Química de carbohidratos

1
2.5 Química de carbohidratos
a. Monosacáridos, disacáridos
b. Polisacáridos de reserva
c. Polisacáridos estructurales
d. Mucopolisacáridos

2
 Carbohidratos

•Pertenecen al grupo de biomoléculas mas abundantes:

Carbohidratos, Proteínas, Lípidos y Acidos Nucléicos

•Químicamente se definen como aldehidos o cetonas

polihidroxiladas

•La materia orgánica mas abundante sobre la tierra

Photosynthesis converts more

than 109 metric tons of CO2
and H2O into cellulose
and other plant products.

the word “saccharide” is derived from the Greek sakcharon,

sakcharon meaning “sugar”, a
sweet crystaline substance derived from plants 3
•Función :
Almidón y celulosa

Almacén de energía, combustibles

e intemediarios metabólicos

Ribosa y desoxiribosa, componentes

esenciales de RNA y DNA

4
 Reconocimiento o anclaje
molecular

Elementos estructurales en
paredes celulares de bacterias y
plantas.

5
Diversidad estructural en
carbohidratos :
Propiedad clave que determina su papel
como mediadores de interacciones
celulares

Construidos a partir de unidades de

azúcares (monosacáridos) C3-C9

Tamaño, secuencia y estereoquímica

definida

Unión (N-gly, , , ....) y composición

molecular específica

6
Monosacáridos: los azúcares mas simples

Aldehidos o cetonas con uno o mas grupos hidroxilo

Formula general Cn(H2O)m donde n, m pueden ser iguales o

diferentes y ≥ 3

7
If the carbonyl group is at an end of the carbon chain
(aldehyde group) the monosaccharide is an aldose

Glyceraldehyde has a single asymmetric carbon and,

thus, there are two stereoisomers of this sugar generating
two series of aldoses D-aldosas y L-aldosas.

D-glyceraldehyde and
L-glyceraldehyde are
enantiomers, or mirror
images of each other

If the carbonyl group is at any other position (ketone group)

the monosaccharide is a ketose.

8
C3

C4 *

C5
* *

C6 *
* * *
C3 *

C4
* *

C5
* *

C6
* * *

10
Glyceraldehyde and dihydroxyacetone are referred to as
trioses
Sedoheptulosa
Simple monosaccharides with four, five, six, and seven
carbon atoms are called tetroses, pentoses, hexoses, and
heptoses, respectively.

Because these molecules have multiple asymmetric

carbons, they exist as diastereoisomers, isomers that are
not mirror images of each other, as well as enantiomers.

11
 Neuraminic acid

12
Sialic acid
 The symbols D and L designate the absolute configuration of the asymmetric
carbon farthest from the aldehyde or keto group.

Enantiomers : non-superimposable Epimers: sugars that differ in

COMPLETE mirror images 13
configuration at ONLY 1 POSITION
Two sugars that differ only in the configuration around one carbon atom are called
epimers.

14
Monosaccharides with four, five, six, and seven carbon atoms in their
backbones are called, respectively, tetroses, pentoses, hexoses, and heptoses.

a) There are aldoses and ketoses of each of these chain lengths: aldotetroses
and ketotetroses, aldopentoses and ketopentoses, and so on.

b) The hexoses, which include the aldohexose D-glucose and the ketohexose
D-fructose, are the most common monosaccharides in nature.

c) The aldopentoses D-ribose and 2-deoxy-D-ribose are components of

nucleotides and nucleic acids.

15
Three ways to represent the two
stereoisomers of glyceraldehyde.

The stereoisomers are mirror images of each

other. Ball and-stick models show the actual
configuration of molecules.

By convention, in Fischer projection formulas,

horizontal bonds project out of the plane of the
paper, toward the reader; vertical bonds project
behind the plane of the paper, away from the
reader.

Recall that in perspective formulas, solid wedge-

shaped bonds point toward the reader, dashed
wedges point away.
16
In Solution, The Common Monosaccharides Have Cyclic Structures

Formation of hemiacetals and hemiketals.

An aldehyde or ketone can react with an alcohol in a 1:1 ratio to yield a hemiacetal
or hemiketal. A new chiral center at the carbonyl carbon is created.
Substitution of a second alcohol molecule produces an acetal or ketal. When the
second alcohol is part of another sugar molecule, the bond produced is a
glycosidic bond
17
18
The keto group in the open chain form of a
ketohexose such as fructose, can form an
intramolecular hemiketal by reacting with
either the C-6hydroxyl group to form a six-
membered cyclic hemiketal (pyranose) or
the C-5 hydroxyl group of to form a five-
membered cyclyc hemiketal(furanose)

19
20
21
22
Two cyclic forms of D-glucose.
Reaction
between the aldehyde group at C-1
and the hydroxyl group at C-5 forms a
hemiacetal linkage, producing either of
two stereoisomers, the and anomers,
which differ only in the stereochemistry
around the hemiacetal carbon.

23
The interconversion of  and anomers is called mutarotation.

24
25
26
Son aquellos azúcares que poseen al menos un carbonilo (grupo funcional)
intacto, es decir no formando ni cetal o acetal.

Azúcares que en solución alcalina forman un aldehido o cetona

Reductores: Glucosa, fructosa, gliceraldehido, lactosa, arabinosa, maltosa…..

No reductores: Sacarosa, trealosa

Las cetosas no se oxidan directamente, mas bien al transformarse en aldehidos

por tautomerismo ceto-enólico
27
Conformational formulas of pyranoses.
(a) Two chair forms of the pyranose ring. Substituents on the ring carbons may be either
axial (ax), projecting parallel to the vertical axis through the ring, or equatorial (eq),
projecting roughly perpendicular to this axis. Two conformers such are these are not readily
interconvertible without breaking the ring. However, when the molecule is “stretched” (by
atomic force microscopy), an input of about 46 kJ of energy per mole of sugar can force the
interconversion of chair forms. Generally, substituents in the equatorial positions are less
sterically hindered by neighboring substituents, and conformers with bulky substituents in
equatorial positions are favored. 28
29
 Tautomerismo ceto-enólico

Tautomerismo ceto-
enólico en fructosa bajo
condiciones alcalinas

30
31
 Disacáridos
•Carbono anómericode un azucar se une a –OH
de otro azúcar formando enlace O-glicosídico

•Enlace N-glicosídico C-anomérico => N de

proteína, nucleótido o azúcar

•Sensibles a hidrólisis ácida y resistentes a

hidrólisis básica
Maltosa
•Extremo reductor, presencia de carbonilo α-D-Glucopyranosyl-
intacto, no formando ni cetal o acetal. (1→4)-D-glucose

Lactosa Sacarosa
β-D-galactopyranosyl-(1→4)-D-glucose β-D-fructofuranosyl-(2→1)-α-D-glucopyranoside
 Maltosa

Configuración α de
carbono anomérico,
forma enlace α

The glucose residue with the free

anomeric carbon is capable of
existing in - and -pyranose forms
33
34
 Isómeros α de maltosa (Glc-Glc)

Trealosa α(1→1) Kojibiosa α(1→2)

Nigerosa α(1→3)

Maltosa α(1→4) Isomaltosa α(1→6)

35
 Isómeros  de maltosa

,-Trealosa (1→1) Soforosa (1→2)

Laminaribiosa (1→3)

celobiosa (1→4) Gentobiosa (1→6)

36
37
38
39
Polisacáridos

40
Polisacáridos

lineal homogéneo
ramificado homogéneo

alternado

bloques
lineal heterogéneo

ramificado heterogéneo

interumpido ramificado
Glicógeno glucosa α-(1-4) ramificado en α-(1-6) cada 8-12 résidus

42
Almidón, formado por dos homopolímeros, amilosa (no ramificada
α-(1-4)) y amilo pectina (ramificado en α-(1-6) cada 24-30 résiduos)

amilosa no ramificada α-(1-4)

amilo pectina ramificada en α-(1-6) cada 24-30

résiduos

Almidón : motivo de repetición la maltosa

Celulosa : motivo de repetición la celobiosa 43

Cadenas lineales mejor soporte estructural

Hélices abiertas mejor almacén de energía

44
45
46
47
48
49
50
51
52
53
54
55
56
57