Biomolecule-functionalized exfoliated-graphene and graphene oxide as heteronucleants of nanocrystalline apatites to make hybrid nanocomposites with tailored mechanical, luminescent, and biological properties

IF 5.1 2区材料科学 Q1 MATERIALS SCIENCE, CERAMICS

Ceramics International Pub Date : 2024-10-08 DOI:10.1016/j.ceramint.2024.10.034

Francisco Javier Acebedo-Martínez , Paula Alejandra Baldión , Francesca Oltolina , Antonia Follenzi , Giuseppe Falini , Jorge Fernando Fernández-Sánchez , Duane Choquesillo-Lazarte , Jaime Gómez-Morales

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Abstract

Nanocrystalline apatite (Ap), known for its exceptional biological properties, faces limitations in hard tissue engineering due to its poor mechanical properties. To overcome this limitation, we investigated the preparation of nanocomposites through heterogeneous nucleation of calcium phosphate on exfoliated graphene (G) and graphene oxide (GO) flakes, selected for their outstanding mechanical properties. The flakes were treated (functionalized) with amino acids of varying isoelectric points—namely L-Arginine (Arg), L-Alanine (Aln) and L-Aspartic acid (Asp)— as well as citrate (Cit) molecules. Furthermore, Tb³⁺ was incorporated into the formulations to introduce luminescence and further enrich the functionality of the composite. The synthesis was conducted using the sitting drop vapor diffusion method. Functionalized GO/Ap nanocomposites significantly improved roughness, adhesion forces and elastic modulus compared to Ap and G-based particles. GO-Asp-Ap-Tb nanocomposites exhibited the highest roughness (163.8 ± 116.2 nm), while G-Cit-Ap had the lowest (6.8 ± 5.6 nm). In terms of adhesion force, GO-Cit-Ap-Tb reached the highest value (31.06 ± 13.3 nN), while G-Arg-Ap had the lowest (3.7 ± 1.8 nN) compared to Ap (13.6 ± 3.2 nN). For the elastic modulus, GO-Aln-Ap-Tb demonstrated the greatest stiffness (3489 ± 101.01 MPa) compared to Ap (30.2 ± 6.5 MPa), while G-Aln-Ap-Tb showed the lowest (17.2 ± 8.4 MPa). Concerning their luminescence, regardless of G/Ap and GO/Ap, the relative luminescence intensities depended on the biomolecule used and decreased in the order Arg > Aln > Asp and Cit. Furthermore, G/Ap and GO/Ap nanocomposites demonstrated good biocompatibility on murine mesenchymal stem cells at low concentrations, showing cell viabilities exceeding 80 % at 0.1 μg/mL. This research offers a novel approach to enhancing the mechanical properties of apatites while preserving their good biocompatibility properties and introducing new functionalities (i.e. luminescence) in the composites, thereby expanding their range of applications in hard tissue engineering.

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将生物分子功能化的剥离石墨烯和氧化石墨烯作为纳米晶磷灰石的异质核，制成具有定制机械、发光和生物特性的混合纳米复合材料

纳米晶磷灰石（Ap）以其优异的生物特性而闻名，但由于其机械特性较差，在硬组织工程中面临着局限性。为了克服这一限制，我们研究了通过在剥离石墨烯（G）和氧化石墨烯（GO）薄片上异质成核磷酸钙制备纳米复合材料的方法。用不同等电点的氨基酸--即 L-精氨酸（Arg）、L-丙氨酸（Aln）和 L-天冬氨酸（Asp）--以及柠檬酸盐（Cit）分子对这些薄片进行处理（功能化）。此外，配方中还加入了 Tb3+，以引入发光并进一步丰富复合材料的功能。合成采用坐滴蒸发扩散法。与基于 Ap 和 G 的颗粒相比，功能化 GO/Ap 纳米复合材料明显改善了粗糙度、附着力和弹性模量。GO-Asp-Ap-Tb 纳米复合材料的粗糙度最高（163.8 ± 116.2 nm），而 G-Cit-Ap 的粗糙度最低（6.8 ± 5.6 nm）。在粘附力方面，GO-Cit-Ap-Tb 达到最高值（31.06 ± 13.3 nN），而 G-Arg-Ap 与 Ap（13.6 ± 3.2 nN）相比最低（3.7 ± 1.8 nN）。在弹性模量方面，与 Ap（30.2 ± 6.5 兆帕）相比，GO-Aln-Ap-Tb 的刚度最大（3489 ± 101.01 兆帕），而 G-Aln-Ap-Tb 的刚度最小（17.2 ± 8.4 兆帕）。关于它们的发光，无论 G/Ap 和 GO/Ap，相对发光强度都取决于所使用的生物大分子，并按照 Arg > Aln > Asp 和 Cit 的顺序降低。此外，G/Ap 和 GO/Ap 纳米复合材料在低浓度下对小鼠间充质干细胞具有良好的生物相容性，在 0.1 μg/mL 浓度下，细胞存活率超过 80%。这项研究提供了一种新方法，既能增强磷灰石的机械性能，又能保持其良好的生物相容性，还能在复合材料中引入新的功能（如发光），从而扩大其在硬组织工程中的应用范围。

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来源期刊

Ceramics International 工程技术-材料科学：硅酸盐

CiteScore

9.40

自引率

15.40%

发文量

4558

审稿时长

25 days

期刊介绍： Ceramics International covers the science of advanced ceramic materials. The journal encourages contributions that demonstrate how an understanding of the basic chemical and physical phenomena may direct materials design and stimulate ideas for new or improved processing techniques, in order to obtain materials with desired structural features and properties. Ceramics International covers oxide and non-oxide ceramics, functional glasses, glass ceramics, amorphous inorganic non-metallic materials (and their combinations with metal and organic materials), in the form of particulates, dense or porous bodies, thin/thick films and laminated, graded and composite structures. Process related topics such as ceramic-ceramic joints or joining ceramics with dissimilar materials, as well as surface finishing and conditioning are also covered. Besides traditional processing techniques, manufacturing routes of interest include innovative procedures benefiting from externally applied stresses, electromagnetic fields and energetic beams, as well as top-down and self-assembly nanotechnology approaches. In addition, the journal welcomes submissions on bio-inspired and bio-enabled materials designs, experimentally validated multi scale modelling and simulation for materials design, and the use of the most advanced chemical and physical characterization techniques of structure, properties and behaviour. Technologically relevant low-dimensional systems are a particular focus of Ceramics International. These include 0, 1 and 2-D nanomaterials (also covering CNTs, graphene and related materials, and diamond-like carbons), their nanocomposites, as well as nano-hybrids and hierarchical multifunctional nanostructures that might integrate molecular, biological and electronic components.