Freeze–Thaw-Promoted Fabrication of Clean and Hierarchically Structured Noble-Metal Aerogels for Electrocatalysis and Photoelectrocatalysis

Noble-metal aerogels (NMAs) have drawn increasing attention because of their self-supported conductive networks, high surface areas, and numerous optically/catalytically active sites, enabling their impressive performance in diverse fields. However, the fabrication methods suffer from tedious procedures, long preparation times, unavoidable impurities, and uncontrolled multiscale structures, discouraging their developments. By utilizing the self-healing properties of noble-metal aggregates, the freezing-promoted salting-out behavior, and the ice-templating effect, a freeze–thaw method is crafted that is capable of preparing various hierarchically structured noble-metal gels within one day without extra additives. In light of their cleanliness, the multi-scale structures, and combined catalytic/optical properties, the electrocatalytic and photoelectrocatalytic performance of NMAs are demonstrated, which surpasses that of commercial noble-metal catalysts.     

Synthesis of PAN/ferrocyanide composite incorporated with cetrimonium bromide and its employment as a bifunctional adsorbent for coremoval of Cs+ and HCrO4− from aqueous solutions

Polyacrylonitrile/ferrocyanide composite incorporated with cetrimonium bromide (PFICB) was synthesized and evaluated as a novel bifunctional adsorbent for coremoval of Cs⁺ and HCrO₄^?. Results of the reaction time effect showed that adsorption of Cs⁺ and HCrO₄^? onto PFICB were rapid processes. The effect of the solution pH in the range 2.5–10 revealed that PFICB had the ability to simultaneously remove Cs⁺ and HCrO₄^?. The maximum adsorption capacity of PFICB was found to be 41.79 mg/g for Cs⁺ and 19.39 mg/g for HCrO₄^?. These values were compared with those reported in literature using other adsorbents.

     

Interface‐fitted moving mesh method for axisymmetric two‐phase flow in microchannels

A boundary‐fitted moving mesh scheme is presented for the simulation of two‐phase flow in two‐dimensional and axisymmetric geometries. The incompressible Navier‐Stokes equations are solved using the finite element method, and the mini element is used to satisfy the inf‐sup condition. The interface between the phases is represented explicitly by an interface adapted mesh, thus allowing a sharp transition of the fluid properties. Surface tension is modelled as a volume force and is discretized in a consistent manner, thus allowing to obtain exact equilibrium (up to rounding errors) with the pressure gradient. This is demonstrated for a spherical droplet moving in a constant flow field. The curvature of the interface, required for the surface tension term, is efficiently computed with simple but very accurate geometric formulas. An adaptive moving mesh technique, where smoothing mesh velocities and remeshing are used to preserve the mesh quality, is developed and presented. Mesh refinement strategies, allowing tailoring of the refinement of the computational mesh, are also discussed. Accuracy and robustness of the present method are demonstrated on several validation test cases. The method is developed with the prospect of being applied to microfluidic flows and the simulation of microchannel evaporators used for electronics cooling. Therefore, the simulation results for the flow of a bubble in a microchannel are presented and compared to experimental data.     

Dinuclear gold (I)-di-N-heterocyclic carbene complexes: syntheses,structure, density functional theory calculation and photoluminescence study

The synthesis and characterizations for a series of dinuclear gold (I)-di-NHC complexes, 1–8 through the trans-metalation method of their respective silver (I)-di-NHC complexes, i–viii are reported (where NHC = N-heterocyclic carbene). The successful complexation of a series of unusual non-symmetrical and symmetrical di-NHC ligands, 3,3'-(ethane-1,2-diyl)-1-alkylbenzimidazolium-1'-butylbenzimidazolium (with alkyl = methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, benzyl) with the gold (I) ions are suggested by elemental analysis, Fourier transform-infrared, ¹H- and ¹³C-NMR data. The ¹³C-NMR spectra of 1–8 show a singlet sharp peak in the range of 190.00–192.00 ppm, indicating the presence of a carbene carbon that bonded to the gold (I) ion. From single crystal X-ray diffraction data, the structure of complex 6 with the formula of [di-NHC-Au (I)]₂·2PF₆ is obtained [where NHC = 3,3'-(ethane-1,2-diyl)-1-hexylbenzimidazolium-1'-butylbenzimidazolium]. The photophysical study in solid state of 6 displays an intense photoluminescence with a strong emission maxima, λ_em = 480 nm, upon excitation at 340 nm at room temperature. Interestingly, the emission maximum at 77 K shows a structural character with a strong peak at 410 nm, a medium at 433 nm and a weak at 387 nm, accompanied by a tail band to about 500 nm.     

Two-Photon Absorption Enhancement by the Inclusion of a Tropone Ring in Distorted Nanographene Ribbons

A new family of distorted ribbon-shaped nanographenes was designed, synthesized, and their optical and electrochemical properties were evaluated, pointing out an unprecedented correlation between their structural characteristics and the two-photon absorption (TPA) responses and electrochemical band gaps. Three nanographene ribbons have been prepared: a seven-membered-ring-containing nanographene presenting a tropone moiety at the edge, its full-carbon analogue, and a purely hexagonal one. We have found that the TPA cross-sections and the electrochemical band gaps of the seven-membered-ring-containing compounds are higher and lower, respectively, than those of the fully hexagonal polycyclic aromatic hydrocarbon (PAH). Interestingly, the inclusion of additional curvature has a positive effect in terms of non-linear optical properties of those ribbons.     

A preliminary assessment of the provenance of ancient pottery through instrumental neutron activation analysis at the Monte Castelo site,Rondônia,Brazil

Journal of Radioanalytical and Nuclear Chemistry - This research aims to contribute to the discussion of ceramic objects found at the Monte Castelo shellmound, an archaeological site located at...     

Synthesis of lupeol derivatives and their antileishmanial and antitrypanosomal activities

The natural product lupeol 1 was isolated from aerial parts of Vernonia scorpioides with satisfactory yield, which made it viable to be used as starting material in semisynthetic approach. Ten lupeol derivatives 2–11 were prepared by classical procedures. Including, five new esters derivatives 7–11, which were obtained by structural modifications in the isopropylidene fragment. All semisynthetic compounds and lupeol 1–11 were confirmed by ¹H NMR, ¹³C NMR and HRMS. Their antiprotozoal activity was evaluated in vitro against L. amazonensis and T. cruzi. Derivative 6 showed the best antitrypanosomal activity (IC₅₀ = 12.48 μg/mL) and the lowest cytotoxic derivative (CC₅₀ = 161.50 μg/mL). The mechanism of action of the most active derivatives (4, 6 and 11) is not dependent from the enzyme trypanothione reductase.