Sweeteners

Intense Bulk

(nonnutritive) (nutritive)
sweeteners
swecteners

Natural
Synthetic Refined Sugar
sweeteners Sweeteners Sugars replacements
(of plant origin)

c.g. saccharin, e.g. dihydrochalcone, 8 . SucroSe, c.g.polyols/sugar

sucralose, aspartame, steriosides, glycyrrhizin iructose, alcohols; sorbitol,
cyclamate dextrose, mannitol, xylitol
maltose

Scheme 4.1 Classification of sweeteners based on their nutritive status (Rogers et al. 1988; Ager et al.
1998).

Molecules referred to as sweeteners are numerous. A common method of classifying them

is according to their nutritive status (Scheme 4.1): (1) intense (non-nutritive) sweeteners (see
Section 4.3) and (2) bulk (nutritive) sweeteners (see Section 4.4).
 4.3.1 Synthetie intense sweeteners
4.3.1.1 Aspartame
The synthetic subclass includes compounds such as aspartame, which is a methyl ester of
the dipeptide compound of L-aspartic acid and L-phenylalanine amino acids (Figure 4.2).
Aspartame is 200 times sweeter than table sugar (sucrose) (Ager et al. 1998). However, the
compound is not stable under extreme pH conditions as it hydrolyses to yield methanol.
If the pH conditions or even temperature are more stringent, the peptide bonds undergo
hydrolysis to form free amino acids (Ager et al. 1998). For this reason, the application
of aspartame as sweeteners in baked products is unrealistic and other ways to improve its
stability under heating conditions have been devised. These techniques include the encasing
of aspartame in fats or maltodextrin (Prodolliet and Bruelhart 1993). Alternatively, aspartame
has been blended with other more stable sweeteners to improve its heat stability (Prodolliet
and Bruelhart 1993).

4.3.1.2 Sucralose
Another type of artificial intense sweetener is a chlorinated sugar known as sucralose,
produced by substituting the three hydroxyl groups in sucrose with chlorine atoms (Wasik
et al. 2007: Figure 4.3). Sucralose is 600 times sweeter than sucrose and is known to be heat
stable, an attribute which qualifies it to be used in fried and baked products in addition to
other uses in beverages, chewing gums and frozen desserts (Mazurkiewicz et al. 2006).

4.3.1.3 Saccharin
Saccharin, a chemical compound containing a benzoic sulphimide base structure (Figure 4.4),
is another artificial sweetener that finds application in drinks, cakes and biscuits (Nofre and
Tint 2000), among other products. It is also unstable at higher temperatures and is therefore

88 Chemistry ofFood Additives and Preservatives

H

Fig.4.3 Chemical structure of sucrolose (Wasik et al. 2007).

=o

Fig. 4.4 Chemical structure of saccharin (Nofre and Tint 2000)

used in synergy with other stable sweeteners. It is mostly used as a sodiunm salt which is very
soluble, unlike its acidic form which is insoluble.

4.3.1.4 Cyclamate
The artificial sweetener which has been in existence longer than many others curently in
use is cyclamate (Figure 4.5), which is 30 times sweeter than sucrose (Nofre and Tint 2000).
Cyclamate has a wide application because of its safety record, its stability in heat and its
good qualities in the context of combined sweetening (Hellekant and Danilova 1996).
4.3.2 Natural intense sweeteners
Plants such as sugarcane, sugar beets, maple trees and corn produce sugars (sweeteners) via
the process of photosynthesis. The sweeteners from natural or plant origin include perillalde
hyde, stevioside, rabaudioside, glycyrrhizin, osladin, thaumatins, monellin, dihydrochalcones
and miraculin. Although the former is not sweet, it has the property of modifying the taste
of sour food into a delightfully sweet taste (Sardesai and Waldshan 2005).

NaSO Na

Fig. 4.5 Chemical structure of cyclamate (Nofre and Tint 200o

Sweeteners 89

a) (b)
Fig.4.6 lo)} Perillaldehyde structure and (b) perillartine structure (Hellekant and Danilova 1996).

4.3.2.1 Perillaldehyde
Perillaldehyde, also known as perilla aldehyde, is a monoterpenoid natural organic com
pound found most abundantly in the perenial herb perilla (Hellekant and Danilova 1906)
Perillartine, the oxime of perilaldehyde which is also known as perilla sugar, is about 2000
times as sweet as sucrose and is used as an intense natural sweetener (Hellekant and Danilova

1996; Figure 4.6a, b).

4.3.2.2 Glycyrrhizin
Glycyrrhizin is another natural intense sweetener that exists in liquorice and is about 170
times sweeter than sucrose (Hellekant and Danilova 1996). One of the derivatives of this
compound, the glycyrrhizic acid monoglucuronide, is also an intense natural sweetener
which is 1000 times sweeter than sucrose. Structurally. glycyrrhizin isa triterpenoid saponin
glycoside found in the roots of liquorice plants of the species Glycyrrhiza glabra. It is used as
sweetener in baked products, frozen dairy. non-alcoholic beverages and vinegars (Hellekant
and Danilova 1996).

4.3.2.3 Steviol glycosides

Steviol glycosides are natural sweeteners extracted from the leaves of Stevia rebaudiana
(Bertoni) Bertoni (Geuns 2003). Stevioside compounds are prepared by connecting glucose
molecules to the steviol molecule. This diterpene exists as an aglycone and is synthesised
by replacing the carboxyl hydrogen atom of steviol (Figure 4.7) with glucose to generate an
ester, and replacing the hydroxyl hydrogen with mixtures of glucose and rhamnose sugars.
When only glucose is used, the resulting compounds are stevioside which contains two
glucose units and rebaudioside which is made up of three glucose units (Brandle 2004).
Stevioside and rebaudioside are the two main compounds that are responsible for the sweet

taste of stevia species (Bridel and Lavielle 1931).

Previous reports described serious concerns with regards to steviol, as it was linked to the
and mutagenesis activities (Pezzuto et al. 1985). This
possibility of triggering carcinogenic
report was later disapproved by the World Health Organisation (WHO) (Benford et al. 2006
 OHOH

OH

HO

HO

H
on

CH2

ROR

HC
0 On
HO

HO OH
CH2

On

Ol

Fig. 4.7 Chemical structures of stevioside and rebaudioside (Bridel and Lavielle 1931; Geuns 2003).

as well as other researchers (Procinska et at. 1991). On the contrary, WH0 has suggested
that steviol has health benefits, especially to people suffering from hypertension and diabetes
type-2 (Benford et al. 2006).

4.3.2.4 Naringin dihydrochalcone

From the dihydrochalcone class of natural intense sweetener, there is a compound known
as naringin dihydrochalcone (lIkan 1991) which is a phloretin glycoside (Figure 4.8). The

Sweeteners 91

on OH
10

Fig. 4.8 Chemical structure of naringin hydrochalcone (Tomasik 2003).

reaction of naringin dihydrochalcone with strong bases such as potassium hydro

a further catalytie hydrogenation results in dihydrochalcone, a compound which
300-1800 times sweeter than sucrose at threshold concentrations (Tomasik 2003).

4.3.2.5 Neohesperidin dihydrochalcone

Another natural intense non-calnric ewnotonor dorivnd from citrus is a glycosilated compound
n o m ae tha nachacnaridin a d-noo DUC lu uhi 10 0
 HU

OR
OH

Hm

HO

Chemical structure of naringin hydrochalcone (Tomasik 2003).

Fig. 4.8

bases such as potassium hydroxide with

reaction of naringin dihydrochalcone with strong which is about
a further catalytic hydrogenation
results in dihydrochalcone, a compound
300-1800 times sweeter than sucrose at threshold concentrations (Tomasik 2003).

4.3.2.5 Neohesperidin dihydrochalcone

Another natural intense non-caloric sweetener derived from citrus is a glycosilated compound
4.9), which is about 1000
known as the neohesperidin dihydrochalcone (Neo-DHC: Figure sweetener has limited
times as sweet as sucrose and very
stable to heat (Tomasik 2003). This
use however due to a number of drawbacks. It has an intense cooling effect on the tongue,
slow in its onset and has a lingering taste that
has a liquorice-like bitter off-taste, tends to be
differentiates it from the taste of sucrose; it is not popular with consumers. Another limitation
of neohesperidin dihydrochalcone is that it has very limited solubil
is synthesised by chemical treatment of neohesperidin (Scheme 4.2 104/335
It is
grapefruit and other citrus fruit peel and pulp.
usec
bitter orange.

HO
HO-
OH
CHs

HC o
HO-

10 OH

Fig. 4.9 Chemical structure of neohesperidin dihydrochalcone (Tomasik 2003).

92 Chemistry ofFood Additives and Preservatives

OH

Ho Ncohesperidin
HO

HO

KOH
Stream or

Hydrogen gas
-CHs
OH

HC HO

Neohepseridin dihydrochalcon
Scheme 4.2 Synthesis of neo-dihydrochaleone (Tomasik 2003).

in citrus, in the enhancement of the sweetness of other sweeteners and to mask bitterness in
pharmaceuticals (Tomasik 2003).
4.4.1 Refined sugars
Refined sugars (sweeteners) such as dextrose (Figure 4. 10a-i) are obtained naturally in food
stuffs, and have the attributes of a moderately sweet saccharide. Saccharide is a monosac
charide which forms the basic building block unit of carbohydrates (CH120,) and has a high
glycemic index (GI), a parameter reflecting the ability of digested carbohydrates to raise
blood glucose. Another useful parameter is the glycemic load (GL), which gives a measure
of blood glucose of any food product. This parameter is important as it provides a measure

Sweeteners 93

J
OH OH

HO On
DH 5H OH OH
(a) (b)

O
HO on
OH

HO
(c) (C)

OH

HO
Ho
OR

OR -OH
- OH H OH

O
OR

OR

OH
HO HO
H

HO O

OH
H
On
HO

(h) ()
Fig.4.10 Chemical stuctures of bulk sweeleners: (o) D-dextrose; (b} xylitol; (c) sorbitol; ld) 1-menthol;
e) erythritol; {} isomalt; lg) lactitol; (h) maltitol; and (i) mannitol.
of the total glycemic response of food items. Mathematically, the glycemic load is calculated
by multiplying the amount of carbohydrate (weight in grams or volume in millilitres) by the
GI value of that particular food item, divided by 100. The glycemic response for a particular
food item is therefore a measure of the impact of a food on the level of blood glucose.
Food items which hydrolyse easily and rapidly or which are absorbed easily also have
a faster and greater impact on blood glucose (i.e. have high impact) and thus have high
glycemic indices. On the other hand, food products with either slow or incomplete digested
carbohydrates also lower glycemic indices because glucose is released gradually into the
blood and the corresponding blood glucose response is lower and steady (Jenkins et al.
1981).
It should however be noted that the glucose response to foods tends to vary between
individuals and on the way the food is being consumed.

4,4.2 Sugar replacements

4.4.2.1 Polyols
Polyols have a cooling effect and play the role of distribution of taste over time where they
have a high molecular weight (Jenkins et al. 1981). Xylitol (a sugar alcohol) and sorbitol
(known as glucitol, also a sugar alcohol) are the most cooling (Figure 4.10b and c). Their
sweetness is 1.0 and 0.62 that of sucrose, respectively. Contributions from, for example
1-mentol (Figure 4.10d), may be incorporated in the total perception of coolness.
For consumers with effective metabolism, polyols are slowly and incompletely absorbed
in the intestines. They normally require no or very little insulin and do not cause spikes in
blood sugar (Jenkins et al. 1981). For this reason, polyols are suitable for use by diabetics
because they play a key role in reducing glycemic index as well as reducing the risk of tooth
decay. However, some of the polyols have drawbacks in that they are not absorbed by the
blood and instead just pass through the small intestines (Jenkins et al. 1981). Also, large
consumption of polyols can result in intestinal gas or diarrhoea.

4.4.2.2 Sugar alcohols

The compounds here referred to as sugar alcohols are neither sugar by their nature nor
alcohols; however, their chemical structures partially resemble that of sugars and of alcohols.
As food additives (sweeteners), they have a sweet taste which can mask the aftertaste of other
sweeteners and can also add bulk and texture. They have the property of providing the cooling
effect or taste, they inhibit browning during heating and retain moisture in foods.