Supporting Information

A facile method to incorporate tetraphenylethylene into polymeric amphiphiles: high emissive nanoparticles for cell-imaging

Lan Ding,a Shixin Zhou,b Dahua Li,a Chengfeng Wu,a Yuzhi Xing,a and Bo Song*a

a. Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China.

Email: songbo@suda.edu.cn

b. Department of Cell Biology, School of Basic Medical Sciences, Peking University Health Science Center, Beijing 100191, China.

1. Materials and Characterization

4-methylbenzophenone, n-butyllithium (n-BuLi), 2,2’-bipyridyldisulfide, benzoyl peroxide (BPO), phthalimide potassium salt were bought from J&K China Chemical Co., Ltd. Diphenylmethane was purchased from TCI (Shanghai) Development Co., Ltd. p-Toluenesulfonic acid (p-TSA) was bought from Sun Chemical Technology (Shanghai) Co., Ltd. N-bromosuccinimide (NBS) was purchased from Ark Pharm, Inc. Hydrazine hydrate (N2H4·H2O) was bought from Jiangsu Yonghua Fine Chemistry Co., Ltd. Anhydrous MgSO4, anhydrous NH4Cl, NaOH, NaCl and all solvents were purchased from Sinopharm Chemical Reagent Company (China). Gel permeation chromatography (GPC) analysis was conducted on a TOSOH HLC-8320 with THF as the eluent.

Fig. S1 1H NMR spectrum of PFPA in CDCl3.

Fig. S2 19F NMR spectrum of PFPA in CDCl3.

Fig. S3 GPC trace of PPFPA, the unit of the molecular weight showing in the GPC trace is g mol-1.

2. The synthesis of TPE-NH2

2.1. Compound A

After diphenylmethane (8.0 g, 47.5 mmol) was dissolved in dry THF (60 mL) under N2 atomosphere, the temperature of the solution decrease to 0 °C and n-BuLi (18.9 mL) was dropwise added to the solution with syringe. After the solution was stirred at 0 °C for 1 h, 4-methylbenzophenone (9.0 g, 51.5 mmol) was added into the reaction mixture. Since then, the solution was continuously stirred at room temperature for 6 h. The unreacted n-BuLi was quenched with saturated NH4Cl solution slowly. The crude product was extracted with dichloromethane and organic phase was collected. The collected product was concentrated in high vacuum condition and could be used in the next step without any other purification.

Fig. S4 The synthetic route of TPE-NH2

The collected product and p-TSA (1.0 g, 5.8 mmol) were dissolved in toluene (100 mL) and refluxed at 120 °C for 12 h. Upon cooling down, the mixture was extracted by dichloromethane. The organic layer was concentrated and purified by a silica gel column chromatography with petroleum ether/ethyl acetate (50/1, v/v) as eluent to get the white solid product A (Yield, 50.1%). 1H NMR (400 MHz, CDCl3, δ): 7.15–7.06 (m, 9H), 7.06–6.97 (m, 6H), 6.90 (s, 4H), 2.25 (s, 3H).

Fig. S5 1H NMR spectrum of compound A in CDCl3.

2.2. Compound B

Compound A (5.3 g, 15.3 mmol), NBS (3.0 g, 16.9 mmol) and BPO (75 mg, 0.3 mmol) were dissolved in CCl4 (70 mL) and refluxed for 24 h. The product was concentrated and purified with column chromatography with petroleum ether/ethyl acetate (50/1, v/v) as eluent to obtain white solid powder B (Yield, 85.5%). 1H NMR (400 MHz, CDCl3, δ): 7.15–7.06 (m, 11H), 7.04–6.97 (m, 8H), 4.42 (s, 2H).

Fig. S6 1H NMR spectrum of compound B in CDCl3.

2.3. Compound C

A solution of compound B (6.0 g, 14.1 mmol), phthalimide potassium salt (3.1 g, 16.7 mmol) in DMF (50 mL) was stirred at room temperature for 12 h. After adding CHCl3 (100 mL) into the solution, the solution was washed by 0.2 M NaOH and saturated NaCl aqueous solution, respectively. The solution was dried over anhydrous MgSO4 and condensed. Then, the crude product was purified by column chromatography on silica gel with petroleum ether/dichloromethane (50/1, v/v) as eluent (Yield, 90.5%). 1H NMR (400 MHz, CDCl3, δ): 7.87–7.82 (m, 2H), 7.73–7.67 (m, 2H), 7.12–7.03 (m, 11H), 7.03–6.92 (m, 8H), 4.75 (s, 2H).

Fig. S7 1H NMR spectrum of compound C in CDCl3.

3.4. TPE-NH2

Compound C (6.4 g, 13.0 mmol) and N2H4·H2O (80 wt% in H2O, 8 mL) was added in the mixture of THF (100 mL) and C2H5OH (20 mL) and continuously refluxed for 12 h. After removing the solvent, the concentrated product was chromatographed on silica gel column chromatography using dichloromethane/methanol (10/1, v/v) as eluent (Yield, 69.3%). 1H NMR (400 MHz, CDCl3, δ): 7.12–7.05 (m, 11H), 7.03–6.96 (m, 8H), 3.87 (s, 2H).

Fig. S8 1H NMR spectrum of TPE-NH2 in CDCl3.

Fig. S9 The emission spectra of PAF in aqueous solution at different concentrations.

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