Chemistry491/591

MetabolicBiochemistry
Winter2016
MeetingTime:MWF,11:30AM12:35PM,ASRC230
Instructor:DrJohnPerona;perona@pdx.edu
Office:SRTC414
OfficeHrs:W1011:20AM
Text:PrinciplesofBiochemistry,6thedition,Lehninger,Nelson&Cox

PartIEnzymes,Bioenergetics,andMetabolicPrinciples.
PartIIMetabolicpathwaysandregulation.
PartIIINcycle,oxidativephosphorylationandphotosynthesis.
MidtermIJan27

MidtermIIFeb24 FinalExamMar17

PartI.Enzymes,bioenergetics,andmetabolicprinciples.
January4
Introductiontoenzymesandcatalyticpower.
January6
Enzymekinetics.
January8
Regulatorycontrol;classesofreactions
January11
Enzymemechanisms.
January13
Bioenergetics:Freeenergies,phosphoryltransfer.
January15
Bioenergetics:Oxidationreductionreactions.
January18
MLKHolidaynoclass

PartII.Metabolicpathwaysandregulation
January20
Pathwayofglycolysis.
January22
Glycolysis:Feederpathways.Anaerobicfermentation.
January25
ReviewforMidtermI
January27
MidtermI:Chapters6and13;
Chapter14(glycolysisonly)

E:dihydrofolatereductase
S1:NADP+
S2:tetrahydrofolate

Complexandhighly
differentiatedsurface
JuxtapositionofEandSmoieties
Lockandkeymechanism

INDUCEDFIT

Hexokinase
unliganded

Hexokinase+glucose

Uncatalyzedreaction
S=>S=>P

Thermodynamic
equilibriumfavorsP

Enzymecatalyzed
Activationenergylowered
ESandEParereaction
intermediates
Gunaffected

Ratelimitingstep
atthestepwiththe
highestenergybarrier

RateenhancementI
Transitionstate
complementarity
Enzymeactually
slowsrate;
Transitionstate
notstabilized
GMisreallyGB

ActualcaseGMrepresents
therateenhancementfromthe
enzymeweaknoncovalentcontacts

RateenhancementIIProximity

Entropyreduction
or
Proximity
or
Propinquity

RateenhancementIIIacidbasecatalysis

Whatisneededisa
generalbasetoaccept
theproton(eg,histidineimidazole)

pHdependenceofvelocityimportanceoftitratedgroups

RateenhancementIVCovalentCatalysis
Acovalentbondformsbetweenenzymeandsubstrate
Changesthereactionpathway
Uncatalyzed:
Catalyzed:

H2O

AB AB
H2O

A B X : A X B A X : B

Requiresanucleophileontheenzyme[X:]
Canbeareactiveserine,thiolate,amine,or
carboxylate