A sensitive chromatographic determination of hydrazines by naphthalene-2,3-dialdehyde derivatization

A new high-performance liquid chromatography (HPLC) method for the sensitive simultaneous determination of hydrazine (Hy), monomethylhydrazine (MMH) and 1,1-dimethylhydrazine (UDMH) based upon the derivatization of hydrazines with naphthalene-2,3-dialdehyde and the separation of the derivatives on Zorbax Eclipse AAA column in a single chromatographic run under acidic conditions (pH 2.4) was developed. Hydrazine and monomethylhydrazine derivatives were found to be strongly fluorescent at λ_ex?=?273?nm, λ_em?=?500?nm. It was shown that UDMH derivative can be detected as non-fluorescent hydrazone at 290?nm by UV-detection. Limits of detection were 0.05?µg?·?L^?1 for Hy and MMH, and 1?µg?·?L^?1 for UDMH for the injection volume of 100?µL. The method was validated for water sample analysis. It proved to be selective, accurate and precise with the supplementary advantage of the simple and rapid sample preparation.     

Extremal loading of soft fibrous tissues: multi-scale mechanics and constitutive modeling

In the current contribution, we present a multi-scale constitutive model capturing macroscopic inelastic effects (like stress softening and permanent set) in soft tissues under cyclic loading. Soft biological tissues can be described as a biological composite material. The extracellular matrix is hereby reinforced by collagen fibers which themself are an assembly of collagen fibrils embedded in a proteoglycan (PG) rich matrix. Micro-damage induced by cyclic loading is treated by an interaction scenario between the fibrils and the PGs. At the low strain regime PGs promote sliding between fibrils [1] which leads to the yielding of statistical distributed overlapping segments. The breakage of the PG-bridges is defined by a decreasing PG-density. Due to the accumulated damage of the PG connections at high tissue strains, the strains at the fibril level increases. This finally drives the over-stretching of the fibrils, which is associated with a permanent rupture of the hydrogen bonds inside of the tropocollagen molecules [2]. The so obtained model is in line with recent experimental findings [1, 2] and was additionally validated against experimental data available in literature. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

One-Pot and Two-Chamber Methodologies for Using Acetylene Surrogates in the Synthesis of Pyridazines and Their D-Labeled Derivatives

Acetylene surrogates are efficient tools in modern organic chemistry with largely unexplored potential in the construction of heterocyclic cores. Two novel synthetic paths to 3,6-disubstituted pyridazines were proposed using readily available acetylene surrogates through flexible C₂ unit installation procedures in a common reaction space mode (one-pot) and distributed reaction space mode (two-chamber): (1) an interaction of 1,2,4,5-tetrazine and its acceptor-functionalized derivatives with a CaC₂−H₂O mixture performed in a two-chamber reactor led to the corresponding pyridazines in quantitative yields; (2) [4+2] cycloaddition of 1,2,4,5-tetrazines to benzyl vinyl ether can be considered a universal synthetic path to a wide range of pyridazines. Replacing water with D₂O and vinyl ether with its trideuterated analog in the developed procedures, a range of 4,5-dideuteropyridazines of 95–99% deuteration degree was synthesized for the first time. Quantum chemical modeling allowed to quantify the substituent effect in both synthetic pathways.     

SO2–ethanol–water (SEW) fractionation process: production of dissolving pulp from spruce

SO₂–ethanol–water (SEW) fractionation process is a highly attractive platform for future lignocellulosic Biorefineries. Its governing advantages include high flexibility in the selection of the raw material, simple and efficient recovery of fractionation chemicals, absence of carbohydrate degradation (both cellulose and hemicelluloses), and high reaction rates. The process is suitable for production of various carbohydrate- and lignin-based products including papermaking pulp, glucose, bioalcohols and lignosulfonates. The present paper addresses the possibility of producing dissolving pulp from spruce using SEW fractionation followed by ECF bleaching with and without hot caustic extraction. Comprehensive characterisation of chemical and macromolecular properties of the SEW dissolving pulps was complemented by determining the quality of viscose. The comparison with conventional viscose-grade acid sulfite pulps revealed close proximity in all properties. Therefore, considering the advantages of SEW process, it is suggested as a possible replacement for acid sulfite process in dissolving pulp manufacturing.     

Synthesis and fine-tuning of thermal stability of the negative nitrile-rich photochromes of hydroxytricyanopyrrole (HTCP) series

Research on Chemical Intermediates - A series of negative T-type nitrile-rich photochromes containing a hydroxytricyanopyrrole acceptor was synthesized. It was shown that thermal stability of the...     

Dust-Acoustic Nonlinear Waves in a Nanoparticle Fraction of Ultracold (2K) Multicomponent Dusty Plasma

The nonlinear dust-acoustic instability in the condensed submicron fraction of dust particles in the low-pressure glow discharge at ultra-low temperatures is experimentally and theoretically investigated. The main discharge parameters are estimated on the basisof the dust-acoustic wave analysis. In particular, the temperature and density of ions, as well as the Debye radius, are determined. It is shown that the ion temperature exceeds the temperature of the neutral gas. The drift characteristics of all plasma fractions are estimated. The reasons for the instability excitation are considered.     

Comparison of Proton Acceptor and Proton Donor Properties of H2O and H2O2 in Organic Crystals of Drug-like Compounds: Peroxosolvates vs. Crystallohydrates

Two new peroxosolvates of drug-like compounds were synthesized and studied by a combination of X-ray crystallographic, Raman spectroscopic methods, and periodic DFT computations. The enthalpies of H-bonds formed by hydrogen peroxide (H₂O₂) as a donor and an acceptor of protons were compared with the enthalpies of analogous H-bonds formed by water (H₂O) in isomorphic (isostructural) hydrates. The enthalpies of H-bonds formed by H₂O₂ as a proton donor turned out to be higher than the values of the corresponding H-bonds formed by H₂O. In the case of H₂O₂ as a proton acceptor in H-bonds, the ratio appeared reversed. The neutral O∙∙∙H-O/O∙∙∙H-N bonds formed by the lone electron pair of the oxygen atom of water were the strongest H-bonds in the considered crystals. In the paper, it was found out that the low-frequency Raman spectra of isomorphous crystalline hydrate and peroxosolvate of N-(5-Nitro-2-furfurylidene)-1-aminohydantoin are similar. As for the isostructural hydrate and peroxosolvate of the salt of protonated 2-amino-nicotinic acid and maleic acid monoanion, the Raman spectra are different.     

Stochastic Preisach operator: definition within the design approach

Nonlinear Dynamics - In this paper, we generalize the Preisach model to the case when parameters of elementary relays are random variables. We show that an output state of the stochastic Preisach...     

Conformationally controlled intramolecular heterocyclization of 2,4-diaminoperfluoro-4-methyl-2-pentenethiocyanate-3

Perfluoro-2-methyl-2-pentene-thiocyanate-3 reacts with ammonia to give 2,4-diaminoperfluoro-4-methyl-2-pentenethiocyanate-3 ( 4 ) and 2-aminoperfluoro-4, 4-dimethyl-4,5-dihydro-5-ethylidene-1,3-thiazole ( 5 ). Compound 4 is kinetically stable and at 150°C under-goes rotational isomerization to afford the cyclic isomer 2-amino-4,4-bis(trifluoromethyl)-4,5-dihydro-5-(1-aminoperfluoroethylidene) -1,3-thiazole ( 6 ). Intramolecular cyclizations, resulting in the thiazolines 5 and 6 , proceed likewise via the Thorpe reaction. For compounds 4–6 , X-ray diffraction analyses were undertaken and IR spectra in solution and in solid state were investigated. It is supposed that a high kinetic preference for formation of 4 and the fact that it does not undergo spontaneous cyclization in ammonolysis stem from the NH …︁ N intramolecular hydrogen bonding between two amino groups.