蛋白质吸附对医用金属材料体外腐蚀行为的影响

doi:10.11900/0412.1961.2020.00198

金属学报

2021, Vol. 57

Issue (1): 1-15 DOI: 10.11900/0412.1961.2020.00198

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蛋白质吸附对医用金属材料体外腐蚀行为的影响

王鲁宁¹^,²(

), 刘丽君¹, 岩雨¹^,³, 杨坤¹, 陆黎立¹

^1.北京科技大学材料科学与工程学院北京材料基因工程高精尖创新中心北京 100083
^2.北京科技大学新金属材料国家重点实验室北京 100083
^3.北京科技大学新材料技术研究院北京 100083

Influences of Protein Adsorption on the in vitro Corrosion of Biomedical Metals

WANG Luning¹^,²(

), LIU Lijun¹, YAN Yu¹^,³, YANG Kun¹, LU Lili¹

^1.Beijing Advanced Innovation Center for Materials Genome Engineering, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China
^2.State Key Laboratory for Advanced Metals and Materials, University of Science and Technology Beijing, Beijing 100083, China
^3.Institute for Advanced Materials and Technology, University of Science and Technology Beijing, Beijing 100083, China

引用本文:

王鲁宁, 刘丽君, 岩雨, 杨坤, 陆黎立. 蛋白质吸附对医用金属材料体外腐蚀行为的影响[J]. 金属学报, 2021, 57(1): 1-15.
Luning WANG, Lijun LIU, Yu YAN, Kun YANG, Lili LU. Influences of Protein Adsorption on the in vitro Corrosion of Biomedical Metals[J]. Acta Metall Sin, 2021, 57(1): 1-15.

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摘要:

医用金属材料与体液接触时，蛋白质会快速吸附在其表面，并对材料的腐蚀行为产生影响。体外测试结果表明，蛋白质的吸附会减缓腐蚀；蛋白质-金属复合物脱离材料表面会加速腐蚀，如果沉积在材料表面，则会减缓腐蚀。蛋白质在金属材料表面的吸附及对腐蚀的影响与自身的种类和浓度、金属材料的性质等因素有关。目前，蛋白质吸附对医用金属材料腐蚀行为的影响尚未达成共识。蛋白质作为体液中重要的成分之一，体外测试中需要考虑其对医用金属材料腐蚀的影响，以便于明确体内外测试结果的差异和寻找合适的体外测试环境，这将有利于对医用金属材料在体内的腐蚀行为做出合理的预测。

关键词 ：蛋白质, 医用金属材料, 腐蚀, 吸附, 体外测试

Abstract：

Protein could adsorb on the surfaces when biomedical metals contact with body fluids and then affect the corrosion behavior of metals. In vitro results demonstrate that protein adsorption retards metal dissolution, while the detachment of metal-protein complex from the surface accelerates the corrosion or its deposition could impede the metal corrosion. Protein adsorption and its influences on the metal corrosion are related to many factors, such as the type and content of proteins as well as the pro-perty of metals. Therefore, consensus has not been made on the influences of protein on metal corrosion. However, as one of most important components in the body fluids, it should be taken into consideration for the effects of protein on the corrosion behavior of metals in vitro. So that we can find the discrepancy between in vivo and in vitro tests and find the suitable simulated environment in vitro. This will help predict reasonably the corrosion behavior of biomedical metals in the human body.

Key words： protein biomedical metal corrosion adsorption in vitro test

收稿日期: 2020-06-03

ZTFLH:

TG146.13

基金资助:国家重点研发计划项目(2016YFC251100);国家自然科学基金项目(51503014)

作者简介: 王鲁宁，男，1980年生，教授，博士

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表1 Mg及镁合金体内外测试中的腐蚀速率[3~7] (mm/a, unless otherwise indicated)

图1 体内外测试中镁合金腐蚀速率的对比(少于3组数据所得的条形图无误差棒)

Fluid	Na⁺	K⁺	Ca²⁺	Mg²⁺	Cl^-	HCO $3 -$	HPO $4 2 -$	H₂PO $4 -$	SO $4 2 -$
	mmol·L^-1	mmol·L^-1	mmol·L^-1	mmol·L^-1	mmol·L^-1	mmol·L^-1	mmol·L^-1	mmol·L^-1	mmol·L^-1
Blood plasma^[10,13]	134-143	3.5-4.7	2.1-2.7	1.5	100-108	25-30	1.0	-	0.5
Synovia fluids^[10]	133-139	3.5-4.5	1.2-2.4		87-138	-	-	-
SBF^[15]	142.0	5.0	2.5	1.5	148.0	4.2	1.0	-	0.5
PBS^[3]	154.1	4.1	-	-	140.6	-	8.1	1.5	-
HBSS^[3,12]	142.8	5.8	2.5	0.8	143.3	4.2	0.3	0.4	0.8
DMEM^[3,12]	155.3	5.3	1.8	0.8	115.7	44.1	0.9	-	0.8
Ringer??s^[14]	147	4.1	4.3	-	160	-	-	-	-
SBP^[11]	142.0	5.0	2.5	1.5	103.0	27.0	1.0	-	0.5
Fluid	Amino acids	Glucose	Uric acid	Vitamins	Phenol red	Albumin	IgG	Fibrinogen
	g·L^-1	g·L^-1	g·L^-1			g·L^-1	g·L^-1	g·L^-1
Blood plasma^[10,13]	20-51	650-966	30.5-70.7	-	-	37.6-54.9	6.4-13.5	2-4
Synovia fluids^[10]	-	-	39	-		6-10	1.47-4.62	-
SBF^[15]	-	-		-	-
PBS^[3]	-	-		-	-
HBSS^[3,12]	-	5.6		-	-
DMEM^[3,12]	10.6	25.0		0.15	0.04
Ringer??s^[14]	-	-		-	-
SBP^[11]	-	-		-	-

表2 血浆、关节滑液、几种常用模拟体液和模拟血浆的主要化学成分[3,10~15]

表3 金属粉末在生理盐水和含有蛋白质的溶液中浸泡16 h后，金属离子的释放量[29] (10-6)

图2 牛血清白蛋白(BSA，PDB bank：4f5s)的结构示意图

图3 分子动力学模拟BSA在2种表面吸附后的优化构型[39]

表4 不同蛋白质的结构、尺寸、分子量及等电点[42]

图4 在模拟体液中，蛋白质通过静电吸引作用吸附在材料表面(a) BSA adsorbs on Mg surface with positive charges(b) LYS adsorbs on Fe surface with negative charges

表5 BSA和纤维蛋白在材料表面的结合常数和吸附饱和值[44]

图5 模拟海水环境中，BSA在不锈钢表面的吸附模型图：BSA先是牢固地吸附在氧化层上，溶液中的Mg2+与之连接，促使第二层BSA吸附[46]

图6 CoCrMo合金表面及BSA吸附在CoCrMo合金表面后的AFM形貌图和对应的扫描Kelvin探针测量的电势图，每张图下的曲线表示图中绿线位置的形貌起伏和电势变化，以及BSA在CoCrMo表面吸附后，诱导表面电子聚集的示意图[36]

图7 PBS中添加不同浓度BSA (0~4 g/L)时，316L[66]、CoCrMo[66]、Ti-6Al-4V[66]和纯Zr[28]的动电位极化曲线

图8 M1A镁合金在SBF和含有BSA的SBF (A-SBF)中的腐蚀模型[15](a) M1A sample (b-d) M1A suffered pitting corrosion in SBF (e-g) BSA adsorption protected the M1A from pitting corrosion in A-SBF

表6 体外测试中，不同溶液中添加蛋白质对医用金属材料腐蚀速率的影响

图9 BSA吸附过程中，钛合金/液体界面之间电荷转移的理论模型[55]

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