Inrecentyears,thesynthesisofpolymerbrusheshasreceivedsignificantattention.Inthis presentationwetalkedaboutseveraldifferentaspectsofpolymerbrushesandsyntheticstra tegiesforthegenerationofpolymerbrushes.Finally,exampleisprovidedthathighlightsom erecentdevelopmentsaimedatstrategiesforthefunctionalizationofsurfaceswithpolymer brushes,atwaysofrealizingsmartsurfaceswithswitchableproperties. 1 2 Polymerbrushes Apolymerbrushconsistsofend-tethered(grafted,anchored)polymerchainsstretchedawayf romthesubstratesothatinthegivensolventthebrushheight(h)islargerascomparedtotheen d-to-enddistance(<r2>1/2)ofthesamenon-graftedchainsdissolvedinthesamesolvent.Inp olymerbrushesthedistancebetweengraftingpoints(d)issmallerthanthechainend-to-endd istance.Polymerbrushescanbeintroducedasthinfilmsofend-graftedpolymermoleculeswhe nthefollowingconditionsaresatisfied:h><r2>1/2,d<<r2>1/2.Outsidetheseconditionsth egraftedlayersareinthemushroomregime(seenextslide).

3 PolymerBrushes:GeneralFeatures Whenpolymermoleculesaretethered(grafted)toasurface,twobasiccasesmustbedistinguis heddependingonthegraftdensityoftheattachedchains. 1.Ifthedistancebetweentwoanchoringsitesislargerthanthesizeofthesurface-attachedp olymers,thesegmentsoftheindividualchainsdonotfeeleachotherandbehavemoreorlesslikes inglechainsnaileddownontothesurfacebyoneend.Dependingonthestrengthofinteractionoft hepolymersegmentswiththesurface,againtwocasesmustbedistinguished.Iftheinteractio nbetweenthepolymerandthesurfaceisweak(orevenrepulsive),thechainsformatypicalrand omcoilthatislinkedtothesurfacethroughastemofvaryingsize.Forsuchasituation,thetermmu shroomconformationhasbeencoined(Slide).However,ifthesegmentsofthesurfaceattachedc hainsadsorbstronglytotheunderlyingsurface,thepolymermoleculesobtainaflat,pancake-l ikeconformation(Slide) 2.Acompletelydifferentpictureisobtainedifthechainsareattachedtothesurfaceatsuchs hortdistancesbetweentheanchorpointsthatthepolymeroleculesoverlap.Inthiscase,thes egmentsofthechainstrytoavoideachotherasmuchaspossibleandminimizesegmentsegmentint eractionsbystretchingawayfromthesurface(slide).Thischainstretching,however,reduc esthenumberofpossiblepolymerconformations,whichisequivalenttoareductionintheentr opyofthechains. 4 This loss of entropy gives rise to a retracting force trying to keep the chains coiled, as occurs in a stretched piece of rubber. Thus, a new equilibrium at a higher energ y level is obtained in which the chains are stretched perpendicular to the surface. The structure of a surface-immobilized polymer can be evaluated by the inverse v alue of the distance between grafting points (D). As the size of grafted polymer chai ns approaches the distance between grafting points, the grafted chains overlap. Thi s point is a transition point between a single grafted chain (mushroom) regime and brush regime. A commonly used literature parameter for quantitative characterization of this transition is the reduced tethered density where Rg is radius of gyration of a tethered chain at specific experimental cond itions of solvent and temperature. The definition of grafting density () is determined b y Where h is the brush thickness; , bulk density of the brush composition; and NA, Avogadros number. It is generally recognized that three regimes occur in brush formation: (1) the mushroom or weakly interacting regime ( < 1), (2) the crossover regime ( ~ 1), and (3) the highly stretched regime ( >1). However, in re al systems, the transition between single grafted chains and a polymer brush is les s

sharp because of the statistical characteristic of grafting and polydispersity o f the tethered chains 5 Thetermresponsivebehaviorisratheratermwhichreflectsapplications,andconsequently,th ereisnouniversaldefinitionofresponsiveness.Formanyapplicationswesupposetoobtaina steepandwellnoticeablechange(switching)ofthegivenproperty,thus,transitionsfromth estatewhichcanbecharacterizedbysomepropertytothestatewiththecontraproperty.Respo nsivenessofpolymerbrushestoexternalstimulireferstochangesofpolymermoleculeconfor mations.Thesizeofpolymerchainsissensitivetoitsenvironment.Insolvents(attractionan drepulsionarecompensated)isolatedpolymerchainsofthedegreeofpolymerizationNposses sidealcoilconformationwhen<r2>1/2~N1/2.Thesizeoftheisolatedchainisafunctionofsol ventquality(thatmaybeexpressedintermsofthe-Flo y-Huggin inte a tionpa amete o temp e atu e). Ingood olvent andathighpolyme on ent ation theex ludedvolumeeffe t(Chain annot takethepo itionofothe hain )modifie hain onfo mation ub tantially.In emi-dilu tedpolyme olution the hain izede ea e withthe1/8thpowe ofthepolyme volumef a t ioninagood olvent.Intheta olvent thepolyme hain izei on ent ationindependent.I npoo olvent bulkpolyme olution unde goapha e epa ationintotwopha e :almo tpu e olventand on ent atedpolyme olutionofove lappingGau ian oil .Boththe alingex ponentandthep efa to a e en itiveto olventquality.Con t aint duetotheendg afting ofthepolyme hain int odu ea pe ifi ha a te ofthe e pon ewhi hi omewhatdiffe e ntf omthe e pon efi olated hain in olutiono melt.Inthe owdedg aftedlaye (polym e b u he )the hain t et houtoftheg afting u fa euntiltheex ludedvolumeeffe ti ompen atedbyela ti ene gy( t et hingent opy)ofpolyme oil .Polyme b u he expandi ngood olvent and ollap einpoo olvent .The hangeof ha a te i ti izebetweengooda ndpoo olvent i mu hla ge fo polyme b u he a ompa edtothepolyme hainin olution . 6 Me hani m of Responsiveness The general idea behind the theoretical description of polymer brushes is that t he free energy F of the chains is obtained from a balance between the interaction e nergy between the statistical segments Fint and energy difference between stretched an d unstretched polymer chains Fel (elastic free energy) caused by the entropy loss of the chains: F = Fint + Fel The most important parameters, which are of interest for a description of brush systems, are the segment density profile ( (z)) of the surface-attached chains and /or the brush height h as a function of the graft density , the molecular weight (/de gree of polymerization) of the surface-attached chains, and the solvent quality of th e contacting medium (Fig.1). 7 (Fig.1)Two hundred chains of a polymer brush (chain length N = 100) under good solvent conditions. The first description of such a brush system has been attempted by Alexander for monodisperse chains consisting of N segments, which are attached to a flat, nona dsorbing surface with an average distance of the anchor points d much smaller than the radius of gyration of the same unperturbed chains not in contact with the su rface (Fig.2). If both the interaction energy resulting from binary monomer monomer interactions and the elastic energy of a Gaussian chain are calculated and minimized in respe

ct to the brush height h, the following equation is obtained for brushes in a good sol vent: In a poor solvent that is, close to conditions the exponent describing the influence of the grafting density is slightly different and is obtained. It should be noted, that in both cases the brush height scales linearly with the degree of polymerization/molecular weight of the polymer molecules, which is a much stronger dependency than that of the size of a polymer coil in solution on the molecular weight, where the radius of gyration Rg, scales with Rg ~ N0.59 for a polymer in a good solvent and Rg ~ N0.50 for solutions close to conditions. In addition to these somewhat straightforward calculations, more complicated situations have also been tackled where the polymer chains have a distinct polydispersity, which exhibit a significant curvature also on the molecular scal e, and to brushes which carry charges along the polymer chain. In particular, the latte r case can become very complicated if the polymer chains interact specifically with ion s in the surrounding medium, as under these circumstances the situation can no longer be described by simple mean field approaches, but specific complex formation and (local) changes in the solubility of the polymer play a key role in describing t he swelling behavior of such brushes. 8 (Fig.2).Schematic illustration of the Alexander model for the theoretic description of polymer brushes. The chain segments with the blobs (indicated by the circles) behave as random (Gaussian) coils. (d represents the average distance between anchor points.) Thisslidepresentsthedensityprofilesvs.distancefromthegraftingsurfaceatdifferent-s tretchingparametervalues(1/=d=<r2>1/2/h).Asthegraftingdensityincreasesfromthemush roomregime(<1)tothestrongstretchinglimit(=100)theprofilechangesdramatically.Theimp enetra legraftingsurfacecausesadecreaseofthepolymerdensityclosetothegraftingsurf acewhenthegraftingdensitymaximumislocatednsomedistancefromthegraftingsurface.Thi sdistanceincreasesasthegraftingdensitydecreases.Thegraftingdensityprofileismuchm oresensitivetothe rushcharacteristicatmoderategraftingdensitiesascomparedtoavery highstretchingrgime. 9 Typesofpolymer rushesTherearemanydifferentcriteriatoclassifypolymer rushes ut as edontheconstitutionwehavefollowingtypesofpolyme rushes:Homopolymer rushesPolyele ctrolyte rushesBlockcopolymer rushesMolecular rushesReversi leSelfassem led rush 10 Typicallytherearethreemainmethodsforsynthesisingpolymer rushes: Graftingonto(graftingto) Graftingfrom Graftingthrough Amongethesethree,thefirsttwoonearemoreimportant,sosomeoftheadvantageanddisadvant ageshave eenmentioneda ove. 11 InGraftingontomethodapolymerchainwhichhasafunctionalgroupattheenddiffusesthrough thesurface,onthesurfacethereareotherfunctionalgroups,whichcanreactandthereforech ainwillgrafttothesurface. Ithasto emetionedthatduetothestereochemicalhinderence,densityofgraftinginthismet hodisnothigh. 12 InGraftingfrommethodaproperinitiaterisattachtothesurfacefirst,andthensurfacewill encounterwiththemonomeratapproprateconditionforpolymerizationinsidethereactor.At thepolymerizationmediachainswillgrowonthesurface,whiletheyhave eengraftedtoitfro mthe egining.

13 14 Theuniformedpolymerchaingrowth,whichleadstolowpolydispersity,stemsfromthetransit ionmetal asedcatalyst.Thiscatalystprovidesanequili rium etweenactive,andtherefor epropagating,polymerandaninactiveformofthepolymer;knownasthedormantform.Sincethe dormantstateofthepolymerisvastlypreferredinthisequili rium,sidereactionsaresuppr essed. Thisequili riuminturnlowerstheconcentrationofpropagatingradicals,thereforesuppre ssingunintentionalterminationandcontrollingmolecularweights. Therearefiveimportantvaria lecomponentsofAtomTransferRadicalPolymerizations.They arethemonomer,initiator,catalyst,solventandtemperature.Thefollowingsection reaks downthecontri utionsofeachcomponenttotheoverallpolymerization. Monomer MonomersthataretypicallyusedinATRParemoleculeswithsu stituentsthatcansta ilizeth epropagatingradicals;forexample,styrenes,(meth)acrylates,(meth)acrylamides,andac rylonitrile.ATRParesuccessfulatleadingtopolymersofhighnum eraveragemolecularweig htandanarrowpolydispersityindexwhentheconcentrationoftheproagatingradical alance stherateofradicaltermination.Yet,thepropagatingrateisuniquetoeachindividualmonom er.Therefore,itisimportantthattheothercomponentsofthepolymerization(initiator,ca talysts,ligandsandsolvents)areoptimizedinorderfortheconcentrationofthedormantspe ciesto egreaterthantheconcentrationofthepropagatingradicalandyetnottoogreatoslow downorhaltthereaction. 15 Initiator Thenum erofgrowingpolymerchainsisdetermined ytheinitiator.Thefastertheinitiation ,thefewerterminationsandtransfers,themoreconsistentthenum erofpropagatingchainsl eadingtonarrowmolecularweightdistri utions.Organichalidesthataresimilarintheorga nicframeworkasthepropagatingradicalareoftenchosenasinitiators.[Alkylhalidessucha salkyl romidesaremorereactivethanalkylchloridesand othhavegoodmolecularweightcon trol. Catalyst ThecatalystisthemostimportantcomponentofATRP ecauseitdeterminestheequili riumcon stant etweentheactiveanddormantspecies.Thisequili riumdeterminesthepolymerizatio nrateandanequili riumconstanttoosmallmayinhi itorslowthepolymerizationwhileanequ ili rimconstanttoolargeleadstoahighdistri utionofchainlengths. Thereareseveralrequirementsforthemetalcatalyst: thereneedsto etwoaccessi leoxidationstatesthatareseparated yoneelectron themetalcenterneedstohaveareasona leaffinityforhalogens thecoordinationsphereofthemetalneedsto eexpanda lewhenitsoxidizedsoto ea letoacc ommodatethehalogen astrongligandcomplexation. Themoststudiedcatalystsarethosethatpolymerizationsinvolvingcopper,whichhasshownt hemostversatility,showingsuccessfulpolymerizationsregardlessofthemonomer. Solvent Toluene,1,4-dioxane Temperature 16 ATRPhas eenconductedfromarangeofsurfacessincetheconceptwasfirstdisclosed,Because oftheirappearancethesematerialshave eencalledpolymer rushes.Thetwomostcommontype sofpolymer rushesareillustrateda oveandhave eenformed y oth"graftingfrom"and"gra ftingto"inorganicparticlesandflatsurfaces.Thesynthesisoforganic/inorganichy ridm aterialsisanareaofgrowinginterestastheusefulpropertiesofdisparatecomponentscan e com inedintoasinglematerial.Sphericalparticles:Organic/inorganichy ridnanopartic lescontaininganinorganiccoreandtetheredglassyorru eryhomopolymersorcopolymersha ve eenprepared ytheATRofstyreneand(meth)acrylatesfromcolloidalinitiators.FlatSur faces:Modificationofsurfaceswiththinpolymericfilmsallowsonetotailorsurfaceproper tiessuchasweta ility, iocompati ility, iocidalactivity,adhesion,adsorption,corro sionresistanceandfriction.Polymerswithreactivegroupsorsegmentscan epreparedfor"g raftingonto"surfacesorfunctionalgroupscan eattachedtothesurfaceforamoreefficient "graftingfrom"approach.Thepropertiesofsurfacesareaddressedelsewhereonthissiteint

hissectionweprimarilyaddress"graftingfrom"surfacetetheredinitiators.Itisalsoposs i letoprepare lockcopolymerswhereoneormoresegmentsofthe lockcopolymerhad eenprep ared yanon-CRPprocedure.Theonlyrequirementistoensuretheterminalfunctionalgroupsp resentontheinitialfunctionalpolymercan econvertedintoradicallytransferaleatom(s) forthesecondcontrolledATRPstep 17 18 Diffrentproductswithdiffrentmorphology,fordiffrentsufesticatedapplycationscan ep roduced yATRP. Manyresearchinggroupsareworkinginthisarea,thereforejustformakinganimpressiona oa tvisatilityofATRPthefollowingslideshavemade. Ineachphotothemodeofgraftsarediffrent. 19 20 21 Themajoro jectivefortheapplicationofresponsivepolymer rushesistoregulate,adjust, andswitchinteractionforces etweenthe rushanditsenvironmentconstitutedofliquid,va por,solid,another rush,particles,etc.ThesimplestformulationoftheResponsivePolyme rBrushespro lemisswitching etweenattractionandrepulsion.Forexample,thepolymer ru shlikelayersta ilizescolloidaldispersion,however,uponchangeofitsenvironmenttheco lloidcoagulates ecausetherepulsiveforcesofthe rushhave eenswitchedoff.Thissimpleef fecthasnumerousimportantapplicationsinvarioustechnologiesanditisnotfullyexplored andengineeredyet.Thesamesimplepro lemisimportantifthefrictioncoefficient,adhesio n,orwettingcould erapidlychangedtoswitchoffandoncapillaryflow,celladhesion,prote inadsorption,cellgrowth,mem ranepermea ility,anddrugrelease.Oneofthetargetsisthe applicationoftheresponsive rushesforsmartdevicessuchasdrugdeliverydevices,microf ludicanalyticaldevices,andsensors.Smartdrugdeliverydevicesareseenasadrugloadedca psulecoatedwitha rush-likeshell.Expansionandshrinkingofresponsivepolymer rushesc an eusedtofa ricatemechanicalactuators.Theeffectofswitchingofwetting ehaviorofth emixedweakPEL rushesuponachangeofpHwasrecentlyexploredforthefa ricationofsmartmicr ofluidicdevices.Thepassageofliquidsthroughthemicrofluidicchannelswasregulated yr esponsivenessofthemixed rushesofdifferentcompositions.Reversi lechangesofmixed r ushmorphologiesinsolventsofdifferentthermodynamicqualitywereusedforthemotionofna noparticlesdepositedothe rushsurface.Thesimplestdevicewhichexplorespolymer rushr esponsivenessisasensorworkingontheprincipleofthe rushexpansioncollapsetransitions uponchangesinitsenvironment.Currently,researchisfocusedonhowtheinteractionswithp olymer rushesmay epreciselytunedandmonitoredinacontrolledenvironment. 22 Reversi leCantileveractuation yPEL-Brushes The endingofmicrocantileversuponadsorptionofpolymers(DNA,proteins)orsmallmolecul eshasgreatpotentialforthedevelopmentofhighlysensitivesensorsandefficientnanoactu ators.Formicrocantileversto eusefulasactuators,precisepositioning,reversi ility, andlarge-scale endingareprerequisites.Conventionalmodification yself-assem ledmo nolayers(SAMs)usuallygeneratessmallcantileverdeflections.Bygraftingpolymerstothe cantileversurface,amuchwiderrangeofresponsescan eachievedduetoconformationalchan gesinthepolymer ack ones,andrecently,the endingofpHresponsivecopolymer rush-coat edAFMcantileverswasstudiedunderdifferentconditions.However,reversi leandmulti-st ageactuationofcantileversremainsasignificantchallenge.Theuseofpolyelectrolytesan dtheircollapseinresponsetosalthasrecentlyemergedasapromisingpotentialsyntheticeq uivalentofoneofthemospowerful iologicalmotors:thespasmonemespring. 23 Polyelectrolyte rushes Polyelectrolytesarepolymerswhoserepeatingunits earanelectrolytegroup.Thesegroups willdissociateinaqueoussolutions(water),makingthepolymerscharged.Polyelectrolyte propertiesarethussimilarto othelectrolytes(salts)andpolymers(highmolecularweight compounds),andaresometimescalledpolysalts.PELinaqueoussolutionsattractgreatinter est ecauseoftheirrelevancetomany iologicalsystems.Interactionswhichinvolvecharge dmacromoleculesarestronglymodified yCoulom forces.Thechargedensityonapolymerchai ninapolarsolventdependsonthechainconstitutionanddegreeofdissociation(f)ofioniza legroups.Ifioniza legroupsarestrongacidsor ases(strongPE)fisequalto1andisnotaffe

cted ytheenvironment.Ifioniza legroupsareweakacidsor ases(weakPEL)fdependsonloca lpH.Forthelattercasechargesaremo ilewithinthepolymerchain. 24 25 ForthedensestrongPEL rush(highfandgraftingdensity)allcounterionsaretrappedinside the rush(Slide. ).The rushheightisdetermined ythe alance etweenosmoticpressureof thetrappedcounter-ionsandthestretchingentropyofthechains(socalledosmotic rushreg ime).Thecontri utionoftheexcludedvolumeeffectdependsonthegraftingdensity.Atveryh ighdensitiestheexcludedvolumeeffectmaydominatewhileatmoderatedensitiestheelectro staticnaturewillhaveamajorcontri ution.Thelatterwill ereflectedintheprefactorint hescalingrelationshiph~N.These rushesareinsensitivetolocalpH.Addedsaltdoesnotaff ectthe rushunlesstheionicstrengthofthesolutionapproachestheleveloftheionicstreng thinsidethe rush(Slide.d).Inthatcasetheprefactorisaninversecu icrootfunctionofth eexternalsaltconcentrationandthegraftingdensity(socalledsalted rushregime).Thus, intermsofresponsiveapplicationsstrongPELareinterestingfordesignofresponsivenesst ohumidandaqueousenvironmentswhenthehighswellingfthe rushinwaterorahumidatmospher eisresultedfromstrongosmoticpressureoftrappedcounterions(Slide.a, ).WeakPEL rush esrepresentoneofthemostinterestingresponsive ehaviors.Theydemonstrateresponsiven esstochangesinexternalpHandionicstrength.WeakPEL rushescarrying asicfunctionalit iesexpanduponadecreaseofpH,whileacidicPEL rushesexpanduponanincreaseofpH(Slide.c ,d).AtahighsaltconcentrationweakPEL rushesshrinkduetothesamemechanismasstrongPEL rushes.However,itisnoteworthy,thatinsomerangeofpHvaluestheyshrinkalsoatnosaltad dedoratverysmallsaltconcentrations,thus,expressingnon-monotonousdependenceofthe rushheightvs.saltconcentration.This ehaviororiginatesfromthesensitivityoffforwea kPEL(s)tothelocalelectricfield. 26 Slideshowstheexperimentalsetuptomeasurethedeflectionofcantileverwhileswitching e tweendifferentenvironments. 27 BehaviourofPMEP rushmodifiedcantileverTheconformationalchangesofthe rushesinresp onsetosaltsolutionorpHareschematicallyshowninSceme1.Scheme 1. Schematic of Rever sible Swollen/Collapse of PMEP BrushPMEPcanbeswitchedbetweenthreeionicstates:ful lyprotonated,monoprotonated/monobasic,anddipotassiumsalt/dibasicstates,depending dependingonpH.Slide(above)displaysthebendingofbrush-coatedcantileverswhenvarying thepHofthesolutionbetween1and13.InregionI,thebrushesarefullyprotonated,whileinre gionIII,theyarefullydeprotonated,andcompressivestressisgeneratedinbothstronglyac idic(pH<2)andbasic(pH>8)environments.AtpH<2,theprotonatedbrushesarenolongersolub leandwillcollapse,generatingacompressivesurfacestresssincethefootprintofthepolymer sistoosmalltoaccommodatethecollapsingchain.Thiseffectisconsistentwithpreviousrep ortsthatpolymerbrushesgenerateacompressivesurfacestressuponpolymercollapse. 28 AtpH>8,thePMEPbrushesarefullydeprotonated,andtheelectrostaticrepulsionbetweencha rgedpolymerchainsleadstothedevelopmentofalargecompressivestress.Themaximumdeflec tionofthecantilevers,uptomicrometerscale(approximate1300nm),isfoundinthisfullych argedstate.Itshouldbenotedthatthecantileverdeflectionsarehighlyreversible,andtha tthebrushescanbecycledthroughanumberofpHcycles.Themagnitudeandsensitivityofthere sponsetosaltdependstronglyonthelengthofthebrushes,thegraftingdensity,andthedegre eofchargingofthepolymer.Generallythereisnoorverysmalldeflectionforlow(<10%initia tor)graftingdensitiesofbrushes. 29 Slideshowsthereversiblebendingandreturntoequilibriumpositionofthebrush-coatedcan tileverwhenswitchingbetweena100mMKClsolutionandpurewater,respectively.Therespons eofthecantilevertochangesofsolutionisveryfast(30s).Thereturntozerodeflectionupon additionofwaterisslowduetotheslowdiffusionofexcesssaltawayfromthebrushlayer.Thec ompressivestressisgeneratedbythebrushescollapsingundertheinfluenceofthehighsalte nvironment;thissituationissimilartothecompressivestressgeneratedatlowpH(seeabove ).Thecontrolexperiments(blackline)showthatnon-brush-modifiedcantileversshownores ponsetochangesinsaltconcentration. 30 Controlovertheactualpositionofcantilevercanbeachievedbyexposingthebrush-coatedca

ntileverstodifferentsaltconcentrationsbetween0and100mM.Bygraduallyincreasingorde creasingthesaltconcentration,theactuationcanbepreciselymanipulatedindiscretemult iplesteps.Byplottingthebendingofthecantileverversusthesaltconcentration(slide),o rtothelogarithmofthesaltconcentration(inset),onecandistinguishtwodistinctrespons eregimes.Atsaltconcentrationsbelow1mM,theresponseissmall(remainingbelow10%ofmaxi mumbendingamplitude),whereasathigherconcentrations,amuchlargerresponseisobserved .Conversely,whenloweringthesaltconcentration,wecanseeanapproximatelylineardepend enceoflog[salt]versusnormalizedbendingamplitude.Polyelectrolytebrushtheorypredic tsthatforannealedbrushesatlowsaltconcentrationsthebrushheights(andthereforesurfa cestress)firstincreaseslightlyduetotheexchangebetweenexternalcationsandassociate dprotons.Athigherconcentrations,chargescreening(removal)isthedominanteffect,lead ingtocollapseofthebrushesandgenerationofmuchmoresignificantcompressivestress.Its houldbenotedthatthechemicalnatureoftheions(valency,lipophilicity,etc.)alsoinflue ncesthecollapseprocess,openinguppossibilitiesforselectivity. 31 Conclusion Thefieldofresponsivepolymerbrushesisacontinuouslyexpandingareaofresearch.Theexpa nsionisnotveryfastbecauseofthecomplexityofthesystemsforthefabricationaswellasfor investigations.Nevertheless,thecontinuousandsuccessfuldevelopmentofthefieldispre determinedbythefactthatthepolymerbrushesarethemosteffectivestructurestoreguateco mplexinteractionsinsyntheticcolloidalandnaturallivingsystems.Thepotentialforthed esignoftheinteractionsisveryhigh.Mimickingnaturalsystemsanddesigningnewstructure swillaccompanythedevelopmentofthefieldofpolymerbrushes.Thatwillstimulateexpansio noftheoreticalandexperimentalinvestigations.Wemayalsobenefitfromthecombinationof polymerbrushesandgelsincomplexresponsivedevices. 32 33