Smart Colloidal Materials

191 Pages·2006·8.073 MB·English

by  Daoji Gan, L. Andrew Lyon (auth.), Walter Richtering (eds.)

Progress in Colloid and Polymer Science · Volume 133 · 2006
ProgressinColloidandPolymer Science
RecentlyPublishedandForthcomingVolumes
SmartColloidalMaterials TrendsinColloidandInterfaceScienceXVII
VolumeEditor:Richtering,W. VolumeEditors:Cabuil,V.,Levitz,P.,Treiner,C.
Vol.133,2006 Vol.126,2004
CharacterizationofPolymerSurfacesandThinFilms FromColloidstoNanotechnology
VolumeEditors:Grundke,K.,Stamm,M.,Adler,H.-J. VolumeEditors:Zrinyi,M.,Hórvölgyi,Z.D.
Vol.132,2006 Vol.125,2004
AnalyticalUltracentrifugationVIII AqueousPolymerDispersions
VolumeEditors:Wandrey,C.,Cölfen,H. VolumeEditor:Tauer,K.
Vol.131,2006 Vol.124,2004
ScatteringMethodsandtheProperties TrendsinColloidandInterfaceScienceXVI
ofPolymerMaterials VolumeEditors:Miguel,M.,Burrows,H.D.
VolumeEditors:Stribeck,N.,Smarsly,B. Vol.123,2004
Vol.130,2005
AqueousPolymer–CosoluteSystems
Mesophases,Polymers,andParticles VolumeEditor:Anghel,D.F.
VolumeEditors:Lagaly,G.,Richtering,W. Vol.122,2002
Vol.129,2004
MolecularOrganisationonInterfaces
SurfaceandColloidScience VolumeEditor:Lagaly,G.
VolumeEditor:Galembeck,F. Vol.121,2002
Vol.128,2004
LipidandPolymer-LipidSystems
AnalyticalUltracentrifugationVII VolumeEditor:Nylander,T.
VolumeEditors:Lechner,M.D.,Börger,L. Vol.120,2002
Vol.127,2004
Progress in Colloid and Polymer Science
Editors:F.Kremer, LeipzigandW.Richtering,Aachen
Volume 133 · 2006
Smart Colloidal Materials
Volume Editor:
Walter Richtering
123
IV
TheseriesProgressinColloidandPolymerScienceisalsoavailableelectronically(ISSN1437-8027)
– Accesstotablesofcontentsandabstractsisfreeforeverybody.
– Scientistsaffiliatedwithdepartments/institutessubscribingtoProgressinColloidandPolymerScience
asawholealsohavefullaccesstoallpapersinPDFform.PointyourlibrariantotheSpringerlinkaccessregistrationform
athttp://www.springerlink.com
ISSN0340-255X This workis subject tocopyright. All rights are SpringerisapartofSpringerScience+
ISBN-103-540-32701-0 reserved,whetherthewholeorpartofthematerial BusinessMedia
ISBN-13978-3-540-32701-1 isconcerned,specificallytherightsoftranslation,
DOI10.1007/11593256 reprinting,reuseofillustrations,recitation,broad-
http://www.springer.com
SpringerBerlin,Heidelberg,NewYork casting,reproductiononmicrofilmorinanyother
way, and storage in data banks. Duplication of
thispublicationorpartsthereofispermittedonly ©Springer-VerlagBerlinHeidelberg2006
under the provisions of the German Copyright PrintedinGermany
LawofSeptember9,1965,initscurrentversion,
andpermissionforusemustalways beobtained
fromSpringer. Violations areliable forprosecu- Coverdesign:eStudioCalamarS.L.,
tionundertheGermanCopyrightLaw. F.Steinen-Broo,Pau/Girona,Spain
Theuseofregistered names, trademarks, etc. in
Typesettingandproduction:LE-TEX
this publication does not imply, even in the ab-
Jelonek,Schmidt&VöcklerGbR,Leipzig
senceofaspecificstatement,thatsuchnamesare
exemptfromtherelevant protective lawsandre-
gulationsandthereforefreeforgeneraluse. Printedonacid-freepaper
ProgrColloidPolymSci(2006)133:V
PREFACE
©Springer-Verlag2006
Thisvolumecontainsselectedpaperspresentedatthe42ndBiennialMeeting(Hauptversammlung)oftheKolloid-Gesellschaft
heldattheRWTHAachenUniversitySeptember26–28,2005.Themeeting’semphasiswasgivento“SmartMaterials:Foams,
GelsandMicrocapsules”butalsoprovidedageneraloverviewoncurrentaspectsofcolloidandpolymerscienceinfundamental
researchandapplications.
Thecontributionsinthisvolumearerepresentativeofthediversityofresearchtopicsincolloidandpolymerscience.They
coverabroadfieldincludingtheinvestigationofsynthesisandpropertiesofadvancedtemperaturesensitiveparticlesandtheir
biomedicalapplications,drugdeliverysystems,foams,capsules,vesiclesandgels,polyelectrolytes,nanoparticlessurfactants
andhybridmaterials.
The meeting brought together people from different fields of colloid, polymer, and materials science and provided the
platformfordialoguebetweenscientistsfromuniversities,industry,andresearchinstitutions.
WalterRichtering
ProgrColloidPolymSci(2006)133:VI–VII
CONTENTS
©Springer-Verlag2006
PolymerParticlesandCapsules
D.Gan,L.A.Lyon: Amphiphilic,Peptide-ModifiedCore/ShellMicrogels..................... 1
A.Elaissari: ThermallySensitiveColloidalParticles:
FromPreparationtoBiomedicalApplications............................ 9
J.Siepmann,F.Siepmann: MicroparticlesUsedasDrugDeliverySystems.......................... 15
C.Mayer,A.Bauer: MolecularExchangeThroughCapsuleMembranes
ObservedbyPulsedFieldGradientNMR............................... 22
M.Herold,M.Håkanson, ModularSurfmerswithActivatedEsterFunction–
H.Brunner,G.E.MTovar: AColloidalToolforthePreparationofBioconjugativeNanoparticles...... 30
I.Berndt,J.S.Pedersen, StructureofDoublyTemperatureSensitiveCore-ShellMicrogels
P.Lindner,W.Richtering: BasedonPoly-N-Isopropylacrylamide
andPoly-N-Isopropylmethacrylamide.................................. 35
M.Faivre,C.Campillo, ResponsiveGiantVesicles
B.Pepin-Donat,A.Viallat: FilledwithPoly(N-isopropylacrylamide)SolsorGels.................... 41
Polyelectrolytes,ColloidalInteractions
J.E.Wong,W.Richtering: SurfaceModificationofThermoresponsiveMicrogels
viaLayer-by-LayerAssemblyofPolyelectrolyteMultilayers.............. 45
D.Kleshchanok,J.E.Wong, PotentialProfilesBetweenPolyelectrolyteMultilayers
R.v.Klitzing,P.R.Lang: andSphericalColloidsMeasuredwithTIRM............................ 52
A.Wittemann,B.Haupt,M.Ballauff: Polyelectrolyte-mediatedProteinAdsorption............................ 58
B.W.Ninham: ThePresentStateofMolecularForces.................................. 65
M.Boström,F.W.Tavares, IonSpecificInteractionsBetweenPairs
D.Bratko,B.W.Ninham: ofNanometerSizedParticlesinAqueousSolutions...................... 74
F.LoVerso,C.N.Likos,L.Reatto: StarPolymerswithTunableAttractions:
ClusterFormation,PhaseSeparation,ReentrantCrystallization............ 78
P.Wette,H.J.Schöpe: ConsistenceoftheMeanFieldDescription
ofChargedColloidalCrystalProperties................................. 88
A.Uvarov,S.Fritzsche: RestrictedRotationalDiffusion
ofNon-rigidDumbbell-TypeMacromoleculesonSurfaces:
EffectsoftheBead-BeadandBead-SurfaceInteraction................... 95
VII
Surfactants
D.Weaire,S.Hutzler,W.Drenckhan, TheRheologyofFoams............................................... 100
A.Saugey,S.J.Cox:
J.Eastoe: Photo-destructibleSurfactantsinMicroemulsions........................ 106
H.Ning,R.Kita,S.Wiegand: SoretEffectinaNonionicSurfactantSystem............................ 111
T.Shin,G.H.Findenegg,A.Brandt: SurfactantAdsorptioninOrderedMesoporousSilicaStudiedbySANS..... 116
C.Eckert,H.Durchschlag, ThermodynamicAnalysisofLysozymeDenaturationbySurfactants....... 123
K.-J.Tiefenbach:
P.A.R.Pires,O.A.ElSeoud: Benzyl(3-Acylaminopropyl)DimethylammoniumChlorideSurfactants:
StructureandSomePropertiesoftheMicellarAggregates................. 131
ParticlesandCharacterization
B.Ullrich,E.Ilska, LongRangeParticleTransportinLiquidCrystal-alkaneMixtures.......... 142
N.Höhn,D.Vollmer:
P.Wilhelm,C.Zetzsch,D.Stephan: TitaniaCoatedSilicaNano-spheresasCatalyst
inthePhotodegradationofHydrocarbons............................... 147
Q.Tong,S.Kosmella,J.Koetz: FormationofRod-likeCdSNanoparticles
inSDS/DecanolBasedMultilamellarVesicles........................... 152
A.Nennemann,M.Voetz,G.Hey, ColloidchemicalInteractionsofSilicaParticlesintheCu-CMP-Process.... 159
L.Puppe,S.Kirchmeyer:
T.Sobisch,D.Lerche, CharacterizationofPorousBeadCellulosesbyAnalyticalCentrifugation... 169
S.Fischer,C.Fanter:
J.Köser,F.Kuhnen, Light-scatteringinTurbidFluids:ScatteringIntensityandAmplitude
D.Saracsan,W.Schröer: oftheAuto-correlationFunction....................................... 173
Author/TitleIndex.................................................... 181
KeyWordIndex...................................................... 183
ProgrColloidPolymSci(2006)133:1–8
DOI10.1007/2882_058
©Springer-VerlagBerlinHeidelberg2006
POLYMER PARTICLES AND CAPSULES
Publishedonline:19April2006
DaojiGan Amphiphilic, Peptide-Modified
L.AndrewLyon
Core/Shell Microgels
Abstract Thermoresponsive inparticledeswellingvolumeratios
poly(N-isopropylacrylamide) wereobservedasaresultofgrafting
(pNIPAm) core/shell particles hydrophobicPBLG chainsto the
bearing primaryamine groupsin particles.Furtherstudiesby1HNMR
eithercoreorshellwere prepared in differentsolventsindicate that
via two-stage, free radical pre- thePBLG chainsgraftedfromthe
cipitation polymerization,using particleshellphaseseparateonthe
2-aminoethylmethacrylate(AEMA) pNIPAmnetworksinaqueousmedia
asacomonomer.Theaminegroups butremainwellsolvatedinDMSO.
were then used to initiate ring- Together, these results suggest
openingpolymerizationofγ-benzyl that both core- and shell-grafted
L-glutamate N-carboxyanhydride architecturescan be synthesized
DaojiGan (BLG-NCA), producingpoly(γ- withequalease,andthattheparticle
Presentaddress:
benzylL-glutamate)(PBLG) side structureandcolloidalbehaviorcan
E&ACompany,Indianapolis,IN, USA
chainscovalentlyanchoredto the bemanipulatedbytuningtherelative
DaojiGan·L.AndrewLyon((cid:1)) particles.PhotonCorrelationSpec- solubilityofthenetworkandgraft
troscopy(PCS)and1H NMRwere portionsoftheparticle.
GeorgiaInstituteofTechnology,
SchoolofChemistryandBiochemistry, employedtocharacterizethesepar-
Atlanta,GA30332-0400, USA ticles.Ashiftofphasetransitionto Keywords Microgel·Core/shell·
e-mail:[email protected] alowertemperatureandanincrease PBLG·pNIPAm·Phaseseparation
Introduction The phase-separatingnature of pNIPAm can be exploited
to synthesize microgels in the sub-micron size range
Considerable research attention has been paid to the by precipitation polymerization. Such particles are col-
stimuli-responsive polymers since they can offer many loidally stable and possess a sharp volume phase tran-
greatpotentialapplicationsinbiomedicalfieldsandinthe sition (VPT) near the polymer LCST [6]. Furthermore,
creation of environmentally responsive materials. Poly- strong modulation of the physical properties of these
mers that respond to pH [1], temperature [2], light [3], particles is observed at the phase transition, including
and protein binding [4] have been reported. Among these hydrophobicity, porosity, refractive index, colloidal sta-
polymers,thermosensitivepoly(N-alkylacrylamides),par- bility, scattering cross section, and electrophoretic mo-
ticularly poly(N-isopropylacrylamide) (pNIPAm), have bility. Along with this progress, the particles that have
been most widely studied [2,5–7]. In aqueous media, a more advanced architecture have been pursued to gen-
pNIPAm exhibits a “coil-to-globule” phase transition erate multifunctional properties. One example of these
◦
around 31 C, which is commonly referred to as a lower couldbetheresponsivecore/shellorcore/coronaparticles
critical solution temperature (LCST). This is due to dis- that have been synthesized either to spatially localize the
ruption of water-polymer hydrogen bonds and the con- chemical functionalities to the particles [1,8–11], to ren-
comitant hydrophobic association of isopropyl groups. derthermoresponsityto non-responsiveparticles[12,13],
2 D.Gan·L.A.Lyon
or to modify a specific physical property of the par- anhydride (BLG-NCA) was synthesized via the reac-
ticles[14]. tion of γ-benzyl L-glutamate (BLG) with excess phos-
Previously, we have reported preparation of multi- gene/benzene solution (Fluka) in dry tetrahydrofuran
◦
responsive core-shell particles via incorporation of poly (THF) at 65 C; it was purified by crystallization from
(acrylic acid) into the pNIPAm particles [1]. The par- petroleum ether [22]. Water used in all synthesis and
ticlesappearedtobesensitivetobothsolutiontemperature measurements was distilled, and particulate matter was
and pH. It was also found later that introduction of small removed via a 0.2µm filter incorporated into a Barn-
amounts of hydrophobic monomer units into the particle stead E-Pure system that was operated at a resistance of
shellcouldsignificantlychangetheparticledeswellingki- 18MΩ.
neticswithoutperturbationofthetransitionthermodynam-
ics[15].Theresultssuggestthatthelocationoffunctional Synthesis
groups is very important in the design of responsive col-
Low polydispersity pNIPAm microgels were prepared by
loidal gels. In this contribution, core/shell particles that
free-radicalprecipitationpolymerization,usingABMPAm
contain primary amine groups in either the core or the
(1mol% based on the monomer NIPAm) as a cationic
shellwerefirstconstructedusingthesametwo-stagepoly-
initiator and BIS (5mol%) as a crosslinker. Core/shell
merizations described previously [1,9,11,15–21]. The
microgels were constructed via two-stage polymeriza-
amine-bearingparticles were then used to initiate another
tion, where the particle core prepared at the first stage
polymerization, producing a hydrophobic polypeptide
poly(γ-benzyl L-glutamate) (PBLG) covalently anchored served as nuclei in the second-stage polymerization. It
shouldbeemphasizedthatthepolymersynthesizedin the
to the desired portion of the particle (Scheme1). PBLG
second stage preferentially precipitates onto the existing
is an interesting synthetic polypeptide [22] that has been
seed particles, leading to formation core/shell morph-
studied in the design of complex colloidal [23] and poly-
ology [1,8,16,26]. Both core particles and core/shell
mericstructures[24,25].
particles were purified via dialysis (Spectra/Pro 7 dialy-
sis membrane, MWCO 10000, VWR) against water for
14 days, with daily replacement of fresh water. Grafting
of poly(γ-benzyl L-glutamate) (PBLG) to the microgels
was achieved using primary amine groups incorporated
intotheparticlestoinitiatering-openingpolymerizationof
BLG-NCA(Scheme1).Table1liststhechemicalcompo-
sitions and particle size information of microgels used in
thisstudy.
SamplesCandC–NH
2
Tosynthesizesimplecoreparticles(sampleC)andamine-
modified core particles (sample C−NH ), NIPAm, BIS,
2
andAEMA(1.5mol%basedonNIPAm,SampleC−NH
2
only)weredissolvedindegassedwaterwithaNIPAmcon-
centration of 0.01g/mL. The solution was bubbled with
nitrogenfor2h,followedbyadditionofABMPAmtostart
the polymerization. The reaction was then carried out at
Scheme1
◦
70 Cfor6h.
SampleC/S–NH andC–NH /S
2 2
ExperimentalSection
TopreparesampleC/S–NH ,NIPAm,BIS,and1.5mol%
2
Materials AEMA were introduced to a suspension of sample C;
the polymer concentration of the dispersion of sample C
All the chemicals were purchased from Aldrich unless was that which resulted from the initial synthesisof sam-
otherwise stated. The monomer N-isopropylacrylamide ple C. Sample C−NH /S was prepared via addition of
2
(NIPAm)wasrecrystallizedfromhexanes(J.T.Baker)be- NIPAmandBIS to a suspensionofsampleC−NH . The
2
(cid:2)
foreuse.Thecross-linkerN,N -Methylenebis(acrylamide) monomerconcentrationsusedinbothshellsyntheseswere
(BIS), and 2-aminoethyl methacrylate (AEMA), 2,2(cid:2)- 0.01g/mL.Bothreactionmixtureswerenitrogen-bubbled
◦
azobis(2-methylpropionamide) dihydrochloride (ABM- at 70 C for 2h. Addition of the ABMPAm triggered the
PAm), and dimethyl sulfoxide (DMSO) were used as re- second-stage polymerization, which was then carried out
ceived.Theaminoacidγ-benzylL-glutamate N-carboxy- at70◦Cfor6h.
Amphiphilic,Peptide-ModifiedCore/ShellMicrogels 3
Table1 ChemicalcompositionsandparticlesizeinformationofpNIPAm-basedmicrogels
Corea Shella Core-shell PBLGGrafts
Sample AEMA, R,c Polyd, AEMA, R,c Polyd, Mass, R,c R,d
mol-%b nm %c mol-%b nm %c wt%e nm nm
C 0 102 22
C/S−NH 0 102 22 1.5 124 23
2
C/S-BLG10 0 102 22 1.5 124 23 10 128 112
C/S-BLG20 0 102 22 1.5 124 23 20 135 124
C/S-BLG60 0 102 22 1.5 124 23 60 –f 136
C−NH 1.5 106 20
2
C−NH /S 1.5 106 20 0 125 17
2
C-BLG10/S 1.5 106 20 0 125 17 10 120 109
C-BLG20/S 1.5 106 20 0 125 17 20 117 107
a BothcoreandshellweresynthesizedwithBIS(5mol%basedonmonomer,NIPAm)asacross-linker
b feedratiobasedonNIPAm
c Particleradii(R)andpolydispersity(Polyd.)weremeasuredbyPCSat25◦Cinwatersuspension
d radiusmeasuredinDMSOat25◦C
e feedratioofBLG-NCAcomparedtothemicrogelused
f notmeasurableduetoformationofflocs
SampleC/S-BLG10andC/S-BLG20 with a 15s integration time for each measurement. The
deswellingvolumeratios(V/V∗)oftheparticleswerecal-
The freeze-dried sample C/S−NH2 (0.07g) was re- culated via the relation: V/V∗ =(R/R∗)3, where R and
dispersed in 15mL of DMSO, to which BLG-NCA ∗
R are the PCS measured particle radii at the measured
(10wt% for C/S-BLG10, and 20wt% for C/S-BLG20, ◦
temperatureandat25 C,respectively.
basedon the C/S−NH used)was introduced.The reac-
2
tion mixture was vigorously stirred at room temperature
1HNMR
for 3days. After this reaction was completed, 15mL wa-
terwasaddedtothesolution,andtheorganicsolventwas Thefreeze-driedparticleswerere-dispersedineitherD O
2
removedviadialysisagainstwaterfor10days. or DMSO-d , and the spectra were then recorded at am-
6
bient temperature using a Varian Unity 300MHz NMR
SampleC-BLG10/SandC-BLG20/S
spectrometer. The water peak caused by residual water
To a C−NH /S suspension in DMSO, BLG-NCA inside the particles was supressed, in order to more effi-
2
cientlyobservetheprotonsignalsoftheparticles.
(10wt% for C-BLG10/S, and 20wt% for C-BLG20/S,
based on the C−NH /S used) was added, and the graft-
2
ing reaction was carried out using the same procedure as
ResultsandDiscussion
describedabove.
Synthesis
Measurements
In these studies, the pNIPAm-based particles were pre-
pared via free radical, precipitation polymerization in
PhotonCorrelationSpectroscopy(PCS)
◦
aqueous solution at a temperature (70 C) well above the
The particle sizes and the size distributions in aque- LCST of pNIPAm. At that temperature, water is a good
ous solutions were measured by PCS (Protein Solutions, solvent for the monomer but a poor one for the polymer.
Inc.), with a programmable temperature controller. Prior Therefore, the growing polymer chains, once reaching
to taking measurements, the particle solutions were al- acriticallength,precipitatefromthesolutionandformsta-
lowed to thermally equilibrate at each temperature for ble particles via coagulation of multiple unstable nuclei
10min. Longer equilibration times did not lead to vari- and by monomerand oligomer capture. A cationic initia-
ations in the observed hydrodynamic radii, polydisper- tor(ABMPAm)renderstotheparticlespositivelycharged,
sities, or scattering intensities. All correlogram analyses which is largely responsible for the colloidal stability of
wereperformedwithmanufacturer-suppliedsoftware(Dy- theparticles.Inthesynthesis,acrosslinker(BIS)isusedto
namics v.5.25.44, Protein Solutions, Inc.). The data pre- generatepolymericnetworks,andthusmaintainthespher-
sentedbelowaretheaveragedvaluesof20measurements, ical shape and network connectivity of the particles once