Thermodynamic modeling of gas solubility in aqueous sodium chloride solution

An electrolyte Equation of State is presented by combining the Cubic Plus Association Equation of State,Mean Spherical Approximation and the Born equation.This new model uses experimental relative static permittivity,intend to predict well the activity coefficients of individual ions (ACI) and liquid densities of aqueous solutions.This new model is applied to model water + NaCl binary system and water + gas +NaCl ternary systems.The cation/anion-water interaction parameters of are obtained by fitting the exper-imental data of ACI,mean ionic activity coefficients (MIAC) and liquid densities of water + NaCl binary system.The cation/anion-gas interaction parameters are obtained by fitting the experimental data of gas solubilities in aqueous NaCl solutions.The modeling results show that this new model can correlate well with the phase equilibrium and volumetric properties.Without gas,predictions for ACI,MIAC,and liquid densities present relative average deviations of 1.3％,3.6％ and 1.4％ compared to experimental ref-erence values.For most gas-containing systems,predictions for gas solubilities present relative average deviations lower than 7.0％.Further,the contributions of ACI,and salting effects of NaCl on gases are ana-lyzed and discussed.     

A Highly Sensitive,Reversible, and Bidirectional Humidity Actuator by Calcium Carbonate Ionic Oligomers Incorporated Poly(Vinylidene Fluoride)

Sensitivity and multi-directional motivation are major two factors for developing optimized humidity-response materials, which are promising for sensing, energy production, etc. Organic functional groups are commonly used as the water sensitive units through hydrogen bond interactions with water molecules in actuators. The multi-coordination ability of inorganic ions implies that the inorganic ionic compounds are potentially superior water sensitive units. However, the particle forms of inorganic ionic compounds produced by classical nucleation limit the number of exposed ions to interact with water. Recent progress on the inorganic ionic oligomers has broken through the limitation of classical nucleation, and realized the molecular-scaled incorporation of inorganic ionic compounds into an organic matrix. Here, the incorporation of hydrophilic calcium carbonate ionic oligomers into hydrophobic poly(vinylidene fluoride) (PVDF) is demonstrated. The ultra-small calcium carbonate oligomers within a PVDF film endow it with an ultra-sensitive, reversible, and bidirectional response. The motivation ability is superior to other bidirectional humidity-actuators at present, which realizes self-motivation on an ice surface, converting the chemical potential energy of the humidity gradient from ice to kinetic energy.     

Note of Caution for the Aqueous Behaviour of Metal-Based Drug Candidates

Poor aqueous solubility is one of the recurrent drawbacks of many compounds in medicinal chemistry. To overcome this limitation, the dilution of drug candidates from stock solutions of an organic solvent is common practice. However, the precise characterisation of these compounds in aqueous solutions is often neglected, leading to some uncertainties regarding the nature of the actual active species. In this communication, we demonstrate that two ruthenium complexes previously reported by our group for their chemotherapeutic potential against cancer, namely [Ru(DIP)₂(sq)](PF₆) and [Ru(DIP)₂(3-methoxysq)](PF₆), where DIP is 4,7-diphenyl-1,10-phenanthroline, sq=semiquinonate and 3-methoxysq=3-methoxysemiquinonate, form colloids in water-DMSO (1 % v/v) mixtures that are invisible to the naked eyes. [Ru(DIP)₂(3-methoxysq)](PF₆) was found to form a highly stable and monodispersed colloid with nanoaggregates of ∼25 nm. In contrast, [Ru(DIP)₂(sq)](PF₆) was found to form large reticulates of mostly spherical aggregates which size was found to increase over time. The difference in size and shape distribution of drug candidates is of tremendous significance as the study of their biological activity might be severely affected. Overall, we strongly believe that these observations should be taken into account by the scientific community working on the development of metal-based drugs with poor water solubility.     

Carbon nanotube filter for heavy metal ion adsorption

This study investigated carbon nanotube filtration technology using catalyst particles supported on silicalite-1–biomorphic carbon materials (BCMs). Aqueous solutions of Mn(II), Cu(II), Cr(III), Cd(II), and Pb(II) were used to test the efficiency of heavy metal ions removal. Carbon nanotubes (CNTs) were synthesized and grown on BCMs by the chemical vapor deposition method catalyzed with the catalyst (Co, Fe, and Ni). The synthesized CNTs with Co– and Fe– nanoparticles were typically multi-walled carbon nanotubes, and they showed good crystallinity (I_D/I_G = 1.05) and yield of (11.10 and 8.86) %. The removal efficiency of Mn(II), Cu(II), Cr(III), Cd(II), and Pb(II) ions using Co-catalyzed CNT filter was 97.57%, 98.01%, 97.89%, 97.42%, and 99.99%, respectively.     

Microstructural and electrical changes in Ca0.9R0.1CeNbMoO8 (R = Y,Sm, Nd,La) ceramics induced by rare-earth ion doping

Rare-earth ions doped Ca_0.9R_0.1CeNbMoO₈ (R = Y, Sm, Nd, La) ceramics have been successfully prepared by solid-state method, and their modifications to the microstructure and electrical properties are also investigated. The rare-earth ions doped ceramics exhibit the scheelite structure. With the increase in the radius of rare-earth ions, the lattice distortion and bond interaction will be enhanced, and the consistency of grain size will be reduced. The ceramics exhibit negative temperature coefficient (NTC) thermistor characteristics in the temperature range of 473 K-1273 K, and the activation energy decreases with the increase of the radius of rare-earth ions. Rare-earth ions doping can increase the content of Ce³⁺ ions and promote the conductivity of ceramics. Except for Sm³⁺-doped ceramics, the high-temperature aging rate of other ceramics is less than 2%. The existence of some metastable Sm²⁺ ions in Sm³⁺-doped ceramics not only increases the activation energy, but also reduces the high-temperature stability of the ceramics.     

Rare-earth free sensitizer in NaLuCrF4:Er upconversion material

Upconversion phosphors are known as a material system that can convert near-infrared light into visible/ultraviolet emissions by sequentially absorbing multiple photons. The studies on upconversion materials often use two rare earth (RE) ions as a sensitizer-activator pair. We investigated the influences on luminescence intensity depending on Cr-doping content (x) of hexagonal NaLu_0.98–xCr_xF₄Er_0.02 (x = 0–0.9) upconversion material by substituting Lu³⁺ ions with Cr³⁺in the absence of Gd³⁺. The change in upconversion luminescence intensity appears with saddle-like shape. We suggest that Cr³⁺ ions play the dual role as a constituent in host lattice and a sensitizer in the upconversion process. Optimal conditions for gaining the strongest upconversion emission correspond to x = 0.3–0.5, where there are effective energy transfers between Cr³⁺ and Er³⁺ ions and CrEr dimers. Apart from these values, the emission intensity decreases rapidly which can be ascribed to the absence of multiple-photon absorption for the case of low Cr³⁺ contents, and to the coupling between Cr³⁺ and/or Er³⁺ ions for the case of high Cr³⁺ contents. Magnetization and electron-spin-resonant measurements were performed to understand the correlation between the optical and magnetic properties.     

Synthesis and characterization of a novel Ca-alginate-biochar composite as efficient zinc (Zn2+) adsorbent: Thermodynamics,process design,mass transfer and isotherm modeling

In this present work, Ca-alginate-biochar adsorbent has been synthesized, characterized and tested its effectiveness in the removal of aqueous phase Zn²⁺ metal. The removal efficiency was studied under various physicochemical process parameters. External mass transfer model, intraparticle diffusion model and pseudo-first-order and pseudo-second-order models were used to fit the experimental Zn²⁺ adoption kinetic results and to identify the mechanism of adsorption. The desorption studies indicate the possibilities of ion-exchange and physical–chemical adsorption of Zn^2+. The adsorption was best described by Langmuir isotherm model. Thermodynamic parameters suggested that the adsorption process becomes spontaneous, endothermic and irreversible in nature.     

Grain size influence on the flexibility and luminous intensity of inorganic CaTiO3:Pr3+ crystal nanofibers

Traditional inorganic materials exhibit rigidity owing to the lack of polymer chains in polymer materials or atom slipping in metals. However, nanometerization has been recently proposed for the conversion of inorganic oxide materials into flexible materials. Herein, the flexible inorganic luminescent material, CaTiO₃:0.2%Pr³⁺, was synthesized through electrospinning, and the macroscopic flexibility of pure inorganic CaTiO₃:0.2%Pr³⁺ was achieved. The flexible membrane was characterized via X-ray diffraction, thermogravimetry, scanning electron microscopy (SEM), and photoluminescence analyses. The grain size was analyzed at various calcination temperatures via SEM, and the results suggested that the increase in the calcination temperature resulted in the growth of crystal grains. Studies have reported that the growth of crystal grains is beneficial for improving the luminescence performance; however, to obtain better flexibility, smaller crystal grains are required. This study provides an important reference for the design of flexible inorganic materials.     

Colloidal Synthesis of Hollow Cobalt Sulfide Nanocrystals

Formation of cobalt sulfide hollow nanocrystals through a mechanism similar to the Kirkendall Effect has been investigated in detail. It is found that performing the reaction at > 120 °C leads to fast formation of a single void inside each shell, whereas at room temperature multiple voids are formed within each shell, which can be attributed to strongly temperature‐dependent diffusivities for vacancies. The void formation process is dominated by outward diffusion of cobalt cations; still, the occurrence of significant inward transport of sulfur anions can be inferred as the final voids are smaller in diameter than the original cobalt nanocrystals. Comparison of volume distributions for initial and final nanostructures indicates excess apparent volume in shells, implying significant porosity and/or a defective structure. Indirect evidence for fracture of shells during growth at lower temperatures was observed in shell‐size statistics and transmission electron microscopy images of as‐grown shells. An idealized model of the diffusional process imposes two minimal requirements on material parameters for shell growth to be obtainable within a specific synthetic system.