Amphiphilic Properties of Dodecylammonium Chloride/4-(1-Pentylheptyl) Benzene Sodium Sulfonate Aqueous Mixtures and Study of the Catanionic Complex

Surfactants are often used in supramolecular chemistry, due to their ability to self-organize. Surfactant molecules aggregate spontaneously and reversibly to adopt a defined intermolecular arrangement. In this work, general phase behavior, adsorption and association in aqueous mixtures of dodecylammonium chloride, DACl and sodium 4-(1-pentylheptyl) benzenesulfonate, NaDBS, were studied by a combination of techniques including surface tension and conductivity measurements, light scattering and optical microscopy. The strong synergistic properties of the system were brought out with the Regular Solution Theory. Various colloidal objects are observed in wide range of composition: conventional small vesicles, large giant multilamellar or multivesicular vesicles. An excess of NaDBS provides extremely large tubular and elongated multilamellar vesicles. The new catanionic 1:1 complex, dodecylammonium-4-(1-pentylheptyl) benzenesulfonate, formed in the equimolar conditions is a result of intramolecular charge neutralization. The thermal properties of this solid compound were examined by thermal polarizing microscopy, differential scanning calorimetry, and X-ray diffraction. The most probable ion-pair amphiphilic cluster of the crystal smectic phase, at room temperature, consists of ionic groups formed in ordered layers with dodecyl chains packed into somewhat disordered layers, tilted to the layer plane.     

Anticancer Potential of (Pentamethylcyclopentadienyl)chloridoiridium(III) Complexes Bearing κP and κP,κS‐Coordinated Ph2PCH2CH2CH2S(O)xPh (x=0–2) Ligands

Iridium(III) complexes of the type [Ir(η⁵‐C₅Me₅)Cl₂{Ph₂PCH₂CH₂CH₂S(O)_xPh‐κP}] (x=0–2; 1 – 3 ) and [Ir(η⁵‐C₅Me₅)Cl{Ph₂PCH₂CH₂CH₂S(O)_xPh‐κP,κS}][PF₆] (x=0–1; 4 and 5 ) with 3‐(diphenylphosphino)propyl phenyl sulfide, sulfoxide, and sulfone ligands Ph₂PCH₂CH₂CH₂S(O)_xPh were designed, synthesized, and characterized fully, including X‐ray diffraction analyses for complexes 3 and 4 . In vitro studies against human thyroid carcinoma (8505C), submandibular carcinoma (A253), breast adenocarcinoma (MCF‐7), colon adenocarcinoma (SW480), and melanoma (518A2) cell lines provided evidence for the high biological potential of the neutral and cationic iridium(III) complexes. Neutral iridium(III) complex 5 proved to be the most active, with IC₅₀ values up to about 0.1 μM , representing activities of up to one order of magnitude higher than cisplatin. Using 8505C cells, apoptosis was shown to be the main mechanism through which complex 5 exerts its tumoricidal action. The described iridium(III) complexes represent potential leads in the search for novel metal‐based anticancer agents.     

Thermoplastic polyurethane elastomers from modified oleic acid

Two novel potentially biodegradable thermoplastic polyurethane elastomers with unique structure and morphology were prepared from modified oleic acid. The hardness and mechanical properties were controlled by adjusting the soft segment concentration (SSC). Epoxidized methyl oleate was converted to methyl‐9‐ or ?10‐hydroxystearate (hydroxystearate) by catalytic hydrogenation. The formed hydroxystearate was transesterified with 1,6‐hexanediol to obtain polyesterpolyol with molar mass 2500. Segmented polyurethanes with 50% and 70% SSC were prepared using the prepolymer method by reacting polyesterpolyol with diphenylmethane diisocyanate and 1,4‐butanediol as chain extender. Thermal and mechanical properties of the polymers indicated good micro‐phase separation. Both soft and hard segments displayed a certain degree of crystallization. Tensile strengths were 18 and 2.4 MPa for samples with 50% and 70% SSC, respectively. Elongations of 130% (50% SSC) and 43% (70% SSC) were somewhat lower than in comparable materials, presumably due to lower molar mass. © 2014 Society of Chemical Industry     

Mechanochemical synthesis of YNbO4:Eu nanocrystalline powder and its structural,microstructural and photoluminescence properties

In this research we prepared nanocrystalline YNbO₄:Eu³⁺ phosphor, i.e. nanophosphor, powder using an efficient mechanochemical method followed by annealing. X-ray diffraction analysis revealed that YNbO₄:Eu³⁺ crystallizes in monoclinic structure C2/c where, from the point of view of A and B in ABO₄ compounds, cation coordination can be noted as [6+2, 4+2]. Crystallite size of about 40 nm, was estimated using Debye Scherrer's equation. Raman spectroscopy with 785 and 532 nm excitation wavelengths is performed to record a majority of materials phonon modes and to provide more in depth understanding of the YNbO₄ structure. Scanning electron microscopy observations indicate that the mechanical treatment during synthesis is causing non-uniformity of the powder microstructure. High resolution photoluminescent measurements upon UV excitation showed intense emission coming from f–f transitions of the europium ion with the lifetime of 0.68 ms, suggesting that the obtained YNbO₄:Eu³⁺ is a good potential phosphor. A comparison of emissive properties with microcrystalline YNbO₄:Eu³⁺ was made and it showed higher values of emission intensity and lifetime of the nanocrystalline sample.     

Kinetics of Isothermal Ethanol Adsorption onto a Carbon Molecular Sieve under Conventional and Microwave Heating

The isothermal kinetics of ethanol adsorption from aqueous solution onto a zeolite type carbon molecular sieve (CMS‐3A) under conventional heating (CH) and microwave heating (MWH) was investigated. The adsorption kinetics is described by the model of a phase‐boundary controlled reaction for both heating modes. The activation energy (E_a) for the adsorption process under MWH is lower than under CH while the preexponential factor (lnA) is higher. Ethanol adsorption is a kinetically complex process whose complexity changes with the mode of heating. The established decrease in E_a and increase in lnA under MWH compared to CH is explained with the increase in the ground vibrational level of the – OH twisting vibrations in the ethanol molecule and with the decrease in its anharmonicity factor which is caused by the selective resonant transfer of energy from CMS‐3A to the OH oscillators.     

Influence of calcium carbonate filler and mixing type process on structure and properties of styrene–acrylonitrile/ethylene–propylene–diene polymer blends

The properties of styrene–acrylonitrile (SAN) and ethylene–propylene–diene (EPDM) blends containing different types of calcium carbonate filler were studied. The influence of mixing type process on the blend properties was also studied. Two different mixing processes were used. The first one includes mixing of all components together. The other process is a two‐step mixing procedure: masterbatch (MB; EPDM/SAN/filler blend) was prepared and then it was mixed with previously prepared polymer blend. Surface energy of samples was determined to predict the strength of interactions between polymer blend components and used fillers. The phase morphology of blends and their thermal and mechanical properties were studied. From the results, it can be concluded that the type of mixing process has a strong influence on the morphological, thermal, and mechanical properties of blends. The two‐step mixing process causes better dispersion of fillers in blends as well as better dispersion of EPDM in SAN matrix, and therefore, the finest morphology and improved properties are observed in blends with MB. It can be concluded that the type of mixing process and carefully chosen compatibilizer are the important factors for obtaining the improved compatibility of SAN/EPDM blends. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The effect of lignin on the structure and characteristics of composite coatings electrodeposited on titanium

Composite coatings based on lignin, obtained by electrophoretic deposition (EPD) on titanium, were investigated. The aim of this work was to produce hydroxyapatite/lignin (HAP/Lig) coatings on titanium and to investigate the effect of the lignin concentration on microstructure, morphology, phase composition, thermal behavior and cytotoxicity of the HAP/Lig coatings. An organosolv lignin was used for the production of the composite coatings studied in this research. The properties of HAP/Lig coatings were characterized using X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), thermogravimetric analysis (TGA), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FT-IR) and X-ray photoelectron spectroscopy (XPS), as well as the MTT test of cytotoxicity. The results showed that higher lignin concentrations protected the HAP lattice during sintering, thereby improving the stability of the HAP/Lig coatings. The cell survival of peripheral blood mononuclear cells (PBMC) after proliferation indicates that the HAP/Lig coating with 1 wt% Lig electrodeposited on titanium was non-toxic with significant promise as a potential bone-repair material.     

IR-change and colour changes of long-oil air drying alkyd paints as a result of UV irradiation

In this study the formation of photo-oxidative species was studied by monitoring the changes in the FT-IR spectra and colour changes. To stabilize long-oil air drying alkyd paint, separate and synergistic influence of two stabilizers were used Uvasorb^®S28 as the UV-absorber and Uvasorb^®HA29 as the stabilizer which inhibits the degradation of some groups. In the presence of UV radiation (450 h, λ > 300 nm), the alkyd paint undergoes photodegradation with gradual change of its colour. The photochemical degradation of the alkyd paint is associated with an increase in the hydroxyl content and broadening of the absorption in the carbonyl region. Analysis of the colour changes in alkyd surface during photodegradation was carried out by measuring CIEL*a*b* colour components (L*, a*, b* and ΔE*). Overall, ΔE* colour change correlates well with photodegradation of alkyd paint by relative increase of the concentration of carbonyl and hydroxyl groups determinated by FT-IR measurements.     

Nanocrystaline solid solution CeO2–Bi2O3

Nanocrystalline powders of solid solution CeO₂–Bi₂O₃ were synthesized by self-propagating room temperature reaction (SPRT) procedure with composition (Ce_1?xBi_xO_2?δ where the x = 0.1–0.5). X-ray diffraction analyses show that for x < 0.50 a solid solution with fluorite structure is formed. Rietveld's structure refinement method was applied to characterize prepared powders and its microstructure (size–strain). The lattice parameters increase according to Vegard's rule with increasing of Bi concentration. The average crystallite size is about 2–3 nm. Spectroscopic ellipsometry and Raman scattering measurements were used to characterize the samples at room temperature. The Raman measurements demonstrated electron molecular vibrational coupling and increase of oxygen vacancy concentration whereas increase of Bi content provokes a small decrease of optical absorption edge in comparison with pure ceria. Specific surface area of obtained powders was measured by Brunauer–Emmet–Teller (BET) method.