SUPPLEMENTARY INFORMATION Poly(vinylmine) Microgels: ph-responsive Prticles with High Primry Amine Contents Sineent Thioonro, Cory Berkln, Amir H. Milni, Rein Ulijn c n Brin R. Suners, * Polymer Science Reserch Group, Mterils Builing, School of Mterils, The University of Mnchester, Grosvenor Street, Mnchester, M 7HS, U.K. Deprtment of Chemicl n Petroleum Engineering n Deprtment of Phrmceuticl Chemistry, The University of Knss, Lwrence, Knss 6647, US. c Deprtment of Pure n Applie Chemistry/WestCHEM, University of Strthclye, Ctherl Street, Glsgow G XL, UK NVEE synthesis n chrcteristion NVEE is potentilly importnt ifunctionl monomer ecuse it cn e lkli-hyrolyse without cleving the ether linkge etween crosslinking junctions. The prouct ws conveniently prepre in multigrm qunitities (See Experimentl Section). The synthetic metho employe is epicte in Scheme S. Scheme S. Depiction of metho use to synthesize NVEE. The mesure (n expecte) %C, %H n %N vlues from elementl nlysis for NVEE were 56. % (56.6 %), 8. % (7.6 %) n 3.4 % (3. %), respectively. This greement shows the prouct cn e consiere compositionlly pure. The H NMR spectrum of NVEE is shown in Fig.
S(). The pek positions mtch those reporte erlier y Shi et l. For comprison, the spectrum for s-supplie NVF is shown in Fig. S(). For NVF there re two environments for the hyrogen ttche to the mie ( n ) n the vinyl hyrogen closest to the nitrogen tom ( n ) (Fig. S()). These re scrie to 3-4 trns n cis isomers. From our spectrl integrtions for NVF thns-to-cis molr rtio ws 3:. This is the sme rtio reporte y White et l. 4 for NVF. In the cse of NVEE (Fig. S()) there re lso two environments for the hyrogen ttche to the mie ( n ) n the vinyl hyrogen closest to the nitrogen tom ( n ). The rtio of the integrte res for ns / n ns / re oth to. Accoringly, the H NMR t show tht the proportion of trns-to-cis species for s me NVEE is :. The rtio of trns to cis ws significntly smller for NVEE compre to NVF. We speculte tht th isomer is fvoure ecuse it mximises seprtion of the unpire oxygen electrons (from C=O) n the hyrogen toms (lelle s f ) in the CH groups from the ether linkge.
3 cis * f trns f f () 9 8 7 6 5 4 3 Chemicl shift / ppm cis trns () 9 8 7 6 5 4 3 Chemicl shift / ppm Fig. S. H NMR spectrum of () NVEE n () NVF. The sterisk inictes solvent (CHCl 3 ) pek. NVEE n NVF exist s mixtures of cis n trns isomers. The FTIR spectrum for NVEE is shown in Fig. S. The spectrum for NVF is shown for comprison The spectr show tht reltive heights of the ns ue to the vinyl groups 5 (63 cm - ) n tht of the NHC(=O)H stretch (68 cm - ) re similr for NVEE n NVF. The key ifference etween the spectr is the loss of stretches ssocite with NH groups for the NVEE system. The NVEE spectrum oes not hve the mie II n (5 cm - ), the N-C-H ening moe t 6 38 cm -, n the N-H n t 36 cm -. Our prouct i not contin resiul NVF. Furthermore, there is new pek for NVEE t 9 cm -. This is scrie to n ether-type n 7 (CH -O-CH ).
4 NVEE NVF 68 NVEE NVF Asornce / u 36 Asornce / u 63 5 9 38 38 () 34 3 Wvenumer / cm - 6 () 8 6 4 Wvenumer / cm - 8 Fig. S FTIR spectr of NVEE n NVF. Key positions for the spectr re inicte. Tle S. Elementl t for the microgels. Coe %C %H %N PNVF 45. 7.9 7. PNVF-4NVEE 47. 7.9 7. PNVF-9NVEE 48.6 7.8 7. PNVF-3NVEE 46.9 7.6 6. PVAM 45.. 4.3 PVAM-4BEVAME 4.7 9.4 9.9 PVAM-9BEVAME 43..4.6 PVAM-3BEVAME 43..3.3 From ref.8.
5 Fig. S3. Opticl microscopy imges of PNVF prticles () eposite on glss microscope slie from ethnol n () 5 minutes fter ethnol h evporte. The prticles h egun to spre n colesce in ir.. 36 PNVF PNVF-4NVEE PNVF-3NVEE. PNVF PNVF-4NVEE PNVF-3NVEE 65.5 Asornce.5 Asornce 54 -.5 -.5 -. 38 () 34 3 Wvenumer / cm - 6 -. 8 () 6 4 Wvenumer / cm - 8 Fig. S4 FTIR spectr of PNVF n PNVF-xNVEE prticles.
6..5 ph = 4 ph = 7 ph = h / m. Q.5 (). 4 6 8 4 x () 4 6 8 4 x 6 Moility / -8 m V - s - 5 4 3 4 6 8 4 (c) x Fig. S5 Vrition of () hyroynmic imeter, () nominl swelling rtio n (c) electrophoretic moility for PVAMxBEVAME microgels with x. The lines re guies for the eye. References. Z. Mohmmi, A. Cole, n C. Berkln. J. Phys. Chem. C. 9, 3, 765.. L. Shi, n C. Berkln. Mcromolecules 7, 4, 4635. 3. L. Shi, K. A. Bouch Lee, J. T. Henssler, E. J. Beckmn, n T. M. Chpmn. J. Polym. Sci. A., Polym. Chem. 4, 4, 4994. 4. L. A. White, C. E. Hoyle, S. Jonsson, n L. J. Mthis. Designe Mon. Polym. 5, 8, 97. 5. M. Yng, C. Liu, Z. Li, G. Go, n F. Liu. Mcromolecules, 43, 645. 6. J. S. Kwitkowski, n J. Leszczynski. J. Molec. Struct. 993, 97, 77. 7. R. C. West, M. J. Astle, n W. H. Beyer (985) CRC Hnook of Chemistry n Physics, 65 e., CRC, Boc Rton. 8. S. Thioonro, F. Cellesi, R. V. Ulijn, n B. R. Suners. Lngmuir, 8, 57.