Copper-Based Complexes with Adamantane Ring-Conjugated bis(3,5-Dimethyl-pyrazol-1-yl)acetate Ligand as Promising Agents for the Treatment of Glioblastoma.

The new ligand L2Ad, obtained by conjugating the bifunctional species bis(3,5-dimethylpyrazol-1-yl)-acetate and the drug amantadine, was used as a chelator for the synthesis of new Cu complexes 1-5. Their structures were investigated by synchrotron radiation-induced X-ray photoelectron spectroscopy (SR-XPS), near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and by combining X-ray absorption fine structure (XAFS) spectroscopy techniques and DFT modeling. The structure of complex 3 was determined by single-crystal X-ray diffraction analysis. Tested on U87, T98, and U251 glioma cells, Cu(II) complex 3 and Cu(I) complex 5 decreased cell viability with IC50 values significantly lower than cisplatin, affecting cell growth, proliferation, and death. Their effects were prevented by treatment with the Cu chelator tetrathiomolybdate, suggesting the involvement of copper in their cytotoxic activity. Both complexes were able to increase ROS production, leading to DNA damage and death. Interestingly, nontoxic doses of 3 or 5 enhanced the chemosensitivity to Temozolomide.

Metal nanostructures in polymeric matrices for optical detection and removal of heavy metal ions, pesticides and dyes from water.

Water pollutants such as heavy metal ions, pesticides, and dyes pose a worldwide issue. Their presence in water resources interferes with the normal growth mechanisms of living beings and causes long or short-term diseases. For this reason, research continuously tends to develop innovative, selective, and efficient processes or technologies to detect and remove pollutants from water. This review provides an up-to-date overview on metal nanoparticles loaded in polymeric matrices, such as hydrogels and membranes, and employed as optical sensors and as removing materials for water pollutants. The synthetic pathways of nanomaterials loading into polymeric matrices have been analyzed, particularly focusing on noble metal nanoparticles, noble metal nanoclusters, and metal oxide nanoparticles. Moreover, the sensing properties of modified matrices towards water pollutants have been discussed in addition to the interaction mechanisms between the sensors and the toxic compounds. The last part of the review has been devoted to illustrating the separation mechanism and removal performance of membranes loaded with nanomaterials in the treatment and purification of water streams from different contaminants (heavy metals, dyes and pesticides).

Resorbable engineered barrier membranes for oral surgery applications.

Population aging, reduced economic capacity, and neglecting the treatments for oral pathologies, are the main causal factors for about 3 billion individuals who are suffering from partial/total edentulism or alveolar bone resorption: thus, the demand for dental implants is increasingly growing. To achieve a good prognosis for implant-supported restorations, adequate peri-implant bone volume is mandatory. The Guided Bone Regeneration (GBR) technique is one of the most applied methods for alveolar bone reconstruction and treatment of peri-implant bone deficiencies. This technique involves the use of different types of membranes in association with some bone substitutes (autologous, homologous, or heterologous). However, time for bone regeneration is often too long and the bone quality is not simply predictable. This study aims at engineering and evaluating the efficacy of modified barrier membranes, enhancing their bioactivity for improved alveolar bone tissue regeneration. We investigated membranes functionalized with chitosan (CS) and chitosan combined with the peptide GBMP1α (CS + GBMP1α), to improve bone growth. OsseoGuard® membranes, derived from bovine Achilles tendon type I collagen crosslinked with formaldehyde, were modified using CS and CS + GBMP1α. The functionalization, carried out with 1-ethyl-3-(3 dimethylaminopropyl)carbodiimide and sulfo-N-Hydroxysuccinimide (EDC/sulfo-NHS), was assessed through FT-IR and XPS analyses. Biological assays were performed by directly seeding human osteoblasts onto the materials to assess cell proliferation, mineralization, gene expression of Secreted Phosphoprotein 1 (SPP1) and Runt-Related Transcription Factor 2 (Runx2), and antibacterial properties. Both CS and CS + GBMP1α functionalizations significantly enhanced human osteoblast proliferation, mineralization, gene expression, and antibacterial activity compared to commercial membranes. The CS + GBMP1α functionalization exhibited superior outcomes in all biological assays. Mechanical tests showed no significant alterations of membrane biomechanical properties post-functionalization. The engineered membranes, especially those functionalized with CS + GBMP1α, are suitable for GBR applications thanks to their ability to enhance osteoblast activity and promote bone tissue regeneration. These findings suggest a potential advancement in the treatment of oral cavity problems requiring bone regeneration.

Three-Dimensional Printed Filters Based on Poly(ethylene glycol) Diacrylate Hydrogels Doped with Silver Nanoparticles for Removing Hg(II) Ions from Water.

Nowadays, due to water pollution, more and more living beings are exposed to dangerous compounds, which can lead to them contracting diseases. The removal of contaminants (including heavy metals) from water is, therefore, a necessary aspect to guarantee the well-being of living beings. Among the most used techniques, the employment of adsorbent materials is certainly advantageous, as they are easy to synthesize and are cheap. In this work, poly(ethylene glycol) diacrylate (PEGDA) hydrogels doped with silver nanoparticles (AgNPs) for removing Hg(II) ions from water are presented. AgNPs were embedded in PEGDA-based matrices by using a photo-polymerizable solution. By exploiting a custom-made 3D printer, the filters were synthesized. The kinetics of interaction was studied, revealing that the adsorption equilibrium is achieved in 8 h. Subsequently, the adsorption isotherms of PEGDA doped with AgNPs towards Hg(II) ions were studied at different temperatures (4 °C, 25 °C, and 50 °C). In all cases, the best isotherm model was the Langmuir one (revealing that the chemisorption is the driving process and the most favorable one), with maximum adsorption capacities equal to 0.55, 0.57, and 0.61 mg/g, respectively. Finally, the removal efficiency was evaluated for the three temperatures, obtaining for 4 °C, 25 °C, and 50 °C the values 94%, 94%, and 86%, respectively.

Cu(I) Coordination Compounds Conjugated to Au Nanorods for Future Applications in Drug Delivery: Insights in Molecular, Electronic and Cu Local Structure in Solid and Liquid Phase.

In the framework of the design, synthesis and testing of a library of copper complexes and nanostructured assemblies potentially endowed with antitumor and antiviral activity and useful for several applications, from drugs and related delivery systems to the development of biocidal nanomaterials, we present the detailed spectroscopic investigation of the molecular and electronic structure of copper-based coordination compounds and of a new conjugated system obtained by grafting Cu(I) complexes to gold nanorods. More in detail, the electronic and molecular structures of two Cu complexes and one AuNRs/Cu-complex adduct were investigated by X-ray photoelectron spectroscopy (XPS), synchrotron-induced XPS (SR-XPS) and near edge X-ray absorption spectroscopy (NEXAFS) in solid state, and the local structure around copper ion was assessed by X-ray absorption spectroscopy (XAS) both in solid state and water solution for the AuNRs/Cu-complex nanoparticles. The proposed multi-technique approach allowed to properly define the coordination geometry around the copper ion, as well as to ascertain the molecular structures of the coordination compounds, their stability and modifications upon interaction with gold nanoparticles, by comparing solid state and liquid phase data.