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Biochem Test 2
Info for Biochem Test 2
589
Biochemistry
Undergraduate 3
01/05/2018

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Term
composition of carbohydrates
Definition
they are C based molecules rich in hydroxyl (-OH) groups
Term
empirical formula for many carbohydrates
Definition
(CH2O)n
Term
why carbohydrates can be used for functions as simple as energy storage to as complex as cell-cell recognition
Definition
because of the vast array of 3d structures that can arise due to the variety of monosaccharides and the multiplicity of linkages that form within carbohydrate polymers
Term
why carbohydrates can form a variety of 3d structures
Definition
because of the vast array of 3d structures that can arise due to the variety of monosaccharides and the multiplicity of linkages that form within carbohydrate polymers
Term
monosaccharides
Definition
aldehydes or ketones that have 2 or more hydroxyl (-OH) groups
Term
ketose
Definition
carbohydrate that contains a ketone group
Term
aldose
Definition
carbohydrate that contains an aldehyde group
Term
trioses
Definition
carbohydrates that contain 3 C's
Term
constitutional isomers
Definition
have identical molecular formula, but differ in how the atoms are ordered
Term
stereoisomers
Definition
isomers that differ in spatial arrangement
Term
enantiomers
Definition
mirror-image isomers
Term
diastereoisomers
Definition
stereoisomers that are not mirror images of each other; they're not enantiomers
Term
epimers
Definition
diastereoisomers that differ in one of several C atoms
Term
anomers
Definition
diastereoisomers that differ at a new asymmetric C atom formed on ring closure
Term
the predominant forms of some monosaccharides in solution
Definition
cyclic rings instead of open chains
Term
the chemical basis for ring formation
Definition
an aldehyde can react with an alcohol to form a hemiacetal
Term
hemiacetal
Definition
formed when an aldehyde complexes with an alcohol
Term
hemiketal
Definition
formed when a ketone complexes with an alcohol
Term
α anomer
Definition
OH groups on same side of ring
Term
β anomer
Definition
OH groups on different sides of ring
Term
anomeric C atom
Definition
the C atom where the molecule can be either the α or β anomer
Term
axial bonds
Definition
substituents that are nearly perpendicular to the ring
Term
equatorial bonds
Definition
nearly parallel to the plane of the ring
Term
which tend to be more crowded? axial or equatorial substituents?
Definition
axial
Term
glycosidic bonds
Definition
bonds that join monosaccharides to alcohols and amines
Term
O-gluycosidic bond
Definition
bond between the anomeric C atom of a glucose and the O atom of an alcohol
Term
N-glycosidic bond
Definition
bond between the anomeric C atom of a glucose and the N atom of an amine
Term
3 common reactants in the modification of monosaccharides
Definition
-alcohols
-amines
-phosphates
Term
the type of bond between adjacent monosaccharides in oligo- and polysaccharides
Definition
O-glycosidic bond
Term
glycosyltransferases
Definition
catalyze the formation of glycosidic bonds
Term
glycoside
Definition
carbohydrate that has a substituent on it attached by a glycosidic bond
Term
some common disaccharides
Definition
-sucrose
-lactose
-maltose
Term
some storage forms of glucose
Definition
-glycogen
-starch
Term
homopolymer
Definition
polysaccharide in which all the monomer units are the same
Term
glycogen
Definition
a polysaccharide that is a storage form of glucose in animals; it's the most common storage form of glucose in animal cells
Term
in human tissues, glycogen is most common in...
Definition
muscle and liver
Term
starch
Definition
homopolymer storage form of glucose in plants
Term
types of starch
Definition
-amylose
-amylopectin
Term
amylose
Definition
unbranched form of starch, consisting of glucose molomers in α-1,4 linkage
Term
amylopectin
Definition
branched form of starch having about 1 α-1,6 linkage per 30 α-1,4 linkages
Term
α-amylase
Definition
enzyme secreted by the salivary glands that readily breaks down amylose, amylopectin, and glycogen
Term
cellulose
Definition
structural polysaccharide in plants that is made of glucose monomers joined by a β-1,4 linkage
Term
what α and β linkages do for structure of polysaccharides
Definition
β linkages favor straight chains with H bonding between the strands while α linkages favor bent and helical structures, which are better for storage
Term
glycoprotein
Definition
protein with a carbohydrate covalently attached to it
Term
amount of glycoproteins in the proteome
Definition
glycoproteins are 50% of the proteome
Term
3 classes of glycoproteins
Definition
-glycoproteins
-proteoglycans
-mucins/mucoproteins
Term
composition of glycoproteins
Definition
protein component is the largest constituent by weight
Term
function of glycoproteins
Definition
many, such as components of cell membranes, where they take part in processes such as cell adhesion and binding of sperm to eggs
Term
composition of proteoglycans
Definition
protein component is conjugated to a type of polysac called a glycosyaminoglycan

carbohydrates take up a significant portion of proteoglycans
Term
function of proteoglycans
Definition
-structural components
-lubricants
Term
gluycosaminoglycan
Definition
type of polysac that a proteoglycan is conjugated to
Term
composition of mucins/mucoproteins
Definition
predominantly carbohydrate
Term
function of mucins/mucoproteins
Definition
lubricants
Term
what determines polysac structure?
Definition
glycosidic bonds
Term
amino acids that carbohydrates may be linked to
Definition
-asparagine
-serine
-threonine
Term
glycosylation
Definition
linking of carbohydrates to asparagine, serine, or threonine
Term
some structural functions of proteoglycans
Definition
-connective tissue
-mediate adhesion of cells to the extracellular matrix
-bind factors that regulate cell proliferation
Term
the properties of proteoglycans are determined primarily by...
Definition
the glycosaminoglycan component
Term
composition of many glycosaminoglycans
Definition
made of repeating units of disaccharides containing a derivative of an amino sugar, either glucosamine or galactosamine

at least one of the 2 sugars in the repeating unit has a negatively charged sulfate group
Term
glycan-binding proteins
Definition
they bind specific carbohydrate structures on neighboring cell surfaces
Term
lectins
Definition
they facilitate cell-cell contact
Term
how lectins facilitate cell-cell contact
Definition
the lectins on the surface of one cell interact with arrays of carbohydrates displayed on the surface of another cell
Term
the 3 stages of generating energy from the oxidation of food
Definition
1: digestion (large molecules being broken down into smaller molecules)
2: numerous small molecules being degraded into a few simple units that play a central role in metabolism; most of these simple units are converted into acetyl CoA
3: producing ATP from the complete oxidation of acetyl CoA; this involves the citric acid cycle and oxidative phosphorylation
Term
digestion
Definition
large molecules being broken down into smaller molecules
Term
citric acid cycle aka...
Definition
-tricarboxylic acid (TCA) cycle
-Krebs cycle
Term
catabolism
Definition
the extraction of energy from fuels
Term
depiction of the stages of catabolism
Definition
[image]
Term
3 things living organisms need energy for
Definition
1: mechanical work in muscle contraction and cellular movements
2: active transport of molecules and ions
3: synthesis of macromolecules and other biomolecules from simple precursors
Term
phototrophs
Definition
photosynthetic organisms that obtain energy by trapping sunlight in a chemical form
Term
chemotrophs
Definition
organisms that obtain energy thru the oxidation of C fuels
Term
some basic principles that underlie energy flow in all living systems
Definition
1: fuels are degraded and large molecules are constructed step by step in a series of linked rxns called metabolic pathways
2: an energy currency common to all life forms, ATP, links energy releasing pathways with energy requiring pathways
3: the oxidation of C fuels powers the formation of ATP
4: although there are many metabolic pathways, a limited number of types of reactions and particular intermediates are common to many pathways
5: metabolic pathways are highly regulated to allow the efficient use of fuels and to coordinate biosynthetic processes
Term
metabolic pathways
Definition
series of linked rxns in which fuels are degraded and large molecules are constructed
Term
function of ATP
Definition
links energy releasing pathways with energy requiring pathways

this is the energy currency
Term
what powers the formation of ATP?
Definition
the oxidation of C fuels
Term
metabolism
Definition
a linked series of chemical rxns that begins with a particular biomolecule and converts it into some other required biomolecule in a carefully defined fasion
Term
intermediary metabolism
Definition
defined metabolic pathways in the cell
Term
2 broad classes of metabolic pathways
Definition
1: those that convert energy from fuel into biologically useful forms (catabolic)
2: those that require input of energy to proceed (anabolic)
Term
catabolism
Definition
breaking down fuels to release cellular energy
Term
anabolism
Definition
using energy to synthesize biomolecules
Term
amphibolic
Definition
can be either anabolic or catabolic, depending on conditions in the cell
Term
an important principle of metabolism
Definition
although biosynthetic and degradative pathways often have rxns in common, the regulated, irreversible reactions of each pathway are almost always distinct from each other
Term
how anabolic and catabolic rxns interact
Definition
energy released from catabolic rxns is used to power anabolic rxns
Term
2 criteria a metabolic pathway has to meet
Definition
1: the individual rxns must be specific
2: the entire set of rxns that constitute the pathway must be thermodynamically favored
Term
the nature of a rxn depends on...
Definition
-the nature of the reactants and products
-the concentrations of reactants and products
Term
a thermodynamically unfavorable rxn can be driven by...
Definition
a thermodynamically favorable rxn
Term
ATP can be thought of as...
Definition
the currency that facilitates the commerce of the cell (metabolism)
Term
ATP functions as a...
Definition
free energy donor
Term
composition of ATP
Definition
adenine with a triphosphate unit attached
Term
why ATP is energy rich
Definition
because its triphosphate unit contains 2 phosphoanhydride linkages
Term
phosphoanhydride linkages
Definition
formed between 2 phosphoryl groups accompanied by the loss of a water molecule
Term
how energy is released from ATP
Definition
hydrolyzing ATP into ADP
Term
structure of ATP
Definition
[image]
Term
Pi
Definition
orthophosphate
Term
PPi
Definition
pyrophosphate
Term
phosphates that can be released from ATP hydrolysis
Definition
-Pi -PPi
Term
when ATP is formed from ADP and Pi in chemotrophs
Definition
when fuel molecules are oxidized
Term
when ATP is formed from ADP and Pi in phototrophs
Definition
when light is trapped
Term
how an otherwise unfavorable rxn can be made possible
Definition
by coupling it to ATP hydrolysis
Term
standard free energy of hydrolysis
Definition
the energy released when the phosphorylated compound transfers the phosphoryl group to water under standard conditions
Term
magnitude of ΔG⁰' vs. phosphoryl-transfer potential
Definition
proportional
Term
factors that differentiate the stability of the reactants and products
Definition
1: electrostatic repulsion
2: resonance stabilization
3: increase in entropy
4: stabilization due to hydration
Term
how electrostatic repulsion affects stability of reactants and products
Definition
ATP has 4 negative charges in close proximity to each other; the repulsion between them is reduced when ATP is hydrolyzed
Term
how resonance stabilization affects stability of reactants and products
Definition
phosphate has greater resonance stabilization when released from ATP
Term
how increase in entropy affects stability of reactants and products
Definition
products of ATP hydrolysis have 2 molecules instead of 1
Term
how stabilization due to hydration affects stability of reactants and products
Definition
water binds to ADP and Pi, making the synthesis of ATP less favorable
Term
why ATP is an efficient carrier of phosphoryl groups
Definition
because its phosphoryl-transfer potential is intermediate among the biologically important phosphorylated molecules
Term
characteristics of phosphate and its esters that render it useful for biochemical systems
Definition
1: they are thermodynamically unstable, but kinetically stable, thus their energy can be manipulated by enzymes
2: the stability of phosphate esters is due to the negative charges that make them resistant to hydrolysis in the absence of enzymes
3: their kinetic stability makes them ideal regulatory molecules, added to proteins by kinases and removed only by phosphatases
Term
one of the primary roles of catabolism
Definition
generating ATP
Term
is ATP an immediate or ling term donor of free energy?
Definition
immediate
Term
the fundamental mode of energy exchange in biological systems
Definition
the ATP-ADP cycle
Term
depiction of the ATP-ADP cycle
Definition
[image]
Term
some things that require ATP
Definition
-motion
-active transport
-biosynthesis
-signal amplification
Term
some things that turn ADP into ATP
Definition
-oxidation of fuel molecules
-photosynthesis
Term
redox rxns
Definition
rxns where one atom loses electrons (oxidation) and another gains electrons (reduction)
Term
reduction of a C atom vs. free energy released by its oxidation
Definition
proportional

the more reduced it tis to begin with, the higher the free energy released by its oxidation
Term
why fats are more efficient fuels than carbohydrates
Definition
because the C's in fats are more reduced
Term
what happens to the energy of oxidation in ATP synthesis?
Definition
it is initially trapped as a high-phosphoryl-transfer-potential compound and then used to form ATP
Term
what C oxidation energy is used for in the formation of ATP
Definition
-creating a compound with high phosphoryl-transfer potential
-creating an ion gradient
Term
what is glucose usually metabolized into?
Definition
CO2 and water; this happens when oxygen delivery is adequate
Term
what happens when ATP needs outpace oxygen delivery?
Definition
glucose is metabolized to lactate
Term
some speculated reasons for glucose being such a prominent fuel as opposed to other monosaccharides
Definition
1: it is one of several monosacs formed from formaldehyde under prebiotic conditions, so it might have been available for primitive biochem systems
2: glucose is a stable hexose because the hydroxyl groups and hydroxyymethyl group are all equatorial, minimizing steric clashes
3: relative to other monosacs, glucose has a low tendency to glycolysate proteins; this is due to its strong tendency to form rings
Term
why glucose might have been available for primitive biochem systems
Definition
because it is one of several monosacs formed from formaldehyde under prebiotic conditions
Term
why glucose is a stable hexose
Definition
because the hydroxyl groups and hydroxyymethyl group are all equatorial, minimizing steric clashes
Term
why glucose has a low tendency to glycolysate proteins
Definition
because of its strong tendency to form rings
Term
where glycolysis occurs in eukaryotic cells
Definition
cytoplasm
Term
what glucose is converted to in gylycolysis
Definition
2 molecules of pyruvate with the concomitant generation of 2 molecules of ATP
Term
stage 1 of glycolysis begins with...
Definition
the conversion of glucose into fructose 1,6-biphosphate
Term
the 3 steps of converting glucose into fructose 1,6-biphosphate
Definition
1: phosphorylation
2: isomerization
3: 2nd phosphorylation
Term
the strategy of the initial steps of glycolysis
Definition
to trap the glucose in the cell and form a compound that can be readily cleaved into phosphorylated 3-C units
Term
stage 1 of glycolysis is completed by...
Definition
the cleavage of fructose 1,6-biphosphate into 2 phosphorylated, 3-C fragments
Term
what happens in stage 1 of glycolysis?
Definition
glucose is trapped, destabilized, and cleaved into 2 interconvertible 3-C molecules, generated by the cleavage of 6-C fructose
Term
what happens in stage 2 of glycolysis?
Definition
the 2 3-C units are oxidized to pyruvate, generating ATP
Term
depiction of the stages of glycolysis
Definition
[image]
Term
the one principal fate glucose has inside the cell
Definition
it is phosphorylated by ATP to form glucose 6-phosphate
Term
hexokinase
Definition
catalyzes the transfer of the phosphoryl group from ATP to the hydroxyl group on C6 of glucose

traps glucose in the cell and begins glycolysis
Term
depiction of the function of hexokinase
Definition
[image]
Term
kinase
Definition
enzyme that catalyzes the transfer of a phosphoryl group from ATP to an acceptor
Term
something kinases require for activity
Definition
divalent metal cations, such as Mg2+ and Mn2+ this forms a complex with ATP
Term
fructose 1,6-biphosphate is generated from...
Definition
glucose 6-phosphate
Term
phosphoglucose isomerase
Definition
catalyzes the isomerization of glucose 6-phosphate to to fructose 6-phosphate

this is the conversion of an aldose to a ketose
Term
depiction of the function of phosphoglucose isomerase
Definition
[image]
Term
what happens to fructose 6-phosphate during glycolysis?
Definition
gets phosphorylated by ATP to fructose 1,6-biphosphate
Term
phosphofructokinase (PFK)
Definition
catalyzes the phosphorylation of fructose 6-phosphate to fructose 1,6-biphosphate
Term
depiction of the function of phosphofructokinase (PFK)
Definition
[image]
Term
an allosteric enzyme that is the key regulatory enzyme for glycolysis
Definition
phosphofructokinase
Term
what the oxidation of aldehyde does in glycolysis
Definition
powers the formation of a compound having high phosphoryl-transfer potential
Term
glyceraldehyde 3-phosphate dehydrogenase
Definition
catalyzes the conversion of glyceraldehyde 3-phosphate into 1,3-biphosphoglycerate
Term
derhydrogenase
Definition
enzyme that catalyzes redox rxns, often transferring a hydride ion from a donor molecule to NAD+ or transferring a hydride ion from NADH to an acceptor molecule
Term
depiction of the function of glyceraldehyde 3-phosphate dehydrogenase
Definition
[image]
Term
the energy of C oxidation is transferred as...
Definition
high phosphoryl-transfer potential
Term
detailed depiction of the conversion of glyceraldehyde 3-phosphate into 1,3-biphosphoglycerate
Definition
[image]
Term
what couples the aldehyde oxidation to drive the formation of the acyl phosphate?
Definition
an enzyme that forms a thioester intermediate, replacing the H on the aldehyde group and later being replaced by an orthophosphate group
Term
depiction of the function of the thioester intermediate that couples the aldehyde oxidation to drive the formation of the acyl phosphate
Definition
[image]

reduces the activation energy; intermediate more stable than reactants, but more stable than products, making it spontaneous
Term
in glycolysis, ATP is formed by...
Definition
phosphoryl transfer from 1,3-biphosphoglycerate
Term
phosphoglycerate kinase
Definition
catalyzes the transfer of the phosphoryl group from the acyl phosphate of 1,3-biphosphoglycerate to ADP, which yields ATP and 3-phosphoglycerate
Term
depiction of the function of phodsphoglycerate kinase
Definition
[image]
Term
how additional ATP is generated at the end of glycolysis
Definition
by converting 3-phosphoglycerate into pyruvate, which forms a 2nd molecule of ASTP
Term
depiction of 3-phosphoglycerate being converted into pyruvate to form ATP
Definition
[image]
Term
phosphoglycerate mutase
Definition
shifts the position of the phosphoryl group to convert 3-phosphoglycerate into 2-phosphoglycerate
Term
depiction of the function of phosphoglycerate mutase
Definition
[image]
Term
mutase
Definition
catalyzes the intramolecular shift of a chemical group
Term
enolase
Definition
catalyzes the formation of the enol phosphate phosphoenolpyruvate (PEP), which is unstable and has a high phosphoryl transfer potential
Term
depiction of the function of enolase
Definition
[image]
Term
pyruvate kinase
Definition
catalyzes the irreversible transfer of a phosphoryl group from phosphoenolpyruvate (PEP) to ADP
Term
depiction of the function of pyruvate kinase
Definition
[image]
Term
the net rxn of the transformation of glucose into pyruvate
Definition
glucose + 2 Pi + 2 ADP + 2 NAD+ ---> 2 pyruvate + 2 ATP + 2 NADH + 2 H+ + 2 H2O
Term
why a glycolysis pathway that ends with pyruvate will not proceed
Definition
because this would result in oxidation-reduction imbalance
Term
the final process in glycolysis
Definition
the regeneration of NAD+ thru the metabolism of pyruvate
Term
3 rxns of pyruvate that can occur in living things
Definition
-conversion into ethanol -conversion into lactate -conversion into CO2 and water
Term
types of fermentation that can occur with pyruvate in the absence of O
Definition
-conversion into ethanol
-conversion into lactate
Term
fermentation
Definition
ATP-generating process in which organic compounds act as both donors and acceptors of electrons
Term
what happens to pyruvate in the presence of O?
Definition
gets metabolized to CO2 and water thru the citric acid cycle and the electron transport chain
Term
depiction of the possible fates of pyruvate
Definition
[image]
Term
pyruvate decarboxylase
Definition
catalyzes the decarboxylation of pyruvate
Term
depiction of the function of pyruvate decarboxylase
Definition
[image]
Term
alcohol dehydrogenase
Definition
catalyzes the reduction of acetaldehyde to ethanol by NADH
Term
depiction of the function of alcohol dehydrogenase
Definition
[image]
Term
alcoholic fermentation
Definition
converting glucose into alcohol
Term
the net result of the anaerobic conversion of glucose into ethanol
Definition
glucose + 2Pi + 2 ADP + 2 H+ --> 2 ethanol 2 CO2 + 2 ATP + 2 H2O
Term
how redox balance is maintained in alcohol fermentation
Definition
production and later consumption of NADH; no net proiduction of NADH or NAD+
Term
depiction of how redox balance is maintained in alcoholic fermentation
Definition
[image]
Term
lactic acid fermentation
Definition
converting glucose into lactate
Term
lactate dehydrogenase
Definition
catalyzes the conversion of pyruvate to lactate
Term
depiction of the function of lactate dehydrogenase
Definition
[image]
Term
overall rxn in the conversion of glucose to lactate
Definition
glucose + 2Pi + 2 ADP --> 2 lactate + 2 ATP + 2 H2O
Term
how redox balance is maintained in lactate fermentation
Definition
production and later consumption of NADH; no net proiduction of NADH or NAD+
Term
this sustains glycolysis under anaerobic conditions
Definition
the regeneration of NAD+ from NADH; using the NAD+ that's produced and using the NADH that's produced
Term
depiction of how redox balance is maintained in lactic acid fermentation
Definition
[image]
Term
type of cell in animals that can function anaerobically for a short time
Definition
fast twitch, or type IIb, muscle
Term
which type of glycolysis releases more energy? aerobic or anaerobic?
Definition
anaerobic
Term
how energy is extracted aerobically
Definition
by means of the citric acid cycle and the electron transport chain, which combust, or oxidize, glucose into H2O and CO2
Term
the entry point to the oxidative pathway in aerobic glycolysis
Definition
acetyl coenzyme A (acetyl CoA)
Term
how acetyl CoA is formed
Definition
formed from pyruvate inside mitochondria
Term
the process by which mitochondria form acetyl CoA
Definition
pyruvate + NAD+ + CoA --> acetyl CoA + CO2 + NADH
Term
how the NAD+ needed for aerobic glycolysis is regenerated
Definition
regenerated by the electron transport chain in mitochondria
Term
some recurring motifs in biochemistry
Definition
1: the use of activated carriers
2: the existence of a recurring set of activated characters in all organisms
Term
why ATP is an activated carrier of phosphoryl groups
Definition
because phosphoryl transfer from ATP is energetically favorable
Term
a recurring motif in biochem
Definition
the use of activated carriers
Term
activated carrier
Definition
small molecule carrying activate functional groups that can be donated to another molecule
Term
examples of activated carriers
Definition
-ATP carries activated phosphoryl groups
-coenzyme A carries activated acyl groups
-activated carriers of electrons for fuel oxidation
-activated carriers of electrons for the synthesis of biomolecules
-an activated carrier of 2-Carbon fragments
Term
many activated carriers function as...
Definition
coenzymes
Term
coenzymes
Definition
small organic molecules that serve as cofactors for enzymes
Term
the ultimate electron acceptor in the oxidation of fuel molecules
Definition
O2
Term
the flow of electrons from fuel molecules to O2
Definition
fuel molecules --> pyridine nucleotides or flavins --> O2
Term
an example of a pyridine nucleotide
Definition
NAD+
Term
NAD+
Definition
a pyridine nucleotide that is a major electron carrier in the oxidation of fuel molecules
Term
structure of NAD+
Definition
[image]
Term
depiction of NAD+ reduction
Definition
[image]
Term
depiction of redox rxn involving NAD+
Definition
[image]
Term
major electron carriers in the oxidation of fuel molecules
Definition
-NAD+ -FAD these are both oxidized forms
Term
structure of FAD
Definition
[image]
Term
depiction of redox rxn involving FAD
Definition
[image]
Term
oxidized and reduced forms of FAD/FADH2
Definition
[image]
Term
reductive biosynthesis
Definition
synthesizing something from precursors that are more oxidized than the products
Term
most biosynthesis is this type of biosynthesis
Definition
reductive biosynthesis
Term
the electron donor in most biosynthesis
Definition
NADPH
Term
structure of NADPH
Definition
[image]
Term
key difference between NADH and NADPH
Definition
NADPH contains one more phosphate group
Term
key difference between the uses of NADH and NADPH
Definition
NADPH used almost exclusively for reductive biosynthesis while NADH is used primarily for the generation of ATP
Term
NADPH used for...
Definition
almost exclusively for reductive biosynthesis while NADH is used primarily for the generation of ATP
Term
NADH used for...
Definition
primarily the generation of ATP
Term
structure of coenzyme A
Definition
[image]
Term
function of acetyl CoA
Definition
acetyl group transfer
Term
why acetyl CoA has high acetyl group transfer potential
Definition
because transfer of the acetyl group is exergonic (i.e., thermodynamically favorable)
Term
why the kinetic stability of NADH, NADPH, FADH2, ATP, and acetyl CoA in the absence of specific catalysts is essential foor their biological function
Definition
because it allows enzymes to control the flow of free energy and reducing power
Term
one of the unifying motifs in biochem
Definition
the existence of a recurring set of activated characters in all organisms
Term
structure of acyl CoA
Definition
[image]
Term
structure of acetyl CoA
Definition
[image]
Term
many activated carriers are derived from...
Definition
vitamins
Term
vitamins
Definition
organic molecules needed in small amounts in the diets of many higher animals
Term
the dual role of the glycolytic pathway
Definition
-degrades glucose to generate ATP
-provides building blocks for biosynthetic rxns
Term
potential sites of control in metabolic pathways
Definition
enzymes catalyzing irreversible rxns
Term
the control sites (i.e., enzymes tat catalyze irreversible rxns) in glycolysis
Definition
-hexokinase
-phosphofructokinase
-pyruvate kinase
Term
the type of enzymes that regulate glycolysis
Definition
allosteric enzymes
Term
what glycolysis in muscle does
Definition
primarily provides power for muscle contraction
Term
the primary control of muscle glycolysis
Definition
energy charge of the cell- ratio of ATP to AMP
Term
energy charge of the cell
Definition
ratio of ATP to AMP
Term
glycolysis in muscle is regulated by...
Definition
feedback inhibition to meet the need for ATP
Term
the most important control site in the mammalian glycolytic pathway
Definition
phosphofructokinase
Term
how phosphofructokinase is inhibited in muscle
Definition
ATP binds with phosphofructokinase at a distinct site to lower its affinity for fructose 6-phosphate

can also be inhibited by declining pH
Term
how phosphofructokinase is stimulated in muscle
Definition
AMP binds with phosphofructokinase at the same site to increase its affinity for fructose 6-phosphate
Term
how muscle cells are protected from excess acidity
Definition
lactic acid lowers the pH, augmenting the inhibitory effect of ATP on phosphofructokinase
Term
why AMP, not ADP, stimulates phosphofructokinase activity
Definition
because while ATP is being used, aldenylate kinase can convert ADP into ATP
Term
aldenylate kinase
Definition
converts ADP into ATP
Term
the rxn aldenylate kinase is involved in
Definition
[image]
Term
the primary regulatory enzyme in glycolysis
Definition
phosphofructokinase
Term
how hexokinase is regulated in muscle
Definition
it is inhibited by accumulation of glucose 6-phosphate
Term
how inhibition of phosphofructokinase leads to inhibition of hexokinase
Definition
inhibition of PFK leads to accumulation of fructose 6-phosphate, leading to accumulation of glucose 6-phosphate, leading to inhibition of hexokinase
Term
why hexokinase is not the committed step in glycolysis
Definition
because glucose 6-phosphate can also be converted into glycogen
Term
why PFK is the committed step in glycolysis
Definition
because it's the first step unique to glycolysis
Term
why the committed step is the most important controlled element in a biochemical pathway
Definition
because it regulates flux down the pathway
Term
how pyruvate kinase is inhibited in muscle
Definition
ATP binds to pyruvate kinase to decrease its affinity for phosphoenolpyruvate
Term
how pyruvate kinase is stimulated in muscle
Definition
fructose 1,6-bisphosphate activates the kinase to enable it to keep pace with the oncoming flux of intermediates
Term
depiction of glycolysis being inhibited in muscle (at rest)
Definition
[image]
Term
depiction of glycolysis being stimulated in muscle (during exercise)
Definition
[image]
Term
the regulation of glycolysis in the liver corresponds to...
Definition
the biochemical versatility of the liver
Term
how the liver regulates blood glucose
Definition
-stores it as glycogen when high
-releases glucose when low
Term
some things the liver does with glucose
Definition
-stores it as glycogen when high
-releases glucose when low
-uses glucose to generate reducing power for biosynthesis
-synthesize a host of building blocks for other biomolecules
Term
how PFK in the liver is inhibited
Definition
citrate, since citrate accumulation indicates that there's already enough biosynthetic precursors
Term
the key means by which PFK in the liver responds to changes in blood glucose
Definition
thru the signal molecule fructose 2,6-bisphosphate (F-2,6-BP)
Term
how PFK in the liver is stimulated
Definition
fructose 2,6-bisphosphate stimulates PFK by increasing its affinity for fructose 6-phosphate
Term
the enzyme primarily responsible for phosphorylating glucose in the liver
Definition
glucokinase (hexokinase IV)
Term
glucokinase (hexokinase IV)
Definition
isozyme of hexokinase; this is what's primarily responsible for phosphorylating glucose in the liver
Term
isozymes/isoenzymes
Definition
enzymes encoded by different genes with different amino acid sequences, but catalyze the same rxns
Term
how isozymes/isoenzymes differ
Definition
usually by kinetic or regulatory properties
Term
some differences between hexokinase and glucokinase
Definition
glucokinase has a higher KM value and is not inhibited by its product, glucose 6-phosphate
Term
the role of glucokinase
Definition
to provide glucose 6-phosphate for the synthesis of glycogen and for the formation of fatty acids
Term
what insulin signals
Definition
the need to remove glucose from thew blood for storage as glycogen or conversion into fat
Term
some important forms of pyruvate kinase
Definition
-L form
-M form
Term
the form of pyruvate kinase that predominates in the liver
Definition
L form
Term
the form of pyruvate kinase that predominates in the muscle and brain
Definition
M form
Term
which form of pyruvate kinase is inhibited by alanine?
Definition
the L form (liver enzyme)
Term
reversible phosphorylation regulates the catalytic properties of which form of pyruvate kinase?
Definition
the L form (liver enzyme)
Term
the importance of reversible phosphorylation regulating the catalytic properties of the L form of pyruvate kinase (liver enzyme)
Definition
prevents the liver from consuming glucose when it is more urgently needed by brain and muscle
Term
the function of the GLUT1 to GLUT5 proteins
Definition
enable glucose to enter and leave animal cells
Term
where the GLUT1 protein is found
Definition
nearly all mammalian cells
Term
where the GLUT3 protein is found
Definition
nearly all mammalian cells
Term
the GLUT proteins that essentially continuously transport glucose into cells at a constant rate (function in basal glucose uptake)
Definition
GLUT1 and GLUT3
Term
role of GLUT1 protein
Definition
basal glucose uptake
Term
role of GLUT3 protein
Definition
basal glucose uptake
Term
where the GLUT2 protein is found
Definition
liver and pancreatic β cells
Term
when glucose enters through the GLUT2 protein at a significant rate
Definition
when there is much glucose in the blood
Term
role of GLUT2 protein
Definition
in pancreas: helps regulate insulin

in liver: removes excess glucose from the blood
Term
where the GLUT4 protein is found
Definition
muscle and fat cells
Term
how the number of GLUT4 proteins increases
Definition
-increased insulin, which signals the presence of glucose
-endurance exercise
Term
where the GLUT5 protein is found
Definition
small intestine
Term
function of GLUT5
Definition
primarily as fructose transporter
Term
gluconeogenesis
Definition
the synthesis of glucose from noncarboydrate precursors
Term
why it's important to maintain glucose levels
Definition
because red blood cells need it and the brain uses it as its only fuel source
Term
the part of the body that needs most of the glucose
Definition
brain
Term
when gng is especially important
Definition
during fasting or starvation
Term
where gng occurs
Definition
mostly liver with small amount occurring in kidney
Term
why gng is important
Definition
helps maintain blood glucose so tissues that need it can access it
Term
the gng pathway converts ______ into ______
Definition
pyruvate
glucose
Term
the major noncarbohydrate precursors that get involved in gng
Definition
-lactate
-amino acids
-glycerol
Term
how glycerol may enter the gng pathway
Definition
by conversion of glycerol to dihydroxyacetone phosphate
Term
depiction of the conversion of glycerol to dihydroxyacetone phosphate
Definition
[image]
Term
is gng a complete reversal of glycolysis?
Definition
no
Term
why is gng not a complete reversal of glycolysis?
Definition
because the free energy of glycolysis is -90 kJ/mol, making it irreversible and necessary for gng to bypass the irreversible steps
Term
the gng pathway
Definition
[image]
Term
the conversion of pyruvate into phosphoenolpyruvate begins with...
Definition
the formation of oxaloacetate
Term
the first step in gng
Definition
carboxylation of pyruvate to form oxaloacetate
Term
pyruvate carboxylase
Definition
enyme that catalyzes the carboxylation of pyruvate to form oxaloacetate
Term
where the carboxylation of pyruvate to form oxaloacetate occurs
Definition
mitochondria
Term
depiction of the carboxylation of pyruvate to form oxaloacetate
Definition
[image]
Term
importance of biotin to pyruvate carboxylase
Definition
biotin is a covalently attached prosthetic group that serves as the carrier of activated CO2
Term
the 3 stages of pyruvate carboxylation
Definition
[image]
Term
how oxaloacetate is processed in the mitochondria
Definition
in matrix: pyruvate --> oxaloacetate --> malate

in cytoplasm: malate --> oxaloacetate
Term
depiction of how oxaloacetate is processed in the mitochondria
Definition
[image]
Term
phosphoenolpyruvate carboxykinase (PEPCK)
Definition
catalyzes the decarboxylation and phosphorylation of of oxaloiacetate
Term
depiction of the function of phosphoenolpyruvate carboxykinase (PEPCK)
Definition
[image]
Term
the sum of the rxns catalyzed by pyruvate carboxylase and phosphoenolpyruvate carboxylase
Definition
pyruvate + ATP + GTP + H2O --> phosphoenolpyruvate + ADP + GDP + Pi + 2 H+
Term
importance of decarboxylation
Definition
often drives rxns that are otherwise highly endergonic
Term
fructose 1,6-bisphosphotase
Definition
catalyzes conversion of fructose 1,6-bisphosphate to fructose 6-phosphate
Term
depiction of the function of fructose 1,6-bisphosphotase
Definition
[image]
Term
where gng ends in most tissues
Definition
conversion of fructose 6-phosphate into glucose 6-phosphate, which is often stored as glycogen
Term
where the final step in the generation of free glucose occurs
Definition
primarily the liver
Term
metabolic duty of the liver
Definition
to maintain adequate levels of glucose in the blood for use by other organs
Term
how glucose 6-phosphate gets converted to free glucose
Definition
transported into lumen of endoplasmic reticulum, where it is hydrolyzed to glucose by glucose 6-phosphatase, which is bound to the ER membrane. glucose and Pi are then shuttled out into the cytoplasm by transporters
Term
depiction of generation of glucose from glucose 6-phosphate
Definition
[image]
Term
the NTP difference between glycolysis and gng
Definition
glycolysis yields 2 ATP while gng requires 4 ATP and 2 GTP (6 NTP)
Term
when glycolysis predominates
Definition
when glucose is abundant
Term
when gng predominates
Definition
when glucose is scarce
Term
what determines whether glycolysis or gng will be more active?
Definition
energy charge
Term
the key regulation site in the gng pathway
Definition
the interconversion of fructose 6-phosphate and fructose 1,6-bisphosphate
Term
energy charge
Definition
seems to be ratio of ATP/AMP
Term
something indicated by high AMP concentration
Definition
energy is needed, thus stimulating glycolysis and inhibiting gng
Term
something indicated by high ATP concentration
Definition
the energy charge is high and biosynthetic intermediates are abundant, thus inhibiting glycolysis
Term
something indicated by high citrate concentration
Definition
reports the status of the citric acid cycle; high citrate indicates energy rich situation and precursors for biosynthesis, inhibiting glycolysis and stimulating gng
Term
where the interconversion of phosphoenolpyruvate and pyruvate occurs
Definition
liver
Term
something indicated by high alanine concentration
Definition
energy charge is hidh and building blocks are abundant, inhibiting pyruvate kinase in glycolysis
Term
depiction of the reciprocal regulation of glycolysis and gng in the liver
Definition
[image]
Term
phosphofructokinase 2 (PFK2)
Definition
catalyzes the conversion of fructose 6-phosphate to fructose 2,6-bisphosphate
Term
fructose bisphosphatase 2 (FBPase2)
Definition
catalyzes conversion of fructose 2,6-bisphosphate to frucose 6-phosphate
Term
something striking about PFK2 and FBPase2
Definition
they're both in a single 55-kDa polypeptide chain; it's a bifunctional enzyme
Term
composition of the bifunctional PFK2/FBPase2 enzyme
Definition
N-terminal regulatory domain followed by a kinase domain and a phosphatase domain
Term
how it is determined whether a bifunctional PFK2/FBPase2 enzyme functions as PFK2 or FBPase2
Definition
the activities of PFK2 and FBPase2 are reciprocally controlled by the phosphorylation of a single serine residue
Term
when the bifunctional PFK2/FBPase2 enzyme functions as FBPase2
Definition
when blood glucose is low

gng predominates
Term
how low blood glucose causes the bifunctional PFK2/FBPase2 enzyme to act as FBPase2
Definition
when glucose in scarce, blood glucagon rises and triggers a cyclic AMP signal cascade, leading to the phospkorylation of this enzyme by protein kinase A; this activates FBPase2 and inhibits PFK2
Term
when the bifunctional PFK2/FBPase2 enzyme functions as PFK2
Definition
when blood glucose is high

glycolysis predominates
Term
how high blood glucose causes the bifunctional PFK2/FBPase2 enzyme to act as PFK2
Definition
glucagon falls and insulin rises, causing the phosphoryl group to be removed; this activates PFK2 and inhibits FBPase2
Term
PKA
Definition
protein kinase A
Term
depiction of the bifunctional PFK2/FBPase2 enzyme
Definition
[image]
Term
depiction of the control of the synthesis and degradation of fructose 2,6-bisphosphate
Definition
[image]
Term
what lets contracting skeletal muscle generate ATP in the absence of oxygen?
Definition
the formation and release of lactate
Term
2 possible fates of lactate
Definition
1: diffuses into cardiac and slow-twitch (type 1) muscle to be reverted to pyruvate to be metabolized thru the citric acid cycle and oxidative phosphorylation to generate ATP
2: excess lactate enters the liver to be converted into pyruvate, then to glucose by the gng pathway
Term
what the liver does for active muscles
Definition
restores the levels of glucose needed for active muscle cells, which derive ATP from the conversion of glucose into lactate
Term
depiction of a substrate cycle
Definition
[image]
Term
depiction of the Cori cycle
Definition
[image]
Term
~P
Definition
nucleoside triphosphates
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
Term
electron transport chain aka respiratory chain
Definition
4 large protein complexes that are embedded in the inner mitochondrial membrane
Term
where the electron transport chain is located
Definition
inner mitochondrial membrane
Term
cellular respiration
Definition
generation of high-transfer-potential electrons by the citric acid cycle, the respiratory chain, and the accompanying synthesis of ATP
Term
depiction of a simple overview of oxidative phosphorylation
Definition
[image]
Term
where the flow of electrons thru the electron transport chain takes place
Definition
inner mitochondrial membrane
Term
cristae
Definition
folds in the mitochondrion's inner membrane
Term
the 2 compartments of the mitochondrion
Definition
1: intermembrane space
2: matrix
Term
permeability of the mitochondrion's outer membrane
Definition
very permeable
Term
why the mitochondrion's outer membrane is very permeable
Definition
because it contains many mitochondrial porins, which create pores
Term
function of mitochondrial porin
Definition
regulates flux of molecules crucial to the function of cellular respiration
Term
permeability of mitochondrion's inner membrane
Definition
intrinsically permeable to nearly all ions and polar molecules
Term
matrix side
Definition
inside mitochondrion's inner membrane
Term
cytoplasmic side
Definition
intermembrane space in mitochondrion; called this because it is freely accessible to most small molecules in the cytoplasm cytoplasm
Term
simple depiction of the anatomy of a mitochondrion
Definition
[image]
Term
what oxidative phosphorylation does to O2
Definition
reduces it to water
Term
how oxidative phosphorylation reduces O2 to water
Definition
using electrons from NADH and FADH2
Term
electron transport chain
Definition
set of membrane proteins in which the transfer of electrons to reduce O2 to water takes place
Term
a conversion of potential that occurs in oxidative phosphorylation
Definition
the electron-transfer potential of NADH or FADH2 being converted into the phosphoryl-transfer potential of ATP
Term
how phosphoryl-transfer potential is expressed
Definition
ΔG°'
Term
reduction potentyial
Definition
expression for electron transfer potential
Term
how reduction potential is expressed
Definition
ΔE0'
Term
redox couple
Definition
substance that exists as oxidized and reduced forms
Term
how the reduction potential of a redox couple is determined
Definition
by measuring the electromotive force generated by a sample half cell connected to a standard reference half cell
Term
depiction of how redox potential is measured
Definition
[image]

electrons flow thru the wire and ions flow thru the agar bridge
Term
the reduction potential of the X:X- couple
Definition
the observed voltage at the start of the experiment
Term
the reduction potential of the H+:H2 couple
Definition
defined to be 0 volts
Term
what a positive reduction potential (ΔE0') indicates
Definition
accepts electrons
Term
what a negative reduction potential (ΔE0') indicates
Definition
donates electrons
Term
F
Definition
faraday proportionality constant (96.48 kJ mol-1 V-1, or 23.06 kcal mol-1 V-1)
Term
relationship between ΔE0' and ΔG°'
Definition
ΔG°' = -nFΔE0'
Term
oxidant
Definition
electron acceptor
Term
reductant
Definition
electron donor
Term
the driving force of oxidative phosphorylation
Definition
the electron-transfer potential of NADH or FADH2 relative to that of O2
Term
where does the energy that produces the proton gradient to make ATP come from?
Definition
the energy released by the reduction of each electron carrier
Term
repriasome
Definition
supramolecular complex composed of complexes that carries electrons down the electron transport chain
Term
depiction of the components of the electron transport chain
Definition
[image]
Term
why FADh2 derived electrons pump fewer protons and ATP than NADH derived electrons
Definition
electrons from FADH2 feed into the chain downstream from those from NADH because those from FADH2 have lower reduction potential
Term
why electrons from FADH2 feed into the chain downstream from those from NADH
Definition
because those from FADH2 have lower reduction potential
Term
the 2 types of Fe proteins in the electron transport chain
Definition
1: iron-sulfur proteins aka nonheme-iron proteins
2: cytochromes, which are components of heme prothetic groups
Term
cytochrome
Definition
Fe containing protein that is a component of a heme prosthetic group
Term
another metal that can participate in the electron transport chain
Definition
Cu
Term
how electron transfer works for quinones
Definition
for quinones, electron-transfer rxns are coupled to proton binding and release
Term
how the electron transport chain creates a proton gradient
Definition
electron flow within it leads to the transport of protons accross the inner membrane
Term
a protein complex that does not pump electrons
Definition
succinate-Q reductase
Term
where the electrons from NADH enter the electron transport chain
Definition
at NADH-Q oxidoreductase (complex 1)
Term
depiction of the electron transport chain's complexes
Definition
[image]
Term
depiction of coupled electron-proton transfer rxns thru NADH-Q oxidoreductase
Definition
[image]
Term
what the Q cycle does
Definition
funnels electrons from a 2 electron carrier to a 1 electron carrier and pumps protons
Term
the Q cycle
Definition
the mechanism for the coupling of electron transfer from Q to cytochrome C to transmembrane proton transport
Term
depiction of the Q cycle
Definition
[image]
Term
depiction of the cytochrome oxidase mechanism
Definition
[image]
Term
depiction of proton transport by cytochrome c oxidase
Definition
[image]
Term
depiction of the electron-transport chain
Definition
[image]
Term
some dangerous radicals that can form from O2
Definition
-superoxide (O2-) -peroxide (O22-)
Term
reactive oxygen species
Definition
-superoxide (O2-) -peroxide (O22-) -hydroxyl radical (OH•)
Term
some things reactive oxygen species can cause
Definition
-aging
-some other diseases
Term
superoxide dismutase
Definition
catalyzes the conversion of 2 superoxides into hydrogen peroxide and molecular oxygen
Term
depiction of the function of superoxide dismutase
Definition
[image]
Term
catalase
Definition
catalyzes the dismutation of hydrogen peroxide into water and molecular oxygen
Term
depiction of the function of catalase
Definition
[image]
Term
dismutation
Definition
rxn in which a single reactant is converted into 2 different products
Term
ATPase
Definition
protein protons move thru to generate ATP
Term
chemostatic hypothesis
Definition
proposes that electron transport and ATP synthesis are coupled by a proton gradient across the inner mitochondrial membrane

basically says that flow of protons drives production of ATP by ATP synthase
Term
how electron transport and ATP synthesis are coupled
Definition
by a proton gradient across the inner mitochondrial membrane
Term
depiction of the chemostatic hypothesis
Definition
[image]
Term
proton-motive force
Definition
the energy rich, unequal distribution of protons across the inner mitochondrial membrane
Term
the 2 components of the proton motive force
Definition
1: chemical gradient
2: charge gradient
Term
chemical gradient for protons
Definition
can be represented as a pH gradient
Term
charge gradient
Definition
created by the positive charge on the unequally distributed protons forming the chemical gradient
Term
how protons are transported out of the matrix into the intermembrane space
Definition
electron transfer thru the respiratory chain leads to the pumping of protons
Term
how to calculate proton-motive force
Definition
proton-motive force (Δp) = chemical gradient (ΔH) + charge gradient (Δψ)
Term
the respiratory chain and ATP synthase are biochemically separate. what links them?
Definition
only the proton-motive force
Term
depiction of the link between the respiratory chain and ATP synthase
Definition
[image]
Term
how NADH oxidation is coupled to ATP synthesis
Definition
1: electron transport generates a proton-motive force
2: ATP synthesis by ATP synthase is powered by a proton-motive force
Term
depiction of ATP synthase
Definition
[image]
Term
what makes each of the 3 β subunits different?
Definition
they each interact with a different face of the γ subunit
Term
how formation of cristae makes ATP synthesis more efficient
Definition
localizing the proton gradient to where the ATP synthases are
Term
depiction of how ATP synthase assists in the formation of cristae
Definition
[image]
Term
the rxn ATP synthase catalyzes
Definition
formation of ATP from ADP and orthophosphate ADP3- + HPO42- + H+ <--> ATP4- + H2O
Term
the 3 different functions performed by the 3 active sites in ATP synthase
Definition
1: trapping of ADP and Pi 2: ATP synthesis 3: ATP release and ADP and Pi binding
Term
the 2 parts of ATP synthase
Definition
1: moving unit (rotor) consisting of c ring and γε stalk
2: the stationary unit (stator) consisting of the remainder of the molecule
Term
depiction of the distinct ATP synthase nucleotide-binding sites
Definition
[image]
Term
order in which subunits of ATP synthase change state
Definition
T --> O --> L

repeatedly rotates counterclockwise
Term
depiction of a binding-change mechanism for ATP synthase
Definition
[image]
Term
what drives the rotation of the γ subunit in ATP synthase?
Definition
hydrolysis of ATP
Term
depiction of the components of the proton-conducting unit of ATP synthase
Definition
[image]
Term
what powers the rtation of the c ring in ATP synthase?
Definition
movement of protons thru the half channels from high proton c'tration of intermembrane space to low proton c'tration of matrix
Term
depiction of proton motion across the membrane
Definition
[image]
Term
depiction of the proton path thru the membrane
Definition
[image]
Term
number of c subunits in ring vs. efficiency of ATP synthase
Definition
the more subunits in the ring, the less efficient, that is, the more protons needed to synthesize 1 ATP
Term
depiction of an overview of oxidative phosphorylation
Definition
[image]
Term
how electrons from intermembrane space enter matrix
Definition
shuttles
Term
how NADH is reoxidized to NAD+
Definition
electrons from NADH, rather than NADH itself, are carried across the mitochondrial membrane
Term
the glycerol 3-phosphate shuttle
Definition
introduces electrons from NADH into the electron transport chain
Term
depiction of the glycerol 3-phosphate shuttle
Definition
[image]
Term
malate-aspartate shuttle
Definition
transfers electrons from NADH to oxaloacetate, forming malate
Term
depiction of the malate-aspartate shuttle
Definition
[image]
Term
the major function of oxidative phosphorylation
Definition
to generate ATP from ADP
Term
ATP-ADP translocase
Definition
transports ATP out of matrix and ADP into matrix
Term
when ATP enters the mitochondrial matrix
Definition
only when ADP is present
Term
when ADP enters the mitochondrial matrix
Definition
only when ATP is present
Term
depiction of the mechanism of ATP-ADP translocase
Definition
[image]
Term
ATP synthasome
Definition
large complex of proteins that provide the substrates needed for ATP synthesis
Term
depiction of the mitochondrial transporters
Definition
[image]
Term
cellular respiration is regulated by...
Definition
the need for ATP, since it's the ultimate and product of cellular respiration
Term
how many molecules of ATP are formed when glucose is completely oxidzed to co2?
Definition
about 30
Term
which step of cellular respiration generates most of the ATP?
Definition
oxidative phosphorylation (26 of 30)
Term
how many ATP does anaerobic glycolysis yield?
Definition
2
Term
the rate of oxidative phosphorylation is determined by...
Definition
the need for ATP
Term
when electrons flow thru the electron transport chain to O2
Definition
they usually do this only when ADP is simultaneously phosphorylated to ATP
Term
respiratory control or acceptor control
Definition
regulation of the rate of oxidative phosphorylation by the ADP level
Term
when electrons flow from fuel molecules to O2
Definition
only when ATP needs to be synthesized
Term
depiction of how energy charge regulates the use of fuels
Definition
[image]
Term
depiction of some things proton gradient can be used for
Definition
[image]
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