Morphological and chemical changes in nuclear graphite target under vacuum and high-temperature conditions.

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.

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.

Nano-protrusions in intercalated graphite: understanding the structural and electronic effects through DFT.

Complex phenomena characterize the intercalation of ions inside stratified crystals. Their comprehension is crucial in view of exploiting the intercalation mechanism to change the transport properties of the crystal or obtaining a fine control of crystal delamination. In particular, the relationship between the concentration and nature of intercalated ions and surface structural modifications of the host stratified crystal is still under debate. Here, we discuss a theoretical effort to provide a rationale for some structural changes observed on the highly oriented pyrolytic graphite (HOPG) surface after electrochemical treatment in perchloric and sulphuric acid solutions. The formation of the so-called nano-protrusions on the basal plane of intercalated graphite was previously observed with scanning tunneling microscopy (STM). In this work, we employed both STM and density functional theory (DFT) simulations to elucidate the physical and chemical mechanisms driving the emergence of these nano-protrusions. The DFT results show that, in a bilayer graphene system, the presence of a single ion can generate a nano-protrusion with 2.49 Å height and 21.27 Å width. In the deformed area, the C-C bond length is stretched by about 2.5% more than the normal graphene bond. These values are of the same dimensional scale as those reported in previous STM experimental results.25 However, the simulated STM images obtained by increasing the amount of intercalated ions per area suggest that the presence of more than one ion is needed for the deformation of the uppermost graphite layer during the early stages of intercalation. In contrast, in a multilayer graphene system, no significant surface deformation is detected when ions are intercalated between the third and fourth layers. Charge analysis indicates an altered distribution of the charges as a consequence of the intercalation. The charge transfer from graphene layers to the intercalated ions results in a surface layer more prone to oxidation.

In Vitro Viability Tests of New Ecofriendly Nanosystems Incorporating Essential Oils for Long-Lasting Conservation of Stone Artworks.

The study explores the application of natural biocides (oregano essential oil and eugenol, directly applied in solutions or encapsulated within silica nanocapsules) for safeguarding stone cultural heritage from biodeterioration, using green algae (Chlorococcum sp.) and cyanobacteria (Leptolyngbya sp.) as common pioneer biodeteriogens. Core-shell nanocontainers were built for a controlled release of microbicidal agents, a safe application of chemicals and a prolonged efficacy. The qualitative and quantitative evaluations of biocide efficiency at different doses were periodically performed in vitro, after six scheduled intervals of time (until 100 days). The release kinetics of composite biocide-embedding silica nanocapsules were characterized by the UV-Vis spectroscopy technique. Data showed both promising potential and some limitations. The comparative tests of different biocidal systems shed light on their variable efficacy against microorganisms, highlighting how encapsulation influences the release dynamics and the overall effectiveness. Both the essential oils showed a potential efficacy in protective antifouling coatings for stone artifacts. Ensuring compatibility with materials, understanding their differences in biocidal activity and their release rates becomes essential in tailoring gel, microemulsion or coating products for direct on-site application.

Advances in Structural and Morphological Characterization of Thin Magnetic Films: A Review.

The present review places emphasis on a comprehensive survey of experimental techniques to probe the structural and morphological features at the nanoscale range in thin magnetic films, incorporating those available at in-house laboratories as well as those at state-of-the-art synchrotron radiation facilities. This elucidating the range of available techniques, and the information they can yield represents a step for advancing the understanding of and for unlocking new possibilities in the design and optimization of thin magnetic films across a wide range of applications.

3-APTES on Dendritic Fibrous Mesoporous Silica Nanoparticles for the pH-Controlled Release of Corrosion Inhibitors.

Mesoporous silica nanoparticles (MSNPs) are currently used in different fields like catalysis, nanomedicine, and conservation science, taking advantage of their high surface area. Here, we synthesized and functionalized mesoporous dendritic fibrous nanoparticles to realize a smart delivery system of protective agents for metals. Different MSNPs were obtained via the microemulsion method followed by a hydrothermal or refluxing treatment at different w/o ratios, times, and temperatures. Dendritic spherical silica nanoparticles with specific features such as an appropriate size (450 nm), a very large surface area (600 m2 g-1), and a high yield synthesis (86%) were selected for surface modification. The fiber surface of the selected MSNPs was functionalized with 3-aminopropyl triethoxysilane (3-APTES). 3-APTES works as a pH-driven "nanogate", suppressing the immediate leakage of the total guest molecule load and modulating the release as a function of pH conditions. Surface-modified MSNPs were tested as a reservoir of the most diffused corrosion inhibitors: Mercaptobenzothiazole (MBT) and 1H-Benzotriazole (BTA); their release properties were studied in solutions with pH = 4 and 7. Functionalized and non-functionalized MSNPs showed a good loading efficiency of guest molecules (34-64%) and a pH-dependent release of the corrosion inhibitors on a timescale of several hours.

Driving Organic Nanocrystals Dissolution Through Electrochemistry.

We have recently discussed how organic nanocrystal dissolution appears in different morphologies and the role of the solution pH in the crystal detriment process. We also highlighted the role of the local molecular chemistry in porphyrin nanocrystals having comparable structures: in water-based acid solutions, protonation of free-base porphyrin molecules is the driving force for crystal dissolution, whereas metal (ZnII ) porphyrin nanocrystals remain unperturbed. However, all porphyrin types, having an electron rich π-structure, can be electrochemically oxidized. In this scenario, a key question is: does electrochemistry represent a viable strategy to drive the dissolution of both free-base and metal porphyrin nanocrystals? In this work, by exploiting electrochemical atomic force microscopy (EC-AFM), we monitor in situ and in real time the dissolution of both free-base and metal porphyrin nanocrystals, as soon as molecules reach the oxidation potential, showing different regimes according to the applied EC potential.

Bio-Functionalized Chitosan for Bone Tissue Engineering.

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.

Modular MA-XRF Scanner Development in the Multi-Analytical Characterisation of a 17th Century Azulejo from Portugal.

A modular X-ray scanning system was developed, to fill in the gap between portable instruments (with a limited analytical area) and mobile instruments (with large analytical areas, and sometimes bulky and difficult to transport). The scanner has been compared to a commercial tabletop instrument, by analysing a Portuguese tile (azulejo) from the 17th century. Complementary techniques were used to achieve a throughout characterisation of the sample in a complete non-destructive approach. The complexity of the acquired X-ray fluorescence (XRF) spectra, due to inherent sample stratigraphy, has been resolved using Monte Carlo simulations, and Raman spectroscopy, as the most suitable technique to complement the analysis of azulejos colours, yielding satisfactory results. The colouring agents were identified as cobalt blue and a Zn-modified Naples-yellow. The stratigraphy of the area under study was partially modelled with Monte Carlo simulations. The scanners performance has been compared by evaluating the images outputs and the global spectrum.

Hydroxyapatite Surfaces Functionalized with a Self-Assembling Peptide: XPS, RAIRS and NEXAFS Study.

Hydroxyapatite (HAP) coatings can improve the biocompatibility and bioactivity of titanium alloys, such as Ti6Al4V, commonly used as material for orthopedic prostheses. In this framework, we have studied the surface of HAP coatings enriched with Mg and either Si or Ti deposited by RF magnetron sputtering on Ti6Al4V. HAP coatings have been furtherly functionalized by adsorption of a self-assembling peptide (SAP) on the HAP surface, with the aim of increasing the material bioactivity. The selected SAP (peptide sequence AbuEAbuEAbuKAbuKAbuEAbuEAbuKAbuK) is a self-complementary oligopeptide able to generate extended ordered structures by self-assembling in watery solutions. Samples were prepared by incubation of the HAP coatings in SAP solutions and subsequently analyzed by X-Ray Photoelectron Spectroscopy (XPS), Fourier Transform Infrared (FTIR) and Near Edge X-Ray Absorption Fine Structure (NEXAFS) spectroscopies, in order to determine the amount of adsorbed peptide, the peptide stability and the structure of the peptide overlayer on the HAP coatings as a function of the HAP substrate and of the pH of the mother SAP solution. Experimental data yielded evidence of SAP adsorption on the HAP surface, and peptide overlayers showed ordered structure and molecular orientation. The thickness of the SAP overlayer depends on the composition of the HAP coating.