Carbohydrates

1. General aspects

Definition. Carbohydrates are compounds with mixed functional groups - hydroxyl and carbonyl groups.

The empirical formula for many carbohydrates is so literally a carbon hydrate.

Biological role
• Carbohydrates are an important energy source for the body (4.1 kcal /g), being the first energy reserves used in case
of effort.
• In addition, red blood cells and the nervous system are energy dependent on glucose;
• carbohydrates act as reserve substances - polysaccharides stored in plant cells (starch) or glycogen stored in the liver
and muscle, in humans and animals;
• plastic role - in the form of glycoproteins or giycolipids enters the cell membrane structure;
• carbohydrates can be converted into the body into lipids or amino acids;
• specific role.
2. Gasification

Monosaccharides are aidehydes or ketones that have two or more hydroxyl groups.
• The smallest monosaccharides, composed of three carbon atoms, are dihydroxyacetone and glyceraldehyde.

CH2—OH CH— o

n :0 HC OH

CH2—OH CH2— OH
Dihyd roxya c etc ne Glyceraldehyde
(ketose) (aldose)

monosaccharides with four, five, six,

Trioses (tri- for three carbon atoms) and seven carbon atoms are called
tetroses, pentoses, hexoses and
CONSTITUTIONAL ISOMERS
heptoses, respectively.
Differ in the order of attachment of atoms
 CHO CHO
D -Ribose is the carbohydrate component of RNA, is a five-carbon
H- C OH H-------C ----H

H- C OH
l ^
H-------C ----OH
aldose, as is deoxyribose, the monosaccharide component of
deoxynucleotides.

H- C OH H-------C ----OH
D -Glucose, D -mannose and D -galactose are abundant six-carbon
aldoses.
CH2OH CH2OH
Ribose Deoxyribose

EPSMERS
CHO CHO CHO IfctU* 41I tit wwtd! rt\ynmw<rMr
|
1
H —— C ----- -OH
1
1
HO—— C ---- -H H C
I OH
o
%c ,c h 2o h
tt 40
AitXTIN
040
| H C OH HO c H
I
HO—— c ----- -H HO—— c ------H HO ■C -H HO- H HO c H H<> c H

H—— c ----- -OH

I
1
H—— c ------OH HO c
I -H H- C OH
H c OH M c OH

H— c
1
1
-OH H—— c ------OH H
I
■c- -OH H- C OH
H c - OH
(J4,OH
H c
04,OH
OH

1
D-Oucwe
CH2OH c h 2o h c h 2o h CH2OH (QHsjOj
Glucose Manose Galactose Fructose
 G iycosidic
hydrocarbon chains - a zigzag structure
0 hydroxyl
intramolecular bond is formed by the -H
CH?OH CH?OH

addition of a hydrogen atom from an OH -OH

CYC I. IZATION
.H- -OH c=o jfid )— c
CYCUZATIO

-O h " *■ H -OH HQ-

I H * .........- HO -H O
C
group to the carbonyl group
-OH -OH
I H- -OH
C OH
The new OH group is called glvcdsidic
C—O— _ L _____I h -------c — o — fin )
hydroxyl. I Glucose I Fructose
CH-;OH CH-,OH CH?OH CH-QH

glucose will preferentially adopt the cyclic CHyOH CH ,-OH CH?OH

!/ °\ !
configuration of 6 atoms and fructose of 5 CYC L i/A HON CYCilZATiON HO / \
\ \/ OH
(the most energy-stable) H0H-.C
HOH-,0
HC-------CH

,0H
two anomeric cyclic structures (a and p) \,
HC, ,OH yO OH

HC' a-Fructose
are formed depending on the orientation -CHoOH
HO
HC- -CH
of the -OH group from the carbon atom at I
CH2OH HO
HO
CYCLIZATION
HC' C
position 1 to the hexa-atomic cycle to
\\ \
\,ACHiOH
glucose and to the group -OH from carbon HC------- CH

OH
2 to the penta-atomic cycle to fructose. OH -
(3-Giucose (3-Fructose
 c h 2o h CHjOH
Oisaccharides consists of two sugars joined by an O- glycosidic bond

• when the glycosidic bond is formed between a glycosidic hydroxyl and a % \

non-glycosidic hydroxyl, the disaccharide will have a reducing character.
OH
• if two glycosidic hydroxyl participate in the formation of the disaccharide it
Maltose
is not reducing Two molecules of glucose linked by
an a-1-4 glycosidic bond
(T) Sucrose is obtained C H 2OH
from sugar cane or sugar (2) Maltose comes from the hydrolysis
beets. } O of large polymeric oligosaccharides
• The anomeric carbon / OH such as starch and glycogen and is in
atoms of a alpha-glucose \ . a-glucose turn hydrolyzed to glucose by maltase.
unit and beta-fructose
unit are joined in this
disaccharide by a
glycosidic linkage (2 -OH C H 2OH
glycosidic participate)
• Sucrose can be cleaved (3) Lactose (from milk) consists
into its component of galactose joined to glucose by
monosaccharides by the a beta -1,4-glycosidic linkage.
enzyme sucrase Lactose is hydrolyzed to these
(intestin) monosaccharides by lactase
 Human milk oligosaccharides are non-digestible carbohydrates known to exert health benefits in breastfed infants by
preventing infection, maintaining immune homeostasis and nurturing healthy gut microbiota

Lactose biosynthesis starts from the (A ) ( B ) :M;

precursors of UDP-galactose and •
glucose under the action of lactose-
synthetase Lactose synthase is not ■ 1-,: \ V 4
\i
reported to further elongate lactose
with additional Gal. Rather, the next
A
♦
—•
A
.... . 7r
A * - #

step of lactose elongation is brought * V ♦

«
about by a series of other .* ilil t ;J‘ “'v‘ I h j
t..■ **'.(u
giycosyitransferases in the
mammary gland by the addition on m ^ 9 ■
A A A-
* / --- • %- . ■- * J !,
the structure of lactose of some j f p_:
♦
■' s u l
residues of N-acetylglucosamine —w f **• i'
0 ..N -
.y
f A
A ■- 4 .t> Nfc'liAk *•?
(GlcNAc), galactose (Gal), fucose ---0 ♦
A -0
♦
JB
A /
(Fuc) and N-acetylneuraminic acid -0 t « ni ;
* r- i.i os
(Neu5Ac). *-0
A S t-0 ' :**[>> h i ii t-3)
■k
: N T.f /
A” 0 MHKiM r if i
▲
 Polysaccharides

• free glucose molecules cannot be stored because in high concentrations, glucose will disturb the osmotic balance of the cell,
potentially resulting in cell death.
• The solution is to store glucose as units in a large polymer, which is not osmoticaily active.
• If all of the monosaccharide units in a polysaccharide are the same, the polymer is called a homopolymer

(T) Glycogen - the most common homopolymer

in animal cells, the storage form of glucose.
• most abundant in muscle and liver.
• is a large, branched polymer of glucose
c h 2o h oh ch
residues linked by alpha-1,4-glycosidic bond.

|\L
• The branches are formed by alpha-1,6- °\0
glycosidic bonds, present about once in 10 —o O
OH OH
units

Non glycosidic-OH Glycosidic -OH

Non-reducing end Reducing end
 Starch = the most common homopolymer in plant cells, the storage form of glucose.
Amylose, the unbranched type of starch, consists of glucose residues in a-1,4 linkage.
Amylopectin, the branched form, has about one a-1,6 linkage per 30 ot-1,4 linkages, similar to glycogen except for its lower
degree of branching

cx x x x o 00000000^ ^

Starch Glycogen Celulose

(D Cellulose = major polysaccharide of glucose found in plants, serves a structural rather than a nutritional role
• is among the most abundant organic compounds in the biosphere (1015 kg of cellulose is synthesized and degraded/year)
• unbranched polymer of glucose residues joined by p - 1,4 linkages allowing cellulose to form very long, straight chains.
• Fibrils are formed by parallel chains that interact with one another through hydrogen bonds,
• The straight chains formed by beta linkages are optimal for the construction of fibers having a high tensile strength.
• The a - 1,4 linkages in glycogen and starch form a hollow helix (compact, used for storage) instead of a straight chain
• Although mammals lack celiulases and therefore cannot digest wood and vegetable fibers, cellulose and other plant fibers are
still an important constituent of the mammalian diet as a component of dietary fiber.

H pm, H O ■]
I >1 '-r If
-OH

It u
v. ri

II O'H. 0)3

h < ' >1 ? "

*h > - 1M
l

Starch and glycogen

a-1-4 bond
Cellulose
3-1-4 bond
3. Digestion and absorption of carbohydrates
3.1. General aspects

• most carbohydrates come from food

• plant origin: starch approx. 50%, sucrose, glucose, fructose, pentose
• animal origin: lactose, glycogen,
• synthesized in the body
• the main components of foods are starch, sucrose and lactose.
• glucose and fructose are found in small quantities, in fruit or honey
• In infants and children, milk lactose is the main component
• Cellulose contained plants is not digested by humans, so has no nutritional value
• The absorbable form is monosaccharides,
• polysaccharides and disaccharides are hydrolyzed to the componentmonosaccharides, through the digestion process
• Hydrolases that catalyze the cleavage of glycosidic bonds = glycosidases -are specific both to the natureof the sugar that
forms the glycosidic bond and to the nature of the anomer (alpha or beta).
3.2. Digestion process

oral cavity contains salivary a-amylase (optimal pH = 8), but because of the short time
the food is in the mouth, the process is insignificant.
Gastric juice does not contain amylolytic enzymes, but hydrolysis of starch is continued
in the stomach until acidic pH inactivates amylase.
G lucose
Intestine - the digestion of starch and glycogen is continued under the action of monomers

pancreatic amylase, (hydrolyzes a (1-4) glycosidic bonds

amyiase does not hydrolyse a (1-6) and the a (1-4) glycosidic bonds near the branching
point, so the starch degradation products under the action of amylase will be maltose
Starch

and oligosaccharide fragments of variable size, called limit dextrin

j Salivary or
The latter will be hydrolyzed by an 1-6-glycosidase, to maltose. | pancreatic
j. amylase
the digestion of the disaccharides maltose, sucrose, lactose is catalyzed by lactase,
sucrase (Invertase ) and maltase
Limit < - Maltose
dextrms (disaccharide)
33. Absorption

• After digestion, the products are transported to the portal circulation.

• Glucose and galactose absorption occurs in the small intestine via the SGLT-1 transporter (sodium glucose co-transporter).
• Fructose absorption is completed via the GLUTS transporter by facilitated diffusion
 Paiaceilulai
Ca-1
Lumen pathway glucose
ffUC,to* 9lUCOSe fructose
Glucose is transported together with a sodium gradient (sodium
\2Na-
<£■T,twf’ i ',jf - ,
GlutS
/ Gkrt2 SG LTl is transported from high to low concentration - concentration

f gradient)
I 1 Na+K +ATP-ase pump creates a low intracellular sodium
--.t + 4- -C a
concentration by transporting 3 Na+ ions out of the cell and 2 K +
glucose
fructose * ions into the cell.
t )#•i&
The SGLT-1 transporter utilizes the sodium gradient. Two Na+ ions

t
g(u«se N*'
bind to the outer face of the SGLT-1 transporter which results in a
Blood fructose conformational change permitting subsequent glucose binding.
The two Na+ ions and the glucose molecule are then transferred
to the cytoplasmic side of the membrane following another
conformational change that involves rotation of the receptor.
The glucose is released first followed by the sodium ions.

Na+ ion is subsequently expelled by Na+K +ATP-ase pump to maintain the gradient.
Much of the glucose transported into the cell passes out of the cell at basolateral surface by facilitated diffusion via GLUT-2.
 Pa/ac elbiaf
Lumen pathway

i -n -r:

ft

ffc/Cffctfi

gtucov?
N«
Blood fructose
Facilitated diffusion is the mechanism for fructose transport.
GLUT-5 is present on the apical membrane of the brush
border throughout the small intestine with increased density
in the proximal small intestine.
Little fructose is metabolized in the cell.
Both GLUT-2 and GLUT-5 are present at the basolateral
membrane to transport fructose to the portal circulation.
4. Metabolic pathways of glucose metabolism
Glucose enters cells through specific transport proteins and is phosphorylated by ATP to form glucose 6-phosphate.
This step is notable for several reasons: Glucose 6-phosphate cannot pass through the membrane because of the negative
charges on the phosphoryl group, and it is not a substrate for glucose transporters.
/Also, the addition of the phosphoryl group facilitates the eventual metabolism of glucose into three-carbon molecules
The transfer of the phosphoryi group from ATP to the hydroxyl group on carbon 6 of glucose is catalyzed by
hexokinase/glucokinase.

Glucose Glucose-6-phosphate
 O O

adenosine O P O P- —O P-

O O' G'

ATP Mg2+
Mg2+'

adenosine—

Glucose-6-phosphate ADP Mg2+

 Glucokinase/hexokinctse

Glucose
Hexokinases are in the form of several isoenzymes with different cellular distribution.
They phosphorylate all hexoses, with high affinity for the substrate, so they have low Km values (the brain isoenzyme
has the lowest Km).
In the liver, in addition to hexokinase there is also glucokinase that is specific for glucose only and is found only in this
organ.
GK has high Km, so it is less active compared to HK.
GK is an adaptive enzyme, its activity depends on the concentration of glucose and insulin.
Acting only in the liver, GK allows excess glucose to be stored as glycogen.
At high (post-prandial) glucose concentrations, HK could not cope with glucose phosphorylation at the rate required by
glucose level as it is saturated with glucose, even at physiological concentrations.
Because GK activity is influenced by insulin, in diabetes, decreased activity, together with disruption of glucose uptake
and metabolism, leads to hyperglycemia.
Glucuronic Glycogen Ribose-5P
Q Glycolysis is a pathway for degradation of glucose and
other carbohydrates with energy release equivalent to 2 ATP.
* In aerobic conditions, lactate formation is inhibited, and
pyruvate is oxidatively decarboxylated in acetyl-CoA-forming
mitochondria that initiates the Krebs cycle,
* The reduced coenzymes obtained from the Krebs cycle are
oxidized in the respiratory chain with energy formation
stored as ATP by oxidative phosphorylation.

Q Gluconeogenesis is the de novo biosynthesis process of

glucose from amino acids, glycerol, produced by lipid
metabolism, or lactate resulting from glycolysis.
* The process takes place in the liver and kidney, organs that
have the necessary enzyme equipment.
Glucuronic Glycogen Ribose-SP
acid NADPH
+H+

Pyruvate
A ERO B^\ ANAEROB
Acetyl-CoA Lactate

Respiratory chain __
Oxidative phosphorylation
© Glycogenolvsis is the process of phosphorylated cleavage of
glycogen from liver deposits (with the aim of maintaining
glycemia within normal limits during periods between two
meals) and muscle (during muscle effort).

Q Glycogenogenesis is the process of glycogen biosynthesis

from post prandial carbohydrate excess, which can be stored in
limited quantities in the body.
Glucuronic Glycogen Ribose-5P
0 The pentose phosphates cycle is a special way of
metabolizing glucose, which gives the pentose-phosphates
necessary for the synthesis of nucleic acids, ATP,
coenzymes, etc.
• Also, in this way NADPH is obtained, necessary for the
processes of reductive biosynthesis in the body (de novo
fatty acid biosynthesis), activation of some vitamins
(folic acid, calciferol hydroxylation).
Q The glucuronic acid pathway provides the body with
UDP-glucuronate used in glucuronic acid -conjugations of
catabolites or xenobiotic substances, thus increasing their
solubility and facilitating their elimination.
• Through this pathway, the ascorbic acid can be
synthesized from glucose, but not in humans, guinea
pigs and monkeys.