Chemical-Vapor-Deposition-Synthesized Two-Dimensional Non-Stoichiometric Copper Selenide (ß-Cu2-xSe) for Ultra-Fast Tetracycline Hydrochloride Degradation under Solar Light.

The high concentration of antibiotics in aquatic environments is a serious environmental issue. In response, researchers have explored photocatalytic degradation as a potential solution. Through chemical vapor deposition (CVD), we synthesized copper selenide (ß-Cu2-xSe) and found it an effective catalyst for degrading tetracycline hydrochloride (TC-HCl). The catalyst demonstrated an impressive degradation efficiency of approximately 98% and a reaction rate constant of 3.14 × 10-2 min-1. Its layered structure, which exposes reactive sites, contributes to excellent stability, interfacial charge transfer efficiency, and visible light absorption capacity. Our investigations confirmed that the principal active species produced by the catalyst comprises O2- radicals, which we verified through trapping experiments and electron paramagnetic resonance (EPR). We also verified the TC-HCl degradation mechanism using high-performance liquid chromatography-mass spectrometry (LC-MS). Our results provide valuable insights into developing the ß-Cu2-xSe catalyst using CVD and its potential applications in environmental remediation.

Ultrasound Stimulation of Piezoelectric Nanocomposite Hydrogels Boosts Chondrogenic Differentiation in Vitro, in Both a Normal and Inflammatory Milieu.

The use of piezoelectric nanomaterials combined with ultrasound stimulation is emerging as a promising approach for wirelessly triggering the regeneration of different tissue types. However, it has never been explored for boosting chondrogenesis. Furthermore, the ultrasound stimulation parameters used are often not adequately controlled. In this study, we show that adipose-tissue-derived mesenchymal stromal cells embedded in a nanocomposite hydrogel containing piezoelectric barium titanate nanoparticles and graphene oxide nanoflakes and stimulated with ultrasound waves with precisely controlled parameters (1 MHz and 250 mW/cm2, for 5 min once every 2 days for 10 days) dramatically boost chondrogenic cell commitment in vitro. Moreover, fibrotic and catabolic factors are strongly down-modulated: proteomic analyses reveal that such stimulation influences biological processes involved in cytoskeleton and extracellular matrix organization, collagen fibril organization, and metabolic processes. The optimal stimulation regimen also has a considerable anti-inflammatory effect and keeps its ability to boost chondrogenesis in vitro, even in an inflammatory milieu. An analytical model to predict the voltage generated by piezoelectric nanoparticles invested by ultrasound waves is proposed, together with a computational tool that takes into consideration nanoparticle clustering within the cell vacuoles and predicts the electric field streamline distribution in the cell cytoplasm. The proposed nanocomposite hydrogel shows good injectability and adhesion to the cartilage tissue ex vivo, as well as excellent biocompatibility in vivo, according to ISO 10993. Future perspectives will involve preclinical testing of this paradigm for cartilage regeneration.

Graphene Oxide and Reduced Graphene Oxide Nanoflakes Coated with Glycol Chitosan, Propylene Glycol Alginate, and Polydopamine: Characterization and Cytotoxicity in Human Chondrocytes.

Recently, graphene and its derivatives have been extensively investigated for their interesting properties in many biomedical fields, including tissue engineering and regenerative medicine. Nonetheless, graphene oxide (GO) and reduced GO (rGO) are still under investigation for improving their dispersibility in aqueous solutions and their safety in different cell types. This work explores the interaction of GO and rGO with different polymeric dispersants, such as glycol chitosan (GC), propylene glycol alginate (PGA), and polydopamine (PDA), and their effects on human chondrocytes. GO was synthesized using Hummer's method, followed by a sonication-assisted liquid-phase exfoliation (LPE) process, drying, and thermal reduction to obtain rGO. The flakes of GO and rGO exhibited an average lateral size of 8.8 ± 4.6 and 18.3 ± 8.5 µm, respectively. Their dispersibility and colloidal stability were investigated in the presence of the polymeric surfactants, resulting in an improvement in the suspension stability in terms of average size and polydispersity index over 1 h, in particular for PDA. Furthermore, cytotoxic effects induced by coated and uncoated GO and rGO on human chondrocytes at different concentrations (12.5, 25, 50 and 100 µg/mL) were assessed through LDH assay. Results showed a concentration-dependent response, and the presence of PGA contributed to statistically decreasing the difference in the LDH activity with respect to the control. These results open the way to a potentially safer use of these nanomaterials in the fields of cartilage tissue engineering and regenerative medicine.

Higher Ultrasonic Frequency Liquid Phase Exfoliation Leads to Larger and Monolayer to Few-Layer Flakes of 2D Layered Materials.

Among the most reliable techniques for exfoliation of two-dimensional (2D) layered materials, sonication-assisted liquid-phase exfoliation (LPE) is considered as a cost-effective and straightforward method for preparing graphene and its 2D inorganic counterparts at reasonable sizes and acceptable levels of defects. Although there were rapid advances in this field, the effect and outcome of the sonication frequency are poorly understood and often ignored, resulting in a low exfoliation efficiency. Here, we demonstrate that simple mild bath sonication at a higher frequency and low power positively contributes to the thickness, size, and quality of the final exfoliated products. We show that monolayer graphene flakes can be directly exfoliated from graphite using ethanol as a solvent by increasing the frequency of the bath sonication from 37 to 80 kHz. The statistical analysis shows that ∼77% of the measured graphene flakes have a thickness below three layers with an average lateral size of 13 µm. We demonstrate that this approach works for digenite (Cu9S5) and silver sulfide (Ag2S), thus indicating that this exfoliation technique can be applied to other inorganic 2D materials to obtain high-quality few-layered flakes. This simple and effective method facilitates the formation of monolayer/few layers of graphene and transition metal chalcogenides for a wide range of applications.

Graphene Oxide-Doped Gellan Gum-PEGDA Bilayered Hydrogel Mimicking the Mechanical and Lubrication Properties of Articular Cartilage.

Articular cartilage (AC) is a specialized connective tissue able to provide a low-friction gliding surface supporting shock-absorption, reducing stresses, and guaranteeing wear-resistance thanks to its structure and mechanical and lubrication properties. Being an avascular tissue, AC has a limited ability to heal defects. Nowadays, conventional strategies show several limitations, which results in ineffective restoration of chondral defects. Several tissue engineering approaches have been proposed to restore the AC's native properties without reproducing its mechanical and lubrication properties yet. This work reports the fabrication of a bilayered structure made of gellan gum (GG) and poly (ethylene glycol) diacrylate (PEGDA), able to mimic the mechanical and lubrication features of both AC superficial and deep zones. Through appropriate combinations of GG and PEGDA, cartilage Young's modulus is effectively mimicked for both zones. Graphene oxide is used as a dopant agent for the superficial hydrogel layer, demonstrating a lower friction than the nondoped counterpart. The bilayered hydrogel's antiwear properties are confirmed by using a knee simulator, following ISO 14243. Finally, in vitro tests with human chondrocytes confirm the absence of cytotoxicity effects. The results shown in this paper open the way to a multilayered synthetic injectable or surgically implantable filler for restoring AC defects.

Carbon nanostructures as a scaffold for human embryonic stem cell differentiation toward photoreceptor precursors.

Carbon nanomaterials have been introduced as a scaffold for various biological applications due to their unique physical and electrical properties. Here we studied carbon nanotubes (CNTs) and carbon nanofibers (CNFs) as scaffold materials for the differentiation of human embryonic stem cells (hESCs) towards photoreceptor precursor cells (PRPs). We report on their cytoxicity, their effect on cell morphology, cell-surface interface and the differentiation process. To this end, hESCs were differentiated into PRPs on carbon nanofibers (CNFs), long horizontal CNTs (LHCNTs), vertically aligned CNTs (VACNTs) or glass (control) surfaces. The differentiated cells were investigated by immunohistochemistry, fluorescence imaging and electron microscopy. Our results revealed that the investigated nanomaterials were not cytotoxic to the cells during the differentiation process. The surface interface effect on the cells was apparent, affecting cell directionality, migration and morphology. Interestingly, cell fate was not dependent on the substrate type, as inferred from the similar dynamics of the loss of pluripotency and the comparable expression levels of the photoreceptor marker Crx for all investigated substrates. These results are important for better understanding the effect of nanomaterial surface interaction with differentiating neural cells in general, and for future use of these materials as scaffolds for differentiating photoreceptors for vision restoration in particular.

Scalable Synthesis of Few-Layered 2D Tungsten Diselenide (2H-WSe2) Nanosheets Directly Grown on Tungsten (W) Foil Using Ambient-Pressure Chemical Vapor Deposition for Reversible Li-Ion Storage.

We report a facile two-furnace APCVD synthesis of 2H-WSe2. A systematic study of the process parameters is performed to show the formation of the phase-pure material. Extensive characterization of the bulk and exfoliated material confirm that 2H-WSe2 is layered (i.e., 2D). X-ray diffraction (XRD) confirms the phase, while high-resolution scanning electron microscopy (HRSEM), high-resolution transmission electron microscopy (HRTEM), and atomic force microscopy (AFM) clarify the morphology of the material. Focused ion beam scanning electron microscopy (FIB-SEM) estimates the depth of the 2H-WSe2 formed on W foil to be around 5-8 µm, and Raman/UV-vis measurements prove the quality of the exfoliated 2H-WSe2. Studies on the redox processes of lithium-ion batteries (LiBs) show an increase in capacity up to 500 cycles. On prolonged cycling, the discharge capacity up to the 50th cycle at 250 mA/g of the material shows a stable value of 550 mAh/g. These observations indicate that exfoliated 2H-WSe2 has promising applications as an LiB electrode material.