Biomolecules · Section 95 of 116

Lipids

Practice this — interactive lesson

Lipids are the one biomolecule class defined by a physical property rather than a functional group: they are the biological molecules that dissolve in nonpolar solvents and not in water. That makes the category structurally mixed, and it means the useful question about a lipid is usually what its shape does rather than what its functional group does.

Fatty acids, and the kink that changes everything

A fatty acid is a long unbranched carboxylic acid, typically 12–20 carbons. It is saturated if it has no C=C and unsaturated if it has one or more.

Naturally occurring unsaturated fatty acids have their double bonds in the cis configuration, and that single fact explains the physical behavior of every fat:

Trans fats are the same molecules with the double bond in the other geometry, and a trans double bond does not kink the chain appreciably — so a trans unsaturated fat packs and melts much like a saturated one. They arise from partial catalytic hydrogenation of vegetable oils, where the conditions isomerize some double bonds as well as reducing others. This is the hydrogenation from the Oxidation & Reduction chapter, with a side effect that turned out to matter.

Triglycerides are triesters

saturatedchains lie flat against each otherfalseone cis double bondthe kink breaks the contacttrueone trans double bondstill essentially straightfalseAll three are C18. Only the shape differs — and the shape is what the melting point reads.
Three eighteen-carbon fatty acids, drawn as they pack. Chain length is held constant, so the fifty-six degrees between stearic and oleic acid is entirely the bend that one cis double bond puts in the middle of the chain.The trans column is what makes the rule precise. Elaidic acid is exactly as unsaturated as oleic acid and melts thirty degrees higher, because a trans double bond leaves the chain straight. “Unsaturated means low melting” is a shortcut that stops working the moment partial hydrogenation is in the room.

The storage form of fat is a triglyceride: glycerol, a three-carbon triol, esterified with three fatty acids. Nothing about it is a new reaction — it is three Fischer esterifications, and everything an ester does, a triglyceride does.

In particular, saponification is simply base hydrolysis of those esters. Heating a triglyceride with NaOH gives glycerol and three carboxylate salts, which are soap.

Soap cleans because a carboxylate salt has both halves at once: a long nonpolar tail that dissolves in grease and an ionic head that dissolves in water. Many of them assemble into a micelle — tails inward around a droplet of oil, heads outward facing the water — and the grease leaves with the rinse.

Phospholipids and the bilayer

Replace one of a triglyceride's three fatty acids with a phosphate-containing group and you have a phospholipid: two nonpolar tails and one charged head. That is the same amphipathic arrangement as soap, with two tails instead of one, and the geometry drives it to a different structure.

A single-tailed soap forms a spherical micelle; a double-tailed phospholipid forms a bilayer — two sheets of molecules tail-to-tail, heads facing the water on both sides. That bilayer is the cell membrane, and its existence is a direct consequence of one molecule having a polar end and a nonpolar end.

Membrane fluidity tracks the same packing argument as melting point. More cis unsaturation in the tails means worse packing and a more fluid membrane, which is how organisms adjust to cold — they increase the unsaturated fraction so the membrane does not solidify.

Steroids: the other kind of lipid

Steroids are lipids by solubility and have nothing structurally in common with the fatty acids above. They share a fused four-ring skeleton: three six-membered rings and one five-membered ring.

Cholesterol is the parent of the class in animals, sits within membranes moderating their fluidity, and is the biosynthetic precursor of the steroid hormones. That a rigid fused-ring system and a floppy fatty acid chain end up in the same category is the clearest sign that "lipid" is a solubility class rather than a structural one.

Worked example — ranking three fats by melting point

Stearic acid (C18, no double bonds), oleic acid (C18, one cis double bond) and linoleic acid (C18, two cis double bonds).

Same length, so chain length cannot be the variable. The only difference is the number of kinks.

Stearic is straight, packs best, melts highest. Oleic has one kink and melts lower. Linoleic has two and melts lower still — it is a liquid well below room temperature.

The reasoning is entirely about packing and intermolecular contact, which is the same argument used for boiling points back in Foundations. Biology did not introduce a new principle here; it supplied a case where the principle has consequences you can taste.

What carries forward

Two threads run through this section and neither is new. Ester chemistry — formation, hydrolysis, saponification — is Module 13 applied to a big molecule. And the shape argument, that cis alkenes cannot pack, is the intermolecular-forces reasoning from the very first chapter, arriving at a conclusion about whether something is butter or oil.