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Nuclear-grade graphite is a high-efficiency material, widely used for vacuum applications in nuclear reactors and accelerators as targets facing particle beams. In these contexts, graphite is often exposed to extreme thermal stresses altering its physical and chemical properties. The thermal-induced release of volatile contaminants from targets and the damage of structural components are critical issues that can affect the safety and operation efficiency of beamline facilities. Here, we provide for the first time a detailed picture of the chemical and morphological changes occurring in a nuclear-grade graphite target, obtained through Electrical Discharge Machining (EDM), when exposed in vacuum to high temperatures. The radial temperature gradient induced by the impact of a pulsed energetic (MeV- GeV range) focused particle beams was reproduced by cyclically heating, in the 1300-1800 K temperature range, a disc-shaped graphite target in a vacuum setup. An accurate surface and in-depth chemical analysis of the graphite target was obtained thanks to the high sensitivity (ppm/ppb) of the Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) technique. The chemical maps clearly show the presence of several metal oxides and impurities in the surface and subsurface regions of the untreated sample. Such contaminants were removed because of the thermal treatment in vacuum more or less efficiently, as demonstrated by Thermogravimetric analysis (TGA), X-ray Photoelectron Spectroscopy (XPS), and ToF-SIMS. However, Raman spectroscopy and SEM-EDS revealed that the high-temperature treatment induces a decrease in the crystallite size of the graphite as well as changes in the target surface porosity with the appearance of microvoids, leading the graphite target to be more prone to the breakage., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2024 The Authors.)

Hypothesis: Colloidal gold nanoparticles (AuNPs) functionalised with hydrophilic thiols can be used as drug delivery probes, thanks to their small size and hydrophilic character. AuNPs possess unique properties for their use in nanomedicine, especially in cancer treatment, as diagnostics and therapeutic tools., Experiments: Thiol functionalised AuNPs were synthesised and loaded with methotrexate (MTX). Spectroscopic and morphostructural characterisations evidenced the stability of the colloids upon interaction with MTX. Solid state (GISAXS, GIWAXS, FESEM, TEM, FTIR-ATR, XPS) and dispersed phase (UV-Vis, DLS, ζ-potential, NMR, SAXS) experiments allowed to understand structure-properties correlations. The nanoconjugate was tested in vitro (MTT assays) against two neuroblastoma cell lines: SNJKP and IMR5 with overexpressed n-Myc., Findings: Molar drug encapsulation efficiency was optimised to be >70%. A non-covalent interaction between the π system and the carboxylate moiety belonging to MTX and the charged aminic group of one of the thiols was found. The MTX loading slightly decreased the structural order of the system and increased the distance between the AuNPs. Free AuNPs showed no cytotoxicity whereas the AuNPs-MTX nanoconjugate had a more potent effect when compared to free MTX. The active role of AuNPs was evidenced by permeation studies: an improvement on penetration of the drug inside cells was evidenced., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Researchers in the field of tissue engineering are always searching for new scaffolds for bone repair. Polyetheretherketone (PEEK) is a chemically inert polymer that is insoluble in conventional solvents. PEEK's great potential in tissue engineering applications arises from its ability to not induce adverse reactions when in contact with biological tissues and its mechanical properties, which are similar to those of human bone. These exceptional features are limited by the bio-inertness of PEEK, which causes poor osteogenesis on the implant surface. Here, we demonstrated that the covalent grafting of the sequence (48-69) mapped on the BMP-2 growth factor (GBMP1α) significantly enhances the mineralization and gene expression of human osteoblasts. Different chemical methods were employed for covalently grafting the peptide onto 3D-printed PEEK disks: (a) the reaction between PEEK carbonyls and amino-oxy groups inserted in the peptides' N-terminal sites (oxime chemistry) and (b) the photoactivation of azido groups present in the peptides' N-terminal sites, which produces nitrene radicals able to react with PEEK surface. The peptide-induced PEEK surface modification was assessed using X-ray photoelectron measurements, while the superficial properties of the functionalized material were analyzed by means of atomic force microscopy and force spectroscopy. Live and dead assays and SEM measurements showed greater cell cover on functionalized samples than the control, without any cytotoxicity induction. Moreover, functionalization improved the rate of cell proliferation and the amount of calcium deposits, as demonstrated by the AlamarBlue™ and alizarin red results, respectively. The effects of GBMP1α on h-osteoblast gene expression were assayed using quantitative real-time polymerase chain reaction.

This work aims at preparing and characterizing a versatile multifunctional platform enabling the immobilization of macromolecules on a titanium surface by robust covalent grafting. Functionalized titanium is widely used in the biomedical field to improve its properties. Despite its high biocompatibility and osteointegrability, titanium implants are not very stable in the long term due to the onset of inflammation and bacterial infections. The proposed method allows the superficial insertion of three different organic linkers to be used as anchors for the attachment of biopolymers or bioactive molecules. This strategy used green solvents and is a good alternative to the proposed classic methods that employ organic solvents. The uniformly modified surfaces were characterized by micro-Fourier transform infrared spectroscopy (micro-FTIR), X-ray Photoelectron spectroscopy (XPS) and Near-Edge X-ray Absorption Fine Structure (NEXAFS). The latter made it possible to assess the orientation of the linker molecules with respect to the titanium surface. To test the efficiency of the linkers, two polymers (alginate and 2-(dimethylamino)-ethyl methacrylate (PDMAEMA)), with the potential ability to increase biocompatibility, were covalently attached to the titanium surfaces. The obtained results are a good starting point for the realization of stable polymeric coatings permanently bonded to the surface that could be used to extend the life of biomedical implants.

Polyetheretherketone (PEEK) is a thermoplastic polymer that has been recently employed for bone tissue engineering as a result of its biocompatibility and mechanical properties being comparable to human bone. PEEK, however, is a bio-inert material and, when implanted, does not interact with the host tissues, resulting in poor integration. In this work, the surfaces of 3D-printed PEEK disks were functionalized with: (i) an adhesive peptide reproducing [351-359] h-Vitronectin sequence (HVP) and (ii) HVP retro-inverted dimer (D2HVP), that combines the bioactivity of the native sequence (HVP) with the stability toward proteolytic degradation. Both sequences were designed to be anchored to the polymer surface through specific covalent bonds via oxime chemistry. All functionalized PEEK samples were characterized by Water Contact Angle (WCA) measurements, Atomic Force Microscopy (AFM), and X-ray Photoelectron Spectroscopy (XPS) to confirm the peptide enrichment. The biological results showed that both peptides were able to increase cell proliferation at 3 and 21 days. D2HVP functionalized PEEK resulted in an enhanced proliferation across all time points investigated with higher calcium deposition and more elongated cell morphology.

Several epidemiological studies suggest that a diet rich in fruit and vegetables reduces the incidence of neurodegenerative diseases. Resveratrol (Res) and its dimethylated metabolite, pterostibene (Ptb), have been largely studied for their neuroprotective action. The clinical use of Res is limited because of its rapid metabolism and its poor bioavailability. Ptb with two methoxy groups and one hydroxyl group has a good membrane permeability, metabolic stability and higher in vivo bioavailability in comparison with Res. The metabolism and pharmacokinetics of Ptb are still sparse, probably due to the lack of tools that allow following the Ptb destiny both in living cells and in vivo . In this contest, we propose two Ptb fluorescent derivatives where Ptb has been functionalised by benzofurazan and rhodamine-B-isothiocyanate, compounds 1 and 2 , respectively. Here, we report the synthesis, the optical and structural characterisation of 1 and 2 , and, their putative cytotoxicity in two different cell lines.

Gold nanoparticles (AuNPs) modified with four organoselenium compounds, i.e., 4-selenocyanatoaniline (compound 1), 4,4'-diselanediyldianiline (compound 2), N-(4-selenocyanatophenyl)cinnamamide (compound 3), and N-(3-selenocyanatopropyl)cinnamamide (compound 4), were synthesized following two different approaches: direct conjugation and non-covalent immobilization onto hydrophilic and non-cytotoxic AuNPs functionalized with 3-mercapto-1-propanesulfonate (3MPS). Both free compounds and AuNPs-based systems were characterized via UV-Vis, FTIR NMR, mass spectrometry, and SR-XPS to assess their optical and structural properties. Size and colloidal stability were evaluated by DLS and ζ-potential measurements, whereas morphology at solid-state was evaluated by atomic force (AFM) and scanning electron (FESEM) microscopies. AuNPs synthesized through chemical reduction method in presence of Se-based compounds as functionalizing agents allowed the formation of aggregated NPs with little to no solubility in aqueous media. To improve their hydrophilicity and stability mixed AuNPs-3MPS-1 were synthesized. Besides, Se-loaded AuNPs-3MPS revealed to be the most suitable systems for biological studies in terms of size and colloidal stability. Selenium derivatives and AuNPs were tested in vitro via MTT assay against PC-3 (prostatic adenocarcinoma) and HCT-116 (colorectal carcinoma) cell lines. Compared to free compounds, direct functionalization onto AuNPs with formation of Au-Se covalent bond led to non-cytotoxic systems in the concentration range explored (0-100 μg/mL), whereas immobilization on AuNPs-3MPS improved the cytotoxicity of compounds 1, 3, and 4. Selective anticancer response against HCT-116 cells was obtained by AuNPs-3MPS-1. These results demonstrated that AuNPs can be used as a platform to tune the in vitro biological activity of organoselenium compounds., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Worldwide, over 20 million patients suffer from bone disorders annually. Bone scaffolds are designed to integrate into host tissue without causing adverse reactions. Recently, chitosan, an easily available natural polymer, has been considered a suitable scaffold for bone tissue growth as it is a biocompatible, biodegradable, and non-toxic material with antimicrobial activity and osteoinductive capacity. In this work, chitosan was covalently and selectively biofunctionalized with two suitably designed bioactive synthetic peptides: a Vitronectin sequence (HVP) and a BMP-2 peptide (GBMP1a). Nuclear magnetic resonance (NMR), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FT-IR) investigations highlighted the presence of the peptides grafted to chitosan (named Chit-HVP and Chit-GBMP1a). Chit-HVP and Chit-GBMP1a porous scaffolds promoted human osteoblasts adhesion, proliferation, calcium deposition, and gene expression of three crucial osteoblast proteins. In particular, Chit-HVP highly promoted adhesion and proliferation of osteoblasts, while Chit-GBMP1a guided cell differentiation towards osteoblastic phenotype.

The limitations and difficulties that nerve autografts create in normal nerve function recovery after injury is driving research towards using smart materials for next generation nerve conduits (NCs) setup. Here, the new polymer partially oxidized polyvinyl alcohol (OxPVA) was assayed to verify its future potential as a bioactivated platform for advanced/effective NCs. OxPVA-patterned scaffolds (obtained by a 3D-printed mold) with/without biochemical cues (peptide IKVAV covalently bound (OxPVA-IKVAV) or self-assembling peptide EAK (sequence: AEAEAKAKAEAEAKAK), mechanically incorporated (OxPVA+EAK) versus non-bioactivated scaffold (peptide-free OxPVA (PF-OxPVA) supports, OxPVA without IKVAV and OxPVA without EAK control scaffolds) were compared for their biological effect on neuronal SH-SY5Y cells. After cell seeding, adhesion/proliferation, mediated by (a) precise control over scaffolds surface ultrastructure; (b) functionalization efficacy guaranteed by bioactive cues (IKVAV/EAK), was investigated by MTT assay at 3, 7, 14 and 21 days. As shown by the results, the patterned groove alone stimulates colonization by cells; however, differences were observed when comparing the scaffold types over time. In the long period (21 days), patterned OxPVA+EAK scaffolds distinguished in bioactivity, assuring a significantly higher total cell amount than the other groups. Experimental evidence suggests patterned OxPVA-EAK potential for NCs device fabrication.

In the field of research for designing and preparing innovative nanostructured systems, these systems are able to reveal the presence of heavy metals in water samples, and can efficiently and selectively interact with them, allowing for future applications in the field of water remediation. We investigated the electronic and molecular structure, as well as the morphology, of silver nanoparticles stabilized by mixed biocompatible ligands (the amino acid L-cysteine and the organic molecule citrate) in the presence of cadmium and arsenic ions. The molecular, electronic, and local structure at the ligands/silver nanoparticles interface was probed by the complementary synchrotron radiation-induced techniques (SR-XPS, NEXAFS and XAS). The optical absorption (in the UV-Vis range) of the nanosystem was investigated in the presence of Cd(II) and As(III) and the observed behavior suggested a selective interaction with cadmium. In addition, the toxicological profile of the innovative nanosystem was assessed in vitro using a human epithelial cell line HEK293T. We analyzed the viability of the cells treated with silver nanoparticles, as well as the activation of antioxidant response.

In the last years, intense efforts have been made in order to obtain colloidal-based systems capable of pointing out the presence of melamine in food samples. In this work, we reported about the recognition of melamine in aqueous solution, using gold nanoparticles stabilized with 3-mercapto-1-propanesulfonate (AuNPs-3MPS), with the aim of deepening how the recognition process works. AuNPs were synthesized using a wet chemical reduction method. The synthesized AuNPs-3MPS probe was fully characterized, before and after the recognition process, by both physicochemical (UV-vis, FT-IR, 1 H-NMR, DLS and ζ-potential) and morphostructural techniques (AFM, HR-TEM). The chemical and electronic structure was also investigated by SR-XPS. The sensing method is based on the melamine-induced aggregation of AuNPs; the presence of melamine was successfully detected in the range of 2.5-500 ppm. The results achieved also demonstrate that negatively charged AuNPs-3MPS are potentially useful for determining melamine contents in aqueous solution. SR-XPS measurements allowed to understand interaction mechanism between the probe and the analyte. The presence of sulfonate groups allows a mutual interaction mediated by electrostatic bonds between nanoparticles surface thiols and positively charged amino groups of melamine molecules., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Hybrid biomaterials allow for the improvement of the biological properties of materials and have been successfully used for implantology in medical applications. The covalent and selective functionalization of materials with bioactive peptides provides favorable results in tissue engineering by supporting cell attachment to the biomaterial through biochemical cues and interaction with membrane receptors. Since the functionalization with bioactive peptides may alter the chemical and physical properties of the biomaterials, in this study we characterized the biological responses of differently functionalized chitosan analogs. Chitosan analogs were produced through the reaction of GRGDSPK (RGD) or FRHRNRKGY (HVP) sequences, both carrying an aldehyde-terminal group, to chitosan. The bio-functionalized polysaccharides, pure or "diluted" with chitosan, were chemically characterized in depth and evaluated for their antimicrobial activities and biocompatibility toward human primary osteoblast cells. The results obtained indicate that the bio-functionalization of chitosan increases human-osteoblast adhesion ( p < 0.005) and proliferation ( p < 0.005) as compared with chitosan. Overall, the 1:1 mixture of HVP functionalized-chitosan:chitosan is the best compromise between preserving the antibacterial properties of the material and supporting osteoblast differentiation and calcium deposition ( p < 0.005 vs. RGD). In conclusion, our results reported that a selected concentration of HVP supported the biomimetic potential of functionalized chitosan better than RGD and preserved the antibacterial properties of chitosan.

Despite the well-known favorable chemical and mechanical properties of titanium-based materials for orthopedic and dental applications, poor osseointegration of the implants, bacteria adhesion, and excessive inflammatory response from the host remain major problems to be solved. Here, the antioxidant and anti-inflammatory enzyme-like abilities of ceria (CeO x ) were coupled to the advantageous features of titanium nanotubes (TiNTs). Cost-effective and fast methods, such as electrochemical anodization and drop casting, were used to build active surfaces with enhanced bioactivity. Surface composition, electrochemical response, and in vitro ability to induce hydroxyapatite (HA) precipitation were evaluated. The amount of cerium in the coating did not significantly affect wettability, yet a growing ability to induce early HA precipitation from simulated body fluid (SBF) was observed as the oxide content at the surface increased. The presence of 4%wt CeO x was also able to stimulate rapid HA maturation in a (poorly) crystalline form, indicating an interesting potential to induce rapid in vivo osseointegration process.