Abstract

Environmental stimuli-responsive pesticide release is desirable for enhanced efficiency and reduced side effects. In most cases, the loading and release of pesticides mainly depends on hydrophobic interactions and hydrogen bonding. Electrostatic interaction is less investigated as a weapon for achieving high loading content and controlled pesticide release. In this work, negative-charge decorated mesoporous silica nanoparticles (MSNs) were facilely fabricated by introducing sulfonate groups onto MSNs through a post-grafting method. Sulfonate-functionalized MSNs (MSN-SO3) were synthesized by conversion of epoxy group into sulfonate group using a bisulfite ion as a ring opening reagent. Diquat dibromide (DQ), one of the globally used quaternary ammonium herbicides, was efficiently loaded into these negatively charged MSN-SO3 nanoparticles. The loading content was increased to 12.73% compared to those using bare MSNs as carriers (5.31%). The release of DQ from DQ@MSN-SO3 nanoparticles was pH and ionic strength responsive, which was chiefly governed by the electrostatic interactions. Moreover, DQ@MSN-SO3 nanoparticles exhibited good herbicidal activity for the control of Datura stramonium L., and the bioactivity was affected by the ionic strength of the release medium. The strategy of cargo loading and release dependent on the electrostatic interactions could be generally used for charge-carrying pesticides using carriers possessing opposite charges to mitigate the potential negative impacts on the environment.

Highlights

  • Pesticides play important roles in the high food productivity and farmers’ income through the control of biological disasters

  • These results indicated that the organic groups can be incorporated on P-mesoporous silica nanoparticles (MSNs) by the grafting method

  • A stimuli-responsive cationic herbicide DQ release system has been designed by introducing negative charges on the surface of MSN

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Summary

Introduction

Pesticides play important roles in the high food productivity and farmers’ income through the control of biological disasters. TTo address this limitation, the exploitation of the controlled release formulations (CRFFss)) of DQ could be promising, since CRFs permit the application of minimal amoouunnttss ooff aann aaccttiivvee iinnggrreeddiieenntt ttoommaaiinnttaaiinntthheeddeessiirraabblleeaaccttiivviittyy,, which will mitigate the potentially negative impacts on the eenvironment, and promote sustainable agricultural development [7,8,9,10]. Release profiles were studied under different conditions including ionic strength and pH value. The herbicidal activity of DQ-loaded MSN-SO3 (DQ@ MSN-SO3) against target plant datura (Datura stramonium L.) was investigated. UPsriennpgagratetitornaeattnhhdyylCl hoarrthahcootsesirilliiziccaaattiteoen((ToTfEENOOaSSn)),o,paaassrttichlessilica ssoouurrccee aanndd cceettyyllttrriimmeetthhyylammonium bromide u(isgisansapa(nlCFiiindnralaslzgtuioaiTdnardgrenntsunloAo(isgisansapa(sgwiatsMebdodoaPuiiygtnloCFthiiihepcPdfndnyprrlragflatrfe-iriilzgBsiefteuilrtooaogefaoMaST-ndenarudcaeigere2entfacl)MatPstsgmuunaniwNaleonrAeotlcisru0itniniytgsS-oh2nttanlt-oepp,crredfuptr0tooiriSoisr-etMBsNmeiCofesl.eirdantozcstSoeulacmairefcNtobnanrh)fntalSPesni,emadOetrSccooieabFnunotgbghcste,ui2actrnt-o,teabe.sNhdnnsomwiv)is3ehtMlrfohysweCesbdntzncrsytaromobefasdiynSrehenitlosesoawfio,imrttisauiStpoehFbblocuotdhhhbtete,naisuefStutcnbp.sNhphnsrhseie)eymrqfohobweenedaEotnoss1ypdumogubresoetSrusweoettitsrsipw4MgesslwiraslripcoeheihslnuothyaytmeMpfcnect2oeoSotorntpehlqhnohseeergnh-snooobsneuaepdatEungsdduugosouroianioSootecafsfpwtttrartlasiimeM.peosorstllnc-hrteeheNaylnpntcnevyMMyfryilairtgotpiteflnqatndeoe-lbeTehgtauog-co,enuefiter-igPddhhgltcut(dngtenliogSScorSMarecnhastarileimTi1t-ieordaoaohtceNNayrsietcOcenfgrveeMsmart4nwEtgtgfnlgouSiatsee-,bshagdsormeeiorftf8e3--dgwabeluMnNctlrteostehefogSoirSSangooMilnpintetiesdiagrtnuc(yNeteOadOunessihgrc-byfrhra)fTafoiggngisemStt,rperSagticoermsurtfbmn3o3rrrEewaao2eegcolaOoshf(ctnNworuaaooMlidon,nmste0FrgbOnuseieuasudepductesitlca3bacfrpc0ar.-iiirsnueeiarletoplsorSSettlgticeSetgeouqotnernalgdawean2hesugoeilfstt)nfNO-sruepauunfirlroisenms0yea,ggosoarpaubnPcnvtMetorya.igipratprc03ne-dryrenpirendaoeelsea-mtSnsgocosdMsalgouM.sditsaScfdtnstmulO-repa3un(iworiecpyeeioaPtsiTrNmaoooTbnainMstooAniyrgrSpfrttsi3fcofarni-vhmneinennEbyeihttnsrc-NeMadno1srcru,te.ewdtSeeeStdonimgslBeMdsahtpt(4woollgeosrnelsToNtOoeiTTeypaSd)e2ysuoerfahtcsi(obvdsmh)mse3nnhnNEbhae,rP3Ftm3lli-arlo1arinasewy-eehdeeSftdroi-gigeeMli-np4tgnelletooisnsngtrsiagsoMeOreosbypathdseci2,sdulnolhabulidnetucdsmm)eywngycaoaryPn3att3erinoslosrSlhrasocahehrmciMfryi-gpctetu1g-etfiopnteelfeNcoitengotinpesMeieooashia4treod-daristrlodpalabrclodSwencovaehcgnwnfgd8e3aoeyrnTemobnast(oasSaulNewcrpioatr)yeiepFcetu1nietxvsnnrEgioicxtNict,,oretcsuaiiideotsnii4tyreo-yereiiycmdropgnMhargcwuiisSnaovogswfd8rgranepcnmpnlre(moabaunpwOoueoianere,lfFghtrdnnrra.icxseyatmormltFdfshsusasisraotpito3aieiteeymesnghalgesuisncnrToespbdpPrnytlcorecgpiy(emssuthuehp(3sogeidnirchty,ylFtyn-ihipmduFsnransisrceecaAhcrrdMfessreslpizolosetm.ehioetstrsagtgestostrsogcbeuhhpP,rgrelorrccsnnhagygS-hssMuBeueed(3eiieoduiiytateooryrn-npmmFsoeenNmrn2otsiac)AtrmMeotnsrpwylvaongh.euitw.erhvtsgtwtseaistusogneeuhpl,ieeerccrzetoihTsnSi-hMBdntuest3tocuiee.iplatsnaneorerhhodhheNmtsnddohyti3)dirrDuroetinTsrdisipvhduofsoocmofoh.egw),ceeniseaivslneah,,eeeontrMwzrsaxtxcre(dEnugtehtcseieenslfnnnvecFenoahlysyhsnpya3wdrihre)bltoFaSodoiitoinduofvesse.a,hfosgc)a,rsnaiiigaatviNptaiih,cnmcMnbeInreegyrxetllsgtpusebncotentnfyhavatahi,rovhdsyaliu-crihawriceelarFescafSnnaSoggeiteoclboiesei,ar(hcersaaeiitmyoiNncOmleteeiSMnahcenmoveneeredgnetlaTsu2notonenEanadhi,ianoiv(3mu-cdrdatis2cmfiSoCsaaEfs(GtpnaSgdssaMeeoboe(hrth.Giia.tboNcucnioOFMeeadzni,MtcernvinePoolnFtctaTsyifcTs)TnPsnreoihydoihio-v3Twfigdnr)stli2omhS,eoiEGi(atpzhTatpyotieone(hlumMu.Gti.tphswnbNchueneelnFMaeMrnhrnsaiP,ouhmlrtTyadocecesTmPsdrcigieirShcoestc-eTwgosrcthtlitohxsShtGshToeho)syootifehotrmMtiuowc3wSapy)cheestrtebrcernoMartafnsPPhhraDdlnrEahtpdayecelrcpisegedbeSgpsehbTee-taatcgoihneMoesSo,dsiMrheriedsorimts(siehrEtMscepm3waowpes)tahrnSottfoaftiho)hmaDdtanaowaonpoSyEaoeiudpingt.ttheSieetlcantvamnrgirxhdNhhtehn,MoiIprireroeiedsoaam(gieEtdesnyponsweeeeeeascSsigdrtltafatrsl)ai)gapoeEaiianat.gnttniettcncnnxhoohhthhnMgIroeottaiaidyondnneceooeesceestlfl) show obvious changes before and after modification. These results indicated that the organic groups can be incorporated on P-MSN by the grafting method.

Loading of DQ into MSN-SO3 Nanoparticles
Controlled Release of DQ
Synthesis of the Nanoparticles
Sample Characterization
Loading of DQ into MSN-SO3
In Vitro Release of DQ
Statistical Analysis
Findings
Conclusions
Full Text
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