10/30/06
From Biolk483
Contents |
Phospholipids
- These are the major components of membranes.
- They are built out of glycerol, phosphate, 2 fatty acids and one alcohol.
- Six different alcohols can be attached to one end of the glycerol, plus one diglyceride makes seven major phospholipids
- Some have specific functions
Phosphatidic acid (PA)
- All seven phospholipids can fit in membrane
- If we make pH 7.2, charge would be -1.5
- So we would have large negative charge density
- This is important because many proteins need negative environment to work.
- This is an example of a specific function of a phospholipid.
- A typical membrane has 1500 different lipids.
- Specific functions of phosphatidic acid
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Phophatidyl Ethanolamine (PE)
- When in pH 7, we have slight negative charge because the amine will be almost a full positive charge while the OH group on the phosphate group will have a full -1 charge.
- Egg yolk has lots of phophatidyl choline and cholesterol
- Phophatidyl ethanolamine has a small head area, so when lots of it is side by side it forms a curve.
- This is called nom lameller phase.
- This phase makes hydration hard (the water molecules have a hard time lining up to the surface) so there is a little dry spot on the surface of the membrane where there is much phosphatidyl ethanolamine: a place of weakness.
Phosphatidyl choline (PC)
- This molecule is just like PE only methylated 3 times via s-adenosyl methionine.
- We have more PC than any other phospholipid
- PC has a big head, is easily hydrated, and is can-shaped.
- Because of these features this phospholipid forms membranes perfectly.
- The old name of PC is lesophin.
- At biological pH (7.0), the OH group on the phosphate has a formal -1 charge and the amine group has a formal +1 charge, so there is a formal charge distribution over the head of the phospholipid.
Phosphotidyl Serine (PS)
- This phospholipid has the amino acid serine on it.
- At biological pH, the OH group on the phosphate group has a -1 charge (pKa 2.1), the NH3 group has a +1 charge (pKa 9.1) and the carboxyl group will have a -1 charge (pKa 2.1) thus having a net -1 charge.
- This phospholipid provides a negative density at biological pH.
- At pH 2.1: -0.5, -0.5, +1 = 0. When acitic, these have not charge, think of stomach lining: cells on wall of the stomach will have phospholipids with differing properties on the exterior layer of the bilipid layer verses those of the inner layer.
- Many proteins require phosphotidyl Serine.
- Less than 10% of our phospholipid material is phosphotidyl serine.
- All of our PS is on the interior layer of the bilipid layer. We have flipases to put them on inside whenever they happen to get to the outside layer.
- PS on the outside can trigger apoptosis
- PS on the outside is seen in aging and disease states.
Phosphatidyl Inositol (PI)
- Inositol is a sugar we aren't good at digesting, so it is often put in sugar-free candy because we don't digest it.
- It is not a complete sugar.
- None of the OH on this ring are dissociable at reasonable pH levels.
- Net charge is -1 at 7.2pH because of the OH group on the phosphate group (with pKa 2.1)
- This is the best example of phospholipids responsible for lipid diversity.
- There are unique functions for phophatidyl Inositol
- Can be an anchor in membrane for classes of proteins
- A lipid anchor in the membrane.
- Example: alcoline phophatase -> a protein that anchors on GPI
- So these kinds of proteins are called GPI anchored proteins.
- GPI = Glycosil phosphatidyl inositol
- Hormonal Role
- PI + Phospholipase-c -> diacylglicerol (amphipathic and membrane bound) and the phosphate connected to the inositol (very water soluble, binds with signal proteins).
- Both these products are activators to mechanisms.
- Can be an anchor in membrane for classes of proteins
Phosphatidyl glycerol (PG)
- At pH 7 there is a -1 net charge because of the OH group with pKa 2.1 on the phosphate group.
- These are found in plants and prokaryotes.
- There are two optically active carbons on this phospholipid.
Cardiolipid (CA)
- The old name for this phospholipid is diphosphatidyl glycerol
- At pH 7, there is a net -2 charge from the OH on each of the two phosphate groups (pKa 2.1); each has a -1 charge.
- This phospholipid has 4 acyl chains and two formal charges, therefore it pretty much looks like two phospholipids stuck together.
- This phospholipid is found in the mitochondrial inner membrane, therefore it probably has something to do with the electron transport chain and oxidative phosphorylation (the ability to make ATP).
Phospholipids: Prokaryotes vs. Eukaryotes
- Eukaryotes have Sphingo myelin, Phosphatidyl choline, and Phophatidyl Ethanolamine.
- Prokaryotes have Phophatidyl Ethanolamine and Phosphatidyl glycerol.
Thylocoid Phospholipids
- These are phospholipids found in the thylecoid of plants.
- They are used for photosynthesis:
- CDG = monogalactacyl diacylglycerol: the major photosynthesis phospholipid.
- CDCG = digalactacyl diacylglycerol
- Sophogweno-vacyl (sp?)
- Phosphatidyl glycerol
- We drew the structure of PG, a monogalactycil diacylglycerol, to show each component.
- We also noted that it is the most common monogalactacyl diacylglycerol on the planet.
Phospholipid misc
- A note on ether bonds in phospholipids
- There are two types alkyl and alkenyl
- Ether links cannot be undone by hydrolysis
- Ether linkage found at SN-1
- Ester linkage found at SN-2.
- Examples: ethylolamine or choline.