基于酸-碱动态化学的超支化聚赖氨酸的合成
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摘要
报道了离子型单体e-四氟硼酸盐-L-赖氨酸-N-羧酸酐(NH3BF4-Lys NCA)的合成,其化学结构和纯度采用傅里叶变换红外光谱(FTIR)、核磁共振氢谱(1H-NMR)、碳谱(13C-NMR)、氟谱(19F-NMR)和飞行时间质谱(TOF-MS)进行了确认.在大于20oC时,单体中的胺基氟硼酸盐动态解离出e-胺基,原位转化为AB*型引发单体(inimer-NCA),一锅法生成了超支化聚赖氨酸氟硼酸盐.产物经脱盐处理,得到了支化度为0.34~0.53的超支化聚赖氨酸.在25~55oC聚合温度内,离子单体的开环聚合符合一级动力学,表观速率常数kp,obs从25oC的0.01 h~(-1)逐渐增大到55oC的0.11 h~(-1).采用异核单量子相干谱(1H-13C HSQC)、傅里叶变换离子回旋共振质谱(FTICR-MS)和FTIR对超支化聚合物的结构和聚合机理进行了解析.
Novel Ne-(tetrafluoroboran ammonium)-L-lysine-N-carboxyanhydride(NH_3BF_4-Lys NCA) was synthesized for the first time and fully characterized by Fourier transform infrared spectroscopy(FTIR), nuclear magnetic resonance spectroscopy(1 H-NMR, 13 C-NMR, 19 F-NMR) and time of flight mass spectroscopy(TOF-MS). When the polymerization was conducted at 20 oC, the deactivated NH_3BF_4-Lys NCA does not change within 110 h, implying no polymerization occurred. However, the ionic monomer at 25 oC dynamically dissociates and is transformed into an activated AB* inimer type of NCA containing a primary e-amine(i.e., inimer-NCA), which then triggers ring-opening polymerization(ROP) to produce hyperbranched polylysines salts in one-pot. The ROP of NH_3BF_4-Lys NCA at 25 oC to 55 oC 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 b-turn secondary conformation(about 70%) in solid state, as characterized by FTIR. With the polymerization temperature increased from 25 oC to 55 oC, 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 e-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(1 H-13 C HSQC) confirms that a cyclic dimer is mainly formed from the two NH_3BF_4-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 NH_3BF_4-Lys NCA directly polymerizes itself to generate the hyperbranched polymers without forming a cyclic dimer center.
Novel Ne-(tetrafluoroboran ammonium)-L-lysine-N-carboxyanhydride(NH_3BF_4-Lys NCA) was synthesized for the first time and fully characterized by Fourier transform infrared spectroscopy(FTIR), nuclear magnetic resonance spectroscopy(1 H-NMR, 13 C-NMR, 19 F-NMR) and time of flight mass spectroscopy(TOF-MS). When the polymerization was conducted at 20 oC, the deactivated NH_3BF_4-Lys NCA does not change within 110 h, implying no polymerization occurred. However, the ionic monomer at 25 oC dynamically dissociates and is transformed into an activated AB* inimer type of NCA containing a primary e-amine(i.e., inimer-NCA), which then triggers ring-opening polymerization(ROP) to produce hyperbranched polylysines salts in one-pot. The ROP of NH_3BF_4-Lys NCA at 25 oC to 55 oC 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 b-turn secondary conformation(about 70%) in solid state, as characterized by FTIR. With the polymerization temperature increased from 25 oC to 55 oC, 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 e-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(1 H-13 C HSQC) confirms that a cyclic dimer is mainly formed from the two NH_3BF_4-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 NH_3BF_4-Lys NCA directly polymerizes itself to generate the hyperbranched polymers without forming a cyclic dimer center.
引文
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18 Li P,Dong C M.ACS Macro Lett,2017,6(3):292-297
19 Vacogne C D,Schlaad H.Chem Commun,2015,51(86):15645-15648
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21 Kricheldorf H R,Lossow C V,Schwarz G.Macromolecules,2005,38(13):5513-5518
22 Wang W Y,Chen,L.J Appl Polym Sci,2007,104(3):1482-1486
23 Wang W X,Zheng Y,Roberts E,Duxbury C J,Ding L F,Irvine D J,Howdle S M.Macromolecules,2007,40(20):7184-7194
24 Parzuchowski P G,Grabowska M,Tryznowski M,Rokicki G.Macromolecules,2006,39(21):7181-7186
25 Z??J,Fan J W,He X,Zhang S Y,Wang H,.Wooley K L.Macromolecules,2013,46(10):4223-4226
26 Scholl M,Nguyen T Q,Bruchmann B,Klok H A.J Polym Sci,Part A:Polym Chem,2007,45(23):5494-5508
27 Zelzer M,Heise A.Polym Chem,2013,4(13):3896-3904
28 Fan J W,Zou J,He X,Zhang F W,Raymond J E,Wooley K L.Chem Sci,2014,5(1):141-150
29 Kotharangannagari V K,Sánchez-Ferrer A,Ruokolainen J,Mezzenga R.Macromolecules,2012,45(4):1982-1990
30 Kong J L,Yu S N.Acta Bioch Bioph Sin,2007,39(8):549-559
31 Tao Y H,Chen X Y,Jia F,Wang S X,Xiao C S,Cui F C,Li Y Q,Bian Z,Chen X S,Wang X H.Chem Sci,2015,6(11):6385-6391
32 Ball J B,Alewood P F.J Mol Recognit,1990,3(2):55-64
33 Huesmann D,Birke A,Klinker K,Turk S,Rader H J,Barz M.Macromolecules,2014,47(3):928-936
34 Wolf F K,Frey H.Macromolecules,2009,42(24):9443-9456
35 Zhao T Y,Zheng,Y,Poly J,Wang W X.Nat Commun,2013,4:1873-(16)(23)(23)(16)
2 Tao Youhua(陶友华).Acta Polymerica Sinica(高分子学报),2016,(9):1151-1159
3 Lu H,Wang J,Song Z Y,Yin L C,Zhang Y F,Tang H Y,Tu C L,Lin Y,Cheng J J.Chem Commun,2014,50(2):139-155
4 Deming T J.Chem Soc Rev,2015,116(3):786-808
5 Vacogne C D,Schlaad H.Chem Commun,2015,51(86(8)(25)15645-15648
6 Zhao W,Gnanou Y,Hadjichristidis N.Chem Commun,2015,51(17):3663-3666
7 Dimitrov I,Schlaad H.Chem Commun,2003,23:2944-2945
8 Conejos-Sánchez I,Duro-Castano A,Birke A,Barz M,Vicent M J.Polym Chem,2013,4(11):3182-3186
9 Kramer J R,Deming T J.Biomacromolecules,2010,11(12):3668-3672
10 Habraken G J,Peeters M,Dietz C H,Koning C E,Heise A.Polym Chem,2010,1(4),514-524
11 Pickel D L,Politakos N,Avgeropoulos A,Messman J M.Macromolecules,2009,42(20):7781-7788
12 Wang D L,Jin Y,Zhu X Y,Yan D Y.Prog Polym Sci,2017,64:114-153
13 Wang D L,Zhao T Y,Zhu X Y,Yan D Y,Wang W X.Chem Soc Rev,2015,44(12):4023-4071
14 Huang Y,Wang D L,Zhu X Y,Yan D Y,Chen R J.Polym Chem,2015,6(15):2794-2812
15 Rodríguez-Hernández J,Gatti M,Klok H A.Biomacromolecules,2003,4(2):249-258
16 Klok H A,Rodríguez-Hernández J.Macromolecules,2002,35(23):8718-8723
17 Chang X,Dong C M.Biomacromolecules,2013,14(9):3329-3337
18 Li P,Dong C M.ACS Macro Lett,2017,6(3):292-297
19 Vacogne C D,Schlaad H.Chem Commun,2015,51(86):15645-15648
20 Zhao W,Gnanou Y,Hadjichristidis N.Chem Commun,2015,51(17):3663-3666
21 Kricheldorf H R,Lossow C V,Schwarz G.Macromolecules,2005,38(13):5513-5518
22 Wang W Y,Chen,L.J Appl Polym Sci,2007,104(3):1482-1486
23 Wang W X,Zheng Y,Roberts E,Duxbury C J,Ding L F,Irvine D J,Howdle S M.Macromolecules,2007,40(20):7184-7194
24 Parzuchowski P G,Grabowska M,Tryznowski M,Rokicki G.Macromolecules,2006,39(21):7181-7186
25 Z??J,Fan J W,He X,Zhang S Y,Wang H,.Wooley K L.Macromolecules,2013,46(10):4223-4226
26 Scholl M,Nguyen T Q,Bruchmann B,Klok H A.J Polym Sci,Part A:Polym Chem,2007,45(23):5494-5508
27 Zelzer M,Heise A.Polym Chem,2013,4(13):3896-3904
28 Fan J W,Zou J,He X,Zhang F W,Raymond J E,Wooley K L.Chem Sci,2014,5(1):141-150
29 Kotharangannagari V K,Sánchez-Ferrer A,Ruokolainen J,Mezzenga R.Macromolecules,2012,45(4):1982-1990
30 Kong J L,Yu S N.Acta Bioch Bioph Sin,2007,39(8):549-559
31 Tao Y H,Chen X Y,Jia F,Wang S X,Xiao C S,Cui F C,Li Y Q,Bian Z,Chen X S,Wang X H.Chem Sci,2015,6(11):6385-6391
32 Ball J B,Alewood P F.J Mol Recognit,1990,3(2):55-64
33 Huesmann D,Birke A,Klinker K,Turk S,Rader H J,Barz M.Macromolecules,2014,47(3):928-936
34 Wolf F K,Frey H.Macromolecules,2009,42(24):9443-9456
35 Zhao T Y,Zheng,Y,Poly J,Wang W X.Nat Commun,2013,4:1873-(16)(23)(23)(16)