左旋聚乳酸-聚己内酯-醋酸纤维素三维微-纳米复合纤维多孔支架材料的制备与生物矿化活性

赵瑨云; 刘瑞来; 胡家朋; 穆寄林; 付兴平

doi:10.13801/j.cnki.fhclxb.20210906.007

左旋聚乳酸-聚己内酯-醋酸纤维素三维微-纳米复合纤维多孔支架材料的制备与生物矿化活性

doi: 10.13801/j.cnki.fhclxb.20210906.007

赵瑨云^1,,
刘瑞来^{1, 2},
胡家朋^1, ,,
穆寄林¹,
付兴平¹

1.
武夷学院　生态与资源工程学院，武夷山 354300
2.
福建师范大学　化学与材料学院，福州 350007

基金项目: 福建省自然科学基金(2019J01829；2019J01830；2020J01412；2020J01414)；南平市基金(2019J06)

详细信息

通讯作者:
胡家朋，博士，教授，硕士生导师，研究方向为功能高分子材料　E-mail: 22402414@qq.com

中图分类号: TB323.4
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出版历程
- 收稿日期: 2021-06-23
- 修回日期: 2021-08-11
- 录用日期: 2021-08-14
- 网络出版日期: 2021-09-07
- 刊出日期: 2022-06-01

Fabrication of polycaprolactone-cellulose acetate-poly(L-lactic acid) three-dimensional micro-nanofibrous porous scaffold composites and its bio-mineralization activity

ZHAO Jinyun^1
,,
LIU Ruilai^{1, 2},
HU Jiapeng^{1
, ,},
MU Jilin¹,
FU Xingping¹

1.
College of Ecological and Resources Engineering, Wuyi University, Wuyishan 354300, China
2.
College of Chemistry and Materials Science, Fujian Normal University, Fuzhou 350007, China

摘要

摘要: 3D纳米纤维多孔支架作为骨组织工程支架材料具有很好的发展前景。在无其它任何添加剂条件下，通过低温相分离方法制备了左旋聚乳酸-聚己内酯-醋酸纤维素(PCL-CA-PLLA)三维微-纳米复合纤维多孔支架材料。采用SEM分析聚合物比例、淬火时间、聚合物浓度和淬火温度等条件对纤维支架材料形貌影响。PCL-CA-PLLA(1∶1∶8)的直径为(276±121) nm，该直径与细胞外基质的尺寸大小(50~500 nm)相当，孔隙率和比表面积分别为95.12%和54.18 m²/g。说明PCL-CA-PLLA三维微-纳米复合纤维多孔支架材料为高孔隙率和大比表面积的三维多孔材料。与纯PLLA纤维支架材料相比，PCL-CA-PLLA三维微-纳米复合纤维多孔支架材料的机械强度有所提高，亲水性有所改善。PCL-CA-PLLA三维微-纳米复合纤维有望成为理想的组织工程支架材料。
- 左旋聚乳酸 /
- 醋酸纤维素 /
- 聚己内酯 /
- 微-纳米纤维 /
- 支架 /
- 生物矿化活性
Abstract: 3D nanofiber scaffold composites in bone tissue engineering are promising. Poly(L-lactic acid)-polycaprolactone-cellulose acetate 3D composite micro-nanofibrous porous scaffolds were prepared by low-temperature phase separation, without the assistance of additives. The effects of PCL-CA-PLLA ratio, quenching time, polymer concentration and quenching temperature on the morphology of fibrous scaffolds were investigated by SEM. The diameter of PCL-CA-PLLA (1∶1∶8) is (276±121) nm, which is similar to the size of the extracellular matrix (50-500 nm), and the porosity and specific surface area are 95.12% and 54.18 m²/g, respectively. It is indicated that PCL-CA-PLLA 3D micro-nanofibrous porous scaffold composites are 3D porous materials with high porosity and large specific surface area. Compared with pure PLLA fibrous scaffolds, the mechanical strength and hydrophilicity of PCL-CA-PLLA 3D micro-nanofibrous porous scaffold composites are improved. PLLA-PCL-CA 3D micro-nanofibrous are expected to be ideal tissue engineering scaffold materials.
- poly(L-lactic acid) /
- cellulose acetate /
- polycaprolactone /
- micro-nanofibrous /
- scaffolds /
- bio-mineralization activity

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图 1 不同溶剂的PCL-CA-PLLA复合材料的SEM图像

Figure 1. SEM images of PCL-CA-PLLA composites with diffierent solvents((a) DO; (b) Acetonitrile; (c) DMAc; (d) THF)

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图 2 不同质量比的PCL-CA-PLLA三维微-纳米复合纤维扫描电镜图(其余条件参见表1)

Figure 2. SEM images of PCL-CA-PLLA 3D composites micro-nanofibrous with different mass ratio of PCL-CA-PLLA， (a) 1:1:8，(b) 1.5:1.5:7.5，(c) 2:2:6，(d) 2.5:2.5:6

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图 3 不同淬火时间PCL-CA-PLLA微-纳米复合纤维的SEM图像

Figure 3. SEM images of PCL-CA-PLLA composite micro-nanofibrous with different quenching time ((a) 1 min; (b) 3 min; (c) 5 min; (d) 10 min; (e) 30 min; (f) 60 min)

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图 4 不同聚合物浓度PCL-CA-PLLA微-纳米复合纤维的SEM图像

Figure 4. SEM images of PCL-CA-PLLA composite micro-nanofibrous with different polymer concentrations ((a) 3%; (b) 5%; (c) 7%; (d) 9%; (e) 12%)

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图 5 不同淬火温度PCL-CA-PLLA微-纳米复合纤维的SEM图像

Figure 5. SEM images of PCL-CA-PLLA composite micro-nanofibrous at different quenching temperatures((a) 10℃; (b) 0℃; (c) −10℃; (d) −20℃; (e) -30℃)

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图 6 不同质量比PCL-CA-PLLA微-纳米复合纤维的XRE图谱 (a) 和DSC曲线 (b)

Figure 6. XRD patterns (a) and DSC curves (b) of PCL-CA-PLLA composite micro-nanofibrous with different mass ratios of PCL-CA-PLLA

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图 7 PCL-CA-PLLA微-纳米复合纤维的N₂吸附-脱附等温线 (a) 和孔容-孔径分布 (b)

Figure 7. N₂ absorption-desorption isotherms (a) and pore size distribution curve (b) of PCL-CA-PLLA composite micro-nanofibrous

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图 8 PCL-CA-PLLA微-纳米复合纤维压缩强度和冲击强度

Figure 8. Compressive strength and impact strength of PCL-CA-PLLA composite micro-nanofibrous

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图 9 PCL-CA-PLLA微-纳米复合纤维支架浸泡在模拟体液(SBF)中14天的SEM图像

Figure 9. SEM images of PCL-CA-PLLA composite micro-nanofibrous scaffolds immersion in simulated body fluid (SBF) with 14 days ((a) Before immersion (PLLA); (b) After immersion (PLLA); (c) Before immersion (PCL-CA-PLLA); (d) After immersion (PCL-CA-PLLA))

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表 1 左旋聚乳酸-聚己内酯-醋酸纤维素 (PCL-CA-PLLA)微-纳米纤维的制备条件

Table 1. Preparation condition of polycaprolactone-cellulose acetate-poly(L-lactic acid) (PCL-CA-PLLA) micro-nanofibrous

Experimental condition	Solvent	Mass ratio of PCL∶CA∶PLLA	Concentration/wt%	Quenching time/min	Quenching temperature/℃
1	DO, Acetonitrile, DMAc, THF	1∶1∶8	7	120	−30
2	THF	1∶1∶8, 1.5∶1.5∶7, 2∶2∶6, 2.5∶2.5∶5	7	120	−30
3	THF	1:1:8	7	1, 3, 5, 10, 30, 60	−30
4	THF	1:1:8	3, 5, 7, 9, 12	60	−30
5	THF	1∶1∶8	7	60	10, 0, −10, −20, −30
Notes: DO—1,4-dioxane; DMAc—N,N-dimethylacetamide; THF—Tetrahydrofuran.

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表 2 溶剂和聚合物溶解度参数

Table 2. Solubility parameters of solvents and polymers

Solvent or polymer	Solubility parameter/(J·cm⁻³)^1/2
DO	20.3
Acetonitrile	24.5
DMAc	22.8
THF	18.5
PLLA	20.1
PCL	22.2
CA	21.1

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表 3 PCL-CA-PLLA微-纳米复合纤维的热力学参数

Table 3. Thermal parameters of PCL-CA-PLLA composite micro-nanofibrous

Mass ratio of PCL∶CA∶PLLA	T_m of PCL/℃	T_m of PLLA/℃	ΔH_m of PCL/(J·g⁻¹)	Χ_c of PCL/%	ΔH_m of PLLA/(J·g⁻¹)	Χ_c of PLLA/%
0∶0∶10	−	169.80	−	−	−42.74	45.66
1∶1∶8	57.98	169.01	−4.88	35.10	−34.62	46.23
1.5∶1.5∶7	56.46	169.01	−7.23	34.67	−28.88	44.08
2∶2∶6	56.22	168.90	−10.13	36.43	−25.38	45.19
2.5∶2.5∶5	57.48	168.84	−12.66	36.43	−21.10	45.09
Notes: T_m—Melting temperature; ΔH_m—Melting enthalpy; Χ_c—Degree of crystallinity.

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表 4 PCL-CA-PLLA微-纳米复合纤维各物理参数

Table 4. Physics parameters of PCL-CA-PLLA composite micro-nanofibrous

Mass ratio of PCL∶CA∶PLLA	Water contact angle/(°)	Porosity/%	Water absorption/%	Specific surface area/(m²·g⁻¹)
0∶0∶10	127.1±3.1	94.13	6.13	52.46
1∶1∶8	93.1±4.1	95.12	11.15	54.18
1.5∶1.5∶7	83.1±2.4	90.10	13.29	46.14
2∶2∶6	76.3±2.1	88.23	15.33	45.22
2.5∶2.5∶5	70.2±1.6	90.11	16.19	40.13

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