Swelling and Mechanical Properties of Hydrogels Composed of. Binary Blends of Inter-linked ph-responsive Microgel Particles

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1 Eletroi Supplemetry Mteril (ESI) for Soft Mtter. This jourl is The Royl Soiety of Chemistry 205 SUPPLEMENTARY INFRMATIN Swellig Mehil Properties of Hyrogels Compose of Biry Bles of Iter-like ph-resposive Mirogel Prtiles Amir H. Mili, *, Je Brmhill, Athoy J. Freemot Bri R. Suers, * Polymer Siee Reserh Group, Shool of Mterils, Uiversity of Mhester, Grosveor Street, Mhester, M3 9PL, U.K. Gelexir Helthre Lt, C/o- Wr Hwy, The servtory, Chpel Wlks, UK, M2 HL. Regeertive Meiie, Developmetl Biomeiie Reserh Group, Shool of Meiie, Stopfor Builig, Uiversity of Mhester, xfor Ro, Mhester, M3 9PT Glyiyl oligo(ether ester) rylte hrteristio Glyiyl oligo(ether ester) rylte (GE) ws prepre from HE (Fig.S) is reporte here for the first time to our kowlege. The first step ws sythesis of hyroxyl oligo(ether ester) rylte (HE), whih followe the metho of Gis et l. ur GE esig strtegy ivolve hievig le etwee two opposig effets. A high ws expete to give loger str legths etwee iter-like MGs irese utility. However, high oul lso use the viyl groups to eome urie withi ether ester his restrit the imoleulr free-ril ouplig require to hieve iter-likig of eighourig MG prtiles. ligomeri GE ws the speifi trget for this work. As oligomeristio ivolve step-growth proess, vi Mihel itio, lower moleulr weight prouts (oligomers) oul e otie t lower oversios, this pproh ws use to hieve low ether ester hi legth () 2. The oitios use here (Fig. S) gve optimum oversio vlue of for GE s juge y the mehil properties of the gels (See Results Disussio setio). The H NMR spetr for HE GE (Fig.S) were use to etermie vlues for. For HE, the ppere of the H resoe with shift of 2.6 ppm, whih h the sme itegrte re s

2 2 eh of the viyl resoes (, ppm), together with the methylee proto sigls (, 3.6 ppm), ele e group lysis to lulte vlue for of 6 for HE (Tle. S). Appere of ew peks i the rge of ppm (f g ) ofirme the presee of the epoxie group i GE (Fig.S). By itegrtig the totl sigl res for the three viyl protos (A ), lso methylee protos i repet uit (A ), the vlue of usig for GE ws lulte usig: = 3A 2A () The oversio of glyiylistio ( G ) for GE ws lulte y etermiig the epoxie pek re (A f ) equtio 2. G = 3A f A (2) The vlues for G for GE were fou to e 7 20 mol.%, respetively. The G vlue ws kept low to miimise hi growth urig the glyiylistio retio euse oth proesses ourre simulteously s eviee y GPC t (elow). This met tht the fil prout osiste of mixture of GE (20 mol.%) HE (80 mol.%). Resiul HE ws remove urig the MG viyl futiolistio step (lter). GE HE h moomol size istriutios (Fig.S). A shift i the hromtogrm for GE towr higher moleulr weights ourre ompre to HE (Fig.S) whih is i greemet with H NMR t (Tle S) is ue to oligomer growth. The vlues for M etermie for GE HE from GPC were higher th those etermie from H NMR t. Gis et l reporte muh higher ifferees etwee the M vlues etermie y GPC H NMR th oserve here. These isrepies my e ue to the ifferees etwee the hyroymi volumes oupie y GE HE the PMMA strs use here for GPC. We use the M vlues etermie from H NMR for this stuy.

3 3 H t Bu - K + HE H (26) (4) (2) H Br Cl KH * (3) H () () GE () * (4) (30) (6) e g 2 e f g,2 (3) g f (0.2) (0.2) () Fig. S. Sythesis hrteristio t of glyiyl oligo(ether ester) rylte. () Depitio of the metho use to prepre GE. () H NMR spetr for hyroxyl oligo(ether ester) rylte (HE) (upper) GE (lower). The umers i rkets show the itegrl vlues. For the spetrum of GE, the protos (e) (g 2 ) overlp. () GPC hromtogrms for HE GE. Fig. S2. Potetiometri titrtio t for viyl futiolise mirogels. () shows the first erivtive from the ph vs. NH itio t () shows the vritio of ph s futio of eutrlistio. The mxim for () were use to etermie the MAA otets.

4 GMA = 0.0 G', G" (kp) ().0 GMA = t 0.0 () Fig S3. Physil gel mehil properties stuie y frequey-sweep ymi rheology. () shows ymi storge (G, lose symols) loss (G, ope symols) gist frequey mesure usig ifferet GMA vlues (show). The y-xis sle is the sme for ll of the grphs. () shows the vritio of t with frequey G' (kp) G" (kp) / % Fig. S4. Vritio of ymi storge (G, lose symols) loss (G, ope symols) gist stri ( ) mesure usig ifferet GMA vlues (show) for GE/GMA physil gels. The lege shows vlues for GMA. Tle S. Chrteristio t for HE GE NMR GPC me M (g/mol) M (g/mol) PD HE GE

5 5 Referees. M. Gis, A. Korytkowsk-Wlh. Polymer Bulleti 2003, 5, A. J. Peok, A. Clhou (2006) Polymer hemistry : properties pplitios, Hser, Muih.