A clear coat from a water soluble precursor: A bioinspired paint concept

Article abstract of DOI:10.1039/c5ta09437b

Traditional paints consist of hydrophobic polymers dissolved in hydrocarbons; they are appreciated for their rheological properties and the smooth and glossy films they form upon drying and crosslinking, but are now largely banned because of the hazards associated with the solvents. In terms of health, water borne paints based on colloidal resin dispersions are an improvement but these systems lack the rheological and film forming properties of traditional paints. We present here a bio-inspired alternative that combines the best of both worlds: a water soluble polymer that can crosslink by mild oxidation to a fully water resistant and adhesive coating. Using free radical polymerization, we copolymerized two water soluble monomers, namely borax-protected dopamine acrylamide (DAA-p) and 2-aminoethylmethacrylamide (AEMA) in various proportions. We determined the reactivity ratio of these monomers using an in situ¹H NMR monitoring method and found values of 0.0 and 0.46 for DAA-p and AEMA, respectively. From this we conclude that in the polymers DAA-p pairs do not occur, while DAA-AEMA diads are relatively frequent. After removing the protective borax by hydrolysis, we obtain polymers which are soluble in water at low pH (pH 2) but which undergo rapid oxidative crosslinking when the catechol groups of DAA react with amines from AEMA. This leads to a water resistant, mildly hydrophobic film with a water/air contact angle of about 40 degrees which adheres well to glass substrates.

Full text of DOI:10.1039/c5ta09437b

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1
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Page 1 of 11
Journal of Materials Chemistry A
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DOI: 10.1039/C5TA09437B
A clear coat from a water soluble precursor: a bioinspired paint concept
Juan Yang, Inge Bos, Wim Pranger, Anthonie Stuiver, Aldrik Velders, Martien A. Cohen
Stuart, Marleen Kamperman
Mussel-inspired copolymer P(DAA-co-AEMA) forms water-resistant coating upon pH
increase by self-crosslinking reaction of catechols and amines.

Jo uP rl ne aa sl eo ꢀ fd oM ꢀ na to et rꢀ ai ad l jsu sC t hꢀ me am r gi si nt rs yꢀ A
Page 2 of 11
View Article Online
DOI: 10.1039/C5TA09437B
JournalꢀNameꢀ
ꢀ
ARTICLEꢀꢀ
Aꢀclearꢀcoatꢀfromꢀaꢀwaterꢀsolubleꢀprecursor:ꢀaꢀbioinspiredꢀpaintꢀ
conceptꢀ
Receivedꢀ00thꢀJanuaryꢀ20xx,ꢀ
Acceptedꢀ00thꢀJanuaryꢀ20xxꢀ
a
a
b
b
c
JuanꢀYang, ꢀIngeꢀBos ,ꢀWimꢀPranger ,ꢀAnthonieꢀStuiver ,ꢀAldrikꢀH.ꢀVelders ,ꢀMartienꢀA.ꢀCohenꢀ
a
a†ꢀ
Stuart ,ꢀMarleenꢀKamperman
DOI:ꢀ10.1039/x0xx00000xꢀ
Traditionalꢀpaintsꢀconsistꢀofꢀhydrophobicꢀpolymersꢀdissolvedꢀinꢀhydrocarbons;ꢀtheyꢀareꢀappreciatedꢀforꢀtheirꢀrheologicalꢀ
propertiesꢀandꢀtheꢀsmoothꢀandꢀglossyꢀfilmsꢀtheyꢀformꢀuponꢀdryingꢀandꢀcrosslinking,ꢀbutꢀareꢀnowꢀlargelyꢀbannedꢀbecauseꢀofꢀ
theꢀhazardsꢀassociatedꢀwithꢀtheꢀsolvents.ꢀInꢀtermsꢀofꢀhealth,ꢀwaterꢀborneꢀpaintsꢀbasedꢀonꢀcolloidalꢀresinꢀdispersionsꢀareꢀanꢀ
improvementꢀbutꢀtheseꢀsystemsꢀlackꢀtheꢀrheologicalꢀandꢀfilmꢀformingꢀpropertiesꢀofꢀtraditionalꢀpaints.ꢀWeꢀpresentꢀhereꢀaꢀ
bio-inspiredꢀ alternativeꢀ thatꢀ combinesꢀ theꢀ bestꢀ ofꢀ bothꢀ worlds:ꢀ aꢀ waterꢀ solubleꢀ polymerꢀ thatꢀ canꢀ crosslinkꢀ byꢀ mildꢀ
oxidationꢀtoꢀaꢀfullyꢀwaterꢀresistantꢀandꢀadhesiveꢀcoating.ꢀUsingꢀfreeꢀradicalꢀpolymerization,ꢀweꢀcopolymerizedꢀtwoꢀwaterꢀ
solubleꢀmonomers,ꢀnamelyꢀborax-protectedꢀdopamineꢀacrylamideꢀ(DAA-p)ꢀandꢀ2-aminoethylmethacrylamideꢀ(AEMA)ꢀinꢀ
www.rsc.org/ꢀ
1
variousꢀproportions.ꢀWeꢀdeterminedꢀtheꢀreactivityꢀratioꢀofꢀtheseꢀmonomersꢀusingꢀanꢀinꢀsituꢀ HꢀNMRꢀmonitoringꢀmethodꢀ
andꢀfoundꢀvaluesꢀofꢀ0.0ꢀandꢀ0.46ꢀforꢀDAA-pꢀandꢀAEMA,ꢀrespectively.ꢀFromꢀthisꢀweꢀconcludeꢀthatꢀinꢀtheꢀpolymersꢀDAA-pꢀ
pairsꢀdoꢀnotꢀoccur,ꢀwhileꢀDAA-AEMAꢀdiadsꢀareꢀrelativelyꢀfrequent.ꢀAfterꢀremovingꢀtheꢀprotectiveꢀboraxꢀbyꢀhydrolysis,ꢀweꢀ
obtainꢀpolymersꢀwhichꢀareꢀsolubleꢀinꢀwaterꢀatꢀlowꢀpHꢀ(pHꢀ2)ꢀbutꢀwhichꢀundergoꢀrapidꢀoxidativeꢀcrosslinkingꢀwhenꢀtheꢀ
catecholꢀgroupsꢀofꢀDAAꢀreactꢀwithꢀaminesꢀfromꢀAEMA.ꢀThisꢀleadsꢀtoꢀaꢀwaterꢀresistant,ꢀmildlyꢀhydrophobicꢀfilmꢀwithꢀaꢀ
water/airꢀcontactꢀangleꢀofꢀaboutꢀ40ꢀdegreesꢀwhichꢀadheresꢀwellꢀtoꢀglassꢀsubstrates.ꢀ
Forꢀmussels,ꢀtheꢀfastꢀcuticleꢀcuringꢀcanꢀoccurꢀdueꢀtoꢀtheꢀefficient,ꢀ
10
versatileꢀ andꢀ complicatedꢀ crosslinkingꢀ chemistryꢀ ofꢀ mfps .ꢀ Asꢀ
reportedꢀbyꢀWaite,ꢀetꢀal.,ꢀsignificantꢀamountsꢀofꢀcatecholicꢀaminoꢀ
acidꢀ3,4-dihydroxyphenylalanineꢀ(DOPA)ꢀareꢀpresentꢀinꢀmfps .ꢀTheꢀ
Introductionꢀ
Naturalꢀorganismsꢀoftenꢀuseꢀcoatingsꢀtoꢀprotectꢀthemselvesꢀagainstꢀ
corrosiveꢀ factorsꢀ inꢀ theꢀ environment,ꢀ e.g.ꢀ mechanicalꢀ impact,ꢀ
moisture,ꢀ andꢀ temperature.ꢀ Examplesꢀ includeꢀ musselꢀ byssalꢀ
11
catecholꢀmoietyꢀinꢀDOPAꢀformsꢀcrosslinksꢀinꢀaꢀvarietyꢀofꢀpathways.ꢀ
Briefly,ꢀ catecholsꢀ areꢀ easilyꢀ oxidizedꢀ toꢀ formꢀ reactiveꢀ o-quinones.ꢀ
Theꢀo-quinonesꢀcanꢀthenꢀeitherꢀreactꢀwithꢀcatecholsꢀviaꢀdismutationꢀ
reaction,ꢀ orꢀ withꢀ aminesꢀ viaꢀ Michaelꢀ typeꢀ additionꢀ orꢀ Schiffꢀ baseꢀ
1
2,ꢀ 3
4
threads ,ꢀ squidꢀ beak ,ꢀ andꢀ protectiveꢀ cuticlesꢀ onꢀ plants .ꢀ Theꢀ
productionꢀofꢀtheꢀprotectiveꢀcoating,ꢀgenerally,ꢀinvolvesꢀtwoꢀsteps:ꢀ
i)ꢀsecretionꢀofꢀfluidicꢀandꢀpliableꢀproteins,ꢀandꢀii)ꢀfastꢀcuringꢀtoꢀformꢀ
10
reaction,ꢀorꢀwithꢀthiolsꢀviaꢀMichaelꢀadditionꢀtoꢀformꢀcrosslinks .ꢀInꢀ
1
hardꢀandꢀtoughꢀsolids .ꢀForꢀinstance,ꢀmusselsꢀproduceꢀviscousꢀliquidꢀ
musselꢀfootꢀproteinsꢀ(mfps)ꢀatꢀpHꢀ<ꢀ5ꢀinsideꢀgranules.ꢀUponꢀbeingꢀ
secretedꢀ intoꢀ theꢀ seawater,ꢀ atꢀ pHꢀ 8,ꢀ theꢀ mfpsꢀ solidifyꢀ inꢀ aꢀ fewꢀ
addition,ꢀ catecholsꢀ canꢀ interactꢀ withꢀ transitionꢀ metalsꢀ byꢀ formingꢀ
12
strongꢀcoordinationꢀbondsꢀtoꢀgiveꢀcatechol-metalꢀcomplexes .ꢀTheꢀ
crosslinkingꢀ ofꢀ mfpsꢀ happensꢀ inꢀ responseꢀ toꢀ theꢀ changeꢀ inꢀ
environment,ꢀi.e.,ꢀtheꢀhigherꢀpHꢀinꢀseawater,ꢀandꢀtheꢀexposureꢀtoꢀ
oxygen.ꢀ
5
minutesꢀtoꢀformꢀveryꢀtoughꢀandꢀhardꢀcuticle .ꢀTheꢀformedꢀcuticleꢀ(∼ꢀ
6
5
ꢀµmꢀinꢀthickness) ꢀcoatsꢀtheꢀexposedꢀbyssusꢀsurfaces,ꢀandꢀprotectsꢀ
7-9
theꢀ byssusꢀ againstꢀ microbialꢀ attackꢀ andꢀ roughꢀ seaꢀ waves .ꢀ Aꢀ
similarꢀhydrophobicꢀcoatingꢀhasꢀbeenꢀobservedꢀinꢀsquidꢀbeak,ꢀi.e.ꢀ
Dosidicusꢀbeak.ꢀTheꢀbeakꢀisꢀcomposedꢀofꢀchitinꢀfibers,ꢀproteinsꢀandꢀ
polyphenolicꢀ compounds.ꢀ Theꢀ polyphenolicꢀ compoundsꢀ formꢀ aꢀ
denseꢀ crosslinkedꢀ network,ꢀ providingꢀ anꢀ efficientꢀ hydrophobicꢀ
coatingꢀ aroundꢀ theꢀ softꢀ andꢀ hydrophilicꢀ chitinꢀ nanofibers,ꢀ 15
Inspiredꢀbyꢀtheꢀfascinatingꢀpropertiesꢀofꢀnaturalꢀcoatings,ꢀandꢀtheꢀ
versatileꢀchemistryꢀofꢀcatechols,ꢀmuchꢀeffortꢀhasꢀbeenꢀdevotedꢀtoꢀ
fabricatingꢀ thinꢀ catechol-functionalizedꢀ filmsꢀ forꢀ variousꢀ appliedꢀ
13-
fieldsꢀsuchꢀasꢀbiomedicalꢀengineeringꢀandꢀantimicrobialꢀcoatings
.
ꢀAꢀcommonꢀfabricationꢀmethodꢀisꢀlayer-by-layerꢀ(LBL)ꢀassembly,ꢀ
2
preventingꢀtheꢀchitinꢀfromꢀsofteningꢀbyꢀwaterꢀadsorption. ꢀ
i.e.ꢀ alternatingꢀ depositionꢀ ofꢀ catechol-containingꢀ polymerꢀ andꢀ
amine-containingꢀ polymerꢀ onꢀ substrates.ꢀ Theꢀ reactionꢀ betweenꢀ
catecholꢀandꢀamineꢀisꢀemployedꢀasꢀaꢀtoolꢀtoꢀensureꢀtheꢀstabilityꢀofꢀ
theꢀ multilayerꢀ films.ꢀ Detrembleurꢀ andꢀ co-workersꢀ haveꢀ publishedꢀ
16-18
severalꢀinterestingꢀarticlesꢀonꢀLBL.
ꢀForꢀinstance,ꢀtheyꢀpreparedꢀ
filmsꢀ byꢀ alternativelyꢀ depositing,ꢀ fromꢀ aqueousꢀ solution,ꢀ oxidizedꢀ
catechol-containingꢀ polymerꢀ pox(DOPA)ꢀ andꢀ amine-containingꢀ
polymerꢀpoly(allylamine)ꢀ(PAH).ꢀTheꢀreactionꢀbetweenꢀtheꢀquinonesꢀ
inꢀpox(DOPA)ꢀandꢀprimaryꢀaminesꢀinꢀPAHꢀyieldedꢀfilmsꢀwithꢀlong-
termꢀdurability.ꢀTheꢀfilmsꢀcanꢀfurtherꢀbeꢀmodifiedꢀtoꢀtargetꢀdifferentꢀ
applications.ꢀ Byꢀ dopingꢀ withꢀ silverꢀ nanoparticles,ꢀ theꢀ filmsꢀ wereꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ1ꢀꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Page 3 of 11
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ARTICLEꢀ
JournalꢀNameꢀ
usedꢀ asꢀ antibacterialꢀ coatings.ꢀ Theꢀ filmsꢀ canꢀ alsoꢀ beꢀ graftedꢀ withꢀ Experimentsꢀ
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enzymesꢀ (e.g.ꢀ DispersinB)ꢀ orꢀ poly(ethyleneꢀ glycol)ꢀ toꢀ haveꢀ anti-
DOI: 10.1039/C5TA09437B
16
biofilmꢀandꢀanti-adhesionꢀproperties,ꢀrespectively. ꢀXuꢀetꢀal.ꢀhaveꢀ
alsoꢀreportedꢀsimilarꢀLBLꢀwork.ꢀTheyꢀpreparedꢀmultilayeredꢀfilmsꢀbyꢀ
alternativelyꢀ immersingꢀ aꢀ substrateꢀ inꢀ anꢀ aqueousꢀ solutionꢀ ofꢀ
poly(acrylicꢀ acid-dopamine)ꢀ (PAA-dopamine)ꢀ andꢀ PAH.ꢀ Byꢀ
Dopamineꢀacrylamideꢀ(DAA)ꢀmonomerꢀsynthesisꢀ
Dopamineꢀ acrylamideꢀ (DAA)ꢀ wasꢀ synthesizedꢀ byꢀ reactionꢀ ofꢀ
dopamineꢀ hydrochlorideꢀ andꢀ acryloylꢀ chlorideꢀ inꢀ aꢀ mixtureꢀ ofꢀ
tetrahydrofuranꢀ (THF)ꢀ andꢀ Milli-Qꢀ water,ꢀ seeꢀ Schemeꢀ 1.ꢀ 20ꢀ gꢀ ofꢀ
sodiumꢀ tetraborateꢀ decahydrateꢀ andꢀ 8ꢀ gꢀ ofꢀ sodiumꢀ bicarbonateꢀ
wereꢀ addedꢀ toꢀ 200ꢀ mlꢀ Milli-Qꢀ water.ꢀ Theꢀ aqueousꢀ solutionꢀ wasꢀ
4
immersingꢀtheꢀfinalꢀfilmꢀintoꢀanꢀaqueousꢀsolutionꢀofꢀ1ꢀmMꢀNaIO ,ꢀ
crosslinkingꢀ wasꢀ triggered.ꢀ Theꢀ crosslinkedꢀ filmsꢀ showedꢀ highꢀ
stabilityꢀunderꢀextremeꢀconditions,ꢀe.g.ꢀextremeꢀpHꢀandꢀhighꢀionicꢀ
19
strength. ꢀ
2
bubbledꢀ withꢀ N ꢀ forꢀ 20ꢀ min,ꢀ followedꢀ byꢀ additionꢀ ofꢀ 10ꢀ gꢀ ofꢀ
dopamineꢀhydrochloride.ꢀNext,ꢀ8.6ꢀmlꢀofꢀacryloylꢀchlorideꢀinꢀ50ꢀmlꢀ
ofꢀTHFꢀwasꢀaddedꢀdropwise.ꢀTheꢀpHꢀofꢀtheꢀsolutionꢀwasꢀadjustedꢀtoꢀ
aboveꢀ 8ꢀ byꢀ addingꢀ dropsꢀ ofꢀ 1ꢀ Mꢀ NaOHꢀ solution.ꢀ Theꢀ reactionꢀ
BesidesꢀLBLꢀassemblyꢀthatꢀinvolvesꢀmultiple-stepꢀdeposition,ꢀaꢀone-
potꢀ depositionꢀ strategyꢀ ofꢀ aqueousꢀ solutionsꢀ containingꢀ
catecholamine-containingꢀpolymersꢀonꢀvariousꢀsubstratesꢀhasꢀalsoꢀ
beenꢀdeveloped.ꢀForꢀinstance,ꢀMessersmithꢀetꢀal.ꢀpreparedꢀfilmsꢀbyꢀ
immersingꢀ variousꢀ substratesꢀ (e.g.ꢀ Au,ꢀ Pt,ꢀ PS,ꢀ PMMA)ꢀ intoꢀ anꢀ
aqueousꢀ solutionꢀ ofꢀ copolymerꢀ p(N-(3,4-dihydroxyphenethyl)ꢀ
methacrylamide-co-aminoethylmethacrylamide)ꢀ (catecholꢀ contentꢀ
2
mixtureꢀ wasꢀ stirredꢀ overnightꢀ (aroundꢀ 14ꢀ h)ꢀ underꢀ continuousꢀ N ꢀ
bubblingꢀatꢀroomꢀtemperature.ꢀAfterꢀtheꢀreaction,ꢀaꢀslightlyꢀpinkishꢀ
slurryꢀwasꢀformedꢀwithꢀaꢀwhiteꢀsolidꢀpresentꢀatꢀtheꢀbottomꢀofꢀtheꢀ
flask.ꢀTheꢀreactionꢀmixtureꢀwasꢀfilteredꢀbyꢀvacuumꢀfiltrationꢀandꢀtheꢀ
clear,ꢀslightlyꢀpinkishꢀsolutionꢀwasꢀwashedꢀtwiceꢀwithꢀ100ꢀmlꢀethylꢀ
acetate.ꢀTheꢀobtainedꢀaqueousꢀsolutionꢀwasꢀacidifiedꢀbyꢀ1ꢀMꢀHClꢀtoꢀ
aꢀpHꢀofꢀaroundꢀ2,ꢀfollowedꢀbyꢀextractionꢀwithꢀ100ꢀmlꢀethylꢀacetateꢀ
repeatedꢀthreeꢀtimes.ꢀTheꢀbrownishꢀorganicꢀsolutionꢀobtainedꢀfromꢀ
1
0.6ꢀwt%)ꢀatꢀpHꢀ8.3ꢀforꢀ24ꢀh.ꢀTheꢀfilmsꢀwereꢀfurtherꢀusedꢀforꢀDNAꢀ
20
immobilization. ꢀꢀ
Inꢀthisꢀstudy,ꢀweꢀaimedꢀatꢀreproducingꢀtheꢀworkingꢀmechanismꢀofꢀ extractionꢀ wasꢀ collectedꢀ andꢀ driedꢀ overꢀ MgSO .ꢀ Afterwards,ꢀ theꢀ
4
musselsꢀ byꢀ developingꢀ aꢀ catecholamineꢀ polymerꢀ forꢀ water-borneꢀ volumeꢀ ofꢀ theꢀ solutionꢀ wasꢀ reducedꢀ toꢀ aroundꢀ 50ꢀ mlꢀ byꢀ rotaryꢀ
paintꢀ applications.ꢀ Theꢀ currentꢀ solvent-basedꢀ alkyd-paintsꢀ areꢀ stillꢀ
evaporationꢀ andꢀ precipitatedꢀ intoꢀ 500ꢀ mlꢀ hexane.ꢀ Theꢀ formedꢀ
consideredꢀ superiorꢀ inꢀ termsꢀ ofꢀ rheology,ꢀ butꢀ harmfulꢀ forꢀ theꢀ suspensionꢀwasꢀstoredꢀatꢀ4ꢀ°Cꢀovernightꢀtoꢀaidꢀcrystallization.ꢀAfterꢀ
environmentꢀ sinceꢀ organicꢀ solventsꢀ areꢀ used.ꢀ Ourꢀ catecholamineꢀ 14ꢀh,ꢀtheꢀresultingꢀbrownishꢀsolidsꢀwereꢀcollected,ꢀdissolvedꢀinꢀ100ꢀ
polymer,ꢀ inꢀ contrast,ꢀ isꢀ waterꢀ soluble,ꢀ andꢀ shouldꢀ beꢀ aꢀ promisingꢀ mlꢀethylꢀacetateꢀandꢀprecipitatedꢀinꢀ1000ꢀmlꢀhexane.ꢀTheꢀfinalꢀsolidꢀ
alternativeꢀ havingꢀ similarꢀ rheologicalꢀ characteristicsꢀ asꢀ classicalꢀ obtainedꢀbyꢀfiltrationꢀofꢀtheꢀsuspensionꢀwasꢀdriedꢀinꢀaꢀvacuumꢀovenꢀ
solvent-basedꢀ paints.ꢀ Therefore,ꢀ theꢀ requirementsꢀ theꢀ polymerꢀ
shouldꢀfulfilꢀwereꢀ1)ꢀbeingꢀableꢀtoꢀself-crosslinkꢀinꢀresponseꢀtoꢀanꢀ
externalꢀtriggerꢀsuchꢀasꢀpH;ꢀ2)ꢀbeingꢀwater-solubleꢀatꢀacidicꢀpH;ꢀ3)ꢀ
beingꢀwater-insolubleꢀatꢀbasicꢀpH.ꢀWeꢀsynthesizedꢀaꢀco-polymerꢀbyꢀ
freeꢀ radicalꢀ polymerizationꢀ ofꢀ borax-protectedꢀ dopamineꢀ
overnightꢀatꢀroomꢀtemperatureꢀandꢀtheꢀyieldꢀwasꢀ54%.ꢀ
acrylamideꢀ
(DAA-p)ꢀ
andꢀ
2-aminoethylmethacrylamideꢀ
ꢀ
hydrochlorideꢀ(AEMA).ꢀTheꢀmonomerꢀreactivityꢀofꢀDAA-pꢀandꢀAEMAꢀ
wasꢀinvestigatedꢀbyꢀin-situꢀ HꢀNMRꢀmeasurements.ꢀAtꢀlowꢀpH,ꢀtheꢀ
1
Schemeꢀ1.ꢀTheꢀsynthesisꢀpathwayꢀofꢀDAAꢀꢀ
polymerꢀ isꢀ solubleꢀ inꢀ waterꢀ andꢀ formsꢀ aꢀ stableꢀ solution.ꢀ Polymerꢀ
filmsꢀwereꢀpreparedꢀbyꢀincreasingꢀtheꢀpHꢀandꢀcastingꢀtheꢀpolymerꢀ
solutionsꢀ onꢀ substrates.ꢀ Theꢀ increaseꢀ inꢀ pHꢀ triggersꢀ crosslinkingꢀ
reactions,ꢀwhichꢀresultedꢀinꢀcrosslinked,ꢀwater-insolubleꢀfilms.ꢀTheꢀ
chemistryꢀandꢀmorphologiesꢀofꢀtheꢀfilmsꢀwereꢀinvestigatedꢀbyꢀUV-
VIS,ꢀandꢀAFMꢀmeasurements.ꢀ
DAAꢀProtectionꢀ(DAA-p)ꢀ
TheꢀprotectionꢀofꢀDAA,ꢀseeꢀꢀSchemeꢀ2,ꢀwasꢀcarriedꢀoutꢀbyꢀaddingꢀ3ꢀgꢀ
DAAꢀdissolvedꢀinꢀaꢀmixtureꢀofꢀethanol/H Oꢀ(10ꢀmlꢀethanolꢀandꢀ20ꢀmlꢀ
2
Milli-Qꢀwater)ꢀtoꢀ289.5ꢀmlꢀofꢀdegassedꢀaqueousꢀsolutionꢀofꢀsodiumꢀ
tetraborateꢀdecahydrateꢀ(11.0420ꢀg,ꢀ2ꢀmolarꢀequivalentsꢀcomparedꢀ
toꢀ catecholꢀ moieties).ꢀ Theꢀ reactionꢀ mixtureꢀ wasꢀ keptꢀ underꢀ
nitrogenꢀ forꢀ oneꢀ hourꢀ underꢀ continuousꢀ stirring.ꢀ Afterꢀ that,ꢀ theꢀ
productꢀwasꢀlyophilizedꢀandꢀusedꢀwithoutꢀanyꢀfurtherꢀpurification.ꢀꢀ
MaterialsꢀandꢀExperimentsꢀ
Materials:ꢀ Allꢀ reagentsꢀ wereꢀ usedꢀ asꢀ receivedꢀ unlessꢀ mentionedꢀ
otherwise.ꢀDopamineꢀhydrochloride,ꢀmethacrylicꢀanhydrideꢀ(94%),ꢀ
2
(
-methoxyethylꢀ acrylateꢀ (98%),ꢀ basicꢀ alumina,ꢀ deuterochloroformꢀ
99.96%),ꢀ tetrahydrofuranꢀ (98.5%),ꢀ ethylꢀ acetateꢀ (99%),ꢀ
dimethylformamideꢀ (99.8%),ꢀ 2,2’-Azobis(2-methylpropionitrile)ꢀ
ꢀ
Schemeꢀ2.ꢀTheꢀsynthesisꢀofꢀprotectedꢀDAAꢀ(DAA-p)ꢀfromꢀDAAꢀandꢀ
sodiumꢀtetraborateꢀdecahydrateꢀsolutionꢀ
(
(
AIBN)ꢀ (98%),ꢀ 2,2'-Azobis(2-methylpropionamidine)dihydrochlorideꢀ
95%),ꢀ dichloromethaneꢀ (98.5%),ꢀ methanolꢀ (98.5%),ꢀ 3,4-
dimethoxyphenethylꢀ amineꢀ (97%),ꢀ triethylamineꢀ (>99.5%)ꢀ andꢀ
acryloylꢀchlorideꢀ(97%)ꢀwereꢀpurchasedꢀfromꢀSigma-Aldrich.ꢀSodiumꢀ
hydroxideꢀ solutionꢀ (1ꢀ M)ꢀ andꢀ anhydrousꢀ magnesiumꢀ sulfateꢀ
Polymerꢀsynthesisꢀ
Co-polymerizationꢀ ofꢀ DAA-pꢀ andꢀ 2-aminoethylꢀ methacrylamideꢀ
hydrochlorideꢀ (AEMA)ꢀ wasꢀ carriedꢀ outꢀ byꢀ freeꢀ radicalꢀ
polymerizationꢀatꢀ65ꢀ°Cꢀforꢀ10ꢀhours,ꢀseeꢀSchemeꢀ3.ꢀDAA-pꢀ(0.74ꢀg),ꢀ
andꢀAEMAꢀ(2.3ꢀg,ꢀDAA-p/AEMA=8:92ꢀmol/mol)ꢀwereꢀaddedꢀtoꢀ14.06ꢀ
mlꢀ Milli-Qꢀ waterꢀ inꢀ aꢀ 50ꢀ mlꢀ three-neckꢀ roundꢀ bottomꢀ flask.ꢀ Theꢀ
reactionꢀmixtureꢀwasꢀheatedꢀupꢀtoꢀ65ꢀ°C,ꢀandꢀafterꢀthat,ꢀAIBNꢀꢀ
(
(
(
4
MgSO ,ꢀ97%)ꢀwereꢀpurchasedꢀfromꢀMerck.ꢀHydrochlorideꢀsolutionꢀ
1ꢀ M)ꢀ wasꢀ purchasedꢀ fromꢀ Fluka.ꢀ Hexaneꢀ (p.a.)ꢀ andꢀ diethylꢀ etherꢀ
p.a.)ꢀ wereꢀ purchasedꢀ fromꢀ Biosolve.ꢀ Sodiumꢀ tetraborateꢀ
decahydrateꢀ (p.a.)ꢀ andꢀ sodiumꢀ bicarbonateꢀ wereꢀ purchasedꢀ fromꢀ
J.T.Baker.ꢀ 2-Aminoethylꢀ methacrylamideꢀ hydrochlorideꢀ wasꢀ
purchasedꢀfromꢀPolysciences.ꢀ
2
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
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Page 4 of 11
JournalꢀNameꢀ
ꢀARTICLEꢀ
View Article Online
DOI: 10.1039/C5TA09437B
Schemeꢀ3.ꢀPolymerꢀsynthesisꢀbyꢀfreeꢀradicalꢀpolymerizationꢀofꢀꢀDAA-pꢀandꢀAEMAꢀ
0.02493ꢀg,ꢀ0.152ꢀmmol)ꢀinꢀ1.7ꢀmlꢀDMFꢀwasꢀadded.ꢀItꢀisꢀimportantꢀ
(
toꢀnoteꢀthatꢀatꢀroomꢀtemperature,ꢀDAA-pꢀwasꢀnotꢀfullyꢀdissolved.ꢀ
Theꢀ solubilityꢀ ofꢀ DAA-pꢀ increasedꢀ significantlyꢀ whenꢀ theꢀ
temperatureꢀreachedꢀ55ꢀ°C.ꢀAfterꢀtheꢀreactionꢀhadꢀbeenꢀkeptꢀunderꢀ
nitrogenꢀovernightꢀunderꢀcontinuousꢀstirring,ꢀtheꢀreactionꢀmixtureꢀ
wasꢀallowedꢀtoꢀcoolꢀdown.ꢀThenꢀ1MꢀHClꢀwasꢀaddedꢀtoꢀacidifyꢀtheꢀ
mixtureꢀ toꢀ pHꢀ 1.ꢀ Theꢀ mixtureꢀ wasꢀ transferredꢀ toꢀ aꢀ dialysisꢀ
membraneꢀ (MWCOꢀ =ꢀ 1ꢀ kDa)ꢀ andꢀ dialysedꢀ againstꢀ acidicꢀ Milli-Qꢀ
ꢀ
Schemeꢀ 4.ꢀ Chemicalꢀ structureꢀ ofꢀ theꢀ comonomersꢀ usedꢀ inꢀ theꢀ
copolymerizationꢀincludingꢀtheꢀnomenclatureꢀofꢀtheꢀvinylꢀprotonsꢀ
(
0.001ꢀMꢀHCl)ꢀforꢀtwoꢀdays.ꢀTheꢀproductꢀwasꢀlyophilizedꢀandꢀstoredꢀ
atꢀ4ꢀ°Cꢀuntilꢀfurtherꢀuse.ꢀTheꢀyieldꢀwasꢀ58%.ꢀ
TheꢀNMRꢀspectraꢀwereꢀprocessedꢀandꢀtheꢀsignalsꢀwereꢀintegratedꢀ
usingꢀ theꢀ softwareꢀ Mestrenovaꢀ 10.0.2.ꢀ Theꢀ concentrationsꢀ ofꢀ
unreactedꢀDAA-pꢀandꢀAEMAꢀwereꢀdeterminedꢀasꢀfollows.ꢀ
Staticꢀlightꢀscatteringꢀ(SLS)ꢀ
SLSꢀwasꢀusedꢀtoꢀdetermineꢀtheꢀmolarꢀmassꢀofꢀtheꢀcopolymer.ꢀTheꢀ
measurementsꢀ wereꢀ carriedꢀ outꢀ atꢀ 20ꢀ °Cꢀ withꢀ anꢀ ALVꢀ lightꢀ
scatteringꢀsetupꢀusingꢀanꢀALV5000/60X0ꢀExternalꢀCorrelatorꢀwithꢀaꢀ
CoboltꢀSamba-300ꢀDPSSꢀLaserꢀoperatingꢀatꢀ100mWꢀatꢀaꢀwavelengthꢀ
!
!!!!!!!
ꢀ
ꢁꢁ − ꢀ =
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ(1)ꢀ
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ(2)ꢀ
!
!!
!
!!!!
ofꢀ 660ꢀ nmꢀ andꢀ anꢀ ALVꢀ /ꢀ HIGHꢀ QEꢀ APDꢀ Singleꢀ Photonꢀ Detector.ꢀ ꢀꢁꢂꢀ =
!
Copolymerꢀ solutionsꢀ inꢀ 1ꢀ mMꢀ HClꢀ aqueousꢀ solutionꢀ withꢀ aꢀ
concentrationꢀ ofꢀ 0.26ꢀ g/lꢀ wereꢀ measuredꢀ atꢀ differentꢀ angles.ꢀ Theꢀ whereꢀD ,ꢀD ꢀandꢀD ꢀcorrespondꢀtoꢀtheꢀprotonsꢀassignedꢀtoꢀtheꢀvinylꢀ
1
2
3
angleꢀwasꢀvariedꢀusingꢀanꢀALV-125ꢀgoniometerꢀwithꢀincreasingꢀstepsꢀ groupꢀofꢀDAA-p,ꢀandꢀA ꢀandꢀA ꢀareꢀtheꢀprotonsꢀofꢀtheꢀvinylꢀgroupꢀofꢀ
1
2
ofꢀ 5°ꢀ betweenꢀ 20°ꢀ andꢀ 120°.ꢀ Theꢀ molecularꢀ weightꢀ ofꢀ theꢀ AEMA.ꢀ Rꢀ isꢀ theꢀ referenceꢀ peakꢀ ofꢀ dioxane,ꢀ sinceꢀ dioxaneꢀ isꢀ notꢀ
copolymersꢀ wasꢀ deducedꢀ fromꢀ aꢀ partialꢀ Zimmꢀ analysisꢀ ofꢀ theꢀ expectedꢀ toꢀ react,ꢀ andꢀ thereforeꢀ theꢀ peakꢀ shouldꢀ stayꢀ constant.ꢀ
collectedꢀdata.ꢀ
Theseꢀ valuesꢀ wereꢀ normalizedꢀ toꢀ theꢀ initialꢀ feedꢀ monomerꢀ
0 0
concentrationꢀ[DAA-p] ꢀandꢀ[AEMA] .ꢀ
1
Polymerizationꢀkineticsꢀstudiedꢀbyꢀ HꢀNMRꢀꢀ
1
HꢀNMRꢀspectroscopyꢀ
TheꢀreactivityꢀratioꢀofꢀDAA-pꢀandꢀAEMAꢀwasꢀdeterminedꢀbyꢀin-situꢀ
1
21
1
Hꢀ NMR,ꢀ asꢀ describedꢀ byꢀ Aguilarꢀ etꢀ al. ꢀ Theꢀ experimentsꢀ wereꢀ Hꢀ NMRꢀ ofꢀ theꢀ polymersꢀ wasꢀ performedꢀ inꢀ 0.1ꢀ Mꢀ DCl/D
carriedꢀ outꢀ inꢀ aꢀ 500ꢀ Avanceꢀ IIIꢀ NMRꢀ spectrometer,ꢀ operatingꢀ atꢀ BrukerꢀAMX-400ꢀspectrometerꢀ(400ꢀMHz)ꢀatꢀ298ꢀK.ꢀꢀ
00.137ꢀ MHz,ꢀ equippedꢀ withꢀ aꢀ 5ꢀ mmꢀ TXIꢀ probe.ꢀ Toꢀ performꢀ
2
Oꢀ onꢀ aꢀ
5
Polymerꢀfilmꢀpreparationꢀ
quantitativeꢀ experiments,ꢀ theꢀ followingꢀ measurementꢀ conditionsꢀ
wereꢀused:ꢀAꢀpulseꢀsequenceꢀofꢀ9ꢀμsꢀequivalentꢀtoꢀaꢀ90°ꢀtipꢀangleꢀ
andꢀaꢀ53ꢀsꢀdelayꢀtimeꢀwereꢀappliedꢀtoꢀallowꢀtheꢀtotalꢀrelaxationꢀofꢀ
theꢀprotonsꢀandꢀtoꢀprocessꢀtheꢀindividualꢀdata.ꢀTheꢀspinningꢀrateꢀofꢀ
theꢀsampleꢀwasꢀsetꢀtoꢀ9ꢀHzꢀduringꢀshimming,ꢀandꢀforꢀeachꢀdatumꢀ
onlyꢀ oneꢀ acquisitionꢀ (FID)ꢀ wasꢀ usedꢀ toꢀ ensureꢀ thatꢀ theꢀ
measurementꢀ correspondsꢀ toꢀ instantaneousꢀ compositionꢀ andꢀ notꢀ
toꢀ anꢀ average.ꢀ Theꢀ measurementꢀ wasꢀ carriedꢀ outꢀ atꢀ 56ꢀ °C.ꢀ Aꢀ
solutionꢀ ofꢀ DAA-pꢀ andꢀ AEMAꢀ (totalꢀ monomerꢀ concentrationꢀ isꢀ 5ꢀ
ForꢀAFM,ꢀUV-visꢀmeasurements,ꢀopticalꢀmicroscopy,ꢀcontactꢀangleꢀ
measurementsꢀ andꢀ theꢀ cross-cutꢀ tapeꢀ test,ꢀ polymerꢀ filmsꢀ wereꢀ
preparedꢀ usingꢀ aꢀ castingꢀ method.ꢀ Forꢀ AFMꢀ measurements,ꢀ glassꢀ
coverꢀslips,ꢀ18ꢀmmꢀlongꢀxꢀ18ꢀmmꢀwide,ꢀwereꢀusedꢀasꢀsubstratesꢀforꢀ
theꢀpolymerꢀfilms.ꢀAꢀ10ꢀmg/mlꢀpolymerꢀsolutionꢀwasꢀpreparedꢀusingꢀ
0
.001ꢀMꢀHClꢀ(aq)ꢀasꢀtheꢀsolvent.ꢀFourꢀpolymerꢀfilmsꢀwereꢀpreparedꢀ
underꢀtheꢀfollowingꢀconditions:ꢀa)ꢀlowꢀpH;ꢀb)ꢀhighꢀpH,ꢀbyꢀaddingꢀ1Mꢀ
NaOH;ꢀc)ꢀhighꢀpH,ꢀinꢀtheꢀpresenceꢀofꢀaꢀmoderateꢀamountꢀofꢀNaIO
NaIO /ꢀcatecholꢀ=ꢀ1/ꢀ100);ꢀd)ꢀhighꢀpH,ꢀinꢀtheꢀpresenceꢀofꢀaꢀlargeꢀ
amountꢀofꢀNaIO ꢀ(NaIO /ꢀcatecholꢀ=ꢀ1/ꢀ10).ꢀAꢀvolumeꢀofꢀ0.6ꢀmlꢀofꢀ
4
ꢀ
2 3 2
wt%)ꢀ inꢀ 10ꢀ mMꢀ Na CO ꢀ inꢀ D Oꢀ (0.75ꢀ ml)ꢀ wasꢀ addedꢀ inꢀ aꢀ screw-
(
4
cappedꢀ thinꢀ NMRꢀ tubeꢀ underꢀ argon.ꢀ Threeꢀ setsꢀ ofꢀ experimentsꢀ
wereꢀperformed,ꢀandꢀtheꢀfeedꢀmolarꢀfractionsꢀofꢀDAA-pꢀwereꢀ6,ꢀ10ꢀ
andꢀ15ꢀmol%,ꢀrespectively.ꢀDioxaneꢀ(10ꢀμl)ꢀwasꢀaddedꢀtoꢀbeꢀusedꢀasꢀ
anꢀinternalꢀreferenceꢀforꢀintegrationꢀpurposes.ꢀV50ꢀ(1.19ꢀmg,ꢀ4.39ꢀ
µmol)ꢀwasꢀusedꢀasꢀtheꢀinitiator.ꢀꢀ
4
4
theꢀ respectiveꢀ polymerꢀ solutionꢀ wasꢀ spreadꢀ ontoꢀ aꢀ pre-cleanedꢀ
coverslip,ꢀandꢀleftꢀtoꢀdryꢀunderꢀwell-ventilatedꢀconditionsꢀforꢀmoreꢀ
thanꢀ24ꢀh.ꢀForꢀUV-visꢀmeasurementsꢀandꢀtheꢀcross-cutꢀtapeꢀtest,ꢀ4.5ꢀ
cmꢀlongꢀxꢀ1.25ꢀcmꢀwideꢀquartzꢀslidesꢀandꢀ7.5ꢀcmꢀlongꢀxꢀ2.6ꢀcmꢀglassꢀ
slidesꢀwereꢀusedꢀasꢀsubstrates,ꢀrespectively.ꢀPolymerꢀsolutionsꢀwereꢀ
preparedꢀinꢀtheꢀsameꢀwayꢀasꢀforꢀtheꢀAFMꢀmeasurements;ꢀ1.04ꢀmlꢀofꢀ
polymerꢀsolutionꢀwasꢀspreadꢀontoꢀtheꢀpre-cleanedꢀquartzꢀslideꢀforꢀ
UV-visꢀmeasurements;ꢀandꢀ3.61ꢀmlꢀofꢀpolymerꢀsolutionꢀwasꢀspreadꢀ
ontoꢀ theꢀ pre-cleanedꢀ glassꢀ slideꢀ forꢀ theꢀ cross-cutꢀ tapeꢀ test.ꢀ Theꢀ
ꢀ
ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ3ꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Page 5 of 11
Jo uP rl ne aa sl eo ꢀ fd oM ꢀ na to et rꢀ ai ad l jsu sC t hꢀ me am r gi si nt rs yꢀ A
ARTICLEꢀ
JournalꢀNameꢀ
polymerꢀfilmsꢀwereꢀleftꢀtoꢀdryꢀunderꢀwell-ventilatedꢀconditionsꢀforꢀ measuredꢀatꢀpHꢀ9ꢀfollowedꢀbyꢀanꢀadditionalꢀviscosityꢀVmieweaAsrtuicrlee mOnelinnetꢀ
moreꢀthanꢀ24ꢀh.ꢀꢀꢀ atꢀpHꢀ12.ꢀTheꢀviscositiesꢀwereꢀmeasuredꢀus iDn Og Iꢀ :a 1n0 ꢀ. A1 0n 3t 9o /nC ꢀ 5P Ta Aa 0r 9ꢀ M4 3 C7 BR ꢀ
01ꢀ rheometerꢀ withꢀ aꢀ CC10/TIꢀ probe.ꢀ Theꢀ temperatureꢀ ofꢀ theꢀ
3
Polymerꢀfilmsꢀwereꢀalsoꢀdepositedꢀonꢀstainlessꢀsteelꢀ(2.4ꢀcmꢀxꢀ1.4ꢀ Peltierꢀplateꢀwasꢀsetꢀtoꢀ25ꢀ°C.ꢀBetweenꢀloadingꢀtheꢀsampleꢀandꢀtheꢀ
cm)ꢀ andꢀ onꢀ polystyreneꢀ (2.6ꢀ cmꢀ xꢀ 1.8ꢀ cm)ꢀ followingꢀ theꢀ sameꢀ startꢀofꢀtheꢀmeasurementsꢀthereꢀwasꢀaꢀwaitingꢀtimeꢀofꢀminimalꢀ5ꢀ
procedureꢀunderꢀconditionꢀb)ꢀasꢀdescribedꢀabove.ꢀ0.62ꢀmlꢀandꢀ0.87ꢀ minutes.ꢀ Theꢀ apparentꢀ viscosityꢀ wasꢀ measuredꢀ atꢀ shearꢀ ratesꢀ
mlꢀofꢀpolymerꢀsolutionꢀwereꢀspreadꢀontoꢀpre-cleanedꢀstainlessꢀsteelꢀ rangingꢀfromꢀ0.01ꢀtoꢀ1000ꢀ1/s,ꢀwithꢀfourꢀdataꢀpointsꢀperꢀdecadeꢀandꢀ
andꢀpolystyreneꢀsubstrates,ꢀrespectively.ꢀTheꢀfilmsꢀwereꢀleftꢀtoꢀdryꢀ aꢀmeasuringꢀtimeꢀofꢀ10ꢀsecondsꢀperꢀdataꢀpoint.ꢀForꢀeachꢀpH,ꢀtheꢀ
underꢀwell-ventilatedꢀconditionsꢀforꢀmoreꢀthanꢀ24ꢀh.ꢀ
measurementꢀwasꢀdoneꢀtwice;ꢀinꢀbetweenꢀtheꢀmeasurementꢀthereꢀ
wasꢀ aꢀ waitingꢀ timeꢀ ofꢀ minimalꢀ 5ꢀ minutes.ꢀ Dataꢀ pointsꢀ withꢀ
viscositiesꢀ belowꢀ theꢀ low-torqueꢀ limitꢀ ofꢀ theꢀ rheometerꢀ wereꢀ
removedꢀfromꢀtheꢀgraphs.ꢀ
UV-VISꢀspectroscopyꢀ
UV-visibleꢀcharacterizationꢀwasꢀperformedꢀonꢀaꢀShimadzuꢀUV-2600ꢀ
spectrophotometerꢀ atꢀ wavelengthsꢀ fromꢀ 200ꢀ toꢀ 600ꢀ nm.ꢀ Forꢀ theꢀ
calibrationꢀ ofꢀ theꢀ catechols,ꢀ fiveꢀ solutionsꢀ ofꢀ dopamineꢀ
Cross-cutꢀtapeꢀtestꢀꢀ
hydrochlorideꢀ inꢀ waterꢀ withꢀ differentꢀ concentrationsꢀ (0.18ꢀ –ꢀ Theꢀ cross-cutꢀ tapeꢀ testꢀ ASTMꢀ Dꢀ 3359ꢀ wasꢀ usedꢀ toꢀ measureꢀ theꢀ
.25µM)ꢀ wereꢀ prepared.ꢀ Theꢀ spectraꢀ ofꢀ theꢀ samplesꢀ wereꢀ adhesionꢀbetweenꢀtheꢀdriedꢀpolymerꢀfilmꢀandꢀtheꢀglassꢀsubstrate.ꢀ
0
measuredꢀ (wavelengthꢀ scan)ꢀ inꢀ aꢀ quartzꢀ curvet.ꢀ Theꢀ absorbanceꢀ Briefly,ꢀ aꢀ crosshatchꢀ patternꢀ (elevenꢀ cutsꢀ forꢀ eachꢀ directionꢀ withꢀ
intensityꢀatꢀλꢀ=ꢀ280ꢀnmꢀforꢀtheꢀsamplesꢀwasꢀusedꢀtoꢀcalculateꢀtheꢀ cutsꢀ 1ꢀ mmꢀ apart)ꢀ wasꢀ madeꢀ usingꢀ aꢀ sharpꢀ razorꢀ bladeꢀ thatꢀ cutꢀ
extinctionꢀcoefficientꢀε.ꢀꢀ
completelyꢀthroughꢀtheꢀfilmꢀtoꢀtheꢀsubstrate.ꢀTheꢀdetachedꢀflakesꢀ
ofꢀ coatingꢀ wereꢀ removedꢀ usingꢀ aꢀ softꢀ brush.ꢀ Aꢀ pressure-sensitiveꢀ
tapeꢀwasꢀappliedꢀoverꢀtheꢀcrosshatchꢀcutꢀandꢀtheꢀtapeꢀwasꢀpressedꢀ
intoꢀplaceꢀusingꢀaꢀpencilꢀeraserꢀtoꢀensureꢀgoodꢀcontactꢀbetweenꢀtheꢀ
tapeꢀandꢀtheꢀcoating.ꢀAfterꢀ60ꢀsꢀofꢀapplication,ꢀtheꢀtapeꢀwasꢀquicklyꢀ
removedꢀbyꢀpullingꢀitꢀoffꢀasꢀcloseꢀtoꢀanꢀangleꢀofꢀ180°ꢀasꢀpossible.ꢀ
Adhesionꢀ wasꢀ assessedꢀ basedꢀ onꢀ theꢀ percentageꢀ ofꢀ coatingꢀ areaꢀ
Atomicꢀforceꢀmicroscopyꢀ
Theꢀ roughnessꢀ ofꢀ theꢀ polymerꢀ filmsꢀ wasꢀ analyzedꢀ usingꢀ aꢀ Digitalꢀ
Instrumentsꢀ NanoScopeꢀ Vꢀ equippedꢀ withꢀ aꢀ siliconꢀ nitrideꢀ probeꢀ
TM
(
Veeco,ꢀNY,ꢀU.S.A.)ꢀwithꢀaꢀspringꢀconstantꢀofꢀ0.4ꢀN/mꢀinꢀScanAsyst ꢀ
imagingꢀ mode.ꢀ Imagesꢀ wereꢀ recordedꢀ betweenꢀ 1.5ꢀ Hzꢀ andꢀ 1024ꢀ removedꢀfromꢀtheꢀsubstrateꢀbyꢀtheꢀtapeꢀandꢀratedꢀonꢀaꢀ0Bꢀtoꢀ5Bꢀ
samples/line.ꢀ Imagesꢀ wereꢀ furtherꢀ processedꢀ withꢀ Nanoscopeꢀ scale.ꢀToꢀbeꢀspecific,ꢀ5B,ꢀ4B,ꢀ3B,ꢀ2B,ꢀ1Bꢀandꢀ0Bꢀindicateꢀthatꢀ0%,ꢀlessꢀ
Analysisꢀ1.20ꢀsoftwareꢀ(VeecoꢀInstrumentsꢀInc.ꢀ2010,ꢀU.S.A.).ꢀAꢀfirstꢀ
orderꢀflatteningꢀwasꢀusedꢀforꢀallꢀtheꢀimages.ꢀꢀ
thanꢀ5%,ꢀ5-15%,ꢀ15-35%,ꢀ35-65%ꢀandꢀmoreꢀthanꢀ65%ꢀofꢀtheꢀcoatingꢀ
areaꢀhasꢀbeenꢀremoved,ꢀrespectively.ꢀTheꢀtestꢀwasꢀrepeatedꢀthreeꢀ
times.ꢀ
Contactꢀangleꢀmeasurementsꢀ
Resultsꢀandꢀdiscussionꢀ
Theꢀwettabilityꢀofꢀtheꢀpolymerꢀfilmsꢀwasꢀmeasuredꢀbyꢀautomatedꢀ
staticꢀ waterꢀ contactꢀ angleꢀ measurementsꢀ withꢀ aꢀ Krüssꢀ DSAꢀ 100ꢀ
goniometer.ꢀTheꢀvolumeꢀofꢀtheꢀdropꢀofꢀdeionizedꢀwaterꢀwasꢀ3.0ꢀμL.ꢀ
Theꢀreportedꢀvaluesꢀareꢀtheꢀaverageꢀofꢀatꢀleastꢀtwoꢀdroplets,ꢀandꢀ
theꢀrelativeꢀerrorꢀisꢀlessꢀthanꢀ±3°.ꢀ
Polymerꢀsynthesisꢀ
Inꢀ thisꢀ work,ꢀ weꢀ developedꢀ aꢀ catecholamineꢀ co-polymerꢀ byꢀ freeꢀ
radicalꢀ copolymerizationꢀ inꢀ aqueousꢀ conditionsꢀ ofꢀ twoꢀ vinylꢀ
comonomers,ꢀoneꢀcontainingꢀboraxꢀprotectedꢀcatecholꢀ(DAA-p)ꢀandꢀ
theꢀ otherꢀ containingꢀ aminesꢀ (AEMA).ꢀ Anꢀ essentialꢀ stepꢀ isꢀ theꢀ
protectionꢀ ofꢀ theꢀ catecholsꢀ beforeꢀ polymerization.ꢀ Asꢀ reportedꢀ inꢀ
ourꢀ previousꢀ work,ꢀ usingꢀ vinylꢀ monomersꢀ containingꢀ unprotectedꢀ
Opticalꢀmicroscopyꢀ
Cross-sectionsꢀ ofꢀ theꢀ polymerꢀ filmsꢀ onꢀ theꢀ glassꢀ substratesꢀ wereꢀ
imagedꢀusingꢀanꢀOlympusꢀBXꢀ60.ꢀImagesꢀwereꢀobtainedꢀusingꢀaꢀ40xꢀ
magnification.ꢀ
22
catecholsꢀwouldꢀresultꢀinꢀtheꢀformationꢀofꢀaꢀcrosslinkedꢀpolymer .ꢀ
Theꢀ reasonꢀ isꢀ theꢀ radicalꢀ scavengingꢀ effectꢀ ofꢀ catechols.ꢀ Moreꢀ
specifically,ꢀ duringꢀ radicalꢀ polymerization,ꢀ theꢀ catecholsꢀ inꢀ oneꢀ
polymerꢀ chainꢀ canꢀ reactꢀ withꢀ propagatingꢀ radicalsꢀ inꢀ anotherꢀ
polymerꢀ chain.ꢀ ꢀ Therefore,ꢀ toꢀ synthesizeꢀ aꢀ linearꢀ catechol-
containingꢀpolymerꢀbyꢀradicalꢀpolymerization,ꢀtheꢀcatecholsꢀshouldꢀ
beꢀ protected.ꢀ Differentꢀ protectionꢀ methodsꢀ areꢀ possible,ꢀ
dependentꢀonꢀtheꢀspecificꢀrequirementꢀofꢀtheꢀsystem.ꢀInꢀourꢀcase,ꢀ
weꢀhaveꢀtriedꢀtwoꢀmethods,ꢀnamelyꢀmethoxy-protectionꢀandꢀborax-
protection.ꢀ Forꢀ theꢀ methoxy-protection,ꢀ i.e.,ꢀ protectingꢀ theꢀ
catecholsꢀwithꢀmethylꢀgroups,ꢀweꢀhaveꢀsuccessfullyꢀsynthesizedꢀtheꢀ
FTIRꢀ
Aꢀ10ꢀmg/mlꢀpolymerꢀsolutionꢀwasꢀpreparedꢀusingꢀ0.001ꢀMꢀHClꢀ(aq)ꢀ
asꢀtheꢀsolvent.ꢀSubsequently,ꢀfourꢀpolymerꢀsamplesꢀwereꢀpreparedꢀ
underꢀtheꢀfollowingꢀconditions:ꢀa)ꢀlowꢀpH;ꢀb)ꢀhighꢀpH,ꢀbyꢀaddingꢀ1Mꢀ
NaOH;ꢀc)ꢀhighꢀpH,ꢀinꢀtheꢀpresenceꢀofꢀaꢀmoderateꢀamountꢀofꢀNaIO
NaIO /ꢀcatecholꢀ=ꢀ1/ꢀ100);ꢀd)ꢀhighꢀpH,ꢀinꢀtheꢀpresenceꢀofꢀaꢀlargeꢀ
amountꢀ ofꢀ NaIO ꢀ (NaIO /ꢀ catecholꢀ =ꢀ 1/ꢀ 10).ꢀ Theꢀ fourꢀ polymerꢀ
4
ꢀ
(
4
4
4
solutionsꢀwereꢀallowedꢀtoꢀreactꢀforꢀ24ꢀhꢀandꢀlyophilizedꢀthereafter.ꢀ
TheꢀATR-FTIRꢀmeasurementsꢀwereꢀcarriedꢀoutꢀusingꢀaꢀBrukerꢀTensorꢀ
3
protectedꢀpolymersꢀ(Fig.ꢀS1).ꢀDeprotectionꢀrequiresꢀusingꢀBBr ꢀandꢀ
strictꢀcontrolꢀofꢀtemperatureꢀatꢀ-65ꢀ°C.ꢀThisꢀdeprotectionꢀstrategyꢀ
bringsꢀdifficultyꢀdueꢀtoꢀtheꢀfollowingꢀreasons.ꢀFirstly,ꢀtheꢀcatecholꢀ
2
7ꢀFTIRꢀspectrometer.ꢀꢀ
deprotectionꢀ byꢀ BBr
water,ꢀ sinceꢀ BBr ꢀ reactsꢀ violentlyꢀ withꢀ water.ꢀ However,ꢀ ourꢀ
50ꢀ mgꢀ PAEMAꢀ wasꢀ dissolvedꢀ inꢀ 1ꢀ mlꢀ 1mMꢀ HClꢀ solution.ꢀ Theꢀ pHꢀ copolymerꢀisꢀonlyꢀsolubleꢀinꢀaꢀmixtureꢀofꢀorganicꢀsolventꢀandꢀwater,ꢀ
3
ꢀ needsꢀ toꢀ beꢀ performedꢀ inꢀ theꢀ absenceꢀ ofꢀ
Rheologyꢀmeasurementsꢀ
3
2
wasꢀmeasuredꢀusingꢀaꢀSchottꢀpHꢀmeter.ꢀTheꢀinitialꢀpHꢀwasꢀaroundꢀ2.ꢀ therebyꢀ makingꢀ theꢀ deprotectionꢀ hard.ꢀ Secondly,ꢀ theꢀ removalꢀ ofꢀ
Afterꢀmeasuringꢀtheꢀviscosityꢀofꢀthisꢀsolution,ꢀtheꢀpHꢀwasꢀincreasedꢀ methoxyꢀ groupsꢀ requiresꢀ strictꢀ controlꢀ ofꢀ reactionꢀ conditions,ꢀ i.e.ꢀ
toꢀaroundꢀ9ꢀbyꢀaddingꢀ1.0ꢀMꢀNaOH.ꢀSubsequently,ꢀtheꢀviscosityꢀwasꢀ properꢀ amountꢀ ofꢀ BBr ,ꢀ onlyꢀ organicꢀ solvent,ꢀ andꢀ veryꢀ lowꢀ
3
4
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Jo uP rl ne aa sl eo ꢀ fd oM ꢀ na to et rꢀ ai ad l jsu sC t hꢀ me am r gi si nt rs yꢀ A
Page 6 of 11
JournalꢀNameꢀ
ꢀARTICLEꢀ
temperature.ꢀ Anꢀ additionꢀ ofꢀ inappropriateꢀ amountꢀ ofꢀ BBr
resultꢀ inꢀ partialꢀ deprotectionꢀ ofꢀ catechols .ꢀ Inꢀ viewꢀ ofꢀ theseꢀ
3
ꢀ mayꢀ Monomerꢀreactivityꢀ
View Article Online
DOI: 10.1039/C5TA09437B
23
problems,ꢀweꢀconsideredꢀboraxꢀprotectionꢀasꢀanꢀalternative.ꢀInꢀthisꢀ Generally,ꢀ freeꢀ radicalꢀ polymerizationꢀ isꢀ expectedꢀ toꢀ generateꢀ
work,ꢀ weꢀ startꢀ fromꢀ theꢀ synthesisꢀ ofꢀ vinylꢀ monomersꢀ containingꢀ randomꢀcopolymers.ꢀThisꢀpolymerizationꢀtechniqueꢀisꢀfavorableꢀinꢀ
borax-protectedꢀ catecholsꢀ DAA-p.ꢀ Theꢀ stabilityꢀ ofꢀ theꢀ complexꢀ ofꢀ ourꢀ system,ꢀ sinceꢀ aꢀ randomꢀ copolymerꢀ wouldꢀ leadꢀ toꢀ anꢀ evenꢀ
24
boraxꢀwithꢀcatecholꢀisꢀdependentꢀonꢀpH. ꢀGenerally,ꢀtheꢀpHꢀhasꢀtoꢀ distributionꢀ ofꢀ crosslinksꢀ throughoutꢀ theꢀ material.ꢀ Toꢀ checkꢀ theꢀ
beꢀ highꢀ (>ꢀ 9)ꢀ toꢀ ensureꢀ sufficientꢀ stabilityꢀ ofꢀ theꢀ borax-catecholꢀ randomnessꢀ ofꢀ theꢀ copolymer,ꢀ weꢀ studiedꢀ theꢀ reactivityꢀ ratiosꢀ ofꢀ
complexꢀagainstꢀdissociationꢀorꢀoxidation.ꢀInꢀourꢀsynthesis,ꢀweꢀkeepꢀ theꢀcomonomers.ꢀTheꢀreactivityꢀratioꢀrꢀisꢀaꢀkineticꢀparameterꢀthatꢀ
theꢀpHꢀaboveꢀ9ꢀbyꢀusingꢀ10ꢀmMꢀsodiumꢀcarbonateꢀaqueousꢀsolutionꢀ characterizesꢀtheꢀmonomerꢀsequenceꢀdistributionꢀinꢀaꢀcopolymer.ꢀr
asꢀtheꢀsolvent.ꢀAfterꢀ10ꢀhꢀofꢀreaction,ꢀweꢀdeprotectedꢀtheꢀborax- isꢀ definedꢀ asꢀ theꢀ ratioꢀ ofꢀ theꢀ rateꢀ constantꢀ forꢀ aꢀ reactiveꢀ
catecholꢀcomplexꢀbyꢀloweringꢀtheꢀpHꢀtoꢀaroundꢀ2ꢀusingꢀaꢀ1ꢀMꢀHClꢀ propagatingꢀradicalꢀM ꢀaddingꢀitsꢀownꢀtypeꢀofꢀmonomerꢀM ꢀtoꢀtheꢀ
aqueousꢀ solution.ꢀ Afterꢀ dialysis,ꢀ theꢀ polymericꢀ productꢀ wasꢀ rateꢀconstantꢀforꢀadditionꢀofꢀtheꢀotherꢀmonomerꢀM .ꢀInꢀourꢀstudy,ꢀitꢀ
1
ꢀ
1
1
2
1
obtained.ꢀToꢀcheckꢀtheꢀeffectivenessꢀofꢀtheꢀdeprotectionꢀprocedure,ꢀ wasꢀdeterminedꢀbyꢀin-situꢀ HꢀNMR.ꢀTheꢀcomonomerꢀconcentrationsꢀ
theꢀpolymerꢀandꢀDAA-pꢀaqueousꢀsolutionsꢀwereꢀinvestigatedꢀbyꢀUV- wereꢀ monitoredꢀ asꢀ aꢀ functionꢀ ofꢀ time.ꢀ Fig.ꢀ 2,ꢀ 3ꢀ andꢀ 4ꢀ showꢀ
VISꢀ(Fig.ꢀS2).ꢀDAA-pꢀshowedꢀaꢀpeakꢀatꢀ286ꢀnm,ꢀwhichꢀwasꢀascribedꢀ representativeꢀ spectraꢀ ofꢀ theꢀ DAA-p/ꢀ AEMAꢀ solutionsꢀ duringꢀ
toꢀ theꢀ borax-catecholꢀ complexꢀ (Fig.ꢀ S2).ꢀ Forꢀ theꢀ polymer,ꢀ inꢀ polymerizationꢀatꢀdifferentꢀreactionꢀtimes.ꢀAsꢀshownꢀinꢀFig.ꢀ3,ꢀtheꢀ
contrast,ꢀ anꢀ absorbanceꢀ peakꢀ atꢀ 280ꢀ nmꢀ wasꢀ detected,ꢀ whichꢀ isꢀ peaksꢀascribedꢀtoꢀtheꢀvinylꢀgroupsꢀofꢀDAA-pꢀ(δꢀ=ꢀ6.52-6.36ꢀppm,ꢀandꢀ
19
typicallyꢀ ascribedꢀ toꢀ freeꢀ catechols .ꢀ Therefore,ꢀ theꢀ catecholꢀ δꢀ=ꢀ6.02-5.96ꢀppm)ꢀandꢀAEMAꢀ(δꢀ=ꢀ5.8-5.75ꢀppm,ꢀandꢀδꢀ=ꢀ6.06-6.02ꢀ
groupsꢀinꢀourꢀpolymerꢀhaveꢀbeenꢀcompletelyꢀdeprotected.ꢀꢀ
ppm)ꢀdecreasedꢀinꢀtimeꢀ(markedꢀinꢀgreen).ꢀTheꢀaromaticꢀpeaksꢀatꢀδꢀ
ꢀ 7.0-6.75ꢀ ppmꢀ (markedꢀ inꢀ blue)ꢀ becameꢀ broaderꢀ withꢀ increasingꢀ
=
Polymerꢀcharacterizationꢀ
time.ꢀ Meanwhile,ꢀ broadꢀ peaksꢀ thatꢀ canꢀ beꢀ ascribedꢀ toꢀ theꢀ -CH2-ꢀ
groupsꢀinꢀtheꢀpolymerꢀmainꢀchain,ꢀe.g.,ꢀδꢀ=ꢀ1.4-1.1ꢀppmꢀ(markedꢀinꢀ
blue),ꢀ increased.ꢀ Theseꢀ changesꢀ inꢀ theꢀ spectraꢀ inꢀ timeꢀ clearlyꢀ
indicateꢀ thatꢀ theꢀ polymerizationꢀ takesꢀ placeꢀ rapidlyꢀ atꢀ elevatedꢀ
temperatures.ꢀWeꢀstudiedꢀthreeꢀreactionsꢀhavingꢀfeedꢀmolarꢀratiosꢀ
ofꢀ DAA-pꢀ ofꢀ 6,ꢀ 10ꢀ andꢀ 15ꢀ mol%,ꢀ respectively.ꢀ Byꢀ integratingꢀ theꢀ
peaksꢀascribedꢀtoꢀtheꢀvinylꢀgroupsꢀofꢀDAA-pꢀandꢀAEMA,ꢀasꢀshownꢀinꢀ
Fig.ꢀ3,ꢀtheꢀmonomerꢀconcentrationsꢀcanꢀbeꢀobtainedꢀasꢀaꢀfunctionꢀ
ofꢀ time.ꢀ Fromꢀ theꢀ variationꢀ ofꢀ theꢀ monomerꢀ concentrations,ꢀ theꢀ
reactivityꢀratiosꢀofꢀtheꢀcomonomersꢀcanꢀbeꢀobtainedꢀbyꢀfittingꢀtheꢀ
experimentalꢀ dataꢀ toꢀ anꢀ integralꢀ formꢀ ofꢀ theꢀ copolymerꢀ
1
HꢀNMRꢀwasꢀusedꢀtoꢀcharacterizeꢀtheꢀcopolymer,ꢀandꢀtheꢀspectrumꢀ
isꢀshownꢀinꢀFig.ꢀ1.ꢀByꢀcomparingꢀtheꢀintegrationꢀareaꢀofꢀpeaksꢀatꢀδꢀ=ꢀ
7
.2-6.6ꢀ ppmꢀ thatꢀ canꢀ beꢀ assignedꢀ toꢀ theꢀ threeꢀ protonsꢀ ofꢀ theꢀ
aromaticꢀringꢀinꢀDAAꢀ(positionsꢀa),ꢀandꢀpeaksꢀatꢀδꢀ=ꢀ3.75-2.8ꢀppmꢀofꢀ
theꢀ alkylꢀ groupsꢀ inꢀ bothꢀ monomersꢀ (positionsꢀ e,ꢀ f,ꢀ b,ꢀ c),ꢀ weꢀ
calculatedꢀtheꢀDAAꢀcompositionꢀinꢀtheꢀfinalꢀpolymerꢀtoꢀbeꢀaroundꢀ
7
.2ꢀmol%.ꢀThisꢀresultꢀagreesꢀwellꢀwithꢀthatꢀfromꢀUV-VIS,ꢀobtainedꢀasꢀ
follows.ꢀꢀToꢀcalculateꢀtheꢀDAAꢀcompositionꢀinꢀtheꢀfinalꢀpolymer,ꢀweꢀ
madeꢀ aꢀ calibrationꢀ curveꢀ basedꢀ onꢀ dopamineꢀ hydrochloride.ꢀ Byꢀ
preparingꢀ dopamineꢀ hydrochlorideꢀ solutionsꢀ withꢀ differentꢀ
concentrationsꢀ inꢀ 1ꢀ Mꢀ HClꢀ aqueousꢀ solution,ꢀ weꢀ obtainedꢀ theꢀ
25
compositionꢀequation :ꢀꢀ
2
-1
!
!
extinctionꢀ coefficientꢀ ofꢀ catecholꢀ asꢀ 2500ꢀ m ⋅mol .ꢀ Byꢀ usingꢀ theꢀ
Lambert-beerꢀ law,ꢀ theꢀ catecholꢀ concentrationꢀ wasꢀ obtained,ꢀ andꢀ
theꢀDAAꢀcompositionꢀinꢀtheꢀfinalꢀpolymerꢀwasꢀdeterminedꢀtoꢀbeꢀ8.2ꢀ
mol%.ꢀꢀ
=
!
!"
!
!
!!!!
!!!!!! ( !!!! !!!! )
!
!"!!
!!!! !! !! !!!!!
!!!! !!" !!" !!!!!
×
(3)ꢀ
!!"!!
whereꢀM
whichꢀ canꢀ beꢀ calculatedꢀ byꢀ comparingꢀ theꢀ integrationꢀ ofꢀ theꢀ
protonsꢀpeaksꢀofꢀtheꢀvinylꢀgroupsꢀinꢀmonomerꢀiꢀtoꢀthatꢀofꢀdioxane),ꢀ
ꢀisꢀtheꢀreactivityꢀratioꢀofꢀmonomerꢀi,ꢀandꢀMi0ꢀisꢀtheꢀinitialꢀmolarꢀ
i
ꢀisꢀtheꢀinstantaneousꢀmolarꢀconcentrationꢀofꢀmonomerꢀiꢀ
Theꢀdeterminationꢀofꢀtheꢀmolecularꢀweightꢀwasꢀcarriedꢀoutꢀbyꢀstaticꢀ
lightꢀ scattering.ꢀ Theꢀ copolymerꢀ hasꢀ aꢀ weight-averagedꢀ molecularꢀ
(
weightꢀ M
w
ꢀ ofꢀ 4912ꢀ kg/mol,ꢀ correspondingꢀ toꢀ aꢀ weight-averagedꢀ
r
i
degreeꢀofꢀpolymerizationꢀofꢀaboutꢀ29000.ꢀꢀ
concentrationꢀofꢀmonomerꢀi.ꢀꢀ
ꢀ
ꢀ
ꢀ
1
Figureꢀ2.ꢀ HꢀNMRꢀspectraꢀofꢀtheꢀcopolymerizationꢀreactionꢀDAA-pꢀ
1
andꢀAEMAꢀwithꢀanꢀinitialꢀfeedꢀmolarꢀratioꢀofꢀDAA-p:ꢀAEMAꢀ=ꢀ15:ꢀ85ꢀ
Figureꢀ1.ꢀ HꢀNMRꢀspectraꢀofꢀpoly(DAA-AEMA)ꢀinꢀ0.1ꢀMꢀDCl/D
2
Oꢀ
ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ5ꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Page 7 of 11
Jo uP rl ne aa sl eo ꢀ fd oM ꢀ na to et rꢀ ai ad l jsu sC t hꢀ me am r gi si nt rs yꢀ A
ARTICLEꢀ
JournalꢀNameꢀ
2
afterꢀreactionꢀatꢀ56ꢀ°Cꢀforꢀ12ꢀmin.ꢀTheꢀcharacteristicꢀpeakꢀofꢀD Oꢀisꢀ
View Article Online
atꢀ4.79ꢀppm.ꢀꢀꢀ
DOI: 10.1039/C5TA09437B
ꢀ
Figureꢀ5.ꢀReactivityꢀratiosꢀofꢀDAA-pꢀ(rDAA-p)ꢀvsꢀAEMAꢀ(rAEMA)ꢀofꢀthreeꢀ
reactionsꢀwithꢀtheꢀfeedꢀratioꢀofꢀDAA-pꢀasꢀ6ꢀmol%,ꢀ10ꢀmol%ꢀandꢀ15ꢀ
mol%,ꢀrespectively.ꢀꢀ
Basedꢀ onꢀ theꢀ obtainedꢀ reactivityꢀ ratios,ꢀ weꢀ calculatedꢀ theꢀ
copolymerꢀ compositionꢀ asꢀ aꢀ functionꢀ ofꢀ comonomerꢀ compositionꢀ
25
accordingꢀtoꢀtheꢀfollowingꢀequation :ꢀꢀ
ꢀ
1
Figureꢀ3.ꢀRepresentative HꢀNMRꢀspectraꢀofꢀtheꢀcopolymerizationꢀ
reactionꢀDAA-pꢀandꢀAEMAꢀwithꢀanꢀinitialꢀfeedꢀmolarꢀratioꢀofꢀDAA-p:ꢀ ꢀ! = !
AEMAꢀ=ꢀ15:ꢀ85.ꢀTheꢀpeaksꢀmarkedꢀwithꢀgreenꢀboxesꢀindicateꢀtheꢀ
vinylꢀprotonsꢀofꢀtheꢀmonomers;ꢀredꢀboxesꢀshowꢀthatꢀtheꢀprotonsꢀinꢀ
!
!
!
!
!!! !!!!!
!ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ(4)ꢀ
!
!! !!!!!!!!!!
whereꢀF
i
ꢀisꢀtheꢀmoleꢀfractionꢀofꢀM
i
ꢀinꢀtheꢀcopolymer,ꢀandꢀf
i
ꢀisꢀtheꢀ
theꢀalkylꢀgroupsꢀdecreaseꢀwithꢀtime,ꢀandꢀblueꢀboxesꢀindicateꢀpeaksꢀ
thatꢀbroaden.ꢀꢀ
feedꢀmolarꢀfractionꢀofꢀmonomerꢀi.ꢀByꢀapplyingꢀtheꢀr
above,ꢀweꢀobtainꢀtheꢀrelationꢀbetweenꢀFDAA-pꢀandꢀfDAA-pꢀ(Fig.ꢀ6).ꢀForꢀ
i
ꢀweꢀobtainedꢀ
ourꢀcopolymer,ꢀtheꢀreactivityꢀratiosꢀofꢀbothꢀmonomersꢀareꢀlessꢀthanꢀ
unity,ꢀ andꢀ rDAA-p
copolymerization.ꢀTheꢀFDAA-pꢀ/fDAA-pꢀplotsꢀcrossꢀtheꢀlineꢀrepresentingꢀ
DAA-pꢀ=ꢀfDAA-p.ꢀAtꢀtheꢀcrossoverꢀpointꢀorꢀazeotropicꢀpoint,ꢀi.e.ꢀfDAA-pꢀ=ꢀ
.35,ꢀ theꢀ copolymerizationꢀ occursꢀ withoutꢀ changeꢀ inꢀ theꢀ feedꢀ
rAEMAꢀ =ꢀ 0,ꢀ givingꢀ riseꢀ toꢀ anꢀ azeotropicꢀ
F
0
composition.ꢀForꢀfeedꢀcompositionsꢀnearꢀtheꢀazeotropicꢀpoint,ꢀtheꢀ
copolymerꢀcompositionꢀdistributionsꢀareꢀnarrowꢀatꢀlowꢀconversions.ꢀ
Atꢀ highꢀ conversions,ꢀ theꢀ copolymerꢀ compositionꢀ driftsꢀ toꢀ eitherꢀ
comonomer,ꢀ dependingꢀ onꢀ theꢀ initialꢀ feed,ꢀ whetherꢀ itꢀ containsꢀ
moreꢀ DAA-pꢀ orꢀ moreꢀ AEMA.ꢀ Theꢀ copolymerꢀ compositionꢀ
distributionꢀ becomesꢀ widerꢀ whenꢀ theꢀ initialꢀ feedꢀ compositionꢀ
deviatesꢀ furtherꢀ fromꢀ theꢀ azeotropicꢀ point.ꢀ Inꢀ ourꢀ copolymerꢀ
system,ꢀwithꢀanꢀinitialꢀfeedꢀmolarꢀratioꢀofꢀDAA-p:ꢀAEMAꢀ=ꢀ8:ꢀ92ꢀasꢀ
shownꢀ inꢀ Fig.ꢀ 7,ꢀ atꢀ lowꢀ conversion,ꢀ itꢀ isꢀ expectedꢀ toꢀ presentꢀ aꢀ
moderateꢀ alternatingꢀ structure.ꢀ Atꢀ highꢀ conversion,ꢀ whenꢀ DAA-pꢀ
hasꢀ beenꢀ largelyꢀ consumed,ꢀ moreꢀ AEMAꢀ isꢀ incorporatedꢀ intoꢀ theꢀ
copolymerꢀchains.ꢀ
ꢀ
Figureꢀ4.ꢀDetailsꢀofꢀtheꢀvinylꢀregionꢀofꢀrepresentativeꢀspectraꢀforꢀtheꢀ
copolymerizationꢀ reactionꢀ DAA-pꢀ andꢀ AEMAꢀ withꢀ anꢀ initialꢀ feedꢀ
molarꢀratioꢀofꢀDAA-p:ꢀAEMAꢀ=ꢀ15:ꢀ85.ꢀ
Theꢀ methodꢀ takesꢀ anyꢀ experimentalꢀ pointꢀ M
pointꢀ forꢀ theꢀ restꢀ ofꢀ theꢀ reaction.ꢀ Moreꢀ specifically,ꢀ forꢀ eachꢀ
reaction,ꢀtheꢀfirstꢀ5-10ꢀpointsꢀwereꢀusedꢀasꢀtheꢀinitialꢀM20,ꢀM10/M20
2 1 2
,ꢀ M /M ꢀ asꢀ startingꢀ
ꢀ
forꢀtheꢀrestꢀofꢀtheꢀreaction.ꢀByꢀusingꢀtheꢀleast-squaresꢀoptimizationꢀ
toꢀ fitꢀ eachꢀ setꢀ ofꢀ experimentalꢀ dataꢀ toꢀ eqꢀ (3),ꢀ weꢀ obtainedꢀ 5-10ꢀ
reactivityꢀ ratiosꢀ ofꢀ rDAA-pꢀ andꢀ rAEMA.ꢀ Theꢀ obtainedꢀ reactivityꢀ ratiosꢀ
21
thatꢀfitꢀeachꢀsetꢀofꢀexperimentalꢀdataꢀareꢀhighlyꢀcorrelated ,ꢀandꢀ
DAA-pꢀvsꢀrAEMAꢀfollowedꢀaꢀstraightꢀlineꢀ(Fig.ꢀ5).ꢀAndꢀforꢀeachꢀreaction,ꢀ
r
asꢀshownꢀinꢀFig.ꢀ5,ꢀweꢀobtainedꢀoneꢀstraightꢀline.ꢀTheꢀpointꢀwhereꢀ
theꢀlinesꢀintersectꢀgivesꢀtheꢀfinalꢀvaluesꢀofꢀreactivityꢀratios,ꢀi.e.,ꢀ0ꢀforꢀ
r
DAA-pꢀandꢀ0.46ꢀforꢀrAEMA.ꢀAsꢀallꢀthreeꢀlinesꢀintersectꢀinꢀoneꢀpoint,ꢀthisꢀ
ꢀ
ꢀ
indicatesꢀthatꢀaꢀreliableꢀreactivityꢀratioꢀhasꢀbeenꢀobtained.ꢀAꢀvalueꢀ
ofꢀ 0ꢀ forꢀ theꢀ reactivityꢀ ratioꢀ ofꢀ DAA-pꢀ indicatesꢀ thatꢀ theꢀ DAA-pꢀ
propagatingꢀradicalsꢀcannotꢀaddꢀaꢀDAA-pꢀmonomerꢀandꢀthereforeꢀ
alwaysꢀaddꢀanꢀAEMAꢀmonomer,ꢀwhileꢀrAEMAꢀ=ꢀ0.46ꢀindicatesꢀthat,ꢀ
AEMAꢀpropagatingꢀradicalsꢀaddꢀtoꢀDAA-pꢀinꢀaboutꢀhalfꢀofꢀtheꢀcases.ꢀ
Figureꢀ 6.ꢀ Copolymerꢀ compositionꢀ asꢀ aꢀ functionꢀ ofꢀ monomerꢀ feedꢀ
fractionꢀ forꢀ poly(DAA-p-AEMA)ꢀ system.ꢀ Theꢀ dashedꢀ diagonalꢀ lineꢀ
representsꢀFDAA-pꢀ=ꢀfDAA-p.ꢀTheꢀblackꢀarrowꢀpointsꢀtoꢀtheꢀazeotropicꢀ
6
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Jo uP rl ne aa sl eo ꢀ fd oM ꢀ na to et rꢀ ai ad l jsu sC t hꢀ me am r gi si nt rs yꢀ A
Page 8 of 11
JournalꢀNameꢀ
ꢀARTICLEꢀ
point.ꢀTheꢀdashꢀdottedꢀlineꢀindicatesꢀtheꢀfeedꢀcompositionꢀforꢀourꢀ
View Article Online
copolymerꢀwithꢀanꢀinitialꢀDAA-pꢀpercentageꢀofꢀ8ꢀmol%.ꢀꢀ
DOI: 10.1039/C5TA09437B
ꢀ
Figureꢀ7.ꢀHypothesizedꢀmonomerꢀdistributionꢀschemeꢀinꢀtheꢀ
copolymerꢀforꢀP(DAA-co-AEMA).ꢀSolidꢀcircle,ꢀDAA-p;ꢀemptyꢀtriangle,ꢀ
AEMA.ꢀ
ꢀ
Polymerꢀfilmsꢀ
ꢀ
Figureꢀ 8.ꢀ Opticalꢀ microscopyꢀ imageꢀ ofꢀ polymerꢀ filmꢀ P(DAA-co-
AEMA)ꢀpreparedꢀatꢀhighꢀpH)ꢀonꢀaꢀpre-treatedꢀglassꢀsubstrate.ꢀTheꢀ
thicknessꢀ ofꢀ theꢀ polymerꢀ layerꢀ wasꢀ measuredꢀ withꢀ opticalꢀ
microscopyꢀ(×40ꢀmagnification).ꢀ
Weꢀaimedꢀatꢀdevelopingꢀaꢀlinear,ꢀwater-solubleꢀpolymerꢀcontainingꢀ
twoꢀ typesꢀ ofꢀ functionalꢀ groups,ꢀ i.e.,ꢀ catecholsꢀ andꢀ amines.ꢀ Byꢀ
triggeringꢀtheꢀcatecholꢀcrosslinkingꢀchemistry,ꢀthisꢀpolymerꢀshouldꢀ
beꢀableꢀtoꢀchangeꢀfromꢀwater-solubleꢀtoꢀwater-insoluble.ꢀToꢀverifyꢀ
theꢀhypothesis,ꢀtwoꢀpolymerꢀfilmsꢀwereꢀpreparedꢀonꢀaꢀpre-cleanedꢀ Theꢀwettabilityꢀandꢀswellingꢀbehaviorꢀofꢀtheꢀfourꢀpolymerꢀfilmsꢀonꢀ
theꢀglassꢀsubstrateꢀwereꢀstudiedꢀbyꢀcontactꢀangleꢀmeasurements,ꢀasꢀ
shownꢀinꢀFig.ꢀ9ꢀandꢀTableꢀ2.ꢀUponꢀdepositingꢀoneꢀwaterꢀdroplet,ꢀtheꢀ
uncrosslinkedꢀ film,ꢀ preparedꢀ atꢀ lowꢀ pH,ꢀ startedꢀ toꢀ absorbꢀ water,ꢀ
andꢀswelledꢀinꢀaꢀfewꢀsecondsꢀasꢀshownꢀinꢀFigꢀ9ꢀ(a).ꢀAfterꢀsomeꢀtime,ꢀ
theꢀwaterꢀdropletꢀwasꢀfullyꢀabsorbedꢀandꢀtheꢀpolymerꢀfilmꢀassumedꢀ
anꢀirregularꢀshape.ꢀTheꢀquickꢀswellingꢀbehaviorꢀclearlyꢀindicatesꢀthatꢀ
theꢀpolymerꢀisꢀstillꢀsolubleꢀinꢀwater.ꢀThisꢀbehaviorꢀisꢀcorroboratedꢀ
byꢀ UV-visꢀ measurements.ꢀ Asꢀ shownꢀ inꢀ Fig.ꢀ 10,ꢀ P(DAA-co-AEMA)ꢀ
preparedꢀatꢀlowꢀpHꢀexhibitedꢀaꢀdistinctꢀpeakꢀatꢀ280ꢀnm,ꢀwhichꢀisꢀ
ascribedꢀtoꢀunreactedꢀcatecholꢀgroups.ꢀAꢀveryꢀbroadꢀandꢀtinyꢀpeakꢀ
atꢀ aroundꢀ 350ꢀ nmꢀ alsoꢀ appeared,ꢀ whichꢀ mightꢀ beꢀ dueꢀ toꢀ slowꢀ
oxidationꢀduringꢀtheꢀevaporationꢀofꢀwaterꢀduringꢀfilmꢀformation.ꢀ
glassꢀsubstrate,ꢀoneꢀatꢀlowꢀpHꢀ(∼ꢀ2)ꢀandꢀoneꢀatꢀhighꢀpHꢀ(∼ꢀ11.5).ꢀTheꢀ
crosslinkingꢀofꢀtheꢀpolymerꢀcanꢀbeꢀenhancedꢀbyꢀaddingꢀtheꢀoxidizingꢀ
agentꢀsodiumꢀperiodateꢀ(NaIO
ofꢀcrosslinkingꢀonꢀtheꢀsolubilityꢀbehavior,ꢀtwoꢀextraꢀpolymerꢀfilmsꢀ
wereꢀpreparedꢀbyꢀaddingꢀdifferentꢀamountsꢀofꢀNaIO ,ꢀi.e.ꢀ1ꢀmol%ꢀ
4
).ꢀToꢀstudyꢀtheꢀeffectꢀofꢀtheꢀdegreeꢀ
4
andꢀ 10ꢀ mol%ꢀ ofꢀ catechol,ꢀ respectively.ꢀ Theꢀ thicknessꢀ ofꢀ theꢀ fourꢀ
polymerꢀfilmsꢀwereꢀmeasuredꢀbyꢀopticalꢀmicroscopy,ꢀandꢀshownꢀinꢀ
Tableꢀ1.ꢀAꢀrepresentativeꢀsampleꢀisꢀshownꢀinꢀFig.ꢀ8.ꢀTheꢀpolymerꢀcanꢀ
alsoꢀ beꢀ depositedꢀ onꢀ otherꢀ substrates,ꢀ suchꢀ asꢀ polystyreneꢀ andꢀ
stainlessꢀsteelꢀ(Fig.ꢀS3).ꢀ
Tableꢀ1.ꢀThicknessꢀofꢀpolymerꢀfilmsꢀasꢀdeterminedꢀbyꢀopticalꢀ
microscopy.ꢀTheꢀstandardꢀdeviationꢀofꢀtheꢀthicknessꢀofꢀeachꢀsampleꢀ
isꢀbasedꢀonꢀthreeꢀmeasurementsꢀatꢀdifferentꢀlocationsꢀinꢀtheꢀsameꢀ
film.ꢀ
Sampleꢀ
Thicknessꢀ
µm)ꢀ
(
P(DAA-co-AEMA)ꢀlowꢀ
9.1ꢀ±ꢀ0.4ꢀ
11.9ꢀ±ꢀ0.7ꢀ
11.1ꢀ±ꢀ0.2ꢀ
12.6ꢀ±ꢀ0.5ꢀ
ꢀ
pHꢀ
Figureꢀ9.ꢀStaticꢀwaterꢀcontactꢀanglesꢀofꢀtheꢀfourꢀpolymerꢀfilms:ꢀa)ꢀ
uncrosslinkedꢀpolymerꢀfilm,ꢀP(DAA-co-AEMA)ꢀpreparedꢀatꢀlowꢀpHꢀ(∼ꢀ
),ꢀb)ꢀslightlyꢀcrosslinkedꢀpolymerꢀfilm,ꢀP(DAA-co-AEMA)ꢀpreparedꢀ
atꢀhighꢀpHꢀ(∼ꢀ11.5),ꢀc)ꢀmoderatelyꢀcrosslinkedꢀpolymerꢀfilm,ꢀP(DAA-
co-AEMA),ꢀ pHꢀ 11.5,ꢀ NaIO /ꢀ catechol=1/100ꢀ (mol/mol),ꢀ d)ꢀ highlyꢀ
P(DAA-co-AEMA),ꢀ
highꢀpHꢀ
2
P(DAA-co-AEMA),ꢀ
4
highꢀpH,ꢀ1/100ꢀNaIO
4
ꢀ
4
crosslinkedꢀ polymerꢀ film,ꢀ P(DAA-co-AEMA),ꢀ pH=11.5,ꢀ NaIO /ꢀ
catechol=1/10ꢀ
P(DAA-co-AEMA),ꢀ
highꢀpH,ꢀ1/10ꢀNaIO
4
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ7ꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Page 9 of 11
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ARTICLEꢀ
Tableꢀ2.ꢀStaticꢀwaterꢀcontactꢀangleꢀofꢀfourꢀpolymerꢀfilmsꢀ
JournalꢀNameꢀ
View Article Online
DOI: 10.1039/C5TA09437B
Sampleꢀ
Contactꢀ
angleꢀ( )ꢀ
o
ꢀ
ꢀ
ꢀ
P(DAA-co-AEMA)ꢀlowꢀpHꢀ
-ꢀ
P(DAA-co-AEMA),ꢀhighꢀpHꢀ
30ꢀ±ꢀ2.4ꢀ
41ꢀ±ꢀ0.2ꢀ
P(DAA-co-AEMA),ꢀhighꢀpH,ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
1
4
/100ꢀNaIO ꢀ
ꢀ
1
P(DAA-co-AEMA),ꢀhighꢀpH,ꢀꢀꢀ
/10ꢀNaIO
46ꢀ±ꢀ0.2ꢀ
4
ꢀ
ꢀ
ꢀ
Figureꢀ10.ꢀUV-visꢀspectraꢀofꢀpolymerꢀfilmsꢀdepositedꢀonꢀquartzꢀ
slidesꢀwithꢀdifferentꢀdegreeꢀofꢀcrosslinking.
Increasingꢀ theꢀ pHꢀ beforeꢀ filmꢀ casting,ꢀ i.e.,ꢀ P(DAA-co-AEMA)ꢀ
preparedꢀatꢀpHꢀ11.5,ꢀresultedꢀinꢀaꢀpolymerꢀfilmꢀthatꢀdidꢀnotꢀswellꢀ
uponꢀloadingꢀtheꢀfilmꢀwithꢀaꢀwaterꢀdroplet,ꢀasꢀshownꢀinꢀFig.ꢀ9(b).ꢀ
Theꢀ polymerꢀ filmꢀ wasꢀ stableꢀ inꢀ theꢀ presenceꢀ ofꢀ waterꢀ duringꢀ theꢀ
measurement,ꢀandꢀexhibitedꢀaꢀstableꢀcontactꢀangleꢀofꢀaroundꢀ30°.ꢀ
TheꢀdifferentꢀbehaviorꢀbetweenꢀtheꢀlowꢀandꢀhighꢀpHꢀtreatmentꢀcanꢀ
beꢀinterpretedꢀasꢀfollows.ꢀFirstly,ꢀatꢀhighꢀpHꢀ11.5,ꢀwhenꢀtheꢀpHꢀisꢀ
26
higherꢀthanꢀtheꢀpKaꢀofꢀtheꢀaminoꢀgroupꢀinꢀAEMAꢀ(∼ꢀ9.6) ,ꢀAEMAꢀisꢀ
deprotonated,ꢀandꢀfreeꢀaminesꢀareꢀformed.ꢀTheꢀo-quinonesꢀformedꢀ
byꢀ oxidationꢀ fromꢀ theꢀ catechols,ꢀ canꢀ thenꢀ reactꢀ withꢀ theꢀ freeꢀ
aminesꢀbyꢀeitherꢀaꢀSchiff-baseꢀreactionꢀorꢀaꢀMichael-typeꢀaddition,ꢀ
10
orꢀwithꢀcatecholsꢀbyꢀdismutationꢀreactions. ꢀWeꢀhaveꢀshownꢀinꢀaꢀ
separateꢀstudyꢀthatꢀtheꢀreactionꢀbetweenꢀo-quinonesꢀandꢀamineꢀisꢀ
predominantꢀoverꢀtheꢀdismutationꢀreactionꢀwithꢀcatechols.ꢀInꢀtheꢀ
presentꢀ study,ꢀ weꢀ usedꢀ UV-visꢀ andꢀ FTIRꢀ measurementsꢀ toꢀ
corroborateꢀthisꢀfinding.ꢀAsꢀshownꢀinꢀFig.ꢀ10,ꢀtheꢀpeakꢀatꢀλꢀ=ꢀ280ꢀnmꢀ
shiftedꢀtoꢀaꢀslightlyꢀhigherꢀwavelength,ꢀλꢀ=ꢀ288ꢀnm.ꢀMeanwhile,ꢀaꢀ
strongꢀpeakꢀatꢀλꢀ=ꢀ340ꢀnmꢀappeared.ꢀTheꢀpeakꢀatꢀλꢀ=ꢀ340ꢀnmꢀhasꢀ
beenꢀ ascribedꢀ toꢀ theꢀ formationꢀ ofꢀ theꢀ reactionꢀ intermediateꢀ ofꢀ
ꢀ
Figureꢀ 11.ꢀ FTIRꢀ spectraꢀ ofꢀ fourꢀ polymersꢀ preparedꢀ atꢀ differentꢀ
conditions:ꢀa)ꢀatꢀlowꢀpHꢀ(blackꢀline);ꢀb)ꢀhighꢀpHꢀ(readꢀline);ꢀc)ꢀhighꢀ
pH,ꢀ1/100ꢀNaIO ꢀ(blueꢀline);ꢀd)ꢀhighꢀpH,ꢀ1/10ꢀNaIO ꢀ(darkꢀcyanꢀline).ꢀ
4 4
27
catecholꢀcrosslinking. ꢀTheꢀabsorbanceꢀspectraꢀofꢀtheꢀfilmꢀdidꢀnotꢀ
changeꢀ overꢀ theꢀ courseꢀ ofꢀ 71ꢀ hoursꢀ (Fig.ꢀ S4),ꢀ indicatingꢀ thatꢀ theꢀ
polymerꢀfilmꢀisꢀchemicallyꢀstableꢀforꢀatꢀleastꢀ3ꢀdays.ꢀFurthermore,ꢀinꢀ
theꢀFTIRꢀspectrumꢀofꢀtheꢀpolymerꢀasꢀshownꢀinꢀFig.ꢀ11,ꢀtheꢀpolymerꢀ
-
1
Theꢀgreenꢀarrowꢀindicatesꢀtheꢀsmallꢀpeakꢀatꢀ1163ꢀcm .ꢀ
-1ꢀ
Theꢀ crosslinkingꢀ rateꢀ ofꢀ theꢀ catecholamineꢀ polymerꢀ filmꢀ canꢀ beꢀ
preparedꢀ atꢀ lowꢀ pHꢀ showedꢀ peaksꢀ atꢀ 1163ꢀ cm ascribedꢀ toꢀ C-Nꢀ
-1
enhancedꢀ byꢀ theꢀ additionꢀ ofꢀ NaIO
4
.ꢀ Asꢀ shownꢀ inꢀ Fig.ꢀ 9(c),ꢀ uponꢀ
/ꢀ catecholꢀ =ꢀ 1/ꢀ 100),ꢀ theꢀ
stretchꢀforꢀaliphaticꢀamines,ꢀandꢀaꢀbroadꢀpeakꢀaboveꢀ3000ꢀcm ꢀforꢀ
phenolicꢀO-Hꢀstretch.ꢀTheseꢀtwoꢀpeaksꢀbothꢀdecreasedꢀsignificantlyꢀ
forꢀtheꢀotherꢀthreeꢀcrosslinkedꢀsamples,ꢀindicatingꢀthatꢀtheꢀOHꢀ(onꢀ
theꢀaromaticꢀringꢀofꢀcatechols)ꢀandꢀaminesꢀhadꢀreacted.ꢀSecondly,ꢀ
inꢀ ourꢀ catecholamineꢀ polymer,ꢀ atꢀ lowꢀ pH,ꢀ theꢀ aminesꢀ areꢀ
protonatedꢀ andꢀ charged,ꢀ whichꢀ favorsꢀ theꢀ solubilityꢀ inꢀ water.ꢀ Byꢀ
increasingꢀtheꢀpH,ꢀtheꢀdeprotonationꢀofꢀtheꢀaminesꢀleadsꢀtoꢀaꢀlossꢀ
ofꢀcharge,ꢀwhichꢀreducesꢀtheꢀsolubility.ꢀThisꢀdecreaseꢀinꢀsolubilityꢀ
uponꢀpHꢀincreaseꢀisꢀreflectedꢀbyꢀaꢀdecreaseꢀinꢀviscosity.ꢀAsꢀshownꢀinꢀ
Fig.ꢀ S5,ꢀ theꢀ viscosityꢀ ofꢀ PAEMAꢀ decreasesꢀ fourfoldꢀ whenꢀ theꢀ pHꢀ
increasesꢀfromꢀ2ꢀtoꢀ12.ꢀHoweverꢀinꢀgeneral,ꢀtoꢀswitchꢀfromꢀwater-
addingꢀ aꢀ smallꢀ amountꢀ ofꢀ NaIO ꢀ (NaIO
4
4
polymerꢀfilmꢀshowedꢀaꢀhigherꢀstaticꢀwaterꢀcontactꢀangleꢀofꢀ41°.ꢀThisꢀ
increaseꢀ indicatedꢀ aꢀ moreꢀ crosslinkedꢀ polymerꢀ film.ꢀ Theꢀ higherꢀ
degreeꢀ ofꢀ crosslinkingꢀ isꢀ alsoꢀ reflectedꢀ inꢀ theꢀ UV-visꢀ spectra:ꢀ theꢀ
peakꢀisꢀshiftedꢀtoꢀtheꢀright,ꢀi.e.,ꢀλꢀ=ꢀ290ꢀnm,ꢀandꢀtheꢀintensityꢀofꢀtheꢀ
peakꢀatꢀλꢀ=ꢀ340ꢀnmꢀisꢀincreased.ꢀAꢀfurtherꢀadditionꢀofꢀmoreꢀNaIO
4
ꢀ
(
NaIO /ꢀ catecholꢀ =ꢀ 1/10)ꢀ yieldedꢀ aꢀ polymerꢀ filmꢀ withꢀ evenꢀ higherꢀ
4
intensityꢀofꢀabsorbanceꢀatꢀλꢀ=ꢀ340ꢀnmꢀ(Fig.ꢀ10),ꢀandꢀaꢀhigherꢀstaticꢀ
contactꢀangleꢀofꢀ46°ꢀ(Fig.ꢀ9(d)).ꢀꢀ
28
Theꢀ effectꢀ ofꢀ crosslinkingꢀ onꢀ theꢀ morphologyꢀ ofꢀ theꢀ polymerꢀ filmꢀ
wasꢀstudiedꢀbyꢀAFMꢀmeasurements,ꢀasꢀshownꢀinꢀFig.ꢀ11.ꢀAsꢀshownꢀ
inꢀFig.ꢀ12(a),ꢀtheꢀuncrosslinkedꢀpolymerꢀfilmꢀshowedꢀaꢀveryꢀsmoothꢀ
surfaceꢀ withꢀ negligibleꢀ roughness.ꢀ Forꢀ theꢀ crosslinkedꢀ films,ꢀ
however,ꢀasꢀshownꢀinꢀFig.ꢀ12ꢀ(b),ꢀ(c)ꢀandꢀ(d),ꢀtheꢀroughnessꢀofꢀtheꢀ
filmsꢀ increased.ꢀ Theꢀ roughnessesꢀ forꢀ theꢀ variousꢀ crosslinkedꢀ filmsꢀ
didꢀnotꢀdifferꢀmuch,ꢀindicatingꢀthatꢀaꢀmoreꢀcrosslinkedꢀfilmꢀdoesꢀnotꢀ
necessarilyꢀleadꢀtoꢀaꢀrougherꢀsurface.ꢀItꢀisꢀknownꢀthatꢀtheꢀroughnessꢀ
ofꢀ theꢀ surfaceꢀ hasꢀ anꢀ amplifyingꢀ effectꢀ onꢀ theꢀ contactꢀ angle.ꢀ
Accordingꢀ toꢀ theꢀ Wenzelꢀ equation,ꢀ forꢀ anꢀ intrinsicꢀ water/ꢀ airꢀ
contactꢀangleꢀ(referringꢀtoꢀaꢀperfectlyꢀflatꢀsurface)ꢀsmallerꢀthanꢀ90°,ꢀ
solubleꢀtoꢀwater-insolubleꢀaꢀlargerꢀchangeꢀinꢀviscosityꢀisꢀexpected ,ꢀ
whichꢀindicatesꢀthatꢀtheꢀformationꢀofꢀtheꢀwater-insolubleꢀnetworkꢀ
isꢀmainlyꢀdueꢀtoꢀtheꢀcrosslinkingꢀreactions.ꢀTheꢀeffectsꢀofꢀcatecholꢀ
crosslinking-chemistryꢀ onꢀ theꢀ polymerꢀ solubilityꢀ haveꢀ alsoꢀ beenꢀ
observedꢀinꢀcatechol-modifiedꢀchitosan.ꢀTheꢀuncrosslinkedꢀpolymerꢀ
wasꢀ solubleꢀ inꢀ water.ꢀ Byꢀ exposingꢀ theꢀ polymerꢀ toꢀ NaIO
4
ꢀ solution,ꢀ
theꢀ crosslinkingꢀ chemistryꢀ betweenꢀ catecholꢀ andꢀ theꢀ aminesꢀ inꢀ
29
chitosanꢀwasꢀtriggered,ꢀresultingꢀinꢀaꢀwater-insolubleꢀpolymer. ꢀꢀ
8
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
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Jo uP rl ne aa sl eo ꢀ fd oM ꢀ na to et rꢀ ai ad l jsu sC t hꢀ me am r gi si nt rs yꢀ A
Page 10 of 11
JournalꢀNameꢀ
roughnessꢀ decreasesꢀ theꢀ apparentꢀ contactꢀ angle,ꢀ soꢀ thatꢀ theꢀ
surfaceꢀseemsꢀtoꢀbeꢀmoreꢀhydrophilic. ꢀInꢀourꢀcase,ꢀweꢀobservedꢀ
thatꢀtheꢀcontactꢀanglesꢀforꢀcrosslinkedꢀfilmsꢀareꢀlowerꢀthanꢀ90°.ꢀByꢀ
takingꢀ intoꢀ accountꢀ theꢀ amplifyingꢀ effectꢀ ofꢀ roughness,ꢀ weꢀ canꢀ
concludeꢀthatꢀtheꢀintrinsicꢀcontactꢀangleꢀforꢀtheꢀcrosslinkedꢀfilmsꢀisꢀ
mostꢀlikelyꢀhigherꢀthanꢀtheꢀdataꢀweꢀcurrentlyꢀobtained.ꢀTheꢀeffectꢀ
ꢀARTICLEꢀ
Acknowledgementsꢀ
View Article Online
DOI: 10.1039/C5TA09437B
30
WeꢀwouldꢀlikeꢀtoꢀthankꢀRemcoꢀFokkinkꢀforꢀhelpꢀwithꢀdynamicꢀ
andꢀ staticꢀ lightꢀ scatteringꢀ measurements.ꢀ Weꢀ gratefullyꢀ
acknowledgeꢀtheꢀfinancialꢀsupportꢀofꢀAkzoNobel.ꢀ
ꢀ
ofꢀcrosslinkingꢀonꢀtheꢀintrinsicꢀcontactꢀangleꢀshouldꢀstillꢀfollowꢀtheꢀ Referencesꢀ
sameꢀtrendꢀasꢀtheꢀoneꢀweꢀobserved.ꢀꢀ
1
2
3
4
5
.ꢀ
.ꢀ
.ꢀ
.ꢀ
.ꢀ
J.ꢀH.ꢀWaite,ꢀComparativeꢀBiochemistryꢀandꢀPhysiologyꢀPartꢀ
B:ꢀComparativeꢀBiochemistry,ꢀ1990,ꢀ97,ꢀ19-29.ꢀ
A.ꢀMiserez,ꢀD.ꢀRubinꢀandꢀJ.ꢀH.ꢀWaite,ꢀJournalꢀofꢀBiologicalꢀ
Chemistry,ꢀ2010,ꢀ285,ꢀ38115-38124.ꢀ
A.ꢀ Miserez,ꢀ T.ꢀ Schneberk,ꢀ C.ꢀ Sun,ꢀ F.ꢀ W.ꢀ Zokꢀ andꢀ J.ꢀ H.ꢀ
Waite,ꢀScience,ꢀ2008,ꢀ319,ꢀ1816.ꢀ
H.ꢀBargel,ꢀK.ꢀKoch,ꢀZ.ꢀCermanꢀandꢀC.ꢀNeinhuis,ꢀFunct.ꢀPlantꢀ
Biol.,ꢀ2006,ꢀ33,ꢀ893–910.ꢀ
N.ꢀ Holten-Andersen,ꢀ M.ꢀ J.ꢀ Harrington,ꢀ H.ꢀ Birkedal,ꢀ B.ꢀ P.ꢀ
Lee,ꢀP.ꢀB.ꢀMessersmith,ꢀK.ꢀY.ꢀC.ꢀLeeꢀandꢀJ.ꢀH.ꢀWaite,ꢀProc.ꢀ
Natl.ꢀAcad.ꢀSci.ꢀU.ꢀS.ꢀA.,ꢀ2011,ꢀ108,ꢀ2651.ꢀ
Inꢀaddition,ꢀourꢀpolymerꢀfilmsꢀattachꢀwellꢀtoꢀtheꢀglassꢀsubstrate.ꢀByꢀ
performingꢀ aꢀ cross-cutꢀ tapeꢀ test,ꢀ weꢀ measuredꢀ theꢀ adhesionꢀ
betweenꢀ theꢀ polymerꢀ filmꢀ preparedꢀ atꢀ pHꢀ 11.5ꢀ andꢀ theꢀ glassꢀ
substrate.ꢀ Threeꢀ testsꢀ atꢀ differentꢀ locationsꢀ ofꢀ theꢀ filmꢀ wereꢀ
performed.ꢀ Weꢀ foundꢀ that,ꢀ accordingꢀ toꢀ ASTMꢀ Dꢀ 3359,ꢀ theꢀ
adhesionꢀisꢀratedꢀasꢀ4B.ꢀThisꢀmeansꢀthatꢀonlyꢀlessꢀthanꢀ5%ꢀofꢀtheꢀ
coatingꢀ areaꢀ hasꢀ beenꢀ removedꢀ byꢀ theꢀ tape,ꢀ indicatingꢀ thatꢀ ourꢀ
coatingꢀattachesꢀwellꢀtoꢀtheꢀglassꢀsubstrate.ꢀTheꢀgoodꢀperformanceꢀ
ofꢀ theꢀ polymerꢀ filmꢀ inꢀ theꢀ cross-cutꢀ adhesionꢀ testꢀ alsoꢀ impliesꢀ aꢀ
goodꢀmechanicalꢀstabilityꢀofꢀtheꢀfilm.ꢀꢀ
6
7
.ꢀ
.ꢀ
L.ꢀVitellaroꢀZuccarello,ꢀTissueꢀCell,ꢀ1981,ꢀ13,ꢀ701–713.ꢀ
J.ꢀH.ꢀDreisbachꢀandꢀJ.ꢀR.ꢀMerkel,ꢀJ.ꢀBacteriol.,ꢀ1978,ꢀ135,ꢀ
5
21–527.ꢀ
8
.ꢀ
G.ꢀI.ꢀZardi,ꢀK.ꢀR.ꢀNicastro,ꢀC.ꢀD.ꢀMcQuaidꢀandꢀJ.ꢀErlandsson,ꢀ
Mar.ꢀBiol.ꢀ,ꢀ2008,ꢀ153,ꢀ853–858.ꢀ
9
1
.ꢀ
0.ꢀ
J.ꢀR.ꢀE.ꢀHarger,ꢀVeliger,ꢀ1970,ꢀ12,ꢀ401–414.ꢀ
J.ꢀ Yang,ꢀ M.ꢀ A.ꢀ Cohenꢀ Stuartꢀ andꢀ M.ꢀ Kamperman,ꢀ Chem.ꢀ
Soc.ꢀRev.,ꢀ2014,ꢀ43,ꢀ8271-8298.ꢀ
1
1
1.ꢀ
2.ꢀ
J.ꢀH.ꢀWaiteꢀandꢀM.ꢀL.ꢀTanzer,ꢀScience,ꢀ1981,ꢀ212,ꢀ1038.ꢀ
M.ꢀ J.ꢀ Harrington,ꢀ A.ꢀ Masic,ꢀ N.ꢀ Holten-Andersen,ꢀ J.ꢀ H.ꢀ
WaiteꢀandꢀP.ꢀFratzl,ꢀScience,ꢀ2010,ꢀ328,ꢀ216-220.ꢀ
J.ꢀJi,ꢀJ.ꢀH.ꢀFuꢀandꢀJ.ꢀC.ꢀShen,ꢀAdv.ꢀMater.,ꢀ2006,ꢀ18,ꢀ1441–
1
1
1
1
3.ꢀ
4.ꢀ
5.ꢀ
6.ꢀ
1
444.ꢀ
Y.ꢀD.ꢀWang,ꢀP.ꢀP.ꢀJoshi,ꢀK.ꢀL.ꢀHobbs,ꢀM.ꢀB.ꢀJohnsonꢀandꢀD.ꢀ
W.ꢀSchmidtke,ꢀLangmuir,ꢀ2006,ꢀ22,ꢀ9776–9783.ꢀ
T.ꢀBoudou,ꢀT.ꢀCrouzier,ꢀK.ꢀF.ꢀRen,ꢀG.ꢀBlinꢀandꢀC.ꢀPicart,ꢀAdv.ꢀ
Mater.,ꢀ2009,ꢀ22,ꢀ441–467.ꢀ
E.ꢀ Faure,ꢀ C.ꢀ Falentin-Daudré,ꢀ T.ꢀ S.ꢀ Lanero,ꢀ C.ꢀ Vreuls,ꢀ G.ꢀ
Zocchi,ꢀ C.ꢀ Vanꢀ Deꢀ Weerdt,ꢀ J.ꢀ Martial,ꢀ C.ꢀ Jérôme,ꢀ A.-S.ꢀ
Duwezꢀ andꢀ C.ꢀ Detrembleur,ꢀ Advancedꢀ Functionalꢀ
Materials,ꢀ2012,ꢀ22,ꢀ5271-5282.ꢀ
ꢀ
Figureꢀ12.ꢀAFMꢀimagesꢀofꢀP(DAA-co-AEMA)ꢀfilms,ꢀa)ꢀuncrosslinkedꢀ
film,ꢀP(DAA-co-AEMA)ꢀatꢀlowꢀpH;ꢀb)ꢀslightlyꢀcrosslinkedꢀfilm,ꢀP(DAA-
co-AEMA),ꢀ atꢀ pHꢀ 11.5;ꢀ c)ꢀ moderatelyꢀ crosslinkedꢀ film,ꢀ P(DAA-co-
AEMA),ꢀ pHꢀ 11.5,ꢀ NaIO /ꢀ catechol=1/100;ꢀ d)ꢀ stronglyꢀ crosslinkedꢀ
4
4
film,ꢀP(DAA-co-AEMA),ꢀpHꢀ11.5,ꢀNaIO /ꢀcatechol=1/10.ꢀ
1
1
7.ꢀ
8.ꢀ
E.ꢀ Faure,ꢀ P.ꢀ Lecomte,ꢀ S.ꢀ Lenoir,ꢀ C.ꢀ Vreuls,ꢀ C.ꢀ Vanꢀ Deꢀ
Weerdt,ꢀ C.ꢀ Archambeau,ꢀ J.ꢀ Martial,ꢀ C.ꢀ Jerome,ꢀ A.-S.ꢀ
Duwezꢀ andꢀ C.ꢀ Detrembleur,ꢀ Journalꢀ ofꢀ Materialsꢀ
Chemistry,ꢀ2011,ꢀ21,ꢀ7901-7904.ꢀ
A.ꢀCharlot,ꢀV.ꢀSciannamea,ꢀS.ꢀLenoir,ꢀE.ꢀFaure,ꢀR.ꢀJerome,ꢀ
C.ꢀJerome,ꢀC.ꢀVanꢀDeꢀWeerdt,ꢀJ.ꢀMartial,ꢀC.ꢀArchambeau,ꢀ
N.ꢀ Willet,ꢀ A.-S.ꢀ Duwez,ꢀ C.-A.ꢀ Fustinꢀ andꢀ C.ꢀ Detrembleur,ꢀ
JournalꢀofꢀMaterialsꢀChemistry,ꢀ2009,ꢀ19,ꢀ4117-4125.ꢀ
J.ꢀ Wu,ꢀ L.ꢀ Zhang,ꢀ Y.ꢀ Wang,ꢀ Y.ꢀ Long,ꢀ H.ꢀ Gao,ꢀ X.ꢀ Zhang,ꢀ N.ꢀ
Zhao,ꢀY.ꢀCaiꢀandꢀJ.ꢀXu,ꢀLangmuir,ꢀ2011,ꢀ27,ꢀ13684-13691.ꢀ
H.ꢀ O.ꢀ Ham,ꢀ Z.ꢀ Liu,ꢀ K.ꢀ H.ꢀ A.ꢀ Lau,ꢀ H.ꢀ Leeꢀ andꢀ P.ꢀ B.ꢀ
Messersmith,ꢀ Angewandteꢀ Chemieꢀ Internationalꢀ Edition,ꢀ
2011,ꢀ50,ꢀ732-736.ꢀ
M.ꢀ R.ꢀ Aguilar,ꢀ A.ꢀ Gallardo,ꢀ M.ꢀ d.ꢀ M.ꢀ Fernándezꢀ andꢀ J.ꢀ S.ꢀ
Román,ꢀMacromolecules,ꢀ2002,ꢀ35,ꢀ2036-2041.ꢀ
J.ꢀYang,ꢀJ.ꢀKeijsers,ꢀM.ꢀHeek,ꢀA.ꢀStuiver,ꢀM.ꢀA.ꢀCohenꢀStuartꢀ
andꢀM.ꢀKamperman,ꢀPolym.ꢀChem.,ꢀ2015,ꢀ6,ꢀ3121-3130.ꢀ
E.ꢀ D.ꢀ Vickery,ꢀ L.ꢀ F.ꢀ Pahlerꢀ andꢀ E.ꢀ J.ꢀ Eisenbraun,ꢀ J.ꢀ Org.ꢀ
Chem.,ꢀ1979,ꢀ44,ꢀ4444.ꢀ
Conclusionsꢀ
Inꢀconclusion,ꢀweꢀdevelopedꢀaꢀone-potꢀcoatingꢀsystemꢀusingꢀtheꢀpH-
responsiveꢀ catecholamineꢀ polymerꢀ P(DAA-co-AEMA).ꢀ Weꢀ 19.ꢀ
synthesizedꢀ theꢀ copolymerꢀ byꢀ freeꢀ radicalꢀ polymerizationꢀ ofꢀ twoꢀ
monomers,ꢀDAA-pꢀandꢀAEMA,ꢀinꢀaqueousꢀconditions.ꢀTheꢀpolymerꢀ 20.ꢀ
worksꢀsimilarlyꢀasꢀmusselꢀproteins,ꢀi.e.,ꢀbeingꢀwater-solubleꢀatꢀlowꢀ
pHꢀ(pHꢀ2),ꢀandꢀbecomingꢀwater-insolubleꢀatꢀhighꢀpHꢀ(pHꢀ11.5).ꢀTheꢀ
water-solubilityꢀswitchꢀwasꢀascribedꢀtoꢀtheꢀself-crosslinkingꢀabilityꢀ 21.ꢀ
ofꢀ theꢀ polymerꢀ atꢀ highꢀ pH.ꢀ Moreover,ꢀ theꢀ crosslinkingꢀ ofꢀ theꢀ
polymerꢀisꢀaffectedꢀbyꢀtheꢀpolymerꢀsequenceꢀdistribution.ꢀUsingꢀanꢀ 22.ꢀ
1
in-situꢀ Hꢀ NMRꢀ monitoringꢀ method,ꢀ weꢀ studiedꢀ theꢀ sequenceꢀ
distributionꢀ byꢀ lookingꢀ atꢀ theꢀ reactivityꢀ ratiosꢀ ofꢀ theꢀ monomersꢀ 23.ꢀ
DAA-pꢀandꢀAEMA.ꢀBothꢀtheꢀreactivityꢀratiosꢀofꢀtheꢀmonomersꢀareꢀ
lowerꢀ thanꢀ unity,ꢀ i.e.,ꢀ rDAA-pꢀ =ꢀ 0,ꢀ rAEMAꢀ =ꢀ 0.46,ꢀ givingꢀ riseꢀ toꢀ aꢀ 24.ꢀ
moderatelyꢀalternatingꢀpolymerꢀstructure.ꢀꢀ
M.ꢀ Rafieeꢀ andꢀ D.ꢀ Nematollahi,ꢀ Electrochimi.ꢀ Acta,ꢀ 2008,ꢀ
53,ꢀ2751–2756.ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ9ꢀ
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ARTICLEꢀ
JournalꢀNameꢀ
2
2
5.ꢀ
6.ꢀ
G.ꢀOdian,ꢀPrinciplesꢀofꢀPolymerization,ꢀWiley-Interscience,ꢀ
thꢀedn.,ꢀ2004.ꢀ
Z.ꢀ C.ꢀ Deng,ꢀ H.ꢀ Bouchekif,ꢀ K.ꢀ Babooram,ꢀ A.ꢀ Housni,ꢀ N.ꢀ
View Article Online
DOI: 10.1039/C5TA09437B
4
Choytunꢀ andꢀ R.ꢀ Narain,ꢀ J.ꢀ Polym.ꢀ Sci.ꢀ Aꢀ Polym.ꢀ Chem.,ꢀ
2
008,ꢀ46,ꢀ4984-4996.ꢀ
2
7.ꢀ
B.ꢀ P.ꢀ Lee,ꢀ J.ꢀ L.ꢀ Dalsinꢀ andꢀ P.ꢀ B.ꢀ Messersmith,ꢀ
Biomacromolecules,ꢀ2002,ꢀ3,ꢀ1038-1047.ꢀ
2
2
8.ꢀ
9.ꢀ
Y.ꢀLiꢀandꢀJ.ꢀC.ꢀT.ꢀKwak,ꢀLangmuir,ꢀ2002,ꢀ18,ꢀ10049-10051.ꢀ
J.ꢀH.ꢀRyu,ꢀS.ꢀJo,ꢀM.-Y.ꢀKohꢀandꢀH.ꢀLee,ꢀAdvancedꢀFunctionalꢀ
Materials,ꢀ2014,ꢀ24,ꢀ7709-7716.ꢀ
3
ꢀ
0.ꢀ
D.ꢀQuere,ꢀPhys.ꢀA,ꢀ2002,ꢀ313,ꢀ32-46.ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
1
0ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ