Preparation and characterization of a guided tissue regeneration membrane constructed by core-shell polycaprolactone/chitosan fibers

doi:10.16085/j.issn.1000-6613.2018-1200

Abstract

Abstract:

High-performance guided tissue regeneration (GTR) membrane is a key factor for successful GTR treatment. Electrospinning has great potential for construction of a GTR membrane because this technique can prepare fibrous structural membrane similar to extracellular matrix, which is beneficial for cell adhesion and proliferation. In this study, the core-shell nanofibers were prepared by coaxial electrospinning technique with polycaprolactone (PCL) as the core and chitosan (CS) as the shell, and the resulting membrane was crosslinked by vanillin. Furthermore, the morphology, internal structure, chemical composition, mechanical properties and cytocompatibility of the fabricated membrane were characterized by scanning electron microscope (SEM), transmission electron microscopy (TEM), X ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), mechanical testing and cell culture experiments. Structure analysis showed a core-shell PCL-CS nanofiber constructed membrane was successfully prepared. The results of mechanical and contact angle test showed that the crosslinked fiber membrane had better water resistance, higher mechanical properties and a tensile strength nearly two times higher than the reported studies. Cell culture results showed that the crosslinked fibrous membrane was a good candidate for MG-63 cell adhesion and proliferation, indicating the fabricated membrane has good cytocompatibility. In general, the fibrous GTR membrane constructed by core-shell PCL-CS nanofibers holds promising application.

Key words: polycaprolactone, chitosan, core-shell structure, nanofiber, guided tissue regeneration membrane

摘要：

高性能的引导组织再生膜是牙周引导组织再生术成功的关键，静电纺丝法因可仿生制备类细胞外基质结构，在引导组织再生膜研制方面显示出巨大潜力。本研究通过同轴静电纺丝法，以聚己内酯（PCL）为核层，壳聚糖（CS）为壳层，制备核壳结构的纳米纤维，并用香草醛对制备的纤维膜进行交联。利用扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X 射线衍射（XRD）、傅里叶变换红外光谱（FTIR）、力学测试及细胞培养等手段对制备的纤维膜进行形貌、内部结构、化学组成、力学性能和细胞相容性表征。结构分析表明本研究成功制备了核壳结构的PCL-CS纤维膜。力学测试和亲疏水性测试结果表明交联后的纤维膜具有较好的耐水性和力学性能，断裂强度高出文献报道值近两倍；体外细胞培养结果显示MG-63细胞能在交联后的纤维膜上黏附和持续增殖，表明纤维膜具有较好的细胞相容性，在引导组织再生领域有较好的应用前景。

关键词: 聚己内酯, 壳聚糖, 核-壳结构, 纳米纤维, 引导组织再生膜

CLC Number:

O631.2

Dan DENG, LIＹubao,Jinhui HUANG,Fuhua SUN,Yi ZUO,Jidong LI,Yaning WANG. Preparation and characterization of a guided tissue regeneration membrane constructed by core-shell polycaprolactone/chitosan fibers[J]. Chemical Industry and Engineering Progress, 2019, 38(03): 1501-1508.

邓丹,李玉宝,黄金会,孙富华,左奕,李吉东,王亚宁. 聚己内酯/壳聚糖核壳结构纤维引导组织再生膜的制备及表征[J]. 化工进展, 2019, 38(03): 1501-1508.

Figures/Tables 9

References 32

1	万蕾蕾, 钮晓勇, 宋萌 . 牙周引导组织再生技术在牙周病治疗中的应用[J]. 口腔医学, 2006, 26(1): 73-74.
	WAN Leilei ， NIU Xiaoyong ， SONG Meng . Application of periodontal guided tissue regeneration in periodontal disease treatment [J]. Stomatology, 2006, 26(1): 73-74.
2	任天斌, 曹春红, 王刚,等 . 可吸收引导组织再生膜[J]. 化学进展, 2010, 22(1): 179-185.
	REN Tianbin , CAO Chunhong , WANG Gang , et al . Absorbable guided tissue regeneration membranes[J]. Progress in Chemistry, 2010, 22(1):179-185.
3	TANIR T E , HASIRCI V , HASIRCI N . Electrospinning of chitosan/poly(lactic acid- co -glycolic acid)/hydroxyapatite composite nanofibrous mats for tissue engineering applications[J]. Polymer Bulletin, 2014, 71(11): 2999-3016.
4	QASIM S B , NAJEEB S , DELAINE-SMITH R M , et al . Potential of electrospun chitosan fibers as a surface layer in functionally graded GTR membrane for periodontal regeneration[J]. Dental Materials, 2017, 33(1): 71-83.
5	HIDALGO PITALUGA L , TREVELIN SOUZA M , DUTRA ZANOTTO E ,et al . Electrospun F18 Bioactive glass/PCL——poly (ε-caprolactone)-membrane for guided tissue regeneration[J]. Materials, 2018, 11(3): 400-413.
6	HE C L , HUANG Z M , HAN X J , et al . Coaxial electrospun poly(L-lactic acid) ultrafine fibers for sustained drug delivery[J]. Journal of Macromolecular Science Part B, 2006, 45(4): 515-524.
7	崔志香, 涂建炳, 司军辉,等 . 同轴静电纺丝制备PCL-PLA芯-壳结构复合纤维及其形态分析[J]. 材料科学与工程学报, 2015, 33(6):786-790.
	CUI Zhixiang , TU Jianbing , SI Junhui , et al . Fabrication and morphology analysis of PCL-PLA core-shell structured composite nanofiber by coaxial electrospinning[J]. Journal of Materials Science & Engineering, 2015, 33(6): 786-790.
8	ZHAO P , JIANG H , PAN H , et al . Biodegradable fibrous scaffolds composed of gelatin coated poly(epsilon-caprolactone) prepared by coaxial electrospinning[J]. Journal of Biomedical Materials Research Part A, 2007, 83A(2): 372-382.
9	YIN A , LUO R , LI J , et al . Coaxial electrospinning multicomponent functional controlled-release vascular graft: optimization of graft properties[J]. Colloids & Surfaces B: Biointerfaces, 2017, 152: 432-439.
10	HE M , XUE J , GENG H , et al . Fibrous guided tissue regeneration membrane loaded with anti-inflammatory agent prepared by coaxial electrospinning for the purpose of controlled release[J]. Applied Surface Science, 2015, 335: 121-129.
11	BALAGANGADHARAN K , DHIVYA S , SELVAMURUGAN N . Chitosan based nanofibers in bone tissue engineering[J]. International Journal of Biological Macromolecules, 2017, 104: 1372-1382.
12	AZAD A K , SERMSINTHAM N , CHANDRKRACHANG S , et al . Chitosan membrane as a wound-healing dressing: characterization and clinical application.[J]. Journal of Biomedical Materials Research Part B: Applied Biomaterials, 2004, 69(2); 216-238.
13	LI Y , CHEN F , NIE J , et al . Electrospun poly(lactic acid)/chitosan core-shell structure nanofibers from homogeneous solution[J]. Carbohydr. Polym., 2012, 90(4): 1445-1451.
14	BHATTARAI N , EDMONDSON D , VEISED O , et al . Electrospun chitosan-based nanofibers and their cellular compatibility[J]. Biomaterials, 2005, 26(31): 6176-6184.
15	RIJAL N , ADHIKARI U , BHATTARAI N . Chapter 9. Production of electrospun chitosan for biomedical applications[M]// Chitosan based biomaterials. Amsterdam: Elsevier, 2016: 211-237.
16	唐圣奎, 熊杰, 李妮,等 . 纳米羟基磷灰石/丝素蛋白/聚己内酯复合超细纤维的制备及表征[J]. 复合材料学报, 2010, 27(2): 31-37.
	TANG Shengkui , XIONG Jie , LI Ni , et al . Preparation and characterization of ultrafine nano-hydroxyapatite/silk fibroin/poly(ε-caprolactone) composite fibers[J]. Acta Materiae Compositae Sinica, 2010, 27(2): 31-37.
17	POK S, MYERS J D , MADIHALLY S V , et al . A multilayered scaffold of a chitosan and gelatin hydrogel supported by a PCL core for cardiac tissue engineering[J]. Acta Biomaterialia, 2013, 9(3): 5630-5642.
18	GHORBANI F M , KAFFASHI B , SHOKROLLAHI P , et al . PCL/chitosan/Zn-doped nHA electrospun nanocomposite scaffold promotes adipose derived stem cells adhesion and proliferation[J]. Carbohydr. Polym., 2015, 118: 133-142.
19	GUNATILLAKE P A , ADHIKARI R . Biodegradable synthetic polymers for tissue engineering[J]. European Cells & Materials, 2003, 5(5): 1-16.
20	KALWAR K , SUN W X , LI D L , et al . Coaxial electrospinning of polycaprolactone@chitosan: characterization and silver nanoparticles incorporation for antibacterial activity[J]. Reactive & Functional Polymers, 2016, 107: 87-92.
21	SURUCU S , SASMASEL H T . Development of core-shell coaxially electrospun composite PCL/chitosan scaffolds.[J]. International Journal of Biological Macromolecules, 2016, 92: 321-328.
22	CHENG T , HUND R D , AIBIBU D , et al . Pure chitosan and chitsoan/chitosan lactate blended nanofibres made by single step electrospinning[J]. Autex Research Journal, 2013, 13(4): 128-133.
23	LI D , XIA Y . Electrospinning of nanofibers: reinventing the wheel[J]. Advanced Materials, 2010, 16(14): 1151-1170.
24	THOMAS V , JOSE M V , CHOWDHURY S , et al . Mechano-morphological studies of aligned nanofibrous scaffolds of polycaprolactone fabricated by electrospinning.[J]. Journal of Biomaterials Science: Polymer Edition, 2006, 17(9): 969-984.
25	SUNG Y T , KUM C K, LEE H S, et al . Effects of crystallinity and crosslinking on the thermal and rheological properties of ethylene vinyl acetate copolymer[J]. Polymer, 2005, 46(25): 11844-11848.
26	STROESCU M , STOICA-GUZUN A , ISOPENCU G , et al . Chitosan-vanillin composites with antimicrobial properties[J]. Food Hydrocolloids, 2015, 48: 62-71.
27	LI D , CHEN W , SUN B , et al . A comparison of nanoscale and multiscale PCL/gelatin scaffolds prepared by disc-electrospinning[J]. Colloids & Surfaces B: Biointerfaces, 2016, 146: 632-641.
28	李峻峰, 张利, 李钧甫, 等 . 香草醛交联壳聚糖载药微球的性能及其成球机理分析[J]. 高等学校化学学报, 2008, 29(9): 1874-1879.
	LI Junfeng , ZHANG Li , LI Junfu , et al . Properties of drug loaded chitosan microspheres crosslinked by vanillin and analysis of microsphere forming mechanism[J].Chem. J. Chinese Universities, 2008, 29(9): 1874-1879.
29	LI A D , SUN Z Z , ZHOU M , et al . Electrospun chitosan-graft-PLGA nanofibres with significantly enhanced hydrophilicity and improved mechanical property.[J]. Colloids & Surfaces B: Biointerfaces, 2013, 102(2): 674.
30	王可, 宋义虎 . 交联剂改性小麦醇溶蛋白/壳聚糖复合膜的制备与性能[J]. 材料科学与工程学报, 2013, 31(1): 78-83.
	WANG Ke , SONG Yihu . Preparation and properties of cross-linked gliadin/chitosan films[J]. Journal of Materials Science & Engineering, 2013, 31(1): 78-83.
31	SINGH K , SURI R , TIWARY A K , et al . Chitosan films: crosslinking with EDTA modifies physicochemical and mechanical properties[J]. Journal of Materials Science Materials in Medicine, 2012, 23(3):687-695.
32	PARK J H , WASILEWSKI C E , Almodovar N , et al . The responses to surface wettability gradients induced by chitosan nanofilms on microtextured titanium mediated by specific integrin receptors[J]. Biomaterials, 2012, 33(30): 7386-7393.

样品	平均断裂伸长率/%	平均断裂强度/MPa
PCL	103.136±17.853	10.294±2.142
未交联的PCL-CS	8.418±0.993	2.641±0.157
交联的PCL-CS	5.517±1.032	3.740±0.590

样品	平均断裂伸长率/%	平均断裂强度/MPa
PCL	103.136±17.853	10.294±2.142
未交联的PCL-CS	8.418±0.993	2.641±0.157
交联的PCL-CS	5.517±1.032	3.740±0.590

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