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Problem solving in enzyme biocatalysis PDF

346 Pages·2014·13.977 MB·English
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Problem Solving in Enzyme Biocatalysis Problem Solving in Enzyme Biocatalysis (cid:1) ANDRES ILLANES, LORENAWILSONAND CARLOS VERA School of Biochemical Engineering Universidad Cat(cid:1)olica de Valpara´ıso, Chile This edition first publishe d 2014 # 2014 John Wiley & Sons, Ltd Registered office John Wiley & Sons Ltd, The Atrium, Southern Gate, Chicheste r, West Sussex, PO19 8SQ , United Kingdom For details of our global editoria l offices, for customer service s and for information about how to apply for permis sion to reuse the copyright material in this book please see our website at www.wiley.com. TherightoftheauthortobeidentifiedastheauthorofthisworkhasbeenassertedinaccordancewiththeCopyright,Designs andPatentsAct1988. Allrightsreserved.Nopartofthispublicationmaybereproduced,storedinaretrievalsystem,ortransmitted,inanyformorby anymeans,electronic,mechanical,photocopying,recordingorotherwise,exceptaspermittedbytheUKCopyright,Designs andPatentsAct1988,withoutthepriorpermissionofthepublisher. Wileyalsopublishesitsbooksinavarietyofelectronicformats.Somecontentthatappearsinprintmaynotbeavailablein electronicbooks. Designationsusedbycompaniestodistinguishtheirproductsareoftenclaimedastrademarks.Allbrandnamesandproduct namesusedinthisbookaretradenames,servicemarks,trademarksorregisteredtrademarksoftheirrespectiveowners.The publisherisnotassociatedwithanyproductorvendormentionedinthisbook.Thispublicationisdesignedtoprovideaccurate andauthoritativeinformationinregardtothesubjectmattercovered.Itissoldontheunderstandingthatthepublisherisnot engagedinrenderingprofessionalservices.Ifprofessionaladviceorotherexpertassistanceisrequired,theservicesofa competentprofessionalshouldbesought. LimitofLiability/DisclaimerofWarranty:Whilethepublisherandauthorhaveusedtheirbesteffortsinpreparingthisbook, theymakenorepresentationsorwarrantieswithrespecttotheaccuracyorcompletenessofthecontentsofthisbookand specificallydisclaimanyimpliedwarrantiesofmerchantabilityorfitnessforaparticularpurpose.Itissoldontheunderstanding thatthepublisherisnotengagedinrenderingprofessionalservicesandneitherthepublishernortheauthorshallbeliablefor damagesarisingherefrom.Ifprofessionaladviceorotherexpertassistanceisrequired,theservicesofacompetentprofessional shouldbesought Theadviceandstrategiescontainedhereinmaynotbesuitableforeverysituation. Inviewofongoingresearch,equipment modifications,changesingovernmentalregulations,andtheconstantflowofinformationrelatingtotheuseofexperimental reagents,equipment,anddevices,thereaderisurgedtoreviewandevaluatetheinformationprovidedinthepackageinsertor instructionsforeachchemical,pieceofequipment,reagent,ordevicefor,amongotherthings,anychangesintheinstructionsor indicationofusageandforaddedwarningsandprecautions.ThefactthatanorganizationorWebsiteisreferredtointhiswork asacitationand/orapotentialsourceoffurtherinformationdoesnotmeanthattheauthororthepublisherendorsesthe informationtheorganizationorWebsitemayprovideorrecommendationsitmaymake. Further,readersshouldbeawarethat InternetWebsiteslistedinthisworkmayhavechangedordisappearedbetweenwhenthisworkwaswrittenandwhenitisread. Nowarrantymaybecreatedorextendedbyanypromotionalstatementsforthiswork. Neitherthepublishernortheauthorshall beliableforanydamagesarisingherefrom. LibraryofCongressCataloging-in-PublicationData Illanes,Andr(cid:1)es. Problemsolvinginenzymebiocatalysis/Andre´sIllanes,LorenaWilson,CarlosVera. pagescm Includesindex. ISBN978-1-118-34171-1(hardback) 1. Enzymes–Biotechnology. 2. Biocatalysis. 3. Enzymekinetics. 4. Enzymes–Industrialapplications. I. Wilson, Lorena. II. Vera,Carlos. III. Title. TP248.65.E59I452013 5720.7–dc23 2013029486 AcataloguerecordforthisbookisavailablefromtheBritishLibrary. ISBN:9781118341711 Setin10/12pt,TimesbyThomsonDigital,Noida,India Contents Preface ix Nomenclature xi EpsilonSoftwareInformation xxi Acknowledgement xxv 1 FactsandFiguresinEnzymeBiocatalysis 1 1.1 Introduction 1 1.1.1 EnzymeProperties 1 1.1.2 EnzymeApplications 2 1.2 EnzymesasProcessCatalysts 3 1.3 EvolutionofEnzymeBiocatalysis:FromHydrolysistoSynthesis 5 1.4 TheEnzymeMarket:FiguresandOutlook 6 References 7 2 EnzymeKineticsinaHomogeneousSystem 11 2.1 Introduction 11 2.1.1 ConceptandDeterminationofEnzymeActivity 11 2.1.2 DefinitionofaUnitofActivity 13 2.1.3 MeasurementofEnzymeActivity 13 2.2 TheoryofEnzymeKinetics 14 2.3 Single-SubstrateReactions 17 2.3.1 KineticsofEnzymeInhibition 18 2.4 Multiple-SubstrateReactions 19 2.4.1 ReactionMechanisms 19 2.4.2 KineticsofEnzymeReactionswithTwoSubstrates 20 2.5 Multiple-EnzymeReactions 21 2.6 DeterminationofKineticParameters 22 2.7 EffectsofOperationalVariablesonEnzymeKinetics 24 2.7.1 EffectsofpH 25 2.7.2 EffectsofTemperature 26 SolvedProblems 29 SupplementaryProblems 72 References 84 3 EnzymeKineticsinaHeterogeneousSystem 87 3.1 Introduction 87 vi Contents 3.2 ImmobilizationofEnzymes 87 3.2.1 ImmobilizationonSolidSupports(Carrier-BoundSystems) 88 3.2.2 ImmobilizationbyContainment 89 3.2.3 ImmobilizationinCarrier-FreeSystems 89 3.2.4 ParametersofEnzymeImmobilization 90 3.2.5 OptimizationofEnzymeImmobilization 91 3.3 Mass-TransferLimitationsinEnzymeCatalysis 92 3.3.1 PartitionEffects 93 3.3.2 ExternalDiffusionalRestrictionsinImperviousBiocatalysts 94 3.3.3 InternalDiffusionalRestrictionsinPorousBiocatalysts 97 3.4 DeterminationofIntrinsicKineticandMass-TransferParameters 102 3.4.1 EDR 102 3.4.2 IDR 104 SolvedProblems 105 SupplementaryProblems 127 References 138 4 EnzymeReactorDesignandOperationunderIdealConditions 141 4.1 ModesofOperationandReactorConfigurations 141 4.2 DefinitionofIdealConditions 142 4.3 StrategyforReactorDesignandPerformanceEvaluation 143 4.4 MathematicalModelsforEnzymeKinetics,ModesofOperation, andReactorConfigurationsunderIdealConditions 143 4.4.1 BatchEnzymeReactor 144 4.4.2 ContinuousEnzymeReactors 148 SolvedProblems 157 SupplementaryProblems 174 References 179 5 EnzymeReactorDesignandOperationunderMass-Transfer Limitations 181 5.1 SequentialBatchandContinuouslyOperatedReactorswith ImmobilizedEnzymes 182 5.2 MathematicalModelsforEnzymeKinetics,ModesofOperation, andReactorConfigurationsunderMass-TransferLimitations 183 SolvedProblems 185 SupplementaryProblems 198 6 EnzymeReactorDesignandOperationunderBiocatalystInactivation 203 6.1 MechanisticallyBasedMathematicalModelsofEnzymeInactivation 203 6.2 EffectofCatalyticModulatorsonEnzymeInactivation 205 6.3 MathematicalModelsforDifferentEnzymeKinetics,Modesof Operation,andReactorConfigurationsunderBiocatalystInactivation 206 6.3.1 NonmodulatedEnzymeInactivation 206 6.3.2 ModulatedEnzymeInactivation 209 Contents vii 6.4 MathematicalModelsforEnzymeKinetics,ModesofOperation, andReactorConfigurationsunderSimultaneousMass-Transfer LimitationsandEnzymeInactivation 212 6.5 StrategiesforReactorOperationunderBiocatalystInactivation 213 SolvedProblems 215 SupplementaryProblems 233 References 240 7 OptimizationofEnzymeReactorOperation 243 7.1 StrategyfortheOptimizationofEnzymeReactorPerformance 244 7.1.1 ObjectiveFunction 244 7.1.2 VariablesforOptimizationofEnzymeReactorPerformance 246 7.1.3 DeterminationofOptimumTemperature 247 7.2 MathematicalProgrammingforStaticOptimization 247 7.3 DynamicProgramming 248 7.4 StatisticalOptimizationbySurfaceResponseMethodology 249 7.4.1 AssessingtheQualityofSRManditsParameters 251 7.4.2 ProcessOptimizationbySRM 252 SolvedProblems 254 SupplementaryProblems 272 References 275 AppendixA MathematicalMethods 277 A.1. Newton’sMethod 277 A.2. CurveFittingbyLeastSquares 280 A.2.1 LinearRegression 280 A.2.2 NonlinearRegression 286 A.3. SolvingOrdinaryDifferentialEquations 296 A.3.1 SolvingFirst-OrderOrdinaryDifferentialEquationsbythe SeparationofVariables 296 A.3.2 SolvingFirst-OrderOrdinaryDifferentialEquationsUsingan IntegrationFactor 297 A.3.3 SolvingSecond-andHigher-OrderLinearHomogeneous DifferentialEquationswithConstantCoefficientsUsing theirCharacteristicEquations 298 A.3.4 SolvingSecond-andHigher-OrderLinearHomogeneous DifferentialEquationswithVariableCoefficients 301 A.4. NumericalMethodsforSolvingDifferentialEquations 302 A.4.1 TheEulerMethod 302 A.4.2 TheFourth-OrderRunge–KuttaMethod 303 A.4.3 TheFinite-DifferenceMethod 303 References 310 Index 311

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