Highly corrosion resistant siloxane-polymethyl methacrylate hybrid coatings

Siloxane-polymethyl methacrylate hybrid films were deposited on carbon steel substrates by dip-coating from a sol prepared by acid-catalyzed hydrolytic co-polycondensation of tetraethoxysilane (TEOS) and 3-methacryloxy propyl-trimethoxysilane (MPTS), followed by radical polymerization of methyl methacrylate (MMA). Structural properties of the hybrids were studied using ²⁹Si and ¹³C nuclear magnetic resonance (NMR), X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA), as a function of the MMA/MPTS ratio, which ranged between 2 and 10. The efficiency of corrosion protection of hybrid-coated carbon steel was investigated by XPS, potentiodynamic polarization curves and electrochemical impedance spectroscopy after immersion of the material in acidic and neutral saline aqueous solution. The NMR and TGA results indicate a high degree of polycondensation (84%) and elevated thermal stability of 410?°C for the hybrid film with a MMA/MPTS ratio of 8, exhibiting also and excellent adhesion to the substrate. The XPS analysis confirmed the variation of the MMA phase in the hybrid, and showed that no corrosion-induced changes had occurred after 18?days immersion of the coated steel in 3.5% NaCl solution. Potentiodynamic polarization curves have shown that the hybrid coating prepared using a TEOS/MPTS ratio of 8 yielded the best anti-corrosion performance. It acts as a very efficient corrosion barrier, increasing the total impedance by almost 6 orders of magnitude and reducing the current densities by 4 orders of magnitude, compared to the bare electrode. The obtained results are discussed based on the correlation of structural information with impedance data presented for both electrolytes in the form of electrical equivalent circuits.     

Interfacial concentrations of chloride and bromide in zwitterionic micelles with opposite dipoles: experimental determination by chemical trapping and a theoretical description

Interfacial concentrations of chloride and bromide ions, with Li(+), Na(+), K(+), Rb(+), Cs(+), trimethylammonium (TMA(+)), Ca(2+), and Mg(2+) as counterions, were determined by chemical trapping in micelles formed by two zwitterionic surfactants, namely N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS) and hexadecylphosphorylcholine (HDPC) micelles. Appropriate standard curves for the chemical trapping method were obtained by measuring the product yields of chloride and bromide salts with 2,4,6-trimethyl-benzenediazonium (BF(4)) in the presence of low molecular analogs (N,N,N-trimethyl-propane sulfonate and methyl-phosphorylcholine) of the employed surfactants. The experimentally determined values for the local Br(-) (Cl(-)) concentrations were modeled by fully integrated non-linear Poisson Boltzmann equations. The best fits to all experimental data were obtained by considering that ions at the interface are not fixed at an adsorption site but are free to move in the interfacial plane. In addition, the calculation of ion distribution allowed the estimation of the degree of ion coverage by using standard chemical potential differences accounting for ion specificity.     

Comparative properties of Amazonian oils obtained by different extraction methods

Pequi (Caryocar brasiliense Camb.), baba?u (Orbignya phalerata Mart.), buriti (Mauritia flexuosa), and passion fruit (Passiflora edulis) oils were studied to determine their antibacterial, antioxidant and cytotoxic activities, as well as their total phenol and carotenoid contents. The fatty acid contents were determined by GC-MS. The three types of passion fruit oils studied were refined, cold pressed or extracted from seeds in a Soxhlet apparatus. The oils thus obtained showed differences in antioxidant activity and carotenoid content, but were similar in regard to total phenols. Buriti and pequi had the highest carotenoid contents, while refined and cold pressed passion fruit oil displayed the highest antioxidant activity. Pequi oil was the only oil to display antibacterial and cytotoxic activity.     

Vibrational coupled cluster response theory: a general implementation

The calculation of vibrational contributions to molecular properties using vibrational coupled cluster (VCC) response theory is discussed. General expressions are given for expectation values, linear response functions, and transition moments. It is shown how these expressions can be evaluated for arbitrary levels of excitation in the wave function parameterization as well as for arbitrary coupling levels in the potential and property surfaces. The convergence of the method is assessed by benchmark calculations on formaldehyde. Furthermore, excitation energies and infrared intensities are calculated for the fundamental vibrations of furan using VCC limited to up to two-mode and up to three-mode excitations, VCC[2] and VCC[3], as well as VCC with full two-mode and approximate three-mode couplings, VCC[2pt3].     

Iron-catalyzed hydroxylation of β-ketoesters with hydrogen peroxide as oxidant

The hydroxylation of β-ketoesters was studied using simple iron catalysts and 30 wt % hydrogen peroxide as the terminal oxidant. The highest activity and yield were achieved in the presence of iron(III) chloride. Cyclic β-ketoesters could be smoothly hydroxylated in 75-90% yield. For linear β-ketoester and β-ketoamide, the chloro-substituted products were obtained.     

Polymeric Membranes Containing Phosphorus in the Chain for Solid Polymer Electrolytes

Abstract

Two new series of solid polymer electrolytes (SPEs) based on phosphorus containing (co)polyesters (PPE) and Lithium triflate were obtained. PPEs are composed of phosphonate moeties (cyclohexyldichlorophosphonate (CHDP)) as linking agent and two diols: PEG (6000) and poly(tetramethylene glycol) (PTMG) in PPE I, and PEG (6000) and 4,4′-cyclohexylidenebisphenol (bisphenol Z, BZ) in PPE II. Polycondensation was carried out in solution in the presence of triethylamine (TEA) as scavenger of HCl side product (PPE I–IIa) and in the absence of any acid acceptor (PPE I–IIb). The Limiting Oxygen Index (LOI) and thermal analysis were performed both on polymers and membranes. The ionic conductivity of SPE membranes based on PPE-salt complexes, with various salt concentrations, was investigated at different temperature and ionic transference numbers were determined. Optimum composition was obtained for the polymer which contains in structure only alkyl units and 15% Lithium triflate.     

Polyamine-based anion receptors: Extraction and structural studies

In the discussion that follows some of the more recent progress in the area of anion binding by synthetic polyamine receptors is presented, with emphasis given to work undertaken by the authors’ groups. A continuing theme in these studies has been the relationship between receptor structure and its anion extraction properties.Systematic solvent extraction and structural studies for halide and perrhenate complexes with polyamines of tripodal, macrocyclic and macrobicyclic architecture that contain both aromatic moieties and four to eight amine functions have been performed in order to derive relevant structure-binding/extractability relationships. The results demonstrate that the binding and extraction behaviour of the polyamines towards halides and perrhenate is a complex function of their structural features, degree of protonation and lipophilic properties. The extraction is characterized by the preferred formation of mono- and diprotonated amine species in the organic phase. X-ray structure studies of iodide and perrhenate complexes with open-chain tetraamino derivatives and octaamino cryptands in different protonation states lead to the conclusion that in the first case only limited chelation of the anion occurs and in the second only highly protonated species are able to encapsulate the anion. The structural patterns observed are strongly influenced by the presence of water molecules in the crystals.     

Skin Cancer Awareness Among 1 271 Black Africans in South Africa

Little is known about levels of awareness and perceptions of skin cancer among Africans living in Africa. This study assessed skin cancer awareness among 1271 deeply pigmented South Africans. Participants (n = 642 males vs n = 629 females) were aware of skin cancer (79%) with more females than males being aware of skin cancer (P = 0.02). Majority of all participants had never checked their skin for signs or symptoms of skin cancer (90%). Palms of hands and soles of feet were the least recognized anatomic sites for skin cancer development, despite these sites being the common sites for acral lentiginous melanoma in individuals with deeply pigmented skin. Results suggest a need for targeted skin cancer awareness among population groups with dark skin on identification, screening, and early detection, professional training for healthcare personnel and content on skin cancer in deeply pigmented skin in medical curricula.