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High I ntensity Sweeteners &

Polyols
Yuan Yao, Associate Professor
yao1@purdue.edu
Whistler Center for Carbohydrate Research
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Outline
Sweetness
High intensity sweeteners
Polyols
Examples
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Sweetness
Sweetness
Hypothesis: sweetness perception is initiated by an interaction
of a sweet molecule with a receptor site in the taste buds
The actual receptor site has not been isolated
Once a sweet molecule interacts with the receptor site, a
series of reactions occurs and the taste signal is sent to brain
Various models have been proposed, and the most widely
accepted one is the three-point attachment theory (AH-B-X)
Relationship between chemical structure and the ability to
initiate sweetness is not well understood
Most sweeteners were discovered by trial and error
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4
Sweetness
AH
+
area contains functional groups with hydrogen to form hydrogen bond with
partially negative atom on the sweet molecule (acid group COO
-
on aspartame)
B
-
area contains partially negative groups available to form hydrogen bond with
hydrogen on the sweet molecule (amine group NH
3+
on aspartame)
X area is a hydrophobic (lipophilic) area interacting with the non-polar area on
the sweet molecule (benzene ring on aspartame)
http://www.elmhurst.edu/~chm/vchembook/549receptor.html
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Sweeteners
High intensity sweeteners
Acesulfame K Alitame
Aspartame Cyclamate
Neotame Saccharin
Stevioside Sucralose
Polyols
Erythritol Isomalt
Hydrogenated starch hydrolysates maltitol
Lactitol Sorbitol
Mannitol Xylitol
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High Intensity Sweeteners
Acesulfame K (200 X sugar sweetness)
5,6-dimethyl-1,2,3-oxathiazine-4(3H)-one
2,2-dioxide, a sweet tasting compound,
was incidentally discovered in 1967 by
Clauss and Jensen
Among different substitutions, 6-methyl-
1,2,3-oxathiazine-4(3H)-one 2,2-dioxide
was demonstrated to be the most
favorable one
Generic name acesulfame potassium was
registered by the world Health
organization (WHO)
Acesulfame K is a white crystalline
powder, dissolving readily in water
http://www.elmhurst.edu/~chm/vchembook/549
acesulfame.html
The additive shall be used in accordance with current good manufacturing
practice in an amount not to exceed that reasonably required to accomplish
the intended effect (FDA 21CFR172.800)
Applications: low-calorie products, diabetic foods, sugarless products, oral
hygiene preparations, pharmaceuticals, and animal feeds
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High Intensity Sweeteners
Saccharin (200 - 800 X)
1,2-benzisothiazolin-3-one - 1,1 - dioxide
Discovered in 1878 by Ira Remsen and
Constantine Fahlberg (obtained the
patents)
Three commercially available saccharin
forms: acid, sodium, and calcium.
Sodium saccharin is the most commonly
used due to its high solubility, stability,
and economics
Synergistic effect with aspartame,
sucralose, sucrose, and fructose; additive
with acesulfame K
Most economic sweetener
http://www.elmhurst.edu/~chm/vchembook/549
saccharin.html
It is required to be used as a sweetening agent only in special dietary foods, for
the indicated technological purposes, and with labeling of the name and
concentration. Go to 21CFR180.37 for details (Part 180--food additives permitted
in food or in contact with food on an interim basis pending additional study)
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High Intensity Sweeteners
Aspartame (160 - 220 X)
1-methyl N-L-[alpha]-aspartyl-L-
phenylalanine, a dipeptide containing L-
aspartic acid and the methyl ester of L-
phenylalanine
Incidentally discovered in 1965 by GD
Searle and James Schlatter
Under certain conditions, the ester bond
is hydrolyzed, forming methanol and
dipeptide, which is ultimately hydrolyzed
to individual amino acids
Maximum stability at around pH 4.3. Very
high temperature reduces stability
Slightly soluble in water (~1.0%)
http://www.elmhurst.edu/~chm/vchembook/549
aspartame.html
The label of any food containing the additive shall bear: Phenylketonurics:
Contains Phenylalanine. When the additive is used in a sugar substitute for table
use, its label shall bear instructions not to use in cooking or baking
(21CFR172.804)
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High Intensity Sweeteners
Sucralose (600 X) (Splenda)
1,6-dichloro-1,6-dideoxy-[beta]-D-
fructofuranosyl-4-chloro-4-deoxy-[alpha]-
D-galactopyranoside
Discovered in 1970s by Hough and his
coworkers, with the support of Tate & Lyle
Selective chlorination of sucrose
A white, crystalline, nonhydroscopic
powder
Highly soluble in water and ethanol
Dry sucralose may show increased
discoloration at higher temperature
Sucralose liquid concentrates show high
storage stability
http://www.elmhurst.edu/~chm/vchembook/549
sucralose.html
The additive may be used as a sweetener in foods generally, in accordance with
current good manufacturing practice in an amount not to exceed that reasonably
required to accomplish the intended effect (21CFR172.831)
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High Intensity Sweeteners
Stevioside (250-300 X)
(5,8,9,10,13)-13-Hydroxykaur-16-en-18-
oic acid
First isolated from Stevia rebaudiana by
Bridel and Labielle (1931). Commercially
used since 1971.
Steviol glycoside found in S. rebaudiana
510% stevioside (250300X)
24% rebaudioside A (350450X), least bitter
12% rebaudioside C
1/21% dulcoside A
Heat and pH stable, do not ferment.
Steviol structure. Steviol is the aglycone
to the four main steviosides (Different
units at R1 and R2) (J.M.C. Geuns,
2003, Phytochemistry 64: 913921)
In 2000, the European Commission did not accept it as a food or food ingredient
because of lack of scientific reports and discrepancies between studies regarding
possible toxicological effects. Lately, Stevioside and Rebaudioside were declared
as not genotoxic, nor carcinogenic and potentially beneficial for hypertension
patients or type-2 diabetes. Acceptable Daily Intake (ADI) of 4 mg/kg bodyweight/day

Online article: Safety data for stevia extracts is robust: Carbill/Coke-funded study
http://www.foodnavigator-usa.com/Science/Safety-data-for-stevia-extracts-is-robust-
Cargill-Coke-funded-study.
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Economics of Commercial Sweeteners
Sweetener
Sweetness over sucrose
at concentration of
Cost
($/lb)
Cost/sweetness for
sucrose concentration of
3% 7% 3% 7%
Sodium
saccharin 2H
2
O 500 300 2.75 1.0 1.0
Aspartame 231 159 30 23.6 20.6
Acesulfame K 188 97 37 35.8 41.6
HFCS 1.0 1.0 0.25 45.5 27.3
Sucralose 664 558 150 ? ?
Sucrose 1.0 1.0 0.36 65.5 39.3
Modified: L. Nabors. AlternativeSweeteners. Third edition, 2001, Marcel Dekker, Inc, NY
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Polyols
Definition and natural occurrence
Structure and manufacture
Physicochemical and organoleptic properties
Nutritive value and health benefit
Applications
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Polyol Natural occurrence
Erythritol Wine, sake, soy sauce, melons, pears, grapes, etc
Xylitol Fruit, vegetables, intermediate in glucose metabolism
Sorbitol Rowan, pears, cherries, plums, apricots, apples, etc
Mannitol Tree exudates, manna ash, marine algae, fresh mushroom
Maltitol
Lactitol
Isomalt
Polyglycitol
Natural occurrence
What are polyols? Are they natural?
Definition
Sugar alcohol and polyol are synonyms
Carbonyl group (>C=O) in the aldose and ketose moieties of mono-, di-,
oligo-, and polysaccharides is replaced by alcohol group (>CH-OH)
Polyols generally carry the suffix itol in place of the suffix ose
Definition and Natural Occurrence
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Structures of polyols are similar:
CH2OH
OH
CH2OH
OH
CH2OH
OH
CH2OH
OH
HO
O
CH2OH
OH
OH
HO
O
OH
CH2OH
OH
OH
CH2OH
CH2OH
OH
CH2OH
OH
HO
OH
CH2OH
HO
CH2OH
OH
HO
OH
O
CH2OH
OH
OH
HO
O
CH2OH
HO
OH
OH
OH
O
CH2OH
OH
OH
HO
O
CH2OH
HO
HO
OH
OH
O
CH2OH
OH
OH
OH
O
OH
CH2OH
OH
OH
CH2OH
Erythritol
Xylitol
Sorbitol
Mannitol
Maltitol
Lactitol
Isomalt: 50%GPM + 50% GPS
Molecular Structure
Carbonyl group is replaced by alcohol group
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Starch
Liquefaction
Fermentation
Saccharification
Hydrogenation
Erythritol Sorbitol
Mannitol
Maltitol
Polyglycitol
Purification Purification
Xylan
Hydrolyzation
Hydrogenation
Purification
Lactose
Hydrogenation
Purification
Sucrose
Hydrogenation
Purification
Isomaltulose
Lactitol Isomalt Xylitol
Enzymatic conversion
Polyols industry is established
Industrial Manufacture
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Polyol/sugar
Melting
point (
o
C)
Hygro-
scopicity
Solubility
g/100g H2O
(25
o
C)
Heat stability
(
o
C)
Acid stability
(pH)
Erythritol 126 Very low 37-43 >160 2-12
Xylitol 94 High 63 >160 2-10
Mannitol 165 Very low 18-22 >160 2-10
Sorbitol 97 Median 70-75 >160 2-10
Maltitol 150 Median 60-65 >160 2-10
Isomalt 145-150 Very low 25-28 >160 2-10
Lactitol 122 Low 55-57 >160 >3
Sucrose 190 Low 67 <160-186
Hyrolyzes at
acidic/alkaline pH
Polyols have diversified properties
Physicochemical Properties
Modified: L. Nabors. AlternativeSweeteners. Third edition, 2001, Marcel Dekker, Inc, NY
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0
20
40
60
80
100
Sweetness Compared with Sucrose
Sweetness 65 100 60 50 90 40 35 100
Erythritol Xylitol Sorbitol Mannitol Maltitol Isomalt Lactitol Sucrose
-50
-40
-30
-20
-10
0
Cooling Effect
Heat of Solution (cal/g) -42.9 -36.6 -26.5 -28.9 -5.5 -9.4 -13.9 -4.3
Erythritol Xylitol Sorbitol Mannitol Maltitol Isomalt Lactitol Sucrose
Polyols are sweet and cool
Organoleptic Properties
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Polyols are not fully digested in the body
Carbohydrate
Small intestine
Large intestine
Not
absorbed
Not
fermented
Feces
Not metabolized Kidneys
Urine
Metabolized
Energy
CO
2
Absorbed
Fermented
Biomass
CH
4
/H
2
Feces
Volatile fatty acids
Food Energy Values
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Energy value of undigested sugars, (kcal/g)
Polyols
Potential energy
(heat of combustion)
Food energy
US self
determined
European
regulations
Erythritol 4.1 0.2 0.2 2.4
Isomalt 4.1 2.1 2 2.4
Lactitol 4.1 2 1.9 2.4
Maltitol 4.1 2.7 2.1 2.4
Maltitol
syrups
Reg./int./high 4.1 3 3 2.4
High-polymer 4.1 2.8 3 2.4
Polyglycitol (HSH) 4.1 2.8 3 2.4
Mannitol 4.0 1.5 1.6 2.4
Sorbitol 4.0 2.5 2.7 2.4
Xylitol 4.1 3 2.4 2.4
Polyols have low calorie
Food Energy Values
Modified from: G. Livesey. Nutrition Research Reviews. 2003, 16, 163 -191
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Polyols are low in glycemic response
Glycemic Response
Maltitol
Isomalt
Lactitol
Erythritol
Sorbitol
Xylitol
Mannitol
Glucose
Sucrose
Glycaemic curves for glucose, sucrose, maltitol, isomalt, lactitol, xylitol, sorbitol,
erythritol, and mannitol in normal individuals. Data from several publications
were pooled to yield curves representative of 25 g doses (2064 g for erythritol)
(Adapted from G. Livesey. Nutrition Research Reviews. 2003, 16, 163 191)
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Tooth Diet
Plaque
Caries
Major areas of plaque accumulation Major factors of dental caries
Loss of mineral (demineralization) occurs when the plaque pH drops below 5.5-5.7
Redisposition of mineral (remineralization) occurs when the plaque pH rises
Fluoride may reduce the critical pH by 0.5 units, exerting its protective effect
Factors of caries formation
Dental Health: Non-cariogenic
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Inhibit
Starch & derivatives Fermentable sugars
Plaque (mutans
streptococci and
lactobacilli)
Acid
Demineralization
Enamel crystal
Carbonated apatite
Partly
dissolved
crystal
Crystal with
new surface
Remineralization
Calcium, Phosphate,
Fluoride
buffering, washing,
neutralizing
Salivary flow
Salivary amylase
Produce
Polyols are non-cariogenic
Dental Health: Non-cariogenic
Polyols are not fermentable. No acid is generated. So polyols
are non-cariogenic
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Polyols are beneficial to colon health
Colon Health
Fermented by microflora, polyols benefit colon health
Enables saccharolytic anaerobes and aciduric organisms to grow in
preference over putrefying, endotoxic, pathogenic, and
procarcinogen-activating aerobic organism
Acidic conditions may normalize epithelial functions
Lactic acid is generated from fermentable carbohydrates
Butyric acid generated from polyols is beneficial to maintaining a
healthy colonic epithelium and improving inflammatory conditions
of the colonic mucosa
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Polyols Specific properties Main applications
Sorbitol
Crystalline
Cooling effect, compressibility,
cryoprotective
Chewing gum, tablets, surimi
Syrup
Micro-crystallization, surface
crystallization, humectancy
Deposited high boiled sweets, biscuits, cakes,
pastry
Maltitol
Crystalline
High sweetness, non-hygroscopic, high
melting point, crystallization
Chocolate, coated chewing gum, bakery
Syrup
Plasticity of massecuites, anti-crystallizing,
plasticizer, HFS substitute
High boiled sweets, chewy sweets, jellies,
chewing gum, gums, bakery
Crystalline mannitol Non-hygroscopic Dusting powder, chewing gum, chewy sweets
Crystalline xylitol
High sweetness, cooling effect,
crystallization
Jellies, chewing gum, coated chewing gum
Lactitol Low-hygroscopic, mild cooling effect
Chewing gum, chocolate, confectionery,
bakery, ice-cream, tablets
Erythritol
Non-calorie, non-hygroscopic, cooling
effects,
Low-calorie beverages, chocolate, chewing
gum, dehydrated fruit, bakery
Isomalt Low cooling effect
Chocolate, high-boiled candy, chewing gum,
pan-coated products
Polyglycitol (HSH)
Non-reducing, cryoprotective, heat/acid
resistant
Corn syrup substitute, confectionery, ice-
cream, hard candies, bakery
Polyols are widely used in foods
Regular Food Applications
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Product
Relative
sweetness
%
GI
Calorie content (kcal/g) Laxation
threshold
(g/day)
Solubility
at 25 C
(g/100g
H2O)
Heat of
solution
(cal/g)
Melting
point (C)
Hygro-
scopicity
Molecular
weight
Regulatory status
USA EU Japan USA EU Japan
Sorbitol 60 20 2.6 2.4 3 50 235 -26.5 99-101 Medium 182 GRAS Yes Yes
Mannitol 50 20 1.6 2.4 2 20 22 -28.9 165-169 Very low 182
Food
additive
Yes Yes
Polyglycitol
(syrup)
30-40 33 3 n/a 2.3-3.4 >100 soluble n/a n/a Medium Variable GRAS1 pending Yes
Polyglycitol
(powder)
<30 33 3 n/a 2.3-3.4 >100 250-350 +7.0-11.0 115 Low Variable GRAS1 pending Yes
Maltitol
syrup
70-80 33 3 2.4 2.3-3.4 >100 soluble n/a n/a Medium Variable GRAS1 Yes Yes
Maltitol 90 33 2.1 2.4 2 90-100 175 -5.5 144-147 Low 344 GRAS1 Yes Yes
Xylitol 100 20 2.4 2.4 3 25-50 200 -36.6 92-95 High 152
Food
additive
Yes Yes
Lactitol
monohydrat
e
30-40 15 2 2.4 2 20-50 140 -13.9 95-101 Low 362 GRAS1 Yes Yes
Anhydrous
isomalt
40 20 2 2.4 2 30-50 39 -9.4 145-150 Very low 344 GRAS1 Yes Yes
Erythritol 60-70 <20 0.2 n/a 0 125 61 -42.9 119-123 Very low 122 GRAS pending Yes
Glycerin 55-75 4.3 4.3 4.3 >125 soluble +16.0 17.8 Medium 99 GRAS Yes Yes
Polydextrose 0 <10 1 1 1 90 80 +9.0 130 High <22,000
Food
additive
Yes Yes
Sucrose 100 60 4 4 4 >>100 185 -4.3 160-186 Low 342 GRAS Yes Yes
Fructose 117 20 4 4 4 50-70 400 -8.0 102-105 High 180 GRAS Yes Yes
Maltose 30 100 4 4 4 >>100 70 -8.0 120-125 Medium 342 GRAS Yes Yes
A polyol table for food technologists
Polyol Table for Food Applications
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Polyol Erythritol Xylitol Sorbitol Mannitol Maltitol Polyglycitol Lactitol Isomalt Sucrose
Laxation
Threshold
125 25-50 50 20 90-100 >100 20-50 30-50 >>100
Wanted: polyols without laxative effect
Challenges Facing Polyol Industry
Laxation
A gentle stimulation of the bowel to render the motion slightly soft
without causing gripes
Each individual may experiment with intake amounts and make
adjustment based on their own experience
Tolerance
Amount of polyols to cause gastrointestinal symptom, e.g. abdominal
discomfort, flatulence, and osmotic diarrhea
Laxation threshold guidance, g/day
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Examples: Ingredient Labels
Diet Coke (UK): Carbonated water, color (caramel E150d), sweeteners (aspartame,
acesulfame-K), flavorings (including caffeine), phosphoric acid, citric acid. Contains a source
of phenylalanine
Coke Zero (UK): Carbonated water, color (caramel E150d), phosphoric acid, sweeteners
(aspartame, acesulfame-K), flavorings (including caffeine), acidity regulator (E331). Contains a
source of phenylalanine
SpringTree sugar free syrup: Water, sorbitol, cellulose gum, natural and artificial flavor,
salt, aspartame, citric acid, caramel color, sodium benzoate and potassium sorbate (as
preservatives), acesulfame potassium, tetrasodium pyrophosphate
PHENYLKETONURICS: CONTAINS PHENYLALANINE
Smuckers flavored drink mix: Citric acid, natural and artificial flavors, maltodextrin,
aspartame, acesulfame potassium (non nutritive sweetener), ascobic acid (vitamin C), silicon
dioxide and magnesium oxide (anticaking agents), red 40, yellow 5
PHENYLKETONURICS: CONTAINS PHENYLALANINE
Pepperidge Farm sugar free Milano: Unbleached enriched wheat flour [flour, niacin,
reduced iron, thiamin mononitrate (vitamin B1), riboflavin (vitamin B2), folic acid], maltitol*,
vegetable oils (canola, palm kernel, and/or palm), polydextrose*, chocolate, whole eggs, cocoa
butter, chocolate processed with alkali, contains 2 percent or less of: corn starch, nonfat milk,
egg whites, salt, milkfat, soy lecithin, natural flavors, peppermint oil, sucralose, vanilla extract
and baking soda. (* Excessive consumption may have a laxative effect)