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SAPONINS• Saponinsareinglycosidicstructure.mostlyofplant
originated,givestablefoamsinwater.• Commonamongplants..• Scrophulariaceae-----Digitalis---digitonoside• Caryophyllaceae---Çöven----glycosidethatcontain
gypsogeninasaglycon• Leguminosae----Glycyrrhiza----glycyrrhizicacid• Dioscoriaceae---Dioscorea---diosgenin• Liliaceae---Smilax------sarsaponoside
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SAPONINS• Theygivestablefoamwithwater• Colourless,odorless,irritantcompounds• Amorphous• Dissolveinboiledwater,MeOH,EtOH;precipatedwhencooled
• Theygivecomplexcompoundswithcholesterolandlecithin
• Toxiccompoundstofish• Poisonforblood---theyconverttheredbloodcellwallpermeabl
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SAPONINS• TheyshowHemolyticeffect• Orallynoteffectiveashemolyticsincetheyarenotresorbed
• Thereisnocollerationbetweenhemolyticproperty,toxicityandprecipitationwithcholesterol.
• Forexample;glycyrrhizicacidgivefoam,butdoesn’thavehemolyticproperty
• HemolysispropertyofEscinsaponinsis2timesmorethanPrimulasaponinsbuttoxicityis10timesless
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SAPONINS• Hemolysispropertyisduetoaglycon• Arrangementofthesugarsalsoeffectsintensityofthe
hemolysis• SaponinsoftheleavesofDigitalislanatadon’thave
hemolysispropertybuttheymakecomlexeswithcholesterol
• Generally,bidesmosidicsaponinsarealmostinactiveintermsofhemolyticactivity
• Acidicsaponins----weakhemolysis
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SAPONINS
• Netralsaponinswithbranchedsubstituents(4-5sugarunits)havemaximumhemolysisindex
• Monodesmosidicsteroidalsaponinsformthestrongestcomplexeswithcholesterol
• Triterpenesformlimitedcomplexes
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SAPONINS
Ø Saponins!hydrolysis!aglycone(sapogenin)+sugar
Ø Theaglyconwhethercanbesteroidal(27C)ortriterpenic(30C).
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SAPONINS
• Assugarunits:• a)Mostlyglucose• b)Arabinose/galactose/xylose/rhamnose• c)Uronicacid
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SAPONINS
• Accordingtothebindingofthesugarstotheaglyconetwodifferenttypesofsaponinsmayoccur:
• 1)Monodesmosidicsaponinshaveasinglesugarchain,normallyattachedtotheaglyconat3rdposition(C-3)andoneattachedthroughanesterlinkage(acylglycoside)atC-28oranetherlinkageatC-26.
• Inacidaglycons,sugarcanattachto-COOH
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SAPONINS
ü STEROIDGLYCOSIDESü 27Carbonunitsü MostarederivedfromSpirostanskeleton
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SAPONINS
• Steroidsaponin’sisomers:• a)normalandiso-isomers:C-25methylgroupisaxiallyorientatedinnormalsapogenins(neosapogenins)andequatoriallyorientatedinisosapogenins
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SAPONINS• b) In Spirostan type
steroids depending onAandB rings cis/transisomersoccur
6.halka A/B OH
Sarsapogenol normal cis 3
Smilasapogenol
iso cis 3
Tigogenol iso trans 3
Gitogenol iso trans 2,3
Digitogenol iso trans 2,3,15
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SAPONINS
• TRITERPENESAPOGENINS• Theycanfoundinanyorganoftheplant(root,leavesetc.)
• Mostlyfoundinparanchymatictissues• SaponinsinDicotyledonesaremostlytriterpenes(exceptDigitalis)
• Morecommoninnature• 30Carbonunits• Theyhaveβ-amirenolmainskeleton
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SAPONINS
• SubstituentsarestatedgenerallywiththeCnumbertheyattachedto.
• Acidicorestersaponinsmayfoundamongtriterpenes:
A. ACIDSAPONINS:§ -COOHcanbefoundwhetherin§ Aglyone(C4,C17,C20)orin§ Sugaror§ Inbothaglyconandsugar
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SAPONINS
• Forexample;• HederageninveGypsogenin---–COOHfoundinaglycon• Primulasaponine-----COOHfoundinsugarasuronic
acid• Glycyrrhizin-----–COOHfoundbothinaglyconandsugar
(uronicacid)• Acidsapogeninscanbeclassifiedaccordingtothe
numberof–COOHtheycontain:
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SAPONINS
B)ESTERSAPONINS:• SecondaryalcoholgroupslocatedatC-16,21ve22isesterifiedwithacidssuchasaceticacid,tiglicacid
• Forexample;Escincomplex
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SAPONINS
• IDENTIFICATION• Foamingproperty• Hemolysisproperty• Colourreactionsareusedforidentification
• A)SteroidSaponins;• 1)SALKOWSKIREACTION:ChloroformsolutionofSapogenin+concentratedH2SO4---layering---atfirstayellowringoccursthanredcolourinchloroformlayerindicatesthepresenceofspirostanring.
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SAPONINS
• 2)LIEBERMANN-BURCHARDREACTION:Solutionwithanhydrousaceticacid+layeringwithconc.H2SO4!violet-puple----blue---thanstablegreencoloursindicatepresenceofcyclopentanophenanthrenering.
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SAPONINS
• B)IdentificationofTriterpeneSaponins;• 1)BRIESKORN-BRINERREACTION:Solutionwithanhydrousaceticacid+chlorosulphonicacid----purple-redcolour.
• 2)ANISALDEHYDETEST:Saponin+freshlypreparedanisaldehyde-H2SO4reagent---colourrangebetweenpinktopurple
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SAPONINS
• QUANTIFICATION• 1)BaritMethod:Drug+extractionwithbolingwater---filteredandwaterisevaporated;thanunwantedcompoundsareprecipatedwithhotethanol.Filtrateisdistilled;saponinsareprecipitatedbyadditionofsaturatedBa(OH)2solution.Washed,driedandweighed!burned,weighed.Differencebetweentwoweighinggivestheamountofsaponins(Gravimetricassay)
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SAPONINS
• 2)Saponinsarehydrolised.Aglyconisseparated,precipatedandweighed(Gravimetric)
• 3)FoamingIndex:Thedilutionlevelof10mlofsaponinsolution,forming1cmoffoamwhichisshakenhorizontallyfor15secondsandrested15minutesinatesttubeof16mmdiameter
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SAPONINS• 0.1%decoctionisprepared• 1,2,3---------10mlofthedecoctionisputrespectivelyto10
tubes.Volumeiscompletedto10mlineachtube.• Afterfoamingprocedures;ifthereisfoamin1cmheightin
3rdtube;• 0.1/100mlX3=0.003gdrugamount• 10ml-----0.003g• Concentration=0.003/10• Dilution(FoamingIndex)=10/0.003=3333.33
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SAPONINS
• 4)HemolysisIndex(HI):Hemolysisindexvaluesaregenerallylargenumbers.Achoosenstandardsaponin’sHemolysisIndexisacceptedas1StandartUNIT---itiscalledHemolysisvalue.Saponariaalbasaponinisacceptedasstandard.
• HI;isthedilutiondegreeofsaponinsolutionwhichhavetheabilitytohemolysisalltheerythrocytesina2mlsolution.
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SAPONINS• EFFECT and USAGE
• Antibiotic • Antiexudative (Escin, Primula saponin, α-
hederin) ü Expectorant ü Primula saponin---- Radix Primulae ü Senegin-----Radix Senegae ü Glycrrhizin----Radix Liquiritiae ü Gypsophila saponin ü Hederasaponin------Hedera helix
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SAPONINS
• Antispasmodic ! Ammonium glycyrrhirizate • Antiinflammatory ! Escin-------Semen
Hippocastanae • Glycrrhizin----Radix Liquiritiae • Diuretic ! Cyclamin, α-hederin, Escin
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SAPONINS• Startingmaterialinthesynthesisofsteroidal
hormones,vit.Dandcardioactiveglycosides• Sincetheyhavefoamingproperty,inthesolutionof
saponins,surfacetensionisreduced• Incosmetologytheyareaddedtoshampoo,bath
bubblesandtoothpastes• Theyareusedinfireextinguishers• Infoodindustry,theyareusedtopreparefoaming
drinks
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SAPONINS
• EscinistheonlysaponinwhichcanbeusedIV(usedintherapy)
• Usedforedemarelief• UsedinPost-operativeedemas• UsedtotreatandpreventThrombosis• Digitalissaponinsareimportantsincetheyincreasethesolubilityofcardiacglycosides
• Saponinshaveprotectingeffectontheplant,againstpathogenfungiandmicroorganisms
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RADIXSARSAPARILLAE(TK),SarsaparillaRoot,Saparnakökü
• ObtainedfromSmilaxspecies(Liliaceae)• (S.febrifuga,S.medica,S.ornata)• GrowsintropicalforestsinCentralandSouthAmerica(Mexico,Brazil)
• Namedaccordingtothepreparationsinthemarket;• Mexicansarsaparilla-(EP)---S.medica• (USP)---S.aristolochiaefolia• Jamaicansarsaparilla----S.ornata• Honduransarsaparilla--S.regelii
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RADIXSARSAPARILLAE(TK),SarsaparillaRoot,Saparnakökü
• Rootsareredwithlongitudinalgrooved• Highlythickenedandlignifiedhypodermacells,endodermathickenedintheshapeofahorseshoeandraphideclusters
• Inthepowdereddrug;raphidesandstarchareabundantalongwithschlerenchymatictissue.ThoughresemblesR.Ipecacuanhaewiththeseproperties,itlackscorktissueandisdifferentiatedwiththehelpofthisdifference.
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RADIXSARSAPARILLAE(TK),Saparnakökü
• Contains2-4%steroidalsaponins• S.medica---Sarsaponoside(Sarsapogenin+2gl+rh)
(normalisomer)• S.aristolochiaefolia---Perilloside(normal)• S.ornata-----Smilasaponoside(Smilasapogenin+2gl+rh)
(isoisomer)• Sarsaparilloside----Bisdesmosidicsaponin
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RADIXSARSAPARILLAE(TK),SarsaparillaRoot
• Antisyphilitic• Antirheumatic• Diuretic,sudorific(leadstosweating)• Inskindiseases• Depurative• Jamaicansarsaparilla(S.ornata)---usedagainstleprosy
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RADIXSENEGAE(TK),PoligalaköküSenegaroot
• Rootsandrhizomes(undergroundparts)ofPolygalasenega(Polygalaceae)
• GrowsinNorthAmerica–inCanadaandTexas• Withlanceolateleaves,whiteflowers,perennial,aplantthatcangrowupto20-30cm.
• ImportedfromCanada• Drugconsistsofasmallrhizomeandthemainrootthatistheextensionofit.
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RADIXSENEGAE(TK),PoligalaköküSenegaroot
• 5%oil• 10%saponinsmixture(triterpenic)(Presenegenin+Senegenin)
• Senegoside----Senegenin+gl+arabinose+methylpentose
• Polygalitol----isapoliolandisthesubstancethatgivesthedrugsweettaste.
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RADIXSENEGAE(TK),PoligalaköküSenegaroot• EFFECT-USAGE
• Expectorant:Canbeusedinchildreninchronicbronchitiswithoutconcern.
• Saponinsreducesthesurfacetensionofsecretions.Thustheyarereleasedfromthemucousmembranes.
• Inaddition,itreducestheviscosityofdensifiedbronchialsecretion.
• Crudedrugwithasingledoseof1g---isequivalentto5%decoctionof20gor2.5gtincture(1:5).
• Dailydoseshouldnotexceed3gsinceitleadstogastrointestinaldisorders(likevomiting,diarrhea)
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RADIXSENEGAE(TK),PoligalaköküSenegaroot
• Diuretic• Canalsobeusedasalaxative.• 11Polygalaspeciesgrowinourcountry.ThemostcommonspeciesinAnatoliaarePolygalaamaraandPolygalapruinosa.
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DIOSGENOL• Firstobtainedfrom
aspeciesfromDioscoreaceae
• D.composita• Allium
fuscoviolaceum• Trigonellafoenum
graecumseeds--1-2%
• Dioscoreasp.----tubers
• Alliumsp.----aerialparts,bulbs
• Sapogenolwithsteroidalstructure 35
DIOSGENOL
• ExtractedwithEtOH• Acidichydrolysisisapplied• Precipitatedsapogeninisextractedwiththesolvent.
• Usedinthesemi-synthesisofsteroidalhormones.
• Diosgenolacetate----16-dehydropregnenolacetateisobtained.
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HECOGENIN• ObtainedfromAgave(Amaryllidaceae)andYucca(Liliaceae)species.
• Agavepromontorii• A.cerulataisrichinsaponins.• Origin:NorthAmerica• A.americanaisfoundinourcountryasanornamentalplant.
• Agaveleavesareused.• Agavesisalana(0.2%)• SapogeninisobtainedfromA.fourcroydes
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HECOGENIN• Leavesareseparatedfromitsfibers.• Juiceisobtained,thenfermented.• Attheendoffermentation,hecogeninprecipitated(alongwithothersubstances)
• Thismasscontains5-10%sapogenins.• Theprecipitateishydrolyzedwithacid.• Extractedwithsolventslikeheptaneorbenzene.• Majorityofthisobtainedsapogeninmixtureconsistsofhecogenin.
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HECOGENIN• Thiscompoundisa
sterolthatcontainsaketonemoietyinthe12thcarbon.
• ThisnameisgivensinceitisobtainedfromHechtiatexensis(Bromeliaceae)forthefirsttime.
• Startingmaterialinthesynthesisofsteroidalhormones.
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