Upload
others
View
0
Download
0
Embed Size (px)
Citation preview
OrganicChemistry-Applica4ons
KNG-CHM-102-Lecture5
Norethindrone(anoralcontracep0ve-a3oalcoholgroup+ketonegroupandcarbon–carbondoubleandtriplebonds)
Alcohols
Ethers-Anaesthe4cs
1842,inflammable
NO(1799)
Fluorocarbons(compoundscontainingonlycarbonandfluorine)haveextraordinarilylowboilingpointswhencomparedtohydrocarbonsofthesamemolecularweight-verylowpolarizabilityoffluorineatoms.
Self-lubrica4ngproper4esthatareexploitedinmaking“nons4ck”fryingpansandlightweightbearings.
FluorocarbonsandTeflon
Pheromones:Communica4onbyMeansofChemicals
Usepheromonesincourtshipassexa[ractants.warningsubstances,and“aggrega4oncompounds”tocausemembersoftheirspeciestocongregate.
Insectsexa[ractants-usedtolureinsectsintotrapsasmeansofinsectcontrol,amuchmoreenvironmentallysensi4vemethodthantheuseofinsec4cides
• Olfactorysensi4vitytomusk-includessteroidssuchasandrosterone,largecyclicketones,andlactones(cyclicesters),
• Mayinfluenceourbehavior.• Compoundsusedinperfumes,
includingcivetone,anaturalproductisolatedfromglandsofthecivetcat,andpentalide,asynthe4cmusk
Humans
Carbon-alonecompounds
Lewisacidstabilizesthenega4vechargethatdevelopsontheoxygeninthetransi4onstate.
Theroleoftheenzyme’sproteinscaffold,istoholdthezincion,coenzyme,andsubstrateinthethree-dimensionalarrayrequiredtolowertheenergyofthetransi4onstate.
Reac4onisen4relyreversible,whentherela4veconcentra4onofethanolishigh
Alcoholdehydrogenasecarriesouttheoxida4onofethanolbyremovalofahydride-importantindetoxifica4on.
Alcoholdehydrogenase
VitaminAfromsourcesincludingdarkgreenleafyvegetables
Cholesterolfromanimals
Naturalrubberfromcertaintrees
Gu[apercha,anothernaturallatexfromthesapofsometrees
Compoundswithdoublebonds
fromtheseaincludedactylyneand(3E)-laurea4n,
TheSea:ATreasuryofBiologicallyAc4veNaturalProductsConcentra4onofhalidesintheoceanisapproximately0.5Min
chloride,1mMinbromide,and1mMiniodideions
Partofdefensemechanismsthatservetopromotethespecies’survivalbydeterringpredatorsorinhibi4ngthegrowthofcompe4ngorganisms
Halomon,-inpreclinicalevalua4onasacytotoxicagentagainstcertaintumorcelltypes,
Dactylyneisaninhibitorofpentobarbitalmetabolism
cyclocymopolenan4omersshowagonis4corantagonis4ceffectsonthehumanprogesteronereceptor
Sharplessasymmetrichydroxyla4on
Freeradicals
RadicalPolymeriza4onofEthene
PolyethylenecanbeproducedinadifferentwayusingZiegler–Na>acatalysts-organometalliccomplexesoftransi4onmetals.Inthisprocessnoradicalsareproduced,nobackbi4ngoccurs,and,consequently,thereisnochainbranching.Thepolyethylenethatisproducedisofhigherdensity,hasahighermel4ngpoint,andhasgreaterstrength
Adhesivecalled“superglue”isaresultofanionicpolymeriza4on.Superglueisasolu4oncontainingmethylcyanoacrylate
Methylcyanoacrylatecanbepolymerizedbyanionssuchashydroxideion,butitisevenpolymerizedbytracesofwaterfoundonthesurfacesofthetwoobjectsbeinggluedtogether.
MolecularOxygenandSuperoxideMolecularoxygeninthegroundstate-diradicalwithoneunpairedelectrononeachoxygen.Asaradical,oxygencanabstracthydrogenatomsjustlikeotherradicals.Thisisthewayoxygenisinvolvedincombus4onreac4onsandautoxida4on
InbiologicalsystemsoxygenisanelectronacceptorandbecomesbecomesaradicalanioncalledSuperoxide.
Superoxideisinvolvedinbothposi4veandnega4vephysiologicalroles:Theimmunesystemusessuperoxideinitsdefenseagainstpathogens,yetsuperoxideisalsosuspectedofbeinginvolvedindegenera4vediseaseprocessesassociatedwithagingandoxida4vedamagetohealthycells.Theenzymesuperoxidedismutaseregulatesthelevelofsuperoxidebycatalyzingconversionofsuperoxidetohydrogenperoxideandmolecularoxygen.Hydrogenperoxide,however,isalsoharmfulbecauseitcanproducehydroxyl(HO·)radicals.Theenzymecatalasehelpstopreventreleaseofhydroxylradicalsbyconver4nghydrogenperoxidetowaterandoxygen:
NitricOxide
Nitricoxide,synthesizedinthebodyfromtheaminoacidarginine,servesasachemicalmessengerinavarietyofbiologicalprocesses,includingbloodpressureregula4onandtheimmuneresponse.Itsroleinrelaxa4onofsmoothmuscleinvascular4ssues
The1998NobelPrizeinPhysiologyorMedicinewasawardedtoR.F.Furchgo[,L.J.Ignarro,andF.MuradfortheirdiscoverythatNOisanimportantsignalingmolecule.
Lipidoxida4on
Calicheamicinγ1I:RadicalDeviceforSlicingDNABackbone
Extraordinarilydeadlyforcancercells,ini4atesapoptosis(programmedcelldeath),ledtodevelopmentofthedrugMylotarg,totreatacutemylogenousleukemia.Mylotargcarriestwocalicheamicin“warheads”onanan4bodythatdeliversitspecificallytothecancerouscells.Innature,bacteriacalledMicromonosporaechinosporasynthesizesCalicheamicinγ1Iachemicaldefenseagainstotherorganisms.
ThelaboratorysynthesisofthiscomplexmoleculebytheresearchgroupofK.C.Nicolaou(ScrippsResearchIns4tute,UniversityofCalifornia,SanDiego),
An4oxidants
• VitaminE(a-tocopherol)iscapableofac4ngasaradicaltrap,inhibitsradicalreac4onsthatcouldcausecelldamage.
• VitaminCisalsoanan4oxidant,butsupplementsover500mgperdaymayhaveprooxidanteffects
• BHTaddedtofoodstopreventautoxida4on,trapsradicals.
OrganicTemplatesEngineeredtoMimicBoneGrowth
Helprepairbrokenbones,offsetosteoporosis,andtreatbonecancer
Arg-Gly-AspRGD
Intersec4onofnanotechnologySelf-assembledfiberpromotescalciumcrystalliza4onalongitsaxis,muchlikenature’scollagentemplateandbioengineering.
Bonesgrowbyadhesionofspecializedcellstoalongfibrousnaturaltemplatecalledcollagen(i)Promotethebindingofbone-growingcells(ii)facilitatecalciumcrystalliza4on.
OzoneDeple4onandChlorofluorocarbons(CFCs)
Stratosphere-al4tudesofabout25km,veryhighenergy(veryshortwavelength)UVlightconvertsdiatomicoxygen(O2)intoozone(O3).
Theozoneproducedinstep2canalsointeractwithhighenergyUVlight:Highlyenerge4cUVlightintoheat
ExistenceofthiscycleshieldsEarthfromradia4onthatisdestruc4vetolivingorganisms
MakeslifepossibleonEarth’ssurface.Evenarela4velysmallincreaseinhigh-energyUVradia4onatEarth’ssurfacewouldcausealargeincreaseintheincidenceofskincancers.
Typicalfreonsaretrichlorofluoromethane,CFCl3(calledFreon-11),anddichlorodifluoromethane,CF2Cl2(calledFreon-12).InJune1974F.S.RowlandandM.J.Molinashowedthatinthestratospherefreonisabletoini4ateradicalchainreac4onsthatcanupsetthenaturalozonebalance.The1995NobelPrizeinChemistrywasawardedtoP.J.Crutzen,M.J.Molina,andF.S.Rowland
Produc4onofchlorofluoromethanes(andofchlorofluoroethanes)calledchlorofluorocarbons(CFCs)orfreonsbeganin1930.usedasrefrigerants,solvents,andpropellantsinaerosolcans.
In1985aholewasdiscoveredintheozonelayeraboveAntarc4ca.Chlorineatomdestruc4onoftheozone-afactorintheforma4onofthehole.Thisozoneholehascon4nuedtogrowinsize,SuchaholehasbeendiscoveredintheArc4cozonelayer.Shouldtheozonelayerbedepleted,moreofthesun’sdamagingrayswouldpenetratetothesurfaceofEarth.Industrializedna4onsoftheworldceasedproduc4onofchlorofluorocarbonsasof1996,andover120na4onshavesignedtheMontrealProtocol1987