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BiochemistryofCarbohydrates PartII Dr.KevinAhern Glycolysis • Summary Glucose + 2 ADP + 2Pi + 2 NAD+ Yields 2 Pyruvate + 2 ATP + 2 NADH + 2 H+ + 2 H2O Glucose Product of Process Glycolysis • Fermentation in Yeast/Bacteria GA3P NAD+ X NADH + H+ O2 Helps to Make NAD+ 1,3 BPG In Absence of Oxygen Pyruvate (PYR) Glycolysis • Fermentation in Yeast/Bacteria Glucose Product of Process Glycolysis • Fermentation in Animals GA3P NAD+ X NADH + H + 1,3 BPG Pyruvate (PYR) O2 Helps to Make NAD+ Glycolysis • Fermentation in Animals Glycolysis • Fates of Pyruvate • Pyruvate Not an End Point • Important for Amino Acids,Energy, Fermentation Glycolysis • Metabolism of Other Sugars - Galactose Glycolysis • Metabolism of Other Sugars - Galactose Reduced Quantities in Adults Leads to Lactose Intolerance Lactase Lactose Galactose Glucose Glycolysis • Metabolism of Other Sugars - Fructose Fructokinase Fructose Fructose-1-Phosphate (F1P) Fructoaldolase F1P DHAP + Glyceraldehyde Glyceraldehyde-3-Phosphate To Glycolysis Fructose Regulatory Enzyme Bypassed Glycolysis • Metabolism of Other Sugars - Fructose Regulatory Enzyme Bypassed F1P DHAP + GA3P Excess Pyruvate? Gluconeogenesis • Synthesis of Glucose • Important for Regulating Blood Glucose • Reactions in Cytoplasm, Mitochondrion, Endoplasmic Reticulum • In the Body - Liver and Kidney Gluconeogenesis • Synthesis of Glucose • Four Reactions in Gluconeogenesis Replace Three Reactions in Glycolysis • All Other Reactions are Simply the Reverse of Glycolysis Reactions • Two Pyruvates Needed for Each Glucose Gluconeogenesis • Synthesis of Glucose G6Pase (Hexokinase) F1,6BPase (PFK) PEPCK Pyruvate Carboxylase (Pyruvate Kinase) Glucose Gluconeogenesis 11. Glucose-6-Phosphatase 1. Hexokinase • Reactions of Gluconeogenesis G6P 10. Phosphoglucoisomerase 2. Phosphoglucoisomerase F6P 9. F1,6 Bisphosphatase 3. PFK1 F1,6BP 8. Aldolase 4. Aldolase DHAP + G3P 7. Triose Phosphate Isomerase 5. Triose Phosphate Isomerase GA3P 6. GA3PDH 6. GA3PDH Run as Reverse of 1,3 BPG Glycolysis Reactions 5. Phosphoglycerate Kinase 7. Phosphoglycerate Kinase 3-PG 4. Phosphoglycerate Mutase 8. Phosphoglycerate Mutase 2-PG 3. Enolase 9. Enolase PEP 2. PEPCK 10. Pyruvate Kinase 1. Pyruvate Carboxylase Pyr Gluconeogenesis • Reactions of Gluconeogenesis • Reaction #1 • Step 1 of Bypassing Pyruvate Kinase • Occurs in Mitochondrion Gluconeogenesis • Reactions of Gluconeogenesis • Reaction #1 • Step 1 of Bypassing Pyruvate Kinase • Occurs in Mitochondrion Pyruvate Carboxylase Pyruvate (Pyr) Oxaloacetate (OAA) Gluconeogenesis • Reactions of Gluconeogenesis CO2 Biotin Carrying CO2 Gluconeogenesis • Reactions of Gluconeogenesis • Reaction #2 • Occurs in Mitochondrion • Second Triphosphate Necessary Phosphoenolpyruvate Carboxykinase (PEPCK) Oxaloacetate (OAA) Phosphoenolpyruvate (PEP) Gluconeogenesis • Reactions of Gluconeogenesis • Reaction # 9 of Gluconeogenesis • Not the Reversal of the PFK Reaction • Energy Realized by Not Regenerating ATP Glycolysis Enzyme Required ATP Fructose 1,6 Bisphosphatase (FBPase) Fructose 1,6 Bisphosphate (F1,6BP) Fructose 6 Phosphate (F6P) Gluconeogenesis • Reactions of Gluconeogenesis • Reaction # 11 of Gluconeogenesis • Not the Reversal of the Hexokinase Reaction • Energy Realized by Not Regenerating ATP • Occurs in Endoplasmic Reticulum Glycolysis Enzyme Required ATP Glucose-6-Phosphatase (G6Pase) Glucose 6 Phosphate (G6P) Glucose GluconeogenesisandGlycolysis • Regulation Glycolysis Glucose + 2 ADP + 2Pi + 2 NAD+ Yields 2 Pyruvate + 2ATP + 2 NADH + 2 H+ + 2 H2O Gluconeogenesis 2 Pyruvate + 2 NADH + 4 ATP + 2 GTP Yields Glucose + 2 NAD+ + 4 ADP + 2 GDP + 6 Pi Gluconeogenesis Requires More Energy Than Glycolysis Generates Futile Cycle Results if Both Running Simultaneously ATP/GTP Burned, Nothing but Heat Produced GluconeogenesisandGlycolysis • Regulation GluconeogenesisandGlycolysisGluconeogenesis • Regulation Glycolysis GluconeogenesisandGlycolysis • Regulation Reciprocal Regulation Low Energy High Energy Other Glycolysis Hexokinase - G6P (-) PFK - AMP (+), ATP (-), F2,6BP (++) Pyruvate Kinase - Alanine (-), ATP (-), F1,6BP (+) Gluconeogenesis FBPase - Citrate (+), AMP (-), F2,6BP (- -) PEPCK - ADP (-) Pyruvate Carboxylase - ADP (-), Acetyl-CoA (+) F2,6BP is Made Upon Insulin Stimulation - Favors Glycolysis F2,6BP is Broken Down Upon Glucagon Stimulation - Favors Gluconeogenesis GluconeogenesisandGlycolysis • Regulation CoriCycle Gluconeogenesis to the tune of "Supercalifragilisticexpialidocious" Copyright © by Kevin Ahern The aldolase reaction puts together pieces so A fructose molecule is made with two phosphates in tow MetabolicMelody gluconeogenesis liver’s specialty And one of Oh these gets cleaved offis by a fructose phosphatase Producing sugar foracting the body most admirably (slow) Unless F2,6BP's blocking path-a-ways When cellsper have lots ofisATP and NADH too Six ATPs glucose the needed energy* They strive to store this energy as sugar yes they do liver’s specialty Oh Gluconeogenesis gluconeogenesis aispathway to revere Inside of mitochondria they start with pyruvate That makes a ton of glucose when it kicks into high gear (slow) Carboxylating it to make glucose, glucose joy oxaloacetate to me The cell'sOh a masterminding metabolic engineer Glucose, glucose joy totome Gluconeogenesis a pathway revere Oh gluconeogenesis is so exhilarating Memorizing it can really be exasperating Converting phosphoglycerate to 1,3BPG Oh glucose, glucose jubilee Liver cells require it so there’s no need for debating Requires a Glucose, phosphate that includes glucose jubileeA-T-P energy Gluconeogenesis is gives so exhilarating Reduction with electrons us all an N-A-D (slow) And G3P’s isomerized to final makephase D-H-A-P From F6P to G6P, that is the Oh, glucose, glucose come to be The enzyme catalyzing it is an isomerase Glucose, glucose iscome to be Ohdrops gluconeogenesis Then G6P phosphate and aanabolic glucosebliss it becomes Reversing seven of glycolysis (slow) Inside the tinymechanisms endoplasmic-al reticulums Oxaloacetate got to turn To do well on the finalhas students havetotoPEP learn all this Employing energy that comes from breaking GTP Gluconeogenesis is anabolic bliss Oh gluconeogenesis is not so very hard From there it goes to make a couple phosphoglycerates I know that on the final we will not be caught off guard (slow) Exploiting ee-nolaseglucose and mutase’ catalytic traits Oh, glucose, factory 'Cause our professor lets us use a filled out index card Glucose, glucose factory Gluconeogenesis is not so very hard BennyBeaverSong (tothetuneof“RedRiverValley”) Copyright © Kevin Ahern MetabolicMelody InCorvallisalovablemascot Wonderswhyhe’sthewaythatheis Everyonethathemeetshasoneanswer Itrelatestothesequencingbiz EngineerssaythatBenny’samazing Buildingdamsofincrediblestrength Andhisfrontteethareworthyofpraising Growingtoanincrediblelength Whyisourcollegemascotsodaunting? Whiletheotherslikeducksaresomeek? DNAinthecellsofourBenny Iswhatmakesallofhistraitsunique SoourBeaverwillsoongethisanswers Tothequestions,revealingunknowns Therewillbealltheinfohe’safter Inthesequenceofhisfullgenome En-er-gy (To the tune of "Let It Be") Copyright © Kevin Ahern When I was walking through the forest And PBK in turn converted MetabolicMelody Grizzly bears came after me 'b's to 'a's and 'I's to 'D's * So I was badly needing So I released a ton of En-er-gy G1P My body dumped some epinephrine Out into the blood for me G1P / energy 'Cause I was badly needing G1P / energy I'll end my story here before I En-er-gy California needs some Get depressed from one last fact G1P En-er-gy / En-er-gy That dephosphorylation En-er-gy / En-er-gy And when the chaos had subsided I was badly needing Favors fat I consumed some Frito Lays En-er-gy Which soon began reversing These pathways Favors fat, favors fat The epinephrine gave a kick to The glucose halted epinephrine Enzymes deep inside of me Favors fat, favors fat Insulin began the race to To make a bunch of cyclic Turn on Phosphoprotein Dephosphorylation AMP Phosphatase And when this hit my protein kinase Favors fat Catalytic ecstasy Phosphatase - cleaves the P's The C subunits started Phosphatase - cleaves the P's Adding P's The dephosphorylation Cleaves the P's Adding P's, adding P's Adding P's, adding P's And so they were removed from action Phosphorylation city Cellular kinases Adding P's Thanks to Phosphoprotein Phosphatase The protein kinase put a phosphate Onto PBK for me Using energy from ATP