ChitinAntimicrobialActivity

Chitinisthesecondmostabundantbiopolymerinnature..foundinthe shellsofcrustaceans,thecuticlesofinsects,andthecellwalloffungi. Chitosan,adeacetylated productofchitin,hasmanyinteresting properties,suchasantimicrobialactivityandnontoxicity.Itisobtained fromshrimpandcrabshellchitinbyalkalinedeacetylation

Biomacromolecules,2007,8 (5),pp 13591384

SiliconeBiomaterials

SourceInformationforthefollowingslides: 1)B.Ratner,A.Hoffman,F.Schoen,andJ.Lemons:BiomaterialsScience, 2nd edition(SanDiego:ElsevierAcademicPress.2004).

SiliconeBiomaterials
ChemicalStructureandNomenclature Otherwiseknownaspolysiloxanes Inorganicpolymerbackbonewithorganicpendantgroups

Polydimethylsiloxane (PDMS)isthemostcommonmaterialinthisclass Inorganic/organiccombinationgivesrisetouniqueproperties

Fluids,emulsions,compounds,resins,elastomers

Usedinabroadrangeofapplicationsincludingelectronics,aerospace, coatings,adhesives,andbiomaterials

TMSterminatedPDMSmostcommonamongpolysiloxanes Linearpolymersremainliquidsevenforhighvaluesofn
CH3 H3C Si O CH3 CH3 Si O CH3 CH3 Si CH3 n CH3

(n = 0, 1, 2,...) Trimethylsilyloxy terminated PDMS

Generalpropertiesofsilicones
LowTg,lowtemperatureflexibility Propertiesretainedoverawidetemperaturerange(100to250C) Stabletohightemperatures,oxidation,chemicalandbiologicalenvironments

PropertiesaconsequenceofthelongSiObond(1.64comparedto1.54 forCC)andwideSiOSibondangle(143 comparedto109.5 forC CC) SiObondisstrongerthanCCbond(450vs.350kJ/mol)

ShorthandNotation

B. Ratner, A. Hoffman, F. Schoen, and J. Lemons: Biomaterials Science, 2nd edition (San Diego: Elsevier Academic Press. 2004). 81.

ShorthandNotation

B. Ratner, A. Hoffman, F. Schoen, and J. Lemons: Biomaterials Science, 2nd edition (San Diego: Elsevier Academic Press. 2004). 81.

B. Ratner, A. Hoffman, F. Schoen, and J. Lemons: Biomaterials Science, 2nd edition (San Diego: Elsevier Academic Press. 2004). 80.

B. Ratner, A. Hoffman, F. Schoen, and J. Lemons: Biomaterials Science, 2nd edition (San Diego: Elsevier Academic Press. 2004). 82.

SiliconeElastomers
Siliconepolymersareeasilytransformedintocrosslinked elastomersusing oneofseveralmethods Radicalcrosslinking

SiliconeElastomers
Siliconepolymersareeasilytransformedintocrosslinked elastomersusing oneofseveralmethods Condensationcrosslinking

PreparedfromhydroxyterminatedPDMS andlargeexcessofmethyltriacetoxysilane Uponexposuretomoisture,acetoxy groupsarehydrolyzedallowing condensationofresultingsilanols

B. Ratner, A. Hoffman, F. Schoen, and J. Lemons: Biomaterials Science, 2nd edition (San Diego: Elsevier Academic Press. 2004). 83.

Condensationcrosslinking(cont)

B. Ratner, A. Hoffman, F. Schoen, and J. Lemons: Biomaterials Science, 2nd edition (San Diego: Elsevier Academic Press. 2004). 84.

Twopartcondensationcuringusingatetrafunctional alkoxysilane and organotin catalyst.

Alcoholreleasedresultinginslightshrinkage

SiliconeElastomers
Siliconepolymersareeasilytransformedintocrosslinked elastomersusing oneofseveralmethods Addition

Thepreferredcuresystemdependsonapplication Siliconetosiliconemedicaladhesivesuseacetoxy cure(condensation)or platinumcure(addition)

B. Ratner, A. Hoffman, F. Schoen, and J. Lemons: Biomaterials Science, 2nd edition (San Diego: Elsevier Academic Press. 2004). 84.

ElastomerFiller
Mostsiliconeelastomersincorporatefiller Fillerreinforcesthecrosslinked matrix Preferredfillerformostmedicalapplicationsisfumedsilica(CabOSil, Aerosil) Reinforcementobtainedthroughhydrogenbondinginteractionofsilanol groupsonhighsurfaceareasilicawiththesiliconepolymer

B. Ratner, A. Hoffman, F. Schoen, and J. Lemons: Biomaterials Science, 2nd edition (San Diego: Elsevier Academic Press. 2004). 85.

PhysicochemicalPropertiesofSilicones
SiXandCXcompoundsbehaveverydifferently Lowerelectronegativityofsilicon(Si 1.80vs.C 2.55)resultsinmorepolar bondscomparedtocarbon Bondpolaritycontributestostrongsiliconbonding,i.e.SiObondishighly ionicandhasalargebondenergy. Consequently,siliconesareresistanttohomolytic cleavage PolarSiObondswouldleadtostrong intermolecularinteractionswithout protectionofthemethylgroups.Methyl groupsinteractweaklywithoneanother andshieldthemainchain LowbarriertorotationaroundtheSiO bondallowssiloxane chaintoadopt configurationthatexposesmaximum numberofmethylgroupstoexterior Leadstolowsurfaceenergymaterials

B. Ratner, A. Hoffman, F. Schoen, and J. Lemons: Biomaterials Science, 2nd edition (San Diego: Elsevier Academic Press. 2004). 85.

SurfaceActivityofSilicones
LowbarriertorotationaroundtheSiObondallowssiloxane chaintoadoptconfigurationthatexposesmaximumnumber ofmethylgroupsatmanyinterfaces
Leadstolowsurfacetension Lowsurfaceenergy Lowintermolecularinteractions, Resultinginalowoveralllevelofinteractionsattheir surfaces..biocompatibility!!

PDMS lowsurfacetensionyieldscapabilityofwettingmost surfaces Siliconesingeneralcanwetthemselves,promotesgoodfilm formationandgoodsurfacecoverage

Otherconsequencesoflowintermolecularinteraction insilicones
Tg verylow Highfreevolumecomparedtohydrocarbonsresultsinhighsolubilityand highdiffusioncoefficientofgasesintosilicones Highpermeabilitytooxygen,nitrogen,watervapor(eventhoughliquid watercannotwetthesiliconesurface Compressibilityisalsohigh

Siliconeelastomers.PeterJerschow. Shawbury,U.K.:Rapra TechnologyLtd.,2001.

Siliconeelastomers.PeterJerschow. Shawbury,U.K.:Rapra TechnologyLtd.,2001.