Controllable Microfluidic Production of Multicomponent Multiple Emulsions

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1 Supplementry Mteril (ESI) or L on Chip This journl is The Royl Society o Chemistry 0 Controllle Microluiic Prouction o Multicomponent Multiple Emulsions Supplementry Mteril Wei Wng, Rui Xie *, Xio-Jie Ju, To Luo, Li Liu, vi A. Weitz, Ling-Yin Chu * School o Chemicl Engineering, Sichun University, Chengu, Sichun, Chin Tel: ; E-mil: chuly@scu.eu.cn; xierui@scu.eu.cn School o Engineering n Applie Sciences/eprtment o Physics, Hrvr University, Cmrige, Msschusetts, USA. Prt S. Experimentl S.. Friction o microluiic evice The microluiic evice is se on three sic uiling locks, s shown in Fig.. Cylinricl cpillries with outer imeter o.0 mm (AIT glss) re use s the injection tue n collection tue. The en o the injection tue is tpere y micropuller (Nrishige, Jpn) n then juste y microorge (Nrishige, Jpn). Squre cpillry tues with inner imension o.0 mm (Vitrocom, USA) re use to ensure the coxility o the cylinricl cpillries neste within them. For the rop mker, the injection tue n collection tue re ligne insie the squre cpillry tue, with the tpere en o the injection tue inserte into the collection tue. The coxil co-low geometry o rop mker is ensure y mtching the outer imeters o the cylinricl cpillries to the inner imensions o the squre cpillry tues, s shown in Fig.S. The isperse lui A is pumpe into the injection tue, n the continuous lui B is pumpe through the outer coxil region etween the squre cpillry tue n the cylinricl injection tue. The coxil low o these two luis results in the ormtion o monoisperse roplets in the collection tue. For the connector, two cylinricl cpillries re integrte to uil Y-shpe connector. For the liqui extrctor, the injection tue n collection tue re ligne insie the squre cpillry tue ut with the tpere en o the injection tue out o the collection tue. Friction o the microluiic evices or vrious multicomponent multiple emulsions is chieve y selective oning o the rop mker, connector n liqui extrctor. For exmple, to ricte the microluiic evice in Fig., uiling locks re one together y using PVC tue to connect the cylinricl cpillries o every two uiling locks, s shown in Fig.S. S

Fig.S Schemtic igrm o the rop mker or generting

Illustrtions -, -, c-c n - re cross-section imges o the

cylinricl cpillries n squre cpillry tues re ssemle in the

Flui A is the isperse phse, n lui B is the continuous phse.

microluiic evice or quruple-component oule emulsions.

multicomponent multiple emulsions y operting luis o queous

2 Fig.S Schemtic igrm o the rop mker or generting monoisperse roplets. Illustrtions -, -, c-c n - re cross-section imges o the rop mker in relevnt positions, which clerly show how the cylinricl cpillries n squre cpillry tues re ssemle in the rop mker. Flui A is the isperse phse, n lui B is the continuous phse. Fig.S Cpillry ssemly o the uiling locks or the riction o microluiic evice or quruple-component oule emulsions. A PVC tue is use to connect the cylinricl cpillries o every two uiling locks. S.. Genertion o multicomponent multiple emulsions We generte multicomponent multiple emulsions y operting luis o queous phse n oil phse into n out o the microluiic evice through syringe pumps. With 5 % (w/v) polyglycerol polyricinolete (PGPR90, nisco) s surctnt, soyen oil n enzyl enzote re use s two kins o oil phses. Aqueous solution contining % (w/v) Pluronic F7 (Sigm-Alrich) n 5 % (w/v) glycerol is use s queous phse. Either 0. S

3 % (w/v) Sun re or 0. % (w/v) Sun lck is use to color the oil phse, n 0.5 % (w/v) methylene lue is use to color the queous phse. For quruple-component oule emulsions, inner luis F - n F - re soyen oil phse with n without Sun re respectively, F -, F -, F -C n F -E re queous phses, n F -M is soyen oil phse, s shown in Fig.. The vrition rnges or the low rtes re - 50~00 μl h -, - 0~00 μl h -, - 00~00 μl h -, - 00~700 μl h -, -C 50~00 μl h -, -E 00~700 μl h - n -M 4000~000 μl h -. For quintuple-component oule emulsions, F -, F - n F - re enzyl enzote oil phse lele with Sun re, Sun lck n without ny ye respectively, F - is queous phse, n the other luis re the sme s those o quruple-component oule emulsions, s shown in Fig.4. The vrition rnges or the low rtes re - 00~00 μl h -, - 00~00 μl h -, - 00~00 μl h -, - 500~00 μl h -, - 500~00 μl h -, - 500~00 μl h -, -C 00~500 μl h -, -E 00~700 μl h -, n -M 4000~000 μl h -. For quintuple-component triple emulsions, F - n F - re enzyl enzote oil phse with n without Sun re respectively, F -, F -, F -C n F -E re queous phses with methylene lue, F -M is enzyl enzote oil phse, n F 4-M is queous phse, s shown in Fig.4c. The vrition rnges or the low rtes re - 00~50 μl h -, - 00~00 μl h -, - 850~900 μl h -, - 700~800 μl h -, -C 00 μl h -, -E 0~400 μl h -, -M 00~4000 μl h - n 4-M 9000~000 μl h -. For sextuple-component triple emulsions, F - n F - re enzyl enzote oil phse with n without Sun re respectively, F - n F - re queous phse n queous phse with methylene lue respectively, F -, F -, F -C n F -E re enzyl enzote oil phses, n F 4-M is queous phse, s shown in Fig.5. The vrition rnges or the low rtes re - 0~400 μl h -, - 0~00 μl h -, - 400~000 μl h -, - 50~000 μl h -, - 700~00 μl h -, - 700~00 μl h -, -C 00~500 μl h -, -E 00~000 μl h - n 4-M 4000~0000 μl h -. Prt S. Results n iscussion S.. Flow-rte-epenent control over numer n rtio o ierent roplets in quruple-component oule emulsions For quruple-component oule emulsions, the inner re n trnsprent roplets re seprtely orme rom the rop mkers in ierent rnch chnnels, so the ormtion rte o ech kin o roplets cn e iniviully tune y chnging the relevnt low rtes, which S

results in regulr rry o re n trnsprent roplets with controlle rtio in the min chnnel, s shown in Fig.S.

roplet rry (Fig.S()). Brek-up in the intervls o perioic units les to co-encpsultion o two kins o roplets with controlle rtio t :.

respectively, with the rtio (R ) o the re roplets to trnsprent roplets ixe t : (Fig.S()).

Brek-up in the intervls o these perioic units results in quruple-component oule emulsions with R controlle t :, : n :, s shown in Fig.S(), (c) n (), respectively.

4 results in regulr rry o re n trnsprent roplets with controlle rtio in the min chnnel, s shown in Fig.S. When the ormtion rtes o two kins o roplets re equl, the re n trnsprent roplets rrnge in the min chnnel one y one, where every one re roplet n one trnsprent roplet mkes perioic unit o the regulr roplet rry (Fig.S()). Brek-up in the intervls o perioic units les to co-encpsultion o two kins o roplets with controlle rtio t :. By chnging the low rte o the outer lui, every one, two n three perioic units cn e encpsulte in oule emulsions, resulte in quruple-component oule emulsions contining two, our n six roplets respectively, with the rtio (R ) o the re roplets to trnsprent roplets ixe t : (Fig.S()). By incresing the ormtion rte o the re roplets, regulr rrys with more re roplets in every perioic unit cn e otine (Fig.S()-()). Brek-up in the intervls o these perioic units results in quruple-component oule emulsions with R controlle t :, : n :, s shown in Fig.S(), (c) n (), respectively. Similrly, increse in the ormtion rte o the trnsprent roplets les to regulr rrys with more trnsprent roplets in every perioic unit (Fig.S(e)-(g)), n perioic rek-up o these rrys results in quruple-component oule emulsions with R controlle t :, : n :, s shown in Fig.S(e), () n (g), respectively. Thereore, the numer n rtio o the encpsulte roplets with ierent contents cn e inepenently n precisely controlle y justing the low rtes o relevnt luis. Fig.S Schemtic igrm o controlle genertion o quruple-component oule emulsions. Brek-up o these regulr roplet rrys in the intervls o perioic units cn le to co-encpsultion o two ierent roplets with precisely controlle numer n rtio. S4

5 S.. Controlle genertion o quruple-component oule emulsions contining two kins o roplets with ierent sizes The size o roplet cn e tune y chnging the low rtes n/or inner the inner imeter ( i ) o the collection tue o rop mkers. We illustrte the controllility o our microluiic evice over the size o co-encpsulte roplets y generting quruple-component oule emulsions tht contin smller re roplets n lrger lue roplets (Fig.S4). Here we use rop mkers with ierent i in rnch chnnels to generte the smller re roplets n lrger lue roplets (Fig.). Also, the numer n rtio o these two ierent roplets cn e controlle y justment o the low rte. The numer o smller re roplets increses rom 0 to 5 while tht o lrger lue roplets keeps ixe t, resulte in controlle rtio o smller re roplets to lrger lue roplets chnging rom : to 5:, s shown in Fig.S4()-(). For genertion o quruple-component oule emulsions contining smller re roplets n lrger lue roplets, the inner luis F - n F - re enzyl enzote oil phse with n without Sun re respectively, F -, F -, F -C n F -E re queous phses, n F -M is soyen oil phse, s shown in Fig.. The vrition rnges or the low rtes re - 0~50 μl h -, - 50~750 μl h -, μl h -, μl h -, -C 500~800 μl h -, -E 00 μl h - n -M 4000~5000 μl h -. Fig.S4 Opticl microgrphs showing controlle prouction o quruple-component oule emulsions with the numer o smller re roplets incresing rom 0 to 5 n tht o lrger lue roplets eing ixe t. Scle r is 00 μm. S.. Inepenent control o connector n liqui extrctor over the size o the outer roplets in quruple-component oule emulsions S5

Besies oning the min chnnel with rnch chnnels, nother importnt unctionlity o connector lies in the justment o intervl istnce etween roplets in the min

To relize the encpsultion o two ierent roplets, it requires more continuous lui tht crries these ierent roplets to e snwiche, resulting in n incresing size

So, less continuous lui nees to e snwiche to relize the encpsultion o two ierent roplets, which results in ecresing size o the outer roplets (Fig.S5()).

Thereore, with comine unctionlities o connector n liqui extrctor, the size o outer roplets in quruple-component oule emulsions cn e inepenently n precisely

The istnce etween roplets cn e juste y chnging the low rtes o connector n liqui extrctor so s to tune the size o outer roplets. S.4.

6 Besies oning the min chnnel with rnch chnnels, nother importnt unctionlity o connector lies in the justment o intervl istnce etween roplets in the min chnnel. When we keep the other luis ixe, the only increse in the injecting low rte o connector les to n incresing istnce etween every two roplets. To relize the encpsultion o two ierent roplets, it requires more continuous lui tht crries these ierent roplets to e snwiche, resulting in n incresing size o the outer roplets (Fig.S5()). Similrly, the increse in the low rte o liqui extrctor les to ecresing istnce etween every two roplets. So, less continuous lui nees to e snwiche to relize the encpsultion o two ierent roplets, which results in ecresing size o the outer roplets (Fig.S5()). Note tht, ecuse the inner roplets re irst generte in rnch chnnels, chnge o the low rtes in min chnnel will not ect the size o these inner roplets. Thereore, with comine unctionlities o connector n liqui extrctor, the size o outer roplets in quruple-component oule emulsions cn e inepenently n precisely controlle. Fig.S5 Schemtic igrm showing the low-rte-epenent control over the size o outer roplets y connector () n liqui extrctor (). The istnce etween roplets cn e juste y chnging the low rtes o connector n liqui extrctor so s to tune the size o outer roplets. S.4. evelopment o preiction equtions or inner structures o quruple-component oule emulsions For quruple-component oule emulsions, the totl numer (N) o oth inner re n trnsprent roplets is controlle y mtching the ormtion rtes o inner re ( - ) n S

7 trnsprent roplets ( - ) with tht o the outer roplets ( ). Accoring to mss conservtion, the ormtion rte o ech roplet cn e escrie s ollows: (S) (S) (S) Where i-j is the low rte o lui F i-j ; is the sum o -, -, -, -, -C n -E ; i is the roplet imeter (s shown in Fig.). For ixe evice imensions ( i ) n solution conitions, the roplet imeter ( i ) in coxil low epens on the velocity o the surrouning low in the ripping regime [S], which cn e escrie s ollows: (S4) (S5) M (S) Where coeicients i n i re the slopes n intercepts o these liner reltions [S]. Bse on Equtions (S) to (S), we cn quntittively preict the vlue o N using the ollowing eqution: ( ) ( ) ( ) ( ) ( ) ( ) M N (S7) The rtio (R ) o inner re roplets to trnsprent roplets is etermine y the numer o inner re n trnsprent roplets encpsulte in the oule emulsions, which cn e seprtely controlle y justing - n -. Thereore, we cn quntittively etermine the vlue o R using the ollowing eqution: R (S8) S7

8 For ixe evices n emulsion systems, i, i n i re constnt, so these equtions or preiction o inner structure llow us to esign multicomponent multiple emulsions with esire internls through ine justment o the low rtes. Moreover, preiction equtions or higher-orer multicomponent multiple emulsions cn e urther evelope ccoring to the mss conservtion o ech lui phse. Reerences [S] L. Y. Chu, A. S. Ut, R. K. Shh, J. W. Kim n. A. Weitz, Angew. Chem. Int. E., 007, 4, S8

Instantaneous Rate of Change of at a :

Instantaneous Rate of Change of at a : AP Clculus AB Formuls & Justiictions Averge Rte o Chnge o on [, ]:.r.c. = ( ) ( ) (lger slope o Deinition o the Derivtive: y ) (slope o secnt line) ( h) ( ) ( ) ( ) '( ) lim lim h0 h 0 3 ( ) ( ) '( ) lim