Additional Aspects of Complexation of Gold(I) with Thiomalate

Some equilibria involving gold(I) thiomalate (mercaptosuccinate, TM) complexes have been studied in the aqueous solution at 25 °C and I?=?0.2 mol·L^?1 (NaCl). In the acidic region, the oxidation of TM by \( {\text{AuCl}}_{4}^{ - } \) proceeds with the formation of sulfinic acid, and gold(III) is reduced to gold(I). The interaction of gold(I) with TM at n_TM/n_Au?≤?1 leads to the formation of highly stable cyclic polymeric complexes \( {\text{Au}}_{m} \left( {\text{TM}} \right)_{m}^{*} \) with various degrees of protonation depending on pH. In general, the results agree with the tetrameric form of this complex proposed in the literature. At n_TM/n_Au?>?1, the processes of opening the cyclic structure, depolymerization and the formation of \( {\text{Au}}\left( {\text{TM}} \right)_{2}^{*} \) occur: \( {\text{Au}}_{4} ( {\text{TM)}}_{4}^{8 - } + {\text{TM}}^{3 - } \rightleftharpoons {\text{Au}}_{ 4} ( {\text{TM)}}_{5}^{11 - } \), log₁₀ K₄₅?=?10.1?±?0.5; 0.25 \( {\text{Au}}_{4} ( {\text{TM)}}_{4}^{8 - } + {\text{TM}}^{3 - } \rightleftharpoons {\text{Au(TM)}}_{2}^{5 - } \), log₁₀ K₁₂?=?4.9?±?0.2. The standard potential of \( {\text{Au(TM)}}_{2}^{5 - } \) is \( E_{1/0}^{ \circ } = -0. 2 5 5\pm 0.0 30{\text{ V}} \). The numerous protonation processes of complexes at pH?<?7 were described with the use of effective functions.     

Molecular design of supramolecular polymers with chelated units and their application as functional materials

This article summarizes the basic concepts and synthetic strategies leading to various types of supramolecular polymers with chelated units, including linear, branched, cross-linked, and heterometallic polymers. Particular attention is paid to such new synthetic approaches to supramolecular polymers as hierarchical and orthogonal self-assembly based on a combination of metal–ligand interaction with hydrogen bonds and host–guest interactions. Metallosupramolecular polyelectrolytes, supramolecular polymer gels, self-assembled metallosupramolecular monolayers, and supramolecular metal chelate dendrimers are analyzed. The stimuli-responsive, self-healing, and shape memory supramolecular polymers with chelated units are considered. The bibliography includes articles published over the past five years.     

Three ABTS<Superscript>•+</Superscript> radical cation-based approaches for the evaluation of antioxidant activity: fast- and slow-reacting antioxidant behavior

This work focuses on the behavior and comparative assessment of the antioxidant activity of several well-known antioxidants using three different approaches with the same ABTS^?+/potassium persulfate radical-generating system: a decolorization assay, kinetic assay, and visual-spectrophotometric titration assay. The decolorization assay is the most common approach but gives little information on antioxidant behavior. The kinetic assay can be used for an in-depth study of the specific features of a particular antioxidant and facilitates identification of the mechanism of action. The visual-spectrophotometric titration assay is complementary to the above assays and subdivided into two stages to demonstrate the contribution of the “fast” and “slow” scavenging properties to the total antioxidant activity. The trolox equivalent antioxidant capacity (TEAC) value ranges for several flavonoids and the endogenous antioxidants derived from these assays vary from 0.7 to 5.1, 0.5–2.8, and 0.4–3.7, respectively, while the sequence of the weakest antioxidant to the strongest is similar. The analysis of the kinetic curves for some flavonoids showed that their interaction with ABTS^?+ has an atypical character. Based on the results of the kinetic and visual-spectrophotometric titration assays, fast-reacting (trolox, α-tocopherol), slow-reacting (naringenin, apigenin) and moderate-reacting antioxidant (dihydroquercetin, quercetin, rutin, morin, and glutathione) compounds were distinguished.     

DBU as a scaffold for the synthesis of [1,3]oxazolo[2’,3’ : 2,3]pyrimido-[1,2-a]azepines: annulation with aromatic cyanopropargylic alcohols

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2,4,6-Trisubstituted 3,4-dihydropyrans from acetylene and ketones: deacetylation in the KOBut/DMSO system

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Reaction of 1-(het)aryl-3-bromoprop-2-ynones with furans in solid metal oxides or salts: cross-coupling or cycloaddition?

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PdZn/α-Al2O3 catalyst for liquid-phase alkyne hydrogenation: effect of the solid-state alloy transformation into intermetallics

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