Selective Synthesis of 2,5‐Diformylfuran by Sustainable 4‐acetamido‐TEMPO/Halogen‐Mediated Electrooxidation of 5‐Hydroxymethylfurfural

A new method was developed for the selective gram‐scale synthesis of 2,5‐diformylfuran (DFF), which is an important chemical with a high application potential, via oxidation of biomass‐derived 5‐hydroxylmethylfurfural (HMF) catalyzed by 4‐acetylamino‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl (4‐AcNH‐TEMPO) in a two‐phase system consisting of a methylene chloride and aqueous solution containing sodium hydrogen carbonate and potassium iodide. The key feature of this method is the generation of the I₂ (co‐)oxidant by anodic oxidation of iodide anions during pulse electrolysis. In addition, the electrolyte can be successfully recycled five times while maintaining a 62–65 % yield of DFF. This novel method provides a sustainable pathway for waste‐free production of DFF without the use of metal catalysts and expensive oxidants. An advantage of electrooxidation is utilized in the preparation of demanding chemical.     

The Polymorphism of 5-n-Hexyl-2-[4-n-pentyloxyphenyl]-pyridine

The phase transitions of 5-n-hexyl-2-[4-n-pentyloxyphenyl]-pyridine were determined by miroscopic and calorimetric investigations. The classification of the smectic modifications was done by investigation of the miscibility relations. Besides the nematic phase smectic phases C, F, G and H were identified.     

Binding of MRI contrast agents to albumin: a high-field EPR study

High-field electron paramagnetic resonance (EPR) experiments to monitor binding of lipophilic Gd(III) complexes to human serum albumin (HSA) are described. It was observed that magnetic interactions between the nitroxide moiety ofn-doxyl-stearic acids bound to HSA and Gd(III) complexes resulted in broadening of nitroxide continuous-wave EPR spectra. The broadening effect can be well described by a one-parameter model of additional Lorentzian broadening At 95 GHz, continuous-wave EPR spectra from Gd(III) complexes are fully resolved from the nitroxide signal allowing for simultaneous and independent line shape analysis. Analysis of the line width broadening effects for spectra from a series ofn-doxyl-stearic acids bound to HSA indicated a progressive decrease of spin label-Gd(III) magnetic interactions along the fatty acid (FA) binding channel, consistent with binding of Gd-DOTAP complex in the vicinity of the main FA binding site. The substantial difference in spin label-metal interactions along the FA binding channel for lipophilic Gd(III) complexes with different chelates is indicative of binding to different sites. We also report measurements of dissociation constant for noncovalent binding of Gd(III) complexes to HSA on the basis of analyses of 95 GHz Gd(III) EPR line shapes.     

Sorption of Metal Ions by Chitosan Copolymers with Vinyl Monomers

Russian Journal of Applied Chemistry - Chitosan copolymers with vinyl monomers: 4-N-vinylpyridine, acrylamide, and acrylic acid, were synthesized and these sorption properties were investigated....     

Base-free aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid over Pt/C catalysts synthesized by pulse alternating current technique

The Pt/C catalysts with various Pt content (5-30 wt%) synthesized via electrochemical pulse alternating current technique have been evaluated for the base-free aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid. The higher Pt content in the catalyst (30 wt%) provides the product yield up to 65% upon performing the process in concentrated (～0.1 M) aqueous solutions of the substrate.     

Following screened perturbations in an elastic medium with a thin layer

The result of the calculation of the field of a longitudinal wave which has passed through an elastic layer is studied and the character of the propagation of different phases of this wave is determined.Translated from Zapiski Nauchnykh Seminarov Leningradskogo Otdeleniya Matematicheskogo Instituta im V. A. Steklova AN SSSR, Vol. 165, pp. 159–165, 1987.     

Calorimetric study of the solvation of benzene and its chloro-, nitro-, and aminoderivatives by n-hexane, 1-butanol, and mixed solvent n-hexane-1-butanol

The heats of dissolution of benzene, chlorobenzene, ortho-dichlorobenzene, nitrobenzene, and aniline in n-hexane and 1-butanol and those of benzene, chlorobenzene, nitrobenzene, and aniline in a mixture of n-hexane and 1-butanol were measured by calorimetry at 25°C. The enthalpies of solvation of the compounds were calculated. The correlation between the enthalpies of solvation of the compounds and their molar refraction was studied. The enthalpies of solvation of the compounds and their functional groups by the mixture of n-hexane and 1-butanol were considered.     

Synthesis and structure of tri-<Emphasis Type="Italic">m</Emphasis>-tolylantimony bis(1-adamantanecarboxylate)

Tri(m-tolyl)antimony bis(1-adamantanecarboxylate) (3-MeC₆H₄)₃Sb[OC(O)C₁₀H₁₅]₂ has been synthesized with a yield of 90.0% by the reaction of tri(m-tolyl)antimony with 1-adamantanecarboxylic acid in the presence of hydrogen peroxide in ether. According to X-ray diffraction analysis data, the antimony atom has a distorted trigonal-bipyramidal coordination with the axially positioned oxygen atoms of carboxyl groups. The axial OSbO angle is 173.1(2)°; the equatorial CSbC angles are 112.0(1)°, 112.0(1)°, and 136.0(3)°; the Sb-O distance is 2.109(3)Å; the Sb-C distances are 2.103(5), 2.103(5), and 2.121(7) Å; intramolecular Sb…O(=C) contacts are 3.069(5) Å.     

Structural,electrostatic and thermodynamic properties of the surface of spherical micelles in solutions of sodium <Emphasis Type="Italic">n</Emphasis>-alkyl sulfate homologues. I. Structural characteristics

Using the aggregation numbers of micelles and the effective sizes of hydrated surfactant ions and counterions of the first coordination sphere, we calculated the average geometric characteristics of the surface layer of ionic spherical micelles in solutions of the sodium n-alkyl sulfate homologues with n _C = 8, 10, 12, and 14 carbon atoms in the molecule; in particular, we established 1) the size of the micelle core; 2) the thickness of the electrical double layer on the surface; 3) the mutual arrangement parameters of hydrophilic and hydrophobic ions; 4) the number of “free” water molecules and showed their dependence on the homologue number and the degree of binding of counterions.     

Titanium(4+) and zirconium(4+) dichloride complexes with pyridinedicarboxylic acid derivatives as ethylene polymerization catalysts

Titanium(4+) and zirconium(4+) complexes with pyridinedicarboxylic acid derivatives have been synthesized. The composition and structure of the synthesized 2,6-bis(diphenylhydroxymethyl)pyridine complexes have been corroborated by NMR and IR spectroscopy, and elemental analysis. The complexes activated with methylaluminoxane (MAO) are catalytically active in ethylene polymerization, Depending on the Ti/Al_MAO ratio, the catalytic activity of the complexes varies between 90 and 420 kg PE/mol Ti h atm.