Dehydration Rearrangements of Derivatives of Methylenedihydrobenzofuran - a New Path to Substituted Benzofurans

When heated with acidic agents derivatives of 3-amino-2-(hydroxydialkylmethyl)methylene-2,3-dihydrobenzofuran undergo rapid dehydration and rearrangement to substituted 2-alkenyl-3-aminobenzofurans.     

Reactions of 3,5-di-<Emphasis Type="Italic">tert</Emphasis>-butyl-1,2-benzoquinone with mercapto carboxylic acids

Heating of an equimolar mixture of 3,5-di-tert-butyl-1,2-benzoquinone with thiosalicylic acid led to 2-[(4,6-di-tert-butyl-2,3-dihydroxyphenyl)thio]benzoic acid. In the case of β-mercaptopropionic acid, 2-[(4,6-di-tert-butyl-2,3-dihydroxyphenyl)thio]propionic acid was formed, which upon reflux in Ac2O was converted to 6,8-di-tert-butyl-9-hydroxy-3,4-dihydro-2H-1,5benzoxathiepin-2-one.     

On almost good triples of vertices in edge regular graphs

Consider a connected edge regular graph Γ with parameters (v, k, λ) and put b ₁ = k?λ?1. A triple (u, w, z) of vertices is called (almost) good whenever d(u, w) = d(u, z) = 2 and µ(u, w)+µ(u, z) ≤ 2k ? 4b ₁ + 3 (and µ(u, w) + µ(u, z) = 2k ? 4b ₁ + 4). If k = 3b ₁ + γ with γ ≥ ?2, a triple (u, w, z) is almost good, and Δ = [u] ∩ [w] ∩ [z] then: either |Δ| ≤ 2; or Δ is a 3-clique and Γ is a Clebsch graph; or Δ is a 3-clique, k = 16, b ₁ = 6, and v = 31; or Δ is a 4-clique and Γ is a Schläfli graph.     

Reactivity of micellar systems based on supernucleophilic functional surfactants in processes of acyl group transfer

Processes of cleavage of 4-nitrophenyl esters of diethylphosphoric, diethylphosphonic, and 4-toluenesulfonic acids were investigated occurring in micelles of surfactants containing supernucleophilic oximate fragment and on their analogs not forming micelles in water. At transferring the reaction from water into the micelles of functional surfactants the reaction accelerates 10²?C10³ times. This acceleration is caused by the concentration of the substrate, for the nucleophilicity of the oximate fragment changes insignificantly. The reactivity of the functional surfactants is described by the Br?nsted dependence with a break, its character is analogous to the dependence of the oximes non-forming micelles.     

Generation of electric potentials during heterogeneous combustion in systems containing VI group elements

The behavior of frontally burning heterogeneous systems containing chromium, molybdenum, and tungsten, which are used in the self-propagating high-temperature synthesis of complex oxide materials, was studies by the potentiometric method. It was revealed that the peak emf between the combustion wave front and the synthesis products can be as high as 2 V, depending on the chemical composition of the initial stock. A mobile registering probe moving with the velocity of combustion wave propagation makes it possible to substantially increase the time of emf recording     

High-Temperature Heat Capacity of Zn<Subscript>2</Subscript>V<Subscript>2</Subscript>O<Subscript>7</Subscript>–Cu<Subscript>2</Subscript>V<Subscript>2</Subscript>O<Subscript>7</Subscript> Solid Solutions

Differential scanning calorimetry has been used to study the influence of temperature on the heat capacity of synthesized vanadates Zn₂V₂O₇, (Cu_0.56Zn_1.44)V₂O₇, and (Cu_1.0Zn_1.0)V₂O₇. It is found that dependences C_p = f(T) have extremes. The thermodynamic properties of Zn₂V₂O₇ have been determined.     

New TEMPO–Appended 2,2′-Bipyridine-Based Eu(III), Tb(III), Gd(III) and Sm(III) Complexes: Synthesis,Photophysical Studies and Testing Photoluminescence-Based Bioimaging Abilities

Linked to Alzheimer’s disease (AD), amyloids and tau-protein are known to contain a large number of cysteine (Cys) residues. In addition, certain levels of some common biogenic thiols (cysteine (Cys), homocysteine (Hcy), glutathione (GSH), etc.) in biological fluids are closely related to AD as well as other diseases. Therefore, probes with a selective interaction with the above-mentioned thiols can be used for the monitoring and visualizing changes of (bio)thiols in the biological fluids as well as in the brain of animal models of Alzheimer’s disease. In this study, new Eu(III), Tb(III), Gd(III) and Sm(III) complexes of 2,2′-bipyridine ligands containing TEMPO fragments as receptor units for (bio)thiols are reported. The presence of free radical fragments of the ligand in the complexes was proved by using the electronic paramagnetic resonance (EPR) method. Among all the complexes, the Eu(III) complex turned out to be the most promising one as luminescence- and spin-probe for the detection of biogenic thiols. The EPR and fluorescent titration methods showed the interaction of the resulting complex with free Cys and GSH in solution. To study the practical applicability of the probes for the monitoring of AD in-vivo, by using the above-mentioned Eu(III)-based probe, the staining of the brain of mice with amyloidosis and Vero cell cultures supplemented with the cysteine-enriched medium was studied as well as the fluorescence titration of Bovine Serum Albumin, BSA (as the model for the thiol moieties containing protein), was carried out. Based on the results of fluorescence titration, the formation of a non-covalent inclusion complex between the above-mentioned Eu(III) complex and BSA was suggested.     

Light quenching and dark states in colloidal solutions of semiconductor CdSe/ZnS quantum dots

The photodynamics of optical limiting in colloidal solutions of different-size CdSe/ZnS quantum dots is studied. The behavior of the dependences points to a multistage process that includes the bleaching and optical limiting stages. The limiting photodynamics is compared with luminescence dynamics of quantum dots under conditions of high-power excitation. It is shown that the optical limiting efficiency in such media is determined by the position of exciting radiation with respect to the main exciton absorption band of the quantum dot. The roles played by so-called dark states and light quenching in limiting photodynamics are discussed.