Reaction of metals with benzenediazonium tetrafluoroborate in aprotic solvents

The reaction of metals and glassy carbon with benzenediazonium tetrafluoroborate (BDFB) in aprotic solvents has been studied. During contact of Pt, Au, Ag, Pd, or V with glassy carbon in concentrated diazonium salt solution no change of color was observed. For Al, Ca, Cr, Cu, Fe, Ga, In, Mg, Li, Na, or Zn the process was accompanied by a rapid solution color change, rapid N₂ release and the loss of metal sample mass. The copper metal ionization-dissolution was studied by ultraviolet and visible absorption spectroscopy, along with gravimetric and volumetric measurements. A dissolution mechanism was proposed based on kinetic, infrared, and X-ray diffraction data. The 432 nm absorption band appearing after Cu-BDFB reaction indicates formation of the mixed complex [Cu(N₂C₆H₅·(N≡C-CH₃)₃]⁺ where the copper atom is covalently bonded to the azophenyl radical and coordinated to acetonitrile (ACN). This complex is thermodynamically unstable and decomposes slowly to a colorless crystalline and a black amorphous phase. The crystalline phase was identified as [Cu(NC-CH₃)₄]BF₄. The amorphous phase is a mixture of products formed by azophenyl and phenyl radical condensation.      

Surface-enhanced Raman scattering of a Ag/oligo(phenyleneethynylene)/Ag sandwich

α,ω-Dithiols are a useful class of compounds in molecular electronics because of their ability to easily adsorb to two metal surfaces, producing a molecular junction. We have prepared Ag nanosphere/oligo(phenyleneethynylene)/Ag sol (AgNS/OPE/Ag sol) and Ag nanowire/oligo(phenyleneethynylene)/Ag sol (AgNW/OPE/Ag sol) sandwiches to simulate the architecture of a molecular electronic device. This was achieved by self-assembly of OPE on the silver nanosurface, deprotection of the terminal sulfur, and deposition of Ag sol atop the monolayer. These sandwiches were then characterized by surface-enhanced Raman scattering (SERS) spectroscopy. The resulting spectra were compared to the bulk spectrum of the dimer and to the Ag nanosurface/OPE SERS spectra. The intensities of the SERS spectra in both systems exhibit a strong dependence on Ag deposition time and the results are also suggestive of intense interparticle coupling of the electromagnetic fields in both the AgNW/OPE/Ag and the AgNS/OPE/Ag systems. Three previously unobserved bands (1219, 1234, 2037 cm(-1)) arose in the SER spectra of the sandwiches and their presence is attributed to the strong enhancement of the electromagnetic field which is predicted from the COSMOL computational package. The 544 cm(-1) disulfide bond which is observed in the spectrum of solid OPE but is absent in the AgNS/OPE/Ag and AgNW/OPE/Ag spectra is indicative of chemisorption of OPE to the nanoparticles through oxidative dissociation of the disulfide bond.     

Soluble Groups with Few Non-Baer Subgroups

We characterize non-finitely generated soluble groups with the maximal condition on non-Baer subgroups and prove that a non-Baer soluble group is a ^ˇCernikov group or it has an infinite properly descending series of non-Baer subgroups.     

Capillary condensation of a binary mixture in slit-like pores

We investigate the capillary condensation of two model fluid mixtures in slit-like pores, which exhibit different demixing properties in the bulk phase. The interactions between adsorbate particles are modeled by using Lennard-Jones (12,6) potentials and the adsorbing potentials are of the Lennard-Jones (9,3) type. The calculations are performed for different pore widths and at different concentrations of the bulk gas, by means of density functional theory. We evaluate the capillary phase diagrams and discuss their dependence on the parameters of the model. Our calculations indicate that a binary mixture confined to a slit-like pore may exhibit rich phase behavior.     

Capillary condensation of short-chain molecules

A density-functional study of capillary condensation of fluids of short-chain molecules confined to slitlike pores is presented. The molecules are modeled as freely jointed tangent spherical segments with a hard core and with short-range attractive interaction between all the segments. We investigate how the critical parameters of capillary condensation of the fluid change when the pore width decreases and eventually becomes smaller than the nominal linear dimension of the single-chain molecule. We find that the dependence of critical parameters for a fluid of dimers and of tetramers on pore width is similar to that of the monomer fluid. On the other hand, for a fluid of chains consisting of a larger number of segments we observe an inversion effect. Namely, the critical temperature of capillary condensation decreases with increasing pore width for a certain interval of values of the pore width. This anomalous behavior is also influenced by the interaction between molecules and pore walls. We attribute this behavior to the effect of conformational changes of molecules upon confinement.     

On the solvation force of water-like fluid models with square-well attraction and site–site association in slit-like pores: density functional approach

The solvation force of the water-like fluid models with square-well attraction and site–site chemical association confined to slit-like pores has been explored. Theoretical procedure is based on the application of the density functional approach with mean-field approximation for the attractive interparticle interactions. The chemical association effects are treated by using the first-order thermodynamic perturbation theory of Wertheim. Trends of behaviour of the solvation force are put in correspondence with the distribution of molecules in the pores and with the average density of the adsorbate. Moreover, the distribution of non-bonded species on pore width is described. The influence of the width of the square-well and of the gas–solid attraction is discussed. A comparison of theoretical predictions with computer simulations results for water models in slit-like pores is performed.     

Novel Peroxide Containing Maleinate Surface-Active Monomers for Obtaining Reactive Polymers

Novel surface-active monomers were synthesized by successive treatment of tert-butylperoxy-6-hydroxyhexanoate with maleic anhydride, 1,3-propane sultone and triethylamine or with maleic anhydride and poly(ethylene glycol) methyl ether. The surface-active properties of monomers were studied. The critical micelle concentrations (cmc) as well as the surface tension at the cmc were determined for obtained monomers. The synthesized compounds were shown to be suitable reactive surfactants for obtaining styrene latexes.     

Colloidal systems containing free radical‐forming particles and composites on their basis

Controlled surface activity and reactivity of new carbon‐chain functional surface‐active oligoperoxides (FSAP) and derived metal complexes (OMC) with side and end di‐tertiary and tert‐alkyl (aryl) peroxidic, respectively, and other active functional groups cause the possibility of their tailored utilization as emulsifiers, surface‐active initiators and modifiers of the phase boundaries of liquid, solid and mixed phases in different colloidal systems in a wide temperature range. New materials can be developed such as water and hydrocarbon polymer dispersions, artificial water dispersions of unsaturated polyesters and alkyd resins, polymer/polymeric blends, active glass and carbon fibers, dispersed fillers, reinfourced and filled polymer composites with the definite special properties. Methods for the obtaining and the application of these materials are described.