Carbohydrates - are a group of naturally occurring carbonyl compounds (aldehydes or ketones) that also contain several hydroxyl groups

- include single sugars (monosaccharides) and their polymers, the oligosaccharides and polysaccharides.

- the most abundant organic molecule in nature (each year, photosynthesis converts more than 100 billion metric tons of CO2 and H2O into cellulose and other plant products) - essential for life because of its wide range of function and widely distributed in plants and animals
- Plants: synthesized from CO2 and H2O through photosynthesis, store as starch or converted to cellulose

- Animals: synthesized from Lipids and CHON through Gluconeogenesis but the bulk is from plants Glucose - primary CHO, most important source of fuel of most organisms
- physiologic sugar since all CHO are converted to glucose for further metabolism

 Functions

1. Source of Energy - 1 gram of CHO = 4 calories 2. Storage form of Energy - plants (starch), animals (glycogen) 3. Structural component of many organisms - cell membrane, bacterial cell 4. Provides building blocks for many processes of body metabolism

 Structure

- Carbon containing the functional group (aldehyde or ketone

group) should have the lowest possible number

-Penultimate Carbon: D and L isomer is determined

 Haworths Projection Formula (Cyclic form)

- ring is formed due to reactions: a. aldehyde and the alcohol group (Hemiacetal ring) b. ketone group and alcohol (Hemiketal ring) - rules: Structure in the left side (above the ring) Structure in the right side (below the ring) Bulky group (placed above the ring)

-Pyranose - the hydroxyl (OH) of 5th carbon reacts with the 1st carbon and the oxygen comprising the oxygen ring - Furanose - the 1st carbon reacts with 4rth carbon
- Pyranose form is more stable than furanose form

 Classification

A. Monosaccharide (CnH2nOn) - simple sugars, named based on: 1. the no. of Carbon atoms 2. based on the reaction group present - aldehyde (aldoses) - ketone (ketoses) - important monosaccharide: 1. Ribose and Deoxyribose (5C) 2. Glucose, Fructose, Galactose (6C)

B. Disaccharides - yield two molecules of monosaccharide when hydrolyzed - e.g. sucrose, lactose, etc. C. Oligosaccharide - contains 2- 12 monosaccharide units - e.g. Malto-riose

D. Polysaccharide - contains more than 10 monosaccharide units - e.g. Starch, Glycogen etc.

 Sugars Exhibit Various Forms of Isomerism

- Isomers are compounds that have the same chemical formula but differ in structural configuration and properties - Isomers is due to the presence of asymmetric carbon (attached to 4 different atoms/groups) - study of Isomerism is focused on Glucose due to its clinical importance

More important types of isomerism in glucose (1) D and L isomerism - the designation of a sugar isomer as the D form or of its mirror image as the L form - based on the orientation of OH group in the penultimate carbon: L-form (left) D-form (right)

- application of polarized light, there is rotation either to the right (Dextrorotatory (+)) or to the left (Levorotatory (-))
- D and L isomer is also known as Enantiomers, means mirror images at each other

(2) Pyranose and furanose ring structures

- stable ring structures of monosaccharides are either pyran (a six-membered ring) or furan (a five-membered ring) - glucose in solution,

more than 99% is in

the pyranose form

(3) Alpha and beta anomers - Isomerism occurs about position 1, the carbonyl or anomeric carbon atom, to give a mixture: 1. -glucopyranose (38%) 2. -glucopyranose (62%)
- less than 0.3% is represented by and anomers of glucofuranose

Beta : OH in C1 is above the rin Alpha: OH in C1 is below the ring Ketosis: C2 is involve
.

- hemiacetal ring formation (aldehyde) and hemiketal ring (ketose)

- Interco version of alpha and beta is termed as Mutarotation, rotation is also either Dextro (+) or Levo (-)
- In mutarotation, there is opening of ring of ring and assume free aldehyde or ketone group

(4) Epimers - Isomers as a result of variations in configuration of the OH and H on carbon atoms 2, 3, and 4 of glucose
-biologically, the most important epimers of glucose are mannose (C2) and galactose (C4)

(5) Aldose-ketose isomerism - Fructose has the same molecular formula as glucose but differs in its structural formula (keto group in position 2, the anomeric carbon)

- Glucose has potential aldehyde group in position 1 of the anomeric carbon

6. Boat and Chair conformers - differs in the shape of the ring - originates from pyranose form - chair is more stable than the boat conformation

Monosaccharide

Aldoses and ketoses family

Some hexose derivatives important in biology

 Derived sugars

1. Sugar acids - produced when monosaccharide undergo oxidation C1 - aldonic type (Gluconic acid) C6 uronic type (Glucoronic acid) C1 and C6 aldaric (Glucaric acid)

2. Sugar alcohol - product of reduction of sugar - e.g. Sorbitol or D-glucitol (sweetener) Mannitol (plasma expander)
3. Sugar amines - known as amino sugars (NH2 attached in C2) - constituent of: Antibiotics, Glycoproteins Glycosaminoglycans

4. Sugar phosphates - product of phosphorylation of sugar - phosphorylation important step in glucose metabolism
5. Deoxy-sugars - removal of Oxygen from carbon - Hydroxyl group is replaced with H-ion - e.g. Deoxyribose (DNA component)

6. Glycosides - formed when CHO is linked to non-CHO such as aglycone or another sugar through glycosidic linkage - aglycone maybe: methanol, phenol, sterol, glycerol or a base (e.g. Adenine) - can be found in drugs, dyes, vegetables, animal tissues - important in the field of medicine

B. Disaccharides - formed when the anomeric hydroxyl group of one monosaccharide is bound glycosidically with one of the OH groups of another (acetal complementation) - type of linkage: 1. head to tail (common) 2. head to head (no free functional group, non-reducing sugar) .

(1) Maltose - occurs as a breakdown product of the starches contained in malt (malt Sugar) and as an intermediate in intestinal digestion - the anomeric OH group of one glucose molecule has an -glycosidic bond with C-4 in a second glucose residue

2. Lactose (milk sugar, - is the most important carbohydrate in the milk of mammals

- Cows milk contains 4.5% lactose, while human milk contains up to 7.5%
- In lactose, the anomeric OH group of galactose forms a - glycosidic bond with C-4 of a glucose

(3) Sucrose - serves in plants as the form in which carbohydrates are transported, and as a soluble carbohydrate reserve - non-reducing sugar

 Polysaccharides

- polymer of several molecules of sugars, are ubiquitous in nature - can be classified into three separate groups, based on their different functions 1. Structural polysaccharides -provide mechanical stability to cells, organs, and organisms

Structural polysaccharide - structural component of cells and tissues 1. Cellulose 2. Chitin 3. Glycoprotein 4. Glycosaminoglycans

2. Waterbinding polysaccharides - are strongly hydrated and prevent cells and tissues from drying out 3. Reserve/Storage polysaccharides - serve as carbohydrate stores that release monosaccharides as required

- due to their polymeric nature, they are osmotically less active, hence can be stored in large quantities within the cell

Storage polysaccharides - source of energy or storage form of CHO 1. Starch 2. Glycogen 3. Inulin 4. Dextrin

Structure
Homopolysaccharides - contain only a single type of monomer Heteropolysaccharides - contains two or more different kinds

Starch - the most important vegetable reserve carbohydrate and polysaccharides from plant cell walls - consist of glucose as building block (glucan or glucosans) - abundant in fruits - important in human diet (50 70%)

Structure: 1. Amylose - linear form consisting of 250 300 glucose units (alpha 1-4 linkage) - 15 20%, soluble in water, when in solution form a helix 2. Amylopectin - branched form with alpha 1-6 linkage in the branch (every 12 18 glucose units) - 80 to 85%, water insoluble

 Glycogen

- the reserve carbohydrate of higher animals, is stored in the liver and musculature in particular - formation and breakdown of glycogen are subject to complex regulation by hormones and other factors

- structure: similar to amylopectin but highly branched (every 8 10 units)

Inulin - a fructose polymer, is used as a starch substitute in diabetics dietary products - it serves as a test substance for measuring renal clearance
Chitin - a homopolymer from 1-4-linked N-acetylglucosamine, - most important structural substance in insect and crustacean shells, thus , the most common animal polysaccharide - also occurs in the cell wall of fungi.

 Dextrin

- formed in the course of hydrolytic breakdown of starch - yield maltose upon hydrolysis by amylase - contains 7 10 glucose units - used in malt preparation for beverages - widely used in infant feeding which facilitates digestions (prevents large heavy curds of milk in the stomach)

 Cellulose

- structural polysaccharide of plants - linear polymer of B-D-glucose joined by B 1-4 glycosidic bond - cellobiose as building block - could not be digested by humans due to lack of B-1-4 glycosidase enzyme - food sources: Fruits, vegetables and other fibrous foods

Physiologic function - serves as a roughage (cleansing of Intestine) by increasing the fecal bulk thereby decreasing the transit time of bowel preventing the effects of toxins and microorganisms in the colon
- decrease in fecal bulk will increase transit time of bowel, increase exposure to carcinogens (waste product of metabolism or in-situ production)

 Glycoproteins

- high CHON content than CHO - found in cell membrane or tissues - widely distributed and perform several functions - contains sialic acid responsible for its (-) charge - substances made up of glcoproteins:
a. Blood group Ag b. Enzymes c. Transport proteins d. Collagen e. Antibodies (Ab)

 Glycosaminoglycans

- known as Mucopolysaccharide or Proteoglycan - special heteropolysaccharide made up of Uronic acid and Amino sugars as building block - present in matrix where in collagen, elastin and bone minerals are embedded - relative to connective tissue function

- responsible for the lubricating function of mucous membrane

- almost all exist as proteoglycan (uronic acid is attached to a CHON): a. Chondroitin b. Heparin c. keratan d. Heparan

 Types of Glycosaminoglycans and their repeating

Disaccharides 1. Hyaluronic acid - largest consist of 400 25,000 linear polymer of repeating disaccharide - main constituent of ground substance of Connective tissues

2. Chondroitin - acts as water bed around cells and fibers

- types: a. Chondroitin-4-SO4 b. Chondroitin-6-SO4 c. Dermatant sulfate

3. Heparin - naturally occurring anticoagulant

- present in Mast cells Lining of arteries Liver, lungs and skin

4. Keratan sulfate - present in corner of the eye and nucleus of Intervertebral disc - repeating disaccharide: N-acetylglucosamine-B-1,3-D-galactose

 Summary of Function

1. Component of ground substances or C.T. e.g. Hyaluronic Acid, Chondroitin 2. Structural component of cell membrane 3. Lubricant in joint spaces e.g. Hyaluronic Acid 4. Anti-coagulant e.g. Heparin

END