ClassificationofNaturaldyesand Syntheticdyes Bystructureandby color

Natural dyes
Onecangetcoloringmatterfromalmostallvegetablematter.However,onlyafewofthesesourcesyield colorantswhichcanbeextractedandworkouttobecommerciallyviable.Similaristhecaseofcolorants obtainedfromanimalorigin. Basically,threeprimarycolorsarerequiredtogetanygivenhue(orcolor).Thistypeofapproachhas beenworkedoutforsyntheticdyes.Howeverinthecaseofnaturaldyes,thedyeingproceduresare differentfordifferentdyesandtheycannotbeblendedtogetrequiredcoloreasily

Why and how natural dyes are different

Nevertheless,whilelookingfordifferentcolorsonefindsthatitisbettertohavealimitednumberof dyeswithgoodfastnessproperties,ratherthanhavingtoomanycolors(sources)withlimitedfastness properties. Whileselectingtheproperpaletteofcolorsonewouldliketohaveatleastoneblue,oneredanda yellowtostartwith.Duetothelimitednumberofnaturaldyesavailable,thecorrectchoiceofthedyes isveryimportant.Informationofsomeimportantnaturaldyesisgivenbelow.

Blue dyes
Thecolorindexlistsonlyfournaturaldyes,thatisNaturalIndigo,sulphonated NaturalIndigo,Kumbh (Manipur)andtheflowersofJapaneseTsuykusausedmainlyformakingawobana paper. TheonlyviablechoiceamongthebluenaturaldyesisIndigo.Naturalindigoisobtainedbyfermenting theleavesofvariousspeciesofIndigofera,runningofftheliquorandoxidizingittoprecipitatethedye. Woad (Isatis tinctoria L.)isanotherimportantsourceofindigo.TheplantisgrownmostlyinNorth EuropeandBritishIsles. Withthesynthesisofindigoin1880anditssuccessfulcommercialexploitationin1897byBASF,the productionofnaturalIndigodecreased.Thekingofnaturaldyeswentintooblivion.Therearesome signsofitsrevival.ThecurrentdemandofIndigoinUSisestimatedtobearound800tonnes peryear, pricedataround$20million.Themainingredientsofnaturalindigoareindigotin (I)andindirubin (II)

Red Dyes
Thecolorindexlists32rednaturaldyes.Theprominentamongthemaremadder(Rubia tinctorum L.), manjistha (Rubia cordifolia L.),brazilwood/sappan wood (Caesalpina sappan L.),Alormorinda (Morinda citrifolia L.)cochineal (Coccus cactiL.)andlac dye (Coccus laccae). Manjistha orIndianmadderisanthraquinone basedreddye.Themostimportantcolorantsinmadder aretheanthraquinones,alizarin(III),purpuroxanthin (IV),rubiadin (V),manjistin (VI),purpurin (VII)and pseudopurpurin (VIII).

More red Dyes

Brazilin(C.I.NaturalRed24)isthemaincoloringcomponentofCeasalpinia echinata Lam(Brazilwood) andCeasapinia sapan L.(Sappan wood). Brazilin(IX)getsoxidizedtoformtheredBrasilein (X)as indicatedbelow.

Red dye- lac dye

Lacisperhapsoneoftheoldestofallknownreddyes.However,cochinealandkermeswerewidelyused inthewesternworldfortheproductionofbrightpurpleandredcolors. Thelac dyeisextractedfromlac,theresinousprotectivesecretionoftinyinsect,Luccifera lacca,whichis apestonanumberofplantsbothwildandcultivated.Itsecretesathickresinousfluidwhichenvelopes theirbodies:andsecretionfromahardcontinuousencrustationoverthetwigs.Theycontainonly12% dye.Therearefourcoloringcompoundsinlac,designatedaslaccaic acidA,B,CandE(XI).Laccaic acid (A)beingthemostabundant.Laccaic acidisalsocalledXanthokermesic acid,anditcloselyresembles Kermesic acidinstructure.Lacdyebeinganaciddyecanbedirectlydyedonproteinfibersuchaswool andsilk.Italsoproducesverydarkshadesonnylon.Thehuescanbemodifiedbypostmordanting treatmentwithmetalsalts.Thedyehasverygoodlightandwashingfastness.

(XI)

Laccaic acid A B C E

R=CH2NHCOCH3) R= CH2OH) R=CH (NH2) COOH) (R= CH2NH2)

Yellow Dyes
Yellow[Mayerandcook,1943;Goodwin,1976;Cardon andChatenet,1990andSinghetal.,2001]isthe mostcommoncolorinthenaturaldyes.Howevermostoftheyellowcolorantsarefugitive.Thecolor indexlists28yellowdyes.Someoftheimportantyellowdyesareobtainedfromberberry (Berberis aristata),tessu flowers(Butea frondosa,monosperma) andkamala(Mallotus philippensis). Othersourcesofyellowdyeareblackoak(Quercus velutina),turmeric(Curcumalonga), weld(Reseda luteola) andhimalalayan rhubarb (Rheumemodi). Somecoloringmattersareberberine (XII),itsderivatives(XIII),chrysophanic acid(XIV)andluteolin (XV).

(XII)

(XIII)

(XIV)

(XV)

Dihydropyran Dihydropyran :Closelyrelatedtoflavonesinchemicalstructurearesubstituteddihydropyrans likethe

oneshownhere.

OH HO O OH

HO

D ih y d r p y r a n

Anthracyanidines

Anthracyanidines :Carajurin obtainedfrombignoniaChica

O OCH3

HO CH3

Anthocyanidine

Carotinoids Carotinoids : Inthesethecolorisduetothepresenceofthelongconjugateddoublebond.Annato and

Saffronareexamplesofthis.

- Carotene

Triaryl methane dyes- Synthetic dyes

Triaryl methanedyes.Theseincludethequininoid arrangementastheactualchromophore.The quininoid ringbutsinceallthreebenzeneringsareequivalenttherecanberearrangementofthebonds andanyofthebenzeneringscouldtakeupthisarrangement. Therearealargenumberofdyesusedinhistologythatfallintothiscategory;afewexamplesare fuchsins,methylviolet,methylblueandanilineblue

Other dye- Synthetic dyes

Anthraquinone.Herethequininoid ringisseenasthemiddleofthethreefusedrings.Examplesare alizarinandcarmine. Xanthene.Herethequininoid ringistherighthandoneofthethreefusedringsandtheringistilted comparedwiththepreviousexample.Examplesincludeeosinandxanthene. Thiazine.Thisisverysimilartothepreviousexampleinoverallstructure,butthemiddleringnowhasS andNasconstituentatoms.Thisgroupcontainsmanyimportantmetachromatic dyes,suchastoluidine blue,methylene blueandazureA.

Basic Dyes
Basicdyesarecationicandwillstain/color anionicoracidicmaterialssuchascarboxylates,sulphates (manycomplexcarbohydratesaresulphated)andphosphates(particularlythephosphatesinnucleic acids).Mostareusedasnuclearstainsandstainingofcytoplasmic carboxylgroupsisdeliberately suppressedbyusingaslightlyacidpH. Acidicsubstancesthatstainwithbasicdyesaretermed basophilic.

Acidic and Neutral dyes

Acidicdyesareanionicandwillcolor cationicorbasicgroupssuchasaminogroups.Mostareusedto stainproteinsinthecytoplasmandconnectivetissues.Substancesthatstainwithaciddyesarecalled acidophilic. Neutraldyesaresimplycompoundsofbasicandaciddyes.Inthiscase,bothionsarecoloured.Suchdye complexeswillstainbothnucleusandcytoplasmfromasingledyebath.Romanowsky stainsareneutral dyesmadefrommorecomplexmixtures.Thesearethecommonestdyesusedinhaematology.Theyare lesscommoninhistologybutstillveryusefulandincludeGiemsa,Leishman andWrightsstains.

Amphoteric dyes
Amphoteric dyesalsohavebothanionicandcationicgroups,buttheseareonthesameion. Amphoteric dyeshavebothpositivelychargeablegroupsandnegativelychargeablegroupspresenton themolecule.Dependingonthechargeactuallypresent,thesedyesmayinteractaseitherpositively chargedionsbasicdyes ornegativelychargedionsaciddyes

Natural dyes
Naturaldyesaresimplydyesubstancesextractedfromnaturalsources.Althoughthemainsourceof dyesforearlytimes,theyhavelargelybeenreplacedbysyntheticdyes,whichareusuallymorereliable, cheaperandcanbesuppliedmorereadily.Naturaldyesstillinuseincludehaematoxylin,carmine,orcein andlitmus,althoughsyntheticvarietiesarealsoavailableforsomeofthese.