Octadecylamine as chemical modifier for tuned hydrophobicity of surface modified cellulose: toward organophilic cellulose nanocrystals

Cellulose - A novel, environmentally friendly and simple method for chemical functionalization of microcrystalline cellulose (MCC) to produce organophilic cellulose nanocrystals (CNC-ODA) is herein...     

Antiproliferative Homoleptic and Heteroleptic Phosphino Silver(I) Complexes: Effect of Ligand Combination on Their Biological Mechanism of Action

A series of neutral mixed-ligand [HB(pz)₃]Ag(PR₃) silver(I) complexes (PR₃ = tertiary phosphine, [HB(pz)₃]⁻ = tris(pyrazolyl)borate anion), and the corresponding homoleptic [Ag(PR₃)₄]BF₄ compounds have been synthesized and fully characterized. Silver compounds were screened for their antiproliferative activities against a wide panel of human cancer cells derived from solid tumors and endowed with different platinum drug sensitivity. Mixed-ligand complexes were generally more effective than the corresponding homoleptic derivatives, but the most active compounds were [HB(pz)₃]Ag(PPh₃) (5) and [Ag(PPh₃)₄]BF₄ (10), both comprising the lipophilic PPh₃ phosphine ligand. Detailed mechanistic studies revealed that both homoleptic and heteroleptic silver complexes strongly and selectively inhibit the selenoenzyme thioredoxin reductase both as isolated enzyme and in human ovarian cancer cells (half inhibition concentration values in the nanomolar range) causing the disruption of cellular thiol-redox homeostasis, and leading to apoptotic cell death. Moreover, for heteroleptic Ag(I) derivatives, an additional ability to damage nuclear DNA has been detected. These results confirm the importance of the type of silver ion coordinating ligands in affecting the biological behavior of the overall corresponding silver complexes, besides in terms of hydrophilic–lipophilic balance, also in terms of biological mechanism of action, such as interaction with DNA and/or thioredoxin reductase.     

Standard enthalpies of formation of “A” type carbonate phosphobaryum hydroxyapatites

Phosphobaryum carbonate hydroxyapatites Ba₁₀(PO₄)₆(OH)_(2?2x)(CO₃) _x with 0????x????1, were synthesized in this study by solid gas reaction at a high temperature. Carbonate content was determined by thermogravimetric analysis and X-ray diffraction. The heat of the solution in a 3 wt% nitric acid solution was measured at 298?K using an isoperibol calorimeter. The combination of the enthalpies of solution with the enthalpies of formation of the reactants allowed us to determine the standard enthalpies of formation of the studied apatites. The result showed a decrease in formation enthalpy with the carbonate amount introduced in the lattice, suggesting an increase in stability of these compounds as the ratio of the substitution increases.     

Synthesis in ionic liquids only: access to α-oxo-γ-thio-esters via Mukaiyama coupling

Ionic liquids are solvents general enough to conduct a multi-step process in organic synthesis. We show that both the preparation of starting materials (thioacetals and enoxysilane) as well as their coupling can be realized in such medium.     

Efficient photoinduced In situ preparation of clay/poly(glycidyl methacrylate) nanocomposites using hydrogen‐donor silane

Clay/poly(glycidyl methacrylate) nanocomposites (clay/PGMA) were prepared by in situ radical photopolymerization using N,N‐dimethylaminopropyltrimethoxysilane(DMA)‐modified bentonite clay acting as hydrogen donor for benzophenone in solution. This initiating system permits to photopolymerize glycidyl methacrylate between the lamellae of the DMA‐modified clay. The approach provides exfoliated nanocomposites as judged by the measurements of X‐ray diffraction. However, a low fraction of persistent intercalated clay regions was visible by transmission electron microscopy. X‐ray photoelectron spectra analyses indicate that the nanocomposites have PGMA‐rich surface. The clay/PGMA nanocomposites can be readily dispersed in ethanol. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 800–808     

Synthesis,Structural Study and Phase Transitions Characterization by Thermal Analysis and Vibrational Spectroscopy of an Ammonium Rubidium Arsenate Tellurate

The Rb_2.42(NH₄)_0.58(HAsO₄)(H₂AsO4)·Te(OH)₆ crystals(denoted by RbNAsTe) crystallize in the monoclinic system, space group P2₁/n with the following parameters:a=1.3059(5) nm, b=0.6755(3) nm, c=1.6675(6) nm, β=94.126(4)°, Z=4 and V=1.46733(10) nm³. Thermal analyses(DSC, DTA and TG) confirm the presence of the phase transition and the temperature of the decomposition. The vibrational spectroscopy study at room temperature show the presence and the independence of anionic groups, cationic groups, and give more importance to the hydrogen bonds. Raman spectra were recorded in the temperature range of 298-503 K. The temperature dependence of the Raman line shift, intensity reduction and the half width detects the phase transitions and confirms their nature. So, the phase transition at 453 K corresponds to the superprotonic-ionic conduction phase transition, and those at 483 and 491 K correspond to the decomposition of our material.     

Innovative Formulations of Phosphate Glasses as Controlled-Release Fertilizers to Improve Tomato Crop Growth,Yield and Fruit Quality

Three phosphate glass compositions, VF1, VF2, and VF3, containing macro and micronutrients with different [K₂O/(CaO+MgO)] ratio, were formulated to be used as controlled release fertilizers for tomato crop, depending on their chemical durability in water and their propriety with respect to the standards of controlled-release fertilizers. This study investigated the influence of [K₂O/(CaO+MgO)] ratio variation on glass properties. For this, the elaborated glasses have undergone a chemical characterization using inductively coupled plasma atomic emission spectroscopy, a thermal characterization using differential thermal analysis, a physicochemical characterization based on density and molar volume measurements, and a structural characterization using Raman spectroscopy, Fourier-transform infrared spectroscopy, and X-ray diffraction. In addition, the chemical durability was determined by measuring the percentage of weight loss and the pH. Results revealed that the glass structure and composition have the mean role in controlling the release of nutrients in water. By increasing [K₂O/(CaO+MgO)] ratio, the dissolution rates of the glasses increased due to the shrinking in the rate of crosslinking between phosphate chains, accompanied with a diminution in transition and crystallization temperatures, and an increase in the molar volume. An agronomic valorization of VF1 and VF2 glass fertilizers, which showed dissolution profiles adequate to the criteria of controlled-release fertilizers, was carried out to evaluate their efficiency on tomato crops. These glass fertilizers improved soil mineral content and tomato performances in comparison to the control and NPK treatments with the distinction of VF2. The results highlight the effectiveness of these smart fertilizers toward their potential large-scale application to improve crop production and quality for high nutritional value foods.     

Structural analysis and thermochemistry of “A” type phosphostrontium carbonate hydroxyapatites

“A” type phosphostrontium carbonate hydroxyapatites, having the general formula Sr₁₀(PO₄)₆(OH)_(2−2x)(CO₃) _x with 0 ≤ x ≤ 1, were synthesised by solid gas reaction at high temperature. The samples were characterised by X-ray diffraction and infrared spectroscopy. Analysis of carbonate was achieved by coulometry and Rietveld refinement of the structure. Using an isoperibol calorimeter, the heat of solution of these products was measured at 298 K in 9 wt% nitric acid solution. Thermochemical cycle was proposed and complementary experiences were performed to reach the standard enthalpies of formation of these compounds. The results showed a decrease of the enthalpy of formation with the amount of carbonate introduced in the lattice, suggesting an increase of stability due to this kind of substitution.     

New Synthetic Route for Reaching Higher Phase Stabilization in LAMOX-Based Electrolyte for Solid Oxide Fuel Cells

S-substituted La₂Mo₂O₉ were synthesized by a solid-state procedure employing ammonium sulfate (NH₄)₂SO₄ as a sulfur source. The synthesized powders were examined using X-ray diffraction (XRD), thermogravimetric analysis (TGA), infrared, and Raman spectroscopies. The results divulged that the stabilization of the β-La₂Mo₂O₉ polymorph occurred in the interval of sulfur composition 0.1≤y≤0.6. This substitution generates a linear dwindling of the unit cell volume. The decomposition of all substituted samples started above 900 °C with a total weight loss linearly dependent on the sulfur content. Electrical studies confirmed that substituting S⁶⁺ for Mo⁶⁺ suppresses the phase transition of La₂Mo₂O₉ and stabilizes the cubic polymorph down to ambient temperature. It was also remarkable that this substitution caused a decrease in the conductivity, and unfortunately, none of the tested compositions allowed exceeding the conductivity of La₂Mo₂O₉. Infrared and Raman spectra confirmed the presence of the characteristic peaks of sulfates and molybdates groups.     

Fabrication and characterization of graphene/sulfonated polyether sulfone octyl sulfonamide hybrid film with improved proton conductivity performance

Journal of Solid State Electrochemistry - In this study, graphene (G) was blended with sulfonated polyether sulfone octyl sulfonamide (SPESOS) in different ratios (1, 1.5, and 2 wt.%) to enhance...