Oxidative Stability of Long-Chain Fatty Acids with Different Unsaturation Degrees into Layered Double Hydroxides

Nowadays, there is increasing evidence that the intake of essential fatty acids (FAs) and oleic acid has high nutritional importance. However, the vulnerability of these FAs to oxidation deserves special attention. FA oxidation may be avoided or delayed by intercalation of its anionic form in inorganic matrices as layered double hydroxides (LDH). Thus, the aim of the study was to evaluate the protective effects of MgAl LDH towards oleate (O), linoleate (L) and α-linolenate (Ln) degradation. The incorporation and the loading of different FAs in anionic form in LDH was determined by X-ray diffraction and thermogravimetric analysis (TGA), respectively. In order to study the selectivity of LDH towards the FA, the inorganic solid was equilibrated with a mixture of O, L and Ln (1:1:1). TGA and gas chromatography showed that Ln was preferentially intercalated. Free FA (FFA) and intercalated FA (IFA) were heated at 40 °C in the dark and then analyzed weekly for a maximum of 42 days. Their oxidative stability was evaluated by monitoring the primary and secondary oxidative compounds. The volatile compounds were determined by solid-phase microextraction, coupled with gas chromatography–mass spectrometry. Peroxide values were higher in FFA samples than in IFA samples, such as hexanal and trans,trans-2,4-heptadienal % contents. The results showed the potential of LDH intercalation for FA preservation from oxidative modification.

PROTOLYTIC EQUILIBRIUM OF TETRA- AND PENTANITROFLUORESCEINS IN A BINARY SOLVENT ACETONITRILE – DIMETHYL SULFOXIDE (MASS RATIO 96 : 4)

In this paper, the acid-base and tautomeric equilibria of four nitrofluorescein dyes, 2,4,5,7-tetranitrofluorescein, 2,4,5,7,4’-pentanitrofluorescein, 2,4,5,7,5’-pentanitrofluorescein, and 2,4,5,7-tetranitrofluorescein methyl ester, were studied. As reaction media, a binary solvent acetonitrile – dimethyl sulfoxide (96 : 4 by mass) was used. The acidity scale in this solvent was established previously. The indices of the dissociation constants of the dyes were determined using the spectrophotometric method. Interpreting the values ​​requires an understanding of the state of tautomeric equilibria. The behavior of these compounds differs significantly from that of other fluorescein dyes, e.g., halogen derivatives. In the case of the first three compounds, i.e., for dyes with a free carboxylic group, the lactonic structure is predominant not only for the neutral form, but even for the double-charged anion. The single-charged anionic form exists as an equilibrium mixture of a colored (and fluorescent) tautomer and an almost colorless lactone. The fourth compound with esterified carboxylic group exhibits extreme stability in its anionic form. Evaluation of the tautomerization constants made it possible to calculate the microscopic equilibrium constants of the stepwise dissociation of dye lactones, k1L and k2L. The consideration of the difference (pk2L – pk1L) allowed estimating the effective relative permittivity of the space between the ionizing groups basing on the Bjerrum – Kirkwood – Westheimer equation. Tautomerism of anions was discussed from the point of view of stabilization of symmetric structures.

Zinc(II) Complexes Derived from Schiff Bases: Syntheses, Structures, and Biological Activity

Three new zinc(II) complexes, [Zn2I2(L1)2] (1), [Zn(HL2)2(NCS)2] (2), and [ZnIL3] (3), where L1 is the anionic form of 2-[(6-methylpyridin-2-ylimino)methyl]phenol (HL1), HL2 is the zwitterionic form of 2-(cyclopropyliminomethyl)-5-fluorophenol (HL2), and L3 is the anionic form of 5-bromo-2-[(3-morpholin-4-ylpropylimino)methyl] phenol (HL3), have been prepared and characterized by elemental analyses, IR, UV and NMR spectra, and single crystal X-ray crystallographic determination. Complex 1 is a dinuclear zinc complex, and complexes 2 and 3 are mononuclear zinc complexes. The Zn atoms in the complexes are in tetrahedral coordination. The effect of the complexes on the antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Candida albicans were evaluated.

Beyond the Simple Copper(II) Coordination Chemistry with Quinaldinate and Secondary Amines

Copper(II) acetate has reacted in methanol with quinaldinic acid (quinoline-2-carboxylic acid) to form [Cu(quin)2(CH3OH)]∙CH3OH (1) (quin− = an anionic form of the acid) with quinaldinates bound in a bidentate chelating manner. In the air, complex 1 gives off methanol and binds water. The conversion was monitored by IR spectroscopy. The aqua complex has shown a facile substitution chemistry with alicyclic secondary amines, pyrrolidine (pyro), and morpholine (morph). trans-[Cu(quin)2(pyro)2] (2) and trans-[Cu(quin)2(morph)2] (4) were obtained in good yields. The morpholine system has produced a by-product, trans-[Cu(en)2(H2O)2](morphCOO)2 (5) (morphCOO− = morphylcarbamate), a result of the copper(II) quinaldinate reaction with ethylenediamine (en), an inherent impurity in morpholine, and the amine reaction with carbon dioxide. (pyroH)[Cu(quin)2Cl] (3) forms on the recrystallization of [Cu(quin)2(pyro)2] from dichloromethane, confirming a reaction between amine and the solvent. Similarly, a homologous amine, piperidine (pipe), and dichloromethane produced (pipeH)[Cu(quin)2Cl] (11). The piperidine system has afforded both mono- and bis-amine complexes, [Cu(quin)2(pipe)] (6) and trans-[Cu(quin)2(pipe)2] (7). The latter also exists in solvated forms, [Cu(quin)2(pipe)2]∙CH3CN (8) and [Cu(quin)2(pipe)2]∙CH3CH2CN (9). Interestingly, only the piperidine system has experienced a reduction of copper(II). The involvement of amine in the reduction was undoubtedly confirmed by identification of a polycyclic piperidine compound 10, 6,13-di(piperidin-1-yl)dodecahydro-2H,6H-7,14-methanodipyrido[1,2-a:1′,2′-e][1,5]diazocine.

Fluoride binding by an anionic receptor: tuning the acidity of amide NH groups for basic anion hydrogen bonding and recognition

Here we report the first family of bis-amide receptors able to bind fluoride in their anionic form.

Aggregation Processes in Hybrid Nanosystem Polymer/Nanosilver/Cisplatin

Hybrid nanosystems consisting of star-like copolymer Dextran-graft-Polyacrylamide in the anionic form (D-g-PAA(PE)), silver nanoparticles (AgNPs), and cisplatin (cis-Pt) have been synthesized in water and characterized by TEM, DLS, FTIR, and UV-Vis spectroscopies. It is shown that cis-Pt forms a complex with carboxylate groups of the polymer. For the ternary system Polymer/AgNPs/cis-Pt, a change in the hydrophilic-hydrophobic balance of a polymer molecule (due to the complexation with cis-Pt) and the aggregation of macromolecules, as well as to some agglomeration AgNPs, are revealed. The decrease of the antitumor efficiency of the hybrid ternary nanosystem Polymer/AgNPs/cis-Pt in comparison with the Polymer/cis-Pt system is discussed.

Molecularly imprinted ‘traps’ for sulfonylureas prepared using polymerisable ion pairs

Polymerisable ion pair captures both neutral and anionic form of acidic sulfonylurea drug in stoichiometrically imprinted polymer.

New types of Cu and Ag clusters supported by the pyrrole-based NNN-pincer type ligand

While the neutral ligand 2,5-bis(3,5-dimethylpyrazolylmethyl)pyrrole gives the dihalide ion bridged binuclear and coordination polymers, its anionic form affords a new type of tetranuclear ‘hourglass’ shaped copper(i) and triangular silver(i) clusters owing to its increased denticity.

Excited-state deactivation in 8-oxo-deoxyguanosine: comparison between anionic and neutral forms

Ab initio explorations of excited-state potential-energy surfaces show that a radiationless deactivation mechanism via intramolecular excited-state proton transfer is available in neutral 8-oxo-deoxyguanosine, whereas it is not available in the anionic form.