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Home > APPLICATIONOFCHITINCHITOSANFROMMARINEBYPRODUCTSINTHAILAND

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AnnualReports

RathPichyangkura1,2
1CenterforChitinChitosanBiomaterials,MetallurgyandMaterialsScience,Research
Institute,ChulalongkornUniversity,Bangkok10330,Thailand
2BiochemistryDepartment,FacultyofScience,ChulalongkornUniversity,Bangkok,
10330Thailand

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Abstract
Thailandisoneofthemajorproducersandexportersofshrimpandothermarineproducts
worldwide.Over600,000metrictonsofmarineproductscontainingchitinousmaterials,shrimp,
crabandsquid,areproducedyearly,whichresultedinabundantamountofrawmaterialsforthe
productionofchitinchitosan.ChitinchitosanindustryinThailandhasgrownconsiderablyinthe
pastdecade.However,from20042007,thenumberofcompaniesproducingandapplyingchitin
chitosanhasslowlydeclinedduetolowlocalconsumptionandlimitedmarketofchitinchitosan.
Thiswascausedmainlybythelackofintensiveresearchandproperproductdevelopment.The
localconsumptionthenincreaseddramaticallyintheselastfewyears.Thereareover20
companiesnationwide,producingchitinchitosanandchitinchitosanrelatedproductsmainlyfor
agriculturalapplications.Theapplicationofchitinchitosanforincreasingresistanceandproduction
ofcropshasbeenthemajorcontributorsforthissignificantincreaseinthelocalconsumption.
Chitinchitosanhasbeenusedasfoliagespraytoinducediseaseresistanceandincreasequality
andproductionoforchid,andotherornamentalplants.Itwasappliedincropssuchasrice,palm,
corn,cassavaandmanytropicalfruitswithsuccess.Ithasalsobeenincorporatedintoanimalfeed
forfishandshrimpsaswellaspoultry,cattleandporcine.However,carefulandextensivestudies
mustbeperformedtoestablishtheproperusageofchitinchitosananditsrelatedproduct.Theuse
ofchitinchitosancanelicitproperresponsewhenthepropermolecularform,chainlengthand
percentdegreeofdeacetylation,andprogramareapplied.Chitinchitosancanalsobeappliedand
useinmanyotherapplicationssuchastextile,cosmetics,medicine,compositesand
nanomaterials,andfoodandneutriceuticalproducts.Foodandneutriceuticalhasbeenoneofthe
majorapplicationsofchitinchitosan,sinceitisthemajorsourceofaminosugar,NacetylD
glucosamineandDglucosamine.
Tofurtherpromotethedevelopmentofchitinchitosanindustry,researchactivitiesonthe
applicationsofchitinchitosanandmarketingofchitinchitosanrelatedproductsarecrucial.
Keywords:Chitinchitosan,Thailand,marineproducts

Introduction
Chitin/chitosanisoneofthemostabundantbiorenewableresources.Itisthemajorwasteproductofmarine
andfisheryindustryespeciallyfromtheexpansionofshrimpandcrabindustryoftheworld.Thailandisoneof
theworldmajorexportersofshrimpandprocessedmarineproducts.Oneofthemajorwastesfromthese
industriesischitinousmaterialssuchasshrimpandcrabshellsandsquidpens.Thesewasteswerenormally
discarded,usedasfertilizer,oruseforflavorandaromaextractions.However,thereareremarkable
advancesinthefieldofchitin/chitosaninthepastdecadeandthesematerialscanbeofgreatvalueforthe
fisheryindustry.Chitin/chitosancanbeappliedandusedwithsuchavastapplication.Furthermorethe
productionofsuchmaterialsarenotcomplicatedandcanbemanufactureanywherewherethereisagood
sourceofchitinousmaterials.Thailandisoneofthemajorproducerandexporterofshrimpandothermarine
productsworldwide.Over600,000metrictonsmarineproductscontainingchitinousmaterials,shrimp,crab
andsquid,areproducedyearly,whichresultedinabundantamountofrawmaterialsfortheproductionof
chitinchitosan.
Chitin/chitosanisanaturallyoccurringbiopolymer.Itwasfoundtobeoneoftheworld'smostabundant
biopolymernexttoonlycellulose.Despitethehighlyabundantofthisbiopolymer,isfoundonlyinasmall
groupoflivingorganisms,arthropods,somemollusk,andyeastandfungi.ChitinisahomopolymerofN
acetylDglucosaminelinkedtogetherbybeta1,4linkages.Structurallyitisverysimilartocellulose.Chitosan
isaderivativeofchitinfromadeacetylationprocessoftheacetamidogroupofchitintoanaminogroup.This
processinindustryisnormallyaheterogeneousprocessinnature,wheresolidchitinissoakedinalkaline
solutiontoremovetheacetylgroup.Theresultofthisprocess,ifthereactioniscompleted,ispolyD
glucosamineorchitosan.However,thisdeacetylationprocessdoesnotoccurhomogeneouslyandnormally
someNacetylDglucosamineresiduesareleftover.
Thepolymerwillbeconsideredaschitosanwhenthepercentdegreeofdeacetylation(%DD)ofchitinexceeds
50%.However,forcommerciallyavailablechitosanthe%DDisnormallyabove80%,duetothefactthatthe
heterogeneouslydeacetylatedmaterialswithlowerthan80%DDdoesnotcompletelysolubilizeinweakorganic
acid,animportantcharacteristicofchitosan.Ontheotherhand,ifchitinhasbeendeacetylatedviaa
homogeneousreaction,lower%DDchitosanthatcompletelysolubilizedinweakacidscanbeachieved.The
importantcharacteristicofchitosanthatseparatesitfromchitin,mentionedearlier,istheabilityofthis
derivativetobecompletelysolubilizedinweakorganicacidssuchasformicacid,aceticacid,lacticacid,and
citricacid.Thispropertyhasbeenuseasacrucialparameterforchitin/chitosanproductionandtrading.
Thereforechitosanisaderivativeofchitinwherethe%DDexceeds50%andiscompletelysolubleinweak
organicacidsolution

SOURCESOFCHITIN/CHITOSAN
Themajorsourceofchitinforindustryisfromshrimpshells,crabshellsandsquidpen.Eachsourcehas
differentchitincontentandthesourceofshellsforchitin/chitosanproductionshouldbecarefullyselected.
Driedshrimpshellscontainapproximately2540%chitin,whereasdriedcrabshellscontain1520%chitin.
Squidpenalthoughcontainshighcontentofchitinbutitishardertocollectandhasmuchloweravailability.
Othersourcesofchitinousmaterialssuchasothermolluskhaveevenlowerchitincontent,anditisnot

economicallyviableforlargescaleproduction.Thereforethemajorsourceofchitin/chitosanproductioninthe
worldiscurrentlyfromcrabandshrimpshells.
Chitinfoundinnatureisnormallypackedintoanorderlycrystallinestructurewhichmadeitstrongandableto
servetheexoskeletonpurposeoftheshellsofarthropods.Chitinexistsinthreestructuralformscalledalpha,
betaandgammachitin.Thepackingandorientationofthechitinstrandsaredifferentineachofthedifferent
types.Alphachitin,foundinshrimpandcrabshell,hasantiparallelchitinstandsthatarepackedtightlywith
bothinterandintramolecularhydrogenbondingwithmakesitthestrongeststructureinallthethreechitin
structuresfound.Betachitin,foundinsquidpens,hasparallelchitinstrandsthatarepacklooserandlackthe
intermolecularhydrogenbondingmakingitweaker.Gammachitinfoundinthestomachliningofsome
mollusk,havearandomlyorientatedchitinstand.Ofthesethreestructuraltypesalphaandbetachitinare
themostabundant.Thestructureofchitinwilldeterminethepropertiesandcharacteristicofthechitosan
producedfromeachtypeofchitin.
Fortheproductionofchitin/chitosantheshellsmustbeusedimmediatelyorassoonasitcameoutofthe
processline.Thehighactivityofmicrobesintheshellswillrapidlyreducethechitincontentwithintheshells.
Iftheshellsarenottobeprocessedrightawayfreezingordryingtheshellscanhelppreservetheshellsfor
laterchitin/chitosanproduction.
Theselectionofshellalsoplaysanimportantfactorinthesuccessofchitin/chitosanproduction.Forinstance,
theheadcarapaceofshrimpscontainsmuchfatandproteinandshouldnotbeusedforchitin/chitosan
production.Theshellonthebacktothetailportionofshrimpisidealforchitin/chitosanproduction.Anideal
rawmaterialofshellsforchitin/chitosanproductionshouldbeuniforminsizeandthicknessandhaslowfat
andlipidcontent.

PRODUCTIONCHITINCHITOSAN
Theproductionofchitinandchitosanfromchitinousmaterialsareratheruncomplicatedandsimplechemicals
suchasHClandNaOHareused.Theprocessintheproductionofchitinisdividedintotwomajorsteps(1)
demineralizationstepbylowconcentrationHCl(12N)and(2)deproteinizationstepbylowconcentration
NaOH(12N).Thesetwostepsarecrucialfortheeliminationofcalciumcarbonateandothermineralsaswell
asproteinswhicharepresentintheshells.Togetthebestextractionresults,thesequenceofthesetwo
treatmentstepsvarydependingontherawmaterialused.Forcrabshells,demineralizationbyacidtreatment
mustprecedethedeproteinizationstep.Forshrimpshells,ontheotherhand,theextractionstepsmuststart
withdeproteinizationstepthenfollowedbydemineralizationstep.Thewastefromeachoftheextractionsteps
canbecombinedandneutralized.WhiteprecipitationofmineralandproteinandNaClsolutionistheby
productofchitinproduction.TheNaClsolutionisnormallytreatedandletitoverflowbackintotheocean.The
whiteproteinandmineralcakeiseitherusedinanimalfeedorfertilizer.
Chitincanbedriedandsoldasitisorcanbefurtherconvertedtochitosanbyadeacetylationprocessin
strongbase(4050%NaOH).Normally,chitinwillbesoakedin4050%NaOHwithorwithoutheatforvarying
amountsoftimedependingonthespecificationofchitosanneeded.Themajorcostinthechitin/chitosan
productioniswater.Cleananddeionizedwatermustbeusedforchitinandchitosanproduction,respectively.
Sincechitosanhasveryhighaffinitytodivalentcationsandimpuritiesinthewater,caremustbetakento
makesuchimpuritiesarenotpresentinchitosanproduct.
Thetreatmentofthestrongbaseuseinthedeacetylationisoneofthemajorimpedimentsforchitosan
production.Someportionofthebasecanbeusedforproteinextractionbuttheamountbaseusedinchitosan
productionismuchmorethanthatcanbeusedforproteinextraction.RegenerationofNaOHsolutionfor
repetitiveusewouldbethemostefficientchoiceofpractice.
Oncechitosaninproduceitmustbeanalyzedfor%DD,molecularweight,ashcontent,moisturecontent,
proteincontent,heavymetalsandmicrobialcontaminations.Therearenointernationalspecificationsfor
chitin/chitosan.Thespecificationisnormallysetbythebuyersandagreedbetweenthesupplierandbuyer.In
Thailandtheministryofindustryhasissuedastandardforfoodgradeandindustrialgradechitin/chitosan,
whichcanbeacquireduponrequest.
Thepriceofchitin/chitosanarehundredsoftimehigherthanthepriceofshellwastes.Shrimpshellwastecost
from25baht/kg(0.050.15USD/kg)canbevalueaddedto120200baht/kg(3.66.0USD/kg)when
precessedintochitinand10005000baht/kg(30150USD/kg)whenprocessedintochitosan.

APPLICATIONSOFCHITINCHITOSAN
Researchanddevelopmentinthefieldofchitin/chitosananditsapplicationincreaseddramaticallyinrecent
years.Thisspursupthedevelopmentofnewproductsandapplicationofchitin/chitosaninvariousfields.
Chitin/chitosanhasbeensuccessfullyappliedandusedinpharmaceuticalandmedicine,foodandfeed,
agriculture,materialsandtextiles,andinthenewemergingfieldofnanotechlonogy.

PharmaceuticalandMedicine
Chitin/chitosanisthemajorsourceofaminosugar,NacetylDglucosamineandDglucosaminefoundinnature.
UnitedStatesFDAhasapprovedonlythehydrolysisproductofchitin/chitosantobethesourceofNacetylD
glucosamineandDglucosamineforhumanconsumption.Thesesimpleaminosugarshavebeenuseforthe
treatmentofosteoarthritisinhumanaswellasjointsinanimals.Chitin/chitosanisbeingstudiedandapplied
fordrugsformulationasameanofcontrolrelease.Itisappliedasanadjuvantinvaccineswithsuccess.
Chitosancoatedwounddressingwasalsoexploredsincechitosanhasantimicrobialactivityandcanaccelerate
thehealingprocess.Biomatrixfortissueengineeringusingchitosanandcompositeofotherinertmaterial
withchitosanwasalsoconstructedandhasbeenshowntohavegreatpotentialsforfurtherdevelopment.

Agriculture
InThailandchitin/chitosanhasbeenusedasfoliagespraytoinducediseaseresistanceandincreasequality
andproductionoforchid,andotherornamentalplants.Itwasresearchedandappliedincropssuchasrice,
palm,corn,cassavaandmanytropicalfruitswithsuccess.Chitin/chitosanhasbeenincorporatedintoanimal
feedforfishandshrimpsasfeedcoatingaswellassupplementedinthedrinkingwaterofpoultry,cattleand
porcine.However,themechanismandhowchitin/chitosanworksintheseapplicationsremainsunclear.
Carefulandextensiveresearchmustbeperformedtoestablishtheproperusageofchitinchitosanandits
relatedproduct.Theuseofchitinchitosancanelicitproperresponsewhenthepropermolecularform,chain
lengthandpercentdegreeofdeacetylation,andprogramareapplied.

PolymerandTextile
Chitinchitosancanalsobeappliedanduseinmanyotherapplicationssuchastextile.Duetoitsantimicrobial
property,chitin/chitosanwhenprocessedintofilmorwetspinintofiberscanbeincorporatedintobothwoven
andnonwovenfabricandcancontroltheodorandpreventmicrobialgrowth.

FoodandNutraceuticalProducts
Foodandneutriceuticalhasbeenoneofthemajorapplicationsofchitinchitosan,sinceitis

themajorsourceofaminosugar,NacetylDglucosamineandDglucosamine.Chitosancanalsoactasa
thickeningagent,andrecentstudieshasshownthatchitosancaninteractwithproteinstochangethe
interactionofproteinresultedinimprovementoftextureoftheproduct,aswellaswaterretentionoffood
products.
Whenchitosanisaddedintosomefoodproductitcanalsoactasafoodpreservativeandinhibitmicrobial
growth.

Conclusion
Thefisherywastefromshrimp,crabandsquidprocessingwhichcontainschitinousmaterialcanbeprocessed
intochitin/chitosanwithhighvalueadded.Chitin/chitosancanbeappliedandusedinvariousapplications
fromtextile,cosmetics,medicine,compositesandnanomaterials,andfoodandneutriceuticalproducts.To
furtherpromotethedevelopmentofchitinchitosanindustry,extensiveresearchactivitiesontheapplications
ofchitinchitosanandmarketingofchitinchitosanrelatedproductsarecrucial.

References
K.V.HarishPrashanthandR.N.Tharanathan.2007.Chitin/chitosan:modificationsandtheirunlimited
applicationpotentialanoverview.TrendsinFoodScience&Technology18:117e131.
MargueriteRinaudo.2006.Chitinandchitosan:Propertiesandapplications.Prog.Polym.Sci.31:
603_632.
PatchraLimpanavechetal.2008.Chitosaneffectsonfloralproduction,geneexpression,andnatomical
changesintheDendrobiumorchid.ScientiaHorticulturae116:65_72.
T.Kachanechai,etal.2008Theinfluenceofchitosanonphysicochemicalpropertiesofchicken
saltsolubleproteingel.FoodHydrocolloids22:74_83.
InmaculadaAranazetal.2009FunctionalCharacterizationofChitinandChitosan.CurrentChemical
Biology3:203230.
YuanGaoandRobinCranston.2008RecentAdvancesinAntimicrobialTreatmentsofTextiles.Textile
ResearchJournal78:6072.

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