Lipids Flashcards
Give some examples of Lipids ?
- Fully saturated stearic acid
- Cholesterol
- Sphingolipids: 3 different fatty acids attached to ceramide backbone
- Glycerolphospholipids: 3 different fatty acids attached to glycerol backbone
Explain the main biological functions of lipids ?
- Storage of energy
- reduced compounds: lots of available energy
- hydrophobic nature: good packing - Insulation from environment
- low thermal conductivity
- high heat capacity (can “absorb” heat)
- mechanical protection (can absorb shocks) - Water repellant
- hydrophobic nature: keeps surface of the organism dry
- prevents excessive wetting (birds)
- prevents loss of water via evaporation - Buoyancy control and acoustics in marine mammals
- increased density while diving deep helps sinking (just a hypothesis)
- spermaceti organ may focus sound energy: sound stun gun?
Explain some more of the main biological functions of lipids ?
- Membrane structure
- main structure of cell membranes & anchors for membrane proteins - Cofactors for enzymes
- vitamin K: blood clot formation
- coenzyme Q: ATP synthesis in mitochondria - Signalling molecules
- paracrine hormones (act locally)
- steroid hormones (act body-wide)
- growth factors
- vitamins A and D (hormone precursors) - Pigments
- colour of tomatoes, carrots, pumpkins, some birds - Antioxidants
- Vitamin E
Lipids that contain fatty acids (complex lipids). Give examples of kinds of lipids ?
Storage lipids: Triacylglycerols
Membrane lipids: Phospholipids & Glycolipids
Name some derived Lipids that do not contain fatty acids ?
Cholesterol, vitamins, pigments
Classification of Lipids ?
- Membrane lipids e.g. Fatty Acids – hydrocarbon chain (4-36 carbons) with carboxylic acid group: can be branched/unbranched, saturated, mono/polyunsaturated. E.g. membrane lipids
Complex/storage lipids (contain fatty acids):
- Triglycerides & Waxes: simple lipids from fatty acids esterified with alcohol
- Phospholipids (Sphingolipids & glycolipids): compound lipids from fatty acids esterified with alcohol & additional groups
- Derived Lipids (do not contain fatty acids): derived by hydrolysis e.g. cholesterol, vitamins, pigments.
In a fatty acid, the carboxyl group behaves as ?
As an acid, is hydrophilic and chemically active
Long hydrocarbon chain is ?
Hydrophobic & not very reactive
The commonest fatty acids in mammalian metabolism are:
Palmitic (16:0) (26% of human fat) Stearic acid (18:0) (45% of human fat)
Almost all natural fatty acids have ?
An even number of carbons
What is the general formula?
General formula CH3(CH2)nCOOH, where n is usually an even number of length 14 - 24 carbon atoms
Most natural fatty acids ?
They are unbranched
Long hydrocarbon chain may be ?
Saturated or unsaturated & terminates in a carboxyl group (1COOH)
Properties of Saturated Fatty Acids ?
- Contain only single C–C bonds
- Closely packed
- Strong attractions between chains
- High melting points
- Solids at room temperature
Properties of Unsaturated Fatty Acids ?
- Contain one or more double C=C bonds
- Nonlinear chains do not allow molecules to pack closely
- Few interactions between chains
- Low melting points
- Liquids at room temperature
Give examples of a saturated and unsaturated fatty acid ?
Stearic Acid – A Saturated Fatty acid
Oleic Acid – Unsaturated Fatty acid (monosaturated omega 9 fatty acid)
Cis-double bond restricts ?
Rotation & introduces a rigid bend in hydrocarbon tail
What is the omega end and the alpha end ?
Omega end = methyl group
Alpha end = carboxyl group
Fatty acids are found in ?
Cell membranes where tightness of packing their hydrocarbon chains affects fluidity (not flexibility) of membrane
Saturated hydrocarbon chains pack ?
Tightly together in membranes stabilised by van der Waals. Structurally a zig-zag configuration. C-C bond forms 109° bond angle with free rotation
Unsaturated hydrocarbon chains (e.g. oleic) have ?
1+ double bonds along their length creating rigid kinks, impairing ability to pack
Explain simple short hand nomenclature ?
- specifies carbon chain length (4-36)
- number of double bonds in chain separated by a colon
What is delta numbering ?
Delta numbering position of the double bond(s) D in relation to carbonyl group
What is Omega numbering ?
Omega numbering position of double bond(s) w in relation to terminal methyl
C18:1 (Δ9) = oleic acid, an omega 9 fatty acid. What is the full name ?
Full name: Cis-9-Octadecenoic acid
How do you number Polyunsaturated fatty acids ?
Carbons are numbered in opposite direction, assigning 1 to the methyl carbon designated
The double bonds are susceptible to ?
The double bonds are very susceptible to PEROXIDATION to form hydroperoxides [ ROOH ] - these can oxidise membrane proteins
What combats this process of peroxidation ?
Antioxidants, such as the vitamins C and E, Q10 (ubiquinone) and glutathione (GSH)
Omega 3 & omega 6 act as?
Competing substrates for the same enzyme
Mammals cannot synthesise so ?
Must obtain from diet
What is the Optimal ratio of omega-6:omega-3 ?
It is between is between 1:1 and 1:4
Presence of double bond in FAs prevents ?
Free rotation & creates two configurations
Double bonds in natural unsaturated fatty acids are?
They are commonly in cis configuration, which kinks the chain
Explain cis configuration ?
If hydrogen atoms attached to the carbon atoms of a double bond are positioned on the same side of the double bond
Explain trans configuration ?
If hydrogen atoms attached to the carbon atoms of a double bond are positioned on a different side of the double bond
Trans fatty acids are rare?
From hydrogenated fats
Branched chain fatty acids (BCFA) are usually ?
Saturated fatty acids with 1+ methyl branches on the carbon chain
BCFAs are mostly found ?
In bacteria
BCFAs are found in the ?
In the vernix caseosa of human infants & play a role in fostering the development of the human intestinal microbiota
Lanolin is another example of?
An animal material containing BCFA
Solubility & melting points are largely determined by ?
The length & degree of unsaturation
Longer FA with few double bonds =
Low solubility
Unsaturated cis fatty acids have ?
A lower melting point
Saturated FA are ?
Waxy and stable (higher melting point)
Solubility decreases as ?
The chain length increases
Melting point decreases as ?
- decreases as the chain length decreases
- decreases as the number of double bonds increases
Catabolism (breakdown) of fatty acids (generate energy) by ? produces ? and where ?
Beta Oxidation.
- produces acetyl-CoA
- produces reducing power (NADH, FADH2)
takes place in the mitochondria
Anabolism (synthesis) of fatty acids (create biologically important molecules e.g. triglycerides, phospholipids, hormones, ketones) synthesised by ? requires ? and where ?
- Synthesised by acetyl-CoA and malonyl-CoA
- requires reducing power from NADPH
- takes place in cytosol in animals, chloroplast in plants
Fatty acids are built in several passes, processing ?
One acetate unit at a time
Explain fatty acid synthesis ?
- Fatty acid synthesis is the creation of fatty acids from Acetyl-CoA and NADPH
- Each acetate is coming from activated malonate (malonyl-CoA)
- Overall goal is to attached acetate from Malonyl-CoA to growing chain & then reduce it
Where does Fatty acid synthesis occur ?
Fatty acid synthesis occurs in cell compartments where NADPH levels are high e.g. cytosol in vertebrates, or in plants the chloroplast
Sources of NADPH are ?
Either pentose phosphate pathway or malic enzyme, or in plants via photosynthesis
Beta oxidation is the catabolic process by ?
Which fatty acids are broken down in the mitochondria to acetyl CoA with the release of energy (ATP) dissipating CO2 & H2O
Once inside the cell, CoA ligase catalyses the reaction between ?
A fatty acid molecule with ATP to give a fatty acyl-CoA molecule which enters the citric acid cycle of each turn of the cycle
What kind of structure do Phospholipids have ?
Phospholipids* have an amphipathic structure: polar, hydrophilic head & two non-polar, hydrophobic tails§
How can the various forms of Phospholipids be diversified ?
Diversification via:
- modifying backbone
- changing fatty acids
- modifying head groups
Different organisms & tissues have different membrane lipid compositions
What are the three components of phospholipid ?
A) Phosphorylated head group
B) Three carbon glycerol backbone
C) Two hydrocarbon fatty acid chains
Similar in structure to TAGs except ?
One of the alcohols of glycerol is esterified by phosphate instead of a fatty acid (= phosphatidic acid PA)
The phosphate group can then be esterified by ?
A second alcohol to form phosphoacylglycerol
The phospholipids comprise two groups based upon a backbone of ?
Glycerol or Sphingosine
The phosphate group in both structures are ?
The phosphate group is charged at physiological pH