Study on Surface Carboxylation Modification and Cytocompatibility of Poly（Lactic Acid）

doi:10.19491/j.issn.1001-9278.2021.05.004

Abstract

Abstract:

The oxygen?containing functional groups such as carboxyl groups were generated on the surface of poly（lactic acid）（PLA） by means of methyl oxidation through ultraviolet?activated sodium chlorite free radicals （ClO·）. This can enhanced the hydrophilicity and cytocompatibility of the PLA surface. The surface element composition， optimum oxidation condition， and influence of oxidation reaction on the surface hydrophilicity of PLA were investigated by X?ray photoelectron spectroscopy and contact angle analysis. The effect of oxidation process on the mechanical properties of PLA was analyzed through a tensile test. The biocompatibility of the surface?modified PLA was studied by cell proliferation and cell activity tests in vitro. The experimental results indicated that the oxygen?containing functional groups such as carboxyl group were successfully generated on the surface of PLA. The optimal oxidation time and temperature were determined to be 10 min and 90 °C， respectively. Under such a condition， the surface contact angle of the oxidized material decreased from 82 ° to 62.5 °， but its surface hydrophilicity was improved. The surface?modified PLA exhibited the unchanged tensile strength and a slight decrease in elongation at break. After oxidation， the surface of PLA showed better cell adhesion and cell proliferation， which was more beneficial to the growth of cells.

Key words: poly（lactic acid）, surface modification, hydrophilia, cytocompatibility

CLC Number:

TQ 321

ZHANG Bo, WANG Xiaofeng, GUO Meng, BAI Zhiyuan, REN Cuihong, HAN Wenjuan, UYAMA Hiroshi, LI Qian. Study on Surface Carboxylation Modification and Cytocompatibility of Poly（Lactic Acid）[J]. China Plastics, 2021, 35(5): 17-23.

Figures/Tables 10

Fig.1. Reaction device for surface modification of PLA

Fig.2. Effect of oxidation time on surface chemical composition of PLA

Fig.3. Effect of oxidation temperature on surface chemical composition of PLA

Fig.4. SEM of PLA under different oxidation conditions（×5 000）

Fig.5. The effect of oxidation time on surface contact angle of PLA

Fig.6. The effect of oxidation temperature on surface contact angle of PLA

Fig.7. Effect of oxidation time on mechanical properties of PLA

Fig.8. Effect of oxidation temperature on mechanical properties of PLA

Fig.9. Live/dead staining of HUVECs for 1 day, 3 days and 5 days

Fig.10. The number of cells proliferated on the surface of the sample after 1 day, 3 days and 5 days

References 22

1	FARAH S， ANDERSON D G， LANGER R. Physical and Mechanical Properties of PLA， and Their Functions in Widespread Applications⁃a Comprehensive Review［J］. Advanced Drug Delivery Reviews， 2016， 107：367⁃392.
2	JINNOUCHI H， TORII S， SAKAMOTO A， et al. Fully Bioresorbable Vascular Scaffolds： Lessons Learned and Future Directions［J］. Nat Rev Cardiol， 2019， 16（5）： 286⁃304.
3	WANG C， LIU Y， ZHANG Y， et al. Study of the Mechanical Behavior of Z⁃Structure Stents Produced by Poly⁃L⁃Lactic Acid Multi⁃Ply Strands［J］. Textile Research Journal， 2019， 85：19⁃20.
4	SINGHVI M S， ZINJARDE S S， GOKHALE D V. Polylactic Acid： Synthesis and Biomedical Applications［J］. J Appl Microbiol， 2019， 127（6）： 1 612⁃1 626.
5	KHALIFEHZADEH R， CIRIDON W， RATNER B D. Surface Fluorination of Polylactide as a Path to Improve Platelet Associated Hemocompatibility［J］. Acta Biomater， 2018， 78：23⁃35.
6	莫志超，刘青，时东陆，等. 低温等离子接枝改性聚乳酸支架的亲水性［J］. 青岛科技大学学报（自然科学版），2017， 361（2）： 58⁃62.
	MO Z C， LIU Q， SHI D L， et al. PDLLA Stent Modified by Low Temperature Plasma Grafting and Its Hydrophily［J］. Journal of Qingdao University of Science and Techno⁃logy （Natural Science Edition），2017，361（2）：58⁃62.
7	LIU T， LIU S H， ZHANG K， et al. Endothelialization of Implanted Cardiovascular Biomaterial Surfaces： The Deve⁃lopment from in Vitro to in Vivo［J］. Journal of Biomedical Materials Research Part A， 2014， 102（10）：3 754⁃3 772.
8	KIPSHIDZE N， DANGAS G， TSAPENKO M， et al. Role of the Endothelium in Modulating Neointimal Formation： Vasculoprotective Approaches to Attenuate Restenosis after Percutaneous Coronary Interventions［J］. Journal of the American College of Cardiology， 2004， 44（4）： 733⁃739.
9	RASAL R M， JANORKAR A V， HIRT D E. Poly（Lactic Acid） Modifications［J］. Progress in Polymer Science， 2010， 35（3）： 338⁃356.
10	CHENG K⁃Y， CHANG C⁃H， YANG Y⁃W， et al. Enhancement of Cell Growth on Honeycomb⁃Structured Polylactide Surface Using Atmospheric⁃Pressure Plasma Jet Modification［J］. Applied Surface Science， 2017， 394：534⁃542.
11	MASSIA S P， HUBBELL J A J J O B M R. Human Endothelial Cell Interactions with Surface⁃oupled Adhesion Peptides on a Nonadhesive Glass Substrate and Two Polymeric Biomaterials［J］. Journal of Biomedical Materials Research Part A， 1991， 25（2）：223⁃242.
12	OHKUBO K， ASAHARA H， INOUE T. Photochemical C⁃H Oxygenation of Side⁃Chain Methyl Groups in Polypropylene with Chlorine Dioxide［J］. Chem Commun （Camb）， 2019， 55（32）： 4 723⁃4 736.
13	JIA Y， CHEN J， ASAHARA H， et al. Photooxidation of the Abs Resin Surface for Electroless Metal Plating［J］. Polymer， 2020， 200：122592.
14	JIA Y， CHEN J， ASAHARA H， et al. Polymer Surface Oxidation by Light⁃Activated Chlorine Dioxide Radical for Metal⁃Plastics Adhesion［J］. ACS Applied Polymer Materials， 2019， 1（12）： 3 452⁃3 458.
15	JIA Y， ASAHARA H， HSU Y I， et al. Surface Modification of Polycarbonate Using the Light⁃Activated Chlorine Dioxide Radical［J］. Applied Surface Science， 2020， 530：147202.
16	OHKUBO K， HIROSE K. Light⁃Driven C⁃H Oxygena⁃tion of Methane into Methanol and Formic Acid by Mole⁃cular Oxygen Using a Perfluorinated Solvent［J］. Angew Chem Int Ed Engl， 2018， 57（8）： 2 126⁃2 129.
17	石淑先，夏宇正，焦书科，等. 聚乳酸及其共聚物的制备和降解性能［J］. 北京化工大学学报（自然科学版）， 2004（1）：51⁃56.
	SHI S X， XIA Y Z， JIAO S K， et al. Mechanism and Comparison of UV Photolysis and Hydrolysis of Poly⁃lactic acid［J］. Journal of Nanjing University of Technology（Natural Science Edition）， 2004（1）：51⁃56.
18	王媛，纪乐，王庭慰. 聚乳酸的紫外光解和沸水降解［J］. 南京工业大学学报（自然科学版）， 2009， 31（2）： 69⁃72，76.
	WANG Y， JI L， WANG T W， et al. Ultraviolet Photoly⁃sis and Boiling Water Degradation of Polylactic Acid ［J］. Journal of Nanjing University of Technology （Natural Science Edition）， 2009， 31（2）： 69⁃72，76.
19	ARIMA Y， IWATA H. Effect of Wettability and Surface Functional Groups on Protein Adsorption and Cell Adhesion Using Well⁃Defined Mixed Self⁃Assembled Mono⁃layers［J］. Biomaterials， 2007， 28（20）： 3 074⁃3 082.
20	YU L， LIU H， XIE F， et al. Effect of Annealing and Orien⁃tation on Microstructures and Mechanical Properties of Polylactic Acid［J］. Polymer Engineering and Ence， 2008， 48（4）： 634⁃641.
21	曹乐，贾仕奎，张奇锋，等. 退火时间及温度对聚乳酸结晶性能的影响［J］. 塑料工业， 2019， 47（10）： 117⁃122.
	CAO L， JIA S K， ZHANG Q F， et al. Effect of Annealing Time and Temperature on Crystallization Properties of Polylactic Acid ［J］ China Plastics Industry， 2019， 47（10）： 117⁃122.
22	刘爱平，霍云，李通，等. 退火对聚乳酸结晶及耐热性能的影响［J］. 中国塑料， 2015， 29（6）： 44⁃48.
	LIU A P， HUO Y， LI T， et al. Influence of Annealing on Crystallization and Heat Resistance Properties of Poly（lactic acid）［J］ China Plastics， 2015， 29（6）： 44⁃48.

[1]	SHEN Xuemei, ZHU Xiaolong, HU Yanchao, SONG Renyuan, ZHANG Xianfeng, LI Xi. Fabrication and properties of poly（lactic acid））/ibuprofen microspheres through electrostatic spray method [J]. China Plastics, 2022, 36(7): 61-67.
[2]	SHAO Linying, XI Yuewei, WENG Yunxuan. Research progress in degradation characteristics of poly（lactic acid） composites [J]. China Plastics, 2022, 36(6): 155-164.
[3]	WANG Rongchen, ZHANG Heng, SUN Huanwei, DUAN Shuxia, QIN Zixuan, LI Han, ZHU Feichao, ZHANG Yifeng. Research progress in preparation and hydrophilic modification of polylactic acid nonwovens for medical and health applications [J]. China Plastics, 2022, 36(5): 158-166.
[4]	ZHAO Xinxin, JIN Xiaodong, SHI Yan, SUN Shibing, LYU Feng, TIAN Yingliang, ZHAO Zhiyong. Surface modification of extruded polystyrene based on ultraviolet⁃ozone irradiation [J]. China Plastics, 2022, 36(5): 8-13.
[5]	SUN Tao, YANG Qing, HU Jian, WANG Yangyang, LIU Bo, YUN Xueyan, DONG Tungalag. Preparation and properties of poly（lactic acid⁃co⁃glycolic acid） film [J]. China Plastics, 2022, 36(2): 33-40.
[6]	WEI Zongchen, XI Yuewei, WENG Yunxuan. Research Progress in Poly（lactic acid）⁃based Composite Materials for Bone Tissue Engineering [J]. China Plastics, 2021, 35(9): 136-146.
[7]	TANG Yujing, WANG Yaqiao, NI Jingyue, WANG Conglong, WANG Xiangdong. Effect of Stereoscopic Composite Crystals on Foaming Behavior of PLA [J]. China Plastics, 2021, 35(8): 117-124.
[8]	LI Yuzhu, YAO Lihui, YE Shiqiang, LYU Guoyong, LIU Panpan, XU Longfei, QIU Dan. Research Progress on Degradation Performance of Biodegradable Materials in Water Environment [J]. China Plastics, 2021, 35(7): 103-114.
[9]	DUAN Xuyuan, ZHENG Hongjuan. Research Progress in Modified Poly（lactic acid） Foaming Technology [J]. China Plastics, 2021, 35(7): 134-139.
[10]	YANG Wenjie, HE Jiawen, ZHU Hanbin, WANG Sisi, LI Xiping. Mechanical Properties and Foaming Behaviors of Graphene⁃reinforced Poly（lactic acid） [J]. China Plastics, 2021, 35(6): 26-32.
[11]	SUN Dongbao, LU Qin, LU Xinyu, JIA Wangyi, CAO Shang. Study on Interface Modification Methods and Properties of PLA/Rice Husk Powder Composites [J]. China Plastics, 2021, 35(6): 80-84.
[12]	XU Jiayi. Preparation and Properties of Hypromellose⁃toughened Poly（lactic acid） Composites [J]. China Plastics, 2021, 35(5): 59-64.
[13]	CAI Hengfang, SUN Ling. Molecular Dynamics Study on Effects of Temperature and Shear Rate on CO₂ Diffusion Behavior in Foaming Process of Injection Molding [J]. China Plastics, 2021, 35(3): 83-89.
[14]	LUO Fei, HAO Lingao, WANG Tengfei, LIU Hongpeng, DANG Xudan, WANG Yaming, LIU Chuntai, SONG Yan. High⁃temperature Stretching Induced Multi⁃structural Deformation of PLA⁃based Composites [J]. China Plastics, 2021, 35(2): 77-83.
[15]	YIN Peng, MA Hongpeng, GUO Bin, LI Panxin. Thermoplastic starch composites reinforced synergistically with PLA fiber and PVA fiber [J]. China Plastics, 2021, 35(12): 16-20.