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concept for green analytical chemistry.
Sandrine Perino, Emmanuel Petitcolas, Miguel de la Guardia, Farid Chemat
To cite this version:
Sandrine Perino, Emmanuel Petitcolas, Miguel de la Guardia, Farid Chemat. Portable microwave as-
sisted extraction: An original concept for green analytical chemistry.. Journal of Planar Chromatog-
raphy, Akadémiai Kiadó, 2013, 1315, pp.200-203. �10.1016/j.chroma.2013.09.053�. �hal-01328735�
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Journal homepage: www.elsevier.com/locate/chroma
Short communication
Portable microwave assisted extraction: An original concept for green analytical chemistry
Sandrine Perino
a,∗, Emmanuel Petitcolas
a, Miguel de la Guardia
b, Farid Chemat
aaUniversitéd’AvignonetdesPaysdeVaucluse,INRA,UMR408,F-84000Avignon,France
bDepartmentofAnalyticalChemistry,ResearchBuilding,UniversityofValencia,50thDr.MolinerSt.,E-46100Burjassot,Valencia,Spain
Keywords:
Portablemicrowaveassistedextraction Miniaturization
Greenanalyticalchemistry Extraction
Essentialoil
a b s t r a c t
Thispaperdescribesaportablemicrowaveassistedextractionapparatus(PMAE)forextractionofbioac- tivecompoundsespeciallyessentialoilsandaromasdirectlyinacroporinaforest.Thedeveloped procedure,basedontheconceptofgreenanalyticalchemistry,isappropriatetoobtaindirectin-field informationaboutthelevelofessentialoilsinnaturalsamplesandtoillustrategreenchemicallesson andresearch.Theefficiencyofthisexperimentwasvalidatedfortheextractionofessentialoilofrose- marydirectlyinacropandallowsobtainingaquantitativeinformationonthecontentofessentialoil, whichwassimilartothatobtainedbyconventionalmethodsinthelaboratory.
© 2013 Elsevier B.V. All rights reserved.
1. Introduction
CurrenttrendsinGreenAnalyticalChemistryarethedevelop- mentofportableinstrumentationasanalternativetomovethe samplestothelaboratoryandthus,nowadaysthere areseveral available instruments to do it as, infrared instruments, energy dispersion X-ray fluorescence systems, portable gas chromato- graph[1]orcapillaryelectrophoresis[2].Aportableinstrument canprovideinstantin-fieldresultswithouttheneedtowaitfor thetransportofcollectedsamplesfromtheforesttothelabora- tory.Thesepastyears,thereisthedevelopmentofportablesample preparationapparatus,whichcanhelptodothein-fieldextrac- tion,samplepreparation,analysisanddataevaluation.Inparallel, aportableinstrumentisdefinedas“easily”movable,convenient forcarrying,andcapableofbeingtransferredoradaptedinaltered circumstances[3].
Miniaturization(downscaling)isanimportantfactorofmodern societyreflectedstronglyinscienceandtechnology[4]including medicine, chemistry, environment, food safety, etc. [5]. Minia- turization of a procedure can be achieved simply by reducing dimensionsofthesystemsusedinearlierapproachesorbydevel- oping completely new set-ups or techniques. When compared toconventionalsystems,miniaturesystemscanperformsimilar
∗Correspondingauthor.Tel.:+330490144426;fax:+330490144441.
E-mailaddresses:sandrine.perino@univ-avignon.fr,
sandrine.issartier@univ-avignon.fr,sandrine.issartier@yahoo.fr(S.Perino).
methodswithremarkablyreducedconsumption ofplantmatrix andsolvents,sizeandpowerrequirement,systemcostandmean- whilefasteranalysistimeandmassivelyparallelanalysiscapability.
Itisanattractivemethodforapplicationrequiringon-fieldrapid assay[6,7].
From the aforementionedperspective, theidea has been to developaportablemicrowaveassistedextraction(PMAE)which canbeuseddirectlyinthecroportheforest.Givenitsreducedsize, thismicrowavetechniquerequiresasmallamountofsampleina smallglasswaresystemwhichisdesignedasaminiaturealembic tobeplacedinsideamicrowaveoven.Itwasachallengetodevelop aminiaturealembic,suitabletoprovideafastextractionofessen- tialoilsfromthefreshsamplesandtocollecttheextractbyusing aVigreux’scolumnasanair-cooledcondenser,suitablealsotobe placedinsidethemicrowaveoven.Inthisway,thePMAEapparatus canprovideinformationabouttheactualstateofthefreshsamples andtheiressentialoilcontent.Thisprocedureisalsoappropriatefor teachinglaboratory,doesnotrequireanyspecialmicrowaveequip- ment.Theexperimentdeveloped,additionallythantoprovideafast informationonrealsamples,allowsthestudentstolearnextrac- tion,chromatographicandspectroscopicanalysisskills,andisa dramaticvisualexampleofrapid,sustainableandgreenextraction ofnaturalproducts,suitabletobeintroducedtocommerciallysuc- cessful,sustainableandgreenchemicalprocessingwithmicrowave energy.
Here,werereportedforthefirsttimethepotentialofportable PMAEcoupledwithabatteryfortheextractionofessentialoilfrom rosemarydirectlyinacroporforest.Theminiatureglasssystem,
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Fig.1.(a)AcropofRosmarinusofficinalisL.(b)Theportablemicrowaveassistedextractionapparatus:alabinthefield.(c)ExtractionofRosmarinusofficinalisL.essentialoil withthePMAEapparatusconnectedtothebattery.(d)EssentialoilandwaterinsituobtainedwithPMAEapparatus.
equippedwithaVigreux’scolumn,wasdesignedtoillustratethe extractionphenomenon ofessential oilin arosemary’sfield. In thispaper,theessentialoilfromrosemaryobtainedbyPMAEhas beencomparedwiththatobtainedbyconventionalhydrodistilla- tion(HD)inthelab,beingsamplesanalyzedbygaschromatography andmassspectrometry(GC–MS).
2. Materialsandmethods 2.1. Plantmaterial
Rosemary(RosmarinusofficinalisL.)wascollectedinthesouth ofFrance,inAvignon.Onlyfreshplantmaterialwasemployedin allextractions.Theinitialmoistureofleaveswasverifiedinthe laboratoryas59.8%.
2.2. Extractionmethods
Portablemicrowaveassistedextraction(PMAE)apparatuscon- sistsofaportablemicrowaveovenNicoleMicrowave,Reimothat worksonacar’sbattery(12V).Aminiaturealembicemployedfor microwaveassistedextractionisillustratedinFig.1.30goffresh rosemarywereweighed intothe100mLErlenmeyerflaskwith groundsocket.Then,aVigreux’scolumnasanair-cooledcondenser followedbyanErlenmeyerflaskdrilled(atatmosphericpressure) tocollectthedistillate,wereadaptedtothesocket.Theglasssystem wasputintothemicrowaveovenandheatedfor15minwithout addedanysolventorwater, usingafixedpowerof100W.The essentialoillayerwascarefullytransferredwithaPasteurpipette toatesttube.Theoilwasdriedoveranhydroussodiumsulphate, wasweighedwithaportablebalancebeforebeingstoredpriorto analysis.
Conventionalhydrodistillation[8] hasbeenachievedaccord- ingtotheEuropeanPharmacopoeia.500goffreshrosemarywere extractedwith2L of water for3hin a conventional apparatus (untilnomoreessentialwasobtained).Theessentialoilwascol- lected,driedunderanhydroussodiumsulphateandstoreduntilto beanalyzed.
2.3. Analysisofessentialoils
Gaschromatography(GC)analysiswascarriedoutusinganAgi- lent 6850gaschromatographequipped witha flame ionization detector(FID),underthefollowingoperationconditions:vector gas,helium;injectoranddetectortemperatures,250◦C;injected volume,1L;splitration1/100;anHP5MSTM(30m×0.25mmI.D), withafilmthickness0.25m;aconstantflowof0.3mL/min.Addi- tionally,aCarbowaxTMpoly(ethyleneglycol)(60m×0.20mmI.D) columnwithafilmthicknessof0.25m,wasused.Theoventem- peratureprogrammewas40◦Cfor8minincreasedat2◦C/minto 250◦Candheldat250◦Cfor30min.Gaschromatographymass spectrometry(GC–MS)analysiswascarriedoutusinganAgilent 6890Ncoupledto anAgilent 5973MS.Samples wereanalyzed usingafused-silica capillarycolumnHP5MSTM (50m×0.20mm I.D.,filmthickness0.50m)andCarbowaxTMpoly(ethylenegly- col) (60m×0.20mm I.D., film thickness 0.25m). Carrier gas, helium;injectoranddetectortemperatures,250◦C;injectedvol- ume,1mL/min;splitratio;theoventemperatureprogrammewas 40◦Cfor8minincreasedat2◦C/minto250◦Candheldat250◦Cfor 30min;ionizationenergy,70eV;electronionizationmassspectra wereacquiredoverthemassrange35–400u.Identificationofthe componentswasbasedoncomputermatchingagainstcommer- ciallibraries(Wiley,MassFinder2.1Library,NIST98), laboratory massspectralibrariesbuiltupfrompuresubstances,andMSlit- eraturedatacombinedwithcomparison ofGCretentionindices (RI)onapolarandpolarcolumn.RIswerecalculatedwiththehelp ofaseriesoflinearalkanesC6–C26onapolarandpolarcolumns (HP5MSTMandCarbowaxTM).Compoundsavailableinthelabora- torywereconfirmedbyexternalstandardcompoundco-injection [9–12].
3. Resultsanddiscussion
3.1. Extractiontime,energyandenvironmentimpact
PMAE procedure was finished after 30min to obtain 3mL of rosemary’s essential oil compared to 3h with conventional
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hydrodistillationapparatusandtheessentialoilyieldwasdeter- mineddirectlyinthefieldwithaportablebalance.PMAEexperimentcanbeperformeddirectlyinacropwitha portablemicrowave ovenconnectedtoa battery. It isnot nec- essarytocollecttheplantmaterialin acroporforestand take themin a nostabilizedstateduring hourstogotothelabora- toryand thenextract rosemary’sessentialoilwitha Clevenger apparatuswhichneedstoheatandboil2L ofwaterwithrose- maryforseveralhours.Thereducedcostofthisgreenextraction isclearlyadvantageousforthePMAEmethodintermsofenergy andenvironmentimpacts.Theenergyrequiredtoperformthetwo extractionmethodsarerespectively2kWhforHD,and0.1kWh forPMAE.Thepowerconsumptionhasbeendeterminedwitha Wattmeteratthemicrowavegeneratorentranceandtheelectrical heaterpowersupply.Regardingenvironmentalimpact,thecalcu- latedquantityofcarbondioxiderejectedintheatmosphereismuch higherwithconventionaldistillation(1600g)thanwithportable microwave(80g). Thesecalculationshavebeenmadeaccording totheliteratureconsideringthatrecovering1kWhfromcoalor fuelcombustionisassociatedwith800gofCO2beingrejectedin theatmosphere.Thelifecycleanalysis(LCA)hasnotbeenapplied fortransportationandtheapparatusused,whichwilldramatically enhancethepositiveimpactofusingPMAE.
3.2. Compositionofessentialoil
The chemical composition of rosemary essential oils varies anddepends onlocality,theclimaticconditionsand harvesting
seasons.Inourstudy,rosemaryleaveswereobtainedfromacrop inAvignon,France(augustharvest).Theoilsobtainedfromeach experimentwereverysimilarinappearance,palecolourandfra- grance.ThecompositionoftheessentialoilsobtainedbyHDand PMAEmethodsaregiveninTable1.Atotalof25compounds(in agreementwith theliterature) wereidentified in essential oils extractedfromthesamesamplesusingthetwotechniques.The essentialoilofrosemaryleavesisolatedeitherbyPMAEorHDcon- tainsthesamedominantcomponentssuchas␣-pinene,camphor, verbenone and camphene. The monoterpene hydrocarbons are presentinalmostequivalentamountsintheHDandPMAEessential oilsand␣-pinene,isthemainabundantcomponentintheessential oilextractedfromrosemarywithequivalentrelativeamountsfor bothextractionmethods:46.3%and46.5%,respectivelyforPMAE and HD. Camphorwasthemain oxygenatedcomponent in the essentialoilisolatedfromrosemaryleavesbuttherelativeamounts arenotdifferedforthetwoisolationmethods.Itisthemostabun- dant oxygenatedcomponentof theessential oil7.9% for PMAE whereastheHDoilcontains7.8%.
3.3. Safetyconsideration
Thisgreenmicrowaveextractionmethodistotallysafeevenfor nonhighlyeducatedoperators,college,highschoolandacademia laboratories.Weonlyuseconventionaldomesticmicrowaveoven
“withoutanymodification”asspecifiedbymanufacturer.Theglass- wareevenVigreuxcolumnissimpletouse,anddonotcreateany
Table1
ChemicalcompositionofRosmarinusofficinalisL.essentialoilsobtainedbyportablemicrowaveassistedextractionapparatus(PMAE)andhydrodistillation(HD).
No. Compoundsa HD(%) PMAE(%) RIb RIc
Monoterpenehydrocarbons 70.1 70
1 Tricyclened 0.2 0.2 921 1011
2 ␣-Pinened 46.5 46.3 936 1023
3 Camphened 5.9 6.0 951 1103
4 Verbenene 0.9 1.1 955 1121
5 -Pinened 2.6 2.5 980 1109
6 Myrcened 1.9 1.8 995 1149
7 ␣-Terpinened 0.8 0.8 1020 1083
8 para-Cymened 1.3 1.3 1025 1250
9 Limonened 5.4 5.4 1030 1206
10 ␥-Terpinened 3.0 3.0 1052 1251
11 Terpinolened 1.6 1.6 1092 1287
Oxygenatedmonoterpenes 24.4 24.9
12 Linaloold 2.3 2.3 1106 1538
13 ␣-Campholenal 1.2 1.3 1122 1471
14 Camphord 7.8 7.9 1149 1514
15 Pinocarvoned 1.3 1.4 1160 1548
16 Borneold 2.5 2.6 1173 1679
17 Terpin-4-old 2.1 2.1 1184 1590
18 ␣-Terpineold 0.7 0.7 1198 1677
19 Verbenoned 6.5 6.6 1207 1696
Sesquiterpenehydrocarbons 1.3 1.0
20 E-caryophyllene 0.9 0.8 1425 1470
21 -Bisabolened 0.4 0.2 1508 1714
Oxygenatedsesquiterpenes 0.3 0.3
22 Caryophylleneoxided 0.1 0.1 1570 1977
23 ␣-Bisabolold 0.2 0.2 1684 2022
Otheroxygenatedcompounds 0.9 1.0
24 Bornylacetate 0.8 0.9 1263 1579
25 Methyleugenol 0.1 0.1 1397 2032
Extractiontime(min.) 180 15
Yield(%) 0.57 0.2
Totaloxygenatedcompounds 25.6 26.2
Totalnonoxygenatedcompounds 71.4 71.0
aEssentialoilcompoundssortedbychemicalfamiliesandpercentagescalculatedbyGC-FIDonnon-polarHP5MSTMcapillarycolumn.
bRetentionindicesrelativetoC5–C28n-alkanescalculatedonnon-polarHP5MSTMcapillarycolumn.
c RetentionindicesrelativetoC5–C28n-alkanescalculatedonpolarCarbowaxTM-PEGcapillarycolumn.
d Compoundsknowintherosemary.
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problemofexplosion,thePMAEbeingmadeatatmosphericpres- sure.4. Conclusion
Theaimofthispaperwastoexplorethefeasibilityofasimple andlow-costportablemicrowaveovencombinedwithaminiatur- izedalembictoextractnaturalproductsandespeciallyessential oilsdirectlyinacroporaforest.Thisoriginalportablemicrowave assistedextractionprovidesafastin-fieldinformationaboutthe contentofessentialoilsinfreshnaturalsamplesandoffersimpor- tantadvantagesovertraditionalhydrodistillationtechnique:itis quicker(lessthan15min),effectiveandinvolvesanenvironmen- tallyfriendly approach,witha reduced consumeof energy and reagents.ThePMAEapparatuscanprovideinstantresultsoncrop withouttheneedtowaitforthetransportfromtheforesttothe lab,thesamplepreparation,analysisanddataevaluation.More- over,PMAEcouldbeemployedasalaboratoryexercisewhicheasily teachesGreenAnalyticalChemistry.ThisPMAEapparatusallows obtainingessentialoilssimilartothoseobtainedbyconventional methodsandsuccessfullyincorporatesgreenanalyticalchemistry principlesintotheeducationalpracticallessons.
Acknowledgement
TheauthorsgratefullyacknowledgeMrBrunoZinck(company Legallais,Montpellier,France) for hishelp in theconception of theglasssystem.Thisscientificstudywascarriedoutaspartof the Alcotra Eco-Extraction Transfrontalière project framework
which brings together private and public-sector stakeholders (University of Avignon, European University of Fragrances &
Flavours,FranceAgriMer,UniversityofTurinandTechnogranda).
We would also like to warmly thank our co-funding partners, i.e.theEuropeanUnion(FEDER),theFrenchandItaliangovern- ments,thePiedmont regionas wellasADEME andthe Conseil Régional Provence-Alpes-Côtes d’Azur through theEtat-Region- ADEMEframeworkprogramme.Theirfinancialsupporthashelped partnerssuccessfullyachievetheproject’sscientificobjectives.
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