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Glucose: Properties and analysis

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Shendurse A.M., and Khedkar C.D. (2016) Glucose: Properties and Analysis. In: Caballero, B., Finglas, P., and
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 Author's personal copy
Glucose: Properties and Analysis
AM Shendurse, Sardarkrushinagar Dantiwada Agricultural University, Sardarkrushinagar, India
CD Khedkar, College of Dairy Technology, Pusad, India
ã 2016 Elsevier Ltd. All rights reserved.
Introduction
D-Glucose, the most abundant carbohydrate and the most
abundant organic compound (if all its combined forms are
considered), belongs to the class of carbohydrates called
monosaccharides. Monosaccharides are carbohydrate mole-
cules that cannot be broken down to simpler carbohydrate
molecules by hydrolysis, so they are sometimes referred to as
simple sugars. They can be joined together to form larger
structures, namely, oligosaccharides and polysaccharides, that
can be converted into monosaccharides by hydrolysis.
Glucose, also called dextrose, belongs to a group of carbohy-
drates known as simple sugars (monosaccharides). Glucose has
the molecular formula C6H12O6. It is found in fruits and honey
and is the major free sugar circulating in the blood of higher
animals. It is the source of energy in cell function, and the
regulation of its metabolism is of great importance (gluconeo-
genesis). Molecules of starch, the major energy-reserve carbohy-
drate of plants, consist of thousands of glucose units, as do those
of cellulose. Also composed of glucose is glycogen, the reserve
carbohydrate in most vertebrate and invertebrate animal cells, as
well as those of numerous fungi and protozoans.
Nomenclature of Glucose and Related Polymers
Glucose
Glucose was first isolated in 1747 from raisins by Andreas
Marggraf. The name glucose was coined in 1838 by Jean
Dumas, from the Greek word gleucos, which means ‘sweet’ or
‘sugar,’ and the structure was discovered by Emil Fischer
around the turn of the century. The compound D-(þ)-glucose
or dextrose is 2,3,4,5,6-pentahydroxyhexaldehyde, more con-
ventionally expressed as C6H12O6, with a molecular weight of
180.16 kDa. Glucose is readily soluble in water in a powder
form. Below 50  C, a-D-glucose hydrate is the stable form; at
50  C, the anhydrous form is obtained; and at higher temper-
atures, a-D-glucose is obtained. Glucose is also present in the
diet as part of the disaccharides sucrose (glucose and fructose),
lactose (glucose and galactose), and maltose (glucose).
D-Glucose is both a polyalcohol and an aldehyde. It is
classified as an aldose, a designation for sugars containing an
aldehyde group. The ending -ose signifies a sugar and- ald
signifies an aldehyde group. Glucose has four chiral carbon
atoms: C-2, C-3, C-4, and C-5. Naturally occurring glucose is
designated as the D form, specifically D-glucose. It has a molec-
ular mirror image, termed the L form, specifically L-glucose.
Since each chiral carbon atom has a mirror image, there are 2n
arrangements for these atoms. Therefore, in a six-carbon
aldose, there are 24 or 16 different arrangements of the carbon
atoms containing secondary hydroxyl groups, allowing forma-
tion of 16 different six-carbon sugars with an aldehyde end.
Encyclopedia of Food and Health http://dx.doi.org/10.1016/B978-0-12-384947-2.00353-6
The Encyclopedia of Food and Health, (2016), vol. 3, pp. 239-247
Eight of these belong to the D-series; eight are their mirror
images and belong to the L-series.
All sugars that have the hydroxyl group on the highest
numbered chiral carbon atom (C-5 in case of glucose) posi-
tioned on the right-hand side are arbitrarily called D-sugars,
and all with a left-hand-positioned hydroxyl group on the
highest numbered chiral carbon atom are designated as
L-sugars. Two structures of D-glucose in its open-chain, acyclic
form (called the Fischer projection) with the carbon atoms
numbered in the conventional manner are given in Figure 1.
In this convention, each horizontal bond projects outward
from the plane of the page and each vertical bond projects
into or below the plane of the page. It is customary to omit
the horizontal lines for covalent chemical bonds to the hydro-
gen atoms and hydroxyl groups as in the structure on the right.
Because the lowermost carbon atom is nonchiral, it is mean-
ingless to designate the relative positions of the atoms and
groups attached to it. Thus, it is usually written as –CH2OH.
D-Glucose and all other sugars containing six carbon atoms are
called hexoses, the most common group of aldoses. The cate-
gorical names are often combined, with a six-carbon atom
aldehyde sugar being termed an aldohexose.
L-Sugars are less numerous and less abundant in nature
than are the D forms but nevertheless have important bio-
chemical roles. Two L-sugars found in foods are L-arabinose
and L-galactose, both of which occur as units in carbohydrate
polymers (polysaccharides).
Glucose Oligosaccharides
Oligosaccharides (Greek oligo, ‘few’) are sugar polymers; the
term usually refers to compounds containing 2–9 units but
may include polymers containing up to 19 units. The dimer,
trimer, and tetramer forms in which glucose molecules are
joined by (1–4) linkages are referred to as maltose, maltotriose,
and maltotetraose, respectively, since these substances are the
products of starch digestion in the malting process. Sucrose,
maltose, and lactose are common dietary disaccharides.
Starches
Starches are large-molecular-weight, a-linked polymers of glu-
cose (C6H10O5)n. Most starches show a mixture of a(1–4) and
a(1–6) linkages. The a(1–4)-linked polymer forms a linear
structure that allows for hydrogen bonding between polymer
chains and a more compact starch structure. Introduction of
(1–6) linkages results in branch points and a more open struc-
ture that allows the (1–4)-linked backbone with the hemiace-
tal bond in the alpha configuration to coil like a spring into a
helical form. Branched starches with the (1–6) linkage are
more readily hydrated and digested compared to the (1–4)-
linked linear starch. The (1–4)-linked starches are referred to as
239
 Author's personal copy
240 Glucose: Properties and Analysis
H C O HC O C-1
H C OH HCOH C-2
HO C H HOCH C-3
H C OH HCOH C-4
H C OH HCOH C-5
H C OH CH2OH C-6
H lies not in the chemical structure but in the fact that hemicel-
Figure 1 Structure of D-glucose (open-chain structure).
amylose starch, and (1–6)-linked starches are amylopectin
starches.
Resistant Starch
Resistant starches are defined by their resistance to digestion in
the human upper gastrointestinal tract. As with the term ‘die-
tary fiber,’ the definition is largely physiological. One proposed
classification divides resistant starches into three classes: RS1,
RS2, and RS3. The first class, RS1, is starch that escapes small
intestinal digestion owing to the food form and incomplete
enzymatic attack (e.g., large particle size or compact nature of
food or starch entrapment by dietary fiber). The second, RS2,
includes the more crystalline starches that resist digestion (e.g.,
high-amylose starches that resist gelatinization). The RS3
starches are retrograded starches (e.g., high-amylose starches
that upon cooling after cooking form a compact, hydrogen-
bonded crystalline structure that excludes water).
Cellulose
Like starch, cellulose is a (1–4)-linked glucose polymer
(C6H10O5)n, but in this instance, the glucose molecules are
b-linked, allowing the development of a linear polymer with
strong intrachain hydrogen bonding. Cellulose polymers may
consist of as many as 10 000 glucose monomer units. Cellulose
is both resistant to small intestinal digestion and insoluble in
cold or hot water and most dilute acids and alkali. It is partially
degraded by colonic bacteria; the proportion degraded is depen-
dent on the source, with cellulose from vegetables broken down
to a greater extent than cellulose from cereals such as wheat.
b-Glucans
In many ways, these predominantly (1–4)-linked glucose poly-
mers are the cellulose equivalent of the starch amylopectin.
Here, it is the (1–3) linkages interspersed throughout the poly-
mer that prevent the compact structure achieved with the cel-
lulose polymer where only the (1–4) linkages exist. As a result
of the more open molecular structure of the b-glucan, unlike
cellulose, it is readily hydrated and soluble in water, forming a
solution of high viscosity. The viscosity, in turn, is dependent
on the molecular weight and the presence of the (1–3) link-
ages. The greater the molecular weight, the greater the viscosity.
Thus, reduction of molecular weight by acid or enzymatic
hydrolysis, which may also occur during food processing,
The Encyclopedia of Food and Health, (2016), vol. 3, pp. 239-247
may greatly reduce viscosity. The common feature shared by
cellulose and the b-glucans is that both are resistant to diges-
tion by small intestinal enzymes. However, whereas cellulose is
only partially fermented by the colonic bacteria, b-glucans are
completely fermented.
Hemicellulose
The term ‘hemicellulose’ should not be taken to imply a class
of (1–4)-linked glucose polymers. The similarity with cellulose
lulose is also insoluble in hot or cold water or hot dilute acid. It
is, however, soluble in dilute alkali. The polymeric structure is
heterosaccharitic with two or more sugars (e.g., arabinoxylans
found in cereals), with a relatively small molecular size
(50–200 saccharide units).
Occurrence
Glucose is the primary carbohydrate energy source of verte-
brates. In healthy humans, fasting blood glucose levels are
approximately 3.5–5.5 mmol l1 (depending on the labora-
tory) and increase postprandially to values considerably
< 10 mmol l1 (the renal threshold for complete reabsorption,
above which glucose ‘spills’ over into the urine). Blood levels
higher than 7.8 mmol l1 2 h after a 75 g glucose load are one
of the diagnostic criteria for diabetes. Glucose is stored as
glycogen, an a-linked polymer, predominantly in the liver
and muscles (‘animal starch’). On average, a 70 kg man may
store 500 g of glycogen. Glucose can also be synthesized de
novo by gluconeogenesis from the gluconeogenic amino acids
lactate, glycerol, and pyruvate. Breakdown of glycogen into
glucose is known as glycogenolysis.
Erythrocytes, renal tissue, and nervous tissue require glu-
cose as an energy source. In erythrocytes and renal tissue, the
glucose is not oxidized but is returned to the liver as part of the
Cori cycle for glucose synthesis. The brain oxidizes glucose and
requires 140 g day1. Despite this requirement, carbohydrate is
still recommended to comprise between 45% and 65% of
dietary calories. Glucose is present in fruit and vegetables,
and although less sweet on a per gram basis than fructose or
sucrose, it is responsible together with fructose and sucrose for
the sweet taste of vegetables and fruit. With the exception of
fruit such as green banana, seeds (grain and dried legumes),
and tubers, in which starch is the major carbohydrate form,
foods containing glucose, fructose, and sucrose in various
ratios comprise the major available (i.e., absorbable in the
small intestine) carbohydrate sources.
Physical Properties of Glucose
Glucose contains alcohol, ester (in the ring form), and aldehyde
(in the linear form) as the functional groups, which are respon-
sible for the majority of the chemistry that glucose undergoes.
Some of the physical characteristics of glucose, such as melting
point, solubility, and density, are listed in Table 1.
 Author's personal copy
Glucose: Properties and Analysis 241

Structure the fifth atom, which links to a sixth carbon atom outside the
ring, forming a CH2OH group. The formation of pyranose and
Glucose (C6H12O6) contains six carbon atoms and an alde-
furanose rings (cyclic hemiacetals) of glucose has been pre-
hyde group and is therefore referred to as an aldohexose. The
sented in Figure 2.
glucose molecule can exist in an open-chain (acyclic) and ring
(cyclic) form (in equilibrium), the latter being the result of an
intramolecular reaction between the aldehyde C atom and the
C-5 hydroxyl group to form an intramolecular hemiacetal. As Solubility
the ring contains five carbon atoms and one oxygen atom,
One of the important physical properties of glucose is its ability
which resembles the structure of pyran, the cyclic form of
to dissolve in aqueous, that is, water-based, solution. Since the
glucose is also referred to as glucopyranose. In this ring, each
blood, the extracellular fluid, and the fluid inside cells are all
carbon is linked to a hydroxyl side group with the exception of
water-based, for glucose to dissolve in the bloodstream and be
able to pass into cells, it must also dissolve well in water. Com-
pounds consisting of only carbon and hydrogen show very poor
Table 1 Physical properties of glucose water solubility. Elements such as oxygen and nitrogen, which
are common in organic and bioorganic molecules, help increase
Physical properties Characteristics
water solubility. Glucose’s six oxygen atoms increase its ability to
Appearance White, crystalline dissolve in water, In particular, since five of those oxygen atoms
Molecular weight 180.16 g mol1 are found in the form of alcohol groups, which allows it to
Melting point 150  C readily form hydrogen bonds with water molecules and makes
Density 1.5620 g cm3 (at 18  C) it very water-soluble, glucose dissolves quite readily in water.
Solubility in: All forms of glucose are colorless and easily soluble in
Water Very soluble water, acetic acid, and several other solvents. They are only
Ethanol Slightly soluble
sparingly soluble in methanol and ethanol. Table 2 shows
Ethyl ether Insoluble
Pyrimidine Soluble
the change in solubility with changing temperature for glucose
in water.

CH2OH CH2OH
H O H H O OH

H H
OH OH
HO OH HO H

HO H HO
H
α-D-Glucopyranose β-D-Glucopyranose

CHO

H C OH

HO C H

H C OH

H C

CH2OH
Aldo-D-glucose
CH2OH CH2OH

CHOH H CHOH OH
O O
H H
OH OH
HO OH HO H

H HO H HO

α-D-Glucofuranose β-D-Glucofuranose

Figure 2 Pyranose and furanose rings (cyclic hemiacetals) of glucose.

The Encyclopedia of Food and Health, (2016), vol. 3, pp. 239-247

 Author's personal copy
242 Glucose: Properties and Analysis

Solid State rate of mutarotation. Certain enzymes, such as mutarotase, will

Depending on conditions, three major solid forms of glucose
can be crystallized from water solutions: a-glucopyranose,
b-glucopyranose, and b-glucopyranose hydrate.
Mutarotation
The open-chain form is thermodynamically unstable, and it
spontaneously isomerizes to the cyclic forms. When sugar
molecules are dissolved in aqueous solutions, a series of reac-
tions, involving molecular rearrangements around the C-1,
take place. These rearrangements are associated with the
change in optical rotation and lead to the formation of a
mixture of products that are in equilibrium. This process, first
observed for D-glucose, is called mutarotation.
If one dissolves a-D-glucopyranose ([a]D þ112 ) or b-D-
glucopyranose ([a]D þ19 ) in water, an equilibrium is formed
with the [a]D of the resultant solution being þ52.7 . Theoret-
ically, the mixture contains five different structural forms of
glucose: a-D-glucopyranose, b-D-glucopyranose, a-D-glucofura-
nose, b-D-glucofuranose, and open-chain free aldehyde
(Figure 2). The four-ring structures are transformed into each
other via the open-chain form. The process will take place if the
starting material represents any of the five forms. The mutar-
otation process is slow (it may take several hours to reach
equilibrium) if conducted in water at 20  C. The rate of mutar-
otation increases, however, 1.5–3 times with each 10  C
increase in the temperature. Both acids and bases increase the
Table 2 Solubility of glucose
Solubility in grams of
Temperature ( C) glucose per 100 ml of water
25 91
30 125
50 244
70 357
90 556
also catalyze the mutarotation reactions. The rate and the
relative amount of products are also affected by the polarity
of the solvent, with less polar solvents decreasing the rate of
mutarotation. The reaction begins upon dissolution of sugar
molecule and an attack, by either acid or base, on the cyclic
sugar. It involves the transfer of a proton from an acid catalyst
to the sugar or the transfer of proton from the sugar to a base
catalyst as shown in Figure 3.
Enolization and Isomerization
In the presence of alkali, sugars are relatively easily intercon-
verted. The transformation involves epimerization of both
aldoses and ketoses as well as aldose–ketose isomerization.
The mechanism of the reaction is shown in Figure 4. The
enolization reaction is a general reaction of a carbonyl com-
pound having an a-hydrogen atom. Starting with aldehydo-D-
glucose, the 1,2 enediol is first formed, which can be converted
into another aldose (with opposite configuration at C-2) and
the corresponding ketose. Therefore, by enolization and isom-
erization, D-glucose, D-mannose, and D-fructose can be easily
interconverted. Either a base or an enzyme catalyzes isomeri-
zation, and it will also occur under acid or neutral conditions,
although at a much slower rate.
Optical Activity
Whether in solution or in the solid form, D-glucose is dextro-
rotatory, meaning it will rotate the direction of polarized light
clockwise. The effect is due to the chirality of the molecules,
and indeed, the mirror-image isomer, L-glucose, is levorotatory
(rotates polarized light counterclockwise) by the same
amount.
The D- prefix does not refer directly to the optical properties
of the compound. It indicates that the C-2 chiral center has the
same handedness as that of D-glyceraldehyde (which was so
labeled because it is dextrorotatory). The fact that D-glucose is
dextrorotatory is a combined effect of its four chiral centers,

Base (pH 10) catalyzed mutarotation

CH2OH CH2OH O CH2OH

−
O O H H O OH
OH OH O OH −
O H− OH
+
HO OH HO HO
OH OH OH

Acid (pH 4) catalyzed mutarotation

CH2OH
+ CH2OH CH2OH CH2OH CH2OH
H H H H
+ + −
O O O O O O OH
OH OH OH OH OH
O
O H O H
HO HO HO HO HO
OH OH OH OH OH
Figure 3 Mechanisms of base- and acid-catalyzed mutarotation reactions.

The Encyclopedia of Food and Health, (2016), vol. 3, pp. 239-247

 Author's personal copy
H C OH HOC
H C OH C OH
HO C H HO C H HO
H C OH H C OH H C
H C OH H C OH H C
CH2OH CH2OH
D-Glucose Trans-enediol D-Fructose
Figure 4 Enolization and isomerization reactions.
not just of C-2; and indeed, some of the other D-aldohexoses
are levorotatory.
Chemical Properties of Glucose
All carbohydrate molecules have hydroxyl groups available for
reaction. Glucose and most other low-molecular-weight carbo-
hydrate molecules also have carbonyl groups available for
reaction.
Oxidation of Glucose to Produce Sugar Acids
One of the earliest methods for quantitative measurement of
glucose employed Fehling solution. Fehling solution is an alka-
line solution of copper(II) that oxidizes an aldose to an aldonate
and in the process is reduced to copper(I), which precipitates as
brick-red Cu2O. Variations, the Nelson–Somogyi and Benedict
reagents, are still used for determining amounts of reducing
sugars in foods and other biological materials.
Glucose is known as a reducing sugar, because in the pro-
cess of oxidizing the aldehyde group of glucose to the salt of a
carboxylic acid group, the oxidizing agent is reduced.
Ketoses are also termed as reducing sugars because, under
the alkaline conditions of the Fehling test, ketoses are isomer-
ized to aldoses. Benedict reagent, which is not alkaline, will
react with aldoses but not with ketoses.
Glucose, when oxidized under different conditions, forms
(i) gluconic acid, (ii) glucaric acid, and (iii) glucuronic acid as
indicated in Figure 5.
Gluconic acid
Glucose is readily oxidized to gluconic acid. The reaction is
commonly used for quantitative determination of glucose.
Oxidation of glucose with Br2–water converts the aldehyde
(–CHO) group to a -COOH group. Br2 reacts with water to
form hypobromous acid, which acts as an oxidizing agent:
Br2
D-Glucose ƒƒƒƒ! D-gluconic acid
H2 O
Another simple and specific method for quantitative oxida-
tion of D-glucose to D-gluconic acid uses the enzyme glucose
oxidase, with the initial product being the 1,5-lactone (an intra-
molecular ester) of the acid (Figure 6). The reaction is com-
monly employed to measure the amount of D-glucose in foods
and other biological materials, including the D-glucose level of
The Encyclopedia of Food and Health, (2016), vol. 3, pp. 239-247
Glucose: Properties and Analysis 243
CH2OH HOC H C O
C O HO C HO C H
C H HO C H HO C H
OH H C OH H C OH
OH H C OH H C OH
CH2OH CH2OH CH2OH
Cis-enediol D-Mannose
blood. D-Gluconic acid is a natural constituent of fruit juices and
honey. The reaction given in Figure 3 is also used for the
manufacture of commercial D-gluconic acid and its lactone.
D-Glucono-delta-lactone (GDL), D-glucono-1,5-lactone accord-
ing to systematic nomenclature, hydrolyzes to completion in
water in about 3 h at room temperature, effecting a decrease in
pH. Its slow hydrolysis, slow acidification, and mild taste set
GDL apart from other food acidulants. It is used in meats and
dairy products but particularly in baked goods as a component
of chemical leavening agents for preleavened products.
Glucaric acid
Oxidation of glucose with conc. HNO3 under proper condi-
tions converts both aldehyde and primary alcohol groups to
–COOH groups, forming a dibasic sugar acid, saccharic or
glucaric acid:
conc: HNO3
D-Glucose ƒƒƒƒƒƒƒƒ! D-Glucaric acid
D-Glucaric acid is a naturally occurring aldaric acid, typi-
cally found in small amounts in a variety of fruits and vegeta-
bles. Potential commercial applications for D-glucaric acid
include use as a metal sequestering agent, retarding agent for
metallic mordants in the dyeing of textiles, and corrosion
inhibitor for metals. A current commercial use of a salt form
of D-glucaric acid as a dietary supplement claimed to help
maintain healthy cholesterol levels and prevent cancer. As a
dietary supplement, D-glucaric acid functions as a precursor to
the b-glucuronidase inhibitor and D-glucaro-1,4-lactone. In
addition to these end uses, D-glucaric acid is the starting mate-
rial for the synthesis of other chemicals, particularly as a diacid
monomer used to make a number of polyhydroxypolyamides.
Glucuronic acid
The terminal carbon atom (at the other end of the carbon
chain from the aldehyde group) of a monosaccharide unit of
an oligo- or polysaccharide may occur in an oxidized (carbox-
ylic acid) form. Such an aldohexose with C-6 in the form of a
carboxylic acid group is called as uronic acid.
When glucose is oxidized in such a way that the primary
alcohol group is converted to –COOH group, without oxida-
tion of aldehyde group, a glucuronic acid is formed:
D-Glucose ! D-Glucuronic acid
In the body, D-glucuronic acid is formed from glucose in the
liver by uronic acid pathway, an alternative pathway for glu-
cose oxidation. It occurs as a constituent of certain moco-
polysaccharides. In addition, it conjugates toxic substances,
 Author's personal copy
244 Glucose: Properties and Analysis

COOH

H C OH
CH2OH CH2OH
HO C H
H OH O O
H
H C OH H H
H
C
H O + OH−
HO OH OH
H C OH O− HO

CH2OH H OH H OH
Oxidation
at C-1 D-Gluconic acid D-Gluconic acid D-δ-Gluconolactone

Note: D-Gluconic acid and other aldonic acids

O H exist in equilibrium with lactone structures
C

H C OH H H
COOH O H O
HO H HO H
HO C H
H H COOH H
H C OH Oxidation
HO OH HO OH
at C-6 OH OH
H C OH H H
D-Glucuronic L-Iduronic acid
CH2OH
acid (GlcUA) (IdUA)
D-Glucose

Oxidation at
C-1 and C-6
COOH

H C OH

HO C H

H C OH

H C OH

COOH

D-Glucaric acid
Figure 5 Oxidation of D-glucose to produce sugar acids.

HC O COO−
CH2OH CH2OH
HCOH HCOH
O O
OH
HOCH
glucose oxidase OH−
O HOCH
OH OH H+
HCOH HO HO HCOH
½O2 H2O1
HCOH OH OH HCOH

CH2OH CH2OH
D-Glucose β-D-Glucopyfanose D-Glucono- D-Gluconate
1,5-lactone
Figure 6 Oxidation of D-glucose catalyzed by glucose oxidase.

The Encyclopedia of Food and Health, (2016), vol. 3, pp. 239-247

 Author's personal copy
Glucose: Properties and Analysis 245

drugs, hormones, and even bilirubin (a breakdown product of
Hb) and converts them to a nontoxic substance, glucuronide,
which is excreted in urine.
Reduction of Glucose to Produce Sugar Alcohols
Hydrogenation is the addition of hydrogen to a double bond.
When applied to carbohydrates, it most often entails addition
of hydrogen to the double bond between the oxygen atom and
the carbon atom of the carbonyl group of an aldose or ketose.
Hydrogenation of D-glucose is easily accomplished with hydro-
gen gas under pressure in the presence of Raney nickel. The
product is D-glucitol, commonly known as sorbitol, where the -
itol suffix denotes a sugar alcohol (an alditol) (Figure 7).
Alditols are also known as polyhydroxy alcohols and as poly-
ols. Because it is derived from a hexose, D-glucitol (sorbitol) is
specifically a hexitol. It is found widely distributed throughout
the plant world, ranging from algae to higher orders where it is
found in fruits and berries, but the amounts present are gener-
ally small. It is 50% as sweet as sucrose, is sold both as syrup
and as crystals, and is used as a general humectant.
Formation of Hydroxyl Group Esters
The hydroxyl groups of carbohydrates, like the hydroxyl groups
of simple alcohols, form esters with organic and some inor-
ganic acids. Reaction of hydroxyl groups with a carboxylic acid
anhydride or chloride (an acyl chloride) in the presence of a
suitable base produces an ester.
Acetates, succinate half-esters, and other carboxylic acid esters
of carbohydrates occur in nature. They are found especially as
components of polysaccharides. Sugar phosphates are common
metabolic intermediates (Figure 8). Monoesters of phosphoric
acid are also found as constituents of polysaccharides. For exam-
ple, potato starch contains a small percentage of phosphate ester
groups. Cornstarch contains even less. In producing modified
food starch, cornstarch is often derivatized with one or the other
or both mono- and distarch ester groups. Other esters of starch,
most notably the acetate, succinate, and substituted succinate
half-esters, and distarch adipates are in the class of modified
food starches. Sucrose fatty acid esters are produced commer-
cially as emulsifiers. Members of the family of red seaweed poly-
saccharides, which includes the carrageenans, contain sulfate
groups (half-esters of sulfuric acid, R-OSO 3 ).
Formation of Hydroxyl Group Ethers
The hydroxyl groups of carbohydrates, like the hydroxyl
groups of simple alcohols, can from ethers as well as esters.
Ethers of carbohydrates are not as common in nature as are
esters. However, polysaccharides are etherified commercially
to modify their properties and make them more useful.
Examples are the production of methyl (–O–CH3), sodium
carboxymethyl (–O–CH2–CO þ
2 Na ), and hydroxypropyl
(–O–CH2–CHOH–CH3) ethers of cellulose and hydroxypro-
pyl ethers of starch, all of which are approved for food use.
A special type of ether, an internal ether formed between
carbon atoms 3 and 6 of a D-galactosyl unit, is found in the
red seaweed polysaccharides, specifically agar, furcellaran,
kappa-carrageenan, and iota-carrageenan. Such an internal
ether is known as a 3,6-anhydro ring, whose name derives
from the fact that the elements of water (HOH) are removed
during its formation.
A series of nonionic surfactants based on sorbitol (D-glucitol)
are used in foods as water-in-oil emulsifiers and as defoamers.
They are produced by esterification of sorbitol with fatty acids.
Cyclic dehydration accompanies esterification (primarily at a
primary hydroxyl group, i.e., C-1 or C-6) so that the carbohy-
drate (hydrophilic) portion is not only sorbitol but also its
mono- and dianhydrides (cyclic ethers). The products are
known as sorbitan esters (Figure 9). The product called sorbitan
monostearate is actually a mixture of partial stearic (C18:0) and
palmitic (C16:0) acid esters of sorbitol (D-glucitol), 1,5-anydro-D-
glucitol (1,5-sorbitan), 1,4-anhydro-D-glucitol (1,4-sorbitan),
both internal (cyclic) ethers, and 1,4:3,6-dianhydro-D-glucitol
(isosorbide), an internal dicyclic ether. Sorbitan fatty acid esters,
such as sorbitan monostearate, sorbitan monolaurate, and sor-
bitan monooleate, are sometimes modified by reaction with
ethylene oxide to produce so-called ethoxylated sorbitan esters,
nonionic detergents for food use.
CHO
CH2OPO3H−
HCOH
O
HOCH OH
OH
HCOH HO
HCOH OH
CH2OPO3H−

D-Glucose 6-phosphate
CHO CH2OH
Figure 8 Example of sugar phosphate metabolic intermediate
HCOH HCOH (D-glucose 6-phosphate).

HOCH reduction HOCH

CH2OH
HCOH HCOH OH
HOH2C O HOCH H
HCOH HCOH O O

OH
CH2OH CH2OH
HO OH O
D-Glucose D-Glucitol OH H
OH
(Sorbitol) OH
Figure 7 Reduction of D-glucose. Figure 9 Anhydro-D-glucitols (sorbitans).

The Encyclopedia of Food and Health, (2016), vol. 3, pp. 239-247

 Author's personal copy
246 Glucose: Properties and Analysis
Nonenzymatic Browning
Under some conditions, reducing sugars produce brown colors
that are desirable and important in some foods. Other brown
colors obtained upon heating or during long-term storage of
foods containing reducing sugars are undesirable. Common brow-
ning of foods on heating or on storage is usually due to a chemical
reaction between reducing sugars, mainly D-glucose, and a free
amino acid or a free amino group of an amino acid that is part of a
protein chain. This reaction is called the Maillard reaction. It is also
called nonenzymatic browning to differentiate it from the often
rapid, enzyme-catalyzed browning commonly observed in freshly
cut fruits and vegetables, such as apples and potatoes.
When aldoses or ketoses are heated in solution with amines,
a variety of reactions ensue, producing numerous compounds,
some of which are flavors, aromas, and dark-colored polymeric
materials, but both reactants disappear only slowly. The flavors,
aromas, and colors may be either desirable or undesirable. They
may be produced by frying, roasting, baking, or storage.
The reducing sugar, D-glucose, reacts reversibly with the
amine to produce a glycosylamine, as illustrated in Figure 10.
This undergoes a reaction called the Amadori rearrangement to
give a derivative of 1-amino-1-deoxy-D-fructose. Reaction con-
tinues especially at pH 5.0 or lower, to give an intermediate
that dehydrates. Eventually, a furan derivative is formed, which
is 5-hydroxymethyl-2-furaldehyde (HMF) (Figure 11). Under
less acidic conditions (higher than pH 5.0), the reactive cyclic
compounds (HMF and others) polymerize quickly to a dark-
colored, insoluble material containing nitrogen.
Maillard browning products, including soluble and insoluble
polymers, are found where reducing sugars and amino acids,
proteins, and/or other nitrogen-containing compounds are
heated together, such as in soy sauce and bread crusts. Maillard
NHR
HC O C(H)(OH)
HCOH HCOH
+RNH2
HOCH HOCH
HCOH HCOH
HCOH HCOH
CH2OH CH2OH
D-Glucose
CH2OH
OH
HO
Glucosylamine
Figure 10 Products of reaction of D-glucose with an amine (RNH2).
The Encyclopedia of Food and Health, (2016), vol. 3, pp. 239-247
reaction products are important contributors to the flavor of
milk chocolate. The Maillard reaction is also important in the
production of caramels, toffees, and fudges, during which reduc-
ing sugars also react with milk proteins. D-Glucose undergoes the
browning reaction faster than does D-fructose. Application of
heat is generally required for nonenzymatic browning.
While Maillard reactions are useful, they also have a nega-
tive side. The reaction of reducing sugars with amino acids
destroys the amino acid. This is of particular importance with
L-lysine, an essential amino acid whose e-amino group can
react when the amino acid is part of a protein molecule. Also,
a relationship has been found between the formation of muta-
genic compounds and cooking of protein-rich foods. Muta-
genic heterocyclic amines have been isolated from broiled
and fried meat and fish and from beef extracts.
Analysis of Glucose
The analysis of glucose may involve chemical, enzymatic, elec-
trochemical, and high-performance liquid chromatography
(HPLC) systems. Prior to the introduction of enzyme-based
analyses, chemical techniques were based on the reducing
ability of glucose, and techniques employing copper sulfate
were popular. Such techniques were influenced by other reduc-
ing sugars and reducing substances, including uric acid and
vitamin C. With the introduction of the more specific glucose
oxidase-based tests, the chemical tests were abandoned,
although there was debate over the potential carcinogenicity
of the early chromogens, O-dianisidine and O-toluidine. Later,
more specific, hexokinase-based enzyme assays were intro-
duced. Current methods for rapid determination of blood
HC NR
HCOH
–H2O
HOCH
HCOH
HCOH
CH2OH
CH2NHR
C O
O
HOCH
NHR
HCOH
OH HCOH
CH2OH
N-Substituted
1-amino-1-deoxy-D-fructose
 Author's personal copy
Glucose: Properties and Analysis 247

+
H2C N HC N HC N

C O COH −OH− COH +H2O

CHOH CHOH CH

CHOH CHOH CHOH

CHOH CHOH CHOH

CH2OH CH2OH CH2OH
Amadori 1,2-Eneaminol 2,3-Enol
product

HC O HC O

C O −H2O C O −H2O
HOH2C O CHO
CH2 CH
5-Hydroxymethyl-
CHOH CH 2-furaldehyde
CHOH CHOH
CH2OH CH2OH
3-Deoxyhexosulose
Figure 11 Conversion of the Amadori product into HMF.

glucose, which no longer require prior precipitation of plasma Further Reading

proteins, involve electrochemical detection. These methods
rely on silver electrodes to detect electrons generated by the
oxidation of glucose by glucose oxidase contained in mem-
branes on the surface of the electrodes. For determination of
glucose and a-limit dextrins resulting from starch digestion,
HPLC techniques have proved useful.
Much attention has been given to the analysis of the
glucose polymers – starches, resistant starches, cellulose, and
b-glucans – in the context of dietary fiber. The ultimate
assessment depends on the use of specific enzymes or enzyme
systems to break the macromolecules down to their compo-
nent glucose and other sugars when mixtures containing
other polymers (dietary fibers) are being analyzed. These are
then assessed by gas chromatography or HPLC and the ratios
of the sugars determined. More routine assessment may
involve a variety of chemical techniques combined with
enzymatic digestion and, in the case of a popular Association
of Official Analytical Chemists (AOAC)-approved technique
for dietary fiber analysis, with a gravimetric determination.
However, there is debate as to whether the resistant starch,
which in the gravimetric AOAC technique is analyzed as
dietary fiber, should be included as fiber or whether it is
physiologically distinct. It is also debated whether a determi-
nation of b-glucan is sufficient without knowledge of its
viscosity and molecular weight – factors that determine its
physiological effect.
See also: Carbohydrate: Digestion, Absorption and Metabolism;
Condensed Milk; Dahi; Food Intolerance: Lactose Intolerance; Glucose:
Metabolism and Regulation; Lactic Acid Bacteria; Lactose; Milk: Role in
the Diet; Milk: Sources and Composition; Sucrose: Dietary Importance;
Whey and Whey Powders: Fermentation of Whey.
Dziewiatkowski DD and Lewis HB (1944) Glucuronic acid synthesis and the glycogen
content of the liver of the rat. Journal of Biological Chemistry 153: 49–52.
Englyst HN, Wiggins HS, and Cummings JH (1982) Determination of the non-starch
polysaccharides in plant foods by gas–liquid chromatography of constituent sugars
as alditol acetates. Analyst 107: 307–318.
Englyst KN, Englyst HN, Hudson GJ, Cole TJ, and Cummings JH (1999) Rapidly
available glucose in foods: an in vitro measurement that reflects the glycemic
response. American Journal of Clinical Nutrition 69: 448–454.
Giugliano D, Ceriello A, and Esposito K (2008) Glucose metabolism and hyperglycemia.
American Journal of Clinical Nutrition 87(Suppl. 1): 217S–222S.
Korol DL and Gold PE (1998) Glucose, memory, and aging. American Journal of
Clinical Nutrition 67(Suppl. 1): 764S–771S.
Moon TS, Yoon SH, Lanza AM, Mayhew JD, and Prather KLJ (2009) Production of
glucaric acid from a synthetic pathway in recombinant Escherichia coli. Applied and
Environmental Microbiology 75(3): 589–595.
Ramachandran S, Fontanille P, Pandey A, and Larroche C (2006) Gluconic acid:
properties, applications and microbial production. Food Technology and
Biotechnology 44(2): 185–195.
Smith TN, Hash K, Davey C, Mills H, Williams H, and Kiely DE (2012) Modifications in
the nitric acid oxidation of D-glucose. Carbohydrate Research 350: 6–13.
Vecihi P, Murat Y, and Ahmet A (2001) The preparation of D-glucaric acid by oxidation
of molasses in packed beds. Journal of Chemical Technology and Biotechnology
76(2): 186–190.
Wadouachi A and Kovensky J (2011) Synthesis of glycosides of glucuronic,
galacturonic and mannuronic acids: an overview. Molecules 16: 3933–3968.
Relevant Websites
http://www.biotopics.co.uk/jsmol/glucose.html – The Glucose molecule - rotatable in 3
dimensions.
http://www.ch.ic.ac.uk/vchemlib/mim/bristol/glucose/glucose.htm – Glucose.
http://en.wikipedia.org/wiki/Glucose – Glucose.
http://www.jbc.org/content/153/1/49.full.pdf – Glucuronic acid synthesis and the
glycogen content of the liver of the rat.
http://www.mdpi.com/1420-3049/16/5/3933 – Synthesis of Glycosides of Glucuronic,
Galacturonic and Mannuronic Acids: An Overview.
http://www.namrata.co/category/chemistry-of-carbohydrates – Chemistry of
Carbohydrates.
http://www.sciencedirect.com/science/journal/00086215 – Carbohydrate Research.

The Encyclopedia of Food and Health, (2016), vol. 3, pp. 239-247

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