1 Chapter

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5 MAIZE (ZEA MAYS) AS A SUPERFOOD
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8 Juan Leopoldo Pech-Almeida1
9 Maritza Alonzo-Macías1
10 Anaberta Cardador-Martínez1
11 Carmen Téllez-Pérez1,2
1
12 Escuela de Bioingenierías, Escuela Nacional de Ingeniería y Ciencias,
13 Tecnológico de Monterrey, Campus Queretaro, Queretaro México
2
14 University of La Rochelle, Intensification of Transfer Phenomena on
15 Industrial Eco-Processes, Laboratory of Engineering Science for Environment
16 LaSIE - UMR-CNRS 7356, 17042 La Rochelle, France
17
18 ABSTRACT
19
20 Maize (Zea mays L.) has been used in human nutrition as a staple food,
21 especially in Latin America and African countries. According to FAO, maize
22 is a primary source of calories in the diets of 230 million inhabitants of
23 developing countries. Recent studies have also identified it as a good source
24 of nutraceuticals compounds, such as phenolics, phospholipids, phytosterols,
25 arabinoxylans, policosanols, carotenoids, vitamins, dietary fiber, among
26 others, which have demonstrated positive health effects. Therefore, this
27 chapter aims to present the potential of maize as a superfood, being highlighted
28 its physicochemical composition, and its antioxidant, anticancer,
29 antihypertensive, anti-diabetic, antiobesogenic, and anti-inflammatory
30 activities. Additionally, it also focuses on the most common food processing
31 methods to face maize mycotoxins, which is one of its main issues.
32
33
34 Keywords: maize (Zea mays L); superfood; nutraceutical compounds; mycotoxins
35 ___________________________
36 * Corresponding Author address: Instituto Tecnológico y de Estudios Superiores de Monterrey, Campus
37 Querétaro. Avenida Epigmenio González No. 500 Fraccionamiento San Pablo, Querétaro, Querétaro,
38 México. Email: ctellezperez@gmail.com
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39 INTRODUCTION
40
41 Since around 20000 years B.C, maize (Zea mays L.) has been used in human
42 nutrition as a staple food, especially in Latin America and African countries [1, 2].
43 In fact, according to the Food and Agriculture Organization (FAO) maize is a
44 primary source of calories in the diets of 230 million inhabitants of developing
45 countries (81 million in sub-Saharan Africa, 141 million in South Asia, and 8
46 million in Latin America) [3]. Moreover, even if maize has been recognized
47 primarily as caloric or starchy, recent studies have also identified it as a good source
48 of nutraceuticals compounds like phenolics, phospholipids, phytosterols,
49 arabinoxylans, policosanols, carotenoids, vitamins, dietary fiber, among others,
50 which have demonstrated positive health effects [4-7]. Furthermore, in recent years
51 to better satisfy consumer’s needs, new special corn varieties, as well as high-
52 amylose, waxy and high-lysine specialty corn varieties, have been developed.
53 Therefore, this chapter aims to present the most accurate picture of the potential of
54 maize as a superfood. The physicochemical composition, and the antioxidant [8],
55 anticancer [9], antihypertensive [10], anti-diabetic [11], antiobesogenic [12] and
56 anti-inflammatory activities of maize have been highlighted [13]. Additionally, it
57 also focuses on the most common food processing methods to face maize
58 mycotoxins (aflatoxins, ochratoxins, fumonisins, trichothecenes, and zearalenone).
59

60 HISTORY OF MAIZE
61
62 Although the exact origin of maize (Zea mays L.) is unclear, the older
63 paleoethnobotany evidence of its domestication has been found in Mexico, in the
64 states of Tamaulipas, Puebla, Oaxaca, and Mexico. In Tamaulipas, corn findings of
65 three primitive caves of the archeological site named “Nac Neish,” recorded data
66 between 6000- and 20000-years B.C. In Puebla, the oldest corn was found in the
67 Valley of Tehuacan (7000 years B.C.). And in Oaxaca and Mexico, the oldest
68 record dated 5000 years B.C. [1, 2]. Mexico has the most extensive diversity of
69 genetic resources in the world, with approximately 64 different races reported (59
70 native landraces and five previously reported in other regions) [14, 15]. Therefore,
71 most experts recognize Mexico as the center of origin and domestication of maize.
72 In this respect, numerous theories about the botanical origin of maize have been
73 offered, being two which receive serious consideration: the first one and the most
74 acceptable is that teosinte (Zea mexicana) is the wild progenitor of corn. The second
75 one is that wild pod corn, now extinct, was the ancestor of domesticated corn [1].
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Maize as a superfood
76 In fact, in both cases, the degree of genetic alteration has converted corn from a
77 wild plant into a plant that is dependent upon humans for survival [1, 16]. The
78 earliest cobs (5000 B.C.) were tiny, with a relatively soft rachis and soft glumes.
79 Beginning at about 2300 B.C., in several sites from the U.S to central Mexico, many
80 maize cobs showed changes, especially in elongation and induration. Over about
81 3000 years, the maize ear became robust and much more productive. Perhaps, the
82 most considerable degree of modification was produced by the indigenous people
83 of Mexico [16, 17]. Noteworthy, today, in Latin America, there are recognized 220
84 races of corn associated with a defined climatic and geographic region [2].
85
86 BOTANICAL DESCRIPTION
87
88 Botanical description tex Zea mays L. is the most economically important
89 species among the other four wild species of the genus Zea found in Mexico and
90 northern Central America (Z. luxurians, Z. Mexicana, Z. perennis and Z.
91 diploperennis). Zea mays L. belongs to the grass family (Poaceae) which includes
92 crops such as wheat (Triticum aestivum) and rice (Orzya sativa) [18, 19]. The
93 number of chromosomes in Zea mays is 2n= 20. The plant is classified as an
94 Angiosperm that forms monocotyledon seeds borne in an ovary and to the tribe
95 Andropogoneae. The tribe Andropogoneae comprises seven genera Coix
96 (2n=10/20), Chionachne (2n=20), Sclerachne (2n=20), Trilobachne (2n=20),
97 Polytoca (2n=20), Zea and Tripsacum [19]. Table 1 shows the taxonomy of the
98 species Zea mays.
99
100 Table 1. Taxonomy of the species Zea mays
Taxonomy of the species Zea mays
Domain Eukaryota
Kingdom Plantae
Phylum Spermatophyta
Subphylum Angioespermae
Class Monocotyledonae
Order Cyperales
Family Poaceae
Subfamily Panicoideae
Tribe Andropogoneae
Genus Zea
Species Zea mays
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102 Based on kernel characteristics, five domesticated varieties are commercially
103 grown specifically for human consumption: Zea mays var. indentata Sturt (dent),
104 Zea mays var. indurate Sturt (flint), Zea mays var. amylacea Sturt (floury), Zea
105 mays var. saccharata Sturt (sweet) and Zea mays var. everta Sturt (popcorn) [1].
106 Moreover, new special corn varieties as well as high-amylose, waxy and high-
107 lysine specialty corn varieties have been developed to satisfy industrial needs better.
108 Maize reproduces via monoecious cross-pollination of male (tassel) and female
109 (ear) organs. Ears are oblong and mature within protective green husks where
110 numerous tiny flowers evolve into rows of kernels along the cob after reproduction.
111 The corn seed is not merely a seed, but a single fruit called the kernel [20].
112 Botanically, the corn kernel is classified as a caryopsis, and it is composed of three
113 main structures: pericarp, germ, and endosperm.
114 The pericarp (seed coat) is the transformed ovary wall. Its main function is to
115 protect the true seed from abiotic and biotic stresses. It constitutes around 5-6% of
116 the dry weight of the whole kernel, and it contributes to the maize kernel color. It
117 is subdivided into three parts: epicarp, mesocarp, and endocarp, which are
118 composed of dead cells that are cellulosic tubes, which play a crucial role in water
119 distribution within the kernel [18].
120 The germ is considered as the first reserve tissues necessary for germination
121 and thus to develop the seedling and new plant. The germ consists of two major
122 parts: embryo and scutellum. The embryo makes up 11% of the kernel dry weight
123 and it contains 83% of the total kernel lipids, 70% of the kernel sugars, 78% of
124 kernel minerals, and 26% of the kernel proteins. The scutellum (cotyledon) is the
125 first reserve tissue rich in protein lipids, and micronutrients and its walls cells
126 facilitate the movement of material among the cells [18, 21].
127 The mature endosperm makes up the more significant part of the kernel, with
128 around 80%-85% of its weight. It represents a source of starch (86–89 % dry bases),
129 protein (7–10 % dry bases), and lipids [18]. Thus, it is considered as the second
130 reserve tissues necessary for germination. It is divided into the aleurone tissue and
131 starchy endosperm. The aleurone tissue is a single layer of cells lying immediately
132 under the pericarp. The starchy endosperm cells are constituted by a thin cell wall,
133 starch granules embedded in a protein matrix, and spherical-shaped protein bodies
134 [22, 23]. The starchy endosperm is subdivided into two zones: the vitreous
135 endosperm characterized by a hard and compact structure and the floury endosperm
136 characterized by a soft and loose structure [24].
137 According to environmental, cultural, genetic background, plant age,
138 geographic location, among others parameters, maize kernels can vary in nutrient
139 composition, color (e.g. white, yellow, orange, red, blue and black), quantity (300
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Maize as a superfood
140 to 1000 kernels per ear), weight (190 to 300 g per 1000 kernels) and spatiality (12
141 to 16 kernels per row) [25]. Therefore, depending on those parameters, the potential
142 of maize as a superfood varied. Table 2 describes the main characteristics of the
143 most commercialized Zea mays varieties.
144
145 Table 2. Main characteristics of the most commercialized Zea mays varieties
Zea mays Characteristics
variety
Dent (Zea mays Vitreous endosperm at the sides and back of the kernel.
var. indentata Soft and floury endosperm at central core extending to the
Sturt) crown.
Grown mainly in US corn belt, Argentina, China, France,
Italy, and Hungary [23, 26].
Flint (Zea mays Thick, hard, vitreous endosperm is surrounding a small
var. indurate granular center. Smooth and rounded kernels with no
Sturt) denting.
Grown mainly in South America and northern Europe [23,
26].
Floury (Zea Endosperm is composed entirely with soft starch with
mays var. almost no vitreous material
amylacea Sturt) Is one of the oldest types of corn grown in the world. Many
indigenous populations in Latin America grow it as staple
food [23].
Sweet (Zea mays The rate of conversion of sugar into starch is reduced.
var. saccharata Kernels are consumed in fresh, canned, and frozen form.
Sturt) Grown mainly in the United States, China, France,
Hungary, and Ukraine [23, 26].

Popcorn (Zea Consumed as snacks

mays var. everta Kernels give a higher expansion volume. Vitreous
Sturt) endosperm expands while floury endosperm can remain
intact. Pericarp plays an essential role in the popping
phenomenon by acting as a pressure vessel.
Grown mainly in United States and Argentina [27].
146
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147 AGRICULTURAL PRODUCTION AND ECONOMIC

148 VALUE OF THE CROP
149
150 Maize has high value and economic importance worldwide as human food, as
151 animal feed and as feedstock for a large number of industrial products and biofuels.
152 Thanks to its ability to grow in a wide diversity of environments located from 58°N
153 in Canada to 40°S in Argentina, it has been easily adopted around the world [28].
154 According to FAO, in 2018 the total world production of corn was 1,147 million
155 tons, being the American continent, which contributed with barely more than half
156 of the whole production (50.4%), followed by the Asian (31.5%), the European
157 (11.2%), the African (6.9%) and Oceania (0.1%). The top ten maize producers of
158 the world were the United States of America, China, Brazil, Argentina, Ukraine,
159 Indonesia, India, Mexico, Romania, and Canada [3]. Figure 1 shows the production
160 share of maize by world regions in 2018.
161

162
163 Figure 1. Production share of maize by world regions in 2018 [3].
164
165 Even if nowadays most of world corn production is used in developing
166 countries as a feedstuff for animals and ethyl alcohol production, for 900 million
167 poor consumers of many countries, especially in Latin America and Africa, its use
168 in human nutrition is considered as a staple food [29]. The FAO recognizes corn as
169 a primary source of calories in the diets of 230 million inhabitants of developing
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Maize as a superfood
170 countries (81 million in sub-Saharan Africa, 141 million in South Asia, and 8
171 million in Latin America) [30].
172 Maize-based food has been recognized primarily as caloric or starchy, and
173 more recently, as a good source of nutraceuticals compounds as phenolics,
174 phospholipids, phytosterols, arabinoxylans, policosanols, carotenoids, vitamins,
175 dietary fiber, among others, which have demonstrated positive health effects.
176
177 PHYSICOCHEMICAL COMPOSITION OF MAIZE
178
179 Chemically, the kernel is constituted by macro and micronutrients distributed
180 in the pericarp, germ, and endosperm. Among the macronutrients, starch, non-
181 starch polysaccharides, proteins, and lipids are distributed heterogeneously in the
182 maize kernel. Respect to micronutrients, recent studies have shown that maize
183 kernel is rich in vitamins, minerals, carotenoids, phenolic compounds, phytosterols,
184 phospholipids, arabinoxylans, among other phytochemicals. Moreover, during the
185 last four decades, research works have emphasized into increase the nutritional
186 potential of maize kernels by generating new types of corn as quality protein maize
187 (QPM) and High-oil hybrids (HOC).
188
189 MACRONUTRIENTS OF MAIZE
190 On the basis that kernel composition varied within and between maize varieties,
191 an average maize kernel contains about 72% of carbohydrates, 9% of proteins, 5%
192 of lipids, and 2% of fiber [25, 31].
193
194 Carbohydrates
195 Carbohydrates in maize kernels could be found in the forms of starch, sugar,
196 and non-starch polysaccharides (NSPs) [26]. Starch is the major carbohydrate and
197 makes up around 72% of the total kernel weight and 85% of the kernel endosperm
198 weight. The non-starch polysaccharides (contained in both the endosperm and
199 pericarp layers) are principally cellulose, hemicellulose, and pectin [32].
200 Starch is found in the cells of the endosperm in the form of granules whose
201 shape and size are characteristic of the grain species. Starch consists primarily of
202 D-glucose linked together to form two kinds of polymers: amylose and
203 amylopectin. Amylose is a smaller linear polymer of D-glucopyranose linked
204 together with α-1,4-glycosidic bond and amylopectin. On the other is a larger
205 branched polymer with linear α-1,4-glycosidic bond and branches connected by α-
206 1,6-glycosidic bonds. Starch from the most commercialized corn (dent or flint) is
207 composed of 27% amylose and 73% amylopectin. However, this proportion can be
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208 altered by genetic modifications. In fact, according to the genotype of maize, the
209 amylose content could vary from 0% to 73%. For example, waxy corn (WCS) is
210 composed of 1% amylose and 99% amylopectin, whereas high amylose corn
211 (HACS) has 55%–70% amylose with only 30%–45% amylopectin [25, 32]. In
212 recent years, nutritional quality and health considerations around starch have
213 centered on glycemic index and response. Corn starch differs in its glycemic profile
214 depending on its ungelatinized or gelatinized state, whether it has been cooled and
215 retrograded, or what kind of food matrix form is found [32]. Therefore, in addition
216 to the content and the kind of starch, the further processing of corn kernel impacts
217 directly on its nutritional quality.
218 Maize kernels contain around 1% to 3% of sugars, being sucrose (glucose-
219 fructose, α-1, 2 glycosidic bonds), maltose (glucose-glucose, α-1, 4 glycosidic
220 bond), glucose, fructose and raffinose (galactose, glucose and fructose) the most
221 representatives. These free sugars are almost exclusively located in the germ, with
222 only 25% present in the endosperm. In the embryo, sugars occur to a greater extent
223 as disaccharides [25, 26].
224 Cellulose, hemicellulose, and pectic substances are major non-starch
225 polysaccharides present in corn kernels, particularly in the pericarp. Cellulose is a
226 linear polysaccharide of β-D-glucopyranose connected by β (1→4) glycosidic
227 bonds. Cellulose content varies among phenotypes, e.g. yellow corn contains only
228 1.7% cellulose [33]. By regarding the composition of corn bran, cellulose represents
229 around 23% of total weight [34]. Hemicellulose consists of heterogeneous groups
230 of pentose and hexose sugars, including xylose, mannose, glucose, and galactose in
231 the backbone chain, and arabinose, galactose, glucose, and glucuronic acid in
232 branches [32]. Its content in corn kernel varied among 5.8–6.7%, and it represents
233 around 70% of the total weight of corn bran [35]. The main hemicelluloses in bran
234 are arabinoxylans and glucuronoxylans. Both have a xylan backbone and a diverse
235 group of derivative units. The xylan backbone is composed of β-D-xylopyranose
236 linked by β (1→4) glycosidic bonds, and the derivative units of the backbone
237 include arabinose, trisaccharides composed of arabinose, 4-O-methylglucuronic
238 acid, xylose, and galactose [34]. Pectins are complex polymers of α-D-(1→4)
239 galacturonic acid with occasional rhamnopyranosil residues bound in different
240 points of the linear chain. In the corn kernel, pectin quantity represents around 0.2%
241 (dry basis) [32, 36].
242 Crude fiber is composed of pectic substances, hemicellulose, cellulose, and
243 lignin, which constitute the cell wall and other non-structural materials of corn
244 kernel [26]. Pericarp fiber and endosperm fiber are the two kinds of fiber in the corn
245 kernel, mainly differentiated by the ratio of xylose to arabinose [37]. In common
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246 maize varieties, insoluble fiber is generally 12%, while soluble fiber is less than 2%
247 [25].
248
249 Lipids
250 Lipids are important nutritional components of the corn kernel, ranging from
251 3.5% to 6% of the total kernel weight. The germ is the most important reserve of
252 lipids with around 76-83% of complete kernel content, followed by the endosperm
253 with 14%–23%, the aleurone layer with 13%–15%, the pericarp with 1%–2%, and
254 the tip cap with <1% [25, 38]. Lipid composition of corn kernel include
255 triacylglycerols, phospholipids, glycolipids, phytosterols (sterols and stanols), free
256 fatty acids, hydrocarbons, carotenoids, tocols (tocopherols and tocotrienols),
257 sphingolipids and waxes [38].
258 Triacylglycerols are the major storage form of kernel lipids. In corn oil, about
259 60% of fatty acids are polyunsaturated, followed by 25% and 15% of
260 monounsaturated and saturated fatty acids, respectively. Among unsaturated fatty
261 acids in maize oil, linoleic (34%-65%), oleic (20%-42%), and palmitic acid (8-
262 16%) are the most predominant. Trace amounts (<1%) of lauric, myristic, margaric,
263 margaroleic, arachidic, gadoleic, behenic, erucic, and lignoceric acids have been
264 found in maize oil [25, 39]. Oils with a high proportion of oleic or linoleic acid and
265 reduced amounts of palmitic and stearic acids are desired and often recommended
266 to reduced heart blockages. Table 3 shows the average fatty acid composition of
267 maize oil.
268
269 Table 3. Typical fatty acid composition of maize oila
Acid name
% Total fatty acids
(abbreviation)
Palmitic (C16:0) 8.6–16.5
Palmitoleic (C16:1) 0.0–0.5
Stearic (C18:0) 0.0–3.3
Oleic (C18:1) 20.0–42.2
Linoleic (C18:2) 34.0–65.6
Linolenic (C18:3) 0.0–2.0
Eicosanoic (C20:0) 0.0–0.1
a Adapted from Barrera-Arellano D. et al. [39]
270
271
272 Phospholipids are functional constituents of cell membranes; they are
273 composed of glycerol, fatty acids, phosphate, and an organic base. Maize oil
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274 contains around 0.7% to 2.0% of phospholipids, being phosphatidylcholine,
275 phosphatidylinositol, and phosphatidylethanolamine the most predominant. The
276 minor phospholipids in maize grain are phosphatidylglycerol,
277 diphosphatidylglycerol, phosphatidylserine, phosphatidic acid, and N-
278 acylphosphatidylethanolamine [38, 40].
279 The glycolipids are formed when a 1,2-diacyl-sn-3-glycerol is linked via the
280 sn-3 position to a carbohydrate molecule. The major glycolipids of maize grain are
281 monogalactosyl-diacylglycerols (MGDG), digalactosyldiacylglycerols (DGDG),
282 and sulfoquinovosyldiacylglycerols (SQDG) [38, 40].
283 Corn oil contains 1.3%–2.3% of unsaponifiable lipids, including mainly
284 hydrocarbons, phytosterols, phytostanols, carotenoids, and tocols (tocopherols,
285 tocotrienols) [41, 42]. Squalene is the major hydrocarbon presented mainly in
286 aleurone and fiber layers of corn [43]. Phytosterols and phytostanols are mainly
287 located in pericarp and endosperm maize fractions. Corn oil contains approximately
288 1% of phytosterols, which could be found in free (about 58%) and esterified with
289 fatty acids (42%) forms. The main phytosterols are β-sitosterol (55%–67%),
290 campesterol (19%– 24%), stigmasterol (4%–8%), and -5-avenasterol (4%–8%)
291 [44, 45]. Phytostanols are localized mainly in the endosperm fraction, being the
292 most predominant in maize oil, sitostanol (77%– 87%), and campestanol (13%–
293 23%) and stigmasterol (4%–10%) [38, 42].
294 Vitamin E consists of tocopherols and tocotrienols, collectively known as
295 tocols. Both classes of compounds are subdivided into four lipophilic isomers (α-,
296 β-, γ-, and δ-) that are naturally found in several vegetable oils. Refined corn oil
297 contains around 0.08% to 0.12% of tocopherols, being the most predominant γ-
298 tocopherol, followed by α-tocopherol and δ-tocopherol [46]. The tocotrienols differ
299 from the tocopherols in having three double bonds in the isoprenoid side chain.
300 Usually, maize contains α-, δ- and γ- tocotrienols, being the last one the most
301 abundant in oil extracted from the whole kernel. The germ contains the major
302 proportion of tocopherols, and endosperm contains the most content of tocotrienols
303 [38, 47].
304 The sphingolipids are a class of lipids containing a long-chain base (commonly
305 sphingosine), fatty acids, and various other compounds, such as phosphate and
306 monosaccharides. The lipid group includes ceramides and glycosylceramides,
307 being 1-O-glucosyl-N-20- hydroxyeicosanoyl-4,8-sphingadienine and 1-O-
308 glucosyl-N-20-hydroxytetracosanoyl-4-hydroxy-8-sphingenine the most
309 representative sphingolipids in corn [40, 48].
310 Waxes are esters of fatty acids and long-chain alcohols. Simple waxes are esters
311 of medium-chain fatty acids (16:0, 18:0, 18:19), and long-chain aliphatic
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Maize as a superfood
312 alcohols. Complex waxes are formed from diols or alcohol acids [40]. The kernel
313 wax is composed mainly of esters (76%), being C46 (21%), C48 (22%), C50 (9%),
314 C52 (10%), and C54 (17%) the dominant chain lengths of the esters. Respect to
315 alcohols, it has been identified C22 (16%), C24 (30%), C26 (10%), C32 (15%) as
316 the major components. In the case of acids, C22 (48%) and C24 (37%) has been the
317 foremost recognized [38]. Corn oil contains about 0.05% of waxes, especially
318 miricil esters. Cutin is a polyester matrix composed mainly of glycerol and long-
319 chain (C16 and C18) fatty acid monomers [49]. According to the study of Espelie
320 K.E. et al. [50] -hydroxylated acids constituted the major class of monomers being
321 -OH-18:1 (51%), diOH-16:0 (20%), 9,10,18-triOH-18:0 (7%), and -OH-16:0
322 (6%). Waxes and cutin provide mechanical strength and protect the kernel from
323 environmental damages as extreme temperatures, UV radiation, and pathogens (e.g.
324 Aspergillus flavus).
325
326 Nitrogenous Compounds
327 The nitrogenous compounds in maize kernel can be divided mainly into protein
328 and non-protein nitrogenous compounds. Amino acids and amides, found mainly
329 in the aleurone layer and the germ, represent the most non-protein nitrogenous
330 compounds. Among free amino acids, the most abundant has been identified as
331 asparagine, glutamine, proline, and alanine. Proteins play important roles in
332 germination, maturation, and storage for the kernel. Albumins, globulins,
333 prolamins, and glutelins represent the main categories of proteins in corn kernel,
334 which are mainly found in the endosperm (70%-79%) and the germ (18%-28%).
335 Average protein content in normal corn kernel ranges between 6% and 12% (dry-
336 weight basis) [25, 26, 34].
337 Albumins are found in minor amounts. They contribute about 7% of the kernel
338 nitrogen, being leucosin the most important albumin in corn grain [25, 26].
339 Globulins contribute about 5% nitrogen of the kernel nitrogen. In germ, they
340 represent 10 – 20% of embryo proteins, and in the starchy endosperm, only small
341 quantities of storage globulins have been identified. The main identified globulins
342 of corn kernel have been mayzin, legumin-1, and α-globulin [26, 51-54]. Glutelins
343 are endosperm-specific proteins. They account for 35%-40% of the protein in the
344 mature corn kernel, being zeanin the most abundant [25, 55]. Prolamins are the
345 primary storage proteins of most cereals. In the case of corn, they accumulate
346 mainly in the starchy endosperm, and they provide about half of the total kernel
347 nitrogen, [54]. Among prolamins, zeins are by far the most abundant storage
348 proteins of the endosperm (60%–70%). Structurally, zeins are divided into three
349 types: α, β-, and γ-zeins. Zein proteins are low in lysine and tryptophan, which are
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350 essential amino acids for human survival. Albumins, globulins, and glutelins are
351 higher in lysine (5%–6%), compared to zeins (0.1%), but they are less abundant
352 [55]. Therefore, in general it is considered that common corn kernel has poor quality
353 proteins as staple food or feed. Fortunately, a natural mutation called opaque2 alters
354 the ratio of zeins to nonzeins in the seed, resulting in kernels with increased
355 concentrations of lysine and tryptophan, and the resulting maize varieties and
356 hybrids are called Quality Protein Maize (QPM). QPM contains almost twice as
357 much lysine and tryptophan than regular counterparts [56].
358
359 MICRONUTRIENTS
360 Maize kernels supply many micronutrients necessary for human metabolic
361 needs, being the pericarp, germ, and aleurone layer the anatomical parts that contain
362 the highest concentration of most of them [57].
363
364 Vitamins
365 Vitamins are vital micronutrients that cannot be synthesized endogenously or
366 in insufficient amounts. Commonly classified as water-soluble or fat-soluble, they
367 act as cofactors for enzymes that play fundamental roles in human metabolism. The
368 water-soluble vitamins include ascorbic acid (vitamin C), thiamin (B1), riboflavin
369 (B2), niacin (B3), pantothenic acid (B5), pyridoxine (B6), biotin (B8), folic acid (B9)
370 and cobalamine (B12). And the fat-soluble vitamins include vitamins A, D, E, and
371 K [58, 59].
372 Water-soluble vitamins are found mainly in the aleurone layer, followed by the
373 endosperm and germ [25]. Corn provides significant quantities of most B-vitamins;
374 however, mature corn kernel lacks vitamins B12 and C. Moreover, specifically in
375 the case of niacin (B3), if the corn kernel is not properly processed (e.g as
376 nixtamalization), this vitamin is biologically unavailable [25]. Table 4 shows the
377 average composition of water-soluble vitamins of common maize.
378 Fat-soluble vitamins play integral roles in a multitude of physiological
379 processes such as vision, immune function, bone health, and coagulation [60]. In
380 corn kernel, fat-soluble vitamins are mainly found in the aleurone layer and the
381 germ. Provitamin A (carotenoids) are mainly located in the endosperm in an
382 average of 2 µg/g [57, 61]. Vitamin E, which is exclusively acquired from the diet,
383 occurs in significant amounts in the germ of corn kernels. Native corn contains
384 around 3.11 µg/g of vitamin E. Respect to vitamins D and K; corn contains a meager
385 amount (0–10 µg/100 g) [57].
386
387
 13
Maize as a superfood
388 Table 4. Water-soluble vitamins of common maizea
Water-soluble Content Physiological functions
vitamin per 100 g
Thiamin (B1) 0.385 mg Serves as a coenzyme for enzymes like
ketoglutarate dehydrogenase and transketolase,
helps to maintain proper functioning of the heart
and nervous and digestive systems
Riboflavin 0.201 mg Acts as a coenzyme in oxidation and reduction
(B2) reactions, as prosthetic group of flavo proteins
Niacin (B3) 3.63 mg Acts as a coenzyme in oxidation and reduction
reactions, as a functional part of NAD+ and
NADP+
Pantothenic 0.424 mg The functional part of coenzyme A and acyl
acid (B5) carrier protein, synthesis and β-oxidation of fatty
acids, synthesis of cholesterol, steroid hormones,
vitamins A and D, synthesis of several amino
acids and δ-aminolevulinic acid.
Pyridoxine 0.622 mg Acts as a coenzyme in transamination and
(B6) decarboxylation of amino acids and glycogen
phosphorylase, synthesis of niacin from
tryptophan, synthesis of several
neurotransmitters, and synthesis of δ-
aminolevulinic acid, inhibits receptor affinity to
DNA and thereby modulates steroid activity.
Folic acid (B9) 19 µg Acts as a coenzyme in the transfer of one-carbon
groups, essential in the de novo synthesis of
nucleotides, metabolism of several amino acids,
as an integral component for the regeneration of
the universal methyl donor
389 aAdapted from Nuss E.T. and Tanumihardjo S.A. [25] and Syeda Juveriya F. et al.

390 [59]

391 Minerals
392 Minerals are inorganic elements found in small or trace amounts in dietary
393 constituents. Based on the amount present in the human body, they are classified as
 14
Pech-Almeida et al.
394 major and trace minerals. Major minerals are those present in the body in amounts
395 greater of 5 g (e.g. calcium, phosphorus, magnesium, and potassium) and trace
396 minerals are those daily required in few milligrams or even micrograms (e.g. iron,
397 zinc, copper, manganese, selenium, iodine, among others) [62]. In the corn kernel,
398 the highest concentration of minerals is found in the pericarp, germ, and aleurone
399 layer, and they constitute <2% of the corn kernel. The germ contains nearly 80% of
400 the total minerals of the kernel, and the endosperm has less than 1% [25, 57].
401 The most prevalent major minerals found in maize are phosphorus (P),
402 potassium (K), and magnesium (Mg), providing nearly 85% of kernel mineral
403 content. Respect to calcium (Ca), corn is a poor source of this mineral (1–
404 17mg/100g) [63]. Among the major minerals, phosphorus is the most abundant
405 (300mg/100g). However, it is mainly found in the form of phytate. About 90% of
406 phytates are located in the germ, 3% in the endosperm, and about 10% in the outer
407 layers [25, 64]. Even if phytic acid has an important physiological role in seeds as
408 a storage compound for phosphate, in food and feed, it is considered as a non-
409 nutritional factor because it chelates minerals rendering them unavailable to the
410 digestive system [65]. To make the phytate-bound minerals biologically available,
411 phytate must be hydrolyzed by 60%–70% [66]. Germination and nixtamalization
412 had shown good results in hydrolyzed phytic acid content in corn kernels [67, 68].
413 Potassium (K) and magnesium (Mg) content in corn is about 287 mg/100g and 127
414 mg/100g, respectively. Magnesium is mainly located in the aleurone layer of corn
415 (87%) as Ca5Mg phytate or as potassium-magnesium phytate [62, 69].
416 Among trace minerals, iron (Fe) and copper (Cu) are mostly found in the bran.
417 Fe content average 2.5 mg/100 g, and Cu ranging from 0.2 to 0.31 mg/100g [70].
418 Zinc (Zn) content average 20 μg/g, and it is mainly found in the endosperm,
419 aleurone, and the scutellum [25, 66]. Selenium (Se) content an average of 9.5
420 µg/100 g, and it is mainly concentrated in the germ [63]. Manganese (Mn) content
421 average of 3.65 mg/100g.
422 Even though maize kernels supply many vitamins and minerals necessary for
423 human metabolic needs, the amounts of some of them are inadequate for consumers
424 that use maize as a staple food. Therefore, the enrichment of cereal-based food is
425 aimed toward the replacement of essential minerals (Fe and Zn) and vitamins
426 (thiamine, riboflavin, niacin, and folic acid) [25, 71].
427
428 BIOACTIVE COMPOUNDS IN MAIZE
429 Whole grain has a wide range of phytochemicals exhibiting health benefits.
430 Corn phytochemicals include phenolics, flavonoids, carotenoids, anthocyanins,
431 phytosterols, phospholipids, policosanols, arabinoxylans, among others.
 15
Maize as a superfood
432 Phenolics compounds
433 Plant phenolics include simple phenols, phenolic acids, flavonoids,
434 anthocyanins, stilbenes, tannins, lignans, and lignins. Phenolics are characterized
435 by possessing one common structural feature, a phenol (an aromatic ring bearing at
436 least one hydroxyl substituent). According to their chemical structure, phenolics
437 have been divided into polyphenols and simple phenols (phenolic acids) [72].
438 Phenolics compounds are the most widely distributed secondary metabolites
439 present in corn, mainly found in the pericarp and the monolayered aleurone cell
440 walls [73, 74].
441 Corn contains an average concentration of 255 mg/100g simple phenolics,
442 including caffeic, cis-p-coumaric, trans-p-coumaric, p-hydroxybenzoic, (p-
443 hydroxyphenyl) acetic, protocatechuic, syringic, vanillic, trans-sinapic, syringic,
444 gallic, and ferulic acids (cis-ferulic, trans-ferulic). The major phenolic compounds
445 from maize are ferulic acids, representing about 70% of the total phenolics
446 compounds [4-6].
447
448 Pigments
449 Pigments are chemical compounds that absorb light in the wavelength range of
450 the visible region. Natural pigments of foods can be classified into four groups: the
451 green chlorophylls, the yellow-orange-red carotenoids, the red-blue-purple
452 anthocyanins, and the red betanin [75]. Corn kernels can be found in a wide range
453 of colors as white, yellow, orange, red, purple, blue, and brown. All these variations
454 may result from genetic differences in pericarp, germ, and endosperm structures.
455 The pericarp can be colorless, orange, cherry red, red, dark red, brown, or
456 multicolored. The germ can be colorless, yellow, orange-red, or purple. And the
457 endosperm can be either colorless, yellow, orange, or orange-red [76]. In mature
458 corn kernel, both carotenoids and anthocyanins are the natural pigments that occur
459 in the largest amounts.
460
461 Carotenoids
462 Carotenoids, which are a provitamin A, are lipid-soluble compounds comprised
463 of eight isoprenoid units whose order is inverted at the molecule center. They are
464 classified by their chemical structure in two groups: (1) carotenes that are
465 constituted by carbon and hydrogen and (2) oxycarotenoids or xanthophylls that
466 have carbon, hydrogen, and, additionally, oxygen [75]. In corn kernel, the
467 predominant carotenes are α-carotene and β-carotenes, and respect to xanthophylls,
468 lutein, zeaxanthin, and β-Cryptoxanthin are the most prevalent.
 16
Pech-Almeida et al.
469 White corn has low levels of total carotenoids with only 3 mg/g of total
470 carotenoids. In contrast, yellow genotypes contain significant amounts of both
471 carotenes and xanthophylls, especially high-carotenoid kernels contain up to 66 and
472 95 mg/g of total carotenoids [77-79].
473 In common yellow dent corn, the total carotenoid content range of 5–80 mg/kg
474 [7]. The yellow color results from the content of carotenoid pigments in the horny
475 endosperm (74%–86%), floury endosperm (9%–23%), germ (2%–4%), and
476 pericarp (1%), being xanthophyll pigments the major responsibility of the color [38,
477 80]. Lutein and zeaxanthin account for 90% of the total carotenoid pigments [81].
478 In red corn, according to Corrales-Bañuelos A.B. et al. [82] total carotenoid content
479 range from 1.49 to 3.49 mg of lutein equivalents per kg dry weight.
480
481 Anthocyanins
482 Anthocyanins are one of the major groups of pigments belonging to the
483 secondary metabolite group of flavonoids. The basic C6-C3-C6 anthocyanin
484 structure is the source of an infinity of colors, from scarlet to blue, produced by its
485 chemical combination with glycosides and/or acyl groups and by its interaction
486 with other molecules and/or media conditions [75]. In fact, according to Urias-
487 Peraldí M. et al. [83], anthocyanin concentrations in maize are sensitive to
488 environmental conditions, growing location, and stresses such as drought and
489 environmental temperatures, especially during grain development and maturation.
490 The term blue corn is used to describe corn varieties that may display colors
491 ranging from light to dark blue as well as red or purple. Blue coloring in corn
492 kernels is due mainly to the presence of anthocyanins (e.g. cyanidin, pelargonidin,
493 and peonidin) in the aleurone layer or pericarp [25, 84].
494 According to various research studies, total monomeric anthocyanin content
495 varied widely in colored corn, being reported values from 51 mg cyanidin-3-
496 glucoside (C3G) equivalent/kg in red corn to 1300–16,400 mg e.q. C3G/kg in
497 purple corn and 368 mg eq. C3G/kg in blue corn [85-87].
498 The main anthocyanins in colored corn are cyanidin, malvidin, pelargonidin,
499 and peonidin based monoglucosides, malonyl and dimalonyl glucosides, and
500 flavonol anthocyanin condensed forms. Among them, the cyanidin is considered
501 the main anthocyanin in colored corn, being cyanidin 3-glucoside the major
502 anthocyanin present in blue corn, representing 75% of the total anthocyanins
503 content [6, 88]. Other predominant anthocyanins in colored corn, include peonidin-
504 3-O-glucoside, peonidin-3-(60-malonylglucoside), peonidin-3-
505 (dimalonylglucoside), peonidin-3-(600- ethylmalonylglucoside), pelargonidin-3-
506 glucoside, pelargonidin-3-(600- malonylglucoside), cyanidin-3-(600-
 17
Maize as a superfood
507 malonyglucoside), cyanidin-3-O-glucoside-2-malonylglucoside, cyanidin-3-(600-
508 succinylglucoside) and cyanidin-3-(600-disuccinylglucoside) [86, 89, 90].
509
510 Policosanols
511 Policosanols are nutraceuticals that consist of long-chain primary aliphatic
512 alcohols derived from plant wax. Total policosanol content of corn kernels varied
513 from 15.2 to 20.5mg/kg, being dotriacontanol, triacontanol, and tetracosanol, the
514 major identified components in corn kernels. Corn pericarp presented higher
515 contents of policosanols (72.7–110.9 mg/kg) than the endosperm (4.0–16.2 mg/kg)
516 and germ (19.3–37.1 mg/kg) fractions [91]. Recent studies have shown anti-
517 hypercholesterolemia and antioxidant activity [92].
518
519 Arabinoxylans
520 Arabinoxylans are the main soluble fiber components of corn. Arabinoylans
521 have a β-(1→4) xylan backbone, and, in its simplest form, β xylopyranosyl units of
522 the backbone are branched with α-arabinofuranose units at their O-2 and/or O-3
523 positions. The corn fiber arabinoxylans yield ranges from 19% to 39%, and they
524 are mainly found in the cell wall material from the endosperm and in the bran [32,
525 57].
526
527 FUNCTIONAL PROPERTIES OF MAIZE
528
529 Maize is a rich source of phytochemicals, for instance, phenolics acids, and
530 carotenoids. The phytochemical compounds derived from maize and their health
531 properties have recently become the major focus of studies. Table 5 describes
532 several properties attributed to phytochemicals present in maize or its derived
533 products.
534 ANTIOXIDANT ACTIVITY
535 The antioxidant activity in maize is one of the most reported biological
536 activities. This activity is related to phytochemicals, such as carotenoids and
537 phenolic compounds. For instance, Beta T. and Hwang T. [93] reported the
538 presence of β-carotene, β-cryptoxanthin, zeaxanthin, and lutein in orange corn
539 flour. Also, identify the presence of ferulic acid. Methanolic extracts of orange corn
540 flour demonstrated the capacity to scavenge free radicals such as ABTS and DPPH.
541 On the other hand, blue maize flour extracts could scavenge ABTS free radical
542 and showed ferric reducing power. The antioxidant activity of blue maize was
543 related to its anthocyanin content [31]. Moreover, Salinas-Moreno Y. et al. [8]
544 analyzed 18 blue corn varieties, for their DPPH scavenging capacity, finding high
 18
Pech-Almeida et al.
545 discoloration activity in all samples, attributing the antioxidant capacity to
546 anthocyanins.
547 Maize beverage enriched with 9% of nejayote solids (the liquid resulting from
548 alkaline cooking of maize) presented antioxidant activity, as measured by nitric
549 oxide inhibition. The activity was attributed not only to the phytochemicals in
550 maize, but also to the ferulic acid contained in nejayote [94].
551 Zavala-López M. et al. [95] reported that teosinte, an ancient corn variety, is
552 rich in phenolic compounds, and present high antioxidant activity.
553 Derived products of maize, such as tortillas and protein concentrates, have also
554 shown antioxidant capacity [9, 96]. Corn tortillas from yellow and red kernels had
555 antioxidant activity related to the presence of carotenoids. Although yellow grains
556 had more quantity of carotenoids than red ones, both tortillas presented high
557 antioxidant capacity as measured by the ORAC method [82]. Blue corn tortillas
558 contain a variety of phenolic compounds, then their antioxidant capacity is high
559 against DPPH free radical and also can inhibit lipid peroxidation [9].
560
561 ANTICANCER ACTIVITY
562 Due to the variety of phytochemicals present in corn kernels, anticancer activity
563 was evaluated by several authors [96-98]. Herrera-Sotero M.Y. et al. [9] evaluated
564 the antiproliferative capacity of blue corn and tortilla extracts against hepatocellular
565 carcinoma (HePG2), lung carcinoma (H-460), mammary adenocarcinoma (MCF-
566 7) and prostate cancer androgen-dependent (PC-3) cells. The effective
567 concentration tested was 1000 μg/mL. The presence of anthocyanins and
568 proanthocyanidins were detected in blue corn and tortilla preparations [9].
569 Not only phenolic compounds in maize are potential anticarcinogenic agents
570 but also bioactive peptides. Díaz-Gómez J.L. et al. [96] suggested several
571 mechanisms through bioactive peptides could act, such as apoptosis induction,
572 caspase modulation, p53 restoration, regulation of cellular mechanisms related to
573 cell proliferation among others. Moreover, Díaz-Gómez J.L. et al. [97] evaluated
574 the cytotoxicity of zein hydrolysates on HepG2 cells, suggesting that peptides
575 contained in the hydrolysates could induce apoptosis. HepG2 cells were also used
576 by Ortiz-Martinez M. et al. [98] to evaluate maize protein hydrolysates achieving
577 similar conclusions, as the mechanisms responsible for anticancer activity was
578 apoptosis induction.
579
580 ANTIHYPERTENSIVE ACTIVITY
581 Hypertension is one of the most common diseases in the world. Chinese and
582 North American natives used corn silk tea to low blood pressure. Corn silk has been
 19
Maize as a superfood
583 claimed to have several benefits to human health, such as anti-inflammatory,
584 reducing edema, and obesity. Several authors had studied corn silk to evaluate its
585 antihypertensive activity and look for its mechanism of action [10, 99-101].
586 Li C.C. et al. [10] studied corn silk extract, prepared in boiling water, finding a
587 significant reduction of blood pressure. These authors used spontaneously
588 hypertensive rats. Moreover, no secondary effects were observed under the
589 subchronic usage of corn silk tea. An interesting finding was a phyto-peptide
590 present in corn silk that could be responsible for the antihypertensive effect through
591 inhibition of the angiotensin-converting enzyme.
592 More studies on peptides found in corn proteins have been done by Puchalska
593 P. et al. [101] and Puchalska P. et al. [100]. After extracting zein, it was digested to
594 produce several peptides, including three highly antihypertensive peptides (LRP,
595 LQP, and LSP), which were identified by liquid chromatography coupled to mass
596 spectrometry [100]. Furthermore, corn germ meal protein was hydrolyzed to
597 produce peptides with angiotensin-converting enzyme inhibitory activity [102].
598 These peptides also had antihypertensive activity in vivo, as tested in spontaneously
599 hypertensive rats.
600
601 OTHER BIOLOGICAL ACTIVITIES
602 There are some other activities reported for corn, corn silk, and other corn
603 products, such as anti-diabetic, antiobesogenic, and anti-inflammatory (Table 5).
604 Nessa F. et al. [103] tested polar and non- polar extracts against twelve
605 pathogenic bacteria. Their findings demonstrated that chloroform extract was active
606 against five out of twelve bacteria, while methanolic extract was effective against
607 Bacillus and Salmonella. Similarly, Morshed S. and Islam S.M. [104] demonstrated
608 that the ethanol extract of corn silk was effective against Gram-positive and Gram-
609 negative bacteria.
610 On the other hand, Ramírez K. et al. [105] evaluated the antimicrobial activity
611 of phenolics contained in nejayote, the remaining liquid of nixtamalization, against
612 several bacterial strains. Their findings showed high activity against nejayote
613 against Salmonella typhimurium and Enterococcus faecalis.
614 Maize is a rich source of simple phenolics such as ferulic acid, which could
615 prevent the accumulation of fat in adipocytes. In this sense, Luna-Vital D. et al. [12]
616 showed that maize extract and ferulic acid at different concentrations could
617 modulate genes related to gluconeogenesis, adipogenesis and inflammation,
618 suggesting that not only ferulic acid but also anthocyanins could modulate obesity
619 by reducing adipogenesis and adipose inflammation, and promoting energy
620 expenditure.
 20
Pech-Almeida et al.
621 Regarding inflammation Zhang Q. et al. [11] and Zhang Q. et al. [13] reported
622 that phenolic compounds such as quercetin, luteolin and rutin had anti-
623 inflammatory and anti-diabetic compounds, which could modulate the production
624 of inflammation mediators.
625 Finally, corn and its diverse phytochemicals had several biological activities,
626 which could be beneficial to human health.
627 Table 5. Biological properties of phytochemicals present in maize and
628 its derivatives.
Functional property Part plant Phytochemical Reference
Carotenoids,
Flour [93]
phenolics
Phenolic
Roasted grain [94]
acids
Antioxidant Phenolics,
Grain flour [8, 31, 95]
anthocyanins
Grain tortillas Carotenoids [9, 82]
Grain protein Peptides [97, 106]
Wastewater Phenolics [105]
Leaf Phenolics [107]
Grain protein Peptides [96-98]
Grain and
Anticancer Anthocyanins [9]
tortillas
Methanolic
Corn silk [108]
extract
Anti-diabetic Seed Anthocyanins [11, 109]
Methanol and
Grain chloroform [104, 110]
extracts
Antimicrobial
Ethanol
Corn silk [103]
extract
Wastewater Phenolics [105]
Antiobesogenic Grain Phenolics [11, 12]
Grain protein Peptides
Antihypertensive [100, 101]
Corn silk
Anthocyanins
Purple maize quercetin,
Anti-inflammatory [11]
pericarp luteolin, and
rutin
 21
Maize as a superfood

629 ISSUES RELATED TO MAIZE CONSUMPTION:

630 MYCOTOXINS
631 Even if maize contains various phytochemicals linked to human health
632 benefits, many studies have shown that the consumption of fungal contaminated
633 maize could be associated to mycotoxicosis and health risks in both humans (e.g.,
634 esophageal cancer, neural tube defects) and farm animals (e.g.,
635 leukoencephalomalacia in horses and pulmonary edema syndrome in swine) [111].
636 In fact, the maize plant is easily infected via fungal attack during their development,
637 harvest, or after their harvest, which in most of the cases triggers the production of
638 mycotoxins [112].
639 The word mycotoxin is derived from 2 words: “mukes” referring to “fungi”
640 (Greek) and “toxicum” referring to “poison” (Latin). Mycotoxin is a broad term
641 that applies to secondary metabolites of fungi that grow in able substrates,
642 especially those with a special humidity content and available nutrients, such as
643 vegetables and grains [113]. Mycotoxins found in corn can be grouped according
644 to the fungi that produce them, being Fusarium, Aspergillus and Penicillium species
645 the major toxigenic fungi [114]. The Fusarium species includes the most
646 widespread toxigenic fungi in corn. The Aspergillus species are associated with the
647 most serious human health impacts for mycotoxin contaminated corn, and
648 Penicillium species are secondarily important because they are not aggressive
649 pathogens [115]. Table 6 shows the major fungi species reported in the corn kernel.
650
651 Table 6. Major fungi species reported in the corn kernel. Adapted
652 from Munkvold G.P. et al. [115]
Fungi species in the corn kernel
Genus Species
Fusarium Fusarium graminearum, Fusarium proliferatum, Fusarium
subglutinans, Fusarium temperatum and Fusarium verticillioides
Aspergillus A. alliaceus, A. chevalieri, A. flavus, A. glaucus, A. nomius, A.
ochraceus, A. parasiticus, A. restrictus, A. rubrobrunneus, A.
sulphureus, A. sydowii, A. pseudotamarii, A. ustus and A.
versicolor
Penicillium P. brevi-compactum, P. chrysogenum, P. citrinum, P. cyclopium,
P. expansum, P. frequentans, P. funiculosum, P. oxalicum, P.
purpurogenum, P. urticae, P. variabile, P. verrucosum and P.
viridicatum
 22
Pech-Almeida et al.
653 One special fact about fungi and their metabolites is that even though swift
654 growth of a particular mold can occur on a substrate, it is not a prerequisite that the
655 mold should produce a mycotoxin. For example, Fusarium molds grow prolifically
656 at temperatures of 25 to 30 °C without producing any mycotoxin, but at near-
657 freezing temperatures, large quantities of mycotoxins are produced without much
658 mold growth [113]. In corn the most important mycotoxins are aflatoxins (AFs),
659 ochratoxins (OTs), fumonisins (FBs), trichothecenes (especially T-2 toxin and
660 deoxynivalenol-DON), and zearalenone (ZEN). When talking about incidence data
661 of mycotoxins on different food matrices across the globe, in Africa and the Asian
662 subcontinents, AFs are the major toxins; in Australia, they are AFs and FUM; in
663 North America, they are AFs, OTs, ZEN, and DON; in South America, they are
664 AFs, FUM, OTs, DON, and T-2 toxin; in Eastern European countries, they are ZEN
665 and DON; and in Western European regions they are OTs, ZEN, and DON [113].
666
667 Aflatoxins (AFs)
668 Aflatoxins possess a high acute and chronic toxicity due to their capacity to
669 bind nucleic acids and cellular nucleoproteins, resulting in deleterious effects on
670 protein synthesis and cellular integrity. They are considered potent hepatotoxins
671 with high genotoxic activity, and they are responsible for hepatocarcinoma [116].
672 They are mainly produced by Aspergillus species, especially A. flavus and A.
673 parasiticus. In maize, the most common types of aflatoxins are B1, B2, G1, G2,
674 and M1, being aflatoxin B1 (AFB1), the most toxic and carcinogenic [117].
675
676 Fumonisins (FBs)
677 Fumonisins are the most recently isolated mycotoxins (first discovered in 1988)
678 that are known to possess high cancer-inducing properties. These toxins were
679 originally isolated from Fusarium verticillioides and Fusarium proliferatum [113].
680 Among the number of different types of fumonisins, B1, B2, and B3 fumonisins are
681 the major forms found in food. In corn, fumonisin B1 (FB1), the diester of propane-
682 1,2,3-tricarboxylic acid and 2-amino-12,16-dimethyl- 3,5,10,14,15-
683 pentahydroxyeicosane, is the most prevalent. Moreover, in the specific case of FB1,
684 in addition to its carcinogenicity, this compound has also revealed immunotoxic,
685 hepatotoxic, pneumotoxic, and nephrotoxic activities [116].
686
687 Ochratoxins (OTs)
688 Ochratoxins (OTs) are a family of mycotoxins (OTA, OTB, and OTC) that can
689 be produced by species of Aspergillus and Penicillium. They are characterized by
690 containing a phenylalanine and dihydroisocumarin moiety joined by a peptide bond
 23
Maize as a superfood
691 [118]. Among ochratoxins family, ochratoxin A (OTA) is considered the most
692 commonly occurring member and a potent toxin; it has presented nephrotoxic,
693 hepatotoxic, teratogenic, and immunosuppressive activities [119]. OTA is mainly
694 produced by Aspergillus ochraceus and Penicillium verrucosum [113]. In cereals,
695 ochratoxins generally appear during storage, and its degradation is particularly
696 complex because they are especially heated stable. Under normal conditions of
697 cooking OTA is partially degraded, and even at 250 °C its destruction is not
698 completed [113, 120, 121].
699
700 Zearalenone (ZEN)
701 Zearalenone (ZEN) is a metabolite produced by Fusarium species, which
702 commonly contaminate most of the cereals [113]. This molecule is a potent fungal
703 estrogen, rather than a toxin. Because it has a special similarity to female hormones,
704 in humans it has been associated with precocious pubertal changes, and in animals
705 with feminizing syndromes. For example, in pigs, ZEN caused genital/urinatory
706 syndromes and atrophy of the testes [113]. To avoid its effects, the Joint FAO/WHO
707 Expert Committee on Food Additives (JECFA) has established a provisional
708 maximum tolerable daily intake for ZEN of 0.5 μg/kg of body weight [122].
709
710 Trichothecenes
711 Trichothecenes are sesquiterpenoid mycotoxins produced by several genera of
712 fungi, including Fusarium, Trichoderma, Trichotecium, Myrothecium,
713 Stachybotrys. Comprising over 160 different trichothecenes compounds, they are
714 classified into four groups (types A, B, C, and D) [123]. In corn, trichothecenes are
715 typical of type A (principally diacetoxyscirpenol -DAS, T-2 and HT-2 toxins) and
716 type B (principally nivalenol -NIV, deoxynivalenol -DON and
717 acetyldeoxynivalenol -Ac-DON) groups; being the group A the most toxic to
718 human and animals [113, 115]. Mycotoxicosis by trichothecenes, also known as
719 scabby grain toxicosis, has been reported to occur within hours after ingestion of
720 contaminated foods, showing symptoms in the range of abdominal pain, nausea,
721 vomiting, diarrhea, dizziness, and headache [113].
722
723 FOOD PROCESSING TECHNOLOGIES TO REDUCE
724 MYCOTOXINS CONTAMINATION IN MAIZE
725
726 Even if good agricultural practices and adequate storage conditions limit
727 mycotoxin levels in the maize food chain, they do not eliminate mycotoxins. Food
728 processing can further reduce mycotoxin levels by physical removal methods,
 24
Pech-Almeida et al.
729 thermal processing, chemical treatments, among others. Therefore, in this part of
730 the chapter, it will be considered the most common processing techniques to reduce
731 mycotoxins in maize.
732
733 Physical removal methods
734 Food processing can further reduce mycotoxin levels by physical removal of
735 contaminated material. In maize, the most applied methods are sorting, trimming
736 cleaning, and milling. The sorting, trimming, and cleaning do not destroy
737 mycotoxins, but they help to reduce its concentrations [124]. The specific
738 operations for cleaning include sieving, aspiration, separation by gravity or by
739 indented cylinders or discs, and/or scouring. Generally, it is custom to apply a
740 coarse cleaning before storage, followed by an intensive cleaning before milling
741 [125]. In maize, fumonisin concentrations were reduced up to 69% by the removal
742 of “fines” (< 3 mm) [126].
743 Milling mainly refers to particle size reduction and fractionation of cereal
744 grains. As for cleaning procedures, this operation does not degrade mycotoxins;
745 however, as mycotoxins tend to be concentrated in germ and bran fractions, both
746 wet and dry milling processes can redistribute them [124, 125]. In wet milling, to
747 facilitate germ separation and to break down of protein matrix, the first step
748 involves soaking of maize in water containing 0.1 to 0.2% SO2 (36-50 h at 50 °C)
749 [127]. Therefore, depending on the polarity of the mycotoxins, they may be
750 dissolved into the steep water or distributed among the byproducts of the process.
751 By the end of the wet milling process, mycotoxins can be mainly found in gluten
752 fiber and germ, while the starch tends to be relatively free of them [124]. In dry
753 milling, the highest concentrations of mycotoxins remain in germ and bran fractions
754 of maize; and fractions used for food production, including flaking grits and flour,
755 had the least amount of mycotoxins contamination [124].
756
757 Thermal Processing methods
758 Even if most of the mycotoxins are chemically and thermally stable, thermal
759 processing still the most important industrial treatment to reduce mycotoxins
760 content in finished products. In maize, reduction of mycotoxin contamination has
761 been mainly studied after cooking [128], canning, roasting [129], flaking [130],
762 nixtamalization [117, 131], extrusion [132], baking and frying [133].
763 Greater degradation of mycotoxins has been achieved under harsh thermal
764 processing (high amounts of heat energy during a long heating time), however,
765 these conditions have also triggered nutritional and organoleptic quality losses of
766 food. Therefore, in order to achieve the maximum degradation of mycotoxins at the
 25
Maize as a superfood
767 lowest possible temperature and time conditions, many studies have been targeting
768 to optimize these parameters. In this respect, Gbashi S. et al. [120] investigated the
769 thermal degradation patterns of multiple mycotoxins (aflatoxins, fumonisins,
770 zearalenone, ochratoxins, T-2 toxin, alternariol monomethyl ether -AME- and
771 sterigmatocystin – STERIG-) in pure form and spiked into maize flour. Their study
772 revealed that mycotoxins with compact molecular structural configuration were the
773 most relatively stable to heat treatment, like Ochratoxin-A (OTA); whereas the
774 more structurally spread-out mycotoxins were more thermolabile, like fumonisins
775 B1, B2, and B3. Moreover, the thermal stability of mycotoxins varied between pure
776 standards and spiked maize flour, showing that matrix interaction strongly
777 influenced the thermal stability of mycotoxins. Studied thermal processing
778 conditions ranged from 103.43 to 216.57 °C and from 6.72 to 63.28 min. And, the
779 optimal processing conditions to degrade pure multi-standards mycotoxins and
780 spiked maize were 216.57 °C during 63.28 min, and 210.85 °C during 54.71 min
781 respectively. Table 7 shows the optimum degradation conditions for each studied
782 mycotoxin.
783
784 Table 7. Optimal thermal treatment conditions for mycotoxin
785 degradation of pure standards and spiked maize matrix. Adapted from Gbashi
786 S. et al. [120]
Pure mycotoxin standard Spiked maize matrix
Optimal Optimal
Mycotoxin Temperature % of Temperature % of
and time degradation and time degradation
conditions conditions
Aflatoxin B1 100.00 ±
100.00 ± 0.00
0.00
Aflatoxin B2 100.00 ±
85.88 ± 5.59
0.00
Aflatoxin G1 216.57 °C/35 216.57 °C/35 100.00 ±
100.00 ± 0.00
min min 0.00
Aflatoxin G2 97.55d ±
100.00 ± 0.00
0.22
AME 62.66b ±
93.86±0.40
2.91
Fumonisin B1 100.00 ±
100.00±0.00
0.00
200 °C/15 min
Fumonisin B2 100.00 ±
100.00±0.00 200 °C/15 min
0.00
Fumonisin B3 216.57 °C/35 100.00 ±
100.00±0.00
min 0.00
 26
Pech-Almeida et al.
Ochratoxin A 58.78±0.63 93.84c±0.18
Ochratoxin B 50.50 ± 2.96 92.36c±0.13
STERIG 98.09d ±
100.00±0.00
216.57 °C/35 0.14
T2 97.53±0.89 min 95.61c±2.19
ZEA 100.00 ± 0.00 93.13c±0.30
α-ZEA 100.00 ± 0.00 96.90f±0.61
β-ZEA 100.00 ± 0.00 97.51e±0.37
787
788 Canning, also known as retorting, is the action of adding the food materials to
789 a metallic container (generally of aluminum), followed by high-temperature
790 processing [134]. In the case of maize mycotoxins, Castelo M.M. et al. [129]
791 showed that canning (121 °C for 60 min) of whole-kernel com and spiked cream-
792 style corn resulted in a decrease in fumonisins of 15% and 9% respectively.
793 On the other hand, corn flaking has also outcome the reduction of aflatoxins,
794 fumonisins, and ochratoxin content [124]. After cooking the corn grits with and
795 without sugars and toasting, the aflatoxins reduction varied between 77 to 85%
796 [135]. And when flaking corn was coupled to extrusion, a 60 to 70% of fumonisins
797 reduction was found, being identified that 30% of the overall reduction was linked
798 to extrusion stage [130]. Extrusion cooking considers the application of high
799 temperature and pressure by forcing a dough-like mixture through a stationary
800 metal tube or barrel by a rotating screw shaft. Through the generated high
801 temperature, pressure, and mechanical shear force, the food matrix is transformed
802 by chemical reactions and molecular modifications, being found the greatest
803 reductions of mycotoxin concentrations at temperatures ≥ 160 °C and longer
804 residence times [124]. Elias-Orozco R. et al. [136] showed that the extrusion
805 process of white corn naturally contaminated with aflatoxins, reduced the levels of
806 AFB1, AFM1, and AFB1- dihydrodiol by 46%, 20%, and 53% respectively.
807 Roasting, frying, and baking also reduced mycotoxins concentration on spiked
808 corn (5 µg of FB1/g). In the case of roasting, it has been reported that at 218°C for
809 15 min, fumonisins of naturally and artificially contaminated cornmeal were
810 reduced up to 98% [129]. Frying (190 °C for 15 min) also performed a 67 % loss
811 of fumonisins [133]. Contrary, baking (200 °C for 20 min) of corn muffins spiked
812 with FB1 resulted in only 27.6% loss, being highlighted that baking caused
813 significantly greater losses of FB1 at the surface than at the core [133].
814 Nixtamalization of maize is an ancient thermal-alkaline process consisting of
815 the three-step process. First, corn kernels are cooking (90-100 °C) in a saturated
816 calcium hydroxide solution (approximately 45 min), followed by steeping for 8–24
817 h and by a final washing to remove the excess of calcium and organic matter [137].
 27
Maize as a superfood
818 According to Schaarschmidt S. and Fauhl-Hassek C. [117], nixtamalization reduces
819 the maize mycotoxins amounts in three ways. The first one by leaching of water-
820 soluble mycotoxins into the liquid fractions during cooking, steeping, and washing.
821 The second one by the removal of the pericarp, tip cap, and germ during final
822 washing. And the last one, linked to chemical degradation, caused by the high pH
823 and elevated temperature, which can result in degradation, modification, and/or
824 binding or release of mycotoxins. In the study of De Girolamo A. et al. [138], the
825 fumonisins (FBs) and partially hydrolyzed fumonisins (PHFBs) of maize naturally
826 contaminated, were reduced by nixtamalization, troughs their conversion into
827 hydrolyzed fumonisins (HFBs). Dombrink-Kurtzman M.A. et al. [131] also showed
828 that nixtamalization reduced the initial amount of FB1 into 81.5%, being identified
829 that an average of 72.5% of FB1 was converted to HFB1 and remained in the
830 steeping and washing water. Elias-Orozco R. et al. [136] exposed that
831 nixtamalization reduced aflatoxin B1, aflatoxin M1, and aflatoxin B1-8,9-
832 dihydrodiol content in 94%, 90%, and 93% respectively. Moreover, Schaarschmidt
833 S. and Fauhl-Hassek C. [117] also reported a reduction of zearalenone (60 to 100%)
834 and vomitoxin (70% to 80%) after maize nixtamalization.
835
836 Chemical processing methods
837 Chemical food processing methods destroy or inactivate mycotoxins. Among
838 chemical treatments, in maize, it has been applied treatment with acids, bases,
839 oxidizing, and reducing agents. For example, lactic acid bacteria fermentation in
840 spiked maize meal, reduced the concentration of fumonisin B1 (75%) and
841 zearalenone (68%) [139]. On the other hand, corn treated with phosphates
842 (tetrasodium pyrophosphate, sodium hexametaphosphate, and sodium
843 tripolyphosphate) prevented or reduced mold growth when added in powder form
844 to corn at 1.0% or 2.0% (w/w). Moreover, whenever mold growth occurred,
845 treatment of corn with tetrasodium pyrophosphate and sodium hexametaphosphate
846 inhibited aflatoxin production [140]. Ammoniation decreased aflatoxin levels in
847 maize by more than 75 % and completely decomposed OTA, however, due to
848 incomplete knowledge about composition and toxicities of end products, this
849 technique has not been approved by the USA Food and Drug Administration [141,
850 142]. Ozonation also significantly affected aflatoxins in cornflour, after treatment
851 with 75 mg/L ozone for 60 min, the contents of AFB1, AFG1, and AFB2 were
852 decreased in 78.7%, 72.1% and 70.6% respectively [143]. Sodium bisulfite also
853 performed the greatest reductions of DON (up to 95%) when contaminated corn
854 was autoclaved for 1h at 121 °C in the presence of 8.33% aqueous sodium bisulfite
855 [144].
 28
Pech-Almeida et al.

856 CONCLUSIONS
857 Maize represents a significant source of macro and micronutrients. Its
858 physicochemical composition has shown that it is rich in carbohydrates, vitamins,
859 minerals, carotenoids, phenolic compounds, phytosterols, policosanols,
860 phospholipids, arabinoxylans, dietary fiber, among other phytochemicals. This
861 composition varies in function of various parameters such as environmental growth
862 conditions, genetic background, plant age, and geographic location. Moreover, in
863 recent years, studies around health benefits of maize consumption have shown its
864 antioxidant, anticancer, antihypertensive, anti-diabetic, antiobesogenic, and anti-
865 inflammatory activities. However, one of the main issues of maize consumption is
866 mycotoxins. Because the maize plant is easily infected via fungal attack during their
867 development, harvest, or after their harvest, it is crucial to ensure the safety and
868 quality of final maize-based products. Even if good agricultural practices and
869 adequate storage conditions limit mycotoxin levels in the maize food chain, these
870 practices are not enough to eliminate mycotoxins. Therefore, food processing
871 becomes a key tool to reduce or even eliminate mycotoxins in maize. Among the
872 most applied food processes, thermal processing is still the most important
873 industrial treatment to reduce mycotoxins content in finished products. Even though
874 there are various studies about the effect of food processing conditions into
875 mycotoxins, to take full advantage of maize as a superfood, it is still necessary to
876 carry out a multicriteria optimization of processing parameters, that assure the
877 preservation of maize phytochemicals, and the elimination or at least the reduction
878 at safe levels of mycotoxins.
879
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