Reviews

Cassava, the Next Corn for Starch Sweeteners

Jay K. Shetty,1 Bruce A. Strohm,2 Sung Ho Lee,3 now cost-competitive with cane sugar. Corn (maize) remains the
Gang Duan,4 and David Bates5 major agricultural feedstock for producing starch and starch-
based sweeteners in the world, with the United States re-
1
DuPont Industrial Biosciences, Palo Alto, CA presenting the major share of production and consumption and
2
Grain Enzyme Technology, Beloit, WI China coming in at a close second. European countries process
3 primarily wheat and corn for starch and starch-based sweeteners
Biorefinery Applied Innovation Center, DuPont Industrial
(glucose, fructose, maltose, and starch hydrolyzates).
Biosciences, Cedar Rapids, IA Due to climate and agricultural practices, cassava tubers are a
4
Biorefinery Applied Innovation Center, DuPont Industrial major source of starch and calories in many African and some
Biosciences, Wuxi, China Asian countries. Cassava’s benefit over many other agricultural
5
DuPont Industrial Biosciences, Cedar Rapids, IA feedstocks for starch is its ability to grow in high yields where
crops like corn, wheat, and sugarcane are not grown in abun-
dance. Cultivation of cassava is expected to improve nutrition,
economic growth, and social stability (as a cash crop for small
Abstract farmers) and will continue to grow as plant science, outside
Cassava, also known as tapioca, is grown for its enlarged investment, and improved agricultural practices benefit small
starch-filled roots in Nigeria, Thailand, Brazil, Zaire, and In- farmers and producing regions.
donesia, and production is continuing to increase in Africa and
Asia. Currently, Southeast Asia is the leading producer of
cassava for industrial uses and trade. As high-quality cassava
World Production
Cassava is mainly identified as Manihot esculenta Crantz,
starch becomes increasingly available, its utilization as a re-
placement for sugar via enzymatic hydrolysis to sweeteners with various common names such as manioc, tapioca, and
yucca. A woody annual, cassava is cultivated for its tuber, which
will offer local producers an opportunity for economic ad-
is reported to contain 24–30% starch. The tubers contain very
vancement and improved standard of living. Knowledge gained
from the processing of starch from maize and wheat can be low levels of protein and fat. Depending on the cultivar and
growing conditions, they may contain lethal concentrations of
applied to cassava processing. Improvements to existing pro-
bound cyanogenic glucosides that must be reduced via proces-
cesses would be needed, however, as cassava has lower amy-
sing methods or cooking. Some literature reports describe cas-
lose content and lower impurities such as lipids and proteins
sava as being either sweet or bitter, indicating the presence of
compared to other plants.
hydrogen cyanide. Sweet is identified as 20 mg/kg of fresh root
and bitter at > 250 mg/kg.
Key words: alpha amylase (AA), autonomous mobile proces-
The world’s average cassava harvest yield currently ap-
sing unit (AMPU), Cassava Mechanization and Agro-Processing
proaches 13 metric tons (mt)/hectare (ha), with total world
Project (CAMAP), Dutch Agricultural Development and Trad-
production exceeding 260 million mt in 2012.1 In 2000, Scott
ing Co (DADTCO), dry basis (DB), dextrose equivalent (DE),
et al. projected the global production of cassava would reach 275
direct starch to glucose (DSTG), direct starch to maltose
million mt by the year 2020.2 Based on production data from the
(DSTM), Federal Institute of Industrial Research Oshodi
last 11 years, this estimate now appears to be low; production
(FIIRO), glucoamylase (GA), granular starch hydrolyzing en-
levels could reach as much as 300 million mt in the 2018–2020
zyme (GSHE), high fructose syrup, high fructose corn syrup,
time frame (Fig. 1). Under ideal cultivation conditions, yields of
high quality cassava flour (HQCF), immobilized glucose isom-
60 mt of cassava root per ha have been reported.3
erase (IGI), scanning electron microscopy (SEM), United According to Food and Agriculture Organization (FAO) es-
Nations Conference on Trade and Development
timates, Africa accounts for nearly 55% of world cassava pro-
duction, with the remaining balance coming from countries in
Introduction Asia, Latin America, and the Caribbean (Table 1).1 Table 1 also
shows that even when adjusting for the fact that grains are 12–

T
he main source of sweetener globally is currently
sugar from cane produced mainly in Asia (Thailand, 15% moisture and cassava is 60–70% moisture (Table 2), cassava
Indonesia, India, etc.) and South and Central America is a major source of starch-based nutrients in Africa—producing
(Brazil). However, due to the development of ad- nearly half as much dry substance starch-based nutrient as grains.
vanced starch-processing enzymes, starch-based sweeteners are When adjusted for the fact that sugarcane is 60–70% moisture and

DOI: 10.1089/ind.2014.0010 ª M A R Y A N N L I E B E R T , I N C .  VOL. 10 NO. 4  AUGUST 2014 INDUSTRIAL BIOTECHNOLOGY 275

SHETTY ET AL.

(DADTCO) BV (The Nether-

lands) states that this will require
farmers to change practices, since
as of 2011, only 1% HQCF was
included in wheat flour.5 DADT-
CO is investing in Nigeria and has
launched the autonomous mobile
processing unit (AMPU), which
processes fresh cassava into cas-
sava cake on or near the cassava
farms—eliminating transport of
perishable roots over long dis-
tances to a central factory.5 The
cassava cake can then be used as
raw material in other industries
that require starch as raw material,
such as beverage, cassava flour,
starch, starch hydrolysis products,
Fig. 1. Global production of cassava in millions of metric tons (mt).
high fructose syrups, and basically
in any process requiring starch.
12–15% fiber, it can be said that cassava is more important to The African Agricultural Technology Foundation has initi-
human nutrition in Africa than sugarcane. ated the Cassava Mechanization and Agro-processing Project
Figure 2 shows the total production of cassava (millions of (CAMAP), the goal of which is ‘‘to enhance the contribution of
mt) and yield (mt/ha) for the top 20 cassava-producing coun- cassava production and processing technologies to sustainable
tries. This chart indicates that if the yields seen in India and other improvements in food security, incomes and livelihoods of
Asian countries are achieved in Africa, a major increase in total farmers, processors, and marketers in the cassava sector.’’6 The
cassava production is possible. The proximate composition of project’s mission is an attempt to overcome the lack of mech-
cassava root shown in Table 2 confirms the value of cassava as a anization or appropriate production and processing tools. Africa
source of starch. is the world’s largest cassava-producing region and accounts
Unlike many other agricultural crops, there is no definite for nearly 55% of the world’s output despite yields that are the
maturation point for cassava tubers, which means that harvest- lowest in the world (10 mt/ha compared to 26 mt/ha in India).
ing may be delayed. This could lead to the tubers being stored in Africa is challenged by limited markets and distribution systems
the ground for several months or even more for some varieties, compared to other cassava-producing regions. It has been es-
which allows producers to store stock in the ground. Long in- tablished that productivity-enhancing technologies are easily
ground storage does result in loss of quality, as the tuber be- adopted by cassava farmers when they have access to markets.
comes woodier. It is recognized that cassava is one of nature’s The use of cassava as feedstock in manufacturing, and any other
richest sources of starch, and the abundant and increasing large scale use, such as the mandated incorporation of cassava
quantity available in less-developed countries in Africa high- flour in wheat flour for bread making in Nigeria, requires a large
lights its potential for producing value-added food and beverage number of small scale processing units. The CAMAP states that
ingredients like sugar sweeteners, beer adjuncts, and specialty ‘‘The existing capacity for manufacturing quality cassava pro-
chemicals. cessing equipment in Africa is limited and unless the capacity is
The government of Nigeria, the world’s largest cassava pro- enhanced, it is unlikely the cassava farmers and entrepreneurs
ducer, has implemented new policies to encourage production of will benefit from these new market opportunities. Manu-
high quality cassava flour (HQCF) in order to create jobs, add to facturers in Africa obtain prototypes from foreign manufacturers
the national economy, and reduce the need to import food. These and fabricate (copy) them. However, the quality of the locally
policies provide incentives for the inclusion of HQCF in wheat made equipment is usually sub-standard and uncompetitive. On
flour at levels up to 40%. The details of the mandated inclusion the other hand, equipment manufacturers outside of Africa are
rate of HQCF into wheat bread in Nigeria are somewhat elusive; reluctant to supply equipment to African businesses for fear of
several sources disclose ranges of 10–40%. Dr. G.N. Elemo of piracy and subsequent loss of market.’’
the Federal Institute of Industrial Research Oshodi (FIIRO) Total global production of cassava root is 256 million mt
explains the legal, cultural, legislative, and supply difficulties annually and is based on fresh cassava root (Table 1). Con-
related to HQCF in achievement of their targets.5 Taste tests and verting this figure to a common dry substance indicates that only
baking trials have shown 10–20% inclusion as realistic, with the about 7% of cassava enters international trade, since the fresh
40% inclusion value being attractive only due to economic cassava root weight is 70% moisture and dried cassava is 14%.
considerations. Nigeria’s action plan includes increasing total The export of cassava is dominated by Thailand, at 56%, fol-
cassava production from 34 million mt to 51 million mt by the lowed by Vietnam at 40%. The remaining 4% of trade is covered
year 2015 by doubling yields from 12.5 mt/ha to 25 mt/ha. by Indonesia (2%) and Paraguay (1%). All other producers
The Dutch Agricultural Development & Trading Company combined export < 1% of the total cassava produced in the

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 CASSAVA, THE NEXT CORN

on the milling sizes prior to extraction. The

Table 1. Global Cassava Productiona
article states that ‘‘up to 15% of stem dry
2012 PRODUCTION IN MILLION METRIC TONS (mt) mass can be currently extracted as starch by
CASSAVA MAIZE SUGARCANE WHEAT means of simple processes—milling, wash-
World + (Total) 256,529 875,099 1,773,815 674,884 ing, and sedimentation—similar to those for
producing starch from cassava roots or po-
Western Africa 77,726 18,279 6,120 151 tatoes. This suggests there would be no need
Southern Africa 0 12,691 24,800 1,820 for a large investment to integrate stem
starch production into the existing cassava
Northern Africa 16 7,146 23,214 18,154 starch industry, although some small ad-
Middle Africa 33,337 3,924 5,060 21 justments, for example, the design of the
feeding devices, may be needed. A higher
Eastern Africa 35,138 27,410 37,389 3,928 rate of starch extraction from the stem than
Africa (Total) 146,217 69,449 96,583 24,074 15% of dry mass could probably be achieved
if the particle size was further reduced and
Central Asia 0 1,061 0 22,412
improved techniques are used, as suggested
Eastern Asia 4,575 210,336 125,279 122,066 by Guo (2004), who shows that the extraction
of root starch increases from 71% to 84% of
Southeastern Asia 64,647 40,024 184,123 187
dry mass using a similar extraction method if
Southern Asia 8,386 30,653 420,602 140,129 the milled particle size is reduced by finer and
Western Asia 0 5,846 13 29,771
double milling.’’ The authors calculated the
yields, as follows: ‘‘Based on the facts that
Asia (Total) 77,608 287,919 730,016 314,565 Cassava stem biomass is about one half of its
Central America 711 25,920 106,121 2,268 root mass and 15% of stem dry mass can be
obtained as starch (using £ 0.5 mm particles),
Northern America 0 285,535 27,900 88,768 the global potential of starch production from
South America 30,427 110,878 758,973 19,434 cassava stems can be estimated at about 5.2
Tg. Thus, at least 87% of all current (6.0 Tg
Caribbean 1,365 630 26,066 0 UNCTAD 2012) root based production of
Americas (Total) 32,503 422,963 919,060 110,470 tapioca starch for industrial use could be re-
placed with that from stems.’’
Southern Europe 0 21,395 5 17,607 The findings of this study are encouraging
Western Europe 0 23,998 0 67,542 since the stems are typically burned for fuel or
are discarded. If stems were considered a
Eastern Europe 0 48,618 0 83,393
valuable starch source, food for an additional
Northern Europe 0 79 0 26,839 30 million people could be produced without
additional land being cultivated for cassava
Europe + (Total) 0 94,090 5 195,382
production. Recently, several non-profit orga-
Australia & New 0 662 25,957 30,394 nizations, non-governmental organizations,
Zealand and governments have promoted, supported,
Melanesia 177 15 2,190 0 and encouraged cassava production by touting
fast-growing, disease-resistant, and higher-
Micronesia 9 0 0 0 starch-content varieties, as well as expanded
Polynesia 15 0 4 0 market opportunities for rural areas in Africa.
For instance, there is support for converting
Oceania (Total) 201 677 28,151 30,394 fresh cassava root to ethanol for cooking fuel
a
Source: Food and Agriculture Organization (www.fao.org) 1 that is cleaner, faster, safer, and cheaper than
charcoal and Kerosene. Ethanol from cassava
has the potential to be used in farming ma-
chinery and for the production of electricity for
local communities.8
regions. The export of cassava from leading producer Nigeria is
basically 0%. Currently, dried tapioca is only a minor item of
commerce for most producing countries.1 Processing
A recently published article showed data confirming that In general, cassava refers to the raw or dried root. The term
cassava stems produced in China contain > 30% of their dry tapioca refers to the extracted starch. The bulk of dried tapioca
mass as starch.7 The article demonstrated that simple water starch that is mostly used as food is produced and exported from
extraction can easily extract about half of the water depending Thailand and Brazil.

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SHETTY ET AL.

African countries represent more than 50% of the world’s

Table 2. Composition of Cassava Root
cassava production, industrial processing of cassava starch for
CASSAVA PROXIMATE COMPOSITION sugar sweetener has not yet been developed there. Regardless of
SCOTT GJ, ET AL., NYERHOVWO the starch source, the process for conversion of starch to sugar
SOURCE FAO1 TABLE 252 JT 4 follows a similar pattern with minor modifications.
Moisture 70 60–70 70 Starch, which is insoluble in cold water, accumulates as mi-
croscopic granules varying in diameter from 0.5 to 175 microns.
Starch (%FW) 20 27–36 24 The granules are composed of a mixture of amylose (15–30%
Soluble sugars (%FW) 5 0.5–2.5 w/w) and amylopectin (70–85% w/w). Amylose contains linear
chains of alpha 1,4-linked glucose units having a molecular weight
Protein (%FW) 1 0.5–2.0 (MW) of about 60,000 to about 800,000 daltons. Amylopectin is
Fats (%FW) 0.4 0.5 a branched polymer containing alpha 1,6 branch points every 24–
30 glucose units; its MW may be as high as 100 million daltons.
Crude fiber (%FW) 1 1 2
The amylose and amylopectin content, impurities, and starch
Ash (%FW) 0.5 0.5–1.5 gelatinization temperature for different starch sources are given in
Table 3.9 Note the reduced level of impurities like lipid, protein, and
Others
ash. Cassava starch also has a lower starch gelatinization temper-
Starch extraction rate (%) 20–25 ature compared to other grain/cereal starches.
Alan Reeve writes, ‘‘When compared with potato starch, for
Starch grain size (l) 5–51
example, maize starch is not technically ideal for hydrolysis.
Amylose (% of starch) 15–29 The virtual absence of lipids in potato starch as opposed to the
o
Gelatinization temperature ( C) 49–73
0.4–0.9% DB [dry basis] in starch from maize ensures that
amylose-lipid complexes are also absent. As a result, a good
liquefaction can be achieved at lower temperature and retro-
gradation problems are far less severe. Another root starch,
Tapioca, is similar in composition and hydrolysis characteristics
Starch represents one of the most available and utilized raw to potato starch.’’9 This leads to the inference that tapioca starch
materials in the commercial agricultural industry. Starch can be is superior to grain starches for low-conversion maltodextrins,
obtained from a number of commercial crop plants, with corn hydrolysis products, and in applications in which soft gels of
and wheat representing the major sources in the US and Europe, textural use in foods is desired at a cost less than potato.
respectively. Cassava is used primarily in some countries in
Asia, including Thailand, Indonesia, and Vietnam. Even though
Cassava, the Next Corn
Cassava starch, after suitable
extraction and washing, can be
dried and stored for further pro-
cessing, or used as a slurry in con-
ventional starch-processing systems
to produce food products such as
modified starches or various sweet-
eners via acid or enzyme hydrolysis,
including enzymatically pro-
duced high fructose syrup. The
discussion in the previous section
on the comparison of tapioca
starch to potato and maize identi-
fies the advantages tapioca starch
offers when used as the starting
feedstock for the production of
industrial- and food-grade star-
ches, hydrolyzed products such as
maltodextrins, maltose syrups,
glucose syrups of all dextrose
equivalent ranges, crystalline glu-
cose, and, of course, the high glu-
cose feed to glucose isomerase for
Fig. 2. Total cassava production (millions of mt) and yield (mt/ha) for the top 20 cassava- the manufacture of high fructose
producing countries. syrup.

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Table 3. Composition of Different Starches (% by weight)10

IMPURITIES (WT% DB) PROPERTIES OF STARCH
STARCH LIPIDS PROTEIN ASH PHOSPHORUS % AMYLOSE % AMYLOPECTIN GEL.TEMP, C
Maize 0.75 0.35 0.1 0.02 26 74 62–74

Waxy Maize 0.25 0.3 0.1 0.01 1 99 63–72

Milo 0.75 0.3 0.1 - - - -

Wheat 0.8 0.35 0.3 0.05 25 75 52–62

Rice 0.8 0.45 0.5 - - - -

Potato 0.15 0.08 0.4 0.08 24 76 56–79

Cassava 0.2 0.1 0.2 0.01 17 83 52–64

Sago 0.15 0.1 0.2 - - - -

Amylo-maize - - - - 50–75 25–50 > 140

The high water content of cassava root has slowed expansion The first stage starts with enzymatic hydrolysis of starch
of the market for fresh cassava roots due to the high cost for its under two different pH conditions because of the differences in
transportation from the farm to processing locations and the high the pH stability of the liquefaction (step 1) and saccharification
risk of microbial spoilage. (The DADTCO’s investment in an (step 2) enzyme systems. This stage is followed by purification
autonomous mobile processing unit, as described previously, is systems in which the high glucose syrup is refined to remove
relevant here.) In order to circumvent these challenges, a simple color bodies and salts prior to the third stage, in which the
drying process is generally adopted by converting cassava root glucose syrup is subjected to an isomerization step, which
into cassava chips, in which the cassava roots are sliced me- converts glucose to fructose using glucose isomerase under al-
chanically and sun dried to reduce the moisture content to less kaline pH conditions. This process, typical of a corn wet milling
than 12–15%. A comparison of the composition of cassava chips system, is summarized in Fig. 3.
and corn is shown in Table 4.
The higher starch content coupled with lower protein and fat First stage: step 1a, primary liquefaction. This process starts
content favor tapioca chips as a starch source for hydrolysis to with starch slurry from a mill house where the separation of non-
intermediate- and high-conversion syrups. However, the asso- starch components of corn is completed. The starch slurry with
ciated co-products from corn refining have much higher value proper dry-substance content is adjusted to the optimal pH and,
than the residue from cassava purification. following addition of the entire liquefying enzyme dose, is
processed through a stem injection cooker at 105–109C. In
CASSAVA STARCH TO SUGAR SWEETENERS general practice, bacterial thermostable alpha amylases from
Commercial starch sweeteners are generally produced in high Bacillus licheniformis (such as SPEZYME FRED or CLEAR-
yields by a two-step process yielding glucose (first and second FLOW, DuPont Industrial Biosciences, Rochester, NY) are
stage), followed by an additional step to high fructose (third stage). used. This initial cook is followed by a series of hold loops or coils
that provide 5–7 min under enough back pressure to hold the
temperature.
Table 4. Comparison of Composition of Cassava Chips
and Corn10 First stage: step 1b, secondary liquefaction-dextrinization. The
first step is continued by a process known as secondary lique-
CONTENT (% DRY BASIS)
faction, which consists of flash cooling the contents from the
COMPOSITION CASSAVA CHIPS CORN first step, often with the aid of vacuum pumps to 90–98C, then
Moisture (%wet) 1–11 7–23 carrying them through a series of stirred tanks to provide 1–3
hours of hold time. A typical extent of de-polymerization
Starch 75–85 64–78
through the liquefaction system results in 8–10 DE, which can
Protein 1.5–3.0 8–14 be used for subsequent hydrolysis.
Fat 0.2 3.1–5.7
Second stage: saccharification. The pH of the liquefied starch
Ash 2–4 1.1–3.9 (liquefact) from the liquefaction step is decreased to pH 4.0–4.6, and
Crude fiber 3–4 1.8–3.5 the temperature is reduced to 60–62C to match the optima for
glucoamylase saccharification enzymes (such as OPTIDEX L-
400, OPTIMAX 4060 VHP, OPTIMAX HiDEX, or OPTIMAX

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SHETTY ET AL.

Fig. 3. Typical process of a corn wet milling system.

Super, DuPont Industrial Biosciences), to convert low DE sub- 1–6 branch points in amylopectin, resulted in significant im-
strate to high glucose syrup. Glucoamylases, enzymes that remove provement in the efficiency of glucose production. It is now
successive glucose units from the non-reducing ends of starch, can common practice to use enzyme blends containing glucoamylase
hydrolyze both linear and branched glucosidic linkages of starch, and debranching enzymes like OPTIMAX 4060 VHP, OPTIMAX
amylose, and amylopectin. The commercial glucoamylases are Hi-Dex, and OPTIMAXSuper (DuPont Industrial Biosciences) in
very fast in hydrolyzing alpha 1–4 glucosidic linkages in high MW varying proportions for saccharification. The addition of a deb-
starch substrate, and the rate decreases with decreasing MW (Km ranching enzyme resulted in a higher glucose yield and reduced
increases) of the oligosaccharides. It is also known that the rate of saccharification time, and allowed saccharification at higher dis-
hydrolysis of alpha 1–6 (branch) linkages in amylopectin is much solved solids. The saccharified liquor containing > 95.5% glucose
slower than the rate of hydrolysis of alpha 1–4 glucosidic linkages. is then clarified via vacuum drum filters or membrane filters, re-
Even though starch contains only 3.8% of alpha 1–6 linkages, the fined with carbon, ion-exchanged, and evaporated to 45–55% dry
resistance on the hydrolysis of liquefied starch by glucoamylase is substance. The highly refined glucose syrup may then be used as
very significant. The introduction of pullulanase in the mid-1980s, fermentation feedstock, feed to glucose crystallization, or feed to
a very specific enzyme for catalyzing the hydrolysis of the alpha isomerization systems.

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due to lower temperature cooking, higher

solids cooking, and reduced evaporation.

Conventional two-stage liquefaction

demonstrating direct replacement of maize
or wheat starch with tapioca. A pilot-
scale liquefaction comparing DE devel-
opment during second-stage dextrinization
of maize starch to tapioca starch at condi-
tions typical for maize starch clearly shows
that tapioca starch may be directly sub-
stituted for maize (Fig. 4)

Direct tapioca starch to glucose. A

suggested flow diagram for an integrated
cassava process utilizing direct starch to
glucose (DSTG) is shown in Fig. 5. The
low energy DSTG process shown in the
flow chart was demonstrated as a viable
Fig. 4. Pilot-scale liquefaction comparing dextrose equivalent (DE) development for maize
process multiple times using various
and tapioca. enzymatic approaches. One such exper-
iment, shown in Fig. 6, indicates that this
system will achieve very acceptable
PROCESSES FOR UTILIZATION OF TAPIOCA STARCH solubility of *93% in 24 h with excellent glucose concentration
The following examples demonstrate different processes that approaching 97%. The chart also shows that allowing this hy-
can be used for the conversion of tapioca starch to glucose. drolysis to progress to 48 h increases solubility with a small
loss of glucose due to reversion. Fine tuning the enzyme dose
Conventional two-stage liquefaction: low temperature, high sol- will provide control of maximum glucose production and corre-
ids. Experimental work at DuPont Industrial Biosciences ap- sponding solubility. The saccharifying enzyme used in this ex-
plications laboratories has shown that temperatures of 105– periment was from GC 871 GSHE, produced from Humicola sp.
109C in the first stage of a two-
stage liquefaction system are not
required for cassava processing
and that 95C is sufficient in the
first stage, followed by 95C sec-
ondary liquefaction to produce
low sediment, non-iodine-staining
saccharified liquor using OPTI-
MAX Super for saccharification.
This has been demonstrated at dry
substance concentrations as high
as 42%. As expected, the high
initial dry substance during sac-
charification resulted in final sac-
charified liquor that is depressed
by about 2% glucose compared to
typical glucose achievement at
35–36% initial starch solids. This
is a trade-off for the final sac-
charified liquor, which will be
> 45% dry substance—resulting in
cost savings during the evapora-
tion process. The process cost
savings when using high dry sub-
stance tapioca starch in a con-
ventional liquefaction system is Fig. 5. Flow diagram for an integrated cassava process utilizing direct starch to glucose. (DSTG,
3-fold—steam costs are decreased direct starch to glucose; DSTM, direct starch to maltose)

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SHETTY ET AL.

small dimples (0.2–0.5 lm in di-

ameter) in the surface of the starch
granules due to enzyme hydrolysis.
Some empty shells are observed,
indicating that amylolysis of the
core of the starch granule has taken
place as early as 2.5 h. Quantity and
size of the dimples increase over
time. At 11 h, dimples widen to as
big as 2 lm. Surface peeling is ev-
ident throughout the reaction time
course, causing dimples to overlap.
Substrate hydrolysis seems to reach
saturation at 11 h, as the amount of
empty shells at this time point is
similar to that observed at 23.5 h.
Micrographs of empty shells depict
complete digestion of the interior of
the granule.
The lower energy approach may
also be used to produce maltose
Fig. 6. Enzyme hydrolysis of tapioca starch measuring percent soluble starch and DP1 generated.
(DP1, degree of polymerization 1; GAU, glucoamylase unit; HGA, humicula glucoamylase)
syrups via the direct tapioca starch
to maltose system (DTSM). The
Enzyme hydrolysis was followed by scanning electron mi- DTSM approach, when using bar-
croscopy (SEM). Micrographs at 0 h (Fig. 7) depict typical ley beta amylase, OPTIMALT BBA, or other maltogenic enzymes
cassava starch granules before amylase treatment. The starch supplemented with a typical Bacillus stearothermophilus thermal
surface is smooth and homogenous and the granule size distri- stable AA will achieve > 60% maltose, with starch solubilities of
bution ranges from 5 to 25 lm, with the majority of the granules 64–73%, depending on the AA dose.
between 15 and 20 lm. On GC871 and SPEZYME Alpha
treatment, the surface morphology of the granules changes with Isomerization to fructose using high glucose syrup from cassava
increased exposure time. After 2.5 h, the enzyme blend produces starch. High fructose corn syrup was developed in the 1970s

Fig. 7. Scanning electron micrographs of granular cassava starch treated with humicula glucoamylase (HGA) and SPEZYME Alpha after 0,
2.5, 7.5, 12.0 and 23.5 h. Dimension of micrographs: first row = 100 lm · 100 lm, second and third rows = 20 lm · 20 lm.

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when the food industry began looking for alternatives to tradi- results in the desired fructose content (e.g., 42–45%) in the li-
tional cane and beet sugar that could provide similar sweetness quor effluent.
and taste and consistently superior quality for a fraction of the
price. Basically all forms of high fructose syrup come from Malto-saccharification for maltose syrups using cassava starch.
starch as a mixture of glucose and fructose produced using en- Maltose, a mildly sweet disaccharide linked by an alpha 1–4
zymes. The resulting high fructose syrup product is extremely linked glucosyl residue, is widely used in many industrial and
similar to cane sugar and has similar taste and sweetness (Fig. 8). consumers applications, such as a sweetener or in the prepara-
High fructose syrup is a useful ingredient because of its tion of maltitol, a low calorie sweetener. The majority of sugar
sweetness and ability to blend with other food and beverage in high maltose syrup is maltose (typically 40–50% by weight)
ingredients and it continues to displace liquid applications of with some commercial products containing as high as 75%. It is
cane sugar (sucrose) in the US and, to a lesser extent, in other less sweet than high fructose syrup, with a relative sweetness of
countries. 30–40% compared to sucrose. It is also used in brewing to in-
By far the most important application of immobilized en- crease throughput and is known to reduce haze caused by
zymes in the food industry is the conversion of glucose to varying quality of wort. Since maltose has a low freezing point,
fructose by the enzyme glucose isomerase. Glucose isomerase high maltose syrup is useful in frozen desserts. Maltose solu-
GENSWEET-IGI (DuPont Industrial Biosciences) catalyzes tions exhibit lower viscosity and less humectancy than equal
the isomerization of glucose to fructose. Immobilized glucose concentrations of glucose syrups and thus find application in
isomerase is normally used in a set of column reactors (Fig. 9) candy formulation to reduce stickiness. Recent increases in
operated in parallel. Each column is operated at a flow rate that maltose production can be correlated to the producion of the

Fig. 8. Relative sweetness of different sugars. HFS, high fructose syrup.

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SHETTY ET AL.

producing high value-added sugar sweeteners. The increased

focus on improving yields from current areas planted through
improved agricultural practices, improved selection of plant
varieties, and the implementation of processes to recover
cassava stem starch will yield surplus quantities of high quality
tapioca starch that can and should be used locally for the
production of starch hydrolyzate products. The deep knowl-
edge base of corn and wheat starch hydrolysis can be readily
applied to the easier to hydrolyze cassava starch to enable the
local production and consumption of cassava sweeteners, en-
hancing local economies and, in general, improving standards
of living.

Acknowledgments
The authors appreciate and wish to acknowledge the valuable
comments and support of Jan Koninckx, Troy Wilson, Jennifer
Lane, Roopa Ghirnikar, and Mariliz Johnson.

Author Disclosure Statement

No competing financial interests exist.

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microbial sources are well characterized; for example, beta- Address correspondence to:
amylase extracted from plants (i.e., barley; OPTIMALT BBA, Jay K. Shetty, PhD
DuPont Industrial Biosciences), wheat, and soybeans, have been DuPont Fellow
or are being used on a commercial scale for producing high- DuPont Industrial Biosciences
maltose syrup. High maltose syrup as a food additive is used as a 925 Page Mill Road
sweetener and preservative in many food formulations. Palo Alto, CA 94304
Phone: (650) 846-5821
Conclusions Fax: (650) 845-6509
Cassava, or tapioca starch, possesses characteristics that make
it an ideal feedstock for processing via enzyme hydrolysis for E-mail: jay.shetty@dupont.com

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