References
Tombs, M.P. & Harding, S.E., An Introduction to Polysaccharide Biotechnology, Taylor & Francis, London, 1997
D.A. Rees, Polysaccharide Shapes, Chapman & Hall, 1977 E.R. Morris in Polysaccharides in Food, J.M.V. Blanshard & J.R. Mitchell (eds.), Butterworths, London. 1979, Chapter 2 The Polysaccharides, G.O. Aspinall (ed.), Academic Press, London, 1985 Carbohydrate Chemistry for Food Scientists, R.L. Whistler, J.N. BeMiller, Eagan Press, St. Paul, USA, 1997
Coded precisely by genes, hence monodisperse ~20 building block residues (amino acids) Standard peptide link (apart from proline) Normally tightly folded structures {some proteins do not possess folded structure gelatin an honorary polysaccharide}
Coded precisely by genes, hence monodisperse ~20 building block residues (amino acids) Standard peptide link (apart from proline) Normally tightly folded structures {some proteins do not possess folded structure gelatin an honorary polysaccharide}
Polysaccharides Often poorly defined (although some can form helices) Synthesised by enzymes without template polydisperse, and generally larger Many homopolymers, and rarely >3,4 different residues Various links a(11), a(12),
a(1-4),a(16), b(13), b(14)etc
Monosaccharides
Contain between 3 and 7 C atoms empirical formula of simple monosaccharides (CH2O)n aldehydes or ketones
from http://ntri.tamuk.edu/cell/carbohydrates.html
SomeTerminology Asymmetric (Chiral) Carbon has covalent bonds to four different groups, cannot be superimposed on its mirror image Enantiomers - pair of isomers that are (non-superimposable) mirror images
Chirality rules
1. Monosaccharides contain one or more asymmetric Catoms: get D- and L-forms, where D- and Ldesignate absolute configuration 2. D-form: -OH group is attached to the right of the asymmetric carbon 3. L-form: -OH group is attached to the left of the asymmetric carbon 4. If there is more than one chiral C-atom: absolute configuration of chiral C furthest away from carbonyl group determines whether D- or L-
An aldose: Glucose
from http://ntri.tamuk.edu/cell/carbohydrates.html
A ketose: Fructose
from http://ntri.tamuk.edu/cell/carbohydrates.html
Ring Structure
Linear known as Fischer structure Ring know as a Haworth projection Cyclization via intramolecular hemiacetal (hemiketal) formation C-1 becomes chiral upon cyclization - anomeric carbon Anomeric C contains -OH group which may be a or b (mutarotation a b) Chair conformation usual (as opposed to boat) Axial and equatorial bonds
Preferred
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
Rotational freedom hydrogen bonding oscillations local (secondary) and overall (tertiary) random coil, helical conformations
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
Chains can align and pack closely together. Also get hydrogen bonding and interactive forces.
from: http://www.sbu.ac.uk/water/hydro.html
from: http://www.sbu.ac.uk/water/hydro.html
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
from: http://www.sbu.ac.uk/water/hydro.html
The liganded amyloseiodine 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
1. Alginate (E400-E404)
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 Not random copolymers but consist of blocks of either MMM or GGG or MGMGMG
from: http://www.sbu.ac.uk/water/hydro.html
view along axis, showing the hydrogen bonding and calcium binding sites
from: http://www.sbu.ac.uk/water/hydro.html
2. Pectin (E440)
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
from: http://www.sbu.ac.uk/water/hydro.html
3. Xanthan (E415)
b-(14)-D-glucopyranose backbone with side chains of -(31)a-linked D-mannopyranose-(21)-b-D-glucuronic acid-(41)b-D-mannopyranose on alternating residues
from: http://www.sbu.ac.uk/water/hydro.html
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 (E412) M:G=3:1 - tara gum M:G=4:1 - locust bean gum (E410)
Locust bean gum - obtained from seeds of carob tree (Ceratonia siliqua)
from: http://www.sbu.ac.uk/water/hydro.html)
5. Cellulose
b-(14) glucopyranose
from: http://www.sbu.ac.uk/water/hydro.html