Titanium is considered to be the most essential metal in the field of implantology. The main factors determining metal biocompatibility, among others, include the morphology and chemical composition of the titanium surface. Therefore, the aim of this work was to develop approaches to control the biological activity of the titanium surface by creating coatings that combine both an inorganic phase with a given morphology and organic molecules containing an integrin-selective peptide that regulate cell adhesion and proliferation. As such, we synthesized new c(RGDfC) derivatives of amino acid bisphosphonates (four examples) with different bisphosphonate anchors and maleimide linkers. These molecules were deposited on a highly developed porous surface obtained via the plasma electrolytic oxidation (PEO) of coarse-grained and nanostructured titanium. In vitro studies demonstrated the increase in the viability degree of mesenchymal stem cells and fibroblasts on the surface of coarse-grained or nanostructured titanium modified with PEO and a c(RGDfC) derivative of ε-aminocaproic acid bisphophonate with an SMCC linker. As a result, the use of conjugates of amino acid bisphosphonates with a cyclic RGD peptide for the modification of PEO-coated titanium opens the ways for the effective control of the biological activity of the metal implant surface.
Gold nanoparticles (AuNPs) are of significant interest due to their unique properties and applications in biomedicine. While hyaluronic acid (HA) has been used to modify pre-formed AuNPs, its thiolated derivative (HA−SH) has been less explored for the direct synthesis and stabilization of AuNPs. This study investigates the use of thiolated hyaluronic acid as a key component in the synthesis of AuNPs. A series of HA-AuNPs (HA-AuNP1-4) were synthesized by reacting HA-SH with HAuCl4 at different mass ratios. The resulting nanoparticles were characterized using UV-Vis spectroscopy, scanning/transmission electron microscopy (SEM/STEM), X-ray photoelectron spectroscopy (XPS), photon cross-correlation spectroscopy (PCCS), and zeta potential measurements. The chemical transformations of the thiol ligand were studied using NMR spectroscopy. The morphologies and sizes of AuNPs depended on the HA-SH-to-HAuCl4 ratio, ranging from icosahedral and triangular particles (≥146 nm) to quasi-spherical particles with a bimodal distribution (6–7 nm and 45–60 nm). XPS confirmed the presence of metallic gold (Au0) and a Au−S bond, while NMR and XPS revealed the partial oxidation of thiol groups to sulfonic acid. Zeta potential measurements showed that lower HAuCl4 concentrations resulted in higher negative charge (up to −41.5 mV), enhancing colloidal stability. This work demonstrates a versatile approach to the synthesis of hyaluronic acid-based gold nanomaterials with tunable properties for potential biomedical applications.
Gold nanoparticles (AuNPs) are promising for biomedical applications, but their synthesis often requires toxic reagents. “Green” methods utilizing biopolymers offer a sustainable alternative. This study presents a novel synthesis of stable gold nanoparticles using a disulfide-crosslinked derivative of alginic acid (AA–S–S–AA) as both a reducing agent and stabilizer. The S–S-cross-linked alginate was synthesized with a degree of substitution of ~4.2% and reacted with HAuCl4 in water at room temperature for just 10 min to give stable and polysaccharide in situ modified gold nanoparticles (AA-AuNPs). The resulting AA-AuNPs were characterized by a surface plasmon resonance peak at 539 nm and exhibited good colloidal stability over 14 days. Electron microscopy revealed spherical nanoparticles with a bimodal size distribution (10 nm and 75–100 nm) and a visible polysaccharide shell (5–9 nm), confirming effective stabilization. X-ray photoelectron spectroscopy confirmed the presence of metallic gold (Au0) and Au1+. NMR analysis indicated the oxidation of disulfide groups to sulfonic acid during synthesis. The nanoparticles demonstrated a high negative zeta-potential of −53.9 mV, attributable to the polyanionic alginate corona, ensuring strong electrostatic stabilization. This work establishes sulfur-modified alginic acid as an efficient platform for the rapid synthesis of stable, hybrid nanoparticles for potential use in catalysis and biomedicine.
Gold nanoparticles (AuNPs) are of significant interest due to their unique properties and applications in biomedicine. While hyaluronic acid (HA) has been used to modify pre-formed AuNPs, its thiolated derivative (HA-SH) has been less explored for the direct synthesis and stabilization of AuNPs. This study investigates the use of thiolated hyaluronic acid as a key component in the synthesis of AuNPs. A series of HA-AuNPs (HA-AuNP1-4) were synthesized by reacting HA-SH with HAuCl₄ at different mass ratios. The resulting nanoparticles were characterized using UV-Vis spectroscopy, scanning/transmission electron microscopy (SEM/STEM), X-ray photoelectron spectroscopy (XPS), photon cross-correlation spectroscopy (PCCS), and zeta potential measurements. The chemical transformations of the thiol ligand were studied using NMR spectroscopy. The morphologies and sizes of AuNPs depended on the HA-SH to HAuCl₄ ratio, ranging from icosahedral and triangular particles (≥146 nm) to quasi-spherical particles with a bimodal distribution (6–7 nm and 45–60 nm). XPS confirmed the presence of metallic gold (Au⁰) and Au-S bond, while NMR and XPS revealed the partial oxidation of thiol groups to sulfonic acid. Zeta potential measurements showed that lower HAuCl₄ concentrations resulted in higher negative charge (up to -41.5 mV), enhancing colloidal stability. This work demonstrates a versatile approach to the synthesis hyaluronic acid-based gold nanomaterials with tunable properties for potential biomedical applications.