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40 Cards in this Set
- Front
- Back
Which enzyme catalyzes the first reaction in glycolysis?
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hexokinase
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What gets turned into what in the first reaction in glycolysis?
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glucose gets turned into glucose-6-phosphate (G6P)
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Kinase
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is an enzyme that transfers phosphoryl groups between ATP and a metabolite
(the metabolite that serves as the phosphoryl group acceptor is indicated in the prefix of the kinase name |
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Is hexokinase a specific enzyme?
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No, it is a nonspecific one because it will also catalyze the phosphorylation of hexoses like D-glucose, D-manose, and D-fructose
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Name one isozyme from hexokinase?
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glucokinase which is found in the liver
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What is the second substrate for hexokinase?
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Mg2+-ATP complex
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Is uncomplexed ATP a potent competitive inhibitor for of hexokinase?
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Yes, because without the Mg2+ shielding the negative charges of the ATP's alpha and beta or alpha and gamma-phosphate oxygen atoms, the nucleophilic attack of the C6-OH group of glucose is more difficult
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Does glucose induce a large conformational change in hexokinase?
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Yes, the two lobes tha tform its active site cleft swing together by up to 8 A engulfing the glucose like the closing of jaws
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What would happen if the catalytic and reacting groups were in the poper position for reaction while the enzyme was in the open position?
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ATP hydrolysis: phosphoryl group transfer to water would be thermodynamically favored
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What is responsible for the hexokinase's specificity?
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substrate-induced conformational change and the active site polarity being reduced by the exclusion of water (expediating nucleophilic rxn)
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What do you call the enzyme that catalyzes the second rxn?
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phosphoglucose isomerase
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Phosphoglucose isomerase catalyzes what to what?
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G6P to fructose-6-phosphate (F6P)
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What type reaction does phosphoglucose isomerase catalyze?
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an isomerization rxn of an aldose to a ketose
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In what form do G6P and F6P predominate?
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cylic
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What are the primary steps in the reaction that phosphoglucose isomerase catalyzes?
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1. Ring opening
2. Isomerization 3. Ring closure |
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What type of catalysis does phosphoglucose isomerase perform?
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acid-base
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What is special about the alpha proton on a carbonyl group?
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it is acidic
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In the second rxn in glycolysis how is the cis-enediolate intermediate formed?
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a base abstracts the acidic proton from C2 to form the intermediate
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In the second rxn in glycolysis which proton is replaced in the overall proton transfer?
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proton on C1
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What enzyme catalyzes the third rxn in glycolysis?
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Phosphofructokinase (PFK)
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Phosphofructokinase catalyzes what to what?
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Fructose-6-phosphate (F6P) to Fructose-1,6-biphosphate (FBP)
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Why is this a biphosphate and not a diphosphate?
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Because the 2 phosphate groups are not attatched to one another
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Which rxn is the PFK reaction similar to?
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hexokinase rxn because the enzyme catalyzes the nucleophilic attack by the C1-OH group of F6P on the electrophilic gamma-phosphorus atom of the Mg2+-ATP complex
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Why does phophofructokinase play a central role in control of glycolysis?
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because it catlyzes one of the pathway's rate-determining reactions
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What can enhance the activity of PFK and what can inhibit the activity of PFK allosterically?
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PFK can be enhanced by AMP and inhibited allosterically by ATP and citrate
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Which enzyme catalyzes the fourth step in glycolysis?
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aldolase
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Aldolase catalyzes what to what?
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it cleaves fructose-1,6-biphosphate to form 2 trioses glyceraldehyde-3-phosphate (GAP) and dihydroxyacetone phosphate (DHAP)
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In the fourth rxn in glycolysis atoms 123 of glucose become what?
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321 of DHAP (has carbonyl in center)
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In the fourth rxn in glycolysis atoms 456 of glucose become what?
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123 of GAP (with carbonyl on outside starting with 1)
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What type of reaction is reaction 4 of glycolysis?
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aldol cleavage (retro aldol condensation)
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What stabilizes the enolate?
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resonance, as a result of the electron-withdrawing character of the carbonyl oxygen atom
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What catalyzes aldol cleavage?
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stabilizing the enolate intermediate through increased electron delocalization
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What type of mechanism does a nonenzyme catalyzed enol rxn use?
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base catalysis
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The aldol cleavage between C3 and C4 of FBP requires a what, and where?
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a carbonyl at C2 and a hydroxyl at C4
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Aldol cleavage of G6P yields what types of products?
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products of unequal carbon chain length
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Aldol cleavage of FBP results in what?
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two interconvertible C3 compounds that can therefore enter a common degradative pathway
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What is a Schiff base?
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an imine that forms between an amine and an aldehyde or ketone
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Which enzyme catalyzes reaction five of glycolysis (which is the final stage of part one)?
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Triose phosphate isomerase
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What type of isomers are DHAP and GAP? Or F6P and G6P?
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ketose-aldose isomers
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Does GAP or DHAP continue in the glycolytic pathway?
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GAP
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