硅烷化介孔硼硅酸盐生物玻璃微球对PMMA骨水泥生物活性和力学性能的影响

doi:10.15541/jim20230039

摘要/Abstract

摘要：

聚甲基丙烯酸甲酯(PMMA)骨水泥因具有良好的力学性能、适宜的凝固时间和低毒性等优点而在骨科手术中作为可注射型人工骨修复材料受到广泛的应用。然而，其生物惰性可能导致假体长期植入后产生无菌性松动。本研究采用模板法制备了介孔硼硅酸盐生物玻璃微球(MBGS), 并用硅烷偶联剂γ-甲基丙烯酰氧基丙基三甲氧基硅烷(γ-MPS)对其进行改性, 制备了MBGSSI。再将硅烷化介孔硼硅酸盐生物玻璃微球(MBGSSI)与聚甲基丙烯酸甲酯(PMMA)骨水泥复合, 制备了一种具有良好生物活性和力学性能的复合骨水泥。实验结果表明, 由于γ-MPS与MBGS的结合主要发生在介孔微球的近表面, MBGSSI比MBGS具有更大的比表面积和更小的孔容积。与MBGS/PMMA复合骨水泥相比, γ-MPS可以改善复合材料中无机相和有机相之间的结合, 因此MBGSSI/PMMA复合骨水泥的力学性能得到了改善, 符合ISO 5833:2002对丙烯酸类骨水泥的力学性能要求。此外, 在SBF溶液中浸泡42 d后, MBGS/PMMA和MBGSSI/PMMA复合骨水泥的表面均生成了羟基磷灰石(HA), 证明复合骨水泥具有良好的生物活性。因此, MBGSSI/PMMA复合骨水泥是一种潜在的骨修复材料。

关键词: 生物玻璃, 硅烷化, PMMA骨水泥, 生物活性, 力学性能

Abstract:

Poly(methyl methacrylate) (PMMA) bone cement is widely used in orthopaedic surgery as an injectable artificial bone repair material due to its advantages such as desirable mechanical properties, suitable curing time and low toxicity. However, its bioinert polymer may lead to aseptic loosening of the prostheses after long-term implantation. Here, silanized mesoporous borosilicate bioglass microspheres (MBGSSI) composite with PMMA bone cement was prepared to obtain ideal bone repair material with desirable bioactivity and mechanical properties. Mesoporous borosilicate bioglass microspheres (MBGS) were prepared by template method and modified by silane coupling agent γ-methylacryloxy propyl trimethoxysilane (γ-MPS) to obtain MBGSSI. The results indicated that MBGSSI possessed increased specific surface area and decreased total pore volume than MBGS did by the binding between γ-MPS and MBGS occurred on the near surface of mesoporous microspheres. Compared with MBGS/PMMA, MBGSSI/PMMA composite bone cements demonstrated improved mechanical properties, which met the mechanical properties requirements of ISO 5833:2002 because γ-MPS improved the combination between inorganic and organic phases of composite. In addition, the hydroxyapatite (HA) could widely form on the surface of both MBGS/PMMA and MBGSSI/PMMA composite bone cements after immersing in SBF for 42 d, demonstrating the excellent bioactivity. Hence, it is suggested that MBGSSI/PMMA can be a potential bone repair material.

Key words: bioglass, silanization, PMMA bone cement, bioactivity, mechanical property

中图分类号:

R318

倪晓诗, 林子扬, 秦沐严, 叶松, 王德平. 硅烷化介孔硼硅酸盐生物玻璃微球对PMMA骨水泥生物活性和力学性能的影响[J]. 无机材料学报, 2023, 38(8): 971-977.

NI Xiaoshi, LIN Ziyang, QIN Muyan, YE Song, WANG Deping. Bioactivity and Mechanical Property of PMMA Bone Cement: Effect of Silanized Mesoporous Borosilicate Bioglass Microspheres[J]. Journal of Inorganic Materials, 2023, 38(8): 971-977.

图/表 9

Fig. 1 Microstructures and constituents of MBGS and MBGSSI (a) XRD patterns of MBGS and MBGSSI; (b, c) FT-IR spectra (b) and TG curves (c) of MBGS, MBGSSI and γ-MPS; (d, e) TEM images of MBGS (d) and MBGSSI (e)

Fig. 2 (a) N2 adsorption-desorption isotherms and (b) corresponding pore size distributions of MBGS, and (c) schematic diagram of the surface silanization

Table 1 Specific surface area, average pore diameter and total pore volume of MBGS and MBGSSI

Sample	Specific surface area/(m²•g^-1)	Average pore diameter/nm	Total pore volume/(mL•g^-1)
MBGS	84.047	33.9676	0.7137
MBGSSI	227.856	10.22	0.5822

Fig. 3 (a) XPS spectra of MBGS and MBGSSI, XPS spectra of C1s in MBGSSI at etching depths of (b) 0 and (c) 100 nm

Table 2 Atomic concentrations of MBGS, MBGSSI and MBGSSI (etching depth at 100 nm)

Sample	C1s/%	O1s/%	Si2p/%	B1s/%	Ca2p/%
MBGS	5.02	72.38	5.27	2.71	14.62
MBGSSI 0 nm	7.91	70.26	5.68	2.27	13.88
MBGSSI 100 nm	5.32	68.88	6.81	2.25	16.74

Table 3 Setting and mechanical properties of PMMA, MBGS/PMMA and MBGSSI/PMMA bone cements

Sample	Dough time/s	Setting time/min	Peak temperature/℃	Compressive strength/MPa	Compressive modulus/MPa	Flexural strength/MPa	Flexural modulus/MPa
PMMA	287.5±7.8	11.38±0.37	49.15±1.45	70.01±1.85	878.67±55.84	67.75±1.88	2925.05±144.71
MBGS/PMMA	136.0±2.8	14.77±0.07	40.65±0.25	71.22±2.20	1029.66±63.54	44.53±2.59	4003.19±125.79
MBGSSI/PMMA	174.0±5.7	18.97±0.20	38.40±0.4	81.77±1.45	1091.50±75.64	59.42±4.34	3330.03±214.02

Fig. 4 Dispersity of MBGS and MBGSSI in MMA at (a) initial or for (b) 5 min, (c) 1 h, (d) 3 h and (e) 5 h

Fig. 5 SEM images of (a, b) PMMA, (c, d) MBGS/PMMA and (e, f) MBGSSI/PMMA

Fig. 6 SEM images and EDS patterns of (a, b) PMMA, (c, d) MBGS/PMMA and (e, f) MBGSSI/PMMA, and (g) XRD patterns of PMMA, MBGS/PMMA, MBGSSI/PMMA

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