NMR determination of crystallinity for poly(ε-L-lysine)

被引:18
作者
Asano, Atsushi [1 ]
Tanaka, Chikako [1 ]
Murata, Yoshifurni [1 ]
机构
[1] Natl Def Acad, Dept Appl Chem, Kanagawa 2398686, Japan
关键词
crystallinity; C-13-T-1; H-1-T-2; solid-state C-13 NMR; poly(epsilon-l-lysine);
D O I
10.1016/j.polymer.2007.04.038
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Crystallinity of poly(epsilon-L-lysine) (epsilon-PL) was discussed by analyzing the differences in the H-1 spin-spin relaxation times (T-2(H)), the C-13 spin-lattice relaxation times (T-1(C)), and the C-13 NMR signal shapes between the crystalline and the non-crystalline phases. The observed H-1 relaxation curve (free induction decay followed by solid-echo method) showed the sum of Gaussian and exponential decays. Similarly, the observed C-13 relaxation curves obtained from the Torchia method were double-exponential. The C-13 NMR spectrum of epsilon-PL was divided into the narrow and the broad lines by utilizing the intrinsic differences in the H-1 spin-lattice relaxation times in the rotating-frame between them, which are attributed to the crystalline and the non-crystalline phases, respectively. Even though the crystallinity is obtained from the identical NMR measurements, the estimated values are different with each other. The crystallinity estimated from the T-2(H) differences was 75.8 +/- 0.1% at 333 K and 60.7 +/- 0.4% at 353 K. From the T-1(C) differences, the value was estimated to be 62 +/- 11%. Furthermore, the value estimated from the NMR signal separation was 54 +/- 5%. In this study we have explained these discrepancies by the difference in susceptibility among the experiments for the inter-phase, which exists in-between the crystalline and the amorphous phases. Furthermore, the estimated crystallinity was ascertained by the X-ray diffraction experiment. (C) 2007 Elsevier Ltd. All rights reserved.
引用
收藏
页码:3809 / 3816
页数:8
相关论文
共 15 条
[1]   HETERONUCLEAR DECOUPLING IN ROTATING SOLIDS [J].
BENNETT, AE ;
RIENSTRA, CM ;
AUGER, M ;
LAKSHMI, KV ;
GRIFFIN, RG .
JOURNAL OF CHEMICAL PHYSICS, 1995, 103 (16) :6951-6958
[2]  
GERSTEIN BC, 1986, HIGH RESOLUTION NMR, pCH9
[3]   Primary and secondary crystallization processes of poly(ε-caprolactone)/styrene oligomer blends investigated by pulsed NMR [J].
Ikehara, T ;
Nishi, T .
POLYMER, 2000, 41 (21) :7855-7864
[4]  
KITAMARU R, 1984, KOBUNSHI KOTAI KOUZO, V17, pCH6
[5]   Structural investigation of microbial poly(ε-L-lysine) derivatives with azo dyes by solid-state 13C and 15N NMR [J].
Maeda, S ;
Mori, T ;
Sasaki, C ;
Kunimoto, KK ;
Kuwae, A ;
Hanai, K .
POLYMER BULLETIN, 2005, 53 (04) :259-267
[6]   Characterization of microbial poly (ε-L-lysine) by FT-IR, Raman and solid state 13C NMR spectroscopies [J].
Maeda, S ;
Kunimoto, KK ;
Sasaki, C ;
Kuwae, A ;
Hanai, K .
JOURNAL OF MOLECULAR STRUCTURE, 2003, 655 (01) :149-155
[7]   Microbial synthesis of poly(ε-lysine) and its various applications [J].
Shih, IL ;
Shen, MH ;
Van, YT .
BIORESOURCE TECHNOLOGY, 2006, 97 (09) :1148-1159
[8]  
STROBL GR, 1996, PHYS POLYM, pCH4
[9]   REAL-TIME MEASUREMENT OF CRYSTALLIZATION PROCESS OF POLYMERS BY PULSED NUCLEAR-MAGNETIC-RESONANCE [J].
TANAKA, H ;
NISHI, T .
JOURNAL OF APPLIED PHYSICS, 1986, 59 (05) :1488-1492