Supporting Information
Facile Synthesis of Thermosensitive Functional Polyaspartamide Derivatives by
Click Chemistry
Guangyan Zhang1,2, Yunti Zhang1, Yanfeng Chu1, Yingying Ma1, Renxi Zhuo1, Xulin Jiang1,*
1
Key Laboratory of Biomedical Polymers of Ministry of Education & Department of Chemistry, Wuhan
University, Wuhan 430072, P.R. China
2
Hubei Provincial Key Laboratory of Green Materials for Light Industry, Hubei University of Technology,
Wuhan 430068, P.R. China
Correspondence to: Xulin Jiang
Tel.: +86-27-68755200; fax: +86-27-68754509.
E-mail: xljiang@whu.edu.cn
Synthesis of phenethyl prop-2-ynyl carbonate [PPA-PEA]
Activated alcohol phenylethyl ester of carbonyl imidazole (PEA-CI) was synthesized according to our
previous work.1 Propargyl alcohol (1.12 g, 20.0 mmol) dissolved in 5 mL dichloromethane was slowly
dropped into a solution of PEA-CI (2.16 g, 10.0 mmol) in dichloromethane (20 mL). 4Dimethylaminopyridine (244 mg, 2.0 mmol) was added as catalyst. Next, the mixture was left to react at
room temperature for 24 h. The resulting solution was washed with water (3 times). The organic phase
was dried over anhydrous MgSO4. After filtration, the organic solvent was removed using a rotary
evaporator to obtain crude product. Then, crude product was further purification to remove residual 4dimethylaminopyridine and obtained light yellow liquid product (1.0 g, yield: 81%). The 1H NMR and FTIR
spectra of PPA-PEA were shown in Figure S1 and S2.
FIGURE S1. 1H NMR spectrum of PPA-PEA in CDCl3.
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FIGURE S2. FTIR spectrum of PPA-PEA on NaCl plate.
Synthesis of prop-2-yn-1-yl (3-(1H-imidazol-1-yl)propyl)carbamate [PPA-IMZ]
The propargyl ester of carbonyl imidazole (PPA-CI) was synthesized according to our previous work.2
N-(3-Aminopropyl)-imidazole (2.5 g, 20.0 mmol) dissolved in 10 mL dichloromethane was slowly
dropped into a solution of PPA-CI (1.5 g, 10.0 mmol) in dichloromethane (15 mL). Next, the mixture was
left to react at room temperature for 24 h. The resulting solution was washed with water (3 times). The
organic phase was dried over anhydrous MgSO4. After filtration, the organic solvent was removed using
a rotary evaporator to yield a yellow liquid of prop-2-yn-1-yl (3-(1H-imidazol-1-yl)propyl)carbamate
(PPA-IMZ) (1.5 g, yield: 72%). The 1H NMR and FTIR spectra of PPA-IMZ were shown in Figure S3 and S4.
FIGURE S3. 1H NMR spectrum of PPA-IMZ in CDCl3.
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FIGURE S4. FTIR spectrum of PPA-IMZ on NaCl plate.
FIGURE S5. P(Asp-Az)56-HPA dissolved in water at 4oC was clear and it became turbidious with a high
temperature above the cloud point (2 mg/mL).
FIGURE S6. Temperature dependence of the light scattering intensity of P(Asp-Az)56-HPA (2 mg/mL) in
water in the heating processes by DLS.
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FIGURE S7. FTIR spectra of P(Asp-Az)39-HPA and P(Asp-Az)39-HPA-IMZ-3 in KBr.
FIGURE S8. Temperature dependence of the light scattering intensity of P(Asp-Az)39-HPA-PEA-1 in water
by DLS in the heating processes (2 mg/mL).
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FIGURE S9. pH dependence of light transmittance of P(Asp-Az)39-HPA-IMZ-2 (1 mg/mL) in aqueous
solution on pH increasing and decreasing processes. The measurement was performed by UV/vis at 500
nm.
Reference
1. Y. Ma, X. Jiang, R. Zhuo, Mater. Lett. 2014, 121, 78-80.
2. X. L. Jiang, M. C. Lok, W. E. Hennink, Bioconjugate Chem. 2007, 18, 2077-2084.
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