基于单片机的氧气检测仪英文原版参考文献word版文档格式.docx

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基于单片机的氧气检测仪英文原版参考文献word版文档格式.docx

stabilisedopticaloxygensensor

AlbertoJ.Palmaa,JavierL´

opez-Gonz´

alezb,LuisJ.Asensioa,MariaDoloresFern´

andez-Ramosb,LuisFerminCapit´

an-Vallveyb,~

aDepartmentofElectronicsandComputerTechnology,CampusFuentenueva,FacultyofSciences,

UniversityofGranada,E-18071Granada,Spain

bSolidPhaseSpectrometryResearchGroup,DepartmentofAnalyticalChemistry,CampusFuentenueva,

FacultyofSciences,UniversityofGranada,E-18071Granada,Spain

Received26January2006;

receivedinrevisedform13March2006;

accepted14March2006

Availableonline5June2006

Abstract

Anovelmeasurementsystemcomprisedofaportableelectronicinstrumentwithanopto-chemicalsensorforatmosphericoxygensensingispresented.Opticalsensorsbasedonluminescencequenchinghavebeenthoroughlyinvestigatedinthesearchforsufficientsensitivityandhighstability.ThedyeplatinumoctaethylporphyrincompleximmobilisedinapolystyrenemembranewasselectedasanoxygenprobethatwasstabilisedwiththeheterocyclicamineDABCO,achievinginthiswayameandriftof0.01%oxygenconcentrationperday.Theportableinstrumentisbasedonamicrocontroller.Itsmainfeaturesare:

asingleopticalsensorchannel,lackofopticalfilters,fullydigitalsignalprocessing,autonomousoperationwithcomputercommunicationcapabilityforreprogramminganddatasavingandlowpowerconsumption.Theuseofadigitaloutputphotodetectormakesitpossibletoavoidanalogueprocessingwiththeconsequentcircuitrysavingandbetternoiseimmunity.Themeasuredparameterinthetransductionprocessisquitesimilartotheluminescencelifetime.Thetypicalmeasurementrangeisfrom0to30%oxygenandtheresponsetimeisbelow30sforfullrangeswing.Typicalinstrumentcharacteristicsaretemperatureeffectcorrection,lowdriftandanaccuracyof0.5%inoxygenconcentrationforthecollectivecalibrationcurve.Betteraccuracycanbeobtainedwithindividualsensorcalibration.Dimensionsandweightare110mm×

66mm×

28mmand95g(withoutbattery),respectively.Poweringitwithastandard9VPP3batteryformorethan10daysofoperationispossible.

©

2006ElsevierB.V.Allrightsreserved.

Keywords:

Opticalchemicalsensor;

Oxygendetermination;

Phosphorescence;

Luminescencequenching;

Portableinstrument;

Microcontroller

1.Introduction

Thedevelopmentofportableanalyticalinstrumentationisaninterestinginterdisciplinaryareaofresearchwhichbringsanalyticalchemistsandelectronicengineerstogether.Tomanufacturelow-costeasy-to-useinstrumentsforuseindifferentfieldssuchastheenvironment,worksafety,defenceandhealth,muchmoretechnologicaldevelopmentmustbedone.Thiswilltakeanalyticalinstrumentationoutoftherealmofdedicatedacademicorresearchlaboratoriesandofferittonontrainedusersandconsumers.Greatresultshavebeenobtained

~Correspondingauthor.

E-mailaddress:

lcapitan@ugr.es(L.F.Capit´

an-Vallvey).

inthisregardinsomeareassuchashealthcareandprocesscontrol.

Inenvironmentalsensing,inparticular,thedevelopmentofhand-heldbattery-operatedmeasurementsystemsforthedeterminationofoxygenisafieldofresearchwithwideapplications.Inthisarea,opticalchemicalsensorsareanattractivealternativetothemoreestablishedelectrochemicalsensors[1].Mostopticalchemicaloxygensensorsarebasedonthequenchingoftheluminescenceofanoxygen-sensitivedyebymolecularoxygen.Extensiveworkhasbeendoneinthisarea,whereavarietyofluminescentdyeshavebeenincorporatedintoagaspermeablemembraneanddifferentmeasurementprocedureshavebeenreported[2–6].Inthepast,instrumentationforsignalprocessingsuchasluminescencewasgenerallyfairlyelaborated,bulkyandcostlyandthereforeunsuitableforportable

630A.J.Palmaetal./SensorsandActuatorsB121(2007)629–638

2.1.Reagents

Platinumoctaethylporphyrin(PtOEP)wasobtainedfromPorphyrinProductsInc.(Logan,UT,USA),1,4-diazabicyclo[2.2.2]octane98%(DABCO),tetrahydrofuran(THF),polystyrene(PS,averageMW280,000,Tg:

100~C,GPCgrade)andhighmolecularweightpoly(vinylchloride)(PVC)werepurchasedfromSigma–AldrichQu´

ımicaS.A.(Madrid,Spain).SiliconeElastosilN-10wasobtainedfromGeneseePolymerCorp.(MI,USA).Thefluopolymerpoly(isobutylmethacrylateco-tetrafluoropropylmethacrylate)wassynthesisedandcharacterisedbyusaccordingtoAmaoetal.[12].SheetsofMylar-typepolyester(Goodfellow,Cambridge,UK)wereusedasasupportformembranes.ThegasesO2andN2usedwereofahighpurity(>

99%)andweresuppliedingascylindersbyAirLiquidS.A.(Madrid,Spain).

2.2.Membranepreparation

Themembraneswereproducedonapolyestersubstrateusingaspin-coatingtechnique.(i)Polystyrenemembranes:

mixturesforthepreparationofoxygen-sensitivemembranesweretypicallymadebydissolving0.5mgofPtOEPin1mLofasolutionof5%(w/w)ofPSinfreshlydistilledTHFinaglassvial.Themembraneswerecastbyplacing30~Lofthecocktailonathicktransparentpolyestersheetoftheappropriatesizeusingahomemadespin-coater[22]rotatingat180rpm.Afterspinningfor2min,themembranewasremovedfromthespincoateranddriedinadryerwithsaturatedTHFatmospherefor24hatroomtemperature.Thesensing6mmdiametercircularfilmthatwasobtainedishomogeneous,transparentandpinkincolourwithacalculatedthicknessofabout4.5~mandanapproximatePtOEPconcentrationof14.4mM.(ii)Polystyrene–DABCOmembranes:

inthiscase,thecocktailcontains12mgofDABCO(25%DABCO)inadditiontoothercomponentsindicatedabove.Thefilmobtainedusingthesametechniqueis10mmindiameterand14~minthickness.(iii)PVCmembranes:

themembraneswerecastusing50~Lofacocktailpreparedbydissolving0.5mgofPtOEPand100mgofPVCin1mLofTHFinaglassvial.Thefilmobtainedis6mmindiameterand5~mthick.(iv)Siliconemembranes:

thesemembraneswerepreparedwith30~Lofacocktailcontaining1gofsiliconeElastosilN-10in1mLoftoluene.ToimpregnatethemembranewithPtOEP,thetechniquedescribedbyBaconandDemas[23]wasused.Themembranewasimmersedina1000mgL-1solutionofPtOEPinCH2Cl2for10min.Itwasthenremoved,rinsedwithCH2Cl2andair-dried.Thefilmobtainedwas11mmindiameterand7~mthick.Allthepreparedmembraneswerestoredinthedarkuntilusetoavoidphotodegradation.

2.3.Measurementsystem

2.3.1.Portableelectronicinstrument

Ourmeasurementsystemconsistsofasensingmembranedirectlyattachedtoaportableelectronicinstrumentwitha

systems.However,thelasttwodecadeshavewitnessedsignifi-2.Experimental

cantdevelopmentofreliable,smallandlow-costsemiconductordevicesforexcitingandcollectingopticalsignals,suchashighintensitylightemittingdiodes(LED),laserdiodesandsemiconductorphotodetectors.Thistechnologyhasbeencontinuouslyincludedinnewportableinstrumentdesigns,particularlyforgassensing.

Inthequenchingprocess,emittedluminescenceintensityandluminescencedecaytimeareaffectedbyoxygenconcentration.Fromthepointofviewofphotostabilityandimmunitytostrayopticalsignalinterference,decaytimemeasurementseemstobemoreadvantageousthanintensity[4,7].However,someresultshavebeenreportedincludingaportableinstrumentfordissolvedoxygendetectionbasedonintensitymeasurement[2,8].Thedecaytimeoftheluminescencecanbedeterminedwithdifferentmethods:

(i)directmeasurementwithhighspeed,largeandexpensiveinstrumentation[9]and(ii)phasemodulationtechniques[2,10].Inthelatterapproach,dedicatedsignalprocessingelectronicshasmadeaninstrumentthatincludesdualopticalchannels,circuitryfortheacsignalandseveralcontrolcircuitsforphaseshiftcorrectionandavoidingamplifiersaturation[7].

Oneofthetypicalproblemsofquenching-basedsensorsforoxygen,especiallyforintensity-basedsensors,istheusuallowphotochemicalstabilityofluminophoreswhichreducesthelifeofthesensorandrequiresfrequentrecalibration.Differentsolutionshavebeendevisedtosolvetheproblem:

(1)modifyingexistingluminophores[11];

(2)modifyingthepolymermatrices[12];

(3)usingrelativesignalsobtainedindifferentways:

(a)fromscatteredexcitationradiation[13],(b)fromtheluminophoreitselfthroughaluminescencebandinsensitivetoO2[14,15]orbyusingaluminophorethatsimultaneouslyshowsphosphorescencequenchablebyO2andfluorescenceinsensitivetoO2[16],(c)fromasecondO2-insensitivefluorophorewithsimilardecayratessuchasindicatordyes[17,18];

(4)introducingstabiliseradditives,mainlytertiaryamines,tomembranestoremovethereactivesingletoxygengivenofffromthequenchingprocessofluminophoreluminescence[19,20].

Inthisreport,aportableinstrumentforatmosphericoxygenconcentrationmeasurementhasbeendeveloped[21].Ourgoalswereareliable,simple,low-costprototypeincludingahighstabilisedsensingmembraneandthelatestsemiconductoroptoelectronicdevices.Wereportonaneasy-to-usemeasurementsystemwithhighopticalandelectricalinterferenceimmunity,extremelysimplesignalprocessingcircuitry,lowpowerconsumptionandenoughaccuracyforinsituatmosphericoxygendetermination.Wehavedesignedaninstrumenttoovercomesomeofthedrawbacksofpreviousportabledesigns,basedonsimpleelectronicsandaonesignalchannelwithoutanyreferencechannel.Oneofthemainadvantagesofourdes

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