Plasmonic-excitonic multi-hybrid glass-based nanocomposites incorporating Ag plus core-shell CdSe/CdS and alloyed CdSxSe1−x nanoparticles

Successful fabrication of glass-based hybrid nanocomposites (GHNCs) incorporating Ag, core-shell CdSe/CdS and CdS_xSe_1?x nanoparticles (NPs) is herein reported. Both metallic (Ag) and semiconductor (CdSe/CdS) NPs were pre-synthesized, suspended in colloids and added into the sol-gel reaction medium which was used to fabricate the GHNCs. During fabrication of the nanocomposites a fraction (20–60%) of core-shell CdSe/CdS NPs was alloyed into CdS_xSe_1?x (0.20 < x < 0.35) NPs without changing morphology. Modulation of in situ alloying is possible via the relative content of organics added into the sol-gel protocol. Within colloids Ag (core-shell CdSe/CdS) NPs presented average diameter and polydispersity index of 49.5 nm (4.2 nm) and 0.41 (0.21), respectively. On the other hand, the Ag (core-shell CdSe/CdS) NPs’ average diameter and polydispersity index assessed from the GHNCs were respectively 51.5 nm (4.1 nm) and 0.43 (0.25), revealing negligible aggregation of the nanophases within the glass template. The new GHNCs herein introduced presented two independent excitonic transitions associated to homogenously dispersed semiconductor NPs, peaking around 420 nm (core-shell CdSe/CdS) and 650 nm (CdS_xSe_1?x) and matching the plasmonic resonance (Ag NPs) in the 400–500 nm range. We envisage that the new GHNCs represent very promising candidates for superior light manipulation while illuminated with multiple laser beams in quantum interference-based devices.     

Antitumor Effects of Vitamin D Analogs on Hamster and Mouse Melanoma Cell Lines in Relation to Melanin Pigmentation

Deregulated melanogenesis is involved in melanomagenesis and melanoma progression and resistance to therapy. Vitamin D analogs have anti-melanoma activity. While the hypercalcaemic effect of the active form of Vitamin D (1,25(OH)₂D₃) limits its therapeutic use, novel Vitamin D analogs with a modified side chain demonstrate low calcaemic activity. We therefore examined the effect of secosteroidal analogs, both classic (1,25(OH)₂D₃ and 25(OH)D₃), and novel relatively non-calcemic ones (20(OH)D₃, calcipotriol, 21(OH)pD, pD and 20(OH)pL), on proliferation, colony formation in monolayer and soft-agar, and mRNA and protein expression by melanoma cells. Murine B16-F10 and hamster Bomirski Ab cell lines were shown to be effective models to study how melanogenesis affects anti-melanoma treatment. Novel Vitamin D analogs with a short side-chain and lumisterol-like 20(OH)pL efficiently inhibited rodent melanoma growth. Moderate pigmentation sensitized rodent melanoma cells towards Vitamin D analogs, and altered expression of key genes involved in Vitamin D signaling, which was opposite to the effect on heavily pigmented cells. Interestingly, melanogenesis inhibited ligand-induced Vitamin D receptor translocation and ligand-induced expression of VDR and CYP24A1 genes. These findings indicate that melanogenesis can affect the anti-melanoma activity of Vitamin D analogs in a complex manner.     

Mixed-Metal MOF-74 Templated Catalysts for Efficient Carbon Dioxide Capture and Methanation

The vast chemical and structural tunability of metal–organic frameworks (MOFs) are beginning to be harnessed as functional supports for catalytic nanoparticles spanning a range of applications. However, a lack of straightforward methods for producing nanoparticle-encapsulated MOFs as efficient heterogeneous catalysts limits their usage. Herein, a mixed-metal MOF, NiMg-MOF-74, is utilized as a template to disperse small Ni nanoclusters throughout the parent MOF. By exploiting the difference in Ni O and Mg O coordination bond strength, Ni²⁺ is selectively reduced to form highly dispersed Ni nanoclusters constrained by the parent MOF pore diameter, while Mg²⁺ remains coordinated in the framework. By varying the ratio of Ni to Mg in the parent MOF, accessible surface area and crystallinity can be tuned upon thermal treatment, influencing CO₂ adsorption capacity and hydrogenation selectivity. The resulting Ni nanoclusters prove to be an active catalyst for CO₂ methanation and are examined using extended X-ray absorption fine structure and X-ray photoelectron spectroscopy. By preserving a segment of the Mg²⁺-containing MOF framework, the composite system retains a portion of its CO₂ adsorption capacity while continuing to deliver catalytic activity. The approach is thus critical for designing materials that can bridge the gap between carbon capture and CO₂ utilization.     

Liquid phase sintering and characterization of SiC ceramics

The present study focuses on the sintering of silicon carbide-based ceramics (SiC) by liquid phase sintering (LPS) followed by characterization of the produced ceramics. AlN/Re₂O₃ mixtures were used as additives in the LPS process. In the first step, the LPS-SiC materials were produced in a graphite resistance furnace in the form of discs at different temperatures. The conditions with the best results regarding real density and relative density were taken as reference for sintering in the form of prismatic bars. In the second step, these samples were evaluated regarding fracture toughness (K_IC), by the Single Edge V Notch Beam – SEVNB – method, and flexural strength. K_IC behavior was evaluated according to the depth and curvature radius of the notches. Reliable K_IC values were presented when the ceramic displayed a small curvature radius at the notch tip. When the radius was large, it did not maintain the square root singularity of the notch tip. Tests were carried out to determine K_IC values in atmospheric air and water. K_IC results were lower in water than air, with a decrease ranging between 2.56% and 11.26%. The observations indicated a direct grain size correlation between K_IC values and fracture strength of the SiC ceramics.     

A Constitutive Equation of Thermoelasticity for Solid Materials

A new constitutive equation of thermoelasticity for crystals is presented based on the interatomic potential and solid mechanics at finite temperature. Using the new constitutive equation, the calculations for crystal copper and graphene are carried out under different loading paths at different temperatures. The calculated results are in good agreement with those of the previous thermoelasticity constitutive equation based on quantum mechanics, which clearly indicates that our new constitutive equation of thermoelasticity is correct. A lot of comparisons also show that the present theory is more concise and efficient than the previous thermal stress theory in the practical application.