Carbohydrates I : Structure & Function

Dr. Nizar Bin Abd Manan Department of Anatomy Faculty of Medicine and Health Sciences Universiti Putra Malaysia

Abasa (80) (24-32)

Let mankind look at his food, (24) How We poured down water in abundance, (25) Then We broke open the earth, splitting [it with sprouts], (26) And caused to grow within it grain, (27) And grapes and herbage, (28) And olive and palm trees, (29) And gardens of dense shrubbery, (30) And fruit and grass, (31) [As] enjoyment for you and your grazing livestock. (32)

Carbohydrate : Introduction
Organic compound that consists only of carbon, hydrogen & oxygen Technically: hydrates of carbon Structurally : > accurate to view them as polyhydroxy aldehydes & ketones Saccharide : from Greek Sakkharon (sugar)

Carbohydrate : Source
It is He who sends down water (rain) from the sky. With it We produce vegetation of all kinds from which (water or plants) We produce greenery (Khadir), out of which We produce grain in clusters. And out of date palms, from their spathes come forth clusters of dates hanging low and near, and (We produce) gardens of grapes, olives and pomegranates, each similar (in leaves or shape), yet different (in fruit and taste). Look at (and think over) their fruits when they begin to bear fruit, and (look at) the ripeness thereof. Behold! In these things there are Signs for people who believe. (Al-Anam: 99)

Carbohydrate : Sources
mainly plants synthesize glucose from CO2 & water; stored as starch or converted to cellulose of the plant framework Animals can synthesize small molecule carbohydrates from lipid & protein (De novo synthesis)

Carbohydrate : Medical Importance

Glucose : major fuel of the mammalian tissue, universal fuel for fetus Converted in liver, & from glucose all other carbohydrates in body are formed. Glycogen : storage Ribose : nucleic acids Galactose : in lactose of milk Combined with lipid & protein to form glycoprotein & proteoglycan Diseases associated with carbohydrates : diabetes mellitus, galactosemia, glycogen storage disease, lactose intolerance

Carbohydrate : Function
1) Source of food and energy for human, most animals and microorganism
Let mankind look at his food, How We poured down water in abundance, Then We broke open the earth, splitting [it with sprouts], And caused to grow within it grain, And grapes and herbage, And olive and palm trees, And gardens of dense shrubbery, And fruit and grass, [As] enjoyment for you and your grazing livestock. (Abasa, 24-32) And the pains of childbirth drove her (Maryam) to the trunk of a palm tree. She said, "Oh, I wish I had died before this and was in oblivion, forgotten. But he called her from below her, "Do not grieve; your Lord has provided beneath you a stream. And shake toward you the trunk of the palm tree; it will drop upon you ripe, fresh dates. So eat and drink and be contented (Maryam, 23-26)

Carbohydrate : Function
2) As structural & supportive elements in the cell

walls of bacteria, plants, in the connective tissues and exoskeleton of animal organism (eg. chitin, cellulose)
And in the earth there are tracts side by side and gardens of grapes and corn and palm trees having one root and (others) having distinct roots - they are watered with one water(Ar-Rad, 4)
Is it you who produced its tree, or are We the producer? (Al-Waqiah, 72)

Carbohydrate : Function
3) synthesis of other compounds e.g: nucleic acid,

coenzymes, glycoprotein 4) Temporary storage of glucose e.g: starch, glycogen

Carbohydrate : Classification
Monosaccharide Disaccharide Oligosaccharide Polysaccharide

Carbohydrate : Monosaccharide
Most abundant & important : glucose Carbohydrates that cannot be hydrolyzed into simpler carbohydrates Subdivided into trioses, tetroses, pentoses, hexoses, heptoses or octoses (depending upon number of carbon atoms they possess. Aldoses or ketoses whether aldehyde or ketone group is present.
Aldoses Trioses (3C) Tetroses (4C) Pentoses (5C) Hexoses (6C) glycerose Erythrose Ribose Glucose Ketoses dihydroxyacetone Erythrulose Ribulose Fructose

Chemical Structure
The structure of glucose can be represented in 3 ways

chair form

Haworth projection straight chain form

Monosaccharide Isomerism
Compound that have same structural formula but differ in spatial configuration.

Monosaccharide Isomerism

1) D and L Isomerism
D form or its mirror image L form Determined by the orientation of -H & -OH groups around the carbon atom adjacent to the terminal primary alcohol carbon When -OH group on this carbon is on the right : Disomer when -OH group is on the left : L-isomer. Most of the monosaccharides occurring in mammals are D sugars, & the enzymes responsible for their metabolism are specific for this configuration.

D and L Isomerism

2) Optical Isomerism
The presence of asymmetric carbon atoms : confers optical activity on the compound. When a beam of plane-polarized light is passed through a solution of an optical isomer, it will be rotated either to the right, dextrorotatory (+); or to the left, levorotatory (). The direction of rotation is independent of the stereochemistry of the sugar, so it may be designated D(), D(+), L(), or L(+). Example:
Naturally occurring form of fructose is the D() isomer. In solution, glucose is dextrorotatory : hence the alternative name dextrose, often used in clinical practice.

3) Pyranose and Furanose Ring

The stable ring structures of monosaccharides are similar to the ring structures of either pyran (a sixmembered ring) or furan (a five-membered ring). For glucose in solution, more than 99% is in the pyranose form.

Pyranose and furanose forms of glucose.

Pyranose and furanose forms of fructose.

4) Alpha and Beta Anomers

Stereoisomers of a cyclic saccharide that differs only in its configuration at the hemiacetal or hemiketal carbon (also called as anomeric carbon). Designated as alpha () or beta ().

5) Epimer
Isomers differing 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 & galactose, formed by epimerization at carbons 2 & 4, respectively.

6) Aldose-Ketose Isomerism
Fructose has the same molecular formula as glucose (C6H12O6) but differs in structural formula Glucose : aldose : aldehyde group (H-C=O) Fructose : ketose : keto group (C-C=O)

Glucose

Fructose

Biochemical Importance of Monosaccharide (1)

Pentoses D-Ribose Where Found Nucleic acids. Biochemical Importance 1. Structural elements of nucleic acids and coenzymes, eg, ATP, NAD, NADP, flavoproteins. 2. Ribose phosphates are intermediates in pentose phosphate pathway.

D-Ribulose D-Arabinose D-Xylose

Formed in metabolic Ribulose phosphate is an intermediate in processes. pentose phosphate pathway. Gum arabic. Plum Constituent of glycoproteins. and cherry gums. Wood gums, Constituent of glycoproteins. proteoglycans, glycosaminoglycans. isolated from

D-Lyxose

muscle. A constituent of a lyxoflavin PentosesHeart & their physiologic importance human heart muscle.

L-Xylulose.

Intermediate in Found in urine in essential pentosuria. uronic acid pathway.

Biochemical Importance of Monosaccharide (2)

Hexoses
D-Glucose

Where Found
Fruit juices. Hydrolysis of starch, cane sugar, maltose, and lactose.

Biochemical Importance
1. The sugar of the body. The sugar carried by the blood, and the principal one used by the tissues. 2. Present in the urine (glycosuria) in diabetes mellitus owing to raised blood glucose (hyperglycemia).

D-Fructose

Fruit juices. Honey. 1. Can be changed to glucose in the liver and Hydrolysis of cane used in the body. sugar & inulin 2. Hereditary fructose intolerance leads to fructose accumulation and hypoglycemia.
Hydrolysis of lactose. 1. Can be changed to glucose in the liver and metabolized. 2. Synthesized in the mammary gland to make the lactose of milk. 3. A constituent of glycolipids and glycoproteins. physiologic importance 4. Failure to metabolize leads to galactosemia and cataract. A constituent of many glycoproteins.

DGalactose

Pentoses & their

D-Mannose Hydrolysis of plant mannans & gums.

Monosaccharide Derivatives
Derivatives Structure Example Function Sugar alcohol Carbonyl group reduced to hydroxyl group Deoxy sugars A hydroxyl group has been replaced by hydrogen. Acidic sugar oxidation of one of its OH groups turning the carbon into carboxyl group Mannitol, Sorbitol, Artificial sweeteners Xylitol. deoxyribose Component of DNA

D-glucuronate

Found in glycosaminoglycans intermediate in uronic acid pathway Vitamin C Component of hyaluronic acid, treatment of osteoarthritis

L-gulonate

Ascorbic acid Amino sugars One of the hydrogen replaced by amine group Glucosamine

Carbohydrate : Disaccharide
Formed when 2 monosaccharides undergo condensation involves the elimination of a small molecule, e.g. water, from the functional groups 3 common examples are sucrose (most abundant), lactose & maltose.
Disaccharide Sucrose Unit 1 Glucose Unit 2 Fructose Bond (12)

Lactose
Maltose Lactulose Trehalose

Galactose
Glucose Galactose Glucose

Glucose
Glucose Fructose Glucose

(14)
(14) (14) (11)

Cellobiose

Glucose

Glucose

(14)

Common disaccharide

Carbohydrate : Disaccharide

Biochemical Importance of disaccharide

Sugar Sucrose Source Cane and beet sugar. Sorghum. Pineapple. Carrot roots. Milk. May occur in urine during pregnancy. Digestion by amylase or hydrolysis of starch. Germinating cereals and malt. Biochemical Importance In sucrase deficiency, malabsorption leads to diarrhea and flatulence.

Lactose

In lactase deficiency, malabsorption leads to diarrhea and flatulence.

Maltose

Trehalose.

Fungi and yeasts. Pentoses their physiologic The & major sugar of insect hemolymph.

importance

Carbohydrate : Other Disaccharides

Disaccharide Kojibiose Unit 1 Glucose Unit 2 Glucose Bond (12)

Nigerose
Isomaltose ,-Trehalose ,-Trehalose Sophorose Laminaribiose Gentiobiose Turanose Maltulose

Glucose
Glucose Glucose Glucose Glucose Glucose Glucose Glucose Glucose

Glucose
Glucose Glucose Glucose Glucose Glucose Glucose Fructose Fructose

(13)
(16) (11) (11) (12) (13) (16) (13) (14)

Palatinose
Gentiobiulose Melibiose

Glucose
Glucose Galactose

Fructose
Fructose Glucose

(16)
(16) (16)

Less common disaccharide

Carbohydrate : Oligosaccharides
Saccharide polymer containing a small (typically 2 to 10) of monosaccharides.
Sugar Fructo-oligosaccharide (FOS) Source Artichoke, burdock, chicory, leeks, onions, & asparagus. (Mainly vegetables) Biochemical Importance 1. Can be only partially digested by humans. 2. The undigested portion serves as food for the intestinal microflora. 3. Increase the number of friendly bacteria in the colon while simultaneously reducing the population of harmful bacteria. 4. Used in nutritional supplements.

number

Galacto-oligosaccharide (GOS)

Soybeans. Can be synthesized from lactose

Same as above

Mannan oligoyeast cell walls saccharide (MOS) (Saccharomyces cerevisiae.)

Used in animal feed to improve gastrointestinal health

Carbohydrate : Glycoprotein
Glycoproteins : proteins that contain oligosaccharide chains (glycans) covalently attached to polypeptide side-chains. Occur in many different situations in fluids and tissues, including the cell membranes. Glycosylation : enzymatic process that attaches oligosaccharides to proteins, lipids, or other organic molecules
N-glycosylation : addition of sugar chains at amide nitrogen of protein / lipid. O-glycosylation : addition of sugar chains at the hydroxyl oxygen of protein / lipid.

Carbohydrate : Glycoprotein

Carbohydrate : Glycoprotein
Function
Structural molecule Lubricant and protective agent Immunologic molecule Hormone Transport molecule Cell attachment recognition site

Examples
Collagens Mucins (Mucus) Immunoglobins, histocompatibility antigens, ABO groups Human chorionic gonadotropin (HCG), thyroidstimulating hormone (TSH) Transferrin, ceruloplasmin Various proteins involved in cellcell (e.g., sperm oocyte), viruscell, bacteriumcell

Antifreeze protein Receptor

Hemostasis & thrombosis

Certain plasma proteins of coldwater fish Various proteins involved in hormone and drug action
Specific glycoproteins on the surface membranes of platelets

Carbohydrate : Polysaccharides
Long carbohydrate molecules / polymer of monosaccharide units joined together by glycosidic bonds. Homopolysaccharide : all the monosaccharides in a polysaccharide are the same type.
Example : starch, glycogen, cellulose, chitin

Heteropolysaccharide : more monosaccharide is present

than

one

type

of

Example : inulin, glycosaminoglycans (mucopolysaccharides)

Storage polysaccharides : starch, glycogen, inulin Structural polysaccharides : cellulose & chitin

Polysaccharides : Starch
Starch : Most abundant dietary carbohydrate in cereals, potatoes, legumes, and other vegetables. Most common carbohydrate in the human diet & is contained in many staple foods. 2 main constituents: 1) Amylose (1520%) : non-branching helical structure, united by (1 4)-glucosidic linkage

Polysaccharides : Starch
2) Amylopectin (8085%) : consists of branched chains composed of 2430 glucose residues united by (14) glucosidic linkages in the chains & by (16) linkages at the branch points.

(16)

(14)

Polysaccharides : Glycogen
Storage polysaccharide in animals. > highly branched structure than amylopectin : chains of 1214 glucose residues in (14)-glucosidic linkage), with branching by means of (16).

(16)

(14)

Polysaccharides : Inulin
Used by some plants to store energy and is typically found in roots or rhizomes. Most plants that synthesize & store inulin do not store other forms of carbohydrate such as starch. Polymer composed of fructose units a terminal glucose. Fructose units joined by a (21) glycosidic bond. Completely filtered at the glomerulus of nephron but neither secreted nor reabsorbed by the tubules.
Allows the clearance of inulin to be used clinically as a highly accurate measure of glomerular filtration rate (GFR) : rate of plasma from the afferent arteriole that is filtered into Bowman's capsule measured in mL/min.

Polysaccharides : Inulin

Polysaccharides : Cellulose
Polysaccharide consisting of a linear chain of thousand (14) linked D-glucose units to form long, straight chains strengthened by cross-linked hydrogen bonds. Important structural component of the primary cell wall of green plants & algae. Most abundant Polysaccharides & organic polymer on Earth. Cannot be digested by mammals because of the absence of an enzyme that hydrolyzes the linkage. Microorganisms in the gut of ruminants and other herbivores can hydrolyze the linkage & ferment the products to short-chain fatty acids as a major energy source.

Polysaccharides : Cellulose
Limited bacterial metabolism of cellulose in the human colon mainly act as bulking agent for feces (dietary fiber) promote bowel movements & alleviate constipation

Hydrogen bond (14)

Polysaccharides : Chitin
Structural polysaccharide in the exoskeleton of crustaceans, insects & cell wall of mushrooms. Consists of N-acetyl-D-glucosamine units joined by (14)-glycosidic linkages.

Polysaccharides : Glycosaminoglycans
Glycosaminoglycans (mucopolysaccharides) : complex carbohydrates heteropolysaccharides consist of amino sugars and uronic acids. Proteoglycans : Glycosaminoglycans chain that attached to protein molecules. Provide the ground or packing substance of connective tissues. Can hold large quantities of water and occupying space cushioning or lubricating other structures. Examples : hyaluronic acid, chondroitin sulfate & heparin.

Polysaccharides : Glycosaminoglycans
GlycosStructure aminoglycans
Heparin

Function

2-O-sulfated iduronic acid and 6-O- 1. Stored within the sulfated, N-sulfated glucosamine. secretory granules of mast cells & released at sites of tissue injury for defense against invading bacteria & foreign materials. 2. medicine for anticoagulation

Polysaccharides : Glycosaminoglycans
GlycosStructure aminoglycans Chondroitin sulfate Function Sulfated glycosaminoglycan 1. important structural composed of a chain of alternating component of cartilage sugars (N-acetylgalactosamine and & provides resistance glucuronic acid). to compression. 2. Along with glucosamine, chondroitin sulfate become dietary supplement for treatment of osteoarthritis.

Polysaccharides : Glycosaminoglycans
GlycosStructure aminoglycans
Hyaluronic acid

Function

D-glucuronic acid and D-N- 1. Major component of acetylglucosamine, linked via the synovial fluid, alternating -1,4 and -1,3 glycosidic increase the viscosity bonds of the fluid. 2. Important component of articular cartilage, responsible for the resilience of cartilage.

Diseases associated with carbohydrates

1) Starvation : state in which the body is responding to prolonged periods of low energy intake levels.
Glucose as primary fuel. Glycogen is broken down to produce glucose for the body. Glycogen stores are used up & the body breaks down fatty acids. Ketone bodies are produced to help feed the brain. After prolonged periods of starvation the body has depleted its body fat and begins to burn lean tissue and muscle as a fuel source.

Diseases associated with carbohydrates

2) Diabetes mellitus : metabolic diseases in which a person has high blood sugar, either because the pancreas does not produce enough insulin, or because cells do not respond to the insulin that is produced. 3) Galactosemia : rare genetic metabolic disorder of galactose metabolism. individuals with galactosemia lack the enzymes needed for further galactose metabolism, leading to toxic levels of galactose 1phosphate in various tissues.

Diseases associated with carbohydrates

4) Glycogen storage disease (GSD / glycogenosis / dextrinosis) : genetic defects in the processing of glycogen synthesis or breakdown within muscles, liver, and other cell types. 5) Lactose intolerance lactase deficiency. Lactose, in the absence of lactase, passes into the colon metabolized by bacteria fermentation causes the various abdominal symptoms such as cramping, flatulence & diarrhea