Modern Methods in Crop Protection Research

429 Pages·2012·4.75 MB·English

EditedbyPeterJeschke,WolfgangKra¨mer,
UlrichSchirmer,andMatthiasWitschel
ModernMethodsinCropProtection
Research
RelatedTitles
Kra¨mer,W.,Schirmer,U.,Jeschke,P., Walters,D.
Witschel,M.(eds.)
PlantDefense
Modern CropProtection
Wardingoffattackbypathogens,
Compounds herbivoresandparasiticplants
2012 2010
ISBN:978-3-527-32965-6 ISBN:978-1-4051-7589-0
Filho,V.C. Tadros,T.F.(ed.)
PlantBioactives andDrug Colloids inAgrochemicals
Discovery ColloidsandInterfaceScience
Principles,Practice,andPerspectives
Volume5oftheColloidsandInterfaceScience
Series
2012
2009
ISBN:978-0-470-58226-8
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Edited by Peter Jeschke, Wolfgang Kra¨mer, Ulrich Schirmer,
and Matthias Witschel
Modern Methods in Crop Protection
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V
Contents
Preface XV
ListofContributors XIX
PartI MethodsfortheDesignandOptimization
ofNewActiveIngredients 1
1 High-ThroughputScreeninginAgrochemicalResearch 3
MarkDrewes,KlausTietjen,andThomasC.Sparks
1.1 Introduction 3
1.2 Target-BasedHigh-ThroughputScreening 6
1.2.1 Targets 6
1.2.2 High-ThroughputScreeningTechniques 9
1.3 OtherScreeningApproaches 13
1.3.1 High-ThroughputVirtualScreening 13
1.4 InVivoHigh-ThroughputScreening 13
1.4.1 CompoundSourcingandIn-SilicoScreening 15
1.5 Conclusions 17
Acknowledgments 18
References 18
2 ComputationalApproachesinAgriculturalResearch 21
Klaus-Ju¨rgenSchleifer
2.1 Introduction 21
2.2 ResearchStrategies 21
2.3 Ligand-BasedApproaches 22
2.4 Structure-BasedApproaches 26
2.5 EstimationofAdverseEffects 33
2.6 In-SilicoToxicology 34
2.7 ProgramsandDatabases 34
2.7.1 In-SilicoToxicologyModels 36
VI Contents
2.8 Conclusion 39
References 40
3 QuantumChemicalMethodsintheDesignofAgrochemicals 43
MichaelSchindler
3.1 Introduction 43
3.2 ComputationalQuantumChemistry:Basics,Challenges,
andNewDevelopments 44
3.3 MinimumEnergyStructuresandPotentialEnergySurfaces 47
3.4 Physico-ChemicalProperties 51
3.4.1 ElectrostaticPotential,FukuiFunctions,andFrontierOrbitals 53
3.4.2 MagneticProperties 55
3.4.3 pKaValues 57
3.4.4 SolvationFreeEnergies 59
3.4.5 AbsoluteConfigurationofChiralMolecules 60
3.5 QuantitativeStructure-ActivityRelationships 60
3.5.1 PropertyFields,Wavelets,andMulti-ResolutionAnalysis 61
3.5.2 TheCoMFASteroidDataset 63
3.5.3 ANeonicotinoidDataset 64
3.6 Outlook 66
References 67
4 TheUniqueRoleofHalogenSubstituentsintheDesign
ofModernCropProtectionCompounds 73
PeterJeschke
4.1 Introduction 73
4.2 TheHalogenSubstituentEffect 75
4.2.1 TheStericEffect 76
4.2.2 TheElectronicEffect 78
4.2.2.1 ElectronegativitiesofHalogensandSelectedElements/Groups
onthePaulingScale 78
4.2.2.2 EffectofHalogenPolarityoftheC–HalogenBond 79
4.2.2.3 EffectofHalogensonpK Value 79
a
4.2.2.4 ImprovingMetabolic,Oxidative,andThermalStability
withHalogens 80
4.2.3 EffectofHalogensonPhysico-ChemicalProperties 82
4.2.3.1 EffectofHalogensonMolecularLipophilicity 82
4.2.3.2 ClassificationintheDisjointPrincipleSpace 84
4.2.4 EffectofHalogensonShiftofBiologicalActivity 84
4.3 InsecticidesandAcaricidesContainingHalogens 86
4.3.1 Voltage-GatedSodiumChannel(vgSCh)Modulators 86
4.3.1.1 Pyrethroidsof TypeA 86
4.3.1.2 Pyrethroidsof TypeB 89
Contents VII
4.3.1.3 Pyrethroidsof TypeC 90
4.3.2 Voltage-GatedSodiumChannel(vgSCh)Blockers 90
4.3.3 Inhibitorsoftheγ-AminobutyricAcid(GABA)Receptor/Chloride
IonophoreComplex 91
4.3.4 InsectGrowthRegulators(IGRs) 93
4.3.5 MitochondrialRespiratoryChain 96
4.3.5.1 InhibitorsofMitochondrialElectronTransportatComplexI 96
4.3.5.2 InhibitorsofQ SiteofCytochromebc1– ComplexIII 97
o
4.3.5.3 InhibitorsofMitochondrialOxidativePhosphorylation 97
4.3.6 RyanodineReceptor(RyR)Effectors 98
4.4 FungicidesContainingHalogens 99
4.4.1 SterolBiosynthesisInhibitors(SBIs)andDemethylationInhibitors
(DMIs) 99
4.4.2 MitochondrialRespiratoryChain 101
4.4.2.1 InhibitorsofSuccinateDehydrogenase(SDH)– ComplexII 101
4.4.2.2 InhibitorsofQ SiteofCytochromebc1– ComplexIII 104
o
4.4.2.3 NADHInhibitors – ComplexI 107
4.4.3 FungicidesActingonSignalTransduction 107
4.5 PlantGrowthRegulators(PGRs)ContainingHalogens 108
4.5.1 ReductionofInternodeElongation:InhibitionofGibberellin
Biosynthesis 108
4.6 HerbicidesContainingHalogens 109
4.6.1 InhibitorsofCarotenoidBiosynthesis:PhytoeneDesaturase(PDS)
Inhibitors 109
4.6.2 InhibitorsofAcetolactateSynthase(ALS) 111
4.6.2.1 SulfonylureaHerbicides 111
4.6.2.2 Sulfonylaminocarbonyl-TriazoloneHerbicides(SACTs) 115
4.6.2.3 TriazolopyrimidineHerbicides 116
4.6.3 ProtoporphyrinogenIXOxidase(PPO) 117
4.7 SummaryandOutlook 119
References 119
PartII NewMethodstoIdentifytheModeofAction
ofActiveIngredients 129
5 RNAInterference(RNAi)forFunctionalGenomicsStudies
andasaToolforCropProtection 131
BerndEssigmann,EricPaget,andFre´de´ricSchmitt
5.1 Introduction 131
5.2 RNASilencingPathways 131
5.2.1 TheMicroRNA(miRNA)Pathway 133
5.2.2 TheSmallInterferingPathway(siRNA) 134
5.3 RNAiasaToolforFunctionalGenomicsinPlants 134
VIII Contents
5.4 RNAiasaToolforEngineeringResistanceagainstFungi
andOomycetes 138
5.5 RNAiasaToolforEngineeringInsectResistance 140
5.6 RNAiasaToolforEngineeringNematodesResistance 142
5.7 RNAiasaToolforEngineeringVirusResistance 144
5.8 RNAiasaToolforEngineeringBacteriaResistance 149
5.9 RNAiasaToolforEngineeringParasiticWeedResistance 150
5.10 RNAiSafetyinCropPlants 153
5.11 SummaryandOutlook 153
References 153
6 FastIdentificationoftheModeofActionofHerbicides
byDNAChips 161
PeterEckesandMarcoBusch
6.1 Introduction 161
6.2 GeneExpressionProfiling:AMethodtoMeasureChanges
oftheCompleteTranscriptome 162
6.3 ClassificationoftheModeofActionofanHerbicide 164
6.4 IdentificationofProdrugsbyGeneExpressionProfiling 165
6.5 AnalyzingtheAffectedMetabolicPathways 169
6.6 GeneExpressionProfiling:PartofaToolboxforModeofAction
Determination 171
References 172
7 ModernApproachesforElucidatingtheModeofAction
ofNeuromuscularInsecticides 175
DanielCordova
7.1 Introduction 175
7.2 BiochemicalandElectrophysiologicalApproaches 176
7.2.1 BiochemicalStudies 176
7.2.2 ElectrophysiologicalStudiesonNativeandExpressedTargets 179
7.2.2.1 Whole-CellVoltageClampStudies 179
7.2.2.2 OocyteExpressionStudies 180
7.2.3 AutomatedTwo-ElectrodeVoltage-ClampTEVCRecording
Platforms 182
7.3 Fluorescence-BasedApproachesforModeofActionElucidation 183
7.3.1 Calcium-SensitiveProbes 183
7.3.2 Voltage-SensitiveProbes 186
7.4 GenomicApproachesforTargetSiteElucidation 187
7.4.1 Chemical-to-GeneScreening 187
7.4.2 Double-StrandedRNAInterference 190
7.4.3 Metabolomics 191
Contents IX
7.5 Conclusion 191
References 192
8 NewTargetsforFungicides 197
KlausTietjenandPeterH.Schreier
8.1 Introduction:CurrentFungicideTargets 197
8.2 ARetrospectiveLookattheDiscoveryofTargetsforFungicides 199
8.3 NewSourcesforNewFungicideTargetsintheFuture? 199
8.4 MethodstoIdentifyaNovelTargetforaGivenCompound 200
8.4.1 MicroscopyandCellularImaging 200
8.4.2 CultivationonSelectiveMedia 200
8.4.3 IncorporationofIsotopicallyLabeledPrecursors
andMetabolomics 201
8.4.4 AffinityMethods 201
8.4.5 ResistanceMutantScreening 201
8.4.6 GeneExpressionProfilingandProteomics 202
8.5 MethodsofIdentifyingNovelTargetswithoutPre-Existing
Inhibitors 202
8.5.1 BiochemicalIdeastoGenerateNovelFungicideTargets 203
8.5.2 GenomicsandProteomics 203
8.6 Non-ProteinTargets 213
8.7 ResistanceInducers 213
8.8 BeneficialSideEffectsofCommercialFungicides 214
8.9 ConcludingRemarks 214
References 214
PartIII NewMethodstoImprovetheBioavailability
ofActiveIngredients 217
9 NewFormulationDevelopments 219
RolfPontzenandArnoldusW.P.Vermeer
9.1 Introduction 219
9.2 DriversforFormulationTypeDecisions 223
9.3 DescriptionofFormulationTypes,TheirProperties,andProblems
duringDevelopment 225
9.3.1 PesticidesDissolvedinaLiquidContinuousPhase 225
9.3.2 CrystallinePesticidesinaLiquidContinuousPhase 228
9.3.3 PesticidesinaSolidMatrix 232
9.4 BioavailabilityOptimization 235
9.4.1 SprayFormationandRetention 236
9.4.2 SprayDepositFormationandProperties 238
9.4.3 CuticularPenetration 240
9.4.3.1 CuticularPenetrationTest 242
X Contents
9.4.3.2 EffectofFormulationonCuticularPenetration 243
9.5 ConclusionsandOutlook 246
References 247
10 PolymorphismandtheOrganicSolidState:Influence
ontheOptimizationofAgrochemicals 249
BrittaOlenikandGerhardThielking
10.1 Introduction 249
10.2 TheoreticalPrinciplesofPolymorphism 250
10.2.1 TheSolidState 250
10.2.2 DefinitionofPolymorphism 251
10.2.3 Thermodynamics 251
10.2.3.1 MonotropismandEnantiotropism 251
10.2.3.2 EnergyTemperatureDiagramsandtheRules 252
10.2.4 KineticsofCrystallization:Nucleation 254
10.3 AnalyticalCharacterizationofPolymorphs 255
10.3.1 DifferentialThermalAnalysisandDifferentialScanning
Calorimetry 256
10.3.2 Thermogravimetry 258
10.3.3 Hot-StageMicroscopy 259
10.3.4 IRandRamanSpectroscopies 261
10.3.5 X-RayAnalysis 265
10.4 PatentabilityofPolymorphs 268
10.5 SummaryandOutlook 270
Acknowledgments 270
References 270
11 TheDeterminationofAbrahamDescriptorsandTheirApplication
toCropProtectionResearch 273
EricD.ClarkeandLauraJ.Mallon
11.1 Introduction 273
11.2 DefinitionofAbrahamDescriptors 274
11.3 DeterminationofAbrahamDescriptors:GeneralApproach 275
11.3.1 VandEDescriptors 276
11.3.2 A,B,andSDescriptors 277
11.3.3 A,B,S,andLDescriptors 277
11.3.4 LSEREquationsforUseinDeterminingDescriptors 278
11.3.5 PredictionofAbrahamDescriptors 280
11.4 DeterminationofAbrahamDescriptors:PhysicalProperties 281
11.5 DeterminationofAbrahamDescriptors:Examples 283
11.5.1 Herbicides:Diuron(1) 284
11.5.2 Herbicides:Simazine(2)andAtrazine(3) 285
11.5.3 Herbicides:Acetochlor(4)andAlachlor(5) 288