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4.Synthesis and Characterization of Hyaluronic Acid

4.Synthesis and Characterization of Hyaluronic Acid

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ContentslistsavailableatSciVerseScienceDirect
Colloids
 
and
 
Surfaces
 
A:
 
Physicochemical
 
andEngineering
 
Aspects
Synthesis
 
and
 
characterization
 
of 
 
hyaluronic
 
acid-supported
 
magneticmicrospheres
 
for
 
copper
 
ions
 
removal
Shi
 
Lan,
 
Xiaomin
 
Wu,
 
Linlin
 
Li,
 
Mengmeng
 
Li,
 
Fengying
 
Guo,
 
Shucai
 
Gan
CollegeofChemistry,JilinUniversity,Changchun130026,PRChina
h
 
i
 
g
 
h
 
l
 
i
 
g
 
h
 
t
 
s
 Hyaluronic
 
acid
 
was
 
successfullyimmobilized
 
onthe
 
magnetic
 
silicasubmicron-sized
 
particles.
 Hyaluronic
 
acid
 
was
 
utilized
 
as
 
adsor-bent
 
for
 
the
 
heavy
 
metal
 
removal.
 Magnetism
 
and
 
adsorption
 
were
 
per-fectly
 
combined
 
into
 
one
 
singleentity.
g
 
r
 
a
 
p
 
h
 
i
 
c
 
a
 
l
 
a
 
b
 
s
 
t
 
r
 
a
 
c
 
t
Hyaluronic
 
acid-supported
 
magnetic
 
submicron-sized
 
particles
 
were
 
fabricated
 
as
 
anovel
 
adsorbent
 
forthe
 
Cu
2+
removal
 
and
 
can
 
be
 
separated
 
magnetically
 
through
 
the
 
application
 
of 
 
amagnetic
 
field
 
in
 
shortertime
 
after
 
the
 
adsorption
 
performance.
a
 
r
 
t
 
i
 
c
 
l
 
e
 
i
 
n
 
f
 
o
 Articlehistory:
Received30October2012Receivedinrevisedform22February2013Accepted28February2013
Available online 7 March 2013
Keywords:
MagneticHyaluronicacidMicrospheresAdsorptionSeparation
a
 
b
 
s
 
t
 
r
 
a
 
c
 
t
Magnetic
 
hyaluronic
 
acid
 
(HA)
 
microspheres
 
were
 
fabricated
 
asanovel
 
adsorbent
 
through
 
the
 
immo-bilization
 
of 
 
hyaluronic
 
acid
 
on
 
the
 
magnetic
 
silica
 
microspheres.
 
The
 
as-prepared
 
microspheres
 
werecharacterized
 
by
 
scanning
 
electron
 
microscopy
 
(SEM),
 
transmission
 
electron
 
microscopy
 
(TEM),
 
Fouriertransforminfrared
 
(FTIR),
 
X-ray
 
powder
 
diffraction
 
(XRD),
 
and
 
X-ray
 
photoelectron
 
spectra
 
(XPS).
 
The
 
as-synthesized
 
microspheres
 
were
 
evaluated
 
for
 
Cu
2+
removal
 
by
 
the
 
adsorption,
 
and
 
the
 
effect
 
of 
 
pH
 
value,interferential
 
metal
 
ions,
 
initial
 
Cu
2+
concentration,
 
and
 
contact
 
time
 
onadsorption
 
capability
 
was
 
inves-tigated,
 
respectively.
 
The
 
adsorption
 
equilibrium
 
study
 
exhibited
 
that
 
the
 
Cu
2+
adsorption
 
of 
 
hyaluronicacid-supported
 
magnetic
 
microspheres
 
had
 
a
 
better
 
fitto
 
the
 
Freundlich
 
isotherm
 
model
 
than
 
the
 
Lang-muir
 
model.
 
The
 
kinetic
 
date
 
of 
 
adsorption
 
of 
 
Cu
2+
onthe
 
synthesized
 
adsorbents
 
was
 
best
 
described
 
bythe
 
pseudo-second-order
 
equation.
 
The
 
resultant
 
microspheres
 
also
 
revealed
 
super-paramagnetic
 
behav-ior,
 
which
 
made
 
these
 
adsorbent
 
magnetically
 
separable
 
after
 
the
 
adsorption
 
performance.
 
This
 
workdemonstrates
 
that
 
the
 
synthesized
 
hyaluronic
 
acid-supported
 
magnetic
 
adsorbent
 
can
 
be
 
considered
 
asapotential
 
adsorbent
 
for
 
hazardous
 
metal
 
ionsfrom
 
wastewater.
© 2013 Elsevier B.V. All rights reserved.
1.Introduction
Recently,naturalpolysaccharidessuchaschitosan,heparin,chondroitin,keratin,andxanthanhavebeendevelopedasenvi-ronmentallyfriendlymaterialsforremovingtoxicpollutantsfromaqueoussolutionandattractedmuchattention[1–4].Inparticular,
Correspondingauthor.Tel.:+8643188502259.
E-mailaddress:
gansc@jlu.edu.cn (S.Gan).
chitosanhasbeenwidelysuggestedasacandidateforanover-whelmingscopeofadsorptionapplications,coveringalmostallthespectrumofbiotechnology[5,6].Hyaluronicacid(HA),onekindof  thenaturalpolysaccharidewithasimilarstructureaschitosan,hasavarietyoffunctionsmainlyincludingrolesinjointlubrication,tis-suehydration,woundrepair,andmodulationofinflammationaspublishedinearlierliteratures.However,tothebestofourknowl-edge,fewhavereportedtheresearchabouttheadsorptionbehaviorofHAtowardpollutantsyet,anditcanbeexpectedasapromisingcandidateforefficientadsorbentofheavymetalionsduetoitslarge
0927-7757/$seefrontmatter
© 2013 Elsevier B.V. All rights reserved.
 
S.Lanetal./ColloidsandSurfacesA:Physicochem.Eng.Aspects
425 (2013) 42–50
43
numberofactivemetal-bindingsitesincludingoxygen,nitrogenandcarboxylwhichcanuptakeheavymentalionsfromwaste-waterthroughvariousmechanismssuchaschelation,electrostaticattraction,andion-exchange,providingpossibilityforsynthesisof HA-basedadsorbentmaterials.However,thereisamajordrawbacktotheapplicationofHAasadsorbentoriginatingfromthesepara-tionduetoitshighsolubilityinaqueoussolution.IsolationofHAfromalargevolumeofwaterrequiresanadditionalprocessandfurtherexpense,andthusitseemsreasonabletoimmobilizeofHAoninsolublecomponenttofacilitatetheseparationprocess[7–9].Adsorptionperformanceofthepolymericadsorbentstronglydependsonitsactivatedsurfaceareaandthequantityofsurfaceactivatedsitesforinteractionwithmetallicspecies.Nanometerandmicrometersizedmaterialshaveshownremarkablepoten-tialbecauseoftheirlargesurfacearea[10].Therefore,toenhance adsorptioncapacity,fabricationoftheadsorbentwithnanometerormicrometersizetoenlargeactivatesurfaceareaisadvisable[11].However,introductionofnanometerormicrometersizedadsor-bentbringsthemdifficultyinseparationprocess,whichinvolvesfurtherexpensetoremovesuchfineadsorbentnanomaterialsfromtheaqueoussuspension[12–14].Magneticadsorbentsinnanometerandmicrometersizehaveattractedgreatattentionfortheirpotentialapplicationinremovalofthepollutantsfromaqueoussolutionduetotheirstrongadsorp-tioncapacity,simplerecoveryfromliquidsolutionundersuitablemagneticfieldandreusableproperty[15].However,puremag- neticparticlesarepronetoformaggregationowingtothemagneticdipolarattractionbetweenmagnetitemicrospheresandmagneticpropertiesaffectedinliquidsystems.Tosolvethisdefect,arationalprotectivelayerincludinginorganicoxideorpolymercompoundscoatedonthesurfaceofmagneticparticlesisoftenutilized.Asaresult,silica-coatedmagneticnanoparticlesandpolymer-coatedmagneticnanoparticlesarecommonlyusedasthesubstrateforthesynthesisofmagnetic-basedadsorbent[16].Herein,novelHA-functionalizedmagneticmicrosphereswerefabricatedasamagneticadsorbentthroughanchoringHAonsilica-coatedmagneticmicrospheres.Adsorptionbehaviorofas-preparedmicrosphereswasevaluatedbyselectingCu
2+
asrepresentativeheavymetal,whichisconsideredasanessentialnutrientintraceamount,butcancauseadversehealtheffectsathighdoses[17–20].Adsorptionexperimentsrevealedthattheas-synthesizedmicrospherespossessexcellentadsorptionbehaviorofCu
2+
ion.Inaddition,HA-functionalizedmagneticmicrospherescanbeenrichedcompletelyaftertheadsorptionperformancewithinshorttimeunderanexternalmagneticfield.Thesynergismbetweenmagnetismandadsorptionwouldresultinpromisingapplicationsinmanyfields.
2.Experimental
 2.1.Materials
HAwascommerciallyobtainedfromQufuguanglongBiochemCo.,Ltd.Ferricchloride(FeCl
3
·
6H
2
O),anhydroussodiumacetate(NaAc),polyethyleneglycol(PEGmolecularweight10000),ethyl-eneglycol,toluene,anhydrousethanol,aqueousammoniasolution(28wt%),andcoppernitrate(Cu(NO
3
)
2
·
3H
2
O)werepurchasedfromBeijingChemicalReagentResearchCompany.Tetraethoxysi-lane(TEOS,98wt%)wasavailablefromShanghaiChemicalReagentsCompany.3-aminopropyltriethoxysilane(APS,98wt%)wasprovidedfromAldrichChemicalCompany.
 2.2.Characterization
TheparticlesizeandstructureofthesynthesizedmagneticnanoparticleswereobservedbyusingaHitachi8100transmissionelectronmicroscope(TEM,Hitachi,Tokyo,Japan).Scanningelec-tronmicroscopy(SEM)wasperformedonaTESCAN5136MMSEMatanacceleratingvoltageof20Kv.Thesampleswereloadedontoaglasssurfacepreviouslysputtercoatedwithahomoge-nousgoldlayerforchargedissipationduringtheSEMimaging.TheinfraredspectraofthenanoparticlesweretakeninKBrpressedpelletsonaNEXUS670infraredFouriertransformspectrometer(NicoletThermo,Waltham,MA).X-raydiffraction(XRD)measure-mentswererecordedonaRigakuD/MAXIIAdiffractimoterusingCuKaradiation.X-rayphotoelectronspectra(XPS)measurementwascarriedoutonaPHI-5000CESCAsystemwithMg
 
Kradiation(hr=1253.6eV).TheX-rayanodewasrunat250W,
 
andthehighvoltagewaskeptat14.0kVwithadetectionangleat540.Allthebindingenergieswerecalibratedbyusingthecontainmentcar-bon(C1s=284.6eV).Thehysteresisloopswereobtainedwithavibratingsamplemagnetometer(VSM7407,LakeShore).
 2.3.Synthesisofthemagneticsilicamicrospheres
Fe
3
O
4
 microsphereswerefirstsynthesizedviaasolvothermalreactionaspreviouslydescribed[21,22].Inthenextprocess,the core-shellmagneticsilicamicroshoeresFe
3
O
4
@SiO
2
werepreparedaccordingtotheStöberprocess[23,24].
Inatypicalprocedure,thesubmicron-sizedmagneticparticleswerefirsttreatedbyHCl(5mL,
 
2M)
 
underultrasonicvibrationfor5min,andthentheFe
3
O
4
microsphereswerethoroughlyrinsedwithdeionizedwaterforsev-eraltimes.Fe
3
O
4
 microsphereswerehomogeneouslydispersedinamixtureofethanol(40mL)
 
anddeionizedwater(10mL)
 
underultrasonicvibrationfor30min,thentheconcentratedammoniaaqueoussolution(1mL,
 
28wt%)wasaddedtothissolutionwiththehelpofultrasonicationtoobtainastablesolution,andfollowedbytheadditionoftetraethoxysilaneevery15min
 
tillthetotalamountofTEOSreached0.2mL 
 
undermagneticallystirring,andthepro-cesswas
 
followed12h.Finally,theproductwas
 
collectedwiththehelpofmagnetandwashedwithrecycleofethanolandwaterforseveraltimes,andthenvacuumdriedat60
C.
 2.4.SynthesisofHA-modifiedFe
 3
O
4
@SiO
 2
 microspheres
InthefunctionalizationofFe
3
O
4
@SiO
2
,theAPSgraftedFe
3
O
4
@SiO
2
 actascoretemplateandhyaluronicacidpoly-mer
 
serveasshell.Typically,theFe
3
O
4
@SiO
2
 magneticsilicamicrosphereswerefirstlyfunctionalizedwithacouplingagent3-aminopropyltriethoxysilane(APS)throughthesiloxanelinkage.Thedetailedexperimentalprocesswasasfollows.Fe
3
O
4
@SiO
2
(0.05g)andcouplingagentAPSweredispersedin50mL 
 
tolueneandrefluxedfor3h.TheobtainedproductsFe
3
O
4
@SiO
2
-APSwerecollectedandwashedwithabsoluteethanolanddeionizedwaterfortimes[25,26].Inthenextstep,hyaluronicacid(50mg)
 
was
 
dis-solvedindeionizedwater(180mL)
 
withthevigorousmechanicalstirringtoformaclearsolution.Fe
3
O
4
@SiO
2
-APS(50mg)
 
wasdis-persedinHCI(2M,
 
5mL)
 
for5min
 
toactivatesurfacefunctionalgroupandwashedwithdeionizedwaterforthreetimes,anddis-persedsubsequentlyinthefreshlypreparedsolutionwiththeaidofultrasonicationfor10min,andthenthesuspensionwasstirredat50
Cforanother12h.ThenalproductFe
3
O
4
@SiO
2
-HAwascollectedbymagneticseparationandwashedwithwater,andthenovendriedat40
C.
 2.5.EffectofinitialCu
 2+
concentrationonadsorption
Batchadsorptionexperimentswerestudiedbyplacing30mg
 
of obtainedFe
3
O
4
@SiO
2
-HAin100mL 
 
conicalflaskscontaining50mL ofvariousconcentration(10–50mg/L)ofCu
2+
solutionsinthepHvalueof6.8at25
Ctemperatureinashakerbathfor7h.Thesolu-tionwasshockedat120rpmusingamechanicalshakertoreach
 
44
 S.Lanetal./ColloidsandSurfacesA:Physicochem.Eng.Aspects
425 (2013) 42–50
equilibrium.TheconcentrationofCu
2+
beforeandaftertreatmentwascalculatedbyatomicabsorptionspectrometer(AAS,Varian220FS,USA).Foraccurateadsorptionresults,themetaladsorptiondatawasanalyzedthreetimesandthemeanvalue(errorrange:ca.
±
5%)wasrepresented.Theadsorptioncapacity(
q
e
)was
 
calculatedusingtheequation[27,28]:
q
e
 =
(
0
e
)
×
where
0
 istheinitialconcentrationofmetalions(mg/L),
e
 istheequilibriumconcentrationofmetalionsafteradsorption(mg/L),
isthevolumeofmetalionssolution(mL),and
istheweightof thesynthesizedadsorbent(mg).
 2.6.EffectofpHvalueonadsorption
ThedesiredpHvalueofsolutionwasadjustedbyaddingeither0.1MHClorNaOHsolutionandthen50mL 
 
oftheabovesolu-tionwastakeninaconicalflaskandtreatedwith30mg
 
sorbent.ThefinalCu
2+
concentrationwasdeterminedafterequilibriumbyatomicabsorptionspectrometer.
 2.7.EffectofinterferentialmetalionsonCu
 2+
removal
Thepossiblycoexistingcationicmetals(i.e.,Na
+
,Mg
2+
,Ca
2+
,Ni
2+
,Pb
2+
,Zn
2+
,Cd
2+
,etc.)inwastewaterwerechosentoinves-tigatetheireffectonCu
2+
removalbytheadsorbent.Differentconcentrationofcationicmetalsandsamedosageofsorbentwasaddedin30mg/LCu
2+
originalconcentrationsolutionandtestedatroomtemperature.Thedifferentmetalssolutionwaspreparedbydissolvingtheirnitrates.
3.Resultsanddiscussion
Hyaluronicacid-functionalizedmagneticmicrospheresFe
3
O
4
@SiO
2
-HAwithmagneticsilicamicrospheresascoreandHAasshellweresuccessfullypreparedandusedasanadsorbenttoremoveheavymetalCu
2+
formaqueoussolution.ThefabricationrouteoftheFe
3
O
4
@SiO
2
-HAmicrosphereswasskillfullydesigned,andthesyntheticprocedurewas
 
schematicallyillustratedinFig.1A.MagneticHA-basedmicrospherescanbe usedasadsorbentforCu
2+
removalfromaqueoussolutionandenrichedcompletelywithinshorttimeunderanexternalmagneticeldasshowninFig.1B.Thecombinationofmagneticproperty andabsorptionperformanceintoonesingleentitycanmaketheHA-basedmaterialsseparablemagneticallyandsignificantlyfacilitatetheirpracticalapplications.Toverifythemorphologyoftheresultantmicrospheresindetail,theobtainedmicrosphereswerecharacterizedbySEMandTEMmeasurement.Fig.2depictedthephysicalappearanceof theironoxidemicrospheres,themagneticsilicamicrospheres,andtheHA-supportedsilica-coatedmagneticmicrospheres.Thequasi-monodisperse,spherical,andsolidFe
3
O
4
 microsphereswithanaveragediameterof105.6nmwereobservedinFig.2A.After silicacoating,theas-synthesizedmicrospherespresentrelativelysmoothparticlesurface,andtheparticlesizewasvividlyincreased.ItcanbeclearlyseenfromtheinsertinFig.2BthattheFe
3
O
4
@SiO
2
microspherespresentedobviouscore-shellstructureandthegrayouterlayeraroundthemagneticFe
3
O
4
 nanoparticlewereamor-phoussilicacoatingwithanaverageshellthicknessof32nm.
 
Thisencapsulationwassignificantbecausethesilicashellnotonlykeptastabledispersionofmagneticmicrospheresforalongtimeinaharshliquidmediabutalsopreventtheircorrosioninanacidicenvironment[29].AsshowninFig.2C,thesurfaceofFe
3
O
4
@SiO
2
-HAmicrosphereswasobviouslycoarserthanthatofFe
3
O
4
@SiO
2
,whichwasfurtherrevealedbytheinsertTEMimageinFig.2C.
Fig.1.
SyntheticprocedureoftheFe
3
O
4
@SiO
2
-HAmicrospheres(A)andtheirCu
2+
removalperformancebytheaidofanexternalmagneticfield(B).
However,nosignificantchangeisfoundinthesphericalshapeandparticlesize,suggestingthatHAintroductionhasnoeffectontheinnercorematerials.FTIRspectrawererecordedtoidentifytheformationofthefunc-tionalgroupsonthemicrospheresatdifferentsyntheticsteps.FTIspectrainthiscasenotonlyconrmedthesilicacoatingonthesurfaceofthemagneticFe
3
O
4
 microspheresbutalsoverifiedtheformationofFe
3
O
4
@SiO
2
-HAmicrospheres.FTIRspectrumoftheas-preparedmicrospheresisshowninFig.3.Thetypicalpeakof  Fe Obondappearedat580cm
1
forthespectrainFig.3A,B,and D[30].Theabsorptionpeaksof3423cm
1
and1651cm
1
wereobservedinallthespectracorrespondingtothestretchingvibrationandbendingvibrationofOHgroupforwater,respectively[31].TheOHstretchingvibrationrelatedtoSiOHgroupsappearedinthesamerangeof3200–3500cm
1
intheFig.3BandD[32]. TheSiO
2
 coatedFe
3
O
4
 microspheres(Fig.3B)havethecharacter- isticpeaksat1105cm
1
,810cm
1
,and950cm
1
,correspondingtotheasymmetricalstretchingvibrationofSiOSi,symmetricalstretchingvibrationofSiOSiband,andstretchingvibrationof SiOH,respectively[33–36].
ThecharacteristicpeaksofHApoly-mer
 
displayedinFig.3Cwereevidentlyobservedinthecurveof  Fe
3
O
4
@SiO
2
-HAmicrospheres,andtheC-HstretchingvibrationpeaksweredramaticallyenlargedaftertheHAimmobilizationinFig.3D.Thecrystallographicstructureandcompositionoftheas-synthesizedmicrosphereswerecharacterizedbyX-raypowderdiffraction(XRD).Fig.4Adisplayedthatthepositionandrelative intensityofallcharacteristicpeaksat2
 
=30.1
,35.5
,43.1
,53.4
,57.0
,and62.6
couldbeindexedtothecubicstructureofFe
3
O
4
powderdiffractiondata(JCPDS:65-3107)[37].Thisresultindicated thattheironoxidemicrospheresweremagnetiteandbelongedtocubicstructure.ItwasapparentthatasshowninFig.4B,thediffrac- tionpeaksforFe
3
O
4
@SiO
2
 weresimilartothoseofironoxide,suggestingthatthemagneticFe
3
O
4
 microspheresweresuccess-fullyencapsulatedbythethinneramorphoussilicalayerwithoutaffectingtheoriginalcrystallinityofFe
3
O
4
 structure[38].

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