10. Bioenergetics Flashcards

1
Q

photosynthetic autotrophs

A

use the energy of sunlight to convert low -G (energy) and H2O into energy-rich complex sugar molecules

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2
Q

photosynthesis equation and notes

A

6 CO2 + 6H2O –> (CH2O)6 + 6O2

the reaction has a large positive ΔH and large negative ΔS (the products have more enthalpy and are more ordered than the reactants)

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3
Q

heterotrophs

A

extract the chemical potential energy stored in sugars and other organic compounds to release CO2 and H2o

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4
Q

equation for glycolysis and notes

A

(CH2O)6 + 6 O2 –> 6CO2 + 6H2O

-reaction has a large negative ΔH and large positive ΔS (the products have lost energy and are less ordered)
-the G is released slowly in many steps using several metabolic pathways

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5
Q

equation for ΔG?

A

ΔG = -RTln(Keq)

(T= temp in K, R = 8.31 J/molK)

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6
Q

what is the formula for ΔG°? what does it mean?

A

ΔG° = -RTln(Keq)

-under “standard” conditions (25° C, 55 M H2O, [reactant] = 1M)

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7
Q

what does ΔG’° mean?

A

correcting the pH to pH=7

if K’eq = 19 at 25°C, then ΔG’°= -(8.315)(298)(ln19) = -7296 J/mol

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8
Q

what does it mean if K’eq if positive? negative? =1?

A

Negative: ΔG’° is negative, spontaneous rxn
positive: ΔG’° is positive, non-spontaneous
=1: ΔG’° is 0, rxn at equilibrium

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9
Q

what does it mean if ΔG’° is negative? positive?

A

negative: the products contain much less energy than the reactants (spontaneous)

positive: the products contain more energy than the reactants (non-spontaneous)

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10
Q

what is the equation for the actual ΔG under non standard conditions?

A

ΔG - ΔG’° + RTln([C][D]/[A][B]

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11
Q

notes on bioenergetics

A
  1. both ΔG and ΔG’° are theoretical maxima. some G is always lost as heat
  2. even if ΔG’° is positive, the reaction can go forward if ΔG is negative
  3. ΔG’s of sequential reactions are additive because ΔG is path-independent (used to drive the next reaction; overall negative even if some steps are positive)
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12
Q

what is the common intermediate between catabolism and anabolism?

A

ATP (product of one, used to drive the other)

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13
Q

what is the equation for synthesis/hydrolysis of ATP

A

ATP + H2O —> ADP + Pi

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14
Q

explain how the synthesis of ATP can be a spontaneous reaction

A

-the synthesis of ATP is highly endergonic (non-spontaneous)
-however, it is coupled with ATP hydrolysis, which is highly exergonic (spontanous)
-the OVERALL reaction is exergonic, allowing ATP synthesis to occur spontaneously

-this is a very common method used in bioenergetics

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15
Q

explain relief of charge repulsion in ATP hydrolysis

A

one molecule with four negative charges is converted into two molecules with two negative charges each
-this reduces the charge repulsion, which is partly why ATP hydrolysis is so exergonic (relieves repulsion)

this is done by:
1. hydrolosis of a phosphate group from ATP (to make ADP)
2. deproponating the phosphate group to create resonance (e- distributed evenly throughout the oxygen atoms)

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16
Q

explain how there is an entropy increase due to ATP hydrolysis

A

there are more resonance forms of ADP + Pi than of ATP, which creates an entropy increase
(products are more stable than reactants; more ways to order itself)

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17
Q

solvation

A

the process of solvent molecules surrounding solute particles

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18
Q

how does solvation impact ATP hydrolysis/synthesis

A

solvation of ADP + Pi > ATP, which stabilizes the products relative to the reactants

-ATP: water molecules form an ordered cage around the charged
-ADP + Pi: phosphates become more hydrated, disrupting the ordered shell and increasing the entropy

19
Q

explain the hydrolysis of 1,3 bis-phosphoglycerate, and say what it is used for

A

used in glycolysis and photosynthesis

-a phosphate is removes to alleviate charge, just like in ATP hydrolysis

equation:
1,3 bis-phosphoglycerate + H2O –> 3-phosphoglycerate + Pi

-overall reaction is exergonic

20
Q

explain the hydrolysis of phosphoenolpyruvate into pyruvate

A

removes a phosphate to alleviate charge and form a more stable molecule (just like in ATP hydrolysis)
-phosphoenolpyruvate is a VERY energetically rich molecule, meaning the energy released can be used to synthesize ATP

21
Q

Substrate Level Phosphorylation

A

cells use high energy compounds to synthesize ATP

-ex: pyruvate, phosphoglycerate

22
Q

what are the three processes used for regenerating ATP?

A
  1. substrate-level phosphorylation (energy comes from other molecules)
  2. photophosphorylation in chloroplasts (energy comes from light)
  3. oxidative phosphorylation in mitochondria (energy comes from oxygen)
23
Q

explain how ATP is used to convert Glu + NH3 into Gln (endergonic process)

A
  1. the phosphate from ATP is transferred to an enzyme (or a substrate) which becomes activated
    -ex: the energy of Glu is raised by phosphorylation
    (hydrolysis of ATP provides energy to convert Glu into Gln)
  2. the reaction is completed by displacement of the Pi by NH3+, which is an exergonic reaction
    (replaces the phosphate with an amino group)
24
Q

if ATP has so much energy, then why does it not spontaneously decompose?

A

although the reaction is spontaneous, it is very slow because it has a HIGH ACTIVATION ENERGY
-therefore, enzymes are used to lower the activation energy and allow the release of energy

25
Q

are there any molecules energetically equivalent to ATP?

A

yes, other nucleoside triphosphates
-also used by cells (ex: GPT)

26
Q

how are nucleoside triphosphates made? what is the equation?

A

ATP + NDP –> ADP + NTP (ΔG’°; equilibrium)

-catalyzed by nucleoside diphosphate kinases

27
Q

what are two reactions that release the same amount of energy as ATP hydrolysis?

A
  1. ADP + H2O –> AMP + Pi
  2. ATP + H2O –> AMP + PPi (removes two phosphates instead of one)
28
Q

PPi

A

inorganic pyrophosphate
-it is the product of hydrolyzing TWO phosphates off of ATP (AMP leftover)
-can then hydrolyze PPi to create two inorganic molecules (releases even more energy)

29
Q

thioester bonds

A

-has a SULFUR attached instead of ozygen
used as another type of energy storage
-thioesters are less stable than oxygen esters, and therefore release more energy when broken

30
Q

what is an example of a molecule that has a thioester bond?

A

Acetyl-Coenzyme A (Acetyl-CoA)

31
Q

explain how Acetyl-CoA is used to drive reactions

A

-has a high-energy thioester bond which can be broken in order to drive endergonic reactions
-breaking the bond releases energy and creates more stability in the product

32
Q

what happens when Zn is placed in a copper sulfate solution and why?

A

electrons flow from Zn to Cu2+ spontaneously because Cu2+ has a higher electron affinity than Zn2+

-the Zn metal erodes and Zn2+ goes into the solution
-Cu is deposited on the Zn (CuSO4 is blue)
-as Cu2+ is converted into Cu, the blue colour of the solution fades

33
Q

what is the equation of Zn in the solution? Cu?

A

Zn –> Zn 2+ + 2e-
Cu 2+ + 2e- –> Cu

34
Q

what is the overall redox reaction of zinc and copper?

A

Cu 2+ + Zn –> Cu + Zn2+

-zinc is oxidized (losses e-)
-copper is reduced (gains e-)

35
Q

what is the second type of electron flow?

A

involved oxygen
(ex: glucose + oxygen forming CO2 and H2O)

36
Q

what is the equation for glucose reacting with oxygen ? what happens?

A

C6H12O6 + O2 –> CO2 + H2O + energy

-oxygen has a higher e- affinity than glucose, so electrons flow to O2, releasing energy
-the carbon is oxidized and oxygen is reduced

37
Q

what is an example of a water-soluble, diffusible electron carrier?

A

Nicotinamide Adenine Dinucleotide (NAD+)
-also called Niacin or Vitamin B6

38
Q

maltate dehydrogenase

A

an enzyme that removes electrons from L-Maltate to produce oxaloacetate and reduce NAD+ to NADH
-maltate is dehydrogenated and oxidized (loses two e- in the form of 2H)
-NAD+ accepts H - and becomes reduced
-this releases a proton

39
Q

how many dehydrogenase enzymes are known? what do they use?

A

over 200
all use NAD+

40
Q

what are two examples of water-soluble, covalently-bound electron carriers

A
  1. Flavine Mononucleotide (FMN)
  2. Flavine Adenine Dinucleotide (FAD)
41
Q

what is the reference point used when measuring the relative affinity for electrons?

A

reference point is a solution containing H2 at 101 kPa + 1M H+ at pH = 0

equation:
1/2H2 —> H+ + e-

42
Q

define standard reduction potential (E°). what does a high or low value indicate?

A

the measure of a molecule’s tendency to accept electrons in a redox reaction

-High E°: stronger oxidizing agent (more likely to GAIN electrons)
-low E°: stronger reducing agent (more likely to GIVE UP electrons)

-electrons flow from species with a lower E° to a higher E°

43
Q

how to find the overall redox reaction between two molecules?

A
  1. find both of their redox reactions, and find which one has the higher E’° value
  2. flip the reaction of the species with the more negative E’° (the one that is giving up its e-)
  3. cancel out intermediates to find the overall reaction
  4. add together the E’° values to find the overall value

note: can also flip the sign of the E’° value of the oxidation rxn then add the values

44
Q

how can ΔG be calculates from redox reactions?

A

from the difference in emf

equation:
ΔG’° = -nFΔE’°

(F= faraday constant = 96.48 kJ/volt*mol)