enzymesandmetabolism(MCAT)atNorthCarolinaCentralUniversityStudyBlue

1.
LizzieS.
Created:20160714
LastModified:20160714
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Functionofenzymesincatalyzingbiologicalreactions
Enzymesarecatalysts,whicharethingsthatincreasetherateofareaction,butdoesnotgetusedupduringthereaction.
Importantbiologicalreactionscatalyzedbyenzymes
Metabolism
DNAsynthesis
RNAsynthesis
Proteinsynthesis
Digestion
Howdoesenzymesspeedsupachemicalreaction?
byreducingtheactivationenergy
whatdoesenzymedo?
Enzymesincreasetherateofareactionbydecreasingtheactivationenergy.
Enzymeswillincreasetherateconstant,k,fortheequationrate=k[A][B].
Enzymeswillmakethereversereactiongofasteralso.
Whatdoenzymesdo?
Enzymesaffectthekineticsofareaction,butnotthethermodynamics.
EnzymesdonotchangeG,thenetchangeinfreeenergy.
EnzymesdonotchangeK(eq)becauseitlowerstheactivationenergyforBOTHforwardandreversereactions.
Whatelsedoesanenzymedo
EnzymesdoNOTchangetheKeqofareaction.
Enzymesdecreasetheactivationenergy(Ea)ofareactionbyloweringtheenergyofthetransitionstate.
Enzymesincreasetherateofareactionbydecreasingtheactivationenergy

Substratesandenzymespecificity
Enzymesubstrateinteractionsoccurattheenzyme'sactivesite.
Enzymesubstratespecificityderivesfromstructuralinteractions.
Lockandkeymodel:rigidactivesite.Substratefitsinsidetherigidactivesitelikeakey.
Substrateandenzymespecificity
Inducedfitmodel:flexibleactivesite.Substratefitsinsidetheflexibleactivesite,whichistheninducedto"grasp"thesubstrateinabetterfit.
Enzymescanbespecificenoughtodistinguishbetweenstereoisomers.
Substrateandenzymespecificity
EnzymescanbeproteinorRNA.
Almostallenzymesinyourbodyismadeofprotein.
ThemostimportantRNAenzymeinyourbodyistheribosome.
substrateandenzymespecificity
Enzymestructurederivesfrom4levels.
Primary:thisisthesequenceoftheproteinorRNAchain.
Secondary:thisishydrogenbondingbetweentheproteinbackbone.Examplesincludealphahelicesandbetasheets(backboneHbonding).
ForRNA,thisisbasepairing.
Tertiary:thisisthe3Dstructureoftheenzyme.ThisinvolvesRgroupinteractionsandspatialarrangementofsecondarystructure.
Quaternary:whenmorethan1chainisinvolved.Whenyouhearabout"dimers","trimers","tetramers","oligomers",that'squaternarystructure.
HeatandextremepHdenaturesenzymesbyalteringtheirstructure.
ControlofenzymeactivityTerm
Theproductofapathwayinhibitsthepathway.
Cellsshutdownpathwaywhennotneededthusconservingenergy.Theendproductofapathwayactsasanallostericinhibitor.Onceenoughofacertain
substanceisrequiredtheendproductwillbindontheallostericsiteonthe1stenzymeandchangetheshapeoftheactivesitetoshutpathwaydown
competitiveinhibition
Aninhibitorcompeteswiththesubstrateforbindingtotheactivesite.
Competitiveinhibitionincreasestheamountofsubstrateneededtoachievemaximumrateofcatalysis.
CompetitiveinhibitiondoesNOTchangethemaximumpossiblerateoftheenzyme'scatalysis.

Youcanovercomecompetitiveinhibitionbyprovidingmoresubstrate.
noncompetitiveinhibition
Aninhibitorbindstoanallostericsiteontheenzymetodeactivateit.
Thesubstratestillhaveaccesstheactivesite,buttheenzymeisnolongerabletocatalyzethereactionaslongastheinhibitorremainsbound.
Noncompetitiveinhibitiondecreasesthemaximumpossiblerateoftheenzyme'scatalysis.
NoncompetitiveinhibitiondoesNOTchangetheamountofsubstrateneededtoachievethemaximumrateofcatalysis.
Youcan'tovercomenoncompetitiveinhibitionbyaddingmoresubstrate.
Metabolism
anothernameofmetabolismiscellularrespiration
metabolismisconsistsoftwoparts
catabolism
anabolism
Anabolism
isusingenergytobuildstuffforstorage.
whataretheStepsofaerobicmetabolism(needsoxygen)
Glycolysis
Oxidativedecarboxylation
Krebscycle
Electrontransportchain.
Glycolysis
AlcoholorlacticacidfermentationDefinition
Aerobicmetabolismofglucose
Completeoxidationofmetabolite(glucose)tocarbondioxide.
~30ATPproducedperglucose.
C6H12O6+6O2=>6CO2+6H2O
C6H12O6:thisisglucose.Yougetitfromyourdiet.
6O2:thisismolecularoxygenthatyoubreathein.

aerobicmetabolism
6CO2:thisiscarbondioxideproducedbytheKrebscycle.BoththecarbonandoxygeninthisCO2comesfromthemetabolite(glucose).
6H2O:thisiswaterproducedintheelectrontransportchain.Theoxygencomescompletelyfromthemolecularoxygenthatyoubreathein.
thingstoknowinaerobicmetabolism
Ifweweretofollowthecarboninthemetabolite(glucose),itwillendupincarbondioxide.
Ifweweretofollowtheoxygeninthemetabolite(glucose),itwillendupincarbondioxide.
Ifweweretofollowtheoxygenyoubreathein,itwillendupinwater.
Asforthehydrogens,they'lleitherbeinwater,existasprotonsinsolution,orbetransferredtosomeotherentity.
Thingstoknowinaerobicmetabolism
Thetotalreactioninvolvescompleteoxidationofthemetabolite(glucose)andcompletereductionofmolecularoxygen.
Whenelectronspassfromthemetabolite(glucose)tomolecularoxygen,energyisreleased.
Theelectrontransportchainharnessesthisenergy.
AnaerobicmetabolismofglucoseTerm
Partialoxidationofmetabolite(glucose)topyruvate.
2netATPproducedperglucose.
Pyruvateisthenreducedtoeitheralcoholorlactate.
Bacteriareducepyruvatetoalcoholinaprocesscalledalcoholfermentation.
Humansreducepyruvatetolactateinaprocesscalledlacticacidfermentation.
Glycolysis(1ststepinaereobicmetabolism)
Glycolysis=convertglucose(6carbons)to2moleculesofpyruvate(3carbons).
Location:cytosol.
2netATPmadeforeveryglucose(2inputATP,4outputATP).
2NADHmadeforeveryglucose.
Occursunderbothaerobicandanaerobicconditions.
GlycolysisisinhibitedbyATP.Definition
Aerobicdecarboxylation(2ndstepinaerobicmeatabolism)
Inthemitochondrialmatrix=convertpyruvate(3carbons)toanacetylgroup(2carbons)

1NADHmadeforeverypyruvate.
Onlyoccursinthepresenceofoxygen.
AcetylgroupattachestoCoenzymeAtomakeacetylCoA.
Anaerobicfermentation
Inthecytosol=redoxreaction:reducepyruvate,oxidizeNADH.
1NAD+madeforeverypyruvate.
Alcoholfermentation=pyruvatereducedtoethanol.
Lacticacidfermentation=pyruvatereducedtolactate.
ThepurposeofanaerobicfermentationistoregenerateNAD+,whichisneededforglycolysis.
Krebscycle,substratesandproducts,generalfeaturesofthepathway
Location:matrixofthemitochondria
AcetylCoAfeedsintothecycle
3NADHmadeperacetylCoA
1FADH2madeperacetylCoA
1ATP(GTP)madeperacetylCoA
CoenzymeAisregenerated(duringthefirststepofthecycle)
Krebscycle,TCA,Tricarboxylicacidcycle,citricacidcycleallmeanthesamething
KrebscycleisInhibitedbyATPandNADH
Electrontransportchainandoxidativephosphorylation,substratesandproducts,generalfeaturesofthepathway
Location:thecristae(innermembraneofmitochondria).
InputNADH
Protongradient
Theelectrontransportchain(ETC)isessentiallyaseriesofredoxreactions,whereNADHgetsoxidizedtoNAD+andO2getsreducedtoH2O.
TheseriesofredoxreactionsconsistsofelectronspassingfromNADHtoFMN,toCoenzymeQ,ironsulfurcomplexes,andcytochromes(cytochromeb,c

andaa3)beforefinallybeingusedtoreduceoxygen.
Electrontransportchainandoxidativephosphorylation,substratesandproducts,generalfeaturesofthepathway
NADHishighestinenergy,whileO2islowestinenergy.WhenelectronsarepassedfromNADHdownaseriesofproteinsandfinallytoO2,energyis
released.
FADH2islowerinenergythanNADH,that'swhyitreleaseslessenergywhenitgetsoxidized.
FADH2skipsFMNandpassesitselectronstoCoenzymeQ.
Theenergyreleasedfromthesereactionsgeneratesaprotongradient,whichdrivesATPsynthasetomakeATP.Thisiscalledoxidativephosphorylation.
Electrontransportchainandoxidativephosphorylation,substratesandproducts,generalfeaturesofthepathway
Term
Protongradient
TheenergyreleasedfrompassingelectronsdowntheETCisusedtopumpprotonsintotheintermembranespaceofthemitochondria.
H+concentrationisveryhighintheintermembranespace(higherthanthoseinthematrix).Thus,thisestablishesanelectrochemicalgradientcalledthe
protongradient.
H+wantstomigratedowntheprotongradient(fromtheintermembranespacebackintothematrix),butitcanonlydothisbygoingthroughtheATP
synthase.
Likeawatermill,ATPsynthaseharnessestheenergyofthefallingprotonstoconvertADPintoATP.
TheETCisinhibitedbycertainantibiotics,bycyanide,azide,andcarbonmonoxide.
Metabolismoffats
Location:betaoxidationoccursinthematrixofthemitochondria.Esterhydrolysisoccursinthecytosol.
Fattyestersgetshydrolyzedintofreefattyacidsbylipases.
Forexample,triacylglycerolgetshydrolyzedintofreefattyacidsandglycerol.
WiththehelpofATP,thefattyacidis"activated"attheacidendbyCoA(tobeprecise,itturnsintoathioester).
AprocesscalledbetaoxidationbreaksdownthefattyCoA,2carbonsatatime,tomakeacetylCoA.
oxidationproducesacetylCoAandalsoFADH2andNADH.
TheacetylCoAfeedsintotheKrebscycle,andtheFADH2andNADHfeedintotheETC.
Onapergrambasis,fatsgivemoreenergythananyotherfoodsource.
Proteinmetabolism
Proteinsarebrokendownintoaminoacidsbypeptidases.

Thenitrogenintheaminoacidisconvertedtourea(fordesertanimals,birdsandreptiles,itisuricacid).
ThecarbonintheaminoacidisconvertedtopyruvateoracetylCoA,(orothermetabolicalintermediatessuchasoxaloacetate),dependingonwhatamino
aciditis.
ThecarbonproductsfromaminoacidmetabolismcaneitherfeedintotheKrebscycle,orbethestartingmaterialforgluconeogenesis.

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