Lipids CH339K

What are lipids? Grab bag of molecular types Common link is their hydrophobicity –Fats –Glycerophospholipids –Sphingolipids –Waxes –Eicosanods –Steroids –And other stuff

FATTYACIDSFATTYACIDS

You can’t make fatty acids where the double bond is 6 carbons or closer to the end of the molecule

In living systems, the double bonds of unsaturated fatty acids are usually cis-.

Melting Temps of Fatty Acids

(Glycerol tripalmitate)

Grandma’s Lye Soap (Saponification)

Fatty Acid Salts are Amphipathic

Waxes Very often – fatty acid + long-chain alcohol.

Plant leaf cuticle

Insect epicuticle

Beeswax components

Spermaceti Largely cetyl palmitate Large whale may have 3 tons May function as lens in echolocation May function as shock absorber in combat Sank the whale ship Essex in 1820

What happens if I substitute something else for a fatty acid in a fat? Like a Phosphate?

This also is Amphipathic

Phospholipids in H 2 O

Cardiolipin(s) Major component of inner mitochondrial membrane (up to 20%) R groups usually c18:2 Glycerol

Major component in heart muscle membranes

Causes platelet aggregation and vasodilation (inflammatory mediator). Important to the process of hemostasis. Important in implantation. Concentration of M causes life threatening inflammation of the airways (asthma-like symptoms). Toxins such as fragments of destroyed bacteria induce synthesis of PAF causes drop in blood pressure reduced volume of blood pumped by the heart shock and possible death.

Glycolipids

Archaea have weird membrane lipids

Archaean membrane lipids Polymers of isoprene Sulfolobus solfataricus

Sphingolipids Sphingosine by itself

Defective ganglioside digestive enzymes cause disease

Tay-Sachs – a Defect inSphingolipid Metabolism As a child with Tay-Sachs grows older, he or she may become blind, mentally retarded, paralyzed, and unresponsive to the environment. The child also may have seizures, difficulty swallowing, and difficulty breathing. Children with Tay-Sachs disease rarely live beyond 4 or 5 years of age.

Tay-Sachs – a Defect inSphingolipid Metabolism Mutation in lysosomal enzyme Hexosaminidase A

Cholesterol

Steroid Hormones

SteroidFunctionSource TestosteroneBoysTestis (ovary) EstradiolGirlsOvary (testis) Cortisol Turns on gluconeogenesis Inhibits immune response Turns on MetabolismAdrenal Cortex Aldosterone Increases sodium retention Increases potassium secretion Increased blood pressureAdrenal Cortex Prednisolone Inflammatory and autoimmune diseasesDrug PrednisoneImmunosuppressantDrug

Bile Salts Bile salts are steroid acids

Bile Salts solubilize fats in the digestive tract

Prostacyclin Derivatives of Arachidonic Acid Leukotrienes – conjugated double bonds vasoconstrictors Thromboxanes – 6-membered ring Clot formation Prostaglandins – 5-membered ring Many functions Inflammatory response Vasodilators Pyogenic

Eicosanoid functions Prostaglandins have 5- or 6-membered ring –Short-range hormones mediating (among other things) pain and inflammation, uterine contraction Prostacyclins have a double ring structure –Inhibit clotting, vasodilators Thromboxanes are made in platelets, contain oxygen in the ring –Vasoconstrictors, hypertensives, aggregate platelets Leukotrienes have 3 conjugated double bonds –Asthmatic, allergic, and inflammatory responses

NSAIDs like aspirin, ibuprofen, and naproxen inhibit eicosanoid formation

Phospholipids in H 2 O

Lipid Bilayer

Cell Membrane

Integral and Peripheral Proteins

Membrane Functions

Membrane Composition

Erythrocyte Membrane – differences between inner and outer layers

2-Dimensional Fluids

Membranes exist in 2 states

Phase transition

Factors Impacting Tm Chain length –Longer chains  more vdW contacts (higher Tm) Unsaturation –Unsaturated FAs  fewer vdW contacts (lower Tm) Size / Charge of head groups –Big head groups  steric interference lower Tm) –Charged head groups  electrostatic repulsion lower Tm) Cholesterol –Interferes with packing at low temps –Stiffens membrane at high temps –Broadens melting curve

Some organisms change their membrane composition seasonally in order to maintain constant fluidity Egregia menziesii WinterSpringSummerFall SFA MUFA PUFA