Thermo 4 Applications To Biomolecules Flashcards

1
Q

What is keq

What happens to Gibbs free energy if there is equilibrium

A

Keq = products / reactants

The free energy is zero , no entropy, no favour between one side or the other of the reaction

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2
Q

What is delta G standard if keq very very big

If very very small

A

Delta G very negative, favourable Gibbs, reaction run to completion

Delta G very postive, unfavourable gibb, reaction doesn’t run at all

This is why Gibbs energy is characteristic of the reaction

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3
Q

What makes standard Gibbs only depend on the reaction equilibrium constant

A

Since delta G = -RT ln (Keq)

Only depends on keq , the state of the reaction after equilibrium , after the reaction has reached completion

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4
Q

What does regular delta G tell us

A

Tells us the Gibbs energy any given point in the reaction and tell us if we’re gonna roll backwards or forward in relation to delta G standard

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5
Q

Why does the evolution of compelx organsims not break the laws of thermodynamics

A

Because us as ordered beings decreasing entropy, causes our activities to make a corresponding increase in entropy on our surroundings

For example the sun gives off energy which is high entropy but we use that to survive and decrease the entropy by creating order

But we are still anomalous organisms, and very unlikely

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6
Q

How does a hydrogen bond still have elements of a bond

A

In water the h bonds are 90 % electrostatic but still 10 % covalent

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7
Q

How many h bond in water

Why is it like this

A

In water you have 3.4 h bonds on average, this value is always changing because it has a short bond lifetime

Instead of staying in the lowest energy conformation which is in the same set of bonds

They change their bonds and positions because they always have a distribution of energy in the molecules

So they occasionally go in the lowest energy state but are able to leave because of this extra energy (KbT)

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8
Q

When melting and boiling a crystal (solvating it) what is the Enthalpy (delta H) and why

So what has to happen for it to be solvated

A

Small and Positive because heat is put into the system to break the bonds

This means that delta S needs to be very large and positive (because disorder occurs, make delta G negative, and the reaction favourable)

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9
Q

What makes non polar things want to stick together

A

They only try to stick together when they are around other polar things and the alternative is to stick to them

But polar things stick together no matter what since there have electric charge interactions

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10
Q

What is the entropic/enthalpoc change for non polar compounds

How do they overcome this

A

If a nonpolar compound is in solution

Two things:

If following the minimum energy, the water makes a cage to be more ordered around the surface of the non polar compound

This makes negative entropy, Meaning needs to be a corresponding decrease in Enthalpy or the reaction won’t be spontaneus (since postive delta G)

But If the cage did not form, there’d be very large postive delta H (because breaking h bonding), this is very unfavourable and wouldn’t happen

To overcome this, the non polar molecules would aggregate to have the least interaction with the order water cage

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11
Q

Explain the Gibbs of non polar molecules (alkanes) in comparison to alcohol and toluene

A

Comparing the alkane to alcohol:

Alkane have higher Gibbs because the water is forming an ordered cage around it, decreasing entropy and making Gibbs postive

Alcohol is more polar and has less carbons so less ordered water forms a cage around it, has lower Gibbs

Comparing the alkane to Toluene:

The toluene has a more comparable Gibbs to the alkane even though it has more carbons atoms

This is because the carbon atoms in toluene are clustered tighter together

Meaning the by clustering into a ring its Gibbs lower and reduced the amount of ordered water it interacts with

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12
Q

Explain how the cage water structure throws of the entropy

A

Usually the water molecules free in solution have h bonds in place 85% of the time

But the cage molecules have them in place 88% of the time

This means the cage molecules move and exchange less, causing the to be more order, causing lower entropy and unfavourable change in Gibbs

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13
Q

Explain the case of amphipathic compunds (lipids) and why they aggregate

What eventually happens

A

They have a large hydrophobic region, meaning a water cage can also form, decreasing entropy and making an unfavourable change in Gibbs

To get over this, aggregation happens with other lipids to reduce the amount of cages forming and order water they interact with

This is entropically favoured, and makes lowest energy and highest entropy structure

This makes a micelle

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14
Q

Why would a micelle be a sphere

What another structure that is similar

A

Two reasons:

Having the tails tucked in minimizes how much ordered water the non polar region have to interact with , higher entropy

Has the lowest SA/V ratio , meaning it also minimizes how much of the surface is
interacting with ordered water molecules

Liposomes (have water on inside and outside , bilayer)

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15
Q

What is critical micelle concentration

A

The point where surfactants fully saturate the surface of the solution

After this point, adding more surfactant causes them to aggregate and make micelles

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16
Q

To get a negative delta g favourable spontaneous reaction Whag has to happen

A

Increase entropy, enthalpy small and postive

17
Q

How do enzymes show change in entropy

A

More favourable for the to bind with their substrates because before binding there is ordered water around them, lower entropy

After binding, less ordered water interacting with them , higher entropy

18
Q

How does protien folding show change in entropy

A

Hydrophobic collapse

Examples are amphipathic alpha helices

Makes the hydrophobic side of the helix go on the inside and not interact with ordered water and the hydrophobic side of it face the water

19
Q

Explain the protien folding model

What if many micro states

A

The protiens fold at each peptide linkage and each linkage can have 3 possible orientation

Up down or side (so a new amino acid binds in either direction)

This means each there are 3^(N-2) configurations for that one amino acid because has can only take one of the 3 paths

N is number of amino acid residues

This gives (N-2) ln 3

Giving delta S = R (N-2) ln (3) as the molar entropy

USE R VERSION

And delta S = kb (N-2) ln (3)

If many microstates, use exponential log rule

delta S = R ln (3^N-2) then the 3^N-2 is to the power of however many residues (microstates)

20
Q

What does the protien folding model neglect

A

The binding of water to non polar surfaces (leading to negative entropy)

Disordering of side chains that become more mobile upon unfolding (leading to postive entropy)

21
Q

What is levinal paradox

A

If there are so many options of protien folding why is the folding so fast

Because they fall down an energy well, and stable in its folded state

22
Q

What would make a protien more stable

A

Tighter hydrophobic packing (like in extermophiles)

Higher density of exposed charged (polar) residues

Folding with ion pairs comic together

Make the protien fall down the energy well

23
Q

How is protien unfolding done

A

Through heat

If warm protien very slowly

Can break the interactions, make it go up the well and start unfolding the protien

Once one interaction breaks, all the other go with it meaning that is not just one interaction making the protien fold but all of them working together

Through organic solvents

Only thing keeping hydrophobic protiens together is the polar environment

If protien in a hydrophobic environment, energetically favourable for it to flip and invert to interact with solvent

24
Q

What is the denaturing temp of the average monomeric protien

A

60 degrees

25
Q

Explain the protien folding clock

A

A behaviour clock built into humans that is based on protien folding and unfolding

Shows how unfolding happens on purpose

Ex. KaiB switches between folded to unfolded then a diff folded state on purpose as part of a biological cycle

26
Q

What are the three distributions

A

Max well Boltzmann

Bose eitneins (-1)

Fermi Dirac (+1)

27
Q

What is the Maxwell Boltzmann distribution

Compare it to Bose einsteins

A

The typical distribution you’d see for a high temp molecule

High population of molecules at a lower energy, all the states have a probability of being populated for this you just have a most likely outcome

Bose Einstein is where the matter occupies the same state at low temps

so if you keep dropping the temperature the line will spike up to one specific point because each particle is only in that one state

Can’t see that they are diff particles

28
Q

Compare Maxwell Boltzmann distribution fermi dirac

A

Fermi Dirac shows molecules that cannot be in the same state at low temps

Shows electrons, electron have to be in independent states

But if go to low enough temp,

IDK