Lecture 5: Lipids and Carbohydrates

Craig Kasper Aquaculture FAS 1012

Part 1: Lipid Characteristics

Lipid = a compound that is insoluble in water, but soluble in an organic solvent (e.g., ether, benzene, acetone, chloroform) lipid is synonymous with fat, but also includes phospholipids, sterols, etc. chemical structure: glycerol + fatty acids

Lipid Molecule

Nutritional Uses of Lipids

We already know that lipids are concentrated sources of energy (9.45 kcal/g) other functions include: 1) provide means whereby fat-soluble nutrients (e.g., sterols, vitamins) can be absorbed by the body 2) structural element of cell, subcellular components 3) components of hormones and precursors for prostaglandin synthesis

Lipid Classes
simple: FAs esterified with glycerol compound: same as simple, but with other compounds also attached phospholipids: fats containing phosphoric acid and nitrogen (lecithin) glycolipids: FAs compounded with CHO, but no N derived lipids: substances from the above derived by hydrolysis sterols: large molecular wt. alcohols found in nature and combined w/FAs (e.g., cholesterol)

Saturated vs. Unsaturated Fatty Acids

saturated: the SFAs of a lipid have no double bonds between carbons in chain polyunsaturated: more than one double bond in the chain most common polyunsaturated fats contain the polyunsaturated fatty acids (PUFAs) oleic, linoleic and linolenic acid unsaturated fats have lower melting points stearic (SFA) melts at 70oC, oleic (PUFA) at 26oC

Fatty Acids Commonly Found in Lipids

Sat. Fatty Acids Butyric Palmitic Stearic Unsat. Fatty Acids Oleic Linoleic Linolenic Formula C4H8O2 C16H22O2 C18H36O2 Formula C18H34O2 C18H32O2 C18H30O2 Melting Point (oC) Liquid 63 70 Melting Point (oC) Liquid Liquid Liquid

Saturated vs. Unsaturated Fats

saturated fats tightly packed, clog arteries as atherosclerosis because of double bonds, polyunsaturated fats do not pack well -- like building a wall with bricks vs. irregular-shaped objects plant fats are much higher in PUFAs than animal fats

Saturated vs. Unsaturated FAs Plant vs. Animal Fat

corn Sat. FAs Myristic Palmitic Stearic Unsat. FAs Oleic Linoleic Linolenic Arachid. soy tallow 3 27 21 40 2 0.5 lard

7.0 2.4 45.6 45.0

8.5 3.5 17 54.4 7.1

32.2 7.8 48 11 0.6

Lipid Digestion/Absorption
Fats serve a structural function in cells, as sources of energy, and insulation the poor water solubility of lipids presents a problem for digestion: substrates are not easily accessible to digestive enzymes even if hydrolyzed, the products tend to aggregate to larger complexes that make poor contact with the cell surface and arent easily absorbed to overcome these problems, changes in the physical state of lipids are connected to chemical changes during digestion and absorption

Lipid Digestion/Absorption
Five different phases:
hydrolysis of triglycerides (TG) to free fatty acids (FFA) and monoacylglycerols solubilization of FFA and monoacylglycerols by detergents (bile acids) and transportation from the intestinal lumen toward the cell surface uptake of FFA and monoacylglycerols into the cell and resynthesis to triglyceride packaging of TGs into chylomicrons exocytosis of chylomicrons into lymph

Enzymes Involved in Digestion of Lipids

lingual lipase: provides a stable interface with aqueous environment of stomach pancreatic lipase: major enzyme affecting triglyceride hydrolysis colipase: protein anchoring lipase to the lipid lipid esterase: secreted by pancreas, acts on cholestrol esters, activated by bile phospholipases: cleave phospholipids, activated by trypsin

What about Bile???

These are biological detergents synthesized by the liver and secreted into the intestine they form the spherical structures (micelles) assisting in absorption hydrophobic portion (tails of FA) are located to the inside of the micelle, with heads (hydrophillic portion) to the outside they move lipids from the intestinal lumen to the cell surface absorption is by diffusion (complete for FA and monoglycerides, less for others)

Factors Affecting Absorption of Lipids

amount of fat consumed ( fat = digestion = absorption) age of subject ( age = digestion) emulsifying agents chain length of FAs (> 18C = digestibility) degree of saturation of FA ( sat = digestibility) overheating and autooxidation (rancidification at double bond) optimal dietary calcium = optimal FA absorption (high Ca = absorption)

Lipid Metabolism/Absorption
short chain FAs are absorbed and enter the portal vein to the liver those FAs with more than 10 carbons are resynthesized by the liver to triglycerides they are then converted into chylomicrons and pass to the lymphatic system some FAs entering the liver are oxidized for energy, others stored blood lipids: 45% P-lipids, 35% triglycerides, 15% cholestrol esters, 5% free FAs

Lipid Digestion/Abs orption

Lipid Digestion/Abs orption

Characteristics of Fat Storage

Most of the bodys energy stores are triglycerides storage is in adipose, source is dietary or anabolism (synthesis) from COH or AA carbon skeletons remember obesity? adipose can remove FAs from the blood and enzymes can put them back

Fatty Acid Nomenclature

Nomenclature reflects location of double bonds also used are common names (e.g., oleic, stearic, palmitic) linoleic is also known as 18:2 n-6 this means the FA is 18 carbons in length, has 2 double bonds, the first of which is on the 6th carbon arachidonic = 20:4 n-6

Essential Fatty Acids

Only recently determined as essential (1930) body can synthesize cholesterol, phospholipids research: same as AAs but via addition (EFAs added improved growth, NEFAs didnt) requirement determined by depleting fat reserves of subject animal: difficult

Essential Fatty Acids (fish)

Most NEAA found in marine food webs Essential fatty acids (to date):
linoleic (18:2 n-6; terrestrials; fish - not really) linolenic (18:3 n-3; terrestrials; fish) arachidonic (20:4 n-6; marine maybe) eicosopentaenoic acid (20:5 n-3, marine) docosohexaenoic (22:6 n-3, marine) Why? Because elongation beyond 18 carbons is very difficult in marine fish (lack pathways) actual EFA requirement is a matter of whether the fish is FW/SW or WW/CW

Essential Fatty Acids (most animals)

salmonids need n-3 FAs for membrane flexibility in cold water trout can elongate and desaturate n-3 FAs Linoleic acid (18:2 n-6) is the most essential addition of arachidonic is also helpful in deficient diets, but can be synthesized from linoleic (maybe sparing effect) EFAs, like EAAs, must be dietary

Essential Fatty Acids

LINOLEIC CH3(CH2)4CH=CHCH2CH=CH(CH2)7COOH
18:2 n-6 LINOLENIC CH3CH2CH=CHCH2CH=CHCH2CH=CH(CH2)7COOH 18:3 n-3 EICOSOPENTAENOIC ACID CH3CH2CH=CHCH2CH=CHCH2CH=CHCH2CH=CHCH2CH=CH(CH2)3COOH 20:5 n-3 DOCOSOHEXAENOIC ACID - YOU CAN DO THIS ONE!

Lipids as Crustacean Energy Sources

Largely, n-6 FAs (linoleic) used for energy as temperature drops, requirement for monounsaturated and PUFAs increases change in temperature = change in diet cold water species = increased dietary HUFAs maturation animals: increased requirement for 20:4 n-6, 20:5 n-3 and 22:6 n-3 for proper spawning

Part 2: Carbohydrate Characteristics

From: Lovell; DAbramo et al.

General Comments
Carbohydrates often written as COH much of what we need to know about them, besides their structure, was covered in Bioenergetics, Parts 1&2 here, we cover structure

Carbohydrate Structure
Basic chemical structure consists of sugar units found as aldehydes or ketones derived from polyhydric alcohols contain: C, H, O often shown as aliphatic or linear structures, but exist in nature as ringed structures

Glucose Structure
O
CH2OH

C-H H- C-OH HO-C-H

HO H OH O H

H OH

H-C-OH
H OH

H-C-OH
Haworth perspective

CH2OH

Carbohydrate Classification
Usually by the number of sugar units in the molecule: monosaccharides (glucose) disaccharides (2 units) maltose (2 glucose units) sucrose (glucose + fructose) polysaccharides (long chain polymers of monosaccharides most important polysaccharides to animals are starch and cellulose

Starch and Cellulose

CH2OH H O O H H CH2OH O H O starch

OH

OH

OH
CH2OH H O OH

OH
CH2OH

O O H H

O O H

OH

OH

OH

cellulose

Starch and Cellulose

Starch contains -D-glucose linkage Cellulose has a -D-glucose linkage we store starch in muscle tissues as glycogen, peeled off by enzymes when needed cellulose is primary component of plant tissue, largely indigestible to monogastrics must have enzyme, cellulase