Karbohidrat 2

Pengantar Biokimia Gizi

Polysaccharides
(also called Glycans)

Most carbohydrates found in nature occur as polysaccharides.

Formation of di- and polysaccharide bonds

Dehydration synthesis of a sucrose molecule formed from condensation of a glucose with a fructose

Lactose:

Maltose:

Disaccharides
Composed of two monosaccharide units by glycosidic link from C-1 of one unit and -OH of second unit 13, 14, 1 6 links most common but 1 1 and 1 2 are possible Links may be a or b Link around glycosidic bond is fixed but anomeric forms on the other C-1 are still in equilibrium

Polysaccharides
Primary Structure: Sequence of residues

N.B.
Many are homopolymers. Those that are heteropolymers rarely have >3,4 different residues

Secondary & Tertiary Structure

Rotational freedom hydrogen bonding oscillations local (secondary) and overall (tertiary) random coil, helical conformations

Movement around bonds:

Tertiary structure - sterical/geometrical conformations Rule-of-thumb: Overall shape of the chain is determined by geometrical relationship within each monosaccharide unit b(14) - zig-zag - ribbon like b(1 3) & a(14) - U-turn - hollow helix b(1 2) - twisted - crumpled (16) - no ordered conformation

Ribbon type structures

(a) Flat ribbon type conformation: Cellulose

(b) Buckled ribbon type conformation: Alginate

Hollow helix type structures

Tight helix - void can be filled by including molecules of appropriate size and shape More extended helix - two or three chains may twist around each other to form double or triple helix Very extended helix - chains can nest, i.e., close pack without twisting around each other

Amylose forms inclusion complexes with iodine, phenol, n-butanol, etc.

The liganded amylose-iodine complex: rows of iodine atoms (shown in black) neatly fit into the core of the amylose helix.

N.B. Unliganded amylose normally exists as a coil rather than a helix in solution

Tertiary Structure: Conformation Zones

Zone A: Extra-rigid rod: schizophyllan
Zone B: Rigid Rod: xanthan

Zone C: Semi-flexible coil: pectin

Zone D: Random coil: dextran, pullulan

Zone E: Highly branched: amylopectin, glycogen

Quarternary structure aggregation of ordered structures

Aggregate and gel formation:
May involve other molecules such as Ca2+ or sucrose Other polysaccharides (mixed gels)

Polysaccharides 6 case studies

1. 2. 3. 4. 5. 6. Alginates Pectin Xanthan Galactomannans Cellulose Starch

1. Alginate
Source: Brown seaweeds (Phaeophyceae, mainly Laminaria)

Linear unbranched polymers containing b(14)-linked D-mannuronic acid (M) and a(14)-linked L-guluronic acid (G) residues

Calcium poly-a-L-guluronate left-handed helix view down axis

view along axis, showing the hydrogen bonding and calcium binding sites

Different types of alginates different properties e.g. gel strength

Polyguluronate: - gelation through addition of Ca2+ ions egg-box
Polymannuronate less strong gels, interactions with Ca2+ weaker, ribbon-type conformation

Alternating sequences disordered structure, no gelation

Properties and Applications

High water absorption Low viscosity emulsifiers and shear-thinning thickeners Used in pet food chunks, onion rings, stuffed olives and pie fillings, wound healing agents, printing industry (largest use)

2. Pectin
Cell wall polysaccharide in fruit and vegetables Main source citrus peel

Partial methylated poly-a-(14)-D-galacturonic acid residues (smooth regions), hairy regions due to presence of alternating a -(12)-L-rhamnosyl-a -(14)-D-galacturonosyl sections containing branch-points with side chains (1 - 20 residues) of mainly L-arabinose and D-galactose

Properties and applications

Main use as gelling agent (jams, jellies) dependent on degree of methylation high methoxyl pectins gel through H-bonding and in presence of sugar and acid low methoxyl pectins gel in the presence of Ca2+ (egg-box model) Thickeners Water binders Stabilizers

3. Xanthan

Extracellular polysaccharide from Xanthomonas campestris

b-(14)-D-glucopyranose backbone with side chains of -(31)-a-linked D-mannopyranose-(21)-bD-glucuronic acid-(41)-b-D-mannopyranose on alternating residues

Properties and applications

double helical conformation pseudoplastic shear-thinning thickener stabilizer emulsifier foaming agent forms synergistic gels with galactomannans

4. Galactomannans b-(14) mannose (M) backbone with a(16) galactose (G) side chains Ratio of M to G depends on source M:G=1:1 - fenugreek gum M:G=2:1 - guar gum M:G=3:1 - tara gum M:G=4:1 - locust bean gum

Guar gum - obtained from endosperm of Cyamopsis tetragonolobus

Locust bean gum - obtained from seeds of carob tree (Ceratonia siliqua)

Properties and applications

non-ionic solubility decreases with decreasing galactose content thickeners and viscosifiers used in sauces, ice creams LBG can form very weak gels

5. Cellulose

b-(14) glucopyranose

Properties and applications

found in plants as microfibrils very large molecule, insoluble in aqueous and most other solvents flat ribbon type structure allows for very close packing and formation of intermolecular H-bonds two crystalline forms (Cellulose I and II) derivatisation increases solubility (hydroxy-propyl methyl cellulose, carboxymethyl cellulose, etc.)

6. Starch
Some homopolysaccharides are stored forms of fuel

Electron micrographs of starch and glycogen granules

Other homopolysaccharides (e.g. cellulose and chitin) serve as structural elements in plant cell walls and animal exoskeletons.

Amylose and amylopectin, the polysaccharides of starch

occurs every 24 to 30 residues

amylopectin

Strands of amylopectin form double helical structures with each other or with amylose strands

Bacterial and algal cell walls contain structural heteropolysaccharides

Peptidoglycan
(alternating b14-linked GlcNac-Mur2Ac crosslinked by short peptides)

Lysozyme kills bacteria by hydrolyzing the b14 bond.

exact structure depends on the bacterial species

The structure of agarose

Repeating units of some common glycosaminoglycans of extracellular matrix

linear polymers composed of repeating disaccharide units

Glucoronic acid

N-Acetylglucosamine

Proteoglycans

glycosaminoglycan-containing macromolecules of the cell surface and extracellular matrix

Proteoglycan structure

Two families of membrane proteoglycans

Mammalian cells have at least 30 types of proteoglycans. Basic unit: a core protein with covalently attached glycosaminoglycan(s).

Heparan sulfate bind a variety of extracellular ligands and thereby modulate the ligands interaction with specific receptors of the cell surface

Interactions between cells and the extracellular matrix

Cross-linked meshwork that gives the whole extracellular matrix strength and resilience

Roles of

oligosaccharides
in recognition and adhesion

at the cell surface