Search Results (8)

In this study, we prepared plastic films composed of modified layered double hydroxides (LDHs), which were incorporated into a low-density polyethylene (LDPE) matrix. The sunscreen additive sulfonic phenylbenzimidazole acid sodium salt was incorporated as counter-anion in the interlayer of a nanoclay by means of ion-exchange reactions to improve thermal and optical properties. The modified LDHs were characterized using FT-IR, XRF, TGA, and XRD techniques. Cast extrusion was employed to obtain the nanocomposites with the new LDH incorporated into LDPE. The mechanical, rheological, and optical properties of the films were assessed, and the influence of a non-ionic surfactant was also evaluated. In addition, accelerated ageing tests were carried out to evaluate the influence of UV light on the mechanical and optical properties of the films. Full article

[Sn(OSO₃)₂(TPy^HP)](HSO₄)₂∙8H₂O (1), an ionic Sn(IV)-porphyrin complex, was prepared by reacting [Sn(OH₂)₂TPyP] with dilute sulfuric acid. X-ray structural analysis revealed that the zwitterionic [Sn(OSO₃)₂TPy^HP]²⁺ species consists of two anionic axial Sn–O–SO₃ units and four peripheral pyridinium moieties, with an overall dicationic charge balanced by two hydrogen sulfate (HSO₄⁻) counter-anions. Ionic hydrogen bonding between the oxygen atoms of axial sulfato ligands and the peripheral pyridinium groups of adjacent Sn(IV)-porphyrin cations led to the formation of a 1D channel filled with counter-anions and water molecules. The supramolecular self-assembly of 1 was further characterized using various spectroscopic techniques, including ¹H NMR spectroscopy, elemental analysis, ESI-mass spectrometry, UV-vis spectroscopy, fluorescence spectroscopy, FT-IR spectroscopy, thermogravimetric analysis (TGA), and powder X-ray diffractometry. The zwitterionic [Sn(OSO₃)₂TPy^HP]²⁺ complex is a structurally well-defined complementary scaffold involved in supramolecular self-assembly. This novel class of ion-assembled metalloporphyrin is a potential functional porphyrin material used in ion exchange applications. Full article

The synthesis and structural characterization of a new triangular Cu₃–μ₃OH pyrazolato complex of formula, [Cu₃(μ₃−OH)(pz)₃(Hpz)₃][BF₄]₂ (1−Cu₃), Hpz = pyrazole, is presented. The triangular unit forms a quasi-isosceles triangle with Cu–Cu distances of 3.3739(9), 3.3571(9), and 3.370(1) Å. This complex is isostructural to the hexanuclear complex [Cu₃(μ₃−OH)(pz)₃(Hpz)₃](ClO₄)₂]₂ (QOPJIP). A comparative structural analysis with other reported triangular Cu₃–μ₃OH pyrazolato complexes has been carried out, showing that, depending on the pyrazolato derivative, an auxiliary ligand or counter-anion can affect the nuclearity and/or the dimensionality of the system. The magnetic properties of 1−Cu₃ are analyzed using experimental data and DFT calculation. A detailed analysis was performed on the magnetic properties, comparing experimental and theoretical data of other molecular triangular Cu₃–μ₃OH complexes, showing that the displacement of the μ₃−OH⁻ from the Cu₃ plane, together with the type of organic ligands, influences the nature of the magnetic exchange interaction between the spin-carrier centers, since it affects the overlap of the magnetic orbitals involved in the exchange pathways. Finally, a detailed comparison of the magnetic properties of 1−Cu₃ and QOPJIP was carried out, which allowed us to understand the differences in their magnetic properties. Full article

Smart gel materials are capable of controlling and switching swelling, water state, and wettability properties triggered by external stimuli. In this study, we fabricated a series of polyelectrolyte hydrogels bearing a 3-trimethylammoniumpropyl pendant to a methacrylamide-based backbone and examined the switchability with hydrophobic-like counteranions. The exchange between the initial chloride and camphor sulfate (CaS), dodecyl sulfate (DS), and perfluorooctanoate (PFO) counterions was investigated. The kinetics of the exchange showed that the fast exchange (within 4 h) of PFO allowed for a favorable coordination for ion pairing, resulting in a decrease in hydration. The reversibility of the exchange to the Cl⁻ ion was only enabled for the CaS ion due to its bulkiness, while the PFO and DS hydrogels were unable to exchange, even by using tetrabutylammonium chloride, which is a structurally similar reagent, due to aggregation or the coagulates in the collapsed state of the linear tails of the counterions. The hydrogels exhibited a modulable water state and water swelling. Moreover, the hydrogels containing DS and PFO, as counterions, showed surface hydrophobic (contact angle 90°) and high hydrophobic (110°) behavior, respectively. The Raman spectrometry fluorescence with a pyrene probe indicated an increase in strong hydrogen-bonded water molecules, water confinement, and hydrophobic domains in the PFO hydrogel. Moreover, the PFO-modified hydrogel demonstrated a free-floating ability on the water surface, with a strong water repellency, showing that it has the potential to be applied in a floating pH detection device to distinguish between volatile and nonvolatile bases in a controlled manner. Full article

The effect of the counteranion of hexadecyltrimethylammonium salts on the physico-chemical properties of organoclays was investigated, using a selected natural clay mineral with a cation exchange capacity of 95 meq/100 g. The uptake amount of C₁₆ cations was dependent on the hexadecyltrimethylammonium (C₁₆) salt solution used, the organoclay prepared from C₁₆Br salt solution exhibited a value of 1. 05 mmole/g higher than those prepared from C₁₆Cl and C₁₆OH salt solutions. The basal spacing of these organoclays was in the range of 1.81 nm to 2.10 nm, indicating a similar orientation of the intercalated surfactants, and could indicated that the excess amount of surfactants, above the cation exchange capacity of 0.95 meq/g could be adsorbed on the external surface of the clay mineral sheets. These organoclays were found to be stable in neutral, acidic, and basic media. The thermal stability of these organoclays was carried out using thermogravimetric analysis and in-situ X-ray diffraction (XRD) techniques. The decomposition of the surfactant occurred at a maximum temperature of 240 °C, accompanied with a decrease of the basal spacing value close to 1.42 nm. The application of these organoclays was investigated to remove an acidic dye, eosin. The removal amount was related to the initial used concentrations, the amount of the surfactants contents, and to the preheated temperatures of the organoclays. The removal was found to be endothermic process with a maximum amount of 55 mg of eosin/g of organoclay. The value decreased to 25 mg/g, when the intercalated surfactants were decomposed. The reuse of these organoclays was limited to four regeneration recycles with a reduction of 20 to 30%. However, noticeable reduction between 35% to 50% of the initial efficiency, was achieved after the fifth cycle, depending of the used organoclays. Full article

The present work reports an efficient synthesis of fluorinated pyridinium salts-based hydrazones under both conventional and eco-friendly ultrasound procedures. The synthetic approach first involves the preparation of halogenated pyridinium salts through the condensation of isonicotinic acid hydrazide (1) with p-fluorobenzaldehyde (2) followed by the nucleophilic alkylation of the resulting N-(4-fluorobenzylidene)isonicotinohydrazide (3) with a different alkyl iodide. The iodide counteranion of 5–10 was subjected to an anion exchange metathesis reaction in the presence of an excess of the appropriate metal salts to afford a new series of fluorinated pyridinium salts tethering a hydrazone linkage 11–40. Ultrasound irradiation led to higher yields in considerably less time than the conventional methods. The newly synthesized ILs were well-characterized with FT-IR, ¹H NMR, ¹³C NMR, ¹¹B, ¹⁹F, ³¹P and mass spectral analyses. The ILs were also screened for their antimicrobial and antitumor activities. Within the series, the salts tethering fluorinated counter anions 11–13, 21–23, 31–33 and 36–38 were found to be more potent against all bacterial and fungal strains at MIC 4–8 µg/mL. The in vitro antiproliferative activity was also investigated against four tumor cell lines (human ductal breast epithelial tumor T47D, human breast adenocarcinoma MCF-7, human epithelial carcinoma HeLa and human epithelial colorectal adenocarcinoma Caco-2) using the MTT assay, which revealed that promising antitumor activity was exhibited by compounds 5, 12 and 14. Full article

In durum wheat mitochondria (DWM) the ATP-inhibited plant mitochondrial potassium channel (PmitoK_ATP) and the plant uncoupling protein (PUCP) are able to strongly reduce the proton motive force (pmf) to control mitochondrial production of reactive oxygen species; under these conditions, mitochondrial carriers lack the driving force for transport and should be inactive. However, unexpectedly, DWM uncoupling by PmitoK_ATP neither impairs the exchange of ADP for ATP nor blocks the inward transport of Pi and succinate. This uptake may occur via the plant inner membrane anion channel (PIMAC), which is physiologically inhibited by membrane potential, but unlocks its activity in de-energized mitochondria. Probably, cooperation between PIMAC and carriers may accomplish metabolite movement across the inner membrane under both energized and de-energized conditions. PIMAC may also cooperate with PmitoK_ATP to transport ammonium salts in DWM. Interestingly, this finding may trouble classical interpretation of in vitro mitochondrial swelling; instead of free passage of ammonia through the inner membrane and proton symport with Pi, that trigger metabolite movements via carriers, transport of ammonium via PmitoK_ATP and that of the counteranion via PIMAC may occur. Here, we review properties, modulation and function of the above reported DWM channels and carriers to shed new light on the control that they exert on pmf and vice-versa. Full article

A broad and simple method permitted halide ions in quaternary heteroaromatic and ammonium salts to be exchanged for a variety of anions using an anion exchange resin (A⁻ form) in non-aqueous media. The anion loading of the AER (OH⁻ form) was examined using two different anion sources, acids or ammonium salts, and changing the polarity of the solvents. The AER (A⁻ form) method in organic solvents was then applied to several quaternary heteroaromatic salts and ILs, and the anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Relying on the hydrophobicity of the targeted ion pair for the counteranion swap, organic solvents with variable polarity were used, such as CH₃OH, CH₃CN and the dipolar nonhydroxylic solvent mixture CH₃CN:CH₂Cl₂ (3:7) and the anion exchange was equally successful with both lipophilic cations and anions. Full article