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.

One-Step Synthesis of a Binder-Free, Stable, and High-Performance Electrode; Cu-O|Cu3P Heterostructure for the Electrocatalytic Methanol Oxidation Reaction (MOR).

Although direct methanol fuel cells (DMFCs) have been spotlighted in the past decade, their commercialization has been hampered by the poor efficiency of the methanol oxidation reaction (MOR) due to the unsatisfactory performance of currently available electrocatalysts. Herein, we developed a binder-free, copper-based, self-supported electrode consisting of a heterostructure of Cu3P and mixed copper oxides, i.e., cuprous-cupric oxide (Cu-O), as a high-performance catalyst for the electro-oxidation of methanol. We synthesized a self-supported electrode composed of Cu-O|Cu3P using a two-furnace atmospheric pressure-chemical vapor deposition (AP-CVD) process. High-resolution transmission electron microscopy analysis revealed the formation of 3D nanocrystals with defects and pores. Cu-O|Cu3P outperformed the MOR activity of individual Cu3P and Cu-O owing to the synergistic interaction between them. Cu3P|Cu-O exhibited a highest anodic current density of 232.5 mAcm-2 at the low potential of 0.65 V vs. Hg/HgO, which is impressive and superior to the electrocatalytic activity of its individual counterparts. The formation of defects, 3D morphology, and the synergistic effect between Cu3P and Cu-O play a crucial role in facilitating the electron transport between electrode and electrolyte to obtain the optimal MOR activity. Cu-O|Cu3P shows outstanding MOR stability for about 3600 s with 100% retention of the current density, which proves its robustness alongside CO intermediate.

Promising Electrocatalytic Water and Methanol Oxidation Reaction Activity by Nickel Doped Hematite/Surface Oxidized Carbon Nanotubes Composite Structures.

Tailoring the precise construction of non-precious metals and carbon-based heterogeneous catalysts for electrochemical oxygen evolution reaction (OER) and methanol oxidation reaction (MOR) is crucial for energy conversion applications. Herein, this work reports the composite of Ni doped Fe2 O3 (Ni-Fe2 O3 ) with mildly oxidized multi-walled CNT (O-CNT) as an outstanding Mott-Schottky catalyst for OER and MOR. O-CNT acts as a co-catalyst which effectively regulates the charge transfer in Ni-Fe2 O3 and thus enhances the electrocatalytic performance. Ni-Fe2 O3 /O-CNT exhibits a low onset potential of 260 mV and overpotential 310 mV @ 10 mA cm-2 for oxygen evolution. Being a Mott-Schottky catalyst, it achieves the higher flat band potential of -1.15 V with the carrier density of 0.173×1024  cm-3 . Further, in presence of 1 M CH3 OH, it delivers the MOR current density of 10 mA cm-2 at 1.46 V vs. RHE. The excellent electrocatalytic OER and MOR activity of Ni-Fe2 O3 /O-CNT could be attributed to the synergistic interaction between Ni-doped Fe2 O3 and O-CNT.

CVD-Assisted Synthesis of 2D Layered MoSe2 on Mo Foil and Low Frequency Raman Scattering of Its Exfoliated Few-Layer Nanosheets on CaF2 Substrates.

Transition-metal dichalcogenides (TMDCs) are unique layered materials with exotic properties. So, examining their structures holds tremendous importance. 2H-MoSe2 (analogous to MoS2; Gr. 6 TMDC) is a crucial optoelectronic material studied extensively using Raman spectroscopy. In this regard, low-frequency Raman (LFR) spectroscopy can probe this material's structure as it reveals distinct vibration modes. Here, we focus on understanding the microstructural evolution of different 2H-MoSe2 morphologies and their layers using LFR scattering. We grew phase-pure 2H-MoSe2 (with variable microstructures) directly on a Mo foil using a two-furnace ambient-pressure chemical vapor deposition (CVD) system by carefully controlling the process parameters. We analyzed the layers of exfoliated flakes after ultrasonication and drop-cast 2H-MoSe2 of different layer thicknesses by choosing different concentrations of 2H-MoSe2 solutions. Further detailed analyses of the respective LFR regions confirm the presence of newly identified Raman signals for the 2H-MoSe2 nanosheets drop-cast on Raman-grade CaF2. Our results show that CaF2 is an appropriate Raman-enhancing substrate compared to Si/SiO2 as it presents new LFR modes of 2H-MoSe2. Therefore, CaF2 substrates are a promising medium to characterize in detail other TMDCs using LFR spectroscopy.

Correction: Thiadiazole containing N- and S-rich highly ordered periodic mesoporous organosilica for efficient removal of Hg(II) from polluted water.

Correction for 'Thiadiazole containing N- and S-rich highly ordered periodic mesoporous organosilica for efficient removal of Hg(II) from polluted water' by Asim Baumik et al., Chem. Commun., 2020, 56, 3963-3966, DOI 10.1039/D0CC00407C.

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.

Bimetallic Phosphides for Hybrid Supercapacitors.

Supercapacitors (SCs) are considered promising energy storage systems because of their high power output and long-term cycling stability; however, they usually exhibit poor energy density. The hybrid supercapacitor (HSC) is an emerging concept in which two dissimilar electrodes with different charge storage mechanisms are paired to deliver high energy without sacrificing power output. This Perspective highlights the features of transition-metal phosphides (TMPs) as the positive electrode in HSCs. In particular, bimetallic nickel cobalt phosphide (NiCoP) with multiple redox sites, excellent electrochemical reversibility, and stability is discussed. We outline how the rational heterostructures, elemental variations, and nanocomposite morphologies tune the electrochemical properties of NiCoP as the positive electrode in HSCs. The Perspective further sheds light on NiCoP-based composites that help in improving the overall performance of HSCs in terms of energy density and cycling stability. The key scientific challenges and perspectives on building efficient and stable HSCs for future applications are discussed.

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.

Robust Room-Temperature NO2 Sensors from Exfoliated 2D Few-Layered CVD-Grown Bulk Tungsten Di-selenide (2H-WSe2).

We report a facile and robust room-temperature NO2 sensor fabricated using bi- and multi-layered 2H variant of tungsten di-selenide (2H-WSe2) nanosheets, exhibiting high sensing characteristics. A simple liquid-assisted exfoliation of 2H-WSe2, prepared using ambient pressure chemical vapor deposition, allows smooth integration of these nanosheets on transducers. Three sensor batches are fabricated by modulating the total number of layers (L) obtained from the total number of droplets from a homogeneous 2H-WSe2 dispersion, such as ∼2L, ∼5-6L, and ∼13-17L, respectively. The gas-sensing attributes of 2H-WSe2 nanosheets are investigated thoroughly. Room temperature (RT) experiments show that these devices are specifically tailored for NO2 detection. 2L WSe2 nanosheets deliver the best rapid response compared to ∼5-6L or ∼13-17L. The response of 2L WSe2 at RT is 250, 328, and 361% to 2, 4, and 6 ppm NO2, respectively. The sensor showed nearly the same response toward low NO2 concentration even after 9 months of testing, confirming its remarkable long-term stability. A selectivity study, performed at three working temperatures (RT, 100, and 150 °C), shows high selectivity at 150 and 100 °C. Full selectivity toward NO2 at RT confirms that 2H-WSe2 nanosheet-based sensors are ideal candidates for NO2 gas detection.

Wear Behavior Characterization of Hydrogels Constructs for Cartilage Tissue Replacement.

This paper aims to characterize the wear behavior of hydrogel constructs designed for human articular cartilage replacement. To this purpose, poly (ethylene glycol) diacrylate (PEGDA) 10% w/v and gellan gum (GG) 1.5% w/v were used to reproduce the superior (SUP) cartilage layer and PEGDA 15% w/v and GG 1.5% w/v were used to reproduce the deep (DEEP) cartilage layer, with or without graphene oxide (GO). These materials (SUP and DEEP) were analyzed alone and in combination to mimic the zonal architecture of human articular cartilage. The developed constructs were tested using a four-station displacement control knee joint simulator under bovine calf serum. Roughness and micro-computer tomography (µ-CT) measurements evidenced that the hydrogels with 10% w/v of PEGDA showed a worse behavior both in terms of roughness increase and loss of uniformly distributed density than 15% w/v of PEGDA. The simultaneous presence of GO and 15% w/v PEGDA contributed to keeping the hydrogel construct's characteristics. The Raman spectra of the control samples showed the presence of unreacted C=C bonds in all the hydrogels. The degree of crosslinking increased along the series SUP < DEEP + SUP < DEEP without GO. The Raman spectra of the tested hydrogels showed the loss of diacrylate groups in all the samples, due to the washout of unreacted PEGDA in bovine calf serum aqueous environment. The loss decreased along the series SUP > DEEP + SUP > DEEP, further confirming that the degree of photo-crosslinking of the starting materials plays a key role in determining their wear behavior. µ-CT and Raman spectroscopy proved to be suitable techniques to characterize the structure and composition of hydrogels.

Electrically conductive cotton fabric coatings developed by silica sol-gel precursors doped with surfactant-aided dispersion of vertically aligned carbon nanotubes fillers in organic solvent-free aqueous solution.

HYPOTHESIS: From the end of the twentieth century, the growing interest in a new generation of wearable electronics with attractive application for military, medical and smart textiles fields has led to a wide investigation of chemical finishes for the production of electronic textiles (e-textiles). EXPERIMENTS: Herein, a novel method to turn insulating cotton fabrics in electrically conductive by the deposition of three-dimensional hierarchical vertically aligned carbon nanotubes (VACNT) is proposed. Two VACNT samples with different length were synthesized and then dispersed in 4-dodecylbenzenesulfonic acid combined with silica-based sol-gel precursors. The dispersed VACNT were separately compounded with a polyurethane thickener to obtain homogeneous spreadable pastes, finally coated onto cotton surfaces by the "knife-over-roll" technique. FINDINGS: Shorter VACNT-based composite showed the best electrical conductivity, with a sheet resistance value less than 4.0 · 104 ± 6.7 · 103 Ω/sq. As demonstrated, developed e-textiles are suitable for application as humidity sensing materials in wearable smart textiles by exhibiting adequate response time for end-users and repeatability at several exposure cycles, still maintaining excellent flexibility. The proposed environmentally-friendly and cost-effective method can be easily widened to the scalable production of CNT-containing conductive flexible coatings, providing additional support to the development of real integration between electronics and textiles.

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.

Thiadiazole containing N- and S-rich highly ordered periodic mesoporous organosilica for efficient removal of Hg(ii) from polluted water.

A new N- and S-rich highly ordered periodic mesoporous organosilica material DMTZ-PMO bearing thiadiazole and thiol moieties inside the pore-wall of a 2D-hexagonal nanomaterial has been synthesized. DMTZ-PMO shows a very high surface area (971 m2 g-1), and can be used for efficient and fast removal of Hg2+ from polluted water with a very high Hg2+ uptake capacity of 2081 mg g-1.

First-Principles Investigation of Black Phosphorus Synthesis.

Black phosphorus (BP) is a layered semiconductor with outstanding properties, making it a promising candidate for optoelectronic and other applications. BP synthesis is an intriguing task largely due to the insufficient understanding of the synthesis mechanism. In this work, we use density functional theory calculations to examine BP and its precursor red phosphorus as they are formed from P4 building blocks. Our results suggest that, without external effects such as pressure or addition of a catalyst, the precursor is energetically favored in the initial steps of the synthesis, even though BP is the more stable allotrope. The higher energy of BP is dictated by its 2D geometry that gives rise to the higher number of high-energy strained bonds at the edge compared to the 1D geometry of red phosphorus. The elucidated BP formation pathway provides a natural explanation for the effectiveness of the recently discovered Sn/I catalyst used in BP synthesis.

Modulation of Oxygen Content in Graphene Surfaces Using Temperature-Programmed Reductive Annealing: Electron Paramagnetic Resonance and Electrochemical Study.

The oxidation level and properties of reduced graphene oxides (rGOs) were fine-tuned using temperature-programmed reductive annealing. rGOs were annealed at different temperatures (from 500 to 1000 °C) in hydrogen to modulate their oxidation levels. The surface of the rGOs was fully characterized using electron paramagnetic resonance backed by Raman, X-ray diffraction, and chemical analysis measurements. These experiments were used to study the changes in the surface of the rGO, its surface functionalities, and its defects as a function of the reduction temperature. In addition, electrochemical measurements to quantify the oxidation level of the rGOs offer a simple tool to correlate the properties of rGOs with their structure. Finally, we explored the effect of different levels of reduction on conductivity, capacitance, and surface reactivity. This research offers simple methodological techniques and routes to control and characterize the oxidation level of bulk quantities of rGO.

Vertically Aligned Nitrogen-Doped Carbon Nanotube Carpet Electrodes: Highly Sensitive Interfaces for the Analysis of Serum from Patients with Inflammatory Bowel Disease.

The number of patients suffering from inflammatory bowel disease (IBD) is increasing worldwide. The development of noninvasive tests that are rapid, sensitive, specific, and simple would allow preventing patient discomfort, delay in diagnosis, and the follow-up of the status of the disease. Herein, we show the interest of vertically aligned nitrogen-doped carbon nanotube (VA-NCNT) electrodes for the required sensitive electrochemical detection of lysozyme in serum, a protein that is up-regulated in IBD. To achieve selective lysozyme detection, biotinylated lysozyme aptamers were covalently immobilized onto the VA-NCNTs. Detection of lysozyme in serum was achieved by measuring the decrease in the peak current of the Fe(CN)6(3-/4-) redox couple by differential pulse voltammetry upon addition of the analyte. We achieved a detection limit as low as 100 fM with a linear range up to 7 pM, in line with the required demands for the determination of lysozyme level in patients suffering from IBD. We attained the sensitive detection of biomarkers in clinical samples of healthy patients and individuals suffering from IBD and compared the results to a classical turbidimetric assay. The results clearly indicate that the newly developed sensor allows for a reliable and efficient analysis of lysozyme in serum.