Molecular Biochemistry I

Carbohydrates

Copyright 1999-2005 by Joyce J. Diwan. All rights reserved.

EL PRINCIPAL CICLO ENERGTICO DE LA BISFERA: Fotosntesis y Respiracin.

Carbohydrates (glycans) have the following

basic composition:
(CH2O)n I or H - C - OH I

Monosaccharides - simple sugars with multiple OH groups. Based on number of carbons (3, 4, 5, 6), a monosaccharide is a triose, tetrose, pentose or hexose. Disaccharides - 2 monosaccharides covalently linked. Oligosaccharides - a few monosaccharides covalently linked. Polysaccharides - polymers consisting of chains of monosaccharide or disaccharide units.

CHOs REPRESENTATIVOS: MONO-, DI- Y POLI-SACRIDO (MONMERO, OLIGMERO Y POLMERO)

Monosaccharides
Aldoses (e.g., glucose) have an aldehyde group at one end.
H C H HO H H C C C C OH H OH OH O

Ketoses (e.g., fructose) have a keto group, usually at C2.

CH2OH C HO H H C C C O H OH OH

EL SUFIJO OSA ALDOSA O CETOSA; TRIOSA, HEXOSA, ETC- DESIGNA COMPUESTOS COMO LOS SACRIDOS O AZCARES

CH2OH

CH2OH

D-glucose

D-fructose

INTERCONVERSIN TAUTOMRICA ALDOSA-CETOSA * TAUTMEROS. Ismeros estructurales que difieren en la distribucin de sus H y =

ENANTIMEROS DEL GLICERALDEHIDO

TRIOSAS, LOS MONOSCARIDOS MS SENCILLOS * ENANTIMEROS: ISMEROS PTICOS

D vs L Designation
CHO CHO HO C H

D & L designations are H C OH based on the CH2OH configuration about the single asymmetric D-glyceraldehyde C in glyceraldehyde. CHO The lower representations are H C OH Fischer Projections. CH OH
2

CH2OH

L-glyceraldehyde
CHO HO C H

CH2OH

D-glyceraldehyde

L-glyceraldehyde

Sugar Nomenclature
O H O H

For sugars with more than one chiral center, D or L refers to the asymmetric C farthest from the aldehyde or keto group. Most naturally occurring sugars are D isomers.

C H C OH HO C H H C OH H C OH CH2OH
D-glucose

C HO C H H C OH HO C H HO C H CH2OH
L-glucose

SISTEMA R-S. Describe la configuracin estereoqumica absoluta

POR CONVENCIN, A CADA GRUPO UNIDO AL C QUIRAL SE LE ASIGNA UNA PIORIDAD: OR>OH>NH2>COOH>CHO>CH2OH>CH3>H. SI LA PRIORIDAD DE LOS GRUPOS DISTINTOS AL H DISMINUYE EN EL SENTIDO DEL RELOJ, LA CONFIGURACIN ABSOLUTA ES R (LATN RECTUS DER), SI ES AL CONTRARIO, LA CONFIGURACIN ES S (LATN SINISTER IZQ)

D & L sugars are mirror O H O H images of one another. C C They have the same H C OH HO C H name, e.g., D-glucose HO C H H C OH & L-glucose. H C OH HO C H Other stereoisomers H C OH HO C H have unique names, CH2OH CH2OH e.g., glucose, mannose, D-glucose L-glucose galactose, etc. The number of stereoisomers is 2n, where n is the number of asymmetric centers. The 6-C aldoses have 4 asymmetric centers. Thus there are 16 stereoisomers (8 D-sugars and 8 Lsugars).

DIASTERMEROS DE TETROSAS

PRESENCIA Y FUNCIONES BIOQUMICAS DE LOS MONOSACRIDOS

Hemiacetal & hemiketal formation

An aldehyde can react with an alcohol to form a hemiacetal. A ketone can react with an alcohol to form a hemiketal.
H C R O H

R'

OH

R'

C R

OH

aldehyde
R C R' O

alcohol

hemiacetal
R

"R

OH

"R

C R'

OH

ketone

alcohol

hemiketal

Pentoses and hexoses can cyclize as the ketone or aldehyde reacts with a distal OH. Glucose forms an intra-molecular hemiacetal, as the C1 aldehyde & C5 OH react, to form a 6member pyranose ring, named after pyran. These representations of the cyclic sugars are called Haworth projections.

CHO C C C C OH H

H HO H H

2 3 4 5 6

D-glucose

OH (linear form) OH

CH2OH
6 CH2OH

6 CH2OH

H
4

O H
2

H
1

H
4

O H
2

OH
1

H OH
3

H OH
3

OH

OH

OH

OH

OH

-D-glucose

-D-glucose

LOS MONOSACRIDOS DE 5 6 CARBONOS SE ENCUENTRAN PREFERENTEMENTE EN FORMA DE ESTRUCTURAS CCLICAS DE 5 6 ESLABONES.

CH2OH O H OH OH HOH2C 6
5

2C

HO H H

C C C

O H HO
3

1 CH2OH 2

4 5 6

CH2OH

OH

OH

D-fructose (linear)

-D-fructofuranose

Fructose forms either a 6-member pyranose ring, by reaction of the C2 keto group with the OH on C6, or a 5-member furanose ring, by reaction of the C2 keto group with the OH on C5.

6 CH 2OH

6 CH 2OH

H
4

O H
2

H
1

H
4

O H
2

OH
1

H OH
3

H OH
3

OH

OH

OH

OH

OH

-D-glucose

-D-glucose

Cyclization of glucose produces a new asymmetric center at C1. The 2 stereoisomers are called anomers, & . Haworth projections represent the cyclic sugars as having essentially planar rings, with the OH at the anomeric C1: (OH below the ring) (OH above the ring).

Glycosidic Bonds
ENLACES METAESTABLES: DEGRADACIN in vivo SLO MEDIADA POR ENZIMAS

The anomeric hydroxyl and a hydroxyl of another sugar or some other compound can join together, splitting out water to form a glycosidic bond: R-OH + HO-R' R-O-R' + H2O E.g., methanol reacts with the anomeric OH on glucose to form methyl glucoside (methyl-glucopyranose).
H OH H O HO HO H H H OH OH H H2O H OH H O HO HO H H OH OCH3

CH3-OH

-D-glucopyranose

methanol

methyl--D-glucopyranose

Glucsidos. Formacin del enlace glucosdico. No sufren mutarrotacin, lo que ayuda en determinar la configuracin de los azcares. Abundan en tejidos animales y vegetales; algunos son muy txicos (inhiben enzimas que median la utilizacin del ATP): ouabaina es inhibidor de la ATPasa Na+/K+, muy til como herramienta farmacolgica; amigdalina, en semillas de almendras amargas HCN

Disaccharides:
Maltose, a cleavage product of starch (e.g., amylose), is a disaccharide with an (1 4) glycosidic link between C1 - C4 OH of 2 glucoses. It is the anomer (C1 O points down).

6 CH2OH

6 CH2OH

H
4

O H
2 1

H
4

O H
2 1

H OH
3

H OH
3

OH

OH

H
6 CH 2OH

OH

maltose

OH

6 CH 2OH

H
4

O H
2 1

H O H
4

O H
2 1

OH

H OH
3

H OH
3

OH

OH

cellobiose

OH

Cellobiose, a product of cellulose breakdown, is the otherwise equivalent anomer (O on C1 points up). The (1 4) glycosidic linkage is represented as a zig-zag, but one glucose is actually flipped over relative to the other.

Polysaccharides
CH2OH H OH H OH O H OH H
1

H O

6CH OH 2 5 O 4 OH 3

CH2OH H O H O H OH H H O OH H H

CH2OH O H OH H H OH H O H

CH2OH O H OH H H OH OH H

H 1
2

OH

amylose

Plants store glucose as amylose or amylopectin, glucose polymers collectively called starch. Glucose storage in polymeric form minimizes osmotic effects. Amylose is a glucose polymer with (14) linkages. It adopts a helical conformation. The end of the polysaccharide with an anomeric C1 not involved in a glycosidic bond is called the reducing end.

CH2OH H H OH OH H CH2OH H OH H OH O H OH H H O H OH CH2OH O H OH H H O H H O H

CH2OH O H OH H H OH H 1 O 6 CH2 5 H OH 3 H CH2OH O H 2 OH 1 O H H O H 4 OH H H O OH H H

glycogen

CH2OH O H OH H H OH OH H

H O

H 4

OH

Glycogen, the glucose storage polymer in animals, is similar in structure to amylopectin. But glycogen has more (16) branches. The highly branched structure permits rapid release of glucose from glycogen stores, e.g., in muscle during exercise. The ability to rapidly mobilize glucose is more essential to animals than to plants.

CH2OH H OH H OH O H OH H
1

H O H
4

6CH OH 2 5 O

CH2OH H O H H OH O H OH H H O H

CH2OH O H OH H H H OH O H

CH2OH O H OH H H H OH OH

H OH
3

H 1
2

OH

cellulose

Cellulose, a major constituent of plant cell walls, consists of long linear chains of glucose with (14) linkages. Every other glucose is flipped over, due to the linkages. This promotes intra-chain and inter-chain H-bonds and van der Waals interactions, that cause cellulose chains to be straight & rigid, and pack with a crystalline arrangement in thick bundles called microfibrils. Schematic of arrangement of
cellulose chains in a microfibril.

These microfibrils are very strong. The role of cellulose is to impart strength and rigidity to plant cell walls, which can withstand high hydrostatic pressure gradients. Osmotic swelling is prevented.

FUNCIONES NO ESTRUCTURALES DE LOS GLUCOSAMINOGLUCANOS.

El cido Hialurnico es un polmero muy soluble en agua; est presente en el lquido sinovial de las articulaciones y en el humor vtreo del ojo. Parece actuar incrementando la viscosidad o como agente lubricante en ambos. La Heparina es un anticoagulante natural localizada en muchos tejidos corporales. Une en la sangre a la protena antiprotrombina III y, el complejo resultante, inhibe las enzimas de la cascada de la coagulacin.

ANTGENOS DEL GRUPO ABO. Los grupos sanguneos estn determinados por un conjunto de oligosacridos antignicos unidos a la superficie de los eritrocitos. El Tipo O no es antignico pero la persona genera anticuerpos contra los antgenos A y B. Los Tipos A y B se forman por adicin de GalNac y Gal, respectivamente; ambos pueden generar anticuerpos especficos contra el Tipo opuesto (A o B). Los portadores del Tipo AB no generan anticuerpos contra ninguno de estos polisacridos.

Lectins are glycoproteins that recognize and bind to

specific oligosaccharides. A few examples: Concanavalin A and wheat germ agglutinin are plant lectins that have been useful research tools. Mannan-binding lectin (MBL) is a glycoprotein found in blood plasma. It associates with cell surface carbohydrates of disease-causing microorganisms, promoting phagocytosis of these organisms as part of the immune response.