The interaction of an azo compound with a surfactant and ion pair adsorption to solid phases

The adsorption of SPADNS (trisodium salt of 2-(p-sulfophenylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic acid) onto resins XAD 2, XAD 7 and silica gel was studied in the presence and in the absence of the cationic surfactant CTAB (cetyl trimethylammonium bromide). At a ratio of 2.5 CTAB to 1 SPADNS, the surfactant caused a marked increase in SPADNS adsorption. The experimental results for adsorption versus time were applied on the basis of three kinetic models (pseudo-first-order Lagergren, pseudo-second-order, and intraparticle diffusion). The interaction between CTAB and SPADNS was investigated using spectrophotometric, conductometric, and computational techniques. Theoretical results point to the formation of an ion pair between CTAB and SPADNS that influences the solution spectra, in agreement with conductometric and spectrophotometric data.     

H2 dissociation on individual Pd atoms deposited on Cu(111)

We present a Molecular Dynamics (MD) study based on Density Functional Theory (DFT) calculations for H(2) interacting with a Pd-Cu(111) surface alloy for low Pd coverages, Θ(Pd). Our results show, in line with recent experimental data, that single isolated Pd atoms evaporated on Cu(111) significantly increase the reactivity of the otherwise inert pure Cu surface. On top of substitutional Pd atoms in the Pd-Cu(111) surface alloy, the activation energy barrier for H(2) dissociation is smaller than the lowest one found on Cu(111) by a factor of two: 0.25 eV vs. 0.46 eV. Also in agreement with experiments, our DFT-MD calculations show that a large fraction of the dissociating H atoms efficiently spillover from Pd (i.e. the active sites), thanks to their extra kinetic energy due to the ~0.50 eV chemisorption exothermicity. Still, our DFT-MD calculations predict a dissociative sticking probability for low energy H(2) molecules that is much smaller than the estimated value from scanning tunneling microscopy experiments. Thus, further theoretical and experimental investigations are required for a complete understanding of H(2) dissociation on low-Θ(Pd) Pd-Cu(111) surface alloys.     

A low‐temperature polymorph of m‐quinquephenyl

A low‐temperature polymorph of 1,1′:3′,1′′:3′′,1′′′:3′′′,1′′′′‐quinquephenyl (m‐quinquephenyl), C₃₀H₂₂, crystallizes in the space group P2₁/c with two molecules in the asymmetric unit. The crystal is a three‐component nonmerohedral twin. A previously reported room‐temperature polymorph [Rabideau, Sygula, Dhar & Fronczek (1993). Chem. Commun. pp. 1795–1797] also crystallizes with two molecules in the asymmetric unit in the space group P. The unit‐cell volume for the low‐temperature polymorph is 4120.5 (4) ų, almost twice that of the room‐temperature polymorph which is 2102.3 (6) ų. The molecules in both structures adopt a U‐shaped conformation with similar geometric parameters. The structural packing is similar in both compounds, with the molecules lying in layers which stack perpendicular to the longest unit‐cell axis. The molecules pack alternately in the layers and in the stacked columns. In both polymorphs, the only interactions between the molecules which can stabilize the packing are very weak C—H...π interactions.     

Functionalization of Reduced Graphite Oxide Sheets with a Zwitterionic Surfactant

Films of a few layers in thickness of reduced graphite oxide (RGO) sheets functionalized by the zwitterionic surfactant N‐dodecyl‐N,N‐dimethyl‐3‐ammonio‐1‐propanesulfonate (DDPS) are obtained by using the Langmuir–Blodgett method. The quality of the RGO sheets is checked by analyzing the degrees of reduction and defect repair by means of X‐ray photoelectron spectroscopy, atomic force microscopy (AFM), field‐emission scanning electron microscopy (SEM), micro‐Raman spectroscopy, and electrical conductivity measurements. A modified Hummers method is used to obtain highly oxidized graphite oxide (GO) together with a centrifugation‐based method to improve the quality of GO. The GO samples are reduced by hydrazine or vitamin C. Functionalization of RGO with the zwitterionic surfactant improves the degrees of reduction and defect repair of the two reducing agents and significantly increases the electrical conductivity of paperlike films compared with those prepared from unfunctionalized RGO.     

Fabrication and characterization of polymer-based magnetic composite nanotubes and nanorods

Herein we present the simple fabrication of magneto-polymer nanostructured composites. Specifically, large aspect ratio polymer-based magnetic nanotubes and nanorods have been prepared by means of wetting nanoporous hard templates with loaded polymer melts and solutions, respectively. Morphological characteristics of both one-dimensional composite nanostructures were evaluated by scanning electron microscopy. Moreover, important parameters of the materials such as elemental composition and distribution of the metallic elements were determined by means of X-ray diffraction, and Rutherford backscattering. The different confinement topology of the nanoparticles within the nanorods and the nanotubes leads to a stronger (i.e. ferro-) magnetic response of nanotube arrays, as determined by magnetometry. The magnetic measurements also allowed estimating the concentration of nanoparticles by means of properly fitting experimental data to a sum of different magnetic contributions to the total magnetic moment. The morphological, structural, compositional and magnetic characteristics of nanotubes and nanorods are related to the different wetting approaches used. It has to be noted that, to our knowledge, we present here the first example of nanoparticulated polymer-based composite nanotubes synthesized from the melt, which, indeed seems to be at the origin of their high morphological and compositional quality. The potential of Rutherford backscattering spectroscopy for characterizing soft composite nanostructures has to be also remarked.     

Thermodynamic characterization of the mixture (1-butanol + iso-octane): Densities,viscosities, and isobaric heat capacities at high pressures

The densities at high pressures of 1-butanol and iso-octane were measured in the range (0.1 to 140) MPa at seven different temperatures, from (273.15 to 333.15) K, and their mixtures were measured in the range (0.1 to 50) MPa at four different temperatures, from (273.15 to 333.15) K. The measurements were performed in a high-pressure vibrating tube densimeter. The pressure–volume–temperature behavior of these compounds and their mixtures was evaluated accurately over a wide range of temperatures and pressures. The data were successfully correlated with the empirical Tamman–Tait equation. The experimental data and the correlations were used to study the behavior and the influence of temperature and pressure on the isothermal compressibility and the isobaric thermal expansivity.Also, the isobaric heat capacities were measured over the range (0.1 to 25) MPa at two different temperatures (293.15 and 313.15) K for the pure compounds and their mixtures. The measurements were performed in a high-pressure automated flow calorimeter. The excess molar heat capacities were assessed for the mixture and a positive deviation from the ideality was obtained.     

Fluorene: An extended experimental thermodynamic study

This work reports new experimental thermodynamic results on fluorene. Vapor pressures of both crystalline and liquid phases were measured using a pressure gauge (capacitance diaphragm manometer) and Knudsen effusion methods over a wide temperature range (292.20 to 412.16) K yielding accurate determination of enthalpy and entropy of sublimation and of vaporization. The enthalpy of sublimation was also determined using Calvet microcalorimetry. The enthalpy of fusion was derived from vapor pressure results and from d.s.c. experiments. Static bomb calorimetry was used to determine the enthalpy of combustion of fluorene from which the standard enthalpy of formation in the crystalline phase was calculated. The enthalpy of formation in the gaseous phase was calculated combining the result derived for the crystalline phase with the enthalpy of sublimation.     

The effect of the nitrogen non-bonding electron pair on the NMR and X-ray in 1,3-diazaheterocycles

The effect of the nitrogen nonbonding electron pair on the ¹J_C,H values of 1,3-diazaheterocycles was analyzed and compared to 1,5-diazabiciclo[3.2.1]octanes, which have a restricted conformation. The ¹J_C,H values were measured by observing the ¹³C satellites in the ¹H NMR spectra and then determining the ¹H-coupled ¹³C NMR spectra. The ¹J_C,H values are 10 Hz larger when the α-hydrogen is synperiplanar rather than antiperiplanar to the nonbonding electron pair on the nitrogen, which serves as experimental evidence of the orbital n_N→σ¹_C,Hap interactions. In addition, the homoanomeric effect from the interactions of the nitrogen lone pair with the antibonding orbital of the equatorial hydrogen, which was in the β position, was discussed (n_N→σ¹_C(β),Heq).     

Evidence of Ternary Inclusion Complexes Formation Using Factorial Design and Determination of Their Formation Constant

Evidence of the interaction among the [PbAc]⁺ and[PbEDTA]^-2 with the -cyclodextrin (-CD)is shown, using a 2⁴ factorial design. The factors used werethe [Pb(II)], [-CD], [Ac^-] and [EDTA] concentrationsat pH = 6.2. The statistical results indicate that the changes inchemical response for these species are associated to theinteraction among these factors. Spectrophotometric andelectrochemical studies were undertaken to assess the interactions.The equilibrium constants for inclusion complexes were determinedFor -CD-[PbAc]⁺ and -CD-[PbEDTA]^-2.