saponins - ankara Üniversitesi

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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•  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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•  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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saponins - ankara Üniversitesi

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