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Ch. 18-19
Ch. 18-19
125
Biochemistry
Undergraduate 3
01/29/2018

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Term
the one way link between glycolysis and cellular respiration
Definition
pyruvate dehydrogenase
Term
what happens to pyruvate in anaerobic conditions?
Definition
converted to lactic acid or ethanol
Term
what happens to pyruvate in aerobic conditions
Definition
converted into acetyl coenzyme A (acetyl CoA), which enters the citric acid cycle
Term
what happens to pyruvate when a cell's oxygen supply is insufficient?
Definition
gets converted to lactate
Term
simplified overview of the citric acid cycle
Definition
[image]
Term
pyruvate dehydrogenase complex
Definition
oxidatively decarboxylates pyruvate to form acetyl CoA
Term
the chemical rxn of the pyruvate dehydrogenase complex
Definition
pyruvate + CoA + NAD+ --> acetyl CoA + CO2 NADH + H+
Term
where oxidative decarboxylation of pyruvate occurs
Definition
matrix of mitochondria
Term
where citric acid cycle occurs
Definition
matrix of mitochondria
Term
the rxn E1 in the pyruvate dehydrogenase complex catalyzes
Definition
oxidative decarboxylation of pyruvate
Term
the rxn E2 in the pyruvate dehydrogenase complex catalyzes
Definition
transfer of acetyl group to CoA
Term
the rxn E3 in the pyruvate dehydrogenase complex catalyzes
Definition
regeneration of the oxidized form of lipoamide
Term
prosthetic group for E1
Definition
TPP
Term
prosthetic group for E2
Definition
lipoamide
Term
prosthetic group for E3
Definition
FAD
Term
the link between glycolysis and the citric acid cycle
Definition
the irreversible conversion of pyruvate into acetyl CoA
Term
depiction of the link between glycolysis and the citric acid cycle
Definition
[image]
Term
catalytic coenzymes
Definition
function as enzymes; not permanently altered by participation in rxn
Term
stoichiometric coenzymes
Definition
they function as substrates
Term
the 3 steps of the conversion of pyruvate into acetyl CoA
Definition
1: decarboxylation
2: oxidation
3: the transfer of the resultant acetyl group to CoA
Term
depiction of the conversion of pyruvate into acetyl CoA
Definition
[image]
Term
flavoproteins
Definition
proteins tightly associated with FAD
Term
what allows lipoamide to move between different active sites?
Definition
flexible linkages
Term
depiction of the structure of the pyruvate dehydrogenase complex
Definition
[image] -has 8 E23) trimers at the core to make a hollow cube -the cube is surrounded by 12 E3 (αβ) dimers and 24 E12β2)
Term
depiction of the structure of the E2 within the pyruvate dehydrogenase complex
Definition
[image]

contains 8 trimers
Term
depiction of the domains within each E23) trimer
Definition
[image]
Term
how the pyruvate dehydrogenase (PDH) complex differs in mammals
Definition
the core contains another protein, E3-binding protein (E3-BP)
Term
depiction of the reactions of the pyruvate dehydrogenase (PDH) complex
Definition
[image]
Term
what happens when the pyruvate dehydrogenase (PDH) complex is missing the E3-binding protein (E3-BP)?
Definition
the PDH complex has greatly reduced activity
Term
how do the 3 distinct active sites of the PDH complex work in concert?
Definition
the flexible lipoamide arm of the E2 subunit carries substrate from active site to active site
Term
how acetyl CoA is formed
Definition
oxidative decarboxylation of pyruvate to acetyl CoA
Term
2 principal fates of the carbons in acetyl CoA
Definition
1: oxidation to CO2 by the citric acid cycle with the concomitant generation of energy 2: incorporation into lipid, because acetyl CoA is an essential precursor for lipid synthesis
Term
simple depiction of the conversion of glucose to pyruvate to acetyl CoA to CO2 and fatty acids
Definition
[image]
Term
the key means of regulation of the PDH complex in eukaryotes
Definition
covalent modification in the form of phosphorylation
Term
what phosphorylation does to the PDH complex
Definition
deactivates it
Term
what dephosphorylation does to the PDH complex
Definition
activates it
Term
PDH kinase
Definition
catalyzes phoisphorylation of PDH complex to deactivate it
Term
PDH phosphatase
Definition
catalyzes dephosphorylation of PDH complex to reactivate it
Term
depiction of the regulation of the PDH complex
Definition
[image]
Term
PDH phosphatase is activated by...
Definition
Ca2+
Term
depiction of PDH regulation under high energy charge
Definition
[image]
Term
depiction of PDH regulation under low energy charge
Definition
[image]
Term
fuel molecule
Definition
carbon compounds capable of being oxidized
Term
the function of the citric acid cycle
Definition
the harvesting of high energy electrons from carbon fuels
Term
how the citric acid cycle begins
Definition
the 2-carbon acetyl unit condenses with a 4-carbon oxaloacetate to yield the 6-Carbon tricarboxylic acid citrate
Term
simple depiction of an overview of the citric acid cycle
Definition
[image]
Term
oxidative phosphorylation
Definition
forming ATP by by the transfer of electrons from NADH or FADH2 to O2 by a series of electron carriers
Term
electron transport chain
Definition
series of membrane proteins electrons from NADH or FADH2 floe thru to generate proton gradient
Term
what proton gradient is used for
Definition
to generate ATP from ADP and inorganic phosphate
Term
the stagers of cellular respiration
Definition
1: citric acid cycle
2: oxidative phosphorylation
Term
depiction of cellular respiration
Definition
[image]
Term
the 2 stages of the citric acid cycle
Definition
1: oxidizing 2 carbon atoms to gather energy rich electrons
2: regenerating oxaloacetate and harvesting energy rich electrons
Term
oxidative decarboxylation
Definition
citrate being oxidized by releasing 2 CO2 to yield a 4-carbon molecule and high transfer potential electrons captured as 2 molecules of NADH
Term
how the citric acid cycle begins
Definition
joining of 4-Carbon oxaloacetate with the 2-carbon acetyl group acetyl CoA to form citryl CoA, which gets hydrolyzed to form citrate
Term
depiction of the formation of citrate
Definition
[image]

citrate synthase involved in both steps
Term
citrate synthase
Definition
catalyzes the merging of 4-carbon oxaloacetate to the 2-carbon acetyl group to form citrate
Term
synthase
Definition
enzyme that catalyzes a synthetic rxn in which 2 subunits are joined usually without the direct participation of ATP or another nucleoside triphosphate
Term
this powers the synthesis of citrate
Definition
the hydrolysis of the thioester in citryl CoA
Term
composition of mammalian citrate synthase
Definition
dimer of identical 49-kDa subunitswith a cleft present between the large and small domains of the subunits, adjacent to the subunit interface
Term
the reason for ordered binding in citrate synthase
Definition
because oxaloacetate induces a major structural rearrangement leading to the creation of a binding site for acetyl CoA
Term
depiction of the structure of citrate synthase
Definition
[image]
Term
how the wasteful hydrolysis of acetyl CoA is prevented
Definition
because citrate synthase is well suited for the hydrolysis of citryl CoA but not acetyl CoA
Term
why citrate is isomerized into isocitrate
Definition
because the hydroxyl (-OH) group in citrate is not properly located in the molecuule for the oxidative decarboxylations that follow
Term
how citrate is isomerized into isocitrate
Definition
dehydrateion, then hydration
Term
aconitase
Definition
catalyzes isomerization of citrate into isocitrate
Term
depiction of how citrate is isomerized into isocitrate
Definition
[image]

aconitase involved in both steps
Term
isocitrate dehydrogenase
Definition
catalyzes the oxidative decarboxylation of isocitrate to α-ketoglutarate
Term
net rxn that oxidizes and decarboxylates isocitrate to α-ketoglutarate
Definition
isocitrate + NAD+ --> α-ketoglutarate + CO2 + NADH
Term
depiction of the oxidative decarboxylation of isocitrate to α-ketoglutarate
Definition
[image]

catalyzed by isocitrate dehydrogenase
Term
depiction of the oxidative decarboxylation of α-ketoglutarate
Definition
[image]
Term
α-ketoglutarate dehydrogenase complex
Definition
catalyzes the oxidative decarboxylation of α-ketoglutarate

structurally similar to PDH
Term
how the citric acid cycle produces ATP
Definition
the cleavage of the thioester of succinyl CoA is coupled with the phosphorylation of ADP
Term
succinyl CoA synthetase (succinate thiokinase)
Definition
catalyzes the cleavage of the thioester of succinyl CoA that gets coupled with the phosphorylation of ADP
Term
depiction of the cleavage of the thioester of succinyl CoA that gets coupled with the phosphorylation of ADP to yield ATP
Definition
[image]

catalyzed by succinyl CoA synthetase (succinate thiokinase)
Term
the 2 forms of succinyl CoA synthetase (succinate thiokinase) in mammals
Definition
1: ADP acceptor
2: GDP acceptor
Term
tissue where the ADP accepting version of succinyl CoA synthetase (succinate thiokinase) dominates in mammals
Definition
tissues that perform lost of cellular respiration, such as skeletal and heart muscle
Term
tissue where the GDP accepting version of succinyl CoA synthetase (succinate thiokinase) dominates in mammals
Definition
tissues that perform lost of anabolic rxns, such as liver
Term
how the GDP-requiring form of succinyl CoA synthetase (succinate thiokinase) is believed to work
Definition
in reverse of the direction observed in the citric acid cycle; that is, GTP is used to power the synthesis of succinyl CoA, which is a precursor for heme synthesis
Term
substrate-level phosphorylation
Definition
generation of ATP a rxn in which a high-phosphoryl-transfer-potential compound (succinyl phosphate) transfers the phosphate to ADP to generate ATP
Term
types of rxns glycolysis uses to form ATP
Definition
substrate-level phosphorylation rxns
Term
depiction of the rxn mechanism of succinyl CoA synthetase
Definition
[image]
Term
how oxaloacetate is regenerated
Definition
by the oxidation of succinate
Term
depiction of the oxidation of succinate
Definition
[image]
Term
how succinate is oxidized to regenerate oxaloacetate
Definition
1: oxidation
2: hydration
3: 2nd oxidation
Term
succinate dehydrogenase
Definition
catalyzes the oxidation of succinate to fumarate
Term
depiction of the function of succinate dehydrogenase
Definition
[image]
Term
how succinate dehydrogenase differs from other enzymes in the citric acid cycle
Definition
it is embedded in the inner mitochondrial membrane in association with the electron transport chain, which is also set in the inner mitochondrial membrane
Term
the link between the citric acid cycle and ATP formation
Definition
the electron transport chain
Term
fumarase
Definition
catalyzes hydration of fumarate to form L-malate
Term
depiction of the function of fumarase
Definition
[image]
Term
malate dehydrogenase
Definition
catalyzes oxidation of malate to form oxaloacetate
Term
depiction of the function of malate dehydrogenase
Definition
[image]
Term
how the energetically unfavorable oxidation of malate is driven
Definition
driven by the use of the products; oxaloacetate by citrate synthase and NADH by the electron-transport chain
Term
the net rxn of the citric acid cycle
Definition
acetyl CoA + 3 NAD+ + FAD + ADP + pi + 2 H2O --> 2 CO2 + 3 NADH + FADH2 + ATP + 2 H+ + CoA
Term
depiction of the complete citric acid cycle
Definition
[image]
Term
substrate channeling
Definition
rxn products passing directly from one active site to the nest thru connecting channels
Term
the key catabolic function of the citric acid cycle
Definition
the production of high energy electrons in the form of NADH and FADH2
Term
does molecular oxygen participate directly in the citric acid cycle?
Definition
no
Term
why the citric acid cycle operates only under aerobic conditions
Definition
because NAD+ and FAD can be regenerated in mitochondria only by the transfer of electrons to molecular oxygen
Term
how NAD+ and FAD can be regenerated in mitochondria
Definition
only by the transfer of electrons to molecular oxygen
Term
why glycolysis can proceed under anaerobic conditions
Definition
because NAD+ is regenerated in the conversion of pyruvate into lactate or ethanol
Term
depiction of the control of the citric acid cycle
Definition
[image]
Term
the primary control points to control the rate of the citric acid cycle
Definition
-isocitrate dehydrogenase
-α-ketoglutarate dehydrogenase
Term
the citric acid cycle is regulated primarily by the concentrations of...
Definition
-ATP
-NADH
Term
something succinyl CoA from the citric acid cycle is used to make
Definition
the heme groups of hemoglobin and myoglobin
Term
something α-ketoglutarate from the citric acid cycle is used to make
Definition
some amino acids
Term
something oxaloacetate from the citric acid cycle is used to make
Definition
some amino acids
Term
depiction of the biosynthetic roles of the citric acid cycle
Definition
[image]
Term
when the citric acid cycle creates intermediates for biosynthesis
Definition
when the energy needs of the cell are met
Term
how are citric acid cycle intermediates replenished when they are drawn out for biosynthesis
Definition
conversion of pyruvate to oxaloacetate
Term
pyruvate carboxylase
Definition
catalyzes the conversion of pyruvate to oxaloacetate
Term
rxn that converts pyruvate to oxaloacetate
Definition
pyruvate + CO?2 + ATP + H2O --> oxaloacetate + ADP + Pi + 2 H+
Term
depiction of pyruvate carboxylase replenishing the citric acid cycle
Definition
[image]
Term
when pyruvate carboxylase is active
Definition
only in the presence of acetyl CoA
Term
what happens to oxaloacetate when the energy charge is high?
Definition
oxaloacetate gets converted into glucose
Term
what happens to oxaloacetate when the energy charge is low?
Definition
oxaloacetate replenishes the citric acid cycle
Term
anaplerotic rxn
Definition
rxn that leads to the net synthesis, or replenishment, of pathway components
Term
example of an anaplerotic rxn
Definition
synthesis of oxaloacetate by the carboxylation of pyruvate
Term
the fate of acetyl CoA that enters the citric acid cycle
Definition
oxidation to CO2 and H2O
Term
what the glyoxylate cycle enables plants and bacteria to do
Definition
convert fats into carbohydrates
Term
some ways the glyoxylate cycle differs from the citric acid cycle
Definition
-bypasses the 2 decarboxylation steps of the cycle
-2 acetyl CoA's enter the cycle instead of just 1
Term
isocitrate lyase
Definition
cleaves isocitrate into succinate and glyoxylate
Term
malate synthase
Definition
catalyzes the condensation of acetyl CoA with glyoxylate to form malate
Term
depiction of the glyoxylate pathway
Definition
[image]
Term
glyoxysomes
Definition
organelles in plants where the glyoxylate pathway takes place
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