Lipids and Proteins are Associated in Biological Membranes

8.1 The definition of a Lipid

are important components in plant, animal and microbial membranes

are marginally soluble in water but readily soluble in organic solvents (chloroform,
acetone)
fats and oils = typical lipids (in terms of solubility)
are a mixed bag of compounds mainly non polar groups
classified into 2 main groups
a. open-chain compounds with polar heads and long non polar tails
- fatty acids
- triacylglycerols
- sphingolipids
- phosphoacylglycerols
- glycolipids
b. fused ring compounds STEROIDS
- cholesterol

8.2 The Chemical Natures of the Lipid Types

A.

What are fatty acids?

carboxyl group at polar end and a Hydrocarbon chain at nonpolar end
amphipathic (Carboxyl = HydroPHILIC; HC tail = HydroPHOBIC)
carboxyl group can ionize under proper conditions
in living systems F.A. occur in Even # Carbon
HC chain is Unbranched
Double Bonds = unsaturated (more of cis)
Single Bonds = Saturated (more of trans)
Cis groups place a kink in the long-chain of HC tails
Double bonds isolated from one another by singly bonded carbons
F.A. do not have conjugated Double-Bond systems
Notation sample 18:0 18 Carbon saturated F.A. with no double bonds
18:1 18 Carbon Fatty acid with 1 double bond
usually the double bond is at the 9th carbon from the Carboxyl end
Unsaturated LOWER melting points than saturated
Hydrogenation process of adding H across double bond of unsaturated fatty acids to
produce saturated counterpart
Fatty acids rarely in nature

B. What are Triacylglycerols?

Glycerol
3 Carbon Compound
Contains 3 hydroxyl groups
Triacylglycerol
Lipid formed by esterification of 3 fatty acids to glycerol
Aka triglyceride
3 ester groups are polar

Tails of fatty acids are nonpolar

3 diff. fatty acids usual to be esterified to alcohol groups of same glycerol
Do not occur as components of membranes
Accumulate in adipose tissue (primarily fat cells)
Means of storing fatty acids (in animals)
o Serve as concentrated store of metabolic energy
o Complete oxidation of fats yield 9kcal g-1
o Oxidation of carbs and proteins yield 4 kcal g-1
Lipases enzymes that hydrolyze ester linkages of triacylglycerol
o Hydrolysis happens during usage of fatty acids
o Hydrolysis can take place outside organism (acids and base = catalyst)
Saponification rxn when a base is used
o Glycerol and Sodium or Potassium salts of Fatty Acids product of
saponification
o Salts are soaps
o Soaps used with hard water Ca and Mg ions in waterreact with fatty acids
to form precipitate
o Glycerol from saponification is used in creams and lotions also in
manufacturing nitroglycerin

C. What are phosphoacylglycerols?

One alcohol group of glycerol esterified by a phosphoric acid and not a carboxylic
acid
2 fatty acids esterified to glycerol molecule PHOSPHATIDIC ACID
Fatty acids monoprotic acids (1 carboxyl group to form an ester bond)
Phosphoric acid triprotic (can form one than 1 ester linkage)
1 mol. Of phosphoric acid form ester bonds both to glycerol and to other alcohol
creating PHOSPHATIDYL ESTER
Phosphatidyl ester classified as phosphoacylglycerol
Classification of phosphatidyl ester depends on NATURE of 2ND ALCOHOL ESTERIFIED
to the phosphoric acid
Important lipids in this class:
Phosphatidyl ethanolamine (cephalin)
Phosphatidyl serine
Phosphatidyl choline (lecithin)
Phosphatidyl inositol
Phosphatidyl glycerol
Diphosphatidyl glycerol (cardiolipin)
All of compounds above have
long, nonpolar hydrophobic tails
polar highly hydrophilic head groups **AMPHIPATHIC
In Phosphoacylglycerol:
Polar head is charged
o Phosphate group is ionized at neutral pH
o Positively charged amino group contributed by amino alcohol
esterified to phosphoric acid
Important components of biological membranes
Phosphatidic acid with another alcohol esterified to the phosphoric acid moiety

D. What are waxes and Sphingolipids?

Waxes
a. complex mixture of ester of long-chain carboxylic acids and long-chain alcohols
b. protective coatings for plants and animals
Spingolipids
a. Do not contain glycerol
b. Contain long-chain amino alcohol sphingosine
c. Found in both plants and animals
d. Abundant in nervous system
e. Simplest class ceramides
Consist of 1 fatty acid linked to amino agroup of sphingosine by an amide
bond
f. Spingomyelins
Primary alcohol group of sphingosin is esterified to phosphoric acid
esterified to another amino alcohol (choline)
Amphipathic
Occur in cell membranes in nervous system
E. What are glycolipids?
Glycolipid
o Lipid to which a sugar moiety is bonded
o Gangliosides
with a complex carbohydrate moiety that contains more than 3 sugars
one of them is a sialic acid
referred to as acidic glycospingolipids (because of net negative charge at
neutral pH)
in nerve tissue
o found as markers on cell membranes
o play role in tissue and organ specificity
Ceramides
o Lipids that contain one fatty acid linked to sphingosine by an amide bond
Cerebroside

o
o
o

A glycolipid that contains sphingosine and a fatty acid in addition to the sugar
moiety
Sugar is usually glucose or galactose
Found in nerves or brain cells (in cell membranes)

F. What are steroids?

Fused-ring system consisting of 3 six-membered rings (A,B,C rings) + 1 five-membered
ring (D ring)
Sex hormones eg of steroids
Cholesterol steroid
o Only hydrophilic group in cholesterol single hydroxyl group
o Molecule is highly hydrophobic
o Present in biological membranes
o Does not occur in prokaryotic cell membranes
o Precursor of other steroids and Vitamin D3
o Harmful to help when excess in blod
o Plays a role in devt of atherosclerosis (condition in which lipid deposits block
blood vessels and lead to heart disease)
8.3 Biological Membranes

every cell has a cell membrane

Molecular basis of membranes structure lines in its lipid and proteins
Phosphoglycerides
o Amphipathic molecules
o Principal lipid components in membranes
Lipid bilayers depend on hydrophobic interactions
Cell membranes contain proteins and lipids
o Protein component make up 20%- 80% of total weight

A. What is the structure of lipid bilayers?

Membranes contain:
a. Phosphoglycerides
b. Glycolipids
Steroids present in eukaryotes
o Cholesterol in animal membranes
o Phytosterols in plants
Lipid Bilayer
o Polar head groups in contact with water
o Non polar tails interior
o Whole bilayer arrangements is held together by:
Noncovalent interactions
Van Der Waals
Hydrophobic interactions
o Surface of the bilayer is polar and contains charged groups
o Nonpolar hydrocarbon interior consists of:
Saturated and unsaturated chains of fatty acids
Fused-ring system of cholesterol

o
o

Bulkier molecules occur in the outer layer

Smaller molecules in the inner layer

How does the composition of the bilayer affect its properties?

-

Bilayers fluidity depends on its composition

Saturated Fatty Acids
o Linear arrangement of HC chains
o Close packing; RIGID
Unsaturated Fatty acids
o Have a kink in the HC chain
Kinks cause disorder in the packing of the chains
Kinks allow a more open structure
o Disordered structure caused by the presence of cis bonds
This causes greater fluidity in the bilayer
Presence of cholesterol enhances order and rigidity
Fused-ring structure of cholesterol
o Rigid in itself
o Cholesterol stabilizes straight-chain arrangement of saturated fatty acids
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