1998; Rolland-Sabate et al., 2013). The starch had both unimodal
and bimodal granule size distributions with the latter centered
at 15 and 12 m. The bimodal distribution became more obvi-
ous as the roots aged up to 16 months (Sriroth et al., 1999). It
should be noted that different techniques (e.g., laser scattering
based techniques vs manual measurement from scanning electron
microscopic photos) for granule size quantication (e.g., the aver-
age size) may give different results for the same sample.
There are various controllable/environmental factors affecting
the granule morphology observed in various studies as the fol-
lowing: The granules in the storage root were larger than in the
brous root. The granule size increased from outermost to inner-
most layers of storage root. Crop planting at the beginning of the
wet season in Asia gave larger granules than in the dry season
(Teerawanichpan et al., 2008). The granule size increased mostly
in the rst 6 months after cultivation, and remained similar there-
after (Moorthy & Ramanujam, 1986). Water stress on the crop led
to decreased granule size and the initial water stress had a greater
inuence than later one (Santisopasri et al., 2001). Crop planted in
raining seasons had larger granule size than that from dry seasons
(Deoor et al., 1998). Pruning, as a way to reduce the post-harvest
deterioration of the roots, reduced the peak size of granules, and the
effect was variety-dependent (Asaoka, Blanshard, & Rickard, 1993).
The granule shape was little affected by rainfall and temperature
(Gu, Yao, Li, & Chen, 2013).
The crop genetics can play a critical role in granule morphol-
ogy. Natural waxy genotype had similar granular morphology
compared with normal ones (Ceballos et al., 2007), whereas a
mutant with high amylose content (30%) induced by -irradiation
had much smaller granules (average size 5.80 m) with great
irregularity in shape as compared with commercial normal ones
(13.9718.73 m) (Ceballos et al., 2008).
3.2. Crystallinity and polymorphic composition
The granules are made up of alternating amorphous and semi-
crystalline shells with a thickness between 100 and 400 nm. At
a more fundamental level, a periodicity of about 910 nm within
the semi-crystalline shells has been observed by small-angle X-ray
scattering analysis (SAXS) (Prez & Bertoft, 2010). The periodic-
ity within the cassava semi-crystalline shells was determined as
9.1 nm by SAXS (Jenkins, Cameron, & Donald, 1993). The crystalline
in the granules are arranged in a specic way that gives rise to the
birefringence which can be observed under polarized light (Prez
& Bertoft, 2010). High-amylose starch (30%) with smaller granules
induced by -irradiation had increased amount of non-birefringent
granules especially among the smallest ones (Rolland-Sabate et al.,
2012).
On the molecular level, the external part of amylopectin chains
is believed to interact with each other and water molecules to
form double helices which are further crystallized. These crystals
are arranged in two basic manners and give rise to A- and B-type
polymorphism as revealed by wide-angle X-ray diffraction analysis
(Prez & Bertoft, 2010). C-type is a mixture of A- and B-types (Prez
& Bertoft, 2010). All the cassava starch analyzed so far exhibited A-
or Ca -type (Ca -type denotes the portion of A-type is dominant over
B-type in the polymorphic composition) (Table 2). A detailed wide-
angle X-ray diffraction study showed that the percentage of B-type
present in the Ca -type starch ranged from 10 to 20% (Rolland-Sabate
et al., 2012, 2013). Unlike the size of the granules, the diffrac-
tion pattern appears little affected by environmental factors and
crop developmental stage. All genotypes had an A-type polymorph
regardless of environmental factors and crop age (Deoor et al.,
1998). Another study showed that the wide-angle X-ray diffrac-
tion pattern and crystallinity percentage (%) were not affected by
 F. Zhu / Carbohydrate Polymers 122 (2015) 456480
the harvesting seasons (Asaoka et al., 1991). The crop genetics such
as partial or total silencing the GBSS1 had little inuence on the
granular structure (Rolland-Sabate et al., 2013). It should be noted
that the methods of calculating the crystallinity can affect the nal
results (Lopez-Rubio, Flanagan, Gilbert, & Gidley, 2008). For the
wide-angle X-ray diffraction analysis, the sample treatment also
can give rise to discrepancies and should be handled properly. For
example, increasing moisture content of starch led to the appear-
ance of C-type pattern from A-type polymorph (Francisco, Silverio,
Eliasson, & Larsson, 1996). The discrepancy in the crystallinity per-
centage (1518%) reported by Asaoka et al. (1993, 1991) and from
other studies (2550%) (Gomand et al., 2010a; Rolland-Sabate et al.,
2012, 2013) (Table 2) is more likely due to the difference in the
analytical and calculation methods.
4. Molecular structural characteristics
4.1. Amylose
Amylose is most linear with a few side chains through -(1-
6)-linkage branched from the -(14)-linked d-glucose backbones
(Prez & Bertoft, 2010). The amylose can interact with iodine
to form inclusion complex which has a characteristic bluish
color. The ability of the iodine inclusion formation reects the
size and structure of the amylose and can be quantied by
iodine afnity (%) (18.819.3%) and blue value (1.431.5) (4 geno-
types) (Charoenkul, Uttapap, Pathipanawat, & Takeda, 2006b).
The size/molecular weight of cassava amylose was reported as
DP (degree of polymerization) 10351202 (4 genotypes har-
vested in 4 different months) measured by high-performance
size-exclusion chromatography (HPSEC) with oligosaccharide
and dextran standards for calibration (Sriroth et al., 1999),
2.442.70 105 (5 genotypes) by HPSEC coupled with multi-angle
laser light scattering and refractive index detectors (HPSEC-MALLS-
RI) (Charles, Chang, Ko, Sriroth, & Huang, 2005), DPn 20504390
(4 genotypes) by HPSEC coupled with uorescent labeling
technique (Charoenkul et al., 2006b), and 2.1 106 by asymmetrical
ow eld ow fractionation (AF4) coupled with multi-angle light
scattering and refractive index detectors (AF4/MALS/RI) (1 geno-
type) (Juna & Huber, 2012). Apart from crop genetics as reected
by the genetic diversity in the amylose size, the measuring method
can have a great inuence on the result and can give different val-
ues for the same sample (Juna & Huber, 2012). The chromatographic
principles between HPSEC and AF4 differ essentially with the latter
having minimal shear forces during separation. This may give rise
to the possible discrepancy in amylose size as measured by these
two different techniques. The average radius of gyration of amylose
determined by AF4/MALS/RI was 73 nm (Juna & Huber, 2012).
The branches of amylose can be detected by using exo-acting
amylases such as -amylase to obtain the -limit dextrins. Among
4 genotypes, the -limit value (%), reecting the removed part dur-
ing the hydrolysis, ranged from 75 to 80%, and the molar amount of
pure linear amylose was 4758% in the amylose fractions (obtained
by1-butanol and 3-methyl-1-butanol based fractionation method).
The average chain lengths were calculated as 450550 glucosyl
residues and the average numbers of chains per molecule were
4.77.5 (Charoenkul et al., 2006b).
4.2. Amylopectin
Amylopectin with about 56% branches is the major molecular
component of cassava starch. The chain segments of amylopectin
can interact with iodine to give the reddish color in solution. The
iodine afnity (%) and blue value of cassava amylopectin (4 geno-
types) were 0.180.23% and 0.0800.091, respectively (Charoenkul
et al., 2006b).
461
The size/molecular weight of cassava amylopectin was
600017,100 (4 genotypes) by HPSEC coupled with uorescent
labeling technique (Charoenkul et al., 2006b), 1.88 108 by HPSEC
coupled with MALLS and differential refractometric index detectors
(HPSEC/MALLS/DRI) (Tetchi, Rolland-Sabate, Amani, & Colonna,
2007), 541.8 107 (8 genotypes) by A4F coupled with MALLS
and quasi-elastic laser light scattering (A4F/MALLS/QELS) (Rolland-
Sabate et al., 2012), and 19 106 (1 genotype) by AF4/MALS/RI (Juna
& Huber, 2012). The apparent average radius of gyration was 87 nm
(Juna & Huber, 2012) or 188 nm (Tetchi et al., 2007). This large
discrepancy to a large extent essentially can be attributed to the
analytical method. As already discussed in the above session about
amylose, the measuring techniques can have a great inuence on
the amylopectin size and should thus be noted when comparing
data from different studies. The dispersity index of amylopectin,
reecting the heterogeneity of amylopectin size, was calculated
(the ratio of weight average molar mass to the number average
molar mass (Mw /Mn )) as 1.252.23 (8 genotypes) (Rolland-Sabate
et al., 2012). The starches from the high-amylose mutants (induced
by -irradiation) had higher molecular dispersity, and also lower
average number of branching points and average number of gluco-
syl units in a linear chain per branching point than the normal ones
(Rolland-Sabate et al., 2012).
The number of chains per amylopectin molecule was estimated
as 300855 (4 genotypes) (Charoenkul et al., 2006b). The unit chain
length of amylopectin can be obtained by the chromatography of
debranched sample (an example of amylopectin unit chain length
distribution by HPSEC shown in Fig. 2). By high-performance anion-
exchange chromatography coupled with pulsed amperometric
detection (HPAEC-PAD), the proportion of unit chains with dened
chain length can be obtained. The ranges of the area percentages
(%) of unit chains with DP 69, DP 612, DP 1324, DP 2536,
and DP > 37 were 9.311.6%, 28.830.9%, 47.949%, 12.313%, and
8.69.4%, respectively (4 genotypes) (Rolland-Sabate et al., 2013).
Some reports showed the inuence of crop genetics and environ-
mental factors on the unit chain prole of cassava amylopectin
(Asaoka et al., 1991; Raemakers et al., 2005). The chromatographic
Fig. 2. Unit chain length distribution of amylopectin with uorescent-labelling
technique for C-chain length distribution (4 genotypes with the names indicated on
the up-left corner of each graph) by high-performance size-exclusion chromatogra-
phy (HPSEC); () uorescent response of C-chain; (----) refractive index response
of unit chain length distribution of amylopectin; () calibration for degree of poly-
merization (DP); arrows indicate actual DP values (Charoenkul et al., 2006b) (with
permission from John Wiley and Sons).
462 F. Zhu / Carbohydrate Polymers 122 (2015) 456480

patterns of isoamylase debranched starch (including the amylose

fraction) were not affected by planting seasons (Asaoka et al., 1991).
Amylopectin from amylose-free starch generated by antisense
inhibition of GBSS1 had similar chain length distribution compared
to the amylose-containing one (Raemakers et al., 2005). C-chain
denotes the single unit chain that carries the sole reducing end in an
amylopectin molecule. The unit chain length distribution of C-chain
was analyzed using HPSEC coupled with uorescent labelling tech-
nique (Charoenkul et al., 2006a). The C-chain length of amylopectin
had an asymmetrical distribution with a peak at DP 4142 and a
shoulder at DP 24 (Charoenkul et al., 2006b) (Fig. 2). Super-long
unit chains of amylopectin were observed with the weight percent-
ages of 0.241.78% (12 genotypes) (Charoenkul et al., 2006b), or
0.83% (2 genotypes) (Laohaphatanaleart, Piyachomkwan, Sriroth,
Santisopasri, & Bertoft, 2009). These two studies employed differ-
ent methods for super-long chains quantication (i.e., HPSEC vs low
pressure gel-permeation chromatography, and two different types
of gel for the latter (Sepharose CL 6B vs Superdex 75)), thus showing
that the result can be rather sensitive to the specic method used.
The average chain length (CL) of amylopectin was 2021 glu-
cosyl residues (4 genotypes) (Charoenkul et al., 2006b), 18.419.5
glucosyl residues (3 genotypes) (Rolland-Sabate et al., 2012), and
18.019.1 glucosyl residues (2 genotypes) (Laohaphatanaleart et al.,
2009). In a comparative study, CL of cassava amylopectin was
shorter than that of potato which had a B-type polymorph (Gomand
Fig. 3. Weight-based (wt%) unit chain composition of debranched , -limit
et al., 2010a). Indeed, a systematic study showed that A-type
dextrins of amylopectins by high performance anion-exchange chromatography
starch tends to have shorter CL than B-type ones in general coupled with pulsed amperometric detection (HPAEC-PAD); arrows indicate the DP;
(Hizukuri, 1985). It should also be noted that the chromato- in the form of , -limit dextrins, all the A-chains of amylopectin appear as maltose
graphic techniques could have a big inuence on the CL values and not shown in this gure (Laohaphatanaleart et al., 2009) (with permission from
(e.g., high-performance anion-exchange chromatography vs high- John Wiley and Sons).

performance size-exclusion chromatography).
4.2.1. Internal molecular structure of amylopectin
The branches in the amylopectin are clustered in a systematic
way (Prez & Bertoft, 2010). The external chain segments of amy-
lopectin can be removed by exo-acting amylases such as -amylase
or phosphorylase a and -amylase to obtain the limit dextrins. The
-limit value (%) (reecting the hydrolyzed part) of amylopectin
was 5965% (4 genotypes), and ,-limit value (%) was 50.659.7%
(2 genotypes) (Laohaphatanaleart et al., 2009). Though -limit dex-
trins structurally possess half a glucose residue more than the
,-limit dextrins, it is likely that this discrepancy in the limit value
(%) between these two studies was to a larger extent due to the ana-
lytical methods used. The unit chain length distribution of - or ,
-limit dextrins, reecting the internal part of amylopectin, can
be obtained by chromatography after debranching. An example of
the amylopectin internal unit chain length distribution analyzed by
HPAEC-PAD is shown in Fig. 3.
The amylopectin unit chains can be categorized into A- and B-
chains. The former carries no other chains while the latter carries
one or more chains (Peat, Whelan, & Thomas, 1952). According to
this nomenclature by Peat et al. (1952), the divisions of amylopectin
unit chains from some reports (Charoenkul et al., 2006a, 2006b)
did not reect the actual situation, and tended to over-estimate
the amount of A-chains. The only accurate way for estimating the
amount of A-chain would be from the , -limit dextrins of amy-
lopectin in which all the A-chains appear as maltose stubs while
the rest are B-chains (DP > 2). The molar amounts of A-chain ranged
from 52.953.6% (2 genotypes) (Laohaphatanaleart et al., 2009). The
unit chain length distributions of B-chains in the , -limit dextrins
of amylopectins are illustrated in Fig. 3. Two populations (weight-
based) of B-chains with peaks at DP 10 (major) and 35 (minor) and
a shoulder at DP 6 have been observed.
By comparing the unit chain proles of amylopectin and the
, -limit dextrins, various structural parameters have been cal-
culated. The average external chain length (ECL), internal chain
length (ICL), and total internal chain length were 10.612.9 glu-
cosyl residues, 5.26.4 glucosyl residues, and 13.115.7 glucosyl
residues, respectively (2 genotypes) (Laohaphatanaleart et al.,
2009). It is interesting to note that the internal molecule struc-
ture of amylopectin was highly correlated to the polymorphism of
the granular starch in a systematic study employing starches from
diverse botanical origins (Bertoft, Piyachomkwan, Chatakanonda,
& Sriroth, 2008). The polymorphism of the granules was further
related to the cluster and building block structure of amylopectin
(Bertoft, Koch, & man, 2012) as shown in the session below.
4.2.2. Cluster structure of amylopectin
The clusters can be isolated by partial hydrolysis of amylopectin
with -amylase of Bacillus amyloliquefaciens (Laohaphatanaleart,
Piyachomkwan, Sriroth, & Bertoft, 2010). The isolated -dextrins
of clusters are sequentially treated with phosphorylase a and
-amylase to obtain the , -limit dextrins, so that the internal
structure of the clusters can be compared between different
samples (Prez & Bertoft, 2010). The clusters can be further
treated with much concentrated -amylase of B. amyloliquefaciens
to obtain the -limit dextrins termed building blocks (Bertoft,
Laohaphatanaleart, Piyachomkwan, & Sriroth, 2010). The structural
composition of clusters and building blocks has been characterized
by diverse chromatographic techniques coupled with debranching
(Table 3). The DP, internal chain length (ICL), number of chains
per cluster (NC), molar amount of a-chains of clusters were 5878,
4.44.8 glucosyl residues, 8.211.1, and 58.261.0%, respectively
(5 fractions) (Laohaphatanaleart et al., 2010; Bertoft et al., 2010).
The nomenclature for a-chain of the clusters (as opposed to the
A-chain of amylopectin) should be noted. The distance between
each building block within a cluster was 6.87.5 glucosyl residues,
and there was 7.38.9 block in each cluster (5 fractions) (Bertoft
et al., 2010). Based on these data, a model of amylopectin clusters
has been visualized on the 2-dimensional and 3-dimensional levels
(Fig. 4). The model highlighted how the building blocks could be
assembled into clusters, amylopectin, and granules with the 9-nm
 F. Zhu / Carbohydrate Polymers 122 (2015) 456480 463

Table 3
Cluster structure of amylopectin.

No. DP ICL NC a-chain (mol%) IB-CL NBbl Reference

5 5878 4.44.8 8.211.1 58.261.0 6.87.5 7.38.9a Laohaphatanaleart et al. (2010) and Bertoft et al. (2010)

No., number of cluster fractions analyzed; DP, average DP of clusters; ICL, internal chain length of clusters; NC, number of chains per cluster; a-chain (mol%), molar percentage
of a-chain in clusters; IB-CL, inter-block chain length; NBbl, number of building blocks per cluster; the unit of ICL and IB-CL is glucosyl residue; a, from the peak-DP of clusters.

repeating distance. It should be noted that this model may be just
one way of visualizing this biomacromolecule, and that the model
or the data is the average description of amylopectin molecules
which actually have a range of molecular structures as reected by
the dispersity index values (Rolland-Sabate et al., 2012). The exact
structure of amylopectin remains a subject of investigation for the
generations to come.
5. Physical properties
The starch granules start to absorb water and swell when heated
in the presence of water. Some starch components mostly in the
form of amylose leach out of the granules and solubilize. As the
temperature and water absorption increase, the granules rupture
with the disordering of the organization of the chains. The general
term gelatinization applies to this process. When the gelatinized
system is subjected to cooling, the disordered chains undergo
re-ordering and re-association through molecular interactions and
hydrogen bonding. This process is termed retrogradation. The gela-
tinization and retrogradation is the core for diverse applications of
starch (Zhu & Wang, 2014). Various methods and techniques are
employed to describe these fundamental properties as below, and
studies have been attempted to reveal how the starch structure
can affect these properties.

Fig. 4. A model of how the building blocks can be organized into a cluster of amylopectin. (a) Black lines symbolize the unit chains of diverse B-chains categories indicated;
building blocks are encircled in light grey and numbered 19; a cluster segment is enlarged to illustrate how the glucose units are involved in building blocks (white and
black circles) and in the inter-block segments (grey circles); the segmental length between branches of two adjacent blocks (inter-block chain length, IB-CL = 78 glucosyl
residues) involves additional residues (4) (black circles inside the blocks). (b) A three-dimensional illustration of the cluster; numbers correspond to the building blocks
from the 2D drawing in (a). IB-CL is similar between all building blocks. (c) A larger structure including two clusters shown in (b) with an amorphous lamella of the granules.
The clusters are interconnected through blocks no. 9 (IC-CL, the inter-cluster chain length). Dotted line denotes the interconnection to more clusters. External chains in
the form of double helices extend from the building blocks at the interfacial area between the lamellae into the crystalline part. Very short A-chains (Afp ) are connected to
building block no. 9 in the amorphous area and may protrude into the crystals, causing structural defects (Bertoft et al., 2010) (with permission from Elsevier). Be noted the
nomenclature: A- and B-chains of clusters were later changed into a- and b-chains to distinguish them from the names of amylopectin chains (Bertoft et al., 2012).
464 F. Zhu / Carbohydrate Polymers 122 (2015) 456480
5.1. Specic heat and thermal diffusivity of starch
Specic heat, thermal conductivity, and thermal diffusivity are
important parameters for thermal processing of starchy food but
have been little reported so far. Specic heat is the amount of heat
taken to raise the temperature of a unit mass of a material by one
degree. It can be accurately determined by DSC at various temper-
atures and water content. Thermal diffusivity may be considered
as the rate at which heat is diffused into the materials and can be
calculated from experimental values of specic heat, thermal con-
ductivity, and bulk density. Thermal diffusivity of cassava starch
at various temperatures and water content has been calculated
(Lan, Fang, Kocher, & Hanna, 2000). Specic heat increased with
the increase in temperature and moisture and thermal conductivity
increased with the increase in moisture content. Models have been
suggested to predict the conductivity, specic heat, and diffusivity
of cassava starch (Lan et al., 2000).
5.2. Glass transition
The glass transition temperature (Tg ) is where the material
changes from the glassy to the rubbery state at a given heating
rate, and it has great signicance related to the food stability and
safety (Slade & Levine, 1991). The Tg of amorphous starch with
water content of 235% was determined by DSC and dynamic
mechanical thermal analysis (DMTA) (Perdomo et al., 2009) (Fig. 5).
Water anti-plasticized starch when its content was lower than
11%, while a plasticizing effect was observed for higher mois-
ture contents (Perdomo et al., 2009). The anti-plasticizing effect
of water on Tg was, however, not observed in another DSC study
(Chang, Cheah, & Seow, 2000). This may be attributed to the differ-
ence in the cassava genotypes (Perdomo et al., 2009). Typical DSC
curves on the Tg (where the specic heat value shifted) as a func-
tion of moisture content was showed previously (Aichayawanich,
Nopharatana, Nopharatana, & Songkasiri, 2011; Chang et al., 2000).
When the starch was in rubbery state, starch particles tended to
agglomerate (Aichayawanich et al., 2011).
Fig. 5. Glass transition temperature (Tg ) as a function of moisture content as mea-
sured by DSC (black round dots) and DMTA (empty triangle), and DSC data (cross)
by Chang et al. (2000). The effects of moisture in Tg were divided into 3 zones.
Zone I represents the moisture range (lower than 11%) where the water had anti-
plastic effect, Zone II (moisture between 11% and 23%) plastic effect with an decrease
in Tg with increased moisture content, and Zone III (moisture > 23%) plastic effect
with a rapid decrease in Tg with increased moisture content (Perdomo et al., 2009);
(with permission from Elsevier) note that the trend in zone I observed by Perdomo
et al. (2009) differed from that by Chang et al. (2000). Due to the contradictory
results (Zone 1) from two different studies using only one genotype, more studies
employing diverse genotypes should be tested to make it conclusive.
5.3. Swelling and solubilization
The extent of granular swelling can be quantied as swelling
power (SP) and the solubilization of starch components as solu-
bility (S) (%) during heating, based on the method developed by
Leach, McCowen, and Schoch (1959). Great diversity in both SP
and S of starch granules at a wide range of temperature (3095 C)
has been observed (Table 4). For example, great genetic variation
in SP (0.815.5) and S (0.216.6%) at 75 C was observed among
4050 genotypes from a world collection (Snchez et al., 2009).
The effect of some genetic modications on the swelling and sol-
ubilization properties has been explored. Both articially (through
GBSS1 suppression) and naturally (natural mutant) made waxy
genotypes had increased swelling power and reduced water sol-
ubility (Ceballos et al., 2007; Zhao et al., 2011). A mutant (induced
by -irradiation technique) with high amylose content (30%) and
much smaller granules had much lower swelling power and solu-
bility compared with commercial ones (Ceballos et al., 2008). The
inuence of some environmental factors and processing parame-
ters on the swelling and solubilization properties has been studied.
The inuence of the crop physiological maturity on the swelling
properties was variety-dependent (Moorthy & Ramanujam, 1986).
Indeed, another study showed that crop harvesting month (up to 16
months) inuenced the swelling power in a genotype-dependent
manner (Sriroth et al., 1999). Water stresses on the crop at both
initial and later stage decreased the SP of starch (Santisopasri et al.,
2001). The form of the root from which the starch was extracted
inuenced the swelling properties. Starch isolated from fresh roots
had lower SP than that from dried roots (Abera & Rakshit, 2003).
The protein content in the granules can be inuential
to the swelling properties. The granule-associated proteins
played an important role in the granular swelling process as
revealed by microscopic evidence (Hongsprabhas, Israkarn,
& Rattanawattanaprakit, 2007; Israkarn, Hongsprabhas, &
Hongsprabhas, 2007). Heat treatment in excess water induced
the redistribution of the granule-associated proteins and the
formation of protein envelope encasing the starch content within
the deformed granules (Hongsprabhas et al., 2007). The protein
envelop, which could retain the granular content during swelling,
thus had a great inuence on the pasting and thermal properties
of starch (Israkarn et al., 2007) described below. The minor com-
ponents (e.g., protein) in the granules can be affected by factors
such as extraction method and cassava genotypes as discussed in
the Composition session.
5.4. Gelatinization analyzed by differential scanning calorimetry
(DSC) and Koer hot stage microscopy (KHSM)
One most commonly used method for quantifying starch gela-
tinization is the differential scanning calorimetry (DSC) (Table 5).
The parameters of gelatinization usually include onset (To ), peak
(Tp ), and conclusion (Tc ) temperatures, and enthalpy change (H).
Quantication of gelatinization temperatures (To , Tp , and Tc ) was
also made by Koer hot stage microscopy (KHSM). It should be
noted that KHSM and DSC differ greatly in their experimental
conditions and may give different results for the same sam-
ple (Francisco et al., 1996). It should also be kept in mind that
water content and heating rate of DSC can have great inuence
on the gelatinization parameters as illustrated in Fig. 6. Insuf-
cient amount of water led to peak multiplicity, peak broadening,
and increased gelatinization temperatures (Fig. 6a) (Garcia et al.,
1996; Francisco et al., 1996). At intermediate water content (45%),
increased heating rate of DSC (from 0.2 to 10 C/min) led to disap-
pearance of the rst transitional peak (Fig. 6b). Increased scanning
rate (from 2.5 to 5 C/min) also led to increased Tp and decreased
H (Freitas, Paula, Feitosa, Rocha, & Sierakowski, 2004).
 F. Zhu / Carbohydrate Polymers 122 (2015) 456480 465

Table 4
Swelling and solubilization properties of granular starch.

No. Parameter Temperature ( C) Reference

50 60 70 80 90
4a SP 17.022.6 27.732 34.843.6 Asaoka et al.
S 7.511.3 14.417.8 18.419.9 (1992)
1 SP 2.88 (30) Gorinstein
S 1.16 (30) and Lii (1992)

1 4b SP 16.719.5 24.627.1 41.146.8 Asaoka et al. (1993)

S 10.211 15.617 20.722.8

1 SP 28.7 (85) Numfor, Walter, and

S 29.7 (85) Schwartz (1996)
4 5c SP 4577 (95) Sriroth et al. (1999)
6 2 4d SP 33.373.0 (85) Santisopasri et al. (2001)
3 3 + 1e SP 18.626 (85) Abera and Rakshit (2003)

5 SP 11.819.9 27.242.3 Charles et al. (2005)

S 4.411.8 10.620.2

40 SP 9.016.9 (85) Onitilo et al. (2007a)

S 1.032.1 (85)

3 SP 30.855.7 (75) Ceballos et al. (2007)

S 614.1 (75)

4 SP 9.2527.92 (75)f Ceballos et al. (2008)

S 8.3436.84 (75)f
4050 SP 0.815.5 (75) Snchez et al. (2009)
S 0.216.6 (75)
8 SP 1632 (64) 3244 (72) 3656 Anggraini et al. (2009)

7 SP 2048.2 (75) 35.254.7 Zhao et al. (2011)

S 4.111.7 (75) 824.1

No., number of genotypes/samples; a, 2 different harvesting months; b, 2 different harvesting months with and without pruning; c, 5 different harvesting months; d, 4
harvesting months with or without water stress; e, 3 different extraction methods plus 1 commercial starch sample; f, starch was cooked by a Rapid Visco-Analyzer (RVA)
based method; SP, swelling power (g/g); S, solubility (%); the gure in the parenthesis denotes the actual temperature used in the specic study.

Great diversity in gelatinization properties has been observed.
For example, analysis of 12 genotypes grown in Thailand showed
the ranges of To , Tp , Tc , and H were 61.171.3 C, 66.874.9 C,
78.485 C, and 15.116.4 J/g, respectively (Charoenkul, Uttapap,
Pathipanawat, & Takeda, 2011). Waxy genotypes as a result of
both natural and articial genetic mutations had higher gelatiniza-
tion temperatures (Ceballos et al., 2007; Raemakers et al., 2005).
Articial genetic modication by suppressing and down-regulating
GBSS1 expression led to decreased H (Zhao et al., 2011). Cor-
relation studies of 5 non-waxy genotypes showed that amylose
content was positively related to the H, and negatively related
to Tp (Charles et al., 2005). Structure-property correlation analy-
sis showed that weight percentage of amylopectin unit chains of
DP 612 was negatively related to Tp and H, and proportion of
longer chains (DP > 35) was positively related to H (Charles et al.,
2005). The shorter chains may cause structural defects in the crys-
tals, decreasing the Tp and H (Genkina, Wikman, Bertoft, & Yuryev,
2007).
Various non-genetic factors (environmental conditions, agro-
nomic practice, and processing parameters) have been focused
to evaluate their inuence on the starch gelatinization. Starch
extracted from fresh roots had lower gelatinization temperatures
than that from dried roots (Abera & Rakshit, 2003). Crop harvest-
ing month had a great inuence on the DSC parameters (Asaoka,
Blanshard, & Rickard, 1992). Pruning aerial growth had little effect
(Asaoka et al., 1993). Both initial and later water stress on the
crop increased the Tp (Santisopasri et al., 2001). Planting some
cassava varieties in the dry season led to peak multiplicity of
which the major peaks shown in Table 5 and the second peak
temperature ranged from 71.4 to 76.1 C (Deoor et al., 1998).
Increased irrigation led to easier gelatinization due to a looser
packing of the amylose and amylopectin chains in the granules as
revealed by proton NMR relaxation analysis (Chatakanonda et al.,
2003).
5.5. Rheological properties
5.5.1. Pasting
Pasting properties is one of the most reported starch charac-
teristics (Table 6). The most used instruments have been rapid
visco-analyzer (RVA) and Brabender visco-amylograph (BVA) with
the former becoming dominant nowadays. The starch granules in
the presence of water are subjected to a programmed heating and
cooling cycle with a constant shearing force, while the viscosity
development is noted. The pasting behavior was found sensitive to
the starch solid content in the system (Caesar & Moore, 1935), and
thus should be noted when comparing data from different studies.
Different heating and cooling programs used in different studies
may also inuence the pasting data. Great genetic diversity in past-
ing properties has been recorded. A studying employing about 4050
genotypes from a world collection grown in Colombia revealed
the ranges for peak viscosity (PV), breakdown (BD), setback (SB),
and pasting temperature (PT) were 1461505 cP, 28.1859 cP,
702273 cP, and 58.871.2 C, respectively (Snchez et al., 2009).
Another study on 40 genotypes grown in Nigeria showed the
ranges for PV, BD, SB, and PT were 261593 RVU, 141.2329.0 RVU,
1979.9 RVU, and 63.865.7 C, respectively (Onitilo, Sanni, Daniel,
Maziya-Dixon, & Dixon, 2007a). Quantitative trait loci (QTL) map-
ping has been conducted on the pasting properties of starch. The
identied loci could be used to improve starch quality during cas-
sava breeding (Thanyasiriwat et al., 2014).
Composition/structure-pasting property relations have been
studied. For normal non-waxy genotypes (5 genotypes), amylose
content was positively related to PV, BD, SB, and PT of pasting
(Charles et al., 2005). Amylopectin structure-property correlation
analysis showed that proportion of longer chains (DP > 35) was pos-
itively related to PV, BD and SB (Charles et al., 2005). It would be
interesting to test if these correlation patterns may still hold when
some waxy genotypes would be included.
466 F. Zhu / Carbohydrate Polymers 122 (2015) 456480

Table 5
Gelatinization measured by differential scanning calorimetry (DSC) and Koer hot-stage microscopy (KHSM).

No Methods Starch:water Heating rate To ( C) Tp ( C) Tc ( C) H Reference

ratio (w/w) ( C/min)

4a DSC 1:2.5 5 50.757.7 54.761.3 59.867.2 1.72.2 (cal/g) Asaoka et al. (1992)
1 KHSM 57 62 65 Gorinstein and Lii (1992)
1 DSC 10 52.3 63.1 74.1 3.3 (cal/g) Gorinstein and Lii (1992)
3 2b DSC 1:2.5 5 53.355.8 58.259.5 64.266.2 1.72.0 (cal/g) Asaoka et al. (1993)
1 DSC 1:3 10 65.6 70.8 75.2 15.6 Francisco et al. (1996)
1 KHSM 57.2 74.6 Francisco et al. (1996)
1 DSC 1:9 10 66.0 Aguilera and Rojas (1996)
1 DSC 1:4 67.7 12.8 Numfor et al. (1996)
1 DSC Garcia et al. (1996)
5 DSC 1:3 10 65.469.4 69.273.2 74.978.5 2.73.4 Moorthy et al. (1996)
1 DSC 1:2 10 62.4 69.3 84.1 4.8 J/g Prez et al. (1998)
4 2 5c DSC 1:2 2 53.962.1 62.968.7 g 76.383.2 Deoor et al. (1998)
4 4d DSC 1:2 10 6971 Sriroth et al. (1999)
6 2 4e DSC 1:2 10 58.367.8 Santisopasri et al. (2001)
3 3 + 1f DSC 1:3 10 63.969.1 68.975.5 80.385.6 14.216.2 Abera and Rakshit (2003)
1 DSC 1:2 2.5, 3, 4, 5 50.552.0 60.563.5 69.571.0 6.58.5 Freitas et al. (2004)
4 DSC 1:3 1.2 59.764.4 64.469.9 71.675.7 12.813.7 Charles et al. (2004)
1 DSC 1:5 3 61.5 69.0 15.0 Tetchi et al. (2007)
3 DSC 1:5 10 60.463.1 Ceballos et al. (2007)
1 DSC 1:9 0.1 60.1 66.2 72.7 14.4 Nwokocha et al. (2009)
17 DSC 4:1 10 63.566.1 6869.5 h 11.114.3 h Anggraini et al. (2009)
12 DSC 1:2 5 61.171.3 66.874.9 78.485.5 15.116.4 Charoenkul et al. (2011)
8 DSC 1:4 3 50.361.2 56.268.6 66.675.7 8.916.9 Rolland-Sabate et al. (2012)
8 DSC 1:4 10 54.061.2 63.369.4 72.778.3 12.916.9 Rolland-Sabate et al. (2013)

No., number of genotypes/samples; DSC, differential scanning calorimetry; KHSM, Koer hot-stage microscopy; To , Tp , Tc , and H denote onset, peak, and conclusion
temperatures, and enthalpy change of gelatinization, respectively; a, 34 different harvesting months; b, with/without pruning aerial growth; c, different harvesting months
and two different planting seasons; d, 4 different harvesting months; e, 4 harvesting months with or without water stress; f, 3 different extraction methods plus 1 commercial
starch sample; g, some genotypes had double peaks and the major one is recorded here; h, Tp and H were from analysis of 7 genotypes.

Table 6
Pasting properties.

No. Method Starch (%) PV BD SB PT ( C) Reference

4a BA 5 635820 58.062.3 Asaoka et al. (1992)

RVA 5 487629 344479 124145 Asaoka et al. (1992)
1b BV 7 690730 220240 70100 71 Padmanabhan and Lonsane (1992)
1 BVA 5 287 Gorinstein and Lii (1992)
1 3c BVA 5 660714 420475 160205 60.762 Asaoka et al. (1993)
1 4d RVA 5 493571 354420 I37150 Asaoka et al. (1993)
1 BVA 4.1 50 10 10 68 Prez et al. (1998)
1 RVA 7.4 73
4 5e RVA 304531 150369 23125 69.573.2 Sriroth et al. (1999)
6 2 4f RVA 317455 64.972.9 Santisopasri et al. (2001)
11 RVA 10.7 414515 53.6111.4 73.675.3 Niba et al. (2002)
3 3 + 1g RVA 9.1 289375 156234 6091 7076 Abera and Rakshit (2003)
1 8h RVA 521615 7677 Olomo and Ajibola (2003)
2 2 11i RVA 9.1 222331 112196 5191 68.874.2 Abera and Rakshit (2004)
5 RVA 88.9142.6 55.8118.0 8.815.6 71.374.6 Charles et al. (2004, 2005)
40 RVA 10.7 261593 141.2329.0 1979.9 63.865.7 Onitilo et al. (2007a)
1 RVA 10 3417 cP 72 Tetchi et al. (2007)
3 RVA 5 577890 249491 161400 65.468.3 Ceballos et al. (2007)
4 RVA 5 221080 cP 60.1764.23 Ceballos et al. (2008)
4050 RVA 5 1461505 cP 28.1859 cP 702273 cP 58.871.2 Snchez et al. (2009)
39 2j RVA 16.7 232485 129.4285.9 1798.4 3.24.2 Eke et al. (2009)
13 RVA 9.1 56.5107.8 9.849.3 6364.7 Ikegwu, Nwobasi, Odoh, and Oledinma (2009)
7 RVA 5 7011094 cp 223699 cp 3659 cp 65.269.2 Zhao et al. (2011)
12 RVA 8 221249 99112 67.470.4 Charoenkul et al. (2011)
1 RVA 10.7 1769 cP 177 cp 859 cp 66.2 Mishra and Rai (2006)

BA, Brabender amylograph; BV, Brabender viscograph; BVA, Brabender Visco-Amylograph; Brabender instruments have BU as viscosity unit; RVA, Rapid Visco-Analyzer has
RVU as viscosity unit; 1 RVU = 12 centipoise (cP); PV, peak viscosity; BD, breakdown viscosity; SB, setback viscosity; PT ( C), pasting temperature; a, 2 different harvesting
months; b, 2 different extraction methods; c, 2 different harvesting months, one set with and without pruning; d, 2 different harvesting months with and without pruning;
e, 5 different harvesting months; f, 4 harvesting months with or without water stress; g, 3 different extraction methods plus 1 commercial starch sample; h, starch was
extracted from chips and our both sun-dried and oven dried; I, fresh root, two storage temperatures with different months; j, two planting seasons.

The impact of genetic modications on the pasting properties
has been reported. A high amylose starch from the mutant (30%)
induced by -irradiation had much lower PV compared with
normal genotypes (Ceballos et al., 2008). On the other end, waxy
genotypes with little amylose had higher PV, BD, and SB than the
non-waxy ones (Ceballos et al., 2007). Genotypes with reduced/nil
amylose content through down-regulation and suppression of
GBSS1 expression had increased BD and SB (Zhao et al., 2011).
Genotypes with reduced amylose content (down-regulation
of GBSS1) resulted in either increased or decreased PV (Zhao
et al., 2011), suggesting the other factors induced by genetic
modications in regulating the pasting behavior.
The effect of agronomic practice and processing conditions on
pasting behaviors has been studied. Water stress on the crop at both
 F. Zhu / Carbohydrate Polymers 122 (2015) 456480
Fig. 6. Inuence of water content ((a) heating rate 3 C/min and the gures above
the trace on the right denote the water portion) and heating rate ((b) water content
45%) on DSC traces of cassava starch (Garcia et al., 1996) (with permission from
Springer).
initial and later stages decreased PV and increased PT of pasting
(Santisopasri et al., 2001). Harvested month inuenced the pasting
properties greatly (Asaoka et al., 1992). Starch from the crop har-
vested at the 16th month had the highest PV and BD and lowest
PT compared to the ones harvest from 6th to 14th month (Sriroth
467
et al., 1999). Pruning the aerial growth had little effect on pasting
(Asaoka et al., 1993). The forms from which the starch got iso-
lated also inuenced the pasting properties. Starch extracted from
fresh roots had higher PV, BD, and SB, and lower PT than that from
dried roots (Abera & Rakshit, 2003). Storage of dried chips up to
8 month reduced the PV, and the inuence was more profound at
storage temperature of 35 C than 5 C (Abera & Rakshit, 2004). PT
of starches extracted from our and chips were comparable (Olomo
& Ajibola, 2003). Little difference in starch pasting from dry chips
by wet and dry millings was noted (Abera & Rakshit, 2003), allow-
ing the industry to manage the low and glut periods of crop supply.
The extraction methods (conventional vs enzyme integrated) had
a big inuence on the pasting properties with the latter giving a
lower PV (Padmanabhan & Lonsane, 1992).
Microscopic changes of freeze-etched starch during heating
revealed possible microstructural details of pasting. The water inl-
trated into the granules from the truncated ends with water-starch
reticulum formed in the central regions which further enlarged
through the granules. Swelling happened after the reticulate bands
formed in the peripheral regions of granules. The bands remained
until the granule integrity lost when the viscosity peaked (Allen,
Hood, & Chabot, 1977).
5.5.2. Rheological properties other than pasting
Apart from the pasting analysis of cassava starch, other types of
rheological tests such as ow behaviors and dynamic rheology with
small deformation of starch gel development have been reported
(Aguilera & Rojas, 1996; Charles et al., 2004; Freitas et al., 2004; Rao
& Tattiyakul, 1999).
For the ow behaviors, the viscosity development of starch dis-
persion under a range of shear force is recorded and the data
can be mathematically modeled to gain structural insight of the
starch system. Shear stress tests have been employed to describe
the rheological properties of starch as affected by various factors
including temperature, concentration, pH, and cooking time. The
ow behavior of starch solutions (26%) were well modelled by
the power-law equation (Chen & Ramaswamy, 1999). The shear-
thinning properties of starch dispersion in relation to granular
size were studied (Rao & Tattiyakul, 1999). The heated starch dis-
persion (2.6%) appeared shear-thickening at the early stages, but
turned shear-thinning at higher temperatures and prolonged time
during gelatinization. The power law consistency index was pos-
itively related to the granule size in an exponential manner (Rao
& Tattiyakul, 1999). The ow behaviors of dilute aqueous starch
solutions were analyzed at a solid concentration under the over-
lap value where the starch chains did not entangle with each other
(Che et al., 2008). The behavior of starch suspension appeared New-
tonian with a concentration of 0.2%, and turned shear-thinning
when the solid content was over 0.4%. The ow behaviors of the
starch suspensions were described by the power-law model. The
consistency indices increased and ow behavior indices decreased
when the concentration increased from 0.2% to 1% (Che et al.,
2008).
For the dynamic and small deformation rheological tests, stor-
age modulus (G ) (related to the energy stored and recovered per
cycle) and loss modulus (G ) (related to the energy lost per cycle)
have been regularly recorded to reect the viscoelastic properties of
starch gel. Genetic diversity in dynamic rheological properties was
observed in starches from 4 genotypes (Charles et al., 2004). The
rheological properties were greatly affected by the amylose content
(Freitas et al., 2004). Based on the kinetic study of gelation of cas-
sava starch in the presence of whey protein by oscillatory rheology,
a model consisting of a two-step reaction with a reversible step
was proposed for starch gelation (Aguilera & Rojas, 1996). Native
starch granules (state A) adsorbed water and swelled to a maxi-
mum packing condition (state R) before starting to soften (state
468 F. Zhu / Carbohydrate Polymers 122 (2015) 456480

S). The transition between A and R was irreversible and R and S been evaluated to control the starch syneresis. Freezing and thaw-
reversible (Aguilera & Rojas, 1996). ing history had a great inuence on paste stability. Freezing by the
Amylose content inuenced the rheological properties of the cryogenic quick freezing and thawing at higher temperature gave
starch gel (Freitas et al., 2004). Amylopectin molecular structure- more stable paste with lower syneresis (Varavinit, Anuntavuttikul,
property correlation analysis showed that the proportion of longer & Shobsngob, 2000). A fast freezing rate (2.3 C/min) gave lower
unit chains (DP > 35) was positively related to resistance to shear- gel retrogradation than the slower ones (0.06 or 0.9 C/min). The
ing and frequency independence of rheological properties (Charles forms of root from which the starch was extracted greatly inu-
et al., 2005). The dynamic rheological properties were related to enced the syneresis of starch. Starch extracted from fresh roots had
thermal behaviors measured by DSC (Asaoka et al., 1992). The lower syneresis than that from dried roots (Abera & Rakshit, 2003).
change in onset temperature of gelatinization (To ) by DSC was par- Again, these articial practices thus could be employed to create a
allel to that in the temperature of maximum G from the oscillation range of variations in retrogradation.
rheology, suggesting a common structural basis for DSC and oscil-
lation rheology data.
6. Nutritional properties
The above described rheological properties of starch were
affected by environmental factors and agronomic practice, in a
6.1. In vitro enzyme susceptibility
similar way as pasting. For example, harvesting month greatly
inuenced the rheological properties (Asaoka et al., 1992), whereas
The nutritional quality of starch is a subject of much inves-
pruning aerial growth had little effect (Asaoka et al., 1993). Thus
tigation. The in vitro enzyme susceptibility of cassava starch
these external factors other than the crop genetics could be ef-
to -amylases and/or amyloglucosidase, reecting the in vivo
ciently utilized to control the starch rheology.
digestibility, has been studied (Gorinstein, 1993; Charles et al.,
2005; Asaoka et al., 1991). The kinetics of starch hydrolysis by
5.6. Retrogradation
bacterial -amylase was described using MichaelisMenten model
(Gorinstein, 1993). Starches from 4 genotypes which were indi-
Upon cooling, the gelatinized starch and water undergo molec-
vidually harvested at different seasons showed similar enzyme
ular interactions by hydrogen-bonding. The re-association of
susceptibility to glucoamylase (Asaoka et al., 1991), suggesting the
starch chains results in re-ordering of the system and partial re-
starch quality for fermentation can remain constant without being
crystallization of molecules with the water molecules expelled.
affected by the selected cultivars and growth conditions. Starch
Amylose re-association is largely responsible for the initial hard-
was subjected to -amylase and glucoamylase mixture. The erosion
ening of the gel, whereas the long-term gelling and retrogradation
occurred mostly at the surface and the amorphous regions in the
are mostly determined by amylopectin re-crystallization (Hoover,
granules, resulting in increased crystallinity (Chen, Huang, Tang,
1995). There are diverse methods (e.g., DSC, syneresis, and NMR)
Chen, & Zhang, 2011). Starch was hydrolyzed by -amylase and
to reect various aspects of starch retrogradation. The retrogra-
amyloglucosidase at 60 C or above, resulting in reduced gelatiniza-
dation (stored at 4 C for 7 days) of starch gels (water to starch
tion temperatures (by DSC) and crystallinity percentage of granules
ratio at 3:1) from 3 genotypes extracted with 3 different meth-
(Gorinstein & Lii, 1992). Fungal -amylase hydrolysis of granules
ods plus one commercial sample were studied by DSC (scanning
reduced the thermal degradation temperatures, but increased H
rate 10 C/min). The retrograded starches had To , Tp , Tc , and H
of gelatinization, suggesting the erosion mostly took place in the
ranges of 48.552.1 C, 54.759.7 C, 61.667.6 C, and 1.22.1 J/g,
amorphous region of the granules (Lacerda et al., 2008). The starch
respectively. The degree of retrogradation (%) calculated as the ratio
remnants (resistant starch) of 5 genotypes after pancreatic -
of H of retrograded starch to that of gelatinization ranged from
amylase and amyloglucosidase hydrolysis ranged from 6.8 to 14%
7.8 to 13.9% (Abera & Rakshit, 2003). Dry-milled starch had lower
(Charles et al., 2005), reecting not only the difference in the in vivo
retrogradation than wet-milled one possibly due to the mechani-
digestibility, but also the structural difference in the granules. Com-
cal damage and degradation of starch chains during the dry-milling
parative study showed that cassava starch was less susceptible to
process (Abera & Rakshit, 2003). These suggested that a range of
-amylase of Bacillus subtilis and amyloglucosidase of Aspergillus
variation in retrogradation properties could be achieved by com-
niger hydrolysis compared with corn starch (Franco & Ciacco, 1987).
bined uses of natural and articial means. Avrami equation was
Microscopic observation showed that enzymatic corrosion of cas-
used to model the retrogradation kinetics of starch gel. The pro-
sava granules mainly occurred on the surface, whereas corn starch
cess of starch re-crystallization was suggested to be instantaneous
had considerable surface corrosion and deep radial corrosion chan-
nucleation followed by rod-like growth of crystals (Kim, Ciacco,
nels (Franco, Preto, Ciacco, & Tavares, 1988). Starch hydrolysates
& DAppolonia, 1976). It would be interesting to microscopically
from bacterial -amylase treatment were rheologically charac-
visualize these suggestions.
terized (Sangeeta & Rai, 2008). Hydrolysates had pseudo-plastic
Another commonly used parameter reecting starch retrogra-
behavior with reduced viscosity and rmness, brittleness, chewi-
dation is the syneresis of pasted gel. During retrogradation, the
ness, and gumminess of gels.
formation of crystals leads to the expelling of water from the gel.
The data of -amylolysis from different studies are difcult to
Low syneresis during storage or freeze-thaw cycle is required for
compare directly due to the difference in the enzyme source and
the stability and shelf-life of some frozen foods. Cassava starch
activity unit denition and experimental conditions.
paste was instable and had poor gelling properties compared with
maize and wheat (Dickinson, McKay, & Thomas, 1982). Another
comparative study showed that waxy cassava starch gel had no 6.2. In vivo digestibility
syneresis after 5 weeks of storage at 20 C and thus possessed
superior potential for formulating frozen or refrigerated foods The in vivo digestion of raw cassava starch has been compared
than the normal and waxy starches from maize, rice, and potato with other types of starch by human trial. The cassava starch had
(Snchez, Dufour, Moreno, & Ceballos, 2010). Indeed, the amylose similar digestibility as taro, true arrowroot, rice, but higher than
free starch had enhanced gel stability (Raemakers et al., 2005). The canna, potato, arrowroot starches (Langworthy & Deuel, 1922).
low syneresis of waxy starch may be attributed not only to the In rat feeding trials, raw starch digestibility was 99%, and was
nil amylose content but also to the amylopectin structure, and the unaffected by variety, cyanide content, drying process, grind-
latter factor is still to be studied in detail. External factors have ing neness, dietary inclusion level (up to 50%), and animal age
 F. Zhu / Carbohydrate Polymers 122 (2015) 456480
(Brough, Neale, Norton, & Wenham, 1995). It would be useful to
establish a correlation between the in vitro enzyme susceptibility
and in vivo digestibility.
6.3. Health benets of native and modied starch
Cassava starch in native or modied forms has nutritional
benets such as cholesterol lowering, hypoglycemic and antidia-
betic effects (Hirao, Igarashi, Fukuda, & Endo, 2000; Kato, Tachibe,
Sugano, Kishida, & Ebihara, 2009; Tachibe, Kato, Sugano, Kishida, &
Ebihara, 2009).
Comparative study using sago and cassava starches (raw and
gelatinized forms) showed that the former (sago) had better
cholesterol lowering effect in rats and may be attributed to the
higher amylose content (Hirao et al., 2000). Thus developing
high-amylose starch may be useful for the in vivo cholesterol
lowering. Retrograded cassava starch (type III resistant starch)
was able to prevent ovarian hormone deciency-induced hyper-
cholesterolemia in female rats (Liu, Sawauchi, Ogawa, Kishida,
& Ebihara, 2006). This effect appeared to be mediated by the
increased intestinal pool of bile acid and its accelerated fecal excre-
tion (Liu et al., 2006). Native and retrograded starches as resistant
starch were benecial for the enhancement of Bidobacterium
populations in the intestine as revealed by an in vitro anaerobic
fermentation study (Wronkowska, Soral-Smietana, & Biedrzycka,
2008).
Various nutritional properties of chemically modied starch
have been tested. Hydroxypropylated starch in the granular form
had increased enzyme susceptibility (-amylase) compared with
control, and the gelatinized starch had the opposite trend. Pancre-
atic -amylase hydrolysis products from hydroxypropylated starch
had fewer amounts of small oligosaccharides (glucose and malt-
ose) than that of native starch as revealed by chromatographic
analysis (Conway & Hood, 1974; Conway & Hood, 1976). Hydrox-
ypropylated and phosphorylated starches drastically inuenced
the microora and pH of the cecum of rats (Bruns & Hood, 1973).
Hypoglycemic and antidiabetic effect of hydroxypropylated starch
with degree of substitution (DS) of 0.0580.180 was studied in rats
and KKAy mice as type 2 diabetes animal model (Kato et al., 2009).
Hydroxypropylated starch with a high DS had higher resistance
to -amylolysis, improving the insulin resistance in KKAy mice
and decreasing the energy intake. The hypoglycemic and antidi-
abetic effects of hydroxypropylated starch were further proved in
male KKAy mice fed with a puried high-fat diet (20% fat) (Tachibe
et al., 2009, 2010). Inuence of hydroxypropylated distarch phos-
phate on fat oxidation and endurance in C57BL/6 J mice were
studied (Haramizu, Shimotoyodome, Fukuoka, Murase, & Hase,
2012). Acute oral administration of this modied starch led to
higher fat oxidation and reduced consumption of liver glycogen
during exercise while increasing the running endurance of mice
(Haramizu et al., 2012). Cross-linked starch phosphate was con-
sumed by human and the glycemic and breath hydrogen responses
were followed. This modied starch was much harder to digest and
ferment than the native one (Tachibe, Ohga, Nishibata, & Ebihara,
2011). Modied starch inuenced the in vivo absorption of min-
erals. Hydroxypropyl-distarch phosphate reduced the absorption
of zinc and iron without affecting that of calcium and magne-
sium in rats, and the effect was dependent on the degree of
substitution (Kishida, Nakai, & Ebihara, 2001). Gelatinized hydrox-
ypropylated starch decreased the iron-retention capacity of rats
with iron deciency (Hood, Vancampen, House, & Szatkowski,
1976).
Though chemically modied starch give consumer an unhealthy
image, these results showed that they may be actually benecial in
a specic way if handled correctly.
469
7. Starch modications
Native starch has limited variations in structure and properties
and is usually modied to diversify the structure and functional-
ity to suit diverse applications. Chemical, physical, and enzymatic
modications or their dual/triple combinations on cassava starch
have been conducted (Table 7). The nature of modications and
their inuence on starch functional properties and structure have
been summarized below. The combined modications to produce
sour starch and resistant starch are discussed individually due to
the focus they have much gained and the bulky literatures available.
7.1. Chemical modications
There are diverse types of chemical modications. Most of the
chemical modications (Table 7) have been well-understood and
applied in food and non-food industry as documented previously
in detail (Wurzburg, 1986). The research on cassava starch chemi-
cal modications from last three decades continues to verify these
observations while creating wider variations in properties and
structures.
7.1.1. Cross-linking (CL)
Cross-linked starch is usually prepared by reacting starch
granules with adipic and acetic mixed anhydrides, phosphorus
oxychloride, sodium trimetaphosphate, and epichlorohydrin in an
alkaline solution (Jyothi, Moorthy, & Rajasekharan, 2006). With
increased degree of CL, the PV of pasting and enzyme susceptibility
to -amylase and glucoamylase of the starch reduced (Jyothi et al.,
2006; Yussof, Utra, & Alias, 2013). CL reduced the swelling volume,
solubility and light transmittance of starch pastes. The H of gela-
tinization by DSC increased as the degree of CL increased (Jyothi
et al., 2006). The CL reduced the glass transition temperature of
starch by 36 C (Tran, Piyachomkwan, & Sriroth, 2007).
Cross-linked starch was produced using a single-screw extruder
as reactor and sodium trimetaphosphate as the reagent (Nabeshima
& Grossmann, 2001). The cross-linking through phosphate groups
with maximum degree of substitution up to 1.5 104 increased
gel strength, water absorption, resistance to high temperature and
shear, and decreased gel cohesiveness, clarity, and water solubility
(Nabeshima & Grossmann, 2001). The use of osmotic pressure by
addition of sodium sulfate and sodium chloride increased the CL
efciency (Varavinit, Paisanjit, Tulkornane, & Pukkahuta, 2007).
7.1.2. Alkaline
Cassava starch was treated with NaOH solution (Raja, 1992). The
alkaline modied starch had lower amylose content, higher alkali
number, and increased enzyme susceptibility to -amylase (Bacil-
lus sp.). It was suggested that this type of modication could be
used to prepare maltodextrins of dextrose equivalent (DE) 2023
(Raja, 1992).
7.1.3. Acid modication in aqueous solution
Hydrolysis of starch by diverse acids (HCl, H2 SO4 , acetic, or
lactic acids) at various concentrations has been conducted to
obtain acid-thinned starch, and the physicochemical, structural,
and morphological changes have been documented. Lintnerization
(a form of acid hydrolysis) of starch usually found two hydrolysis
stages with the rst one being attributed to the hydrolysis of
the amorphous part of the granules and the second one with
lower hydrolysis rate to a high resistance of the crystalline region
(Franco, Cabral, & Tavares, 2002). Acid treatment led to the
loss in pasting viscosities, decreased swelling power, increased
solubility and alkali number, increased H and broadened temper-
ature of gelatinization, and decreased tendency of retrogradation
(Sanguanpong et al., 2003; Beninca, Colman, Lacerda, Carvalho,
470 F. Zhu / Carbohydrate Polymers 122 (2015) 456480

Table 7
Starch modications.

Modication type Reference

CHEMICAL
Cross-linking Nabeshima and Grossmann (2001), Jyothi et al. (2006), Marques, Perego, Le Meins, Borsali, and Soldi (2006), Tran et al.
(2007), Srivasta and Patel (1973), Chabot et al. (1976) and Varavinit et al. (2007)
Acid hydrolysis Osunsami et al. (1989), Raja (1994), Plata-Oviedo and Camargo (1998), Bertolini et al. (1999), Franco et al. (2002),
Sanguanpong et al. (2003), Akubor (2007), Rolland-Sabate et al. (2012), Beninca, Colman, Lacerda, Carvalho, Bannach
et al. (2013) and Atichokudomchai et al. (2000)
Acid hydrolysis in alcohol Ferrini et al. (2008), Cavallini and Franco (2010)
Lactic acid Vatanasuchart et al. (2005), Franco et al. (2010)
Cationization Han and Sosulski (1998)
Alkaline Raja (1992)
Oxidization Tran et al. (2007), Sangseethong et al. (2009, 2010), Amorim et al. (2011), Klein et al. (2014), Dias, Zavareze, Elias et al.
(2011), Dias, Zavareze, Helbig et al. (2011) and Beninca, Colman, Lacerda, Carvalho, Demiate et al. (2013)
Acetylation Moorthy (1985), Osunsami et al. (1989), Agboola et al. (1991a,b), Aiyeleye et al. (1993), Tran et al. (2007), Osundahunsi
and Mueller (2011), Mbougueng, Tenin, Scher, & Tchiegang (2012), Babic et al. (2007) and Chabot et al. (1976)
Hydroxypropylation Schmitz et al. (2006), Jyothi, Moorthy, and Rajasekharan 2007), Takahashi, Maningat, and Seib (1989) and Chabot et al.
(1976)
Citrate Agboola et al. (1991a,b), Jyothi, Moorthy, Sreekumar et al., 2007
Carboxymethylation Qiu and He (1999), Yao, Chen, Manurung, Ganzeveld, and Heeres (2004) and Sangseethonga et al. (2005)
Succinate Jyothi et al. (2005a,b), Cova et al. (2010)
Methylation Hou et al. (2011, 2012)
AKLa Barrios et al. (2013)
ACE-CL Tran et al. (2007)
CBM-AKL Cova et al. (2010)
OX-CL Zhu et al. (2013)
OX-CL-PHOS Zhu et al. (2013)

PHYSICAL
Electricity Han et al. (2012) and Martnez-Bustos et al. (2005)
High-pressure Che, Li, Wang, Ozkan, et al. (2007), Kasemwong et al. (2011), Vittadini et al. (2008) and Francisco and Sivik (2002)
Extrusion Prez-Sira and Gonzlez-Parada (1997), Nabeshima and Grossmann (2001) and Leonel et al. (2009)
UV-Irradiation Bertolini et al. (1999), Bertolini, Mestres, Raf et al. (2001); Bertolini, Mestres, Colonna et al. (2001) and Vatanasuchart
et al. (2005)
-Irradiation Bertolini, Mestres, Colonna et al. (2001) and Elsaadany et al. (1976)
Ball milling Sanguanpong et al. (2003), Che, Li, Wang, Chen et al. (2007), Martnez-Bustos et al. (2007a), Huang et al. (2007), Ren
et al. (2010), Moraes et al. (2013) and Zhang et al. (2013)
Ultrasound Manchun et al. (2012)
Microwave Lan et al. (2012), Lewandowicz et al. (1997), Lu and Yang (2006) and Colman et al. (2014)
Heat-moisture Abraham (1993), Garcia, Colonna, Bouchet, and Gallant (1997), Klein et al. (2013) and Andrade et al. (2014)
Drum drying Prez-Sira and Gonzlez-Parada (1997)
Annealing Gomes et al. (2004, 2005), Osundahunsi and Mueller (2011) and Shariffa et al. (2009)
Thermal degradation Jankovic (2013) and Jankovic (2014)
Blending with other starch Karam et al. (2005, 2006) and Zaidul et al. (2007, 2008)

ENZYMATIC
Fermentation Nakamura and Park (1975), Camargo et al. (1988), Petruccelli et al. (1993), Numfor et al. (1995), Figueroa et al. (1995),
George et al. (1995), Parada et al. (1996), Mestres and Rouau (1997), Gomes et al. (2005), Marcon et al. (2006), Onitilo
et al. (2007b), Dias et al. (2007), Marcon et al. (2007), Adegunwa, Sanni, and Maziya-Dixon (2011), Aquino, Pereira,
Watanabe, and Amante, (2013) and Alvarado et al. (2013)
-Amylase and amyloglucosidase Gorinstein and Lii (1992), Chen et al. (2011), Lacerda et al. (2008), Sangeeta and Rai (2008) and Khatoon et al. (2009)
Lipase Rajan and Abraham (2006) and Rajan et al. (2008)
Pullulanase Hung et al. (2012)
Branching enzyme and maltogenic amylase Le et al. (2009)
a
Alkylation with long alkyl side chains; ACE, acetylation; CBM, carboxymethylation; AKL, Alkylation; OX, oxidation; CL, cross-linking; PHOS, phosphorylation; ACE-CL,
CBMAKL, OX-CL, and OX-CL-PHOS denote the combined modications.

Bannach et al., 2013; Osunsami et al., 1989; Atichokudomchai,
Shobsngob, Chinachoti, & Varavinit, 2001; Atichokudomchai,
Varavinit, & Chinachoti, 2002a).
The surface morphological changes of granules eroded by acid
solution (HCl, 6%) were followed by scanning electron microscopy
(SEM). The erosion took place mostly on the surface without the
formation of the pores (Atichokudomchai, Shobsngob, & Varavinit,
2000). The surface morphology of acid (HCl) modied starch
was mapped by chemical force microscopy (Wuttisela, Triampo,
& Triampo, 2009). The carbon backbone of glucose units had a
plate-like structure. With the increased acid concentration, the
percentages of amylopectin and phosphate containing domains
increased at the surface. The phosphate containing domains were
packed in blocklets (Wuttisela et al., 2009). The surface roughness
of granules was reduced by acid hydrolysis under certain experi-
mental conditions as revealed by atomic force microscopy (AFM)
(Beninca, Colman, Lacerda, Carvalho, Bannach et al., 2013).
Acid treatments (HCl or acetic acid) at low concentration
changed polymorph of starch from C- to A-type (Plata-Oviedo
& Camargo, 1998) and increased the crystallinity percentage
(Beninca, Colman, Lacerda, Carvalho, Bannach et al., 2013).
Another study showed that acid hydrolysis (HCl) either increased
the A- or B-type crystallinity, depending on the specic genotypes
with different structural properties (Rolland-Sabate et al., 2012,
2013). These physical changes were further probed by 13 C cross
polarization magic angle spinning solid-state nuclear magnetic
resonance (13 C CP/MAS solid-state NMR) spectroscopy and com-
pared with the results by wide-angle X-ray diffraction analysis
(Atichokudomchai, Varavinit, & Chinachoti, 2004). Relative crys-
tallinity (%) measured by X-ray diffraction and 13 C CP/MAS NMR
methods increased initially before levelled off in the course of acid
hydrolysis. The initial increase in relative double helix content
and crystallinity was attributed to the destruction of amorphous
region, retrogradation of the partially hydrolyzed amylose, and
 F. Zhu / Carbohydrate Polymers 122 (2015) 456480
re-arrangement of amylopectin double helices leading to crystal-
lization (Atichokudomchai et al., 2004). On the molecular level, the
amylose content (measured by iodine afnity) decreased during
hydrolysis (Atichokudomchai et al., 2000), suggesting most of the
amylose chains were in the amorphous areas of starch granules
(Franco et al., 2002). The resulting product after Lintnerization had
major peaks at DP of 1314 with minor peaks at DP of 2446 after
debranching (Rolland-Sabate et al., 2012, 2013).
7.1.4. Acid modication in methanol/ethanol environment
Starch was hydrolyzed by acids in methanol/ethanol solvent to
obtain novel properties and high yield (Cavallini & Franco, 2010;
Ferrini, Rocha, Demiate, & Franco, 2008). Starch was treated with
HCl (0.36%) in anhydrous methanol, resulting in greatly enhanced
water solubility (up to 100% at 95 C), reduced granule size,
and decreased pasting viscosity. Gel-permeation chromatography
showed that amylose and amylopectin were partially degraded
during the hydrolysis (Ferrini et al., 2008). Using ethanol as the sol-
vent for acid hydrolysis also resulted in increased water solubility
with a high starch yield of 9899% (Cavallini & Franco, 2010).
7.1.5. Cationization
Cationized starch was produced by reacting starch with
3-chloro-2-hydroxypropyltrimethyl ammonium chloride in an
aqueous alcoholic-alkaline solvent (Han & Sosulski, 1998). Degree
of substitution (DS) 0.03 was reached at 5060 C within 2 h of reac-
tion time. Cationization greatly reduced the pasting temperature
and viscosity of starch.
7.1.6. Oxidation
Cassava starch was oxidized by hypochlorite, peroxide, acids,
periodic acid, or ozone to obtain oxidized starch with various
properties (Amorim, Doval, & Cristianini, 2011; Beninca, Colman,
Lacerda, Carvalho, Demiate et al., 2013; Klein et al., 2014; Martnez-
Bustos, Amaya-Llano, Carbajal-Arteaga, Chang, & Zazueta-Morales,
2007b; Sangseethong, Termvejsayanon, & Sriroth, 2010). The type
of oxidation as well as reaction condition determines the outcome
of the oxidized starch.
Starch was oxidized with hypochlorite under pH of 811. The
pH 8 and 9 gave higher contents of carbonyl and carboxyl groups in
the modied starch. Oxidation decreased gelatinization tempera-
tures and H of starch. Analysis of light transmittance in the course
of time suggested that carboxyl groups retarded starch retrograda-
tion (Sangseethong, Lertphanich, & Sriroth, 2009). Another study
showed that starch oxidized by sodium hypochlorite solutions
had increased H and decreased pasting viscosity. The gelatiniza-
tion temperatures and surface roughness was either increased or
decreased depending on the specic concentration of hypochlorite
used (Beninca, Colman, Lacerda, Carvalho, Demiate et al., 2013).
The discrepancy in these two studies (Beninca, Colman, Lacerda,
Carvalho, Demiate et al., 2013; Sangseethong et al., 2009) may
be attributed to the different reaction conditions and experimen-
tal parameters used. The glass transition temperature of oxidized
starch was 36 C lower than control (Tran et al., 2007).
The properties and structure of starch oxidized by peroxide
and hypochlorite were compared. The former favored the carboxyl
group formation while the latter carbonyl group. Peroxide-oxidized
starch had a higher tendency for gelation with a rmer gel. Per-
oxide oxidation increased the gelatinization temperatures while
hypochlorite oxidation had the opposite effect. Both types of oxi-
dation decreased the H of gelatinization and apparent viscosity
while reducing the molecular size of starch (Sangseethong et al.,
2010).
Ozone can introduce carbonyl and carboxyl groups onto starch
(Amorim et al., 2011; Klein et al., 2014). Oxidization of starch by
ozone gas altered the sensory properties of starch and increased
471
the PV of pasting (Amorim et al., 2011). Another study showed that
ozone oxidation of starch in aqueous solution at pH 3.5 reduced
the PV, BD, and SB of pasting without affecting the morphology
(Klein et al., 2014). In that study, it was not clear that if it was
the pH that may have caused these changes. The discrepancy in
the PV of pasting from these two studies (Amorim et al., 2011;
Klein et al., 2014) may be attributed to the different reaction
conditions.
Starch was oxidized by lactic, acetic, and citric acids to intro-
duce the carbonyl and carboxyl groups (Martnez-Bustos et al.,
2007b). Organic acid induced oxidation increased PV of pasting, and
decreased H of gelatinization, crystallinity, and intrinsic viscosity
of starch.
Dialdehyde starch was prepared by oxidizing starch with peri-
odic acid which cleaved the C-2C-3 linkage of the glycosidic
ring (Wongsagon, Shobsngob, & Varavinit, 2005). Compared with
native starch, dialdehyde starch had the same X-ray diffraction
pattern with decreased degree of crystallinity, higher gelatiniza-
tion temperatures, lower H, and higher PT and PV of pasting.
Chromatographic analysis showed that amylose and amylopectin
fractions were partially degraded.
7.1.7. Substitution
7.1.7.1. Acetylation. Acetylated starch was prepared by reac-
ting starch with acetic anhydride in an alkaline solution.
The acetylation increased the water solubility and paste clar-
ity, decreased the pasting viscosities and gelling ability, the
glass transition and gelatinization temperatures, and improved
the freeze-thaw stability (Aiyeleye, Akingbala, & Oguntimein,
1993; Agboola, Akingbala, & Oguntimein, 1991a; Agboola,
Akingbala, & Oguntimein, 1991b; Moorthy, 1985; Osunsami
et al., 1989). Dynamic moduli (G and G ) of starch paste (5%)
were higher or lower than control, depending on the specic
starch genotypes used (Osundahunsi & Mueller, 2011). Gels
(30 and 40% moisture content) of acetylated starch had lower
amounts of freezable water than control (Tran, Thitipraphunkul,
Piyachomkwan, & Sriroth, 2008). Acetylated starches before
and after gelatinization were observed by scanning electron
microscopy (SEM). Chemical modication reduced the amount of
extra-granular materials with an envelope around a cavity lled
with brils (Chabot, Hood, & Allen, 1976).
7.1.7.2. Hydroxypropylation. Hydroxypropylation was usually pre-
pared by treating starch with propylene oxide in an alkaline
solution. Hydroxypropylated starch was also produced from reac-
ting starch with chloropropylene glycol (Schmitz et al., 2006).
Another study tested the inuence of different medium includ-
ing water, water in the presence of tetrabutylammonium bromide,
and 2-propanol on the starch hydroxypropylation (Jyothi, Moorthy,
& Rajasekharan, 2007). The second medium gave better hydrox-
ypropylation efciency at 30 C. Hydroxypropylation increased
swelling power and solubility, light transmittance, freezing-
thawing stability, and water binding capacity, and decreased
the retrogradation, PT and SB of pasting, enzyme susceptibility,
and syneresis of paste (Schmitz et al., 2006; Jyothi, Moorthy, &
Rajasekharan, 2007). Gels (30 and 40% moisture content) of hydrox-
ypropylated starch had lower amounts of freezable water than the
native one (Tran et al., 2008).
7.1.7.3. Citrate. Starch citrate was prepared by treating starch with
citric acid in alkaline solution (Agboola et al., 1991a,b). It was also
synthesized by the microwave-assisted reaction of starch and cit-
ric acid with degree of substitution (DS) of 0.0050.063 (Jyothi,
Moorthy, Sreekumar, & Rajasekharan, 2007). Starch citrate had
lower swelling volume, BD and SB of pasting, and gelatinization
temperatures by DSC, and enhanced water binding capacity and
472 F. Zhu / Carbohydrate Polymers 122 (2015) 456480
freeze-thawing stability, and was less susceptible to -amylase
hydrolysis (Agboola et al., 1991a,b; Jyothi, Moorthy, Sreekumar
et al., 2007).
7.1.7.4. Carboxymethylation. Carboxymethylated starch was made
by treating starch with sodium monochloroacetate (SMCA) as an
etherication agent with reaction medium of mixtures of water
and organic solvents (isopropanol, tert-butanol, and ethanol) (Qiu
& He, 1999; Sangseethonga, Ketsilp, & Sriroth, 2005; Yao, You, Bao,
& Shen, 2005). The reaction parameters and organic solvent type in
relation to the degree of substitution (DS) (up to 1.4) and the reac-
tion efciency of the carboxymethylation have been documented
(Qiu & He, 1999; Sangseethonga et al., 2005; Yao et al., 2005).
Carboxymethylated starch had increased cold water solubility, gel
clarity, freeze-thaw stability, water-holding capacity, susceptibil-
ity to shear-thinning, and reduced gelatinization temperatures,
retrogradation, and had indentation and shrinkage on the granule
surface (Qiu & He, 1999; Sangseethonga et al., 2005). The substi-
tution position preference among anhydroglucose of starch was
C6 > C2 > C3 (Yao et al., 2005).
7.1.7.5. Succinate. Starch succinate was prepared by treating
starch with succinic anhydride in alkaline solution. This pro-
cess was rapidly achieved by microwave-assistance (Jyothi,
Rajasekharan, Moorthy, & Sreekumar, 2005b). Starch succinate (DS
up to 0.022) had increased swelling, viscosity of pasting, and gel
clarity, and decreased enzyme susceptibility to -amylase (Jyothi,
Raiasekharan, Moorthy, & Sreekumar, 2005a; Jyothi et al., 2005b).
Starch octenyl succinate was prepared by treating starch with
octenyl succinic anhydride through microwave radiation assistance
(Cova, Sandoval, Balsamo, & Muller, 2010). Octenyl succinic starch
was more hydrophobic for the whole water activity range of 00.94.
7.1.7.6. Methylation. Methylated starch with DS from 0.033 to
1.087 was prepared using dimethyl carbonate as methyl group
donor, disodium hydrogen phosphate/thiocarbamide as the cata-
lyst, and microwave irradiation as the energy source (Hou, Chen,
Chen, & Li, 2011). With microwave assistance, the methylation was
efciently made in a few minutes, and the whole process was safe,
nontoxic, and environmentally friendly (Hou, Chen, & Li, 2012).
7.1.7.7. Addition of long alkyl side chains. Hydrophobicity of starch
was greatly increased by the esterication of starch with acyl imid-
azoles, acid chlorides, and methyl ester derivatives of fatty acids
with n-alkyl chains with 1222 carbon atoms (Barrios, Giammanco,
Contreras, Laredo, & Lpez-Carrasquero, 2013). The DS ranged from
0.06 to 1.2. Most of the derivatives from acyl imidazoles were sta-
ble up to 300 C. The substituted n-alkyl side chains of 16 or more
carbon atoms was able to crystallize in separate parafnic phases
independent of the starch backbone (Barrios et al., 2013).
7.1.7.8. Carboxymethylation-long alkyl side chains addition. Car-
boxymethylated starch was treated with quaternary ammonium
salts having different alkyl chain lengths (n = 12, 14, 16, and 18)
to form ionic complexes (Cova et al., 2010). The dual modied
starch had more hydrophobicity at low water activity and was more
hydrophilic at high aw from a moisture sorption isotherms analysis.
7.1.7.9. Acetylation-cross-linking. Acetylated starch was cross-
linked to obtain acetylated-cross-linked starch. The properties of
this dually modied starch reected that of individuals. The mod-
ied starch had increased PV and SB and decreased BD of pasting,
and decreased glass transition temperature (Tg ) (up to 6 C) and gel
hardness (Tran et al., 2007). Amylopectin retrogradation was little
affected, suggesting the rather low degree of modication.
7.1.7.10. Oxidation-cross-linking-phosphorylation. Oxidized starch
was cross-linked before phosphorylation to obtain triply modi-
ed starch for warp sizing application. The triply modied starch
had stable viscosity, gave strong adhesion to ber, and formed
tough lm. Modied starch with suitable level of cross-linking (1
cross-linkage for 370590 glucosyl units) and degree of phosphor-
ylation (0.038) was recommended for warp sizing purposes (Zhu,
Xiaochun, & Li, 2013).
7.2. Physical modications
Physical modication of starch is much related to the emerging
concept of green technology for environmentally friendly appli-
cations. It becomes more appealing especially in the context that
registering any new genetic or chemical modied starch for food
applications is very difcult (Hoover, 2010). Diverse physical modi-
cations and their combinations with some chemical modications
have been conducted to create novel properties and structure of
cassava starch.
7.2.1. Electric eld modication
Electric eld was applied in starch modication (Martnez-
Bustos, Lpez-Soto, Zazueta-Morales, & Morales-Snchez, 2005;
Han et al., 2012). Electric current passed through starch with 33%
or 45% moisture to generate heat (termed ohmic heating) to pro-
duce pre-gelatinized starch. This method had minimized solid loss
and was used to obtain modied starch with a range of gelatiniza-
tion degree (Martnez-Bustos et al., 2005). Another study employed
pulsed electric eld to treat starch. The granules and crystallinity of
starch were disrupted, resulting in decreased viscosity during past-
ing and temperatures and H of gelatinization (Han et al., 2012).
7.2.2. High-pressure-based modications
High-pressure-based treatments on starch represent a rela-
tively new physical modication of food to create novel functions
and textures. High hydrostatic pressure processing (600 MPa)
induced the gelatinization and gel formation of starch (Vittadini,
Carini, Chiavaro, Rovere, & Barbanti, 2008). The physicochemi-
cal properties of high pressure induced gel were compared with
that of thermal induced one. The presence of residual granules,
higher ice-melting temperatures of frozen gel, and less retro-
gradation was noted for the former. Another study showed that
pressure up to 600 MPa completely gelatinized the starch (Oh,
Pinder, Hemar, Anema, & Wong, 2008). In supercritical carbon
dioxide medium, starch had lower gelatinization temperatures
at 8 MPa and increased ones at 30 MPa as compared with that
at atmospheric pressure (Francisco & Sivik, 2002). High-pressure
based homogenization was applied in starch suspension at various
pressures up to 100 MPa. High-pressure treatment raised the tem-
perature in the suspension, causing granular swelling and partial
gelatinization, but without affecting the wide-angle X-ray diffrac-
tion pattern (Che, Li, Wang, Ozkan et al., 2007). High-pressure
based micro-uidization was applied in starch suspension. The
micro-uidization resulted in bigger starch granules with partial
gelatinization, and induced a gel-like structure on the granule sur-
face, without affecting the X-ray diffraction pattern. Increasing
pressure (up to 150 MPa) decreased the crystallinity percent-
age and the H of gelatinization (Kasemwong, Ruktanonchai,
Srinuanchai, Itthisoponkul, & Sriroth, 2011).
7.2.3. Extrusion
Extrusion techniques (single- and twin-screw extruders) were
used to prepare pre-gelatinized starch (Leonel, de Freitas, &
Mischan, 2009; Nabeshima & Grossmann, 2001). Extrusion param-
eters such as moisture content, barrel temperature, and screw
speed and number were varied and related to the properties
 F. Zhu / Carbohydrate Polymers 122 (2015) 456480
of the resulted extruded starch (Leonel et al., 2009; Nabeshima
& Grossmann, 2001; Prez-Sira & Gonzlez-Parada, 1997). Pre-
gelatinized starch with various degrees of gelatinization and
degradation was obtainable through extrusion.
7.2.4. Pre-gelatinization by drum drying
Pre-gelatinization of starch was achieved by drum drying
(Prez-Sira & Gonzlez-Parada, 1997). Drum-dried starch had
much increased water absorption, swelling and solubilization, and
decreased apparent viscosity.
7.2.5. UV-irradiation
UV-irradiation depolymerized starch, and may be due to the
existence of uorescent chromophores in the starch and non-
uorescent chromophores in glucosidic units (Bertolini, Mestres,
Raf et al., 2001). UV-irradiation reduced the intrinsic viscosity and
generated free radicals as revealed by electronic spin resonance
(Bertolini, Mestres, Colonna, & Raf, 2001b). Studies on the inu-
ence of UV-irradiation (usually coupled with lactic acid treatment)
on starch properties has been largely related to the sour starch
application and is discussed below.
7.2.6. -Irradiation
-Irradiation decreased the swelling, viscosity and PT of pasting,
while increasing the solubility of starch. -Irradiation generated
free radicals revealed by electronic spin resonance, which may lead
to chain scission (Bertolini, Mestres, Colonna et al., 2001). Indeed,
on the molecular level, degradation of starch chains was induced as
reected by the increased amount of reducing sugars (Elsaadany,
Elsaadany, & Foda, 1976).
7.2.7. Ball milling
Ball milling involves the frictions of the granules against one
another, the ball, and the wall of container, mechanically breaking
down granules into smaller pieces (Martnez-Bustos, Lopez-Soto,
San Martin-Martinez, Zazueta-Morales, & Velez-Medina, 2007a).
The ball milling induced breakdown of the molecules and crys-
talline structure and partial gelatinization of the granules, reduced
granule size, apparent viscosity, the glass transition temperature,
and temperatures and H of gelatinization, increased the water
absorption and cold-water solubility, without creating new chem-
ical groups as revealed by infrared spectroscopy analysis (Che, Li,
Wang, Chen, & Mao, 2007; Huang, Lu, Li, & Tong, 2007; Martnez-
Bustos et al., 2007a; Moraes, lves, & Franco, 2013; Ren, Li, Wang,
Ozkan, & Mao, 2010; Sanguanpong et al., 2003; Zhang et al., 2013).
7.2.7.1. Ball millingAluminate coupling. The ball milled starch was
treated with aluminate coupling agent to increase the hydropho-
bicity of starch. The coupling efciency was facilitated by the ball
milling (Che, Li, Wang, Chen et al., 2007). It was not clear that the
changes in properties by aluminate coupling were caused by the
formation of new chemical linkages or because the remnants of
the reaction agent in starch.
7.2.7.2. Acid-treatmentBall milling. Acid-treated starch was sub-
jected to ball milling without affecting the total double helix
content in the granules under the experimental conditions
(Sanguanpong et al., 2003). The small starch particles produced
were structurally more heterogeneous as reected by wider gela-
tinization range (Sanguanpong et al., 2003).
7.2.7.3. Acid-ethanol treatmentBall milling. Starch treated with
acid in ethanol medium was further subjected to ball milling. The
further ball milling (1 h) modication decreased the crystalline,
473
temperatures and H of gelatinization, and the granule size, with-
out affecting the amylose content and pasting viscosity (Cavallini
& Franco, 2010).
7.2.8. Ultrasound
Ultrasound is waves with a frequency above the threshold of
human hearing (>16 kHz). It produces cavitation in starch-water
system, modifying the starch. Starch granules were subjected
to ultrasonic treatment (24 kHz, 400 W) (Manchun, Nunthanid,
Limmatvapirat, & Sriamornsak, 2012). Ultrasonic treatment at cer-
tain conditions increased the swelling power and solubility, and
disrupted the crystallinity of the granules as revealed by X-ray
diffraction analysis.
7.2.9. Microwave
Microwaving has been used to rapidly create novel starch prop-
erties. The inuence of water content on the microwave processing
of starch was studied (Lewandowicz, Fornal, & Walkowski, 1997;
Lu & Yang, 2006). When water content was over 20%, an isother-
mal phase before the rise of temperature was observed, and
higher moisture contents facilitated the microwaving efciency
(Lewandowicz et al., 1997; Lu & Yang, 2006). Microwaving par-
tially destroyed the crystallinity, reduced the viscosities of pasting,
increased water solubility and gel transparency of starch (Colman,
Demiate, & Schnitzler, 2014; Lan et al., 2012).
7.2.10. Heat-moisture treatment
Heat-moisture treatment (HMT) is usually conducted at a tem-
perature range of 100130 C with a moisture content of less than
35% starch (Hoover, 2010). HMT effect on starch properties are rel-
atively better understood (Hoover, 2010) than many other physical
modications. By selecting suitable processing conditions of HMT,
low swelling power and pasting viscosity, and high thermal stabil-
ity of starch were obtainable (Klein et al., 2013). Heating starch with
about 20% moisture at 110 C for 16 h resulted in excellent freeze-
thaw stability of starch which was suitable for pie lling (Abraham,
1993).
7.2.11. Annealing
Annealing (ANN) is performed at the temperature below the
onset of gelatinization with limited amount of moisture content
(Hoover, Hughes, Chung, & Liu, 2010). Annealing of both fermented
and un-fermented starches decreased swelling power and solubil-
ity, PV, SB, and BD of pasting with an increased PT, and increased
the temperatures and H of gelatinization with narrower tempera-
ture ranges. The polymorph changed from CA - to A-type (Gomes, da
Silva, Ricardo, Sasaki, & Germani, 2004; Gomes, da Silva, & Ricardo,
2005). Heating starch slurry (20%) at sub-gelatinization temper-
ature (60 C) enhanced the enzyme susceptibility to a mixture of
fungal -amylase and glucoamylase (Shariffa, Karim, Fazilah, &
Zaidul, 2009).
7.2.11.1. Acid treatmentAnnealing. Annealing of acid-treated
starch resulted in more perfect crystals, especially when starch
contained more amorphous part (Atichokudomchai, Varavinit, &
Chinachoti, 2002b).
7.2.12. Thermal degradation
The kinetics of the thermal degradation of dried starch was
studied by thermogravimetry (Jankovic, 2013). Three main degra-
dation stages with one additional sub-stage attached to the second
major one were recorded. The rst stage was related to the lib-
eration of water and other small molecules. The second stage
included de-polymerization of amylose and amylopectin. Inten-
sive carbonization reactions happened at the last reaction stage.
The kinetics of the degradation process was modelled (Weibull and
474 F. Zhu / Carbohydrate Polymers 122 (2015) 456480
Weibull-derived models) to derive the shelf-life properties of starch
during thermo-oxidative degradation (Jankovic, 2014).
7.2.13. Blending with other starch
Blending different native starches can give rise to a wide range of
properties, possibly avoiding uses of chemically modied starches.
Undesired properties of gels of individual starches (e.g., excessive
cohesiveness in cassava and exudate in yam and corn) were min-
imized using starch blends (Karam, Grossmann, Silva, Ferrero, &
Zaritzky, 2005; Karam, Ferrero, Martino, Zaritzky, & Grossmann,
2006). DSC and RVA analysis of tuber starches (including cassava)
and wheat our mixtures suggested that tuber starches could par-
tially substitute wheat our in some wheat-based products (Zaidul,
Norulaini, Omar, Yamauchi, & Noda, 2007; Zaidul et al., 2008).
Multiple gelatinization peaks were observed in DSC gelatinization
traces of mixtures (Zaidul et al., 2008).
7.3. Enzymatic modications
Native starch can be subjected to diverse enzyme hydrolysis
to obtain novel properties for diverse applications. The inuence
of amylases including -amylases and amyloglucosidase on starch
digestion and properties are summarized in the Nutritional Prop-
erties session above. In this part, hydrolysis by other enzymes and
amylases related to other applications is summarized.
Starch was modied by bacterial and fungal lipases to impart
fatty acid functional group (lauric acid and palmitic acid) onto the
granules (Rajan & Abraham, 2006; Rajan, Sudha, & Abraham, 2008).
The modied starch had reduced -amylase susceptibility, higher
onset temperature of decomposition and enhanced hydrophobicity
with potential as novel materials for thermoplastics (Rajan et al.,
2008).
Starch was partially hydrolyzed by heat stable -amylase of
Bacillus licheniformis. The granules were broken down into small
particles. The molecular components were degraded into oligosac-
charides with a broad molecular size distribution. Rheological
analysis showed that the solid components in the slurry were
greatly reduced by modication. The spray dried hydrolyzed starch
could be used as fat substitute due to the free owing properties
(Khatoon, Sreerama, Raghavendra, Bhattacharya, & Bhat, 2009).
7.4. Combined modications to increase the resistant starch
content
Resistant starch (RS) is the starch fraction that escapes from
digestion in the small intestine of human and has diverse health
benets (Sajilata, Singhal, & Kulkarni, 2006). Combined modica-
tions have been used to increase the RS content of starch.
Starch was partially hydrolyzed using branching enzyme (from
B. subtilis) and maltogenic amylase (from B. stearothermophilus).
The resulting modied starch had higher branching density and
much lower enzyme susceptibility to -amylase and glucoamylase
as compared with native one (Le et al., 2009).
Enzyme debranched starch was autoclaved and then stored at
18 C to obtain retrograded starch which had RS content of 35%
and a typical B-type crystallinity (Hung, Nguyen, & Tran, 2012).
Starch was subjected to acid-hydrolysisdebranching
annealing/temperature-cycling/heat-moisture and their com-
bined treatments to produce recrystallized particles as resistant
starch (Mutungi, Onyango, Jaros, Henle, & Rohm, 2009a; Mutungi,
Rost, Onyango, Jaros, & Rohm, 2009b; Onyango, Bley, Jacob, Henle,
& Rohm, 2006; Onyango & Mutungi, 2008). The particles had
mono- or bi-modal size distribution (<5 m and >20 m) with
the relative crystallinity of 31.156.1% and in vitro digestibility
rate of 6.862.8% (Mutungi et al., 2010). Starch was also subjected
to debranchingannealing/temperature-cycling/heat-moisture
treatments to enhance the resistant starch content (Mutungi
et al., 2011b). The resulting starch was hydrolyzed by pancreatic
-amylase and amyloglucosidase and the structural changes was
documented by various techniques such as wide-angle X-ray
diffractometry, 13 C CP/MAS NMR spectroscopy, DSC, and Raman
spectroscopy (Mutungi et al., 2011b; Mutungi, Passauer, Onyango,
Jaros, & Rohm, 2012). Upon digestion, average DP of the chains,
percentage of crystallinity, ordered fractions, and melting H of
resulted starch fractions increased. Raman spectroscopy could
be feasibly employed to rapidly measure the starch crystallinity
(Mutungi et al., 2012). The moisture sorption behaviors of these
modied starches were linked to their enzyme susceptibility
(Mutungi et al., 2011a). Adsorbed moisture became internally
absorbed in native starch but not in modied starches suggested
that the enzyme and modied starch could not easily get close to
each other, explaining the resistant nature of the recrystallized
starch.
7.5. Sour starch
Sour starch is a traditional food ingredient made by fermenta-
tion and sun drying of native cassava starch. With good expansion
properties sour starch is widely used in bakery in South America
(Cardenas & Debuckle, 1980). The bread from sour starch without
gluten component could be gluten-free product for people with
celiac disease. A better understanding of the modication process
on the properties of sour starch provides a basis for a large scale pro-
duction with consistent product quality. During fermentation and
sun drying, the granules are modied by enzymes and organic acids
(mostly lactic acid) and the sunlight contributes to the oxidation of
starch (Marcon et al., 2009).
Fermentation (0 or 30 days) and drying (oven or sun) (dual mod-
ications) decreased the pasting PV of sour starch. Amylose content
was negatively related to the dough expansion. Genotype and mod-
ication type contributed together to the expansion and baking
performance of the sour starch (Alvarado et al., 2013; Onitilo,
Sanni, Oyewole, & Maziya-Dixon, 2007b). Low values of intrinsic
viscosity, hot paste viscosities, and hydrodynamic volumes of the
components of sour starch from natural fermentation and dry-
ing were linked to higher baking expansion (Mestres & Rouau,
1997).
Fermentation of starch involves lactic acid bacteria and yeast
(Cardenas & Debuckle, 1980; Figueroa, Davila, & Pourquie, 1995;
George, Moorthy, & Padmaja, 1995). The microora was docu-
mented as species from Streptococcus, Bacillus, Lactobacillus, and
Saccharomyces with lactic acid bacteria being the most abundant
(Parada, Zapata, de Fabrizio, & Martinez, 1996). Addition of glucose
syrup during fermentation reduced the fermentation time while
achieving the desired properties of sour starch (Marcon, Vieira,
Santos, De Simas, & Amboni, 2006). Fermentation decreased past-
ing viscosity and increased the starch solubility (Nakamura & Park,
1975), whereas the chemical composition of the granules was lit-
tle affected (Camargo, Colonna, Bulon, & Richard-Molard, 1988).
Another study showed that fermentation lowered Tp and Tc with-
out affecting H of gelatinization, and decreased paste viscosity
(Petruccelli, Zamponi, Jovanovich, & Ann, 1993). Fermentation
increased apparent amylose content and H of gelatinization,
and decreased average granule diameter, solubility, and swelling
power, reduced PV, BD, and SB of pasting. The altered textural
properties of starch paste were attributed to short amylose-
like fragments formed by enzymatic hydrolysis of amylopectin
(Numfor, Walter, & Schwartz, 1995). The discrepancy observed in
different studies (Camargo et al., 1988; Nakamura & Park, 1975;
Numfor et al., 1995; Petruccelli et al., 1993) may be attributed to
the different experimental conditions and microora composition
used in the specic studies.
 F. Zhu / Carbohydrate Polymers 122 (2015) 456480
Recent efforts have been focused on other modications as
alternatives to fermentation and sun-drying for quality consis-
tence as well as for the underlying mechanism of sour starch
production. Inuence of individual components involved in fer-
mentation on the starch properties has been tested. Lactic acid
treatment at low concentration induced the changes in X-ray pat-
tern from C- to A-type (Plata-Oviedo & Camargo, 1998). Combined
organic acid and enzyme hydrolysis of starch in a controlled man-
ner might be an alternative for fermentation to produce sour starch
(Camargo et al., 1988). Sun drying of the lactic acid treated starch
had good biscuit making performance (Plata-Oviedo & Camargo,
1998). Good expansion property of sour starch was obtained by
treating fermented starch with hydrogen peroxide (H2 O2 ) (Dias,
Elias, Oliveira, & Helbig, 2007), which could oxidize starch as dis-
cussed in the Modication session. This dual modication resulted
in more homogeneous products with properties similar to the sun-
dried fermented one used in bakery (Dias, Zavareze, Helbig et al.,
2011). Fermented starch was oxidized by sodium hypochlorite, and
the dual-modied starch had increased expansion properties and
gave biscuit reduced hardness (Dias, Zavareze, Elias et al., 2011).
Lactic acid and UV-irradiation treatments reduced the viscosities
and setback of pasting with little effect on the DSC gelatiniza-
tion parameters. Structural analysis showed that amylopectin and
amylose molecules were degraded (Bertolini, Mestres, Colonna,
Lerner, & Della Valle, 1999; Franco et al., 2010). Ultraviolet (UV)
can be categorized to UVA (315400 nm), UVB (280315 nm), and
UVC (100280 nm). The lactic acid treated starch irradiated with
UVB or UVC had increased Tp of gelatinization and the desired
baking expansion ability. Chromatographic analysis showed that
UVB mostly degraded the amylose component and UVC both the
amylose and amylopectin (Vatanasuchart, Naivikul, Charoenrein,
& Sriroth, 2005).
Sour starch has been extensively used in bread making.
Expansion during baking of sour starch was attributed to water
vaporization and paste uidity, and was correlated with changes in
thermo-mechanical properties of dough-crumb around the starch
melting temperature (Bertolini, Mestres, Lourdin, Della Valle, &
Colonna, 2001c). The presence of carboxylate functional groups
in starch introduced during fermentation-sun-drying greatly con-
tributed to the expansion during baking which was predicted
by principal component analysis (PCA) from the Fourier trans-
form infrared spectroscopy (FTIR) data (Demiate, Dupuy, Huvenne,
Cereda, & Wosiacki, 2000). The good baking expansion activity of
fermented starch was associated with low paste viscosities and
high swelling and solubilization (Mestres, Boungou, Akissoe, &
Zakhia, 2000).
8. Conclusions and outlook
The world cassava use is expected to reach up to about 290 mil-
lion tonnes in a few years (Westby, 2002). The cheap, large, and
sustainable supply of cassava starch provides a feasible basis for
diverse applications. The various structural and functional prop-
erties of this starch in the majority of reports include, but are not
limited to the following:
(1) The amylose content ranges from 0 to 30.3%; (2) the starch
granules are oval, truncated, and rounded with a size of 232 m,
the size distribution is either uni-modal or bimodal; (3) A- or Ca -
type polymorph; (4) clusters of amylopectin have a size of DP
5878, and 8.211.1 chains and 7.38.9 blocks per cluster; (5) great
diversity in swelling and solubilization, gelatinization, and rheolo-
gical properties, retrogradation, and enzyme susceptibility of starch
exists, this diversity is achieved through natural selection, genetic
modications of starch biosynthetic enzymes, manipulations of
environments and agronomic practice, and varying processing
475
conditions; (6) moderate consumption of some chemically mod-
ied starch may be nutritionally sound through cholesterol
lowering, hypoglycemic and antidiabetic effects, though negative
impact such as reduced mineral absorption may incur as shown
by in vivo animal trials; (7) the diversity in properties and struc-
ture of starch is further diversied by various chemical, physical,
enzymatic, and their combined modications.
Research should be done to address the following major issues
to be able to better understand and utilize this starch:
(1) There appears some repeated research efforts (e.g., starch mod-
ications) to address the questions which have already been
resolved years ago. A more thorough literature review should
be conducted to avoid repeating of the same test already done.
(2) Results from different studies are sometimes difcult to com-
pare directly due to different methods used in specic studies.
Some quality parameters (e.g., amylose content) can be rather
sensitive to the measuring method used. Global initiatives to
establish more standardized methods with the same recom-
mended experimental settings are needed to maximize our
research efforts. Consequently, the method used in each study
should be clearly specied.
(3) There is confusion in uses of nomenclature, especially for the
starch molecular structure (e.g., denitions of A-chain of amy-
lopectin and cluster). This confusion in starch terminology
further contributes to the impossibility to directly compare
data from different studies. The unication of nomenclature is
denitely worth global scientic initiatives.
(4) To continue to explore the genetic means and environmental
factors to diversify the variations in the composition, structure,
and properties of the starch. Starches with high amylose (e.g.,
amylose content >50%) and novel amylopectin structure remain
to be developed.
(5) There is a trend to use green technology to develop novel
products in an environmentally friendly way. There are oppor-
tunities to use novel techniques such as ultrasound and
microwave treatments to modify the chemical and enzymatic
modication process to efciently achieve novel properties in
a time and energy saving way.
(6) Though the efforts in chemical modications of starch are large,
diverse nutritional properties of the resulting starch affecting
human health are relatively little studied.
Acknowledgements
Financial support from the Faculty Research Development Fund
of the University of Auckland is gratefully acknowledged.
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