Carbohydrates

Biomacromolecules: Polymers
A polymer is a long molecule consisting of many similar building blocks called monomers Three of the four classes of lifes organic molecules are polymers: Carbohydrates Proteins Nucleic acids

The Synthesis and Breakdown of Polymers

Monomers form larger molecules by condensation reactions called dehydration reactions Polymers are disassembled to monomers by hydrolysis, a reaction that is essentially the reverse of the dehydration reaction

In the beginningmodified cellulose is the first plastic

Short polymer Dehydration removes a water molecule, forming a new bond

Unlinked monomer

Longer polymer Dehydration reaction in the synthesis of a polymer

Hydrolysis adds a water molecule, breaking a bond

Hydrolysis of a polymer

Carbohydrate definitions
The generic term carbohydrate includes monosaccharides, oligosaccharides and polysaccharides as well as substances derived from monosaccharides The term sugar is frequently applied to monosaccharides and lower oligosaccharides The generic term monosaccharide (as opposed to oligosaccharide or polysaccharide) denotes a single unit, without glycosidic connection to other such units One of the distinguishing features of carbohydrates is that they contain one or more chiral carbon atoms. A chiral carbon atom has four different groups attached to it. A structure containing a chiral carbon atom and its mirror image are
non-superimposable

HO

Anomeric forms ( &)

The e anomeric centre: the new centre of chirality generated by hemiacetal ring closure. The two stereoisomers are referred to as 1 2 3 H HO anomers, designated or according to the configurational relationship between the anomeric centre and the anomeric reference atom. anomer, cis, in the Fischer projection, anomer,

trans

The Diversity of Polymers

Each cell has thousands of different kinds of macromolecules
1

Macromolecules vary among cells of an organism, vary more within a species, and vary even more between species An immense variety of polymers can be built from a small set of monomers

HO

Sugars
1 2 3
H HO

Carbohydrates serve as fuel, building, signaling material

Carbohydrates include sugars and the polymers of sugars The simplest carbohydrates are monosaccharides, or single sugars Carbohydrate macromolecules are polysaccharides, polymers composed of many sugar building blocks

Sugars
Monosaccharides have molecular formulas that are usually multiples of CH2O Glucose is the most common monosaccharide Monosaccharides are classified by location of the carbonyl group and by number of carbons in the carbon skeleton

 A disaccharide is formed when a dehydration reaction joins two monosaccharides This covalent bond is called a glycosidic linkage

Sugar monomers

Sugar monomers

Ring opening
In solution, most simple sugars and many of their derivatives occur as equilibrium mixtures (Mixtures of anomers).

Ring-opening

Dehydration reaction in the synthesis of maltose

14 glycosidic linkage

Glucose Dehydration reaction in the synthesis of sucrose

Glucose

Maltose

12 glycosidic linkage

Glucose

Fructose

Sucrose

Polysaccharides
Polysaccharides, the polymers of sugars, have storage and structural roles The structure and function of a polysaccharide are determined by its sugar monomers and the positions of glycosidic linkages

Storage Polysaccharides
Starch, a storage polysaccharide of plants, consists entirely of glucose monomers Plants store surplus starch as granules within chloroplasts and other plastids

Branched carbohydrates

Chloroplast

Starch

1 m

Amylose

Amylopectin

Starch: a plant polysaccharide

 Glycogen is a storage polysaccharide in animals Humans and other vertebrates store glycogen mainly in liver and muscle cells

LE 5-6b

Mitochondria Glycogen granules

0.5 m

Glycogen

Glycogen: an animal polysaccharide

Structural Polysaccharides
Cellulose is a major component of the tough wall of plant cells Like starch, cellulose is a polymer of glucose, but the glycosidic linkages differ The difference is based on two ring forms for glucose: alpha () and beta ()

Reducing sugar/Non reducing sugar

Glycosylation

Blood type sugar

Biosimilar

Proteoglycans

Bacterial cell walls

LE 5-7

a Glucose

b Glucose

a and b glucose ring structures

Starch: 14 linkage of a glucose monomers.

Cellulose: 14 linkage of b glucose monomers.

 Polymers with alpha glucose are helical Polymers with beta glucose are straight In straight structures, H atoms on one strand can bond with OH groups on other strands Parallel cellulose molecules held together this way are grouped into microfibrils, which form strong building materials for plants

LE 5-8

Cellulose microfibrils in a plant cell wall Cell walls Microfibril

0.5 m Plant cells

Cellulose molecules

Glucose monomer

 Enzymes that digest starch by hydrolyzing alpha linkages cant hydrolyze beta linkages in cellulose Cellulose in human food passes through the digestive tract as insoluble fiber Some microbes use enzymes to digest cellulose Many herbivores, from cows to termites, have symbiotic relationships with these microbes

 Chitin, another structural polysaccharide, is found in the exoskeleton of arthropods Chitin also provides structural support for the cell walls of many fungi

Nutraceuticals
Nutraceuticals: a term combining the words nutrition and pharmaceutical

Biosynthesized ~1010~12tons/yr

stiffness increases with decreasing chitin and hydration

stiffness increases with increasing protein & cross-links

Plant

Marine invertebrate
DOPA & Catechol & Dopamine

Melanin & Eumelanin

Application of Chitin
Membrane (Waste water treatment, heavy metal removal) Anti-microbial & medical materials Preservative Plant growth booster

Limitation of Chitin
Glass transition temp (Tg) is above the thermal degradation temp Anti-microbial & medical materials Preservative Plant growth booster

Carrageenan from E. cottonii (Red algae)

Carrageenan
Another product of the sea is carrageenan
Which is listed as an ingredient in many preserved foods, toothpaste, and cosmetics This sulfate-rich polysaccharide, extracted from red seaweeds, has been used in many products for over 50 years

Carrageenans have been used as thickening agents and for improving food texture Some of the most common applications of carrageenans include their use as stabilizing and bulking agents in
Chewing gum Chocolate milk Beers and wine (to improve the clarity of these drinks) Salad dressing Syrups Sauces Processed lunch meats Adhesives Textiles Polishes, and hundreds of other products.

Carrageenan All carrageenans are high-molecular-weig ht polysaccharides made up of repeating galactose units and 3,6 anhydrogalactose (3,6-AG), both sulfated and nonsulfated. T he units are joined by alternating alpha 1 -3 and beta 1-4 glycosidic linkages (From: Wikipedia)

a Glucose

a and b glucose ring structures

Starch: 14 linkage of a glucose monomers.

Cellulose: 14 linkage of b glucose monomers.

Plant

Alginate
Uronic acid

Alginate

Poly M (D-mannuroic) blocks Poly G (L-guluronic ) blocks M/G ration differs depending on the source As M/H ratio , gel strength Food additives,

From: http://artbios.ru

Macrocystis pyrifera

Environmental pplications - filter

Cellulose/Chitin are not soluble in common solvents nor meltable. Carboxyl/Sulfuric/Amino groups in carbohyrates are capable to catch up transition metal oxides/ions. Cellulose acetate was one of the first materials used in membrane separation technology and still finds utility in many filtration applications. Membranes made from cellulose acetate are characterized as having outstanding formability, reasonable resistance to degradation by chlorine, less fouling and in some applications higher flux compared to alternative materials. They are also a cost-effective alternative to other filtration materials available in the market.