The problem of small negatively ionized water clusters

Structures of the negatively charged water clusters (H₂O)⁻_n with n up to 6 were optimized at the UHF/4–31 + + G** level without any geometrical restriction. There was found a chainlike structure for the trimer anion and both chainlike and cyclic geometries for the larger clusters. According to the MP2 energy estimates, all the clusters with n ≥ 3 are more stable than the combinations of separated water molecules and a free electron. The energy of the cycles is lower than that of the chains of the same size. However, the latter species are energetically closer to the neutral oligomers of the same geometry. The energy of vertical detachment of an electron from the chainlike hexamer anion is already about zero. Addition of a diffuse s function centered equidistantly between the oxygen atoms proved metastability, in particular, of the cyclic (H₂O)⁻₄ structure. © 1997 John Wiley & Sons, Inc. Int J Quant Chem 63: 737–748, 1997     

Absorption of ionic amphiphils by oppositely charged polyelectrolyte gels

Slightly cross-linked polyelectrolytes absorb oppositely charged surfactants in aqueous media. Transfer of amphiphilic ions from solution into the swollen network proceeds as a frontal heterogeneous cooperative reaction causing a collapse of the original polyelectrolyte gel. Small and wide angle X-ray diffraction data show that electrostatic complex formed as a result of the reaction consists of lamellar type surfactant micelles embedded in a polyelectrolyte network. It is also shown that such complexes contain equimolar amount of surfactant ions and ionized polyelectrolyte units paired with amphiphil head groups. In other words a charged network is not able to bind surplus oppositely charged surfactant ions. However, it is still able to solubilize a substantial amount of a nonionized surfactant. Chemical structure of surfactants strongly affect internal structure of lamellae and stability of the complexes.     

Pulse Compression and Tension of Epoxy Resin under Shock-Wave Action

Technical Physics - The shock-wave properties of ED-10 epoxy resin have been studied using VISAR and PDV multiple-channel laser interferometers. The Hugoniot of epoxy resin and pressure dependence...     

Kinetics and mechanisms of the UV-radiation-assisted formation of gold nanoparticles in HAuCl<Subscript>4</Subscript>-doped chitosan solutions

Using methods of optical spectroscopy and small-angle X-ray scattering, the kinetics of the UV radiation-induced formation of gold nanoparticles in HAuCl₄-doped water–acid solutions of chitosan has been studied from the very beginning of the reaction. It has been shown that, during synthesis, as the mean size of nanoparticles grows from 2.9 to 6.3 nm, the maximum of the plasmon resonance shifts toward shorter waves (535–523 nm), whereas for a fully formed ensemble of nanoparticles, the reverse trend is observed. It has been found experimentally that the particle size distribution curve changes during synthesis. Based on the inverse problem analysis, conclusions have been drawn regarding the dominant mechanisms behind nanoparticle growth.     

Highly regioselective synthesis of trifluoromethyl derivatives of pyrazolo[1,5-a]pyrimidines bearing fused cycloalkane rings using (2-ethoxycycloalkenyl)-2,2,2-trifluoroethanones

8-Trifluoromethyl-6,7-dihydro-5H-1,4,8a-triaza-s-indacene and 9-trifluoromethyl-5,6,7,8-tetrahydropyrazolo[5,1-b]quinazolines were efficiently generated by condensation of 5(3)-aminopyrazoles with (2-ethoxycycloalkenyl)-2,2,2-trifluoroethanones and isolated in excellent yields. The regiochemistry of the prepared compounds was established by ¹H, ¹³C and ¹⁹F NMR spectroscopy and X-ray diffraction analysis.     

Thin Film Exfoliation in the Zone of Trapped Elastic Wave Localization

In modern constructions, thin-layer coats are often used as protecting or strengthening elements. Deformations of such constructions may cause significant stresses on the interface between the base and the coat because of the difference in their physical mechanical properties, which leads to the destruction or detachment of the cover. The impact of static or shock loads on the emergence and development of delamination in multilayer constructions has been studied fairly well, but much less is known about destructions of this type under nonstationary (vibrational) loads. The interest in the latter is caused by the fact that even small variable actions may cause the localization of oscillations in a neighborhood of inhomogeneities (such as inclusions, defects, construction elements, etc.) [1] (and lead to the emergence and growth of defects, which strongly affects the reliability and functionality of the whole construction. The possibility of the localization of oscillations near initial delamination and the impact of localization on the growth of the delamination are studied and a model for analyzing conditions under which a detachment zone grows or ceases to grow is suggested. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Competition between non-classical and classical hydrogen bonded sites in [BH3CN]: Spectral, energetic, structural and electronic features

Interaction of the salt (Ph₃PNPPh₃)BH₃CN with the various OH and NH proton donors in low polar media was studied by variable temperature (200–290 K) IR spectroscopy and theoretically by DFT calculations. The formation of two types of complexes containing non-classical dihydrogen bond to the hydride hydrogen (DHB) and classical hydrogen bond (HB) to nitrogen lone pair was shown in solution. The 1:1 complexes of both types (XHH and XHN) coexist in the presence of equimolar amount of proton donor. The addition of excess XH-acid leads to the increase of the classical HB content and appearance of the 1:2 complexes, where two basic sites work simultaneously. The structure, spectral characteristics, energy and electron redistribution were studied by DFT (B3LYP) method. The comparison DHB parameters of [BH₃CN]⁻ with those of the unsubstituted analogue [BH₄]⁻ allowed analyzing the electronic effects of the CN group on the basic properties of boron hydride moiety. The electronic influence of the BH₃ group on CN⁻HX hydrogen bond was also established by comparison with the corresponding classical HB to the CN⁻ anion.     

Synthesis of phosphorylated derivatives of isatin with sterically hindered phenol fragments

The synthesis of N-[dimethoxyphosphoryl-(3,5-di-tert-butyl-4-hydroxyphenyl)] methylisatins has been performed by the addition of isatin and 5-butylisatin to the double bond of dimethyl-(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadienylidene)methylphosphonate. Subsequent functionalization of the compounds synthesized with thiosemicarbazide hydrochloride, 3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionic acid hydrazide, and isonicotinic acid. Hydrazide gave isatin derivatives containing several pharmacophore fragments. Each of them has the ability to the increase the antioxidant and biological activities of these compounds.     

Evaluation of Activation Energies for Pairwise and Non-Pairwise Hydrogen Addition to Propyne Over Pd/Aluminosilicate Fiberglass Catalyst by Parahydrogen-Induced Polarization (PHIP)

Hydrogenation of propyne to propene over Pd/aluminosilicate fiberglass catalyst in the temperature range 175–350 °C was investigated with the use of parahydrogen-induced polarization (PHIP) technique. Activation energies for both pairwise and non-pairwise H₂ addition routes were estimated. It was found that at 175–275 °C the activation energies for hydrogen addition to the triple bond of propyne have similar values (about 60–70 kJ/mol) for both routes of hydrogen addition. At higher temperatures (275–350 °C), the rate constant for pairwise hydrogen addition reaches a maximum value while the rate constant for non-pairwise hydrogen addition continues to increase with increasing temperature.