Plant Lipids Science, Technology, Nutritional Value and … · · 2015-03-31Furthermore oat and...

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Plant Lipids Science, Technology, Nutritional Value and Benefits to Human Health, 2015: 119-145

ISBN: 978-81-308-0557-3 Editors: Grażyna Budryn and Dorota Żyżelewicz

2.6. Composition and functional properties

of lipid components from selected

cereal grains

Justyna Rosicka-Kaczmarek, Karolina Miśkiewicz, Ewa Nebesny and Bartłomiej Makowski

Institute of Chemical Food Technology, Faculty of Biotechnology and Food Sciences, Lodz University of Technology, Stefanowskiego 4/10 St., 90-924 Lodz, Poland

Abstract. Literature overview regarding the quantity and quality of various lipid fractions from cereal grains was conducted. Informations covered in this review will help to explain the functional properties of cereal lipids and their impact on technological processes during food production as well as will help to evaluate the influence of cereal lipids on the nutritional value of food products. Review regards mostly wheat grain, as it consists the main raw material in bakery. Furthermore oat and barley are covered, due to the fact that these are the cereals which are often used as a basic raw material in enriched bakery products as well as other food products with additional functional properties, resulting from rich composition of lipid fraction therein.

Correspondence/Reprint request: Dr. Justyna Rosicka-Kaczmarek, Institute of Chemical Food Technology,

Faculty of Biotechnology and Food Sciences, Lodz University of Technology, Stefanowskiego 4/10 St., 90-924

Lodz, Poland. E-mail: [email protected]

Justyna Rosicka-Kaczmarek et al. 120

Lipids are present in cereals in small quantities, however their role in

human nutrition as well as the technology of cereals processing is quite

significant. These types of compounds are commonly named “fats”, but they

are a complex group of compounds, with incredibly complicated structure

which are susceptible to various chemical changes. Unwanted changes of

lipid compounds, regardless of the fact that lipids are present in cereal

products in small quantities, determine the stability and quality of foodstuffs

[1].

Cereal with currently the biggest importance in worldwide bread and

animal feed production is wheat. Worldwide crop area of wheat reaches

230 mln ha. The most important species of wheat are: common wheat

(Triticumvulgare), which is available in numerous varieties and hard wheat

(Triticum durum). The main direction of wheat grain processing is flour

preparation. Wheat is also used to produce starch, which is then used for

preparation of starch syrups: glucose and glucose-fructose syrups.

Lipids are present in wheat grain in small quantities i.e. 1.7-2.0%, from

which lipids in germ consist 28.5%, in aleurone layer 8%, in endosperm

1.5% and in bran 1%. Lipid content depends heavily on wheat variety.

Grains of durum wheat and red wheat accumulate bigger quantities of lipids

than wheat varieties with white grains. Furthermore weather conditions

during plant growth influence the quantity of synthesized lipids. Colder

years promote bigger lipid content in plants and higher degree of their

unsaturation. Cereal lipids constitute mostly from unsaturated fatty acids, i.e.

oleic, linoleic and linolenic acids. Among wheat lipids especially significant

are complex lipids: glycolipids and phospholipids, mainly those building

protein-lipid and amylose-lipid complexes. Bound with starch lipids, present

inside starch granule do not form complexes with gluten proteins [2].

Due to structural similarities wheat lipids can be divided into 3 main

groups, i.e. simple, complex and secondary lipids. Simple lipids include:

main lipids group – esters of fatty acids and glycerol (acylglycerols). Around

97% of compounds from this group consist of triacylglycerols. They are a

group of lipids stored in plants, present in aleurone and sub-aleurone tissues

of endosperm and germ in a spherosome form. Remaining 3% are known as

partial acylglycerols, namely di- and monoacylglycerols. Another type of

lipids which are included in this group are waxes – esters of fatty acids and

alcohols other than glycerol. They can be found in the bran of cereals and are

considered to take part in water absorption and excretion of the grain [3].

Complex lipids are a group of compounds containing, beside fatty acids

and alcohols, also other chemical structures. They contain phospholipids –

acting in plants as structural components, building biological membranes

(including spherosomes) and taking part in starch creation. Other group in

Composition and functional properties of lipid components from selected cereal grains 121

knows as glycolipids – compounds containing at least one sugar residue

bound via glycosidic bond with lipid part of the structure. They are mostly

present in a form of digalactosyldiglycerols, which can be found in

amyloplasts membranes [3].

Secondary lipids are derivatives of simple and complex lipids, which are

formed mostly as a result of their hydrolysis.They include: fatty acids,

alcohols and carbohydrates [3].

Other criteria by which one can group wheat grain lipids are: their

localization in various parts of the grain (starch lipids, surface and internal

starch lipids), extraction methods (free lipids, bound lipids and their

hydrolysates) and their polarity (polar lipids, including glyco- and

phospholipids and non-polar lipids) [3].

Lipids constitute a main non-starch component in cereal starches [5].

Non-starch lipids, which include triglycerols, diacylglycerols and

phospholipids are created in membranes and spherosomes of endospores and

are loosely bound to starch granule [4].

Cereal starches contain quantities of free fatty acids (FFA) and

lysophospholipids (LPL) similar to amylose content. In table 1 amounts of

these lipid compounds in selected starches are presented.

In wheat starch the most important lipid group are lysophospholipids, in

which the biggest fraction is lysophosphatidylcholine (LPC). The content of

this compound reaches 70-90% of overall lipid quantity. Other cereal

starches contain mostly FFA with only trace amounts of lysophospholipids.

During starch isolation processes starch swelling may occur, which may

result in absorption of free fatty acids and monoacyl lipids into the inner

layers of starch granule. This is why non-starch lipids are described as outer

starch lipids [4]. Those lipids form amylose-lipid complexes during thermal

processing of starch suspensions.

Inner-starch lipids are contained inside intact cereal starch grains. These

are mainly monoacyl lipids, namely free fatty acids and lysophospholipids,

which may also exist as complexes with amylose in native starch.

Surface lipids, present on the surface of starch granules include:

triglycerides, free fatty acids, glycolipids and phospholipids. They contain

more monoacyl lipids, compared to non-starch lipids, which results in an

easier formation of amylose-lipid complexes on the surface of starch

granules. It is believed that they consist a residue of amyloplast membranes.

They are probably a contamination left after starch extraction. Additionally

also genetic factors were proved to influence the quantity of this group of

lipids on the surface of starch granule [6, 7]. It was observed that more polar

lipids (also free lipid fraction) are present on the surface of starch granules

isolated from soft wheat varieties, compared to hard wheat types.


Table 1. Quantities of free fatty acids and phospholipids in starches from various

origins [5].

Starch type

Free fatty acids ( µmol/g d.b. of starch)

Phospholipids

[% ] Total quantity 16:0 18:0 18:1 18:2 18:3

Maize 18.50 5.84 0.44 2.69 8.97 0.56 4.62

Rice 16.47 5.60 0.39 3.22 7.01 0.25 9.15

Wheat 3.21 1.58 0.06 0.62 0.90 0.05 18.68

Free lipids can be easily extracted with non-polar solvents, such as

petroleum ether, ethyl ether and hexane. They consist ca. 1-2% of dry matter

of flour and 2/3 of these lipids are non-polar. Significant part of free lipids,

which are a group of storage lipids, are present in a spherosome form – as

small drops of lipids with a diameter of around 2 µm. They are a place in

which synthesis and storage of lipids occurs. They are mostly present in

germ and aleurone layer of the grain [3].

In order to extract bound lipids polar solvent have to be used. Exemplary

extraction method includes extraction with the use of butanol saturated with

water in a boiling temperature. Lipids belonging to this group are:

lipoproteins, glycolipids and phospholipids, so fractions bound to starch or

constituting the components of cell membranes [3].

Mechanism of lipid-starch interaction is similar to the interaction of

iodine with alcohol, which means they create inclusive complexes [8]. In

wheat starch this type of structures are mostly formed with the participation

of lysophospholipids. It would appear that 1% of lipid quantity in wheat

starch appears to be unessential, however one molecule of lysophospholipid

can form a complex with even 20 glucose molecules, which corresponds to

3.5 grooves of a 6-groove amylose helix. Weight ratio of lysophospholipid to

amylose in approximately 0.13/0.87. As a result it can be observed that 1 g

of lipids can form complexes with 6.7 g of amylose, which consists ca. ¼ of

its quantity in wheat starch [3].

Amylose-lipid complex is a helix type structure formed by an amylose

chain around the hydrophobic part of monoacyl lipid chain, while the polar

part is present at the outer layer of the helix. Helix segments are stabilized by

van der Waals forces, hydrophobic interactions and hydrogen bonds [8].

Beside complexes present in native wheat starch also additional

quantities of these compounds may form during heating of a starch

preparation during gelatinization. They are created from lipids present on the

surface of starch granules and amylose released from starch during gelatinization.


Figure 1. The outline of amylose-lipids complex formation during solubilization of

native starch [11].

Amylose-lysolecithin and amylose-fatty acids complexes are formed under

gelatinization temperature conditions or higher (depending of the amount of

water, the less water the higher complex formation temperature) [9, 10]. The

outline of this process in presented of figure 1 [11].

Heating of wheat starch preparation above gelatinization temperature

causes the appearance on a DSC thermogram of an endothermic peak,

associated with the destruction of AML complexes. However, this process is

fully reversible, which means that cooling the mixture causes an appearance

of an exothermic peak representing the recreation of the structure of

aforementioned complexes [12]. Forming of complexes comprises of two

stages. In the first stage amylose chains associate with lipid molecules.

Second stage consists of crystal growth, namely transformation of AML

helix into a crystal structure. As a result of these processes various forms of

complexes can be formed – form I which is amorphous and forms IIa and IIb

with semi-crystal structure. Semi-crystal forms of complexes vary in the

quantity and the degree of arrangement of crystal areas [13]. The structure of

complexes depends on the temperature in which they are formed. Form I of

the AML complex is created in the temperature of 60 °C and the temperature

of its destruction in 96-104 °C. Form IIa is formed in a temperature above

90 °C and the range in which its destroyed is 114-128 °C. The solubilization

of form IIa increases the amount of a IIb form type [8]. The formation of

various forms of the AML complex depends on the temperature. In a

temperature of 60 °C the degree of nucleation of amylose chains in high,

which results in creation of only amorphous structures. No crystal-like

structures are observed in this case. Temperatures above 90 °C favor slow

nucleation of amylose chains resulting in crystal formation, thus form II


complexes are formed [14]. Various polymorphic forms of complexes,

during heating and cooling of starch preparations may change into each

other. Transition of form I into form II requires a partial melting and

disintegration of the helix, which allows chains to become more mobile

resulting in the ability to form crystals. The transition of form IIa into IIb is

probably caused by partial crystal degradation and their reformation [14].

AML complexes (including individual amylose segments) are stabilized by

van der Waals forces and hydrogen bonds. The ratio of these interactions

varies depending on the complex type. Form I of the complex due to

amorphous structure is stabilized mainly by hydrogen bonds, while type II

forms are stabilized by van der Waals forces, which is why differences in the

degradation enthalpy of various forms of complexes can be observed [15].

The structure and properties of amylose-lipid complexes depends on many

factors, including the temperature of their formation, polymerization degree

of amylose chain, type of lipid partaking in complex creation (including the

length and saturation degree of monoacyl chain) [8, 16].

It was observed that depending on the type of lipid bound to amylose,

complexes vary in their degradation temperature. Complexes with long chain

acyl lipids (C-12 and C-16) are characterized by higher values of melting

temperatures, which is linked with better organization of their inner structure

and the size of formed crystals [8]. Monoglycerides form bigger quantities of

form I complex, while long chain fatty acids form bigger amounts of crystal-

like structures, namely II form type. Shorter heating of the sample results in

creation of bigger quantities of form I AML complex. Furthermore it was

also observed that the stability of AML complex increases more when longer

chain fatty acids form the complex. Short chain fatty acids (C-3 and C-4)

were found to be unable to create complexes with amylose. Chains longer

than C-10 create mostly form I of a complex, while longer chains (C-18 and

longer) form complexes with a semi-crystal structure [17].

The quantity and type of created complex depends on temperature

conditions. Long term heating in temperature above 100 °C favors the

formation of type II complex forms, and its stability increases when long

acyl chain lipids are in its structure. It was proven that lipids with lower

saturation degree are more likely to form complexes with amylose. Lipids

with long monoacyl chains are more likely to form crystal-like structure –

the longer the chain the more crystal type structures are formed [17, 18].

One of the factors which influence the quantity and organization degree

of complex structure, is the polymerization degree of amylose. Both quantity

and the amount of crystal-like complexes increases with increasing

polymerization degree of amylose [19]. Additionally the quantity of amylose

affects the type of created complex. Higher amounts of amylose in waxy


starches cause the formation of crystal forms of the complex [17]. The

conditions in which complex is created, namely gelatinization temperature

and the amount of available water, determine the quantity and type of AML

complex formed in rice starch. Too high moisture on the surface of starch

granule (over 66% of water) inhibits AML complex creation. In these

gelatinization conditions II form of complex can’t be formed, unlike the

amorphous form. On the other hand the lack of water in the inside of the

granule causes that the complex can form only in very high temperature [20].

The stability and susceptibility of AML complex to degradation depends

mostly on its fine structure. More organized structures (crystal-like) are more

resistant to degradation, which can be observed by higher degradation

temperatures of these types of structures [17, 18].

AML complexes significantly influence the properties of food products,

decreasing amyloses ability of amylolysis and preventing amylose leaking

during gelatinization [21]. Thermal and rheological studies of wheat starch

revealed that higher amounts of lipids bound with starch causes an increase

of gelatinization temperature, with simultaneous decrease of gelatinization

enthalpy. Starch-lipid interactions are also suspected to limit starch

retrogradation [17] and increase the shelf life of bread [22]. The presence of

amylose-lipid complexes causes a retardation of heat induced starch

expansion and decreases the ability to bind water by starch [23]. They also

decrease starches solubility and susceptibility to hydrolysis [17]. AML

complexes influence negatively the process of starch hydrolysates

production, causing an opalization and haze phenomena in hydrolysates, as

well as filtration problems. During filtration of wheat hydrolysates the

majority of lipids remain in the filtrate (ca. 90% of free lipids). Performing

decolorization allows limiting the lipid content in the filtrate to 4.5%. Bigger

quantity of lipids in wheat starches causes an occurrence of unpleasant

aroma resulting from their oxidation. Unbeneficial activity of lipids can be

reduced with the use of a lysophospholipase enzyme during wheat starch

hydrolysate production. This action results in a hydrolysis of amylose-lipid

complexes, causing an increase of filtration rate and reducing the amount of

additional filtration improving agents [9].

Factors influencing the content of lipids in cereals

The quantity of lipids in wheat grain is associated with its maturity, class

and cropping conditions [3, 24]. It is believed that the biggest influence on

lipid content in wheat have genetic predispositions. Lipid amount in different

varieties of wheat cropped in the same place varies more than when the same

wheat variety is cropped in different environmental conditions [3].


In unripe cereal grains most abundant lipids are structural lipids, mostly

phospholipids and a small quantity of glycolipids. During grain maturation

they transform into non-polar lipids, mainly triacylglycerols, which

constitute 70-90% of storage lipids in fully matured grains [3]. During

maturation lipid fraction present in the grain becomes poorer in linolenic,

palmitic and stearic acids, while linoleic acid level increases [3]. Fatty acid

composition in also influenced by climatic conditions, mostly by

temperature. This factor causes a decrease of lipid content and their

unsaturation degree: high temperature and low level of rainfall during wheat

vegetation [25].

Among various lipid fractions of lipids the most sensitive to

environmental influences are non-polar lipids [24].

Lipid content is positively correlated with hardness and color of cereal

grain. Hard wheat varieties as well as durum wheat contain more, both

overall lipid quantity and polar lipids, compared to soft wheat types [3].

Additionally durum wheat varieties contain bigger quantities of this type of

compounds than vulgare wheat varieties. Wheat grains harvested in Canada

and Great Britain are characterized by bigger quantitative differentials of

lipids, higher free lipid fraction concentration and lower amount of

glycolipid fraction, than wheat cropped on the territory of USA [3].

Differences in environmental conditions may be the cause of the occurrence

of variations in the content and composition of free lipids. Literature data

indicate that the content of non-polar lipids is influenced mainly by

cultivation methods, glycolipids – cultivation area, and phospholipids – both

these factors [26].

Differences in the quality and quantity of lipids in wheat

flour

The content of lipid fraction in wheat flour increases with its increasing

extraction rate as well as with the increasing content of bran. Wheat flour

contains all endosperm, starch and non-starch lipids, approximately 1/3 of

germ lipids and a small amount of lipids originating from the aleurone layer of

grain. Non-endosperm lipids enrich flour in non-polar compounds, mainly

triacylglycerols. α- and β-tocopherolsand are considered to be an indicator of

the presence of non-endosperm lipids in wheat. β-tocopherols are present

almost entirely in wheat germ, while α-tocopherols are found mainly in the

aleurone layer of grain [3]. A side effect of the transfer of non-endosperm

components to flour - an increase of the content of lipolytic enzymes and non-

gluten proteins (which are mostly present in the aleurone layer) can be

observed.


Another factor influencing the composition of free lipids in flour is the

hardness of endosperm. Hard wheat varieties possess thicker endosperm cell

walls and starch granules are found in a cohesive protein matrix. During milling

endosperm tissues breaks along cell walls and form large fragments, which pass

farther during sieving. Tight bonding of starch and proteins cause, that during

breaking of these agglomerates a mechanical damaging of a significant amount

of starch granules occurs, which may result in a release of lipids bound to

amylose [3]. Released lipids constitute mostly of lisophospholipids. The

cohesiveness of cells of soft wheat varieties is much weaker. This results in

easier grinding of grains and forming smaller fragments. Starch granules from

soft wheat varieties are damaged during grinding in much smaller degree than

starches originating from hard wheat types [3].

Detailed studies of the profile of lipids occurring in wheat flour and

starch were performed with the use of mass spectrometry ESI-MS/MS. 146

different lipid groups were found in analyzed wheat fractions. Main polar

lipid groups consisted of monogalactosyldiacylglycerols (MGDG),

digalactosyldiacylglycerols (DGDG), phosphatidylcholine (PC) and

lysophosphatidylcholine (Lyso-PC). It was observed that more monoacyl

polar lipids are concentrated in the inner fraction of starch lipids. On the

surface of starch granules mostly galactolipids were present. The differences

of lipid quantity are correlated with the method of starch isolation. Most

surface lipids is found in starches isolated from flour with the use of the

“dough method” [27, 28]. The variation of polar lipid composition on the

surface of starch granules is related to the presence of proteins from the

puroindoline group (Pin a and b). In case when isoform Pin b is present in a

mutated form or when one of isoform is completely absent, polar lipid

content on the surface of starch granule decreases. However when these

proteins are present in wild form of wheat the content of polar lipids on the

surface of starch granule increases [27].

Most of the studies regarding the composition of free lipids in wheat flour

were performed on wheat crops harvested in USA [29, 30], Canada, Australia

[31] and Greece [32]. Wheat is mostly classified by the criteria of cropping

period, namely spring and winter varieties. Results of studies regarding the

quantity and quality of free lipid fraction in flours from spring and winter

wheat varieties, harvested in Poland showed a significant variation of these

parameters, depending on vegetation period of crops [33]. Free lipid contents

in flour, fractioned by their polarity are presented in Table 2.

Spring wheat flours were about 17% richer in total lipids, especially in

their non-polar fraction. The contents of glycolipids ranged from 134 to 215

mg/100 g of flour and were more consistent within the winter wheat class.

The percentages of two main fractions, namely DGDG and MGDG were


similar in both wheat classes and reached 77%. Phospholipids constituted the

smallest fraction of flour free lipids in both wheat classes. However, spring

wheat flours were richer in these compounds, which is likely associated with

a greater content of spherosomes in the endosperm of this wheat class. The

free lipids of spring wheat flour contained more oleic and slightly less

linoleic and linolenic acids (Table 3) [33]. Apart from genetic factors, the

fatty acid composition is also determined by climatic conditions.

The crude lipid fraction of flour also includes accompanying compounds

of similar polarity, from which carotenoids are of special nutritional

importance [33]. The main carotenoids of wheat are xanthophylls,

predominantly lutein. The second significant wheat grain carotenoid is

zeaxanthin. The ratio of lutein to zeaxanthin is 9.3 and 2.5 in mature and

green-harvested wheat kernels, respectively [34]. Spring wheat flour is also

richer in carotenoids. Lutein in the form of a trans – isomer, constituted

about 62% and 70% of all carotenoids in spring and winter wheat flours,

respectively [33].

Literature data indicates to a significant variation of both free lipids and

bound lipids, in flour and in whole grain, depending on wheat variety [35].

In this case the analytical material consisted of winter wheat varieties

harvested in Poland. In table 4 results of the analysis of composition of

various lipid fractions in studied material are shown. The content of total free

lipids varied in the range of 1617-1877 and 920-1050 mg in 100 g of wheat

grain and flour, respectively, and was dominated by non-polar lipids (Table 4)

Table 2. Content and composition of flour free lipids of Polish spring and winter

wheat varieties [33].

Variety TFL*

[mg/100 g]

NL*

[mg/100 g]

GL*

[mg/100 g]

PhL*

[mg/100 g]

Spring

varieties

Zebra 1343 1073 215 55

Jasna 1276 1060 166 50

Olimpia 1251 1046 147 58

Koksa 1316 1055 206 55

Opatka 1242 1063 134 45

Winter

varieties

Zyta 1026 801 196 29

Korweta 1173 954 186 33

Finezja 1149 934 183 32

Tonacja 1043 850 160 33

Mewa 1090 904 158 28

Slawa 1132 926 167 39

*TFL–total free lipids, NL-non-polar lipids, GL-glycolipids, PhL-phospholipids


Table 3. Fatty acids composition of flour free lipids of Polish spring and winter

wheat varieties [33].

Variety Fatty acids content[%]

C16:0 C16:1 C18:0 C18:1 C18:2 C18:3 Others

Spring

varieties

Zebra 19.1 0.02 0.68 13.5 63.0 3.38 0.34

Jasna 18.9 0.02 0.57 14.1 62.2 3.72 0.48

Olimpia 19.8 0.04 0.64 13.7 62.8 2.81 0.27

Koksa 20.0 0.02 0.68 14.2 62.0 2.72 0.46

Opatka 19.6 0.01 0.67 15.1 62.8 1.80 0.04

Winter

varieties

Zyta 19.4 0.04 0.69 11.5 63.4 4.74 0.21

Korweta 19.6 0.05 0.54 11.2 63.3 4.97 0.38

Finezja 19.8 0.01 0.48 11.2 63.4 4.59 0.54

Tonacja 19.3 0.02 0.50 11.7 64.2 4.05 0.24

Mewa 19.4 0.01 0.49 11.8 63.5 4.28 0.50

Slawa 20.7 0.01 0.47 11.3 63.2 3.80 0.63

[35]. Free glycolipids occurred in the amount of 57-140 mg in 100 g of grain and 43-107 mg in 100 g of flour. Non-polar fractions dominated in the lipid composition and their ratio was 77-84% in grain and 68-77% in flour. A high content of non-polar lipids in kernels proves their full maturity, as immature cereal grain is characterized by the prevalence of structural lipids, mainly phospholipids, accompanied by a small amount of glycolipids [35]. The wheat cultivated in Australia, United Kingdom and Greece

contained a higher amount of glycolipids than varieties cultivated in the

United States. However it can be explained by the difficulty to compare

results obtained by different researchers due to different analytical methods,

for example different solvent usage (the use of chloroform allows to obtain

higher extraction yield of lipids than ether extraction) [36].

The FNL/FPoL ratio in the composition of free lipids of the investigated Polish wheat varieties varied between 3.22 and 5.14, while its variability in flours was lower and fluctuated from 1.75 to 3.32 [35]. Exemplary values of this index ranged from 6.3 to 11.3 for HRS wheat cultivated in the United States in the years 1971-1976 [36]. The content of free lipids in grain and flour from wheat grown in Poland is typical for that kind of cereal. In their composition occurs, however, relatively few favorable glycolipids, e.g. approximately 2-fold lower than in wheat cultivated in United States [35]. It was found that both the content of free glycolipids and total content of free polar fraction of grain may be predicted on the basis of the color measurement of kernels surface [35]. The content of bound lipid fraction was lower than that of free lipids: 3.0-4.5-fold in grain and 1.9-3.2-fold in flour, and was dominated by


phospholipids (Table 4). Their content varied from 397 to 537 mg in 100 g of grain and from 307 to 490 mg in 100 g of flour [35]. In flours of 4 soft wheat varieties cultivated in Canada, the bound lipid content accounted for 531-753 mg/100 g, while in flours of 22 durum wheat varieties it ranged from 548 to 798 mg/100 g [37].

The influence of lipids on baking properties of wheat flour

Current knowledge of the role of lipids in wheat grain is ambiguous,

especially in the area of various lipid compounds interactions. Possible

knowledge of the quantity and composition of lipid fraction in wheat flour

may be considered as a great quality marker, which will help to select

optimal technological parameters with aim to receive the best product

quality.

The influence of individual lipid groups on baking quality of flour is

quite diverse. A positive effect of polar lipids and a negative effect of

non-polar lipids, especially free fatty acids, was proven [3]. Free

cis-unsaturated fatty acids (linoleic and oleic acids), which are the most abundant

lipid compounds in wheat lipid fraction, decrease the bakery properties of flour

Table 4. Free and bound lipids of Polish winter wheat grain and extraction flours

[35].

Variety Sample FNL*

[mg/100 g]

FPol*

[mg/100 g]

BNL*

[mg/100 g]

BPol*

[mg/100 g]

Zyta

Grain 1367 413 70 393

Flour 683 313 57 270

Rysa

Grain 1487 320 53 343

Flour 807 243 33 400

Korweta

Grain 1290 400 63 349

Flour 586 334 60 380

Elena

Grain 1353 263 90 447

Flour 780 240 43 330

Mewa

Grain 1523 387 73 417

Flour 703 263 47 260

Finezja

Grain 1330 297 80 423

Flour 700 230 63 427 * FNL- free non-polar lipids, FPol- free polar lipids, BNL- bound non-polar lipids, BPol- bound

free polar lipids


[38]. Among polar lipid compound, glycolipids cause an increase of loaf

volume. Among glycolipids mono- and digalactosyldiacylglycerols possess

the most beneficial properties in this regard [36].

Positive effect of polar lipids on the baking properties of flour can be

explained by its foam and emulsion stabilizing ability. This function is mostly

fulfilled by free lipids, which help forming a polar film on gluten network of

dough. Another function of free lipids is creating interactions with proteins of

phase boundary region (gas-liquid), resulting in an increase of loaf volume

[39]. Optimal content of phospholipids determine the formation of an elastic

and resilient dough film, which helps to obtain a proper texture of a final

product. Furthermore lipids show an ability to enclose large volume of liquid

phase as well as significant amounts of small gas bubbles, inside its structure.

This gives products smooth, fine-grained texture and increases the volume of

loaves. Lipids play also an important role in counteracting the phenomena of

bread staling [40]. Lipid derivatives, such as hydroperoxides are also the

precursors of aroma giving compounds in bakery products.

Detailed analysis of free lipids is important, due to proven negative

correlation between the ratio of non-polar and polar lipids (NL/PL) and

bakery properties of wheat flour. Statistical significance of NL/PL ratio is so

high, that it is suggested to introduce this ratio in cropping procedures as a

marker determining the final quality of individual what variety [37].

Lipids are considered to be a determinant of quality of other products of

wheat grain milling. Removal of free lipids from flour used for biscuit

production causes a decrease of volume of the product, damaging its inner

structure and an increase of its hardness [36]. A lack of free lipids in

semolina is the cause of higher viscosity of pasta, loss of lipophilic color

agents as well as smaller yield of pasta after cooking [41]. Additionally

damage rate of pasta as well as its hardness after cooking increases [42].

Wheat grain lipids, regardless of being a micro-component in grain, can

be found in its all anatomical sections, varying significantly in its form and

playing important physiological, structural and storage roles. During milling

they transfer to flour in an amount depending on the properties and type of

the final product. Flour during storage is subjected to various changes,

mostly oxidation, which may improve its bakery properties. Flour lipids may

also influence processes of dough formation and consequently the quality of

final products [3].

Oat and barley are increasingly used in food industry. In food

technology they are perceived not only as a great source of dietary fiber but

also good quality lipids. Due to quite big, compared to other cereals, lipid

content with significant share of unsaturated fatty acids, oat and barley are a

precious cereal type [15].


Oat lipid synthesis

In oat grains lipid compounds are evenly placed in all grain sections

[43]. Lipid content and composition of fatty acids in oat depends on genetic

determinants as well as climatic and soil conditions during plant vegetation

[44, 45]. Most lipids are synthesized during early stages of grain formation,

under moisture conditions over 50%. During this development stage

majority of present in grain lipidsare polar (mainly phospholipids and

glycolipids), which have structural function in the grain. During grain

development and early ripening and maturity, non-polar lipids are stored.

They consist mostly of free fatty acids and small amount of mono-, di and

triacylglycerols [46]. Under 50% air moisture an increase of triacylglycerol

fraction with a simultaneous, significant decrease of mono-, diacylglycerols

and free fatty acids content occurs [47]. Lipid synthesis in oat grains depends

on temperature conditions during plant vegetation [48]. Lower temperatures

(12 °C on average) during plant development cause an increase of overall

lipid content as well the ratio of saturated to unsaturated fatty acids,

comparing to higher temperature conditions (28 °C on average) [49].

Additionally the content and unsaturation degree of fatty acids are higher in

winter oat varieties compared to spring varieties [49]. As literature data

indicates [49] low temperature conditions (ca. 12 °C) promotes the synthesis

of bigger amounts of unsaturated fatty acids in oat grains.

Content and distribution of lipids

Lipid content in dehulled oat grains ranges between 3% and 11.6%

[50, 51, 52]. Depending on lipid content in dehulled oat grain two groups

can be distinguished: high-lipid oat varieties - with 10% and more lipid

content, and low-lipid oat varieties, which contain less than 7% of lipids.

According to data presented in table 5 it can be observed that regardless

of the variation of lipid content depending on oat variety, lipid placement in

selected grain sections is similar. Ether and butanol-water extracts were

obtained by extraction with the use of diethyl ether prior to extraction with

butanol saturated with water. Presented data show that hull of oat grain

contains just a small amount of lipids (below 3%). Bigger quantities of these

compounds can be observed in starchy endosperm (5-6%), bran (8-11%),

germ (15-16%) and scutellum (23-25%) of oat. Scutellum and germ contain

the biggest concentration of lipids, however since they stand for just only 3%

of grain weight they are not considered to be the main source of lipids in oat.

Due to this reason it can be concluded that the biggest content of lipids in oat

grains can be found in bran, aleurone layer and starchy endosperm.


Among oat lipids following compounds are of most importance:

triacylglycerols (non-polar lipids), phospholipids, glycolipids, free fatty acids

and sterols [54]. As literature data suggest the most abundant lipid fraction in

oat grain in triacylglycerols with a high content of unsaturated fatty acids.

Other present in oat lipid fractions are mono- and diacylglycerols, which are

present in smaller quantities, and which are formed as a result of

triacylglycerideshydrolysis by a lipase enzyme. Glycolipids and phospholipids

Table 5. Lipid content in dehulled oat grain and its individual constituents,

depending on solvent used [53].

Grain section

Lipid content [% d.b.]

High-lipid variety Low-lipid variety

Ether extracts Butanol-water

extracts

Ether

extracts

Butanol-water

extracts

Dehulled grain 8.0 1.6 5.5 1.4

Hull 2.3 0.6 2.0 0.6

Bran 9.5 1.2 6.4 1.3

Starchy endosperm 6.8 1.0 5.2 1.0

Scutellum 20.6 2.8 20.4 4.2

Germ 12.6 3.3 10.6 4.1 Specific composition of lipid fractions

Table 6. Percentage of various fractions of lipids in whole grain of dehulled oat and

its individual sections [56].

Lipid fraction

Lipid fraction content [%]*

Dehulled

grain

Individual grain sections

Bran Endosperm Scutellum Germ

Triacyloglycerols 41 39 41 50 58

1,3-diacyloglycerols 2 2 2 1 2

1,2-diacyloglycerols 1 1 1 2 2

Freefattyacids 5 3 3 2 2

Sterols 1 1 1 1 1

Sterol glycosides 1 1 1 1 1

Monogalactosyldiacylglycerols 4 4 5 - -

Digalactosyldiacylglycerols 7 9 8 - -

Phosphatidylethanolamine 2 3 2 1 1

Lysophosphatidylethanolamine 1 2 2 - -

Phosphatidylcholine 5 4 4 3 3

Lysophosphatidylcholine 2 3 3 - -

Otherfractions (calculated) 28 28 27 39 30 *Percentage in relation to overall lipid content


consist 6.9-7.6% and 3.2-6.1% of an overall content of lipids in dehulled oat,

respectively. In glycolipid group of compounds mainly mono- and

digalactosyldiacylglycerols are present (they consist over 60% of overall

glycolipids). Among phospholipid phosphatidylcholine is the most abundant

(29.9%). According to De la Roche et al. [55] high-lipid oat varieties are

characterized by higher content of triacylglycerols (ca. 80%) and lower

phospholipid content (ca. 6%), compared to low-lipid varieties.

Fatty acids compositions

Oat lipids contain fatty acids with a chemical compositions beneficial from both technological and nutritional point of view [57]. Oat fat is rich in unsaturated fatty acids, which constitute 80% of all acids present in oat [58]. Essential unsaturated fatty acids consist around 40% of all raw fat, which in oat flakes stands for 2.5-3.0% of its overall weight. Consumption of 100 g of oat flakes covers ca. 30% of daily recommended intake of linoleic acid [15]. Essential fatty acids are required for proper development of young organisms and maintaining good state of health. Beside structural function of essential unsaturated fatty acids they also play an important role in many biochemical transformations as well they regulate physiological functions of human organisms (i.e. through prostaglandins and other biologically active compounds synthesis) [59]. According to research of many authors [60,61,62], in oat lipids most abundant fatty acids are: myristic (0.1-4.9%), palmitic (13-26%), stearic (1-3%), oleic (22-47%), linoleic (25-52%) and linolenic acid (1-3%), and they consist over 95% of all fatty acids present in oat lipids. Few studies indicate that also other fatty acids can be found in oat lipids: lauric, palmitoleic, arachidic (<0.1%) [63] and nervonic acid [64]. In cereal grain lipids, fatty acids are present mostly in ester form, in such fractions as: triacylglycerols, phospholipids and sterols. In table 7 fatty acid composition in polar and non-polar lipid fractions

from dehulled oat are placed. Showed data indicate to significant variations

of palmitic (16:0) and oleic acid (18:1ω9) in three lipid fractions such as

triacylglycerols, phospholipids and glycolipids. Triacylglycerol fraction is

characterized by smaller palmitic acid quantity, comparing to polar lipid

fractions. In polar lipid fractions (both glycolipids and phospholipids),

palmitic acid percentage in higher and oleic acid lower than in non-polar

lipid fraction. As literature data state [55, 66] an increase of lipid content in

oat grain cause a decrease of palmitic acid quantity with a simultaneous

increase of oleic acid concentration.

In table 8 the concentrations of fatty acids in lipids deriving from

dehulled oat grain and its individual sections are presented [53]. According to


Table 7. Fatty acid composition in main fractions of lipids from dehulled oat [65].

Lipid fraction

Fatty acids [%]

Myristic

acid

(14:0)

Palmitic

acid

(16:0)

Stearic

acid

(18:0)

Oleic

acid

(18:1ω9)

Linoleic

acid

(18:2ω6)

Linolenic

acid

(18:3ω3)

Triacylglycerols 1.5 14.8 2.2 43.3 35.0 2.0

Glycolipids 4.3 22.1 4.4 25.1 36.2 4.0

Phospholipids 2.2 28.1 4.2 21.3 38.1 2.8

Table 8. Fatty acid composition in lipids from dehulled oat grain and its individual

sections [53].

Fatty acids [%]

Myristic

acid

(14:0)

Palmitic

acid

(16:0)

Stearic

acid

(18:0)

Oleic

acid

(18:1ω9)

Linoleic

acid

(18:2ω6)

Linolenic

acid

(18:3ω3)

Ether extracts

Dehulled oat grain 0.4 18.8 2.2 39.4 37.9 1.3

Bran 0.4 18.1 1.9 38.4 39.6 1.6

Starchy endosperm 0.6 18.9 2.3 37.4 39.4 1.4

Scutellum 0.6 21.1 1.2 34.5 39.7 2.8

Germ 0.9 21.6 1.9 28.8 42.5 4.1

Butanol-water extracts

Dehulled oat grain 0.9 25.7 2.0 28.8 41.0 1.4

Bran 1.6 25.7 1.6 27.2 42.2 1.4

Starchy endosperm 0.6 27.3 2.4 28.4 39.7 1.3

data collected in table 8 it can be observed that arrangement of fatty acids in

dehulled oat grain and its individual sections depends on the solvent used for

lipid extraction. In case of lipids extracted with the use of diethyl ether

(ether extracts) the composition and concentrations of fatty acids both in

bran and endosperm are similar to these of dehulled oat grain. In lipids

extracted with the use of butanol-water solvent only myristic acid is

unevenly distributed among starchy endosperm (0.6%) and bran (1.6%).

Presented data indicate also that the percentage of other fatty acids in bran

and starchy endosperm is comparable with dehulled oat grain.

Oat starch lipids

Oat starch possesses unique physical, chemical and structural properties,

which is why it is noticeably different from other starch varieties. They vary in

granule size, lipid content, rheological properties, small retrogradation tendency


and are unique due to the occurrence of “intermediate fraction”, which is a starch

type with properties combining both amylose and amylopectin [67]. Lipids in oat

starch, depending of oat variety, are present in amounts from 1.1 to 2.5%, which

an average value of 1.3% [68]. These compounds are accumulated during the

synthesis of starch granule and they form complexes with amylose by

penetration of the hydrophobic insides of amylose helix [69, 70]. The presence

of lipids significantly decreases the swelling ability and water solubility of starch

as well as delays and inhibits the gelatinization process. They also determine gel

viscosity and inhibit gel formation [71].

Results of research done by Hartunian, Sowa and White [70] point to

significant differences in lipid content in starches from high- and low-lipid

oat varieties. High-lipid oat varieties are characterized by higher lipid

content, on average on a level of 2.5%, than low-lipid oat varieties – lipid

content amounting 2.1%. In oat starch lipids both polar and non-polar lipids

can be found, however non-polar lipids consist a much smaller group.

Literature data [72] show that oat starch lipids contain

lysophosphatidylcholine (51.6%), lysophosphatidylethanolamine (5.1%) and

free fatty acids (7.7%). It can be observed that lysophosphatidylcholine is the

most abundant fraction of lipids in oat starch. Oat starch lipid fraction is also

characterized by the presence of high amounts of palmitic (46.2%) and

linoleic acids (42.1%). Different fatty acids are present on smaller quantities

– oleic acid (9.8%), stearic acid (1%), myristic acid (1%).

Oat grain lipids are often accompanied by substances which are immune

to alkaline saponification. They are named as “unsaponifiable fraction of

lipids”. Following compounds belong to this fraction: sterols, tocopherols,

carotenoids. The main compound of unsaponifiable fraction of lipids in oat are

sterols. In whole oat grain the most abundant sterol is β-sitosterol, which

constitute about 69% of all sterols. Additionally, beside β-sitosterol, in oat

grain the following sterol compounds can be found: 5-avenasterol and 7-

avenasterol, which constitute 21% and 13.5%, respectively [73]. Oat grain as

well oil extracted from this grain is characterized also by the presence of

tocopherols (α- and β-tocopherol) and tocotrienols (α-tocotrienol) [74, 75]. In

oat lipids, compounds with strong antioxidant properties were found. They

include polyphenols, among which hydroxybenzoic and hydroxycinnamic

acids can be distinguished. Activity of these compounds is similar to this of

synthetic antioxidants, i.e. butylhydroxytoluene or propyl gallat [76]. They

have the ability to reduce peroxides and hydroxides as well as inactivate free

radicals, breaking propagation phase in a chain reaction. Oat lipid antioxidant

compounds possess also bacteriostatic and pharmacological activity,

improving heart health, having a positive effect on circulatory system,

preventing chronic inflammations [60] and neoplastic diseases [77]. The


negative effect of their presence is a decrease of protein assimilation [78].

Compounds with antioxidant properties in oat grain, beside Vitamin E, include

also polyphenol compounds: phenolic acids, their esters and amides,

alkylphenols, flavonoids and avenanthramides [79]. Avenanthramides due to

their thermostability are not affected by technological processes.

Lipid barley grains

Barley grains contain lipids such as: phospholipids, glycolipids, fatty acids, acylglycerols and smaller amounts of sterols, terpenes and carotenoids. In barley grain lipid compounds can be found mostly in germ and aleurone layer [80, 81]. During the formation of barley grain endosperm, mostly structural lipids can be observed - phospholipids with smaller quantities of glycolipids. Non-polar lipid fraction during this stage of grain development contains mostly free fatty acids and small quantities of mono-, di- and triacylglycerols. During grain maturation the concentration of triacylglycerols increases and amounts of mono- and diacylglycerols as well as free fatty acids decreases. In fully mature grain triacylglycerols consist 54% of overall lipid content [82]. As literature data state [83, 84] the quantity of polar lipids (structural lipids), non-polar lipids (storage lipids) and starch lipids in barley grain increases from 24

th day after pollination. After 42 days after pollination and

during further maturation a decrease of lipid fraction content takes place.

Content and distribution of lipids

Lipid content in barley grain is very diverse and varies from 1.9% to 4.6%. According to data presented by Newman and Newman [85] barley

varieties with lipid content of even 7% can be found. For two-row and six-row barley lipid content varies between 2.1-3.7% and 1.9-4.6%, respectively [86, 87]. In hulled and naked barley varieties lipid content is also diverse and ranges between 2.1-3.1% and 2.1-3.7%, respectively. Furthermore barley varieties with high amylose content is characterized by higher lipid content than varieties with high amylopectin content, as well as varieties with similar

levels of those two starch fractions. Although lipid concentrations in different barley varieties in often quite diverse its distribution in individual sections of grain is relatively even [88, 89]. According to information presented in table 9 it can be observed that the biggest lipid concentration is in the germ of barley grain (19.6%). In hull, endosperm and bran lipid content does not exceed 3%. Bran and endosperm constitute 87% of grain weight so they can be recognized as the main lipid source in the grain.


Table 9. Lipid content in barley grain and its individual constituents [90].

Barley grain/individual

constituents Lipid content [%]

Grain 3.2

Hull 2.4

Bran and endosperm 2.8

Germ 19.6

Specific composition of lipid fractions

Among barley lipids non-polar lipid fraction constitutes on average 67-78% of all lipids, glycolipids consist 8-13% and phospholipids – 14-21% [91]. Non-polar lipids are the main lipid fraction in barley, so an increase of overall lipid content can be associated with an increase of this fraction [92]. From non-polar lipids triacylglycerols are the main fraction (62%). It consists mainly from unsaturated fatty acids. Mono- and diacylglycerols (ca. 7%), sterol glycosides (ca. 4%), sterols (3%) and free fatty acids can also be found in barley grain [93]. In polar lipid fraction glycolipids and phospholipids can distinguished. Glycolipids consist from monogalactosyldiacylglycerols (27-34%) and digalactosyldiacylglycerols (22-39%) and phospholipids fraction is mostly build from phosphatidylcholine (52%), phosphatidylethanolamine (10%) and phosphatidylinositol (3%) [93]. Literature data [94] indicate that non-polar lipid fraction is present in bigger quantities in all grain section that polar lipids. Furthermore non-polar lipids quantity is similar in all grain sections. Glycolipid and phospholipid concentrations in individual sections of barley grain is quite diverse. Glycolipid content in the germ is usually on a level of 6%, but in endosperm, hull and bran its concentration rises 2-3-fold. Phospholipids are most abundant in the bran (23.1%), and are present in smaller amounts in germ, endosperm and hull, which amount to 17.8% and 5.9%, respectively.

Fatty acids compositions

Barley lipids are a great source of fatty acids, which are valuable from a

nutritional point of view [85, 82]. Among saturated fatty acids the most

abundant one is the palmitic acid (16:0), which can be found in barley in

amounts ranging from 17 to 28%. Other saturated fatty acids are: stearic

(18:0) (0.6-2.0%), and myristic acids(14:0) (below 1%). Unsaturated fatty

acids of barley consist of 52-59% linoleic (18:2, n-6), 10-23% oleic (18:1, n-

9) and 4-8% linolenic acids (18:3, n-3).


Table 10. Fatty acids profile in main fractions of barley lipids [95].

Fatty acids [%]

Myristic

acid

(14:0)

Palmitic

acid

(16:0)

Stearic

acid

(18:0)

Oleic acid

(18:1n9)

Linoleic

acid

(18:2 n6)

Linolenic

acid

(18:3n3)

Non-polar lipids

0.3-0.5 23.4-29.3 0.8-1.3 14.8-20.0 48.2-52.0 3.0-5.8

Polar lipids

Glycolipids 0.5-1.4 20.8-24.4 0.9-1.6 4.6-7.9 58.5-65.8 4.7-6.9

Phospholipids 0.8-1.4 31.0-36.7 0.6-1.5 10.6-15.8 44.9-51.9 1.7-3.9

In table 10 it can be observed that among both polar and non-polar lipids

palmitic and linoleic acids are the most abundant. These acids are present

mostly in polar lipid fraction.

Barley starch lipids

Barley starch contain around 1% of lipids. Barley starch lipids contain both polar and non-polar lipids, however polar lipids are present in much bigger concentrations. As literature data indicate [96] barley starch lipids are a rich source of lysophosphatidylcholine (62.5%). This fraction of barley starch lipids is rich in palmitic (44.3%) and linoleic acids (45.6%). Other fatty acids, such as: myristic, oleic and linolenic are present in aforementioned fraction in concentrations of 0.5%, 3.8% and 4.1%, respectively [97]. Lipid content in oat is 3-5-fold higher than in other cereals. Cereal lipids consist of mono- and polyene fatty acids. Polyene acids, which have the properties of essential unsaturated fatty acids, have to be provided in diet due to the fact that they are vital for proper organism development and functioning. Essential fatty acids possess the role of prostaglandin precursors, which are also called “tissue hormones”. They have numerous functions in human organisms, e.g.: regulation of circulatory system functions, secretion of digestive juices and platelet aggregation. Lipids are also carriers of biologically active compounds, such as vitamins A, D, E and K. In described cereal lipids,palmitic, oleic and linoleic acids are present in the biggest quantities (40-50%). Due to the good quality and quantity of lipid fraction in cereals, they as well as their products can be successfully used for functional food production [98].

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