Lecture 27 - Introduction, a handy reminder Flashcards
Take our fuel molecules from digestion and ….
Break them down in this metabolic pathway to make ATP which goes off to do cellular work
First Law of thermodynamics reminder
Energy cannot be created or destroyed, energy can be converted
ATP
Adenosine triphosphate is the major energy intermediate (currency) of the cell
Gibbs free energy
The delta G of a reaction tells us about…
The relative abundance of the substrates and products
The energy stored in the chemical bonds of the products and substrates
Delta G < 0 for A to B
Then the reaction is spontaneous/energy released/energetically favourable
Means that we have more energy stored in the bond of A than we do in the bonds of B and this means that the reaction is going to be spontaneous i.e. this reaction will happen
Delta G = 0 for A to B
Then the reaction is at equilibrium/no change in energy
Delta G > 0 for A to B
Then the reaction is not spontaneous/energy required/energetically unfavourable
This time we have more energy stored in the bonds of B than stored in the chemical bonds of A so this reaction is non spontaneous and won’t happen as B requires more energy than A so it is energetically unfavourable
ATP hydrolysis and synthesis in terms of Gibbs energy
ATP hydrolysis is energetically favourable with a delta G of -30
ATP synthesis is energetically unfavourable with a delta G of +30
Measured in delta G under standard conditions
Delta G under standard conditions
All at 1 molL-1
Specific temperature
Everything is at 1molL-1 except H+ (protons) - if it was at 1 then it would give a pH that is close to zero which is not actually very reflective of what happens in a cell, it is distant from physiological pH and the enzyme might not work, adapt conditions and make a pH of 7
Reaction/energy coupling
If you have one reaction that has delta G of greater than zero and then another reaction that has a delta G of less than zero - you can couple these reactions
If adding these reactions together means that the collective delta G is still negative then the coupled reaction is still energetically favourable
Enzymes often couple reactions to drive necessary unfavourable reactions
Unfavourable reactions can be coupled with…
ATP hydrolysis
For example the hexokinase reaction in glycolysis (same reaction is catalysed by glucokinase (glucose sensor))
In this example, converting glucose + phosphate to glucose-6-phosphate + water is positive delta G and then ATP hydrolysis is negative delta G
Coupled reaction is energetically favourable so now both of the reactions can occur
Pathways for processing food molecules for ATP synthesis
Two key types of reactions:
1- Phosphorylation of ADP to ATP
2- Redox reactions (fuel molecule gets oxidised, so there needs to be something that provides the oxidising power/gets reduced)
Redox reactions
Involves the transfer of electrons
Oxidation
Loss of electrons = oxidised
OIL = Oxidation is loss
The thing that is oxidised is the reducing agent/provides reducing power
Reduction
Gains electrons = reduced
RIG = Reduction is gain
The thing that is reduced is an oxidising agent/provides oxidising power
Energy is released from fuel molecules by…
Oxidation reactions
Fuel molecules such as carbohydrates (glucose) and lipids (palmitate) are being oxidised
Energetically favourable and therefore release energy
Stepwise oxidation
Of fuel molecules occurs in the pathways
Direct burning of sugar = all of the energy is released as heat
Stepwise oxidation of sugar = energy captured for ATP production
Coenzymes NAD and FAD
These are the things that are reduced when the fuel molecules are oxidised
They interact with various enzymes to accept and donate reducing equivalents
Reducing equivalents
Biological redox reactions often involve the transfer of hydrogen atoms (includes an electron)
H=H+ + e- (proton + electron)
Hydrogen is referred to as a reducing equivalent
The enzymes that catalyse these reactions are called dehydrogenase, you know that when you see one of these enzymes there is going to be a redox reaction and you are using one of the reducing equivalents when moving hydrogen
Coenzymes reminder
Subclass of cofactors Small organic molecules Often derived from vitamins Low concentration in cell Act as carriers Exist in 2 forms
NAD
Nicotinamide adenine dinucleotide
Dervied from niacin (vitamin B3)
Accepts hydrogens and electrons in metabolic pathways (glycolysis, fatty acid oxidation, citric acid cycle)
NAD undergoes …
NAD undergoes a two electron reduction (accepts two reducing equivalents)
NAD+ is the oxidised form
NADH + H+ is the reduced form
FAD
Flavin adenine dinucleotide
Dervived from riboflavin (vitamin B2)
Accepts hydrogens in pathways (fatty acid oxidation, citric acid cycle)
Flavin coenzymes are tightly bound to the proteins with which they interact (flavoproteins)
FAD undergoes …
FAD undergoes a two electron reduction (access two reducing equivalents)
FAD is the oxidised form
FADH2 is the reduced form
Coenzyme A (CoA) is another important…
Coenzyme in the pathways
Derived from pantothenic acid (vitamin B5)
Not a carrier of electrons (it is not reduced/oxidised)
Carries acyl groups
Two forms - free coenzyme A = CoASH or acyl group attached = Acyl-CoA (AcCoA)
Reactive sit is the SH
Two forms of CoA
Two forms - free coenzyme A = CoASH or acyl group attached = Acyl-CoA (AcCoA)