1.福建吉特瑞生物科技有限公司,福州 350001
2.中国医学科学院生物医学工程研究所,天津 300192
E-mail: zhangy@gtrbio.cn
E-mail: zhangqiq@126.com
收稿:2025-09-05,
录用:2025-10-10,
网络出版:2025-11-14,
纸质出版:2025-12-20
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张丽丹, 胡莎莎, 苏玉贤, 许任科, 张瑗, 张其清. 可降解聚(L-丙交酯-co-ε-己内酯)的合成及其在外周神经修复中的应用潜力. 高分子通报, 2025, 38(12), 1874–1886.
Zhang, L. D.; Hu, S. S.; Su, Y. X.; Xu, R. K.; Zhang, Y.; Zhang, Q. Q. Synthesis of biodegradable Poly(L-lactide-co-ε-caprolactone) and its potential application in peripheral nerve repair. Polym. Bull. (in Chinese), 2025, 38(12), 1874–1886.
张丽丹, 胡莎莎, 苏玉贤, 许任科, 张瑗, 张其清. 可降解聚(L-丙交酯-co-ε-己内酯)的合成及其在外周神经修复中的应用潜力. 高分子通报, 2025, 38(12), 1874–1886. DOI: 10.14028/j.cnki.1003-3726.2025.25.260.
Zhang, L. D.; Hu, S. S.; Su, Y. X.; Xu, R. K.; Zhang, Y.; Zhang, Q. Q. Synthesis of biodegradable Poly(L-lactide-co-ε-caprolactone) and its potential application in peripheral nerve repair. Polym. Bull. (in Chinese), 2025, 38(12), 1874–1886. DOI: 10.14028/j.cnki.1003-3726.2025.25.260.
以
L
-乳酸为原料合成
L
-丙交酯(
L
-LA)中间体,随后将
L
-LA与
ε
-己内酯(
ε
-CL)共聚,制备了聚(
L
-丙交酯-
co
-
ε
-己内酯) (PLCL)共聚物,并采用压延成型技术将其加工成膜。结果表明,不同投料比的PLCL共聚物具有相似的分子结构。随着
ε
-CL含量的增加,PLCL材料表现出“高分子量+低结晶度”的矛盾特性,其熔融温度和玻璃化转变温度降低,膜的刚性下降而柔韧性提高,体外降解速率加快。这种非常规变化规律表明,通过调节
L
-丙交酯与
ε
-己内酯的比例,可调控PLCL共聚物的分子量与结晶度,从而实现从“短期快速降解”到“长期稳定支撑” 的全周期性能调控。此外,PLCL膜具备降解周期可调性、柔韧可缝合性以及良好的神经细胞相容性,展现了其在神经修复领域良好的应用前景。
Employs
L
-lactic acid to synthesize the intermediate
L
-lactide (
L
-LA)
which was then polymerized with
ε
-caprolactone (
ε
-CL) to form a poly(
L
-lactide-
co
-
ε
-caprolactone) (PLCL) copolymer. The resulting copolymer was processed into a film using calendering technology
and the results indicated that the PLCL copolymers exhibited similar molecular structures across different feed ratios. As the
ε
-CL content increased
the PLCL copolymer exhibited contradictory characteristics of “high molecular weight+low crystallinity” accompanied by decreases in the melting temperature and glass transition temperature. PLCL films exhibit reduced rigidity
enhanced flexibility
and accelerated in vitro degradation rates. This unconventional variation pattern indicates that by adjusting the ratio of
L
-lactose to
ε
-caprolactone
the molecular weight and crystallinity of PLCL materials can be regulated
enabling full-cycle performance control from “short-term rapid degradation” to “long-term stable support”. Additionally
the adjustable degradation cycle
flexible suturability
and excellent neural cell compatibility of the PLCL membrane demonstrate its promising application prospects in the field of neural repair.
Gaudin, R. ; Knipfer, C. ; Henningsen, A. ; Smeets, R. ; Heiland, M. ; Hadlock, T . Approaches to peripheral nerve repair: generations of biomaterial conduits yielding to replacing autologous nerve grafts in craniomaxillofacial surgery . Biomed Res. Int. , 2016 , 2016 , 3856262 .
Han, Q. ; Guan, W. C. ; Sun, S. L. ; Zheng, T. T. ; Wu, L. L. ; Gao, H. X. ; Liu, Y. Q. ; Yang, Y. M. ; Li, G. C . Anisotropic topological scaffolds synergizing non-invasive wireless magnetic stimulation for accelerating long-distance peripheral nerve regeneration . Chem. Eng. J. , 2024 , 496 , 153809 .
Xue, J. J. ; Li, H. X. ; Xia, Y. N . Nanofiber-based multi-tubular conduits with a honeycomb structure for potential application in peripheral nerve repair . Macromol. Biosci. , 2018 , 18 ( 9 ), e1800090 .
Wang, J. ; Xiong, H. ; Zhu, T. H. ; Liu, Y. ; Pan, H. B. ; Fan, C. Y. ; Zhao, X. L. ; Lu, W. W . Bioinspired multichannel nerve guidance conduit based on shape memory nanofibers for potential application in peripheral nerve repair . ACS Nano , 2020 , 14 ( 10 ), 12579 – 12595 .
Vijayavenkataraman, S . Nerve guide conduits for peripheral nerve injury repair: a review on design, materials and fabrication methods . Acta Biomater. , 2020 , 106 , 54 – 69 .
Grinsell, D. ; Keating, C. P . Peripheral nerve reconstruction after injury: a review of clinical and experimental therapies . Biomed Res. Int. , 2014 , 2014 , 698256 .
Gu, X. S. ; Ding, F. ; Yang, Y. M. ; Liu, J . Construction of tissue engineered nerve grafts and their application in peripheral nerve regeneration . Prog. Neurobiol. , 2011 , 93 ( 2 ), 204 – 230 .
Yu, L. ; Bennett, C. J. ; Lin, C. H. ; Yan, S. ; Yang, J . Scaffold design considerations for peripheral nerve regeneration . J. Neural Eng. , 2024 , 21 ( 4 ), 041001 .
Gu, X. S. ; Ding, F. ; Williams, D. F . Neural tissue engineering options for peripheral nerve regeneration . Biomaterials , 2014 , 35 ( 24 ), 6143 – 6156 .
Parker, B. J. ; Rhodes, D. I. ; O’Brien, C. M. ; Rodda, A. E. ; Cameron, N. R . Nerve guidance conduit development for primary treatment of peripheral nerve transection injuries: a commercial perspective . Acta Biomater. , 2021 , 135 , 64 – 86 .
Jia, B. ; Huang, H. Y. ; Dong, Z. C. ; Ren, X. Y. ; Lu, Y. Y. ; Wang, W. Z. ; Zhou, S. W. ; Zhao, X. ; Guo, B. L . Degradable biomedical elastomers: paving the future of tissue repair and regenerative medicine . Chem. Soc. Rev. , 2024 , 53 ( 8 ), 4086 – 4153 .
Sanchez Rezza, A. ; Kulahci, Y. ; Gorantla, V. S. ; Zor, F. ; Drzeniek, N. M . Implantable biomaterials for peripheral nerve regeneration-technology trends and translational tribulations . Front. Bioeng. Biotechnol. , 2022 , 10 , 863969 .
Kehoe, S. ; Zhang, X. F. ; Boyd, D . FDA approved guidance conduits and wraps for peripheral nerve injury: a review of materials and efficacy . Injury , 2012 , 43 ( 5 ), 553 – 572 .
Hou, Y. J. ; Wang, X. Y. ; Wang, Y. Y. ; Chen, X. ; Wei, B. M. ; Zhang, J. T. ; Zhu, L. ; Kou, H. Z. ; Li, W. Y. ; Wang, H. B . Electrospun nanofibrous conduit filled with a collagen-based matrix (ColM) for nerve regeneration . Molecules , 2023 , 28 ( 22 ), 7675 .
Dai, W. F. ; Yang, Y. T. ; Yang, Y. M. ; Liu, W . Material advancement in tissue-engineered nerve conduit . Nanotechnol. Rev. , 2021 , 10 ( 1 ), 488 – 503 .
Şentürk, M. ; Çakır, M. ; Tekin, A. ; Küçükkartallar, T. ; Yıldırım, M. A. ; Alkan, S. ; Fındık, S . Comparison of primary repair and repair with polyglycolic acid coated tube in recurrent laryngeal nerve cuts (an experimental study) . Am. J. Surg. , 2020 , 219 ( 4 ), 632 – 636 .
Lasprilla, A. J. R. ; Martinez, G. A. R. ; Lunelli, B. H. ; Jardini, A. L. ; Filho, R. M . Poly-lactic acid synthesis for application in biomedical devices: a review . Biotechnol. Adv. , 2012 , 30 ( 1 ), 321 – 328 .
Shuai, C. J. ; Zan, J. ; Yang, Y. W. ; Peng, S. P. ; Yang, W. J. ; Qi, F. W. ; Shen, L. D. ; Tian, Z. J . Surface modification enhances interfacial bonding in PLLA/MgO bone scaffold . Mater. Sci. Eng. C , 2020 , 108 , 110486 .
Zarei, M. ; Shabani Dargah, M. ; Hasanzadeh Azar, M. ; Alizadeh, R. ; Mahdavi, F. S. ; Sayedain, S. S. ; Kaviani, A. ; Asadollahi, M. ; Azami, M. ; Beheshtizadeh, N . Enhanced bone tissue regeneration using a 3D-printed poly(lactic acid)/Ti 6 Al 4 V composite scaffold with plasma treatment modification . Sci. Rep. , 2023 , 13 ( 1 ), 3139 .
Malikmammadov, E. ; Tanir, T. E. ; Kiziltay, A. ; Hasirci, V. ; Hasirci, N . PCL and PCL-based materials in biomedical applications . J. Biomater. Sci. Polym. Ed. , 2018 , 29 ( 7-9 ), 863 – 893 .
Bauer, B. ; Emonts, C. ; Pitts, J. ; Buhl, E. M. ; Eschweiler, J. ; Hänsch, R. ; Betsch, M. ; Gries, T. ; Menzel, H . Topographically and chemically enhanced textile polycaprolactone scaffolds for tendon and ligament tissue engineering . Polymers , 2024 , 16 ( 4 ), 488 .
Ai, S. ; Gao, K. L. ; Huang, Z. H. ; Yu, W. G . One-step synthesis of lactide via separation-promoted catalytic self-transesterification reactions of lactates . Chem. Eng. Process. Process. Intensif. , 2024 , 205 , 109967 .
Abe, G. L. ; Sasaki, J. I. ; Katata, C. ; Kohno, T. ; Tsuboi, R. ; Kitagawa, H. ; Imazato, S . Fabrication of novel poly(lactic acid/caprolactone) bilayer membrane for GBR application . Dent. Mater. , 2020 , 36 ( 5 ), 626 – 634 .
Chu, J. ; Chen, L. ; Mo, Z. S. ; Bowlin, G. L. ; Minden-Birkenmaier, B. A. ; Morsi, Y. ; Aldalbahi, A. ; El-Newehy, M. ; Wang, W. ; Mo, X. M . An atorvastatin calcium and poly( L -lactide- co -caprolactone) core-shell nanofiber-covered stent to treat aneurysms and promote reendothelialization . Acta Biomater. , 2020 , 111 , 102 – 117 .
杨雪梅 , 郭泫华 , 何晓智 , 徐广强 , 王庆刚 . Zn(HMDS) 2 催化剂对丙交酯的开环聚合研究 . 高分子学报 , 2025 , 56 ( 3 ), 442 – 448 .
de Souza, J. R. ; Cardoso, L. M. ; de Toledo, P. T. A. ; Rahimnejad, M. ; Kito, L. T. ; Thim, G. P. ; Campos, T. M. B. ; Borges, A. L. S. ; Bottino, M. C . Biodegradable electrospun poly( L -lactide- co - ε -caprolactone)/poly-ethylene glycol/bioactive glass composite scaffold for bone tissue engineering . J. Biomed. Mater. Res. Part B Appl. Biomater. , 2024 , 112 ( 5 ), e35406 .
Xue, J. J. ; Wu, T. ; Dai, Y. Q. ; Xia, Y. N . Electrospinning and electrospun nanofibers: methods, materials, and applications . Chem. Rev. , 2019 , 119 ( 8 ), 5298 – 5415 .
Robinson, T. M. ; Hutmacher, D. W. ; Dalton, P. D . The next frontier in melt electrospinning: taming the jet . Adv. Funct. Mater. , 2019 , 29 ( 44 ), 1904664 .
Pohanka, M . D -l actic acid as a metabolite: toxicology, diagnosis, and detection . Biomed Res. Int. , 2020 , 2020 , 3419034 .
Aliev, G. ; Toms, R. ; Melnikov, P. ; Gervald, A. ; Glushchenko, L. ; Sedush, N. ; Chvalun, S . Synthesis of L -lactide from lactic acid and production of PLA pellets: full-cycle laboratory-scale technology . Polymers , 2024 , 16 ( 5 ), 624 .
Jeong, S. I. ; Kim, B. S. ; Lee, Y. M. ; Ihn, K. J. ; Kim, S. H. ; Kim, Y. H . Morphology of elastic poly( l -lactide-co-ε-caprolactone) copolymers and in vitro and in vivo degradation behavior of their scaffolds . Biomacromolecules , 2004 , 5 ( 4 ), 1303 – 1309 .
Fernández, J. ; Etxeberria, A. ; Sarasua, J. R . Synthesis, structure and properties of poly( L -lactide- co : capro-lactone) statistical copolymers . J. Mech. Behav. Biomed. Mater. , 2012 , 9 , 100 – 112 .
Zhang, M. Y. ; Chang, Z. H. ; Wang, X. F. ; Li, Q . Synthesis of poly( l -lactide- co - ε -caprolactone) copolymer: structure, toughness, and elasticity . Polymers , 2021 , 13 ( 8 ), 1270 .
Garkhal, K. ; Verma, S. ; Jonnalagadda, S. ; Kumar, N . Fast degradable poly( L -lactide- co -ε-caprolactone) microspheres for tissue engineering: synthesis, characteri-zation, and degradation behavior . J. Polym. Sci. A Polym. Chem. , 2007 , 45 ( 13 ), 2755 – 2764 .
D’Auria, I. ; Lamberti, M. ; Rescigno, R. ; Venditto, V. ; Mazzeo, M . Copolymerization of L -lactide and ε -caprolactone promoted by zinc complexes with phosphorus based ligands . Heliyon , 2021 , 7 ( 7 ), e07630 .
Darensbourg, D. J. ; Karroonnirun, O . Ring-opening polymerization of l -lactide and ε -caprolactone utilizing biocompatible zinc catalysts. random copolymerization of l -lactide and ε -caprolactone . Macromolecules , 2010 , 43 ( 21 ), 8880 – 8886 .
Lu, X. L. ; Cai, W. ; Gao, Z. Y. ; Tang, W. J . Shape memory effects of poly( L -lactide) and its copolymer with poly(ε-caprolactone) . Polym. Bull. , 2007 , 58 ( 2 ), 381 – 391 .
Jeon, O. ; Lee, S. H. ; Kim, S. H. ; Lee, Y. M. ; Kim, Y. H . Synthesis and characterization of poly(l-lactide)–poly(ε-caprolactone) multiblock copolymers . Macromolecules , 2003 , 36 ( 15 ), 5585 – 5592 .
Lu, X. L. ; Cai, W. ; Gao, Z. Y. ; Zhao, L. C . Shape memory property of poly( l -lactide-co- ɛ -caprolactone) copolymers . Mater. Sci. Eng. A , 2006 , 438 – 440 , 857 – 861 .
Feldman, A. ; Gonzalez, M. F. ; Marom, G . Transcrystallinity in surface modified aramid fiber reinforced nylon 66 composites . Macromol. Mater. Eng. , 2003 , 288 ( 11 ), 861 – 866 .
Liu, Z. Q. ; Wang, Y. Q. ; Wu, H. D. ; Li, H. M. ; Tang, L. C. ; Wang, G. ; Zhang, D. X. ; Yin, J. P. ; Miao, Y. G. ; Shi, Y. Q. ; Song, P. G. ; Xie, A. ; Huang, X. W. ; Gu, W. C. ; Mai, Y. W. ; Gao, J. F . Highly oriented bio-mimetic hydrogels by calendering . Adv. Sci. , 2025 , 12 ( 30 ), e04778 .
Giacobazzi, G. ; Rizzuto, M. ; Zubitur, M. ; Mugica, A. ; Caretti, D. ; Müller, A. J . Crystallization kinetics as a sensitive tool to detect degradation in poly(lactide)/poly( ε -caprolactone)/PCL- co -PC copolymers blends . Polym. Degrad. Stab. , 2019 , 168 , 108939 .
谷琳 , 朱钰婷 , 何家隆 , 朱惠豪 , 马玉录 , 谢林生 . 基于微纳层叠共挤的PLA/PCL可降解微层薄膜的制备及性能研究 . 中国塑料 , 2021 , 35 ( 11 ), 7 – 14 .
Matumba, K. I. ; Mokhena, T. C. ; Ojijo, V. ; Sadiku, E. R. ; Ray, S. S . Morphological characteristics, properties, and applications of polylactide/poly( ε -caprolactone) blends and their composites: a review . Macromol. Mater. Eng. , 2024 , 309 ( 8 ), 2400056 .
Huang, B. Y. ; Lai, P. B. ; Hua, H. M. ; Li, R. Y. ; Shen, X. ; Yang, X. Y. ; Zhang, P. ; Zhao, J. B . A copolyether with pendant cyclic carbonate segment for PEO-based solid polymer electrolyte . J. Power Sources , 2023 , 570 , 233049 .
Ann, W. ; Werner, H . The return of a forgotten polymer: polycaprolactone in the 21 st century . Prog. Polym. Sci. , 2010 , 35 ( 10 ), 1217 – 1256 .
Zuza, E. ; Ugartemendia, J. M. ; Lopez, A. ; Meaurio, E. ; Lejardi, A. ; Sarasua, J. R . Glass transition behavior and dynamic fragility in polylactides containing mobile and rigid amorphous fractions . Polymer , 2008 , 49 ( 20 ), 4427 – 4432 .
Pitt, G. G. ; Gratzl, M. M. ; Kimmel, G. L. ; Surles, J. ; Sohindler, A . Aliphatic polyesters II. The degradation of poly ( DL -lactide), poly( ε -caprolactone), and their copolymers in vivo . Biomaterials , 1981 , 2 ( 4 ), 215 – 220 .
Li, R. Y. ; Hua, H. M. ; Zeng, Y. J. ; Yang, J. ; Chen, Z. Q. ; Zhang, P. ; Zhao, J. B . Promote the conductivity of solid polymer electrolyte at room temperature by constructing a dual range ionic conduction path . J. Energy Chem. , 2022 , 64 , 395 – 403 .
Yan, C. Y. ; Zhu, P. ; Jia, H. ; Zhu, J. D. ; Selvan, R. K. ; Li, Y. ; Dong, X. ; Du, Z. ; Angunawela, I. ; Wu, N. Q. ; Dirican, M. ; Zhang, X. W . High-performance 3-D fiber network composite electrolyte enabled with Li-ion conducting nanofibers and amorphous PEO-based cross-linked polymer for ambient all-solid-state lithium-metal batteries . Adv. Fiber Mater. , 2019 , 1 ( 1 ), 46 – 60 .
Marek, A. A. ; Verney, V . Photochemical reactivity of PLA at the vicinity of glass transition temperature. The photo-rheology method . Eur. Polym. J. , 2016 , 81 , 239 – 246 .
Harrison, K. L. ; Jenkins, M. J . The effect of crystallinity and water absorption on the dynamic mechanical relaxation behaviour of polycaprolactone . Polym. Int. , 2004 , 53 ( 9 ), 1298 – 1304 .
Chen, H. W. ; Chiu, C. Y. ; Chang, F. C . Conductivity enhancement mechanism of the poly(ethylene oxide)/modified-clay/LiClO 4 systems . J. Polym. Sci. Part B Polym. Phys. , 2002 , 40 ( 13 ), 1342 – 1353 .
Basak, P. ; V Manorama, S . Poly(ethylene oxide)-polyurethane/poly(acrylonitrile) semi-interpenetrating polymer networks for solid polymer electrolytes: vibrational spectroscopic studies in support of electrical behavior . Eur. Polym. J. , 2004 , 40 ( 6 ), 1155 – 1162 .
Nunes, R. W. ; Martin, J. R. ; Johnson, J. F . Influence of molecular weight and molecular weight distribution on mechanical properties of polymers . Polym. Eng. Sci. , 2004 , 22 ( 4 ), 205 – 228 .
Shalem, A. ; Yehezkeli, O. ; Fishman, A . Enzymatic degradation of polylactic acid (PLA) . Appl. Microbiol. Biotechnol. , 2024 , 108 ( 1 ), 413 .
Navarro-Baena, I. ; Sessini, V. ; Dominici, F. ; Torre, L. ; Kenny, J. M. ; Peponi, L . Design of biodegradable blends based on PLA and PCL: from morphological, thermal and mechanical studies to shape memory behavior . Polym. Degrad. Stab. , 2016 , 132 , 97 – 108 .
Magaz, A. ; Faroni, A. ; Gough, J. E. ; Reid, A. J. ; Li, X. ; Blaker, J. J . Bioactive silk-based nerve guidance conduits for augmenting peripheral nerve repair . Adv. Healthc. Mater. , 2018 , 7 ( 23 ), 1800308 .
Fang, Y. ; Zhang, L. D. ; Chen, Y. M. ; Wu, S. Q. ; Weng, Y. X. ; Liu, H. Q . Polysaccharides based rapid self-crosslinking and wet tissue adhesive hemostatic powders for effective hemostasis . Carbohydr. Polym. , 2023 , 312 , 120819 .
Huang, H. J. ; Xu, R. F. ; Ni, P. ; Zhang, Z. H. ; Sun, C. X. ; He, H. Y. ; Wang, X. Y. ; Zhang, L. D. ; Liang, Z. Y. ; Liu, H. Q . Water-driven noninvasively detachable wet tissue adhesives for wound closure . Mater. Today Bio , 2022 , 16 , 100369 .
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