Rate of Molecular Exchange Through the Membranes of Ionic Liquid Filled. Polymersomes Dispersed in Water

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1 Supportng Informton for: Rt of Molculr Exchng hrough th Mmrns of Ionc Lqud Flld olymrsoms Dsprsd n Wtr Soonyong So nd mothy. Lodg *,, Dprtmnt of Chmcl Engnrng & Mtrls Scnc nd Dprtmnt of Chmstry, Unvrsty of Mnnsot, Mnnpols, Mnnsot 55455, Untd Stts Fgur S. h lnr ft of dcy rt (Г) vs. th squr of th scttrng vctor (q ) from DLS. Г vlus wr from th cumulnt fttng of th corrlton functons. h slop of th lnr ft s dffuson coffcnt of polymrsoms n th soluton.

2 Fgur S. Cryo-EM mg of BO(9-3) polymrsoms n D O (0.5 wt %). h dr ntrors r th onc lqud flld ntrors, nd th gry rgons round dr ntrors r B mmrns. Fgur S3. Normlzd H NMR spctr of polymrsom solutons (0.5 wt %,.0 wt %, nd.5 wt %). wo ps twn 7.4 ppm nd 7.3 ppm r from th H- nd H-c of th fr [EMIM], nd smllr two ps round 7. ppm from th H- nd H-c of th confnd [EMIM] phs. As th polymrsom contnt ncrss, th ps round 7. ppm ncrss.

3 Fgur S4. Chmcl structur of [EMIM][FSI] nd [BMIM], nd H NMR spctrum of [BMIM] soluton wth BO(9-3) polymrsoms. As wth [EMIM], [BMIM] shows lso two sts of chmcl shfts. Mny of ps of [BMIM] r not compltly dstngushl du to smlr chmcl structur wth [EMIM]. Fgur S5. h ntc xprmnt wth trnsnt H NMR msurmnts. Chrgd molculs, [BMIM], whch hv smlr structur wth [EMIM], lso shows two sts of ps. H- of [BMIM] (s Fgur S3) from th xtror nd th ntrors wr ntgrtd sprtly wth tm. h ntnsty chng of ch p cnnot found ftr round 70 scond. 3

4 4 In ths study, th xchng prmtrs wr vlutd y usng th two-st xchng modl (Equton 4).,,3 Apprnt mol frctons (, ), nd rt constnts (, ) r functons of th rl prmtrs,, D, D,,, nd ffctv rlxton tms,,. h suscrpts nd rprsnt th ntror nd th xtror of th polymrsoms, rspctvly. h pprnt rt constnts (, ) cn dscrd y two prmtrs, Q,, whch r dfnd n Equtons S4 nd S5,, Q Q, (S) whl, nd r dfnd y Equtons S nd S3. nd r th mol frctons of th trcr molculs n th polymrsoms nd th mdum, rspctvly. h summton of nd s. (S) ( )( ) 4 Q (S3) h prmtrs Q nd Q r dfnd y,,,,, nd n Equtons S4 nd S5, Q, (S4) Q, (S5) whr nd r pprnt rt constnts dfnd y γ, δ, G, nd two dffuson coffcnts, D, nd D, D G δ γ, (S6) D G δ γ, (S7) nd nd r rsdnc tm of molculs n ch phs, nd nd r ffctv rlxton tms dfnd y Equtons S8 nd S9.

5 δ Δδ Δ,, (S8) δ Δδ (S9) Δ,, In ths study, th spn-lttc ( ) nd th spn-spn ( ) rlxton tms wr consdrd. nd cn ffct th ttnuton profl nd fttng rsult cus th nvronmnt of ch phs s qut dffrnt, whch rsult n dffrnt rlxton tms., nd, r rlxtons of osrvd protons n th ntrors, nd, nd, r tht n th mdum. h nd wr otnd y th protont nd Crr urcll Moom Gll (cpmg) protocol, rspctvly, nd th ps from th ntrors nd xtrors wr procssd sprtly for nd. l S. rmton rt wth two-st xchng modl. Dffusr,,,, [EMIM].9 s 0.79 s 0. s. s -Butylmdzol.5 s 0.9 s 3.3 s 0.5 s REFERENCES [] Momot, K. I.; Kuchl,. W. ulsd Fld Grdnt Nuclr Mgntc Rsonnc s ool for Studyng Drug Dlvry Systms. Concpts Mgn. Rson. 003, 9A, [] Stno,.; Choudhury, R..; Schönhoff, M.; Vn dr Mrn,. V.; Mrtns, J. C. NMR Invstgton of Exchng Dynmcs nd Bndng of hnol nd hnolt n DODAC Vsculr Dsprsons. J. hys. Chm. B 0, 6,

6 [3] Lson, A.; Lson, A.; Huschld, S.; Rn, A.; Nu, A.; Schurt, R.; Forstr, S.; Myr, C. Molculr Exchng hrough Mmrns of oly(-vnylpyrdn-loc-thyln oxd) Vscls. Smll 007, 3,