钼掺杂铜硅钙石的制备及其抗菌性能和细胞相容性研究

doi:10.15541/jim20200506

无机材料学报 ›› 2021, Vol. 36 ›› Issue (7): 738-744.DOI: 10.15541/jim20200506

所属专题：【虚拟专辑】抗菌材料(2020~2021)

钼掺杂铜硅钙石的制备及其抗菌性能和细胞相容性研究

王恩典¹^,²(), 常江¹()

1.中国科学院上海硅酸盐研究所, 高性能陶瓷与超微结构国家重点实验室, 上海 200050
2.中国科学院大学材料与光电研究中心, 北京 100049

收稿日期:2020-08-31 修回日期:2020-10-28 出版日期:2021-07-20 网络出版日期:2020-11-05
通讯作者: 常江, 研究员. E-mail:jchang@mail.sic.ac.cn
作者简介:王恩典(1991-), 男, 博士研究生. E-mail:wangendian@student.sic.ac.cn
基金资助:
国家重点研发计划(2016YFC1100201)

Mo Doped Cuprorivaite: Preparation, Antibacterial and Cytocompatibility

WANG Endian¹^,²(), CHANG Jiang¹()

1. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2020-08-31 Revised:2020-10-28 Published:2021-07-20 Online:2020-11-05
Contact: CHANG Jiang, professor. E-mail:jchang@mail.sic.ac.cn
About author:WANG Endian (1991-), male, PhD candidate. E-mail:wangendian@student.sic.ac.cn
Supported by:
National Key Research and Development Plan of China(2016YFC1100201)

摘要/Abstract

摘要：

含铜生物材料在高浓度铜离子释放时对细菌有优异的抑制作用, 但同时具有细胞毒性; 而在低浓度铜离子释放时虽然具有良好的细胞相容性, 但其抗菌性能低。因此, 开发一种含铜生物材料, 使其能够在高浓度铜离子释放情况下同时具有优异抗菌性能和良好细胞相容性, 具有重要意义。本研究利用钼和铜之间的拮抗作用原理, 采用溶胶-凝胶法制备了钼掺杂铜硅钙石, 并通过细菌平板实验和细胞活力实验评价了材料的抗菌性能和细胞相容性。实验结果显示, 钼掺杂铜硅钙石释放的高浓度铜离子(高于8.87 μg∙mL ^-1)对金黄色葡萄球菌有良好的抑制性能。同时, 由于铜钼离子的拮抗作用能降低高浓度铜离子对细胞的毒性, 钼掺杂铜硅钙石释放的铜离子在9.65 μg∙mL ^-1的高浓度下依然能保证人脐静脉内皮细胞存活率高达90%。因此, 钼掺杂可以作为含铜生物材料降低其细胞毒性的一种有效途径, 为开发低细胞毒性含铜抗菌生物材料提供了新的路径。

关键词: 铜, 生物材料, 钼, 掺杂, 铜硅钙石, 抗菌性能, 细胞相容性

Abstract:

Copper-containing biomaterials have excellent inhibitory effect on bacteria growth by releasing copper ions at high concentration, which may have cytotoxicity at the same time. Although low concentration of copper ions has good cytocompatibility, the antibacterial activity is unsatisfactory. Therefore, it is of great significance to develop copper- containing biomaterials, which have excellent antibacterial property and good cytocompatibility. In this study, on considering the antagonistic effect between copper and molybdenum, molybdenum doped cuprorivaite (Mo-Cup) was synthesized by Sol-Gel method and its antibacterial properties and cell compatibility were evaluated by bacterial plate experiment and cell activity assay. The results showed that copper ions with high concentration (above 8.87 μg∙mL ^-1) released from Mo-Cup had a good inhibitory effect on Staphylococcus aureus. In addition, because the antagonistic effect between copper and molybdenum ions released from Mo-Cup can reduce the cytotoxicity of high concentration of copper ions, the survival rate of umbilical vein endothelial cells (HUVECs) was as high as 90% in the extracts of Mo-Cup at a high Cu ion concentration (9.65 μg∙mL ^-1). Therefore, molybdenum doping can be considered as an effective approach to reduce the cytotoxicity of copper-containing biomaterials for the development of low-toxic antibacterial biomaterials.

Key words: Cu, biomaterial, Mo, doping, cuprorivaite, bacteria inhibition, cytocompatibility

中图分类号:

TQ174

王恩典, 常江. 钼掺杂铜硅钙石的制备及其抗菌性能和细胞相容性研究[J]. 无机材料学报, 2021, 36(7): 738-744.

WANG Endian, CHANG Jiang. Mo Doped Cuprorivaite: Preparation, Antibacterial and Cytocompatibility[J]. Journal of Inorganic Materials, 2021, 36(7): 738-744.

图/表 8

图1 钼掺杂铜硅钙石的性能

Fig. 1 Properties of Mo doped cuprorivaite (Mo-Cup) (a) XRD patterns, SEM images of (b) 5Mo-Cup and (c) 10Mo-Cup, and content of (d) copper ion, (e) molybdenum ion and (f) silicon ion released from Cup, 5Mo-Cup and 10Mo-Cup in bacterial culture medium (BCM) and cell culture medium (ECM)

图2 钼掺杂铜硅钙石(a~f)5Mo-Cup和(g~l)10Mo-Cup的(a,g)SEM照片及其(b~f, h~l)元素分布图

Fig. 2 (a,g) SEM images of (a-f) 5Mo-Cup and (g-l) 10Mo-Cup and (b-f, h-l) corresponding elemental maps (b, h): Si; (c, i): Ca; (d, j): O; (e, k): Cu; (f, l): Mo

图3 不同浓度铜离子溶液和钼离子溶液对金黄色葡萄球菌的作用

Fig. 3 Effect of different concentrations of copper ion (CuSO4·5H2O) solution and molybdenum ion ((NH4)6Mo7O24·4H2O) solution on Staphylococcus aureus

图4 含10 μg?mL-1铜离子培养液、含钼离子细胞培养液及铜钼组合培养液对细胞活力的影响

Fig. 4 Effects of culture medium containing 10 μg?mL-1 copper ion, molybdenum ion and copper-molybdenum ions on cell activity assay (a) Effects of molybdenum ions on the proliferation of human dermal fibroblast (HDFs) and human umbilical vein endothelial cells (HUVECs)(xMo stands for medium containing x μg?mL-1 molybdenum ion; x=2, 4, 6, 8, 10); (b) Effects of copper molybdenum ions combination on the proliferation of HDFs and HUVECs (10Cu+yMo stands for medium containing 10 μg?mL-1 copper ions and y μg?mL-1 molybdenum ions; y=2, 4, 6, 8, 10). **: p<0.01

图5 10Mo-Cup细菌培养基浸提液对金黄色葡萄球菌的抑制作用

Fig. 5 Inhibition effect of extract from 10Mo-Cup bacterial culture medium on Staphylococcus aureus (a) Number of Staphylococcus aureus after being treated with different dilutions of 10Mo-Cup medium extract; (b) Related antibacterial rate. *: p<0.05; **: p<0.01

表1 不同稀释倍数10Mo-Cup细菌培养基浸提液离子浓度

Table 1 Ion contents in the extract with 10Mo-Cup bacterial culture medium after different dilutions

Dilutions of the extract	Cu ion/ (μg∙mL^-1)	Si ion/ (μg∙mL^-1)	Mo ion/ (μg∙mL^-1)
1	709.86	88.71	243.10
1/40	17.75	2.22	6.08
1/80	8.87	1.11	3.04
1/160	4.44	0.55	1.52

图6 不同稀释倍数的10Mo-Cup细胞培养液浸提液对(a)HDFs和(b)HUVECs活力的影响

Fig. 6 Effects of 10Mo-Cup culture medium extracts with different concentrations on (a) HDFs and (b) HUVECs activity assay. **: p<0.01

表2 10Mo-Cup ECM培养基浸提液在不同稀释倍数时的离子浓度

Table 2 Ion contents in the extract with 10Mo-Cup cell culture medium after different dilutions

Dilution of the extract	Cu ion/ (μg∙mL^-1)	Si ion/ (μg∙mL^-1)	Mo ion/ (μg∙mL^-1)
1	154.35	78.85	268.57
1/4	38.59	19.71	67.14
1/8	19.29	9.86	33.57
1/16	9.65	4.93	16.79

参考文献 19

[1]	LI P L, HAN F X, CAO W W, et al. Carbon quantum dots derived from lysine and arginine simultaneously scavenge bacteria and promote tissue repair. Applied Materials Today, 2020,6(19):100601.
[2]	ZHANG Y, CHANG M L, BAO F, et al. Multifunctional Zn doped hollow mesoporous silica/polycaprolactone electrospun membranes with enhanced hair follicle regeneration and antibacterial activity for wound healing. Nanoscale, 2019,11(13):6315-6333. DOI URL
[3]	NING C, WANG X, LI L, et al. Concentration ranges of antibacterial cations for showing the highest antibacterial efficacy but the least cytotoxicity against mammalian cells: implications for a new antibacterial mechanism. Chemical Research in Toxicology, 2015,28(9):1815-1822. DOI URL
[4]	TAN S X, TAN S Z, LIU Y L, et al. Preparation and antibacterial property of copper-loaded activated carbon microspheres. Journal of Inorganic Materials, 2010,25(3):299-305. DOI URL
[5]	WU C T, ZHOU Y H, XU M C, et al. Copper-containing mesoporous bioactive glass scaffolds with multifunctional properties of angiogenesis capacity, osteostimulation and antibacterial activity. Biomaterials, 2013,34(2):422-433. DOI URL
[6]	TIAN T, WU C T, CHANG J. Preparation and in vitro osteogenic, angiogenic and antibacterial properties of cuprorivaite (CaCuSi₄O₁₀, Cup) bioceramics. RSC Advances, 2016,6(51):45840-45849. DOI URL
[7]	孔妮. 掺铜硅酸钙生物陶瓷的制备与表征及其促血管化性能的研究. 上海: 上海交通大学硕士学位论文, 2015.
[8]	KONG N, LIN K L, LI H Y, et al. Synergy effects of copper and silicon ions on stimulation of vascularization by copper-doped calcium silicate. Journal of Materials Chemistry B, 2014,2(8):1100-1110. DOI URL
[9]	YANG Z J, LONG T, RAN L W, et al. Molybdenum's biological function and roles in animal production. Journal of Henan University of Science and Technology (Agricultrual Science), 2004(2):40-43.
[10]	WU M J. Molybdenum and human health. Studies of Trace Elements and Health, 2006,5(23):66-67.
[11]	WANG Q X. Trace element molybdenum and human health. Studies of Trace Elements and Health, 2003,4(20):58-59.
[12]	LIU M. The effect of molybdenum on human health. China Molybdenum Industry, 2001,5(25):43-45.
[13]	田瑶. 四硫代钼酸铵抑制顺铂与人铜伴侣蛋白Atoxl的相互作用. 合肥: 中国科学技术大学硕士学位论文, 2018.
[14]	ALVAREZ H M, XUE Y, ROBINSON C D, et al. Tetrathiomolybdate inhibits copper trafficking proteins through metal cluster formation. Science, 2010,327(5963):331-334. DOI URL
[15]	PAN Q, KLEER C G, VAN GOLEN K L, et al. Copper deficiency induced by tetrathiomolybdate suppresses tumor growth and angiogenesis. Cancer Research, 2002,62(17):4854-4859.
[16]	CHAN N, WILLIS A, KORNHAUSER N, et al. Influencing the tumor microenvironment: a phase II study of copper depletion using tetrathiomolybdate in patients with breast cancer at high risk for recurrence and in preclinical models of lung metastases. Clinical Cancer Research, 2017,23(3):666-676. DOI URL
[17]	MIAO Z Z, LI G W, LIU C Z, et al. Study on antibacterial properties of copper-loaded chitosan particles. Journal of Henan Institute of Science and Technology, 2010,38(2):78-80.
[18]	XU Q, CHANG M L, ZHANG Y, et al. PDA/Cu bioactive hydrogel with "hot ions effect" for inhibition of drug-resistant bacteria and enhancement of infectious skin wound healing. ACS Applied Materials & Interfaces, 2020,12(28):31255-31269.
[19]	LI J, ZHAI D, LU F, et al. Preparation of copper-containing bioactive glass/eggshell membrane nanocomposites for improving angiogenesis, antibacterial activity and wound healing. Acta Biomater., 2016,36:254-266. DOI URL

钼掺杂铜硅钙石的制备及其抗菌性能和细胞相容性研究

Mo Doped Cuprorivaite: Preparation, Antibacterial and Cytocompatibility

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 19

相关文章 15

编辑推荐

Metrics

本文评价

[1]	孔国强, 冷明哲, 周战荣, 夏池, 沈晓芳. Sb掺杂O3型Na_0.9Ni_0.5Mn_0.3Ti_0.2O₂钠离子电池正极材料[J]. 无机材料学报, 2023, 38(6): 656-662.
[2]	孙强强, 陈子璇, 杨子玥, 王毅梦, 曹宝月. 金属镍铜负载钒氧化物的高效电解产氢性能[J]. 无机材料学报, 2023, 38(6): 647-655.
[3]	杨颖康, 邵怡晴, 李柏良, 吕志伟, 王路路, 王亮君, 曹逊, 吴宇宁, 黄荣, 杨长. Cl掺杂对CuI薄膜发光性能增强研究[J]. 无机材料学报, 2023, 38(6): 687-692.
[4]	李悦, 张旭良, 景芳丽, 胡章贵, 吴以成. 铈掺杂硼酸钙镧晶体的生长与性能研究[J]. 无机材料学报, 2023, 38(5): 583-588.
[5]	齐占国, 刘磊, 王守志, 王国栋, 俞娇仙, 王忠新, 段秀兰, 徐现刚, 张雷. GaN单晶的HVPE生长与掺杂进展[J]. 无机材料学报, 2023, 38(3): 243-255.
[6]	王志强, 吴济安, 陈昆峰, 薛冬峰. 大尺寸Er,Yb:YAG单晶的生长及其性能[J]. 无机材料学报, 2023, 38(3): 329-334.
[7]	陆晨辉, 葛万银, 宋盼盼, 张盼锋, 徐美美, 张伟. 用于白光LED稀土Eu掺杂SiAlON基荧光粉的发光性能[J]. 无机材料学报, 2023, 38(1): 97-104.
[8]	盛丽丽, 常江. 光/磁热Fe₂SiO₄/Fe₃O₄双相生物陶瓷及其复合电纺丝膜制备及抗菌性能研究[J]. 无机材料学报, 2022, 37(9): 983-990.
[9]	王洋, 范广新, 刘培, 尹金佩, 刘宝忠, 朱林剑, 罗成果. 钾离子掺杂提高锂离子电池正极锰酸锂性能的微观机制[J]. 无机材料学报, 2022, 37(9): 1023-1029.
[10]	柳琪, 朱璨, 谢贵震, 王俊, 张东明, 邵刚勤. Ce掺杂SrMgF₄超结构多晶体的吸收/光致发光光谱[J]. 无机材料学报, 2022, 37(8): 897-902.
[11]	邹顺, 何夕云, 曾霞, 仇萍荪, 凌亮, 孙大志. 掺铋钇铁石榴石磁光陶瓷的热压烧结及其性能研究[J]. 无机材料学报, 2022, 37(7): 773-779.
[12]	何慧凯, 杨蕊, 夏剑, 王廷泽, 董德泉, 缪向水. 高均一性二维碲化钼忆阻器阵列及其神经形态计算应用[J]. 无机材料学报, 2022, 37(7): 795-801.
[13]	焦博新, 刘兴翀, 全子威, 彭永姗, 周若男, 李海敏. L-精氨酸掺杂钙钛矿太阳电池性能研究[J]. 无机材料学报, 2022, 37(6): 669-675.
[14]	王新健, 朱逸璇, 张鹏, 杨文龙, 王挺, 郇宇. (Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1-_xSn_x)O₃无铅压电陶瓷的相结构与压电性能[J]. 无机材料学报, 2022, 37(5): 513-519.
[15]	安琳, 吴淏, 韩鑫, 李耀刚, 王宏志, 张青红. 非贵金属Co_5.47N/N-rGO助催化剂增强TiO₂光催化制氢性能[J]. 无机材料学报, 2022, 37(5): 534-540.