Revision and Analysis of the Formation Constants of Rare Earth Diketonates.

Over the course of the past several decades, spectroscopic surveys have unveiled the intricate nature of the aqueous chelation of Rare Earth Metals. Herein, we have collected a large data set about the interaction between 16 metal ions (Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, and Lu3+) and perfluorinated nonsymmetric ß-diketones, which contain chalcogen-bearing heterocyclic rings or aromatic moiety. The role and influence of the side ions on the chelation processes have been re-estimated to obtain revised stability constants. After analysis of more than 150 revised formation constants, a better periodic correlation has been shown. Scrutinizing the effects of the substituted group has revealed an "anti-Coulomb" behavior within the chalcogen group of diketones and a strictly electrostatic trend within the Rare Earth Metals series. Within the first-order approximation, the spin-orbit contribution to the Gibbs free energy of chelation has been estimated.

Sulfation of Birch Wood Microcrystalline Cellulose with Sulfamic Acid Using Ion-Exchange Resins as Catalysts.

Cellulose sulfates are important biologically active substances with a wide range of useful properties. The development of new methods for the production of cellulose sulfates is an urgent task. In this work, we investigated ion-exchange resins as catalysts for the sulfation of cellulose with sulfamic acid. It has been shown that water-insoluble sulfated reaction products are formed in high yield in the presence of anion exchangers, while water-soluble products are formed in the presence of cation exchangers. The most effective catalyst is Amberlite IR 120. According to gel permeation chromatography, it was shown that the samples sulfated in the presence of the catalysts KU-2-8, Purolit s390 plus, and AN-31 SO42- underwent the greatest degradation. The molecular weight destribution profiles of these samples are noticeably shifted to the left towards low-molecular-weight compounds with an increase in fractions in the regions Mw ~2.100 g/mol and ~3.500 g/mol, indicating the growth of microcrystalline cellulose depolymerization products. The introduction of a sulfate group into the cellulose molecule is confirmed using FTIR spectroscopy by the appearance of absorption bands at 1245-1252 cm-1 and 800-809 cm-1, which correspond to the vibrations of the sulfate group. According to X-ray diffraction data, amorphization of the crystalline structure of cellulose is observed during sulfation. Thermal analysis has shown that with an increase in the content of sulfate groups in cellulose derivatives, thermal stability decreases.

Sulfation of Wheat Straw Soda Lignin with Sulfamic Acid over Solid Catalysts.

Soda lignin is a by-product of the soda process for producing cellulose from grassy raw materials. Since a method for the industrial processing of lignin of this type is still lacking, several research teams have been working on solving this problem. We first propose a modification of soda lignin with sulfamic acid over solid catalysts. As solid catalysts for lignin sulfation, modified carbon catalysts (with acid sites) and titanium and aluminum oxides have been used. In the elemental analysis, it is shown that the maximum sulfur content (16.5 wt%) was obtained with the Sibunit-4® catalyst oxidized at 400 °C. The incorporation of a sulfate group has been proven by the elemental analysis and Fourier-transform infrared spectroscopy. The molecular weight distribution has been examined by gel permeation chromatography. It has been demonstrated that the solid catalysts used in the sulfation process causes hydrolysis reactions and reduces the molecular weight and polydispersity index. It has been established by the thermal analysis that sulfated lignin is thermally stabile at temperatures of up to 200 °C. According to the atomic force microscopy data, the surface of the investigated film consists of particles with an average size of 50 nm. The characteristics of the initial and sulfated ß-O-4 lignin model compounds have been calculated and recorded using the density functional theory.

TD-DFT assessment of UV-vis spectra palladium and platinum complexes with thiols and disulfides.

Time-dependent density functional theory (TD-DFT) and spectrophotometric methods were used for speciation analysis in systems disulfides (cystine, cystamine, homocystine, 3,3-dithiodipropionic acid) - [PdCl4]2- or [PtCl4]2-. We use the M06-2X and CAM-B3LYP density functionals with Def2-SVP basis set to reproduce the experimental UV-vis spectra; the polarized continuum solvation model (PCM) was fitted to take into account solvation effects of the medium (water). Used methods have shown the good agrees with the experiment - theoretical values of transition energies differ from real parameters within ±0.15 eV for functional CAM-B3LYP. Binuclear disulfide complexes of Pd(II) with cystine and cystamine have form S,N-coordination sites, instead of S,S-conformation. It was shown that Pd(II) thiolate complexes formed by cleavage of the disulfide bond exist as [PdCl3L] and [Pd2S2L2]. Pt(II)-disulfide systems have confirmed the presence of [Pt2Cl6(R-SS-R)] and [PtCl4(S-R)] complex species. The DFT/CAM-B3LYP/Def2-SVP/SMD level can be recommended for theoretical estimations of absorption spectra of complexes of palladium or platinum and sulfur-containing ligands.

Interaction of Rare-Earth Metals and Some Perfluorinated ß-Diketones.

In this work, we demonstrate the fundamental relationships between stability constants and periodic, acid-base, and structural parameters for complexes of some 1,3-diketones. The four analogues of hexafluoroacetylacetone-2-thenoyltrifluoroacetone, 2-furoyltrifluoroacetone, benzoyltrifluoroacetone, and 2-naphthyltrifluoroacetone-have been studied as chelating ligands for 16 rare-earth metals (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) in aqueous solutions. Systems have been investigated spectrophotometrically using a multiwave nonlinear least-squares regression algorithm for data processing. Conditional stability constants were obtained for a wide pH region (2.0-5.4) at constant ionic strength (I = 0.5 M, NaCl). To receive the apparent ("true") equilibrium parameters, acid-base and keto-enol characteristics of the studied ligands have been described and revised for specific conditions. Dissociation constants were obtained in citrate-phosphate buffer media and protonation parameters were received in concentrated hydrochloric acid by the Cox-Yates method. The apparent formation constants for monocomplex species were obtained as thermodynamic invariants (depend only on the temperature) for each ligand and lie from 4.2 to 12.7 logarithmic units. Although the studied ligands have similar values of pKa, the stabilities of their complexes vary considerably. Systematic analysis of 64 apparent stability constants demonstrates that the force of interaction between the metals and nonsymmetric ß-diketones increases as 2-furoyltrifluoroacetone < 2-thenoyltrifluoroacetone < benzoyltrifluoroacetone < 2-naphthyltrifluoroacetone. The studied ligands display varying degrees of the correlation between the periodic parameters and formation constants. Naphthyltrifluoroacetone and its complexes with heavy lanthanides exhibit a clear trend in properties with increasing ionic potential. In general, the received set of data can be described from purely electrostatic grounds within the framework of the periodic law. Spectral, keto-enol, acid-base, and complexing properties were reproduced using density functional theory modeling and explain some of the regularities discovered.