Академический Документы
Профессиональный Документы
Культура Документы
SelfAssembledMonolayers:AdvantagesofPureAlkanethiols|SigmaAldrich
Hello.Signin.
SelfAssembledMonolayers:AdvantagesofPure
Alkanethiols
0Items
By:Dr.MaxiBoeckl,Dr.DanielGraham,MaterialMatters2006,1.2,3.
SeniorScientists,
Asemblon,Inc.
RelatedLinks
VIEWPRODUCTLIST
Categories
SelfAssembly:FromNaturetoTheLab
Inthe1980s,scientistsdiscoveredthatalkanethiolsspontaneouslyassembledonnoblemetals.Thisnewareaofscience
openedthedoorstoasimplewayofcreatingsurfacesofvirtuallyanydesiredchemistrybyplacingagoldsubstrateintoa
millimolarsolutionofanalkanethiolinethanol.Thisresultsincrystallinelikemonolayersformedonthemetalsurface,called
selfassembledmonolayers(SAMs).1
Overtheyears,themechanismoftheselfassemblyprocesshasbeenwellstudiedandelucidated.Researchershavefound
thatatypicalalkanethiolmonolayerformsa(33)R30structure2 ongoldwiththethiolchainstiltedapproximately30
degreesfromthesurfacenormal.36 Theexactstructureofthemonolayerdependsonthechemistryofthechain.
Selfassemblyformsthebasisformanynaturalprocessesincludingproteinfolding,DNAtranscribingandhybridization,and
theformationofcellmembranes.Theprocessofselfassemblyinnatureisgovernedbyinterandintramolecularforcesthat
drivethemoleculesintoastable,lowenergystate.Theseforcesincludehydrogenbonding,electrostaticinteractions,
hydrophobicinteractions,andvanderWaalsforces.
Adsorption
Electrochemicalanalysis
Electronics
Massspectrometry
MicroarrayAnalysis
Nucleicacidhybridization
PAGE
Purification
Spectroscopy
DOWNLOADPDF
Aswithselfassemblyinnature,thereareseveraldrivingforcesfortheassemblyofalkanethiolsontonoblemetalsurfaces.
Thefirstistheaffinityofsulfurforthegoldsurface.Researchershavefoundthatthesulfurgoldinteractionisontheorderof
45kcal/mol,3 formingastable,semicovalentbondincomparison,theCCbondstrengthis~83kcal/mol.
Thenextdrivingforceforassemblyisthehydrophobic,vanderWaalsinteractionsbetweenthemethylenecarbonsonthe
alkanechains.Foralkanethiolmonolayers,thisinteractioncausesthethiolchainstotiltinordertomaximizetheinteraction
betweenthechainsandlowertheoverallsurfaceenergy.Awellorderedmonolayerformsfromanalkanechainofatleast10
carbons.Withcarbonchainsofthislength,hydrophobicinteractionsbetweenthechainscanovercomethemolecules
rotationaldegreesoffreedom.6,7
AsimplealkanethiolmoleculeisshowninFigure1.(nextpage)Analkanethiolcanbethoughtofascontaining3parts:a
sulfurbindinggroupforattachmenttoanoblemetalsurface,aspacerchain(typicallymadeupofmethylenegroups,(CH 2 )n ),
andafunctionalheadgroup.Asmentionedabove,thesulfuratomandthecarbonsinthemethylenegroupsactasthemain
drivingforcesforassemblyofthealkanethiols.Theheadgroupthenprovidesaplatformwhereanydesiredgroupcanbeused
toproducesurfacesofeffectivelyanytypeofchemistry.
Figure1.Schematicdiagramofathiolmolecule.
Thesulfurgrouplinksthemoleculetothegoldsurface.Theheadgroupcanbedesignedtoprovidevirtuallyanysurfacechemistry,
bindingcapacity,orproperty.
Bysimplychangingtheheadgroup,asurfacecanbecreatedthatishydrophobic(methylheadgroup),hydrophilic(hydroxylor
carboxylheadgroup),proteinresistant(ethlyleneglycolheadgroup),orallowschemicalbinding(NTA,azide,carboxyl,amine
headgroups).Thisenablesaresearchertocustomdesignasurfacetoserveanydesiredfunction.
SelfAssembly:PurityMatters
SAMsaretypicallymadefroma1mMsolutionofthedesiredalkanethiolinethanol.Initialmonolayerformationisveryfast,
withmonolayercoveragebeingachievedwithinsecondstominutes.Thisinitiallyformedmonolayerisnotwellorderedand
containsmanygauchedefectswithinthechains.Overtime,thelayersbecomemoreorderedandwellpacked.Reported
assemblytimesvarythroughouttheliterature,buttypicallyare12hoursto2days.
http://www.sigmaaldrich.com/technicaldocuments/articles/materialmatters/selfassembledmonolayers.html
1/4
11/4/2015
SelfAssembledMonolayers:AdvantagesofPureAlkanethiols|SigmaAldrich
assemblytimesvarythroughouttheliterature,buttypicallyare12hoursto2days.
Theformationofawellassembledmonolayercandependonthepurityofthealkanethiolbeingused.Thepresenceofeven
lowlevelsofcontaminantscanresultinadisordered,nonidealmonolayer.Manytypicalimpuritiesinthiolcompoundsare
thiolatedprecursormoleculesthatwerenotseparatedduringthepurificationprocess.Theseprecursormoleculescaneitherbe
straightchainalkanethiolsthatlacktheheadgroupsofthefinalproduct,ortheycanbemoleculesusedtointroducethethiol
functionalgrouptoaprecursormolecule(suchasthioaceticacid).Sincethesecompoundsalsocontainthiolfunctionalities,
theycancompetewiththealkanethiolofinterestforavailablesurfacelocations.Competitiveadsorptioncanbeparticularly
problematicforalkanethiolswithcomplexorbulkyheadgroups.Bulkyheadgroupscanreducethedrivingforceforassembly
bydisruptingtheclosepackedarrangementofthealkanechains.Withthisreduceddrivingforceforassembly,thestraight
chainorsmallthiolcontaminantscanoutcompetethealkanethiolofinterestonthesurface.
Theseeffectswerenoticedinearlyalkanethiolselfassemblyresearchandseveraldetailedstudieswereperformedonthe
preferentialadsorptionofonealkanethiolversusanother.Adsorptionfromadilutesolutioninethanolofamixtureoftwo
alkanethiols,onewithapolartheotherwithanonpolarheadgroup,showedthatadsorptionofthealkanethiolwiththenonpolar
headgroupwasfavored.7 Bainetal.alsonoticedthatalkanethiolswithequivalentheadgroups,butlongerchainsadsorbed
preferentiallyovershorteralkanethiols.4 Whenonetriestointentionallyobtainamixedmonolayer,wheretwoormorehead
groupsarepresentatadesiredratio,itisverydifficulttopredicttherelativesurfaceconcentrationfromthesolution
concentrationandacalibrationcurveistypicallynecessary.4 AnexampleisgivenbyNelsonetal.,whostudiedmixed
monolayersofbiotinylatedalkanethiolmixedwitheithermercaptohexadecaneor(1mercapto11undecyl)tetra(ethyleneglycol)
andcorrelatedthesolutionconcentrationtothesurfaceconcentrationusingelectronspectroscopyforchemicalanalysis
(ESCA)andTimeofFlightSecondaryMassSpectrometry(ToFSIMS).8 Thisstudydemonstratedhowthesurfaceand
solutioncompositioninmixedmonolayerscanvarysignificantlyandwhyacalibrationcurveisnecessarywhenengineering
mixedmonolayersurfaces.
AsademonstrationoftheeffectsofthiolimpuritiesinSAMformation,Table1showsESCAsurfacecompositiondatafroma
seriesofSAMspreparedfromthiolsolutionsthatwerepurposelyspikedwithimpurities.Forthisexperiment,solutionsof(1
mercapto11undecyl)tetra(ethyleneglycol)(PEG4 thiol,AldrichProd.No.674508)weremixedwith0%,1%and10%(v/v)
thioaceticacid(TAA).Allmonolayerswerepreparedfrom1mMsolutionsinabsoluteethanol.Thepercentagesshownforthe
variousthiolcomponentsarevolumepercentages.
Table1.ESCAcompositiondatafromPEG4thiolmonolayerswithandwithoutimpurities.Alldataisshowninatomic
percent.Twoanalysisspotsareshownforeachsample.
PEG4thiol=(1mercapto11undecyl)tetra(ethyleneglycol)AldrichProd.No.674508TAA=thioaceticacid
ThefirstobservationnotedfromTable1istheincreaseintheatomicpercentageofgoldwithincreasingamountofthioacetic
acidintheassemblysolution.Thegoldsignalcomesfromthegoldsubstrateunderlyingthemonolayer.Thisgoldsignalis
attenuatedbytheoverlyingmonolayerfilm.Athinnerormoredisorderedoverlayercausesadecreaseinsignalattenuation
(increaseinthegoldsignal).Thissuggeststhattheadditionofeven1%thioaceticacidtotheassemblysolutioncauseda
markeddecreaseinthemonolayerthickness.Thioaceticacidisasmallmoleculewhichifinsertedintothemonolayerwould
disruptthelocalmonolayerordercausingthenoteddecreaseinthelayerthickness.
Table2showsthedatafromTable1rescaledwithoutthegoldsignal.Thisallowscomparisonoftheatomicpercentageswith
thatexpectedbasedonthesolutionmixtureatomiccomposition.AsseeninTable2,theexperimentalvaluescomparewell
withthecalculatedvalues.Theatomicpercentageofsulfuristypicallyobservedtobelowerthanexpectedduetoattenuation
bytheoverlyingmonolayer.Thisisthecaseforthe100%PEG4 thiol.Thefactthatthesulfurdatafromtheothertwo
monolayersisclosetothepredictednumbers,suggeststhatthelayersaredisordered(consistentwiththegoldatomic
percentages)orthatthereisahighamountofthioaceticacidonthesurface(whichhasahighrelativepercentageofsulfurvs.
theotheratoms).
Table2.ESCAcompositiondatafromPEG 4 thiolmonolayerswithandwithoutimpuritiesrescaledwithoutgoldsignal.All
dataisshowninatomicpercent.Twoanalysisspotsareshownforeachsample.Thevaluesinboldarethecalculatedatomic
percentagesbasedonthesolutionmixtureratioofthecompoundsused.
http://www.sigmaaldrich.com/technicaldocuments/articles/materialmatters/selfassembledmonolayers.html
2/4
11/4/2015
PEG
SelfAssembledMonolayers:AdvantagesofPureAlkanethiols|SigmaAldrich
4 thiol=(1mercapto11undecyl)tetra(ethyleneglycol)AldrichProd.No.674508TAA=thioaceticacid
ItisinterestingtonotethatwhenlookingatTable2,onemightthinkthatsincetherelativepercentagesofcarbonandoxygen
donotchangesignificantlyfromsampletosample,thatthesurfacesarestillpurePEG4 thiol.Itisonlythehighpercentageof
sulfurthatsetsthesamplesapartandindicatesthatanimpurityislikelypresent.
Overall,thisdatademonstratesthatevensmallamountsofcontaminantsinasolutioncancausesignificantdifferencesinthe
monolayercompositionandstructure.Thebestwaytoavoidtheseproblemsistousemoleculeswiththehighestpossible
purities.
ResultssimilartothesewereseenwhenthioaceticacidwaspresentinPEG3 andPEG6 thiolsamples.Bothofthesesamples
showedahigherthanexpectedgoldandsulfursignalsindicatingthelayersweredisorderedandasulfurcontaminantwas
present.Themostimportantpropertyofpoly(ethyleneglycol)alkanethiols(PEGn thiols)istheabilitytoformanonfoulingself
assembledmonolayer,butthepresenceofjustsmallamountsofcarboxylicacidterminatedPEGn thiols(possiblyintroduced
frompoly(ethyleneglycol)startingmaterial)leadstosignificantproteinadsorption,makingthesurfacemorefoulingthanbare
golditself,asshownbyRobertsetal.9
TheinterferenceofthiolcontaminationwithmonolayerformationhasalsobeenreportedfortheassemblyofthiolatedDNAon
gold.10 Itwasfoundthatthepresenceofathiolcontaminant,dithiothreitol,impededtheassemblyofthethiolatedDNAonto
thegoldsurface.TheauthorsshowedthatwhencontaminatedthiolatedDNAwasusedfortheassembly,theatomic
percentagesofcharacteristicDNAelements(P,N)didnotincreasewithincreasingassemblytimesastheydidwithpurer
samples.Increasedassemblytimesinsteadresultedinincreasedamountsofthecontaminantmoleculesonthesurface.
SamplespreparedfromrelativelypureDNAshowedlogicaltrendsfortheDNAelementsinatimeseriesassembly.
SelfAssembly:UnlimitedOpportunities
SAMshavebeenusedforstudiesandapplicationsinmanyareas.Afewexamplesincludesurfacewetting,nonfouling
property,electrochemistry,surfacepassivation,proteinbinding,DNAassembly,corrosionresistance,biologicalarrays,cell
interactions,andmolecularelectronics.Theseandothertopicshavebeensummarizedinpreviousreviewarticles.1113
SAMshavetrulyopenedthedoorstowarddirectsurfaceengineering.Onlytheimaginationlimitsthepossibilitiesavailableto
theinterestedresearcher.Figure2showsschematicdiagramsofseveralpossibleapplicationsforalkanethiolmonolayers.
ThesetypesofapplicationswilllikelyrelyonhighpurityalkanethiolswithheadgroupssuchasthoselistedinTable3.
Figure2.Possibleapplicationsforalkanethiolmonolayers.
A)NonfoulingsurfacesB)SAMswithspecificbindingreceptorsC)CellsupportsfornativecellgrowthandstudiesD)Molecular
electronicsE)MicroarraysF)Separations.
Table3:SomeheadgroupexamplesusefulfortheapplicationsshowninFigure2.
http://www.sigmaaldrich.com/technicaldocuments/articles/materialmatters/selfassembledmonolayers.html
3/4
11/4/2015
SelfAssembledMonolayers:AdvantagesofPureAlkanethiols|SigmaAldrich
Materials
Product#
Image
674508
SKUPackSize
674508250MG
Description
MolecularFormula
(11Mercaptoundecyl)tetra(ethyleneglycol)90%
C19H40O5S
Availability
Estimatedtoshipon02.01.16
Price(INR)
33,655.20
Bulkorders?
AddtoCart
close
Quantity
ADDTOCART
674176
[11(Methylcarbonylthio)undecyl]tetra(ethyleneglycol)
95%
C21H42O6S
pricing
736678
Tetra(ethyleneglycol)dithiol97%
C8H18O3S2
pricing
References
1. Nuzzo,R.G.Allara,D.L.J.Am.Chem.Soc.1983,105,4481.
2. Strong,L.Whitesides,G.M.Langmuir1988,4,546.
3. Dubois,L.H.Nuzzo,R.G.Annu.Rev.Phys.Chem.1992,43,437.
4. Bain,C.D.Whitesides,G.M.J.Am.Chem.Soc.1989,111,7164.
5. Bain,C.D.Whitesides,G.M.Angew.Chem.Int.Ed.1989,28,506.
6. Porter,M.D.Bright,T.B.Allara,D.L.Chidsey,C.E.D.J.Am.Chem.Soc.1987,109,3559.
7. Bain,C.D.Evall,J.Whitesides,G.M.J.Am.Chem.Soc.1989,7155.
8. Nelson,K.E.Gamble,L.Jung,L.S.Boeckl,M.S.Naeemi,E.Golledge,S.L.Sasaki,T.Castner,D.G.Campbell,C.T.
Stayton,P.S.Langmuir2001,17,2807.
9. Roberts,B.J.Naeemi,E.Ratner,B.D.JURBIE2004,4,103107.
10. Lee,C.Y.Canavan,H.E.Gamble,L.J.Castner,D.G.Langmuir2005,21,5134.
11. Love,J.C.Estroff,L.A.Kriebel,J.K.Nuzzo,R.G.Whitesides,G.M.Chem.Rev.2005,105,1103.
12. Chaki,N.K.Vijayamohanan,K.Biosensors&Bioelectronics2002,17,1.
13. Ulman,A.Chem.Rev.1996,96,1533.
SERVICE&SUPPORT
CORPORATE
CUSTOMERSUPPORT
INVESTORRELATIONS
TECHNICALSERVICE
BUSINESSDEVELOPMENT
WEBHELPDESK
SDS
WORLDWIDEOFFICES
ABOUTUS
COFA
SITEMAP
CAREERS
ORDERING
EVENTS
PROGRAMS
CUSTOMPRODUCTS
ECOMMERCESOLUTIONS
REACHREGULATIONS
CONTACTUS
ORDERCENTER
PRODUCTS
LITERATUREPORTAL
TOOLBOX
TERMS&CONDITIONSOFSALE
http://www.sigmaaldrich.com/technicaldocuments/articles/materialmatters/selfassembledmonolayers.html
4/4