Section 3: Energetics of Life Flashcards
3 key common features of life
Proton gradients
Reducing power (FAD/FADH, NAD+/NADH, Fe2+/Fe3+, FeS compounds)
ATP (energy currency)
Proton gradients
Essentially universal for metabolism by all living organisms
An energy-coupling mechanism that uses energy stored in the form of an H+ gradient across a membrane to drive cellular work
Proton gradients - mitochondria
Energy for gradient from: food
Proton gradient concentrated in: intermembrane space
Proton gradients - bacteria
Energy for gradient from: nutrients
Proton gradient concentrated in: intermembrane space
Proton gradients - chloroplasts
Energy for gradient from: light
Proton gradient concentrated in: thylakoid lumen
Electron donor AKA
Reducing agent
Electron acceptor AKA
Oxidising agent
Oxygen is an example of a(n) _____ agent
Oxidising
What is ferredoxin
An example of an FeS compound
What does nature use to produce cellular products
Both reducing power and ATP
What are NAD(P)H and ATP widely used in
Widely used in metabolism to reduce CO2
Structure of NAD+, NADP+ and FAD
Share structural similarities
NADP+ is NAD+ except with a phosphate group attached to the ribose sugar
FAD also structurally similar
(must be able to recognise the structures!)
Levels of NAD+ and NADH that indicate energy state of a cell
Low NADH compared to NAD+ = low energy
High NADH compared to NAD+ = high energy
What was present in LUCA
Proton gradients
Reducing power (ferredoxin)
ATP
What did LUCA’s metabolism rely on
Relied on using H2 as an energy source to reduce CO2
O2 was largely absent –> very reducing atmosphere
LUCA genes
Those of a strictly anaerobic H2-dependent thermophilic
Genetic data places LUCA in a ___ setting, rich in ____
Hydrothermal vent setting
H2, CO2, transition metals, sulfur
Lots of abundant Fe2+
LUCA might have evolved at…
Alkaline hydrothermal vents
White smokers
Chimneys characterised by barium, calcium and silicon deposit which are white
What did the alkaline vent provide
Provided a natural proton gradient
Ocean had pH 6 and vent had pH 9
pH = ?
-log10 [H+]
Each pH unit represents a 10-fold change in H+ conc
Hadean ocean - H+ conc
Contained 1000x more H+ than the alkaline vent
What led to the reduction of CO2 by hydrogen
A combination of proton gradients and reducing power (FeS clusters)
Vents: Reduction of CO2 by H - steps
H2 within vent transfers its e- to FeS clusters at vent interface
FeS clusters transfer these e- to CO2 to reduce it to formic acid (HCOOH) and more reduced compounds (CH2O)
Vents: Reduction of CO2 by H - reducing power is generated where?
Within the FeS clusters which mediate the reduction of CO2 by H
Reduction of CO2 by H ultimately led to..
The development of the building blocks needed for LUCA to evolve
LUCA now had an established genetic code and ability to produce proteins
Protocel membrane
Leaky –> provides some protection
LUCA - ATP synthase
After reduction of CO2, ATP was produced through ATP synthase utilising proton gradient provided by vent
LUCA: ECh
Energy converting hydrogenase
Harnessed power of natural proton gradient by vent to generate reducing power (e- from H2) in the form of ferredoxin
Ancestor of complex I
LUCA: Reduced ferrodoxin and ATP can then be used to…
Reduce CO2 directly to provide the building blocks LUCA needed to function Forms C(x)H(y)O(z)
Archaea bacteria producing methane
Known as methanogens
Still use H2 as an energy source to reduce CO2
Has similarities in process to LUCA
Methanogens - FeS clusters
Methanogens still use FeS clusters within proteins to catalyse reactions (preserved within active sites of proteins)
What could methane indicate
Existence of methane on other planets (Mars) could indicate presence of life by microbes
Problem with genetic analysis of LUCA
Things like bacteria can transfer its DNA which then becomes incorporated into the genome
Reducing power of FeS complexes
Accept e- then donate them to something else
Where is the alkaline vent located
Along the mid-Atlantic ridge - the point in the earth’s crust where 2 tectonic plates are moving away from each other
Mid-Atlantic ridge
Responsible for breaking up the potent Pangea
Comes to surface in Iceland
Vents form
LUCA: Ocean was rich in..
CO2
LUCA: Where were FeS clusters located
In wall of the vent itself
What is free energy
A quantity used to determine the spontaneity of a process, i.e. what direction a reaction will occur
Refers to change of enthalpy and change of entropy, the combination of which determines whether a process occurs
ΔH
Enthalpy change
Describes heat of a reaction
Describes first law of thermodynamics
ΔS
Entropy
Change in order to disorder
The entropy (disorder) of any closed system not in thermal equilibrium almost always increases (2nd law of thermodynamics)
Gibbs free energy (G)
The energy that can be converted into work at a uniform temp and pressure throughout a system
Free energy - -ve, +ve and 0 values
If ΔG -ve (E° +ve), reaction proceeds in direction indicated
If ΔG zero, reaction is in equilibrium
If ΔG +ve (E° -ve), reaction proceeds in opposite direction, i.e. becomes a strong reducing agent
A reaction towards ‘more organised’ can only proceed if…
The enthalpy change (ΔH) overrides the decrease in entropy (ΔS)
ATP to ADP - entropy
Entropy increases as one ATP molecule is split into one ADP and one Pi (i.e. one molecule to 2 molecules)
First step of glycolysis
Reaction is regarded as essentially irreversible as it proceeds with a large -ve free energy change
However, the driving force comes from the free energy change that occurs during the conversion of ATP to ADP
Attaching a phosphate group to glucose doesn’t proceed spontaneously under standard conditions, so couple to ATP hydrolysis to make it spontaneous
Rust - what is oxidised and reduced
Iron is oxidised
Oxygen is reduced
Reduction potential
A measure of the tendency of a chemical species to acquire from or lose e- to an electrode and thus be reduced or oxidised
i.e. measures free energy changes for REDOX reactions
What reduction potential measured in
Volts (V)
Reduction potential - a higher E° value means…
It has a higher ‘pulling’ power to accept electrons (i.e. takes e- from other compound reaction)
Standard reduction potential is defined relative to…
A standard H reference electrode, given a potential of 0V
Standard reduction potential - concentrations
Each compound is at a conc of 1M (pH 0) and H2 is 1 atm
Reduction potential - the half reaction with the more -ve E° value is…
Reversed
Reactions - pH
Changing the pH (H+ conc) can alter the direction of the reaction
E°’
The reduction potential under physiological conc; a H+ conc of 10^-7 mol/litre (i.e. pH 7)
A very large -ve change in free energy essentially means…
The reaction is irreversible (steep waterfall)
ATP conversion to ADP and Pi - enthalpy and entropy change
Enthalpy change is -ve
Entropy change is +ve (1 –> 2 molecules)
Overall ΔG is -ve
Half reactions have a _____ associated with it
Standard reduction potential (E°)
Calculating standard reduction potential - agar bridge
Links two solutions for charge neutrality
If calculating reduction of compound x by H2..
Reverse the H2 reaction
Chiral molecule
Non-superimposable on its mirror image
4 diff groups attached
Glucose - numbering of Cs
Numbering of Cs starts from aldehyde group
In what forms do glucose and ribose exist in
Both exist in equilibrium as open and ring structurse
Glucose and ribose - chiral or non-chiral?
Both have chiral Cs and non-chiral Cs
What does the D/L notation tell us
Which of the two chiral isomers we are referring to
Glucose and ribose: Determining D/L notation
If -OH on highest numbered chiral C points to the right, isomer is D-isomer
If -OH on highest numbered chiral C points to the left, isomer is L
Which D/L form is usually found in nature
D form
Fischer projection - right vs left
Straight line
Right = below plane of ring
Left = above plane of ring
Haworth projection
Ring structure
Cyclic form - aldehyde
In cyclic form, the aldehyde group is lost because it’s used to complete the cyclic structure
Equilibrium - cyclic vs straight chains
Equilibrium heavily favours cyclic structures, so only a small amount of straight chain form of carbohydrate is present
Cyclic form - forms of glucose
2 distinct forms of glucose
C1 can have its attached -OH group either below the plane of the ring (α-glucose) or above the ring (β-glucose)
In aqueous solution, are in equilibrium
How do α and β forms interchange
Molecules pass through the straight-chain form to get from one structure to the other
Difference between α and β ring structures
Position of hydroxyl group attached to C1
In α form, it’s below plane of ring
In β form, it’s above plane of ring
Anomeric C and anomers
Since there can be 2 diff orientations around C1, it’s referred to as the anomeric C, and the two forms of glucose (α and β) are called anomers
Enantiomers
Compounds that are mirror images of each other
Diastereomers
Other compounds that aren’t enantiomers
Epimers
Compounds that differ only in the orientation of ONE hydroxyl group attached to a chiral C
i.e. hydroxyl group can occur on left or right-hand side
Cellulose - α or β?
Cellulose is a polymer of glucose monomers, using β-1,4-glycosidic linkages - allows cellulose to form very long and straight chains - tend to be very strong
Cellulose - how do hydroxy groups on glucose molecules align
Side-by-side (straight road)