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SelfAssembledMonolayers
SelfAssembledMonolayers
Advantages
Longchainaliphaticmoleculesare fullyextendedtomaximizepacking densityandvander Waalsinteractions Formationfacilitatedonplanarand/or curvedsurfaces Introducealmostanyfunctionalgroup onthesurface
MostwidelystudiedSAMs:
goldalkylthiolate alkylsilane
SH SiH3
Disadvantages
DepositionMethods:
vapordeposition electrodeposition electroless deposition
Selfassembledmonolayers onsurfaces(SAMs)
SelfassembledmonolayersonAusurfaces:MODEL
ThemostpopulartypeofSAMisthatformedbythechemisorption oflongchainalkanethiol moleculesoncleangoldsurfaces.Themaindrivingforcesforthisselfassemblyprocessare i) TheformationofSAubonds(bondingenergyestimatedtobe4050kcal/mol),and ii) ThefavorablelateralVander Waalsinteractionsamongthealiphaticchainsofneighboring alkanethiol molecules Parameters:Concentration(high),Solvents,Temperature,ReactionTime,PurityofSolutions, CleanlinessofSubstrates
Determinessurfaceproperties Presentschemicalfunctionalitygroups OrganicInterphase (13nm) Provideswelldefinedthickness Actsasaphysicalbarrier Alterselectronicconductivityandlocal opticalproperties MetalSurfaceInterface Stabilizessurfaceatoms Modifieselectronicstates
Selfassembledmonolayers onAusurfaces
Wheredoes
H go?
TheseSAMsarepreparedsimplybyexposingacleangoldsurfacetoasolution ofthealkanethiol.Nospecialequipmentorconditionsarerequired.Foralkanethiols Withchainslongerthan10carbonatoms,itisgenerallytruethat: 1) Astable,organizedanddenselypackedmonolayerisreadilyformedontheAusurface. 2) Thethicknessofthemonolayerisdirectlyproportionaltothelengthofthealkane thiol chain.Typicalthicknessesrangefrom1to3nm. 3) Themainaxesofindividualmoleculesaretiltled byanangleofca.30degfromthenormal tothesurface.
Selfassembledmonolayers onAusurfaces
SurfaceImpurities Defectsatgold Stepedges Vacancyislands Defectsat Goldgrain boundaries Exposed Chainat Goldstep edges
DefectsatSAM Crystaledges
Schematicillustrationofsomeoftheintrinsicandextrinsic DefectsfoundinREALSAMsformedonpolycrystallinesubstrates
Selfassembledmonolayers onAusurfaces
SAMsareapowerfulmeanstoaccomplishchemicalmodificationofasurface,andare Wellsuitedforstudiesinnanoscience andtechnologybecause 1) Theyareeasytoprepare. 2) Theyfromonobjectsofallsizesandarecriticalcomponentsforstabilizingandadding functiontopreformed,nanometerscaleobjects(forexample:thinfilms,nanowires, colloids,andothernanostructures). 3) Theycancoupletheexternalenvironmenttotheelectronic(currentvoltageresponses, electrochemistry)andoptical(localrefractiveindex,surfaceplasmon frequency) propertiesofmetallicsurfaces. 4) Theylinkmolecularlevelstructurestomacroscopicinterfacialphenomena,suchas wetting,adhesion,andfriction.
Thefigurebelowillustratesanotherimportantfeature OfSAMs.Syntheticmodificationofthethiol permitsthe Attachmentoffunctionalgroups(R)tothemonolayer.
BiomaterialApplicationsofSAMs
ExamplesofSAMsforsensorapplications
BiomaterialApplicationsofSAMs
ProteinimmobilizationofHistaglabeledproteins
ControlledCellAdhesion
UltrathinSurfaceCoatings
Ultrathinpolymerfilms filmsorcoatingslessthan100nminthickness Developsyntheticmethodologiesandcharacterizationcapabilitiesfor ultrathinfilms
<100nmthickness
GraftingTovs.GraftingFrom
Mushroom:non interacting regime Crossover regime: mushroomto brushtransition Brush:highly stretchedregime
h ~ N 1 / 3
hN A MN
2 Rg
h ~ N 0
D
graftingto Surfaceboundmonomer graftingfromorSIP
3.73.8
614?
=reducedtetheringdensity
GraftingTovs.GraftingFrom
Graftingto
Graftingthrough
Graftingfrom
Graftingto
Physisorption:Adsorptioninwhichtheforcesinvolvedareintermolecularforces (vanderWaalsforces) Chemisorption:Adsorptioninwhichtheforcesinvolvedarevalenceforces(i.e. chemicalbondformation) Bothcasesrequiresuitableendfunctionalizedpolymerswithanaffinitytowardsa substratesurface Facile,butwithmanylimitations!!(i.e.lowgraftingdensity)
Advincula,R.(Ed.)PolymerBrushes2004WileyVCH:Weinheim.
GraftingFrom
Graftingto
Graftingthrough
Graftingfrom
Graftingfrom
Aninitiatormoleculeisdepositedonasurfacebymeansofaselfassembly processviathereactionofananchorgrouptosuitablesurfacesites,and subsequently,chainsaregrownonthesurfacefromtheinitiatingsite. Controlledfilmthickness,homogeneoussurfacecoverage,highlyfunctionalized surfaces Highbrushdensity:avg.distancebetweengraftingpoints<radiusofgyration(Rg). Accesstocomplexarchitecturesonthesurface(i.e.blockcopolymers)using controlledradicalpolymerizationtechniques
Advincula,R.(Ed.)PolymerBrushes2004WileyVCH:Weinheim.
GraftingtoChemistries
SurfaceInitiatedPolymerization
PolymerBrushes
MonomerA
MonomerB MonomerA
MonomerB MonomerA
(1)
(2)
Homopolymer Brush
Adhesion Corrosionresistance Wettability Biocompatibility
BlockCopolymer Brush
Nanostructured surfaces Environmentally responsivethinfilms
StatisticalCopolymer Brush
Tailoredfunctionalityw/o segmentationand segregation Stableexpressionof complexchemistriesat interface
CommonMonomers
BrushArchitectures
PhotoinitiatedSIP
Synthesisofsurfacereactivephotoinitiator Irgacure2959 modifiedinitiator designedwithether linkage improved stability
ControlledRadicalSIP
Examplesofnitroxidemediatedpolymerization
Senaratne,W.;Andruzzi,L.;Ober,C.Biomacromolecules 2005,6,2427.
ControlledRadicalSIP
ExampleofSIATRP
ControlledRadicalSIP:RAFT
Postmodification ofPolymerBrushes
Ex.1:ClickingPolymerBrushes
ynemoietiesserveasreactive handlesforpostpolymerization modification Largelibraryofcommercially availablethiols,common functionalgroupinbiomolecules Highthroughput,rapidreaction kinetics quantitativeconversion inminutes
Hensarling,R.;Doughty,V.;Chan,J.;Patton,D.J.Am.Chem.Soc.2009,131,1467314675.
MolecularLayerDeposition(MLD)
MLDisanemergingdepositiontechniqueforultrathinorganicfilms Reactantsundergoselflimiting,sequentialreactionsresultinginfilm growthalayerbylayermanner MLDuseshomobifunctionalorganicmonomerstobuildoligomericthin films,i.e.acidchloridesandamines Advantages Precisecontroloverfilmthickness Conformalcoatingofsurfaces Unprecedentedcontroloverthefilmcomposition Developedforthegrowthofpolyamides andpolyimidesandrecentlyextendedto organicinorganichybrids
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StevenM.George;Chem.Rev. 2010,110,111131.
Ex.1:MolecularLayerDeposition(MLD)
ABBinaryReactionSequence
MLDofpoly(pphenylene terephthalamide) (PPTA)
Ex.2:MolecularLayerDeposition(MLD)
HybridMLDFilms
Accomplishedusinginorganicand organicreactants Aluminum,silicon,titanium exampleshavebeenreported
Ex.3:MolecularLayerDeposition(MLD)
HybridMLDFilms
Siliconexample 1)Acyclicazasilane (AZ),suchas2,2 dimethoxy1,6diaza2 silacyclooctane,canreactwitha surfacehydroxyltocreatea siliconoxygenbond 2)Thecyclicazasilane alsounfolds, leavingaminespeciesattheterminal surface 3)Acycliccarbonate,suchasethylene carbonate(EC),canthenreactwitha surfaceaminetoformaurethane linkage
Illustrationofsurfacechemistryinvolvingtworingopening reactionswithAZandECasreactants.Reprintedfrom 30 George,S.etal.Acc.Chem.Res. 2009,42,498508
MLDLimitations
Challengesofperformingorganicchemistryinthegasphase
Findingandutilizingorganicreactantsthathavesufficientvapor pressure Understandingtheeffectofthesolutionphaseonthereaction.Many organicreactionsarecatalyzedbyacidorbaseorinfluencedby solvationeffectsthatareabsentinthegasphase Porousnatureofpolymersleadstodiffusionofgasphasereactants intothefilmleadingtobothsurfaceandbulkgrowthmechanisms
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LayerbyLayer(LBL)Assembly
Decher,G.Science 1997,277,12321237.
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LayerbyLayer(LBL)Assembly
Applicabletoabroadrangeofsubstratesurfaces Applicabletoabroadrangeoforganicmolecules,polymers, nanoparticles,nanotubes,biomolecules,.etc.(Highly versatileapproach!!) Conformalcoatingswithcontrolovercompositionand stratification
polyelectrolyte polyelectrolyte
+ ` + + + + +
+ + + + + + +
+ + + + +
+ +`+ + + +
+ + + + + + + + + + + +
Colloid particles
+ + + + + +
Polyelectrolytes coated-particles
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Example1:CovalentClickLBL
Hydrogenbondedassemblywiththiolene clickstabilizationofthemultilayers UVinducedthiolene reactionfacilitatesrapid crosslinkingbetweenlayers Excessthiolpresentattheparticleinterface facilitatesformationoflowfoulingLBLcoated capsules
Connal,L.etal.Chem.Mater. 2009,21,576578.
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Example2:CovalentClickLBL
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Example2:CovalentClickLBL
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LBLApplications
Energy
Photovoltaics Batteries FuelCellMembranes
Electronics
Organiclightemittingdiodes(OLEDs)
Biomaterials
Drugdelivery Antifoulingcoatings
Membranes
Gasbarrier/separationmembranes
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AdsorptionfromSolution
AdsorptionfromSolution
SurfaceSegregation
PlasmaTreatment
PlasmaTreatment
PlasmaModification
PlasmaSprayedCoatings
VacuumPlasmaSpray
Vacuumplasmaspraying(VPS)isa technologyforetchingandsurface modificationtocreateporouslayers withhighreproducibilityandfor cleaningandsurfaceengineeringof plastics,rubbersandnaturalfibers Thisprocesscanimproveproperties suchasfrictionalbehavior,heat resistance,surfaceelectrical conductivity,lubricity,cohesive strengthoffilms,ordielectric constant,oritcanmakematerials hydrophilicorhydrophobic. Theprocesstypicallyoperatesat 39120Ctoavoidthermal damage.
OtherOrthopedicBiomaterialsTreatments
Fig. 1. electrolytic ZrO2 coating on CoCrMo implant alloys of hip prosthesis: SEM observations of deposited specimen (a) after natural drying, then annealed for 120 min at (b) 773 K and (c) 873 K.
PatternedSurfaceModification
Patternsdesiredfor: Gene,protein,andcellmicroarrays Biosensors Combinatorialstudies Directedcellmigration,cellsorting Structuringengineeredtissues
Microcontact Printing
InkjetPrinting
w
Photopatterning Methods
Ex.SelectivecleavageunderUVlight
J.Am.Chem.Soc.,2004,126 (30),pp91709171
Photopatterning Methods
Figure2Schematicprocedureofdualstreptavidinpatterning.
Figure3Fluorescentmicroscopyofdualstreptavidinpatternedsurface.(a)SAv TRfluorescence.(b)SAvFITCfluorescence.(c)Overlay.
Photopatterning Methods
Ex.SelectivecrosslinkingunderUVlight