One-Pot and Rapid Synthesis of Uniformed Silica Spheres. Via Mediation of Linear Poly(ethyleneimine)s and Dyes

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1 Supporting Information One-Pot and Rapid Synthesis of Uniformed Silica Spheres Via Mediation of Linear Poly(ethyleneimine)s and Dyes Ren-Hua Jin* and Jian-Jun Yuan Synthetic Chemistry Lab, Kawamura Institute of Chemical Research, 631 Sakado, Sakura, Chiba , Japan 1

2 Synthesis of Poly(ethyleneimine)s Typical Synthesis of S4-200 The four-armed star S4-200 was produced from hydrolysis of the corresponding poly(oxazoline) precursor in the presence of HCl. The precursor four-armed star poly(methyloxazoline) (PMOZ) was prepared by performing a ring-opening living polymerization of 2-methyl-2-oxazoline (MOX, Aldrich) in DMA (N,N- dimethylacetamide) using 1,2,4,5-tetrakis (bromomethyl)benzene (TKBB, Aldrich) as a initiator. Typically, TKBB (0.068 g, 0.15 mmol) was firstly added to a flask equipped with a three-way stop-cock and a magnetic bar, and the flask was vacuumed for 2 h and purged with dried N 2. Then, 10 ml of MOX (120 mmol) and 20 ml DMA were subsequently added by syringe under N 2 flow. The reaction mixture was first stirred at 60 o C for 1 h for dissolution of initiator, and then the polymerization was carried out at 100 o C for 24 h. The 1 H NMR measurement of a small amount of polymerization mixture in CDCl 3 showed that MOX completely converted into the corresponding polymer. After polymerization, the mixture was poured into ethyl acetate (500 ml) for precipitation. The obtained polymer was dried under vacuum at 60 o C. The polymerization degree of per arm was estimated to be 200 from quantitative polymerization by feeding ratio. GPC trace showed M w and M w /M n 1.48 relative to PEG/PEO standard using a solution of 0.1 M NaCl in MeOH/H 2 O (5/5 vol) as eluent. Five gram of the above star PMOZ was dissolved into 38 ml of 5 M HCl, and the mixture was stirred at 100 o C for 12 h. White precipitates (associated with HCl) appeared were filtered and washed by acetone. The obtained solid was dissolved into water and subsequently was dialyzed against an ammonia solution (ph = 11-12) for 3 days with changing the ammonia solution three times. The crystalline solid (free base) precipitated in the dialysis tube was washed with acetone, and then dried. Typically, this procedure resulted in hydrated crystalline PEI containing about wt% water estimated from TGA measurement. Synthesis of S4-50 According the same above method, a precursor four-armed star was synthesized by polymerization of MOX (30 mmol) with the initiator (TKBB, 0.15 mmol). The precursor (M w = 7600 and M w /M n = 1.54) was hydrolyzed and precipitated by the above method described in Typical Synthesis of S Synthesis of S6-200 According to the same above method, a precursor four-armed star was synthesized by polymerization of MOX (180 mmol) with initiator 1,2,3,4,5,6-hexakis(bromomethyl)benzene (HKBB, 0.15 mmol). The precursor (M w = and M w /M n = 1.52) was hydrolyzed and precipitated by the above method described in Typical Synthesis of S

3 Synthesis of S6-50 According to the same above method, a precursor four-armed star was synthesized by polymerization of MOX (45 mmol) with initiator 1,2,3,4,5,6-hexakis(bromomethyl)benzene (HKBB, 0.15 mmol). The precursor (M w = 8300 and M w /M n = 1.5) was hydrolyzed and precipitated by the above method described in Typical Synthesis of S Synthesis of PS-240 The details were described in Chem Commun (2005) Synthesis of L1560 The details were described in Chem Commun (2005)

4 Figures S1-S4 a b c Fig. S1. TEM images of silica spheres. a) spheres obtained by mediation of S4-200/TSPP; b) spheres obtained by mediation of S4-200 without TSPP; c) sectioned slices of the spheres shown in (a). 4

5 Fig. S2. SEM images of the silica spheres produced by mediation of S4-200 with incorporation of TCPP. Bottom is a magnified image of the top. 5

6 Fig. S3. UV-Vis spectra of the methanol solutions of S4-200/TSPP (left) and TSPPentrapped silica spheres dispersed in methanol (right). 6

7 a d b e c f Fig. S4. SEM images of the silicas obtained by mediation of 0.7 wt% S4-200 with association of different amount of H 3 PO 4 in medium of methanol/water (70/30 in volume). Molar ratio of EI unit/h 3 PO 4 were 15, 150 and 1200, respectively, for (a), (b) and (c). Images of (d), (e) and (f) were magnified images of (a), (b) and (c), respectively. 7