Topic 1D Flashcards

(99 cards)

1
Q

Gibbs free energy (G)

A

maximum amount of non-PV work that can be performed within a closed system in a completely reversible process at a constant temperature and pressure.

◦ Indicates the total amount of chemical potential energy available in a system

◦ Reflects the overall favorability of the rxn that it describes

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2
Q

What is the Gibbs free energy equation and what do the variables represent?

A

∆G = ∆H - T∆S

◦ (-)∆G = spontaneous reaction = exergonic = will release energy that can be used to perform work in the surroundings ◦ (+)∆G = non-spontaneous reaction = endergonic = require work to be put in to make them go forward

◦ Mneumonic: goldfish are (=) horrible without (-) tarter sauce

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3
Q

Differentiate ∆G with ∆G˚

A

while ∆G = max free energy that can be produced, ∆G˚ = standard free energy change = the free energy that occurs if the concentration of reactants and products is 1 M; temp = 298K

◦ ∆G˚ for formation of any element under standard state conditions = 0

◦ ∆G˚ = accurate predictor of rxn spontaneity under standard conditions

◦ +∆G˚ (unfavorable) = can proceed spontaneously to produce products

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4
Q

Equilibrium

A

ratio of products:reactants = Keq

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5
Q

∆G˚= -RTlnKeq

what are the variables and what are their relationship?

A

R = ideal gas constant (8.314 J/mol・K); T = temperature in K; Keq = equilibrium constant
↑ Keq value = more + ln value = more (-) ∆G˚

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6
Q

∆G = ∆G˚ + RTlnQ

what are the variables, meanings, relationship?

A

Not at equilibrium- ratio of products:reactants = Q

R = ideal gas constant; T = temperature in K; Q = reaction quotient = the ratio of products to reactants @ a given time

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7
Q

Law of mass action

A

the rate of the chemical rxn is directly proportional to the product of the activities or [reactants]; explains & predicts behaviors of solutions in dynamic equilibrium. Only includes gases & aqueous species.

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8
Q

Keq

A

The ratio of products to reactants @ equilibrium; each species is raised to its stoichiometric coefficient

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9
Q

what is “Q”

A

can be calculated at any concentrations of reactants and products

◦ It’s a calculated value that relates the reactant and product concentrations at any given time during a reaction

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10
Q

define enthalpy vs entropy in terms of spontaneous, nonspontaneous, and temp-dependent reactions

A
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11
Q

what is Le Chatlier’s Principle

A

if an equilibrium mixture is disrupted, it will shift to favor the direction of the reaction that best facilitates a return to equilibrium
A rxn will shift in the direction that relieves the stress put on the system

◦ Aka the system shifts to relieve a stress and eventually regains equilibrium

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12
Q

ATP group transfers

A

covalent transfer of a portion of the ATP molecule to a substrate (ie enzyme active site) which then makes subsequent metabolic rxns involving this substrate more thermodynamically favorable

◦ Most of the ATP in a cell is produced by mitochondrial ATP synthase

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13
Q

Hydrolysis equation

A

ATP + H₂O → ADP + Pi + free energy (exergonic)

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14
Q

Adenosine triphosphate (ATP)

A

1 adenosine + 3 phosphate groups

◦ Adenosine is a nucleoside (adenine, a nitrogenous base, and a 5-carbon sugar ribose)

◦ Bonds b/t the phosphates = phosphoanhydride bonds (high energy)

◦ Formed from substrate-level phosphorylation & oxidative phosphorylation; ∼30 kJ/mol of energy

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15
Q

Oxidation half reactions

A

species that loses electrons (↑ in charge)

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16
Q

Reduction half-reactions

A

species that gains electrons (↓ in charge)

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17
Q

Oxidation

A

Loss of e⊖ , loss of H atom, gain of O atom

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18
Q

Reduction

A

Gain of e⊖, gain of H atom, loss of O atom

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19
Q

water soluble electron carriers

A

FADH₂, NADH, NADPH

◦ FAD (oxidized version) → accepts electrons (reduced) in glycolysis ‣ Side note- FADH₂ = reduced form

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20
Q

Fat soluble electron carriers

A

membrane proteins in the electron transport chain (FMN, CoQ, iron-sulfur complexes, cytochromes)

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21
Q

Flavoproteins

A

electron carriers in oxidation-reduction reactions = FAD, FMN

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22
Q

FAD

A

electron carrier (FADH₂ = reduced form) that is oxidized @ the 2ⁿᵈ complex in the ETC

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23
Q

FAD⁺

A

oxidizing agent in the TCA

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24
Q

FMN

A

a cofactor for the ETC’s Complex I enzymatic activity.

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25
carbohydrate formula
Simple monomeric sugars: Cn(H₂O)n
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Monosaccharides
single carbohydrate units; simplest = triose
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enantiomers
Same D- and L- forms of the same sugar
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α/β = anomeric configuration
The α form = anomeric carbon is in the axial position (OH below the plane) ‣ The β form = anomeric carbon is in the equatorial position (OH above the plane)
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Diastereomers
=nonsuperimposable configurations of molecules w/ similar connectivity; differs at least one but not all chiral carbons
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epimers
(different configuration @ exactly 1 chiral carbon)
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anomers
(subtype of epimers that differ at the chiral, anomeric carbon)
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Aldoses
carbohydrates that contain an aldehyde group as their most oxidized functional group
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Ketoses
has a ketone as their most oxidized functional group
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rules For classification as a carbohydrate:
◦ At least a 3-carbon backbone ◦ An aldehyde or a ketone group ◦ At least 2 hydroxyl groups
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D-fructose
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D-glucose
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D-galactose
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D-mannose
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Disaccharides
formed when two monosaccharides join together via a dehydration rxn (aka condensation rxn or dehydration synthesis). Here, the hydroxyl group of one monosaccharide combines with the H of another, releasing a molecule of water and forming a covalent bond = glycosidic linkage
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Sucrose
made from α-glucose and β-fructose joined @ the hydroxyl groups on the anomeric carbons (creating acetals); glycosidic bond is formed b/t C1 of the α-anomer of glucose & C2 of the β-anomer of fructose; Glu(α1→β2)Fru Glucose-α-1,2-fructose
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Lactose
requires lactase to be hydrolyzed; made from β-galactose and α/β-glucose joined by a 1,4-linkage; Gal(β1→4)Glu ◦ Galactose-β-1,4-glucose
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Maltose
two glucose molecules; produced when amylase breaks down starch; Glu(α1→4)Glu
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Polysaccharides
long chains of monosaccharides linked by glycosidic bonds
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Starch
main energy storage form for plants; made of glucose molecules joined by α-1,4-linkages
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Amylose
linear polymer of glucose; connected by α-1,4-glycosidic bonds; 20%-30% of starch
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Amylopectin
made of α-1,4-glycosidic bonds and α-1,6-glycosidic branches every 24-30 units; 70%-80% of starch
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Glycogen
main energy storage form for animals; has α-1,4-glycosidic bonds and α-1,6-glycosidic bonds
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Cellulose
main structural component for plant cell walls; main source of fiber for humans; made of repeating β-1,4glycosidic bonds
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Peptidoglycan
major component of bacterial cell walls; polymer of carbohydrates that have been modified w/ amino acids
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Chitin
made of N-acetylglucosamine; connected by β-1,4-glycosidic bonds; major component of cell walls in the exoskeletons of crustaceans, insects, and fungi
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key enzymes of glycolysis
hexokinase, phosphofructokinase, pyruvate kinase
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glycolysis converts _____ to make _____
Glycolysis = converts glucose (6-C) to 2 molecules of pyruvate (3-C each); 2 NADH made for every glucose
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glucokinase
converts glucose → glucose 6-phosphate | present in the pancreatic β-islet cells; is responsive to insulin in liver; catalyzes an irreversible reaction
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hexokinase
converts glucose → glucose 6-phosphate in peripheral tissues; is activated by insulin and inhibited by G6P and glucagon; also catalyzes an irreversible rxn
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phosphofructokinase-1 (PFK-1)
phosphorylates fructose 6-phosphate → fructose 1,6-ibsphosphate (rate-limiting step of glycolysis); is activated by AMP (indicates that energy is required → glycolysis is activated), fructose 2,6 bisphosphate, insulin (postprandial state); indirect stimulation by ↑ these levels; inhibited by ATP (energy is plentiful → slow glycolysis), citrate (indicates plentiful supply of intermediates for producing energy), low pH, in the liver only = glucagon = indirectly inhibits glycolysis by ↓ levels of fructose-2,6-bisphophate during fasting state; catalyzes an irreversible rxn
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phosphofructokinase-2 (PFK-2)
makes the F2,6-BP; activated by insulin; inhibited by glucagon
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glyceraldehyde-3-phosphate dehydrogenase
makes NADH which can feel into the ETC
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3-phosphoglycerate kinase
substrate-level phosphorylation putting Pi onto ADP → ATP
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pyruvate kinase
substrate level phosphorylation, putting Pi onto ADP → ATP; converts PEP → pyruvate; activated by fructose 1,6-bisphosphate in a feed-forward stimulation; inhibited by ATP and alanine; catalyzes an irreversible reaction
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pyruvate dehydrogenase
complex of enzymes that convert pyruvate → acetyl coA; activated by insulin; inhibited by acetyl-coA
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glycogen synthase
creates α-1,4-glycosidic links b/t glucose molecules
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branching enzymes
moves a block of oligoglucose form one chain and adds it to the growing glycogen as a new branch using an α-1,6 glycosidic link
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glycogen phosphorylase
removes a single glucose 1-phosphate molecule by breaking α-1,4 glycosidic links; activated by liver-glucagon to prevent low blood sugar; skeletal muscle— epinephrine & AMP to provide glucose for the muscle
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debranching enzyme
moves a block of oligoglucose from one branch and connects it to the chain using an α-1,4 glycosidic link and removes the branch point
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Aerobic decarboxylation
occurs in the mitochondrial matrix. Converts pyruvate (3-C) to an acetyl group (2-C). (Pyruvate decarboxylation / pyruvate oxidation) • Key enzyme: pyruvate dehydrogenase * 1 NADH made for every pyruvate * Only occurs in the presence of oxygen * Acetyl group attaches to Coenzyme A to make acetyl CoA
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Lactate dehydrogenase
oxidizes NADH → NAD⁺ which replenishes the oxidized coenzyme for glyceraldehyde-3-phosphate dehydrogenase.
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Lactic acid fermentation
Pyruvate [reduction] → lactate
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Alcohol fermentation
Pyruvate [reduction] → ethanol
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pyruvate carboxylase
converts pyruvate → oxaloacetate; activated by acetyl-coA from β-oxidation
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phosphoenolpyruvate carboxykinase (PEPCK)
converts oxaloacetate → phosphoenolpyruvate; activated by glucagon and cortisol; inhibited by insulin
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fructose 1,6-bisphophosphatase
converts fructose 1,6-bisphosphate → fructose 6-phosphate; activated directly by ATP and indirectly by glucagon (from ↓ levels of F2,6-BP); inhibited directly by AMP and indirectly by insulin (from ↑ levels of F2,6-BP); it bypasses phosphofructokinase; is the rate-limiting step of gluconeogenesis
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glucose 6-phosphatase
converts glucose 6-phosphate → free glucose
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Glycogenolysis
the catabolism of glycogen (glycogen break down); is induced by adrenaline
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Glycogen phosphorylase
= rate-limiting enzyme; converts the G1P → G6P Involves the removal of one glucose monomer via cleavage w/ an inorganic phosphate → glucose-1-phosphate which is then converted to glucose-6-phosphate * Process is caused by glucagon & epinephrine which stimulates glycogenolysis and are produced in response to low BGL * Takes place in the muscle (keeps the glucose) & liver tissue (releases the free glucose into the bloodstream)
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Acetyl CoA
a molecule that assists in the transfer of the CO₂ molecule from pyruvate to the TCA for energy production. It's produced by the oxidation of pyruvate (the end product of glycolysis). Acetyl-CoA acts as the link b/t glycolysis and the TCA. This step takes place in the mitochondrial matrix in eukaryotes, so pyruvate is first transported across the mitochondrial membrane. (Prokaryotes = cytoplasm).
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Fat metabolism
◦ In β-oxidation, fatty-CoA is broken down, 2C at a time, to make acetyl-CoA which feeds into the TCA ◦ β-oxidation also produces FADH₂ & NADH. These feed into the ETC
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Protein metabolism
The catabolism of some amino acids (phenylalanine, tyrosine, leucine, lysine, and tryptophan) can make acetyl-CoA
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TCA— takes place in the _____; produces ____
TCA consists of a series of rxns that produces 2 CO₂ molecules, 1 GTP/ATP, and reduced forms of NADH & FADH₂ • It takes place in the mitochondrial matrix; captures the energy stored in the bonds of acetyl-CoA from the products of glycolysis. The trapped energy from the TCA goes on to oxidative phosphorylation where its converted to the usable energy form ATP. AcetylCoA (main) & oxaloacetate are substrates for citrate synthase. Oxaloacetate can be produced by pyruvate carboxylase that converts pyruvate to oxaloacetate, however this is not as energy efficient. • In total for one round of the cycle (aka 1 pyruvate molecule) ◦ 1 GTP ◦ 3 NADH ◦ 1 FADH₂ ◦ 2 CO₂ ◦ 1 regenerated oxaloacetate molecule * Since each glucose molecule has 2 pyruvate molecules = 2 turns of the cycle so then we have 6 NADH & 3 FADH₂ per glucose * GTP produced becomes a phosphate donor to ADP → ATP Net yield of: ◦ 2 ATP/glucose molecule (per 2 acetyl CoA) = 4 ATP ◦ 3/turn = 6 NADH ◦ 1/turn = 2 FADH₂ ◦ 2/turn = 4 CO₂ ◦ 1 FADH₂ = 1.5 ATP ◦ 1 NADH = 2.5 ATP
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Phospholipids
Fatty acids bound to glycerol, phosphate, and other groups ◦ Amphipathic (hydrophilic + hydrophobic components) - used for cell membranes
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Cholesterol
◦ Fatty acids in ring form ◦ Cholesterol is amphipathic. The ring is nonpolar and the -OH head group is polar
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Eicosanoids
◦ Derived from arachidonic acid ◦ Structure = 5-C ring; 20 C overall ◦ Includes prostaglandins (signaling molecules) & thromboxanes (clotting)
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Lipases
(mouth- lingual lipase), pancreas (pancreatic lipase), and bile (liver) facilitate fat digestion and their catabolism into fatty acids. Bile
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Acetyl-CoA
(2C; inner mitochondrial matrix) = precursor for fatty acid synthesis. Acetyl-CoA is converted to citrate so that the citrate shuttle can transport it into the cytoplasm, where its broken back up to oxaloacetate & acetyl-CoA. For OAA to return to pyruvate, a C is lost as CO₂ and NADP⁺ is reduced to NADPH • Acetyl-CoAs are linked together → a large fatty acid chain = Palmitic acid (16C) = primary product of fatty acid synthesis in the body. Requires 8 acetyl-CoA molecules (since they're 2 C each). 7 ATP molecules are required for this rxn. 14 NADPH are required to reduce the carbonyl group in the acetyl-CoA to just C-C bonds; end up with 7 ADP & Pi & 14 NADP⁺ (thermodynamically unfavorable) = necessary to couple w/ ATP hydrolysis; charged with a CO₂ molecule
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Fatty acid synthase
the enzyme that polymerizes the manlonyl-CoA subunits together. It has 2 identical subunits, each w/ a thiol group. Acetyl-CoA attaches to one and malonyl-CoA attaches to the other. Decarboxylation makes the carbon very nucleophilic, so it wants to attack the other carbon that's nearby, making a C=C. The ultimate fate of these fatty acids is to be attached to a glycerol backbone to form a triacylglycerol molecule, that are sent off by the liver via VLDL to deliver these fats to rest of our tissues.
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Enteropeptidase
enzyme in the wall of the small intestine; activates trypsin which then activates chymotrypsin. These enzymes liberate the individual AAs that conveyed across the intestinal wall into the cell; they're eventually transported into the bloodstream for dispersal to the liver and cells throughout the body to make new proteins.
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Glycerol 3-phosphate shuttle:
E⊖ are transferred from NADH → DHAP making glycerol-3-phosphate. These e⊖ can then be transferred to mitochondrial FAD making FADH₂
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Malate-aspartate shuttle:
E⊖ are transferred from NADH → oxaloacetate making malate which can then cross the inner mitochondrial membrane and transfer the e⊖ to mitochondrial NAD⁺ making NADH.
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Describe/explain Complex I - IV in the ETC
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describe the differences between eukaryotes and prokaryotes for the ETC
* In eukaryotes, ETC is in the inner mitochondrial membrane | * In prokaryotes, ETC is in the plasma membrane
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Electron carriers Q & cytochrome C
Q * Oxidized form = ubiquinone * Reduced form (QH₂) = ubiquinol * Partially reduced form (intermediate) = ubisemiquinone (example of a semiquinone) * Has 2 carbonyl (C=O) groups which can be reduced to hydroxyl (—OH) groups; carries 2 e⊖ Cytochrome C * Much larger than Q; is a hemeprotein * Mechanism of e⊖ shuttling is for the iron atom to alternate b/t the +2 & +3 oxidation state * Has the heme group and it only carries 1 e⊖
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NADH, NADPH
◦ NADH is a very good e⊖ donor (its e⊖ are at a high energy level) ◦ NADPH is primarily produced in the oxidative part of the pentose phosphate pathway and is used in anabolic synthesis to make cholesterol, fatty acids, transmitter substances & nucleotides ◦ NADH & NADPH are both reductive agents
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Chemiosmotic coupling
the process that links the ETC (which creates an electrochemical gradient across the inner mitochondrial membrane) to the production of ATP through ATP synthase.
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Chemiosmosis
the movement of ions across a selectively permeable membrane, down their electrochemical gradient. It's used to generate 90% of the ATP made during aerobic glucose catabolism. (By H going through ATP synthase)
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Conformational coupling
the relationship b/t the proton gradient and ATP synthesis is indirect; ATP is released by the synthase as a result of a conformational change caused by the gradient. The F₁ portion of ATP synthase harnesses the gradient energy for chemical bonding from the spinning that occurs when protons go through it.
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Explain the regulation of the TCP and OP
* In both the TCA and OP, they are upregulated when the cell needs more ATP; negative feedback— certain products inhibit upstream steps. * 1st regulatory step: production of acetyl-CoA ◦ Pyruvate dehydrogenase complex converts pyruvate → acetyl-CoA and this is upregulated by high levels of AMP, CoA, and NAD⁺ (signs that the cell needs to make more energy). ◦ It is downregulated by ATP, NADH, and acetyl-CoA (indicates the cell has ample energy) ◦ High levels of fatty acids = major negative regulator of the PDC since these fatty acids have the potential to become acetyl-CoA • TCA is regulated @ 3 major exergonic steps: ◦ 1) formation of citrate ‣ Upregulated: high levels of ADP ‣ Downregulated: ATP, NADH, [citrate, and succinyl-CoA = negative feedback] ◦ 2) Conversion of isocitrate → α-ketoglutarate ‣ Upregulated: ADP ‣ Downregulated: ATP ◦ 3) α-ketoglutarate → succinyl-CoA ‣ Upregulated: Ca²⁺ ‣ Downregulated: NADH & [succinyl-CoA = negative feedback] • Regulation of OP: ◦ Upregulated via upstream elements like the TCA & glycolysis; large amount of ADP present ◦ Downregulated: ATP
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Hormones
signals produced in the endocrine system & released into bodily fluids to be transferred to the target cells.
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Insulin
released by the β cells of the pancreas; stimulates glucose uptake by target cells; is released upon the entry of glucose into pancreatic β cells through the GLUT2 glucose transporters.
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Glucagon
``` synthesized by α-cells of the pancreas; compensatory ↑ in BGL by causing the liver to convert stored glycogen → glucose which is then released into the bloodstream. Glucagon antagonizes insulin's action on BGL (aka glucagon and insulin forms a feedback system that ensures blood glucose homeostasis if properly regulated) promotes lipolysis (breakdown of triglycerides) by activating protein kinase A → activates hormone-sensitive lipase → releases free fatty acids & glycerol into the bloodstream. Glycerol can enter the TCA (s/p conversion to glycerol 3-phosphate by glycerol kinase) in the liver & kidneys ```
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Hormones that control hunger & satiety
ghrelin, orexin, and leptin