Zulfiya R. Galimshina

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 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 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.

The work presents the results on the development of organic coatings based on conjugates of hyaluronic acid with bisphosphonates of amino acids and oligopeptides – KRGD or the osteogenic growth peptide (OGP) – for modifying the metal surface with a porous inorganic sublayer obtained through plasma-electrolytic oxidation (PEO). Derivatives of hyaluronic acid (HYA) were synthesized via a Michael reaction involving maleimides of γ-aminobutyric acid bisphosphonate and oligopeptides, as well as SH-functionalized HYA. The conjugates were introduced into the pores of PEO coating on coarse-grained Ti (Grade 2) by immersing the metal samples in the solutions. The presence of organic molecules in the PEO sublayer was confirmed by X-ray photoelectron spectroscopy (XPS). The immobilization of organic molecules on the metal surface led to an increase in its hydrophilicity. Further, studies were carried out on human dermal fibroblasts (hDF) and human adipose-derived mesenchymal stem cells (hASC) to assess the cytotoxicity of the materials, as well as to evaluate the adhesion and proliferation of cells on the modified surface. Research has demonstrated a reduction in cell adhesion and proliferation on the samples modified with conjugates of HYA with peptides and bisphosphonates, which may be attributed to the high hydrophilicity of the surface. OGP applied to the Ti-PEO sublayer exhibited a significant positive effect on hASC adhesion and proliferation.

The general trend of increasing life expectancy will consistently drive the demand for orthopedic prostheses. In addition to the elderly, the younger population is also in urgent need of orthopedic devices, as bone fractures are a relatively common injury type; it is important to treat the patient quickly, painlessly, and eliminate further health complications. In the field of traumatology and orthopedics, metals and their alloys are currently the most commonly used materials. In this context, numerous scientists are engaged in the search for new implant materials and coatings. Among the various coating techniques, plasma electrolytic oxidation (PEO) (or micro-arc oxidation—MAO) occupy a distinct position. This method offers a cost-effective and environmentally friendly approach to modification of metal surfaces. PEO can effectively form porous, corrosion-resistant, and bioactive coatings on light alloys. The porous oxide surface structure welcomes organic molecules that can significantly enhance the corrosion resistance of the implant and improve the biological response of the body. The review considers the most crucial aspects of new combined PEO-organic coatings on metal implants, in terms of their potential for implantation, corrosion resistance, and biological activity in vitro and in vivo.

According to the world statistics, the proportion of older people in the total population is increasing. The general trend of increasing life expectancy will consistently drive the demand for orthopedic prostheses. In addition to the elderly, the younger population is also in urgent need of orthopedic devices, as bone fractures are a relatively common injury type; it is important to treat the patient quickly, painlessly and eliminate further health complications. In the field of traumatology and orthopedics, metals and their alloys are currently the most commonly used materials. Nevertheless, the application of such materials can bring infections and subsequent rejection. In this context, numerous scientists are engaged in the search for new implant materials and coatings. Among the various coating techniques employed for metal implants, plasma electrolytic oxidation (PEO) (or micro-arc oxidation – MAO) occupy a distinct position. This method offer a cost-effective and environmentally friendly approach to modification of metal surfaces. PEO can effectively form porous, corrosion-resistant and bioactive coatings on light alloys. The porous oxide surface structure welcomes organic molecules that can significantly enhance the corrosion resistance of the implant and improve the biological response of the body. This review collates and organizes the current advances in the investigation of various surface modifications of temporary and permanent metal implants using PEO (MAO) surface treatments in combination with organic compounds. The review considers the most crucial aspects of new combined PEO-organic coatings on metal implants, in terms of their potential for implantation, corrosion resistance and biological activity in vitro and in vivo.

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.