Citation: Li Pan, Dong Chang-ming. Synthesis of Hyperbranched Polylysine Based on Acid-base Dynamic Chemistry[J]. Acta Polymerica Sinica, ;2018, (1): 63-71. doi: 10.11777/j.issn1000-3304.2018.17160 shu

Synthesis of Hyperbranched Polylysine Based on Acid-base Dynamic Chemistry

Li Pan ,
Dong Chang-ming ^,

School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240

Corresponding author: Dong Chang-ming, cmdong@sjtu.edu.cn
Received Date: 16 June 2017
Revised Date: 17 July 2017

Novel N_ε-(tetrafluoroboran ammonium)-L-lysine-N-carboxyanhydride (NH₃BF₄-Lys NCA) was synthesized for the first time and fully characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy(¹H-NMR, ¹³C-NMR, ¹⁹F-NMR) and time of flight mass spectroscopy (TOF-MS). When the polymerization was conducted at 20 ℃, the deactivated NH₃BF₄-Lys NCA does not change within 110 h, implying no polymerization occurred. However, the ionic monomer at 25 ℃ dynamically dissociates and is transformed into an activated AB* inimer type of NCA containing a primary ε-amine (i.e., inimer-NCA), which then triggers ring-opening polymerization (ROP) to produce hyperbranched polylysines salts in one-pot. The ROP of NH₃BF₄-Lys NCA at 25 ℃ to 55 ℃ in DMF solution conforms to first-order kinetics and the observed kinetic rate constant increases from 0.01 h^-1 to 0.11 h^-1, due to the enhanced dissociation kinetics of tetrafluoroboran ammonium. The resulting hyperbranched polylsines salts mainly exhibits a β-turn secondary conformation (about 70%) in solid state, as characterized by FTIR. With the polymerization temperature increased from 25 ℃ to 55 ℃, the degree of branching of the hyperbranched polylysines apparently decreases from 0.53 to 0.34, while the molar percentage of cyclic dimer units increases conversely from 6.4% to 11.5%. During the polymerization process, monomers, dimers and the resulting oligomers concomitantly dissociate to generate primary ε-amine, leading to an increasing initiator concentration coupled with a decreasing monomer concentration. By consequence, the molecular weight of the hyperbranched polymers cannot be adjusted by changing the polymerization temperature and the monomer concentration. However, the degree of branching and the molar percentage of cyclic dimer units within the hyperbranched polymers can be tuned to some extent by adjusting the polymerization temperature. Finally, both Fourier transform ion cyclotron resonance mass spectroscopy (FTICR-MS) and heteronuclear single quantum coherence spectroscopy (¹H-¹³C HSQC) confirms that a cyclic dimer is mainly formed from the two NH₃BF₄-Lys NCA monomers at initial stage, which further initiates ROP to produce the hyperbranched polymers according to the well-known normal amine mechanism. Meanwhile, a little amount of NH₃BF₄-Lys NCA directly polymerizes itself to generate the hyperbranched polymers without forming a cyclic dimer center.
- Hyperbranched polypeptide,
- Ionic NCA,
- Inimer,
- Secondary structure
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