CARBONYL: Hydroxyl:

1. DEFINITION AND CLASSIFICATION

 the most widely distributed and abundant organic compound on earth
 common components in food
 large use in terms of quantity consume and variety of products
 safe
 central role in metabolism of animals and plants
biosynthesis in plant  photosynthesis

generic formula: CnH2nOn ; belom tentu yg formula nya ini tuh carbo tp mostly formula nya ini.

So, We cannot identify from formula if its carb or not, we can only identify by structure,
polyhydroxy several OH that is aldehydes or ketones

carbohydrates are polyhydroxy

aldehydes or ketones atau turunannya

 Contohnya

Ada aldehyde group/ketone group yg

berikatan sama banyak hydroxyl
group

Cara buat dapetin turunan:

a. Reduction of the carbonyl group to produce sugar alcohols

b. Oxidation of the carbonyl group and/or hydroxyl groups to sugar acids
c. Replacement of one or more of the hydroxyl moieties by various chemical
groups, e.g., hydrogen (H) to give deoxysugars, amino groups (NH2 or acetyl-
NH2 ) to give amino sugars
d. Derivatization of the hydroxyl groups by various moieties, e.g., phosphoric acid
to give phosphosugars, sulphuric acid to give sulpho sugars
e. Their polymers having polymeric linkages of the acetal type
 Function of Carbs:

 sweetener
 gel or paste forming
 thickener
 stabilizer
 precursors for aroma & coloring substance

Food carbohydrates divided into two classes:

a. Available  readily utilized and metabolize. may be either mono-, di-, oligo- or
polysaccharides, e.g., glucose, fructose, sucrose, lactose, dextrins, starch.

b. Unavailable not utilized directly but instead broken down by symbiotic bacteria,
yielding fatty acids, and thus not supplying the host with carbohydrate. This includes
structural polysaccharides of plant cell walls and many complex polysaccharides, e.g.,
cellulose, pectins, beta-glucans

2. Monosaccharide (low molecular weight)

Represents stereoisomers:

a. Ball and stick

b. Fischer projection formulas
c. Perspective formulas

Monosaccharides are chiral polyhydroxy aldehydes and polyhydroxy

ketones that often exist in cyclic hemiacetal forms. Hemiacetal forms  aldehyde or ketone yg
contain alcohol and carbonyl group yg nnti nya bisa undergo intramolecular reaction dan
menghasilkan cyclic hemiacetal (aldehyde)/hemiketal (ketone) (cyclic lebih stable compared to
normal one).

Hemiacetal : c connects to O and OH

Acetal : c connects to O and O
 Fischer Projection Formula

The numbering of the carbon atoms in monosaccharides always starts from the
carbonyl group or from the chain end nearest to the carbonyl group.

If there are 6 carbons like glucose, the D and L, see the last chiral carbon.
Start counting from aldehyde (C aldehyde diitung).
The C holds 4 different groups = chiral. Non chiral when it hold 2 O.
• These two compounds have the same empirical
formula, C3 H6 O3, but are distinct, having
different chemical and physical properties.
• D -glyceraldehyde rotates the plane polarized light
to the right (+) and has a specific optical rotation
([α] D) at 25°C of +8.7°;
• L-glyceraldehyde rotates the plane polarized light
to the left (-) and has a different specific optical
rotation, [α] D, at 25°C of –8.7°.
Intinya kaya ketuker gitu horizontal line di chiral centre.

 Ring Form of Sugar

Mau ngubah fischer (yg cuman garis2) ke bentuk cyclic gitu.
Steps:
1. Draw Fisher Projection (D-form)
2. Change to L-form if required
3. Connect C1 with the last chiral carbon
4. Draw Haworth projection with oxygen on right
5. Attached hydrogen, hydroxyl and CH2OH group
6. Convert to beta (β) form

Rules to convert fischer to Haworh (Cyclic):

• All hydroxyl groups on the right in the Fischer projection are placed below the plane
of the ring in the Haworth projection; all those on the left are above.
• In D-aldoses, the CH2OH group is written above the plane of the ring in the Haworth
formulae; in L-aldoses, it is below. For D -glucose and other monosaccharides in the
D –series,α –anomers have the –OH group at the anomeric carbon (C-1) projected
downwards in the Haworth formulae;
• β -anomers have the –OH group at the anomeric carbon (C-1) projected upwards. The
opposite appliesto the L-series;Α-L -monosaccharides have the –OH group at the
anomeric carbon (C-1) projected upwards, whereas Β -L -monosaccharides have the
–OH group at the anomeric carbon (C-1) projected downwards.
 Monosaccharide Transformation

 mutarotation  change in optical rotation gara2 sugar molecule dissolved di

aqueous solution.

When the sample is dissolved in water, however, a mixture is soon produced

containing both anomers as well as the straight-chain form, in dynamic
equilibrium (part (a) of Figure 16.4.2). You can start with a pure crystalline
sample of glucose consisting entirely of either anomer, but as soon as the
molecules dissolve in water, they open to form the carbonyl group and then
reclose to form either the α or the β anomer. The opening and closing repeats
continuously in an ongoing interconversion between anomeric forms and is
referred to as mutarotation.

Antara α sama β Yang ketuker tempat itu C di sebelah kanan O.

 Enolization and Isomeration

Enolization  The mechanism whereby enols are formed in acidic solution;
general reaction of a carbonyl compound having an α-hydrogen atom
An alpha (symbol: α) hydrogen is a hydrogen atom on an alpha carbon in an
organic molecule

Isomerization, the chemical process by which a compound is transformed into

any of its isomeric forms, i.e., forms with the same chemical composition but
with different structure or configuration and, hence, generally with different
physical and chemical properties.
  Monosaccharide Conformation
• recognized forms of the pyranose (saccharides that have a chemical structure that
includes a six-membered ring consisting of five carbon atoms and one oxygen atom.)
ring include chair (C), boat (B), half chair (H), skew (S), and sofa forms.
• Furanose (carbohydrates that have a chemical structure that includes a five-
membered ring system consisting of four carbon atoms and one oxygen atom) rings
are the envelope (E) and the twist (T).
• Of the many possible conformations, one conformer is preferred or favored.

 Occurance of Monosaccharide
• The majority of the naturally occurring carbohydrates have the D -configuration.
– L -monosaccharides are less abundant in nature, although L -arabinose and L
-galactose are present as carbohydrate units in many carbohydrate polymers
(polysaccharides).
– It is not well understood why and how carbohydrates with only D -
configuration were formed on earth.
– Interestingly, the configuration of the 20 naturally occurring amino acids is
opposite (L -configuration) to that of carbohydrates.
• While the pyranose forms dominate in aqueous solution of most monosaccharides, it
is quite common to find furanose form when the sugar is incorporated into a
biomolecule.
• The popular names of sugars often indicate their principal sources and their optical
rotary properties.
– Synonyms for D -glucose are dextrose, grape sugar, and starch sugar.
– Synonyms for fructose are levulose, honey sugar, fruit sugar.

 Glycosidic Linkage/Bond
glycosidic bond is a covalent bondthat joins a carbohydrate to another functional
group or molecule.

3. Disaccharide (Low molecular weight)

sugar formed when two monosaccharides (simple sugars) are joined by glycosidic linkage
The acetal linkage between the monosaccharide residues is called a glycosidic linkage.

- Reducing sugars

 Sugars that contain aldehyde groups that are oxidized to carboxylic acids; has a
free ketone or aldehyde group, meaning it can act as a reducing agent.
 Reducing disaccharides: when one lactolgroup and one alcoholic HO-group are
involved.
 All monosaccharides, lactose, maltose.
 Test: Fehling’s, Nylander’s, Benedict’sreactions.
 Important for Maillardreaction, fermentation.
 - Non-reducing disaccharide
When a glycosidiclinkage is established only between the lactolgroups of two
monosaccharides, e.g. sucrose.

 Sucrose
 Commonly known as sugar table
 common in many baked products, breakfast cereals, deserts, and beverages
 commercially obtained from sugar cane and sugar beets.
 chemical name is α -D -glucopyranosyl-β -D -fructofuranoside.
 Hydrolyzed into D-Glucose and D-Fructose by the enzyme sucrase, which is
present in the human intestinal tract, and therefore can be utilized by humans for
energy.

 Lactose
• occurs in the milk of mammals, It serves as an energy source for developing
mammals.
• chemical name is β -D -galactopyranosyl-D -glucopyranoside.

4. Oligosaccharide
oligosaccharides are compounds containing 3-9 monomeric sugar units.
The number of sugar residues determines the degree of polymerization of oligosaccharides

Example:

 Raffinose

• a nonreducing trisaccharide
• formed from sucrose by the addition of α -D galactopyranose to the C-6 of the
glucose moiety of sucrose.
• Widely distributed in many plants and commercially prepared from beet
molasses and cotton seeds.

 Stachyose
• another derivative of sucrose
• occurs as a free oligomer in many legumes and pulses.

 Fructo-oligosaccharide vs Inulin
• Fructo-oligosaccharides.
– DP<9
– found in many types of edible plants, including onion, garlic, bananas,
Jerusalem artichoke, asparagus, wheat and rye.
– can be prepared on a commercial scale from sucrose through the
transfructosylating action of fungal enzymes such as β -
fructofuranosidases (E.C. 3.2.1.26) or β –fructosyltransferases
2.4.1.100)
 – can also be prepared from inulin by partial hydrolysis using endo-
inulinase
– They are not digested in the human upper intestine, but they are
fermented in the colon to lactate and short chain fatty acids (acetate,
propionate and butyrate).
– They stimulate the growth of bifidobacteria, while suppressing the
growth of some unfavorable bacteria such as Escherichia coli or
Clostridium perfringens .
– have been shown to be effective in preventing colon cancer, reduction of
serum cholesterol and triacylglycerols, and promotion of mineral
absorption.

• Inulin.
- Higher DP
- mainly in chicory and Jerusalem artichoke.

 Polydextrose
- developed as a low calorie replacement for sugar and a partial replacement for fat
and starch.
- has a very low glycemicindex (15%) compared to glucose (100%).
- increases the amount of beneficial bacteria (e.g., Lactobacillus and
Bifidobacterium ) at the cost of detrimental species (Clostridium ).
-
5. Polysaccharide
- Glycan is a general term given to polysaccharides in which large numbers of glycoses
(monosaccharides) are mutually joined by O-glycosidic linkages.
- Polysaccharides are condensation polymers in which glycosidic linkage is formed
from the glycosyl moiety of hemiacetal (or hemiketal) and a hydroxyl group of
another sugar unit, acting as an acceptor molecule or aglycone

 Starch

- Naturally present in grains used to make breakfast cereals (bread/bakery

products), or in some fruits and vegetables.
- Starch and starch hydrolysis products constitute most of the digestible
carbohydrate in the human diet

- Characteristics:
a)depends on source of granules: composition of glucan, amylose and
amylopectin.
b)relatively dense and insoluble
c)hydrate only slightly in cold water: producing low-viscosity slurries that
can be easily mixed and pumped.
 ►viscosity-building (thickening) power of starch is enhanced with thermal
process (cooking)
- Usesof starches and modified starches:
a)raw materials in preparation of food products
b)other uses: adhesive/binding, clouding, dusting, film forming, foam
strengthening, anti-staling, gelling, glazing, moisture retaining stabilizing,
texturizing, and thickening applications

 Cellulose
- Main constituent of plant cell walls (usually occurs together with
hemicelluloses, pectin and lignin).
- Insoluble in water
- Since cellulose enzymes are absent in the human digestive tract, cellulose,
together with some other inert polysaccharides, constitute the indigestible
carbohydrate of plant food (vegetables, fruits or cereals), referred to as
dietary fiber.
 Pectin
- A polysaccharide mixture with a complicated structure containing at least
65% of galacturonicacid (GalA)  sugar acid, an oxidized form of D-
galactose
- Pectin stability is highest at pH 3–4; at a pH of about 3, and in the presence
of Ca2+ions also at higher pH’s, pectin forms a thermally reversible gel
- Produced commercially from peels of citrus fruits and from apple pomace
(crushed and pressed residue).
- Since pectin can set into a gel, it is widely used in marmalade and jelly
production.
In low-sugar products, low-ester pectin is used in the presence of Ca2+ions,
to stabilize soured milk beverages, yoghurts and ice creams.

6. REACTION OF CARBOHYDRATE
 Oxidation and Reduction
 Sugar Alcohol
 The aldo and keto groups of carbohydrates can be readily reduced in
aqueous solutions to give sugar alcohols (alditols). The sugar alcohols
retain some properties of carbohydrates, e.g.,sweetness, high water
solubility, and optical activity.
 Aldoses and ketoses can be reduced easily in sodium borohydrate at pH
between 6 to 10.
 D -Glucose can be specifically reduced by the enzyme, D –sorbitol
dehydrogenase
 The reduction of D -glucose yields D -glucitol (commonly known as
sorbitol); The reduction of D -fructose results in two epimeric alcohols,
D -glucitol and D –mannitol.
 Sugar alcohols are absorbed at a slower rate than glucose, they find some
uses in the production of low calorie soft drinks.
 In puddings and jellies, the addition of sorbitol improves texture.
  Sugar alcohol will also lower water activity in various products and,
therefore, helps to prevent mold formation.

 Xylitol occurs naturally in raspberries, strawberries, and plums. Xylitol is

produced by hydrogenation of D -xylose obtained from hydrolysis of
hemicelluloses.
 Solubilization of xylitol is an endothermic reaction and gives a cooling
sensation when xylitol is placed in the mouth.
 Xylitol is not metabolized by the mouth microflora and, therefore, does
not promote formation of plaques.

 Aldonic Acid
 Aldehyde group of aldoses can be readily oxidized to carboxylic group
and the reaction leads to formation of aldonic acids.
 All aldoses are reducing sugars since they contain an aldehyde carbonyl
group
 Fehling reagent ,an alkaline solution of copper(II) which is reduced to
copper(I) during oxidation of sugars, has been used for determining the
amount of reducing sugars in foods and other biological materials
 Deoxy Sugar
• hydroxyl group of a carbohydrate is substituted by a hydrogen atom  deoxy
sugar
• Theoretically, any hydroxyl group can be substituted; however, there are
only a few naturally occurring deoxy sugars.
• D -Ribose substituted in the 2-position results in 2-deoxy-D –ribose, the
carbohydrate constituent of DNA (deoxyribonucleic acid).
• The replacement of hydroxyl group at C-6 of D -mannose results in 6-deoxy-
D mannose, commonly called D -rhamnose.
• The replacement C-6 of D –galactose results in 6-deoxy-D -galactose,
commonly called D –fucose

 Amino Sugar
• Replacement of a hydroxyl group by an amino group
• The most common amino sugars are 2-amino-2-deoxy-D –glucose, known as D -
glucosamine, and 2-amino-2-deoxy-galactose, known as D -galactosamine.

 Sugar Esters and Ethers

• Esterification is normally carried out by treating of carbohydrate with acid
chloride or acid anhydride in the presence of base

• Carbohydrates can be converted into ethers by treatment with an alkyl halide in

the presence of base.
• Ethers of carbohydrates are not very common in nature
 Glycosides
• Carbohydrate acetals are called glycosides. They are formed in the reaction of
sugar hemiacetal with alcohol
• They can be converted back to the original monosaccharide by hydrolysis with
aqueous acid.
• Glycosides are distributed widely in nature, and many biologically important
molecules contain glycosidic linkages.

 Browning Reaction
 MAILLARD REACTION (non-enzymatic browning)
• When amines, amino acids, or proteins are heated with sugars, aldehydes,
and ketones, a series of complex reactions, referred as the Maillard reactions,
occurs, leading to formation of flavors, aromas, and dark colored pigments
• Bisa desired sama undesired: contoh desired itu kaya bikin roti; contoh
undesired itu bisa jadi toxicity and mutagenicity during reaction
• Initial step in maillard  amadori arrangement.
• Yang bikin warna coklat  melanoidin

 CARAMELIZATION
• reactions involving the degradation of sugars during heating. Produced by
heating sucrose solution in ammonium bisulfite, is used in colas and other soft
drinks, baked goods, candies, and other food products as a colorant and flavor
compound.
• If not controlled, it will create bitter, burned, and unpleasant tasting products.