Learning Outcomes
• Course Learning Outcomes:
• 1) Discuss how chemical, physical, and thermodynamic rules govern the structure,
organization, and function of biological molecules and biochemical reactions essential for
life.
• 2) Compare the biochemical and functional differences between the fundamental
molecules of life: proteins, nucleic acids, lipids, and carbohydrates.
• 5) Understand how the structure, composition and dynamics of biological membranes
adapt to the needs of the cell and discuss the diverse transport mechanisms of
molecules across these membranes.
• 9) Apply reading comprehension, critical thinking, writing, data interpretation, graphical
and numerical analysis skills to answer biochemical questions.
Key Concepts
• Key Concepts:
• Define lipids and understand their nomenclature, including unsaturated vs. saturated
lipids, and nomenclature based on the number of carbon atoms and double bonds
present.
• Understand the biological functions of lipids (structure, energy storage, signaling,
cofactors/vitamins, etc.).
• Describe the structure and physical properties of lipids (solubility, melting point, fluidity).
• Identify and describe different types of lipids, including triacylglycerols, phospholipids,
sphingolipids, glycolipids and sterols.
• Identify biologically active lipids and describe their roles in signaling and metabolism.
Lipids
Lipids
• Biological compounds that are insoluble in water
(hydrophobic).
• They are soluble in organic solvents such as chloroform
and methanol (and can be easily separated from other
biological materials!).
[Link]
Equivalent to Protein Data Bank (PDB)
Examples of Lipid Functions
• Storage of energy
• reduced compounds: lots of available energy
• hydrophobic nature: good packing
• Membrane structure
• main building block of cell membranes
• Cofactors for enzymes
• Signaling molecules
• paracrine hormones (act locally)
• steroid hormones (act body-wide)
• Pigments
• color of tomatoes, carrots, pumpkins, some birds
Examples of Lipid Functions
• Antioxidants
• vitamin E
• Insulation from environment
• low thermal conductivity
• high heat capacity (can “absorb” heat)
• mechanical protection (can absorb shocks)
• Water repellant
• prevents excessive wetting (birds)
• prevents loss of water via evaporation
Fatty Acids
Carboxylic acids with hydrocarbon chains containing anywhere from
4 to 36 carbons (even number of carbons).
Polar
Longer chains:
less solubility
Nonpolar
Saturated: no Unsaturated: one
double bonds or more double
between carbons in bond between
the chain carbons in the alkyl
chain
Fatty Acid Nomenclature
C1 is carboxyl carbon
Double bond Δ
Chain length Position of double bond
Δ
Number of
double
bonds
Fatty Acid Nomenclature
Polyunsaturated Fatty Acids
omega (ω) numbering of carbon
delta (Δ) numbering of carbon
skeleton
skeleton
First carbon in relationship to the First carbon in relationship to the
terminal methyl
carbonyl carbon
ω-3 (first double found in C3)
ω-6 (first double found in C6)
These ω fatty acids are essential nutrients:
Humans need them but cannot synthesize
them. Need to get them from diet.
Unsaturated Saturated
F.A. Properties – Solubility and Melting Point
Length of
nonpolar
chain
Number of double bonds
• Solubility in water
• Longer chain less solubility
• Fewer double bonds less solubility
• Melting Point
• Longer chain higher melting point
• More double bonds lower melting point
F.A. Properties – Solubility and Melting Point
Saturated:
- Waxy consistency at 25oC
- Higher melting point
- More flexible
- Extended conformation is more stable
- Pack tightly, ordered, many interactions
Unsaturated:
- Liquid oils at 25oC
- Lower melting point
- Less flexible
- Cis double bond produce kink
- Different degree of packing
“Trans Fats”
cis cis
tran
s
trans double bond extended conformation can pack more regularly higher melting points
Trans fatty acids form by partial hydrogenation of
unsaturated fatty acids done to increase shelf life or
stability at high temperature of oils used in cooking
(especially deep frying).
Storage Lipids
Fatty Acids Triacylglycerols
Waxes Adipocytes store triacylglycerides
Triacylglycerols
Fatty acid
Glycerol
3 times:
Triacylglycerol
Triacylglycerols
Esterification
+
Fatty acid
O
R O C R’
Glycerol H2O
3 times:
Ester bond
Triacylglycerol
Triacylglycerols
• Less soluble in water than fatty
acids due to the esterification of
the carboxylate group.
• The primary storage form of
lipids (body fat).
Lipases: enzymes that catalyze the
hydrolysis of stored triacylglycerols,
releasing fatty acids
Triacylglycerols
• Less soluble in water than fatty
acids due to the esterification of
the carboxylate group.
• The primary storage form of
lipids (body fat).
O
R O C R’
H2O Saponification
O
Lipases: enzymes that catalyze the
hydrolysis of stored triacylglycerols, R OH HO C R’
releasing fatty acids
Waxes
• Waxes are esters of long-chain saturated and unsaturated fatty acids with
long-chain alcohols.
• Insoluble and have high melting points (60 to 100oC)
H2O O
O
HO C R’ R OH R O C R’ Ester
Fatty Acid Alcohol
•Variety of functions:
–storage
–protection and pliability for hair and skin in vertebrates
–waterproofing of feathers in birds
–protection from evaporation in tropical plants and ivy
–used by people in lotions, ointments, and polishes
Energy storage in Lipids is Efficient
Fat stores in cells (adipocytes)
Fats: for long-term (months)
energy storage needs.
Carbohydrates are effective for short
term energy storage because they are
soluble, but fats are better for long term
storage because they are highly reduced
compounds (lots of electrons, more
energy). Also, they can pack tightly and
exclude excess water.
Structural Lipids – Membranes and the Lipid Bilayer
• Contain polar head groups and nonpolar tails
• Diversification can come from:
• modifying a different backbone
• changing the fatty acids
• modifying the head groups
Lipid bilayer
Glycerophospholipids
• Primary constituents of cell membranes.
• L-glycerol-3-phosphate is the backbone of
phospholipids.
• The phosphate group is charged at physiological pH.
Fatty acid
Phosphate
group
2 times:
Glycerophospholipids
• Primary constituents of cell membranes.
• L-glycerol-3-phosphate is the backbone of
phospholipids.
• The phosphate group is charged at physiological pH.
Fatty acid
Phosphate
group
2 times:
Glycerophospholipids
The highly polar phosphate
group may have substituent
groups called the head groups.
C16 or C18
C18 or C20
Unsaturated fatty acids are commonly found
connected to C2 of glycerol-3-phosphate.
Glycerophospholipids
parent
compound
Lipid bilayer
Glycerophospholipids
Glycerol
Fatty acids Head group
Cardiolipin
Sphingolipids
Polar head group connected
to sphingosine by a
phosphodiester linkage
…or a glycosidic linkage
Glycolipids: In outer cell membrane
Sphingolipids
The backbone of sphingolipids is NOT glycerol but sphingosine
Sphingosine
Fatty acid
A fatty acid is joined to sphingosine via an
amide linkage rather than an ester linkage
Sphingolipids
The backbone of sphingolipids is NOT glycerol but sphingosine
Sphingosine
Fatty acid
O
A fatty acid is joined to sphingosine via an R N C R’ Amidification
amide linkage rather than an ester linkage H
Sphingolipids – Nerve Cells
Sphingomyelin is abundant in
myelin sheath that surrounds some
nerve cells in animals.
Sphingolipids – Blood Groups
The blood groups are determined in part by the type of
sugars located on the head groups in glycosphingolipids.
The structure of sugar is determined by
an expression of specific
glycosyltransferases.
Galactolipids in Plants
• Phosphate-free lipids.
• 70-80% of membrane lipids in plants.
• If sulfonated: have negative charge as
phospholipids.
Phospholipases
• Most cells continually degrade and replace their membrane lipids.
• Phospholipids are degraded by phospholipases A−D
Each phospholipase
cleaves a specific bond.
Sterols and Cholesterol
• Sterols: structural lipids in the membrane of most eukaryotic cells
– steroid nucleus: four fused rings
– hydroxyl group (polar head) at C-3
– various nonpolar side chains
Almost
planar, rigid
Derivatives with many biological functions: steroid hormones
(regulate gene expression), bile acids (detergents in intestine), etc.
Biologically Active Lipids
Present in much smaller amounts than storage or structural lipids.
• Signaling molecules
– Intracellular signals
– paracrine hormones (act locally)
– steroid hormones (act body-wide)
– growth factors
– vitamins A and D (hormone precursors)
• Cofactors for enzymes
– vitamin K: blood clot formation
– coenzyme Q: ATP synthesis in mitochondria
• Pigments
– color of tomatoes, carrots, pumpkins, some birds
– Light-capturing pigments in vision and photosynthesis.
Intracellular Signaling
Phosphatidylinositol 4,5-biphosphate (PIP2)
serves as a reservoir of messenger
molecules that are released inside the cell DAG stays is
Cytosolic face of the
the
plasma membrane
in response to extracellular signals membrane
IP3 is water-soluble.
Triggers release of
intracellular Ca2+
Endocrine Hormones (Steroids)
• Steroids are oxidized derivatives of sterols.
• Steroids have the sterol nucleus but lack the alkyl chain found in cholesterol.
• They are more polar than cholesterol.
• Steroid hormones are synthesized from cholesterol in gonads and adrenal glands.
• They are carried through the body in the bloodstream, usually attached to carrier proteins.
Paracrine Hormones (Eicosanoids)
20:4(D5,8,11,14)
Several OH groups
5C ring
3 conjugated Antiinflammatory agents
Inflammation & fever. double bonds
Smooth muscle contraction
during labor and menstruation.
6C ring
Smooth muscle contraction in lungs
formation of blood clots (overproduction: asthma attacks)
Nonsteroidal anti-inflammatory drugs (NSAIDs) such as aspirin and
ibuprofen reduce the formation of prostaglandins and thromboxanes by
inhibiting cyclooxygenase (COX1/COX2) enzymes.
Enzyme Cofactors (Vitamins)
Enzyme Cofactors (Vitamins)
β-carotene and
Vitamin A1
Polyketide Drugs
Polyketides are a diverse family of compounds synthesized similarly to
fatty acid biosynthesis.
• commonly “secondary metabolites” with specialized function
Terpenes
Amazing Chemical Diversity!!
geranyl diphosphate
Plants each make hundreds of terpenes, many
of which are found in “essential oils.”
Amazing Chemical Diversity!!
Terpenes
