Quadrupolar and Chemical Shift Tensors Characterized by 2D Multiple-Quantum NMR Spectroscopy

The present work discusses a new 2D NMR method for characterizing the principal values and relative orientations of the electric field gradient and the chemical shift tensors of half-integer quadrupolar sites. The technique exploits the different contributions that quadrupolar and shielding interactions impart on the evolution of multiple-quantum and of single-quantum coherences, in order to obtain 2D powder lineshapes that are highly sensitive to these nuclear spin coupling parameters. Different spinning variants of this experiment were assayed, but it was concluded that a static version can yield the highest sensitivity to the values of the principal components and to the relative geometries of the local coupling tensors. It was found that correlating the central transition evolution with the highest available order of the spin coherence was also helpful for maximizing this spectral information. Good agreement between data obtained on ⁸⁷Rb (S = ) and ⁵⁹Co (S = ) samples and ideal theoretical lineshape predictions of this experiment was obtained, provided that heterogeneities in the multiple-quantum excitation and conversion processes were suitably accounted by procedures similar to those described in the spin- multiple-quantum NMR literature.     

Organotin compounds: an ionophore system for fluoride ion recognition

Ion-selective properties were established for membrane electrodes prepared by using organotin compounds of type (L^CNRSnF₂)_n, (R = n-Bu (I), = Ph (II)) and (L^CNSnF₃)_n (III) (L^CN = C₆H₄(CH₂NMe₂)-2). Electrodes formulated with the optimized membranes containing the organotin compounds I-III as ionophores and sodium tetraphenylborate (10-30%) exhibited high selectivity for fluoride over other anions. An electrode prepared with ionophore II using dibutyl phthalate as the plasticizer and 15% sodium tetraphenylborate (NaTPB) as anion additive, possesses the best potentiometric response characteristics. It shows a detection limit of 7.9 × 10⁻⁷ M with a slope of 62.7 mV decade⁻¹ of activity in buffer solutions of pH 5.5. The interference from other anions is suppressed under this optimized measurement conditions. An entirely non-Hofmeister selectivity sequence (F⁻ > CH₃COO⁻ > Cl⁻ > I⁻ ∼ Br⁻ >ClO₄⁻ > NO₂⁻ > NO₃⁻ > SCN⁻) with remarkable preference towards fluoride is obtained. The influence on the electrode performances by anion additive was studied, and the possible response mechanism was investigated by UV-vis spectra. The electrode has been used for direct determination of fluoride in drinking mineral water with satisfactory results.     

17O NMR spectra of some organotin(IV) compounds containing O,C,O-chelating ligands

The 17O chemical shifts of substituted benzyl ethers and a set of organotin(IV) derivatives containing O,C,O-chelating ligands were studied. Measured 17O chemical shifts were correlated with the additivity substituent increments for carbon atoms in the alkyl groups, and intramolecular Sn-O distance was obtained by X-ray diffraction techniques in the solid state.     

Lipid diffusion in giant unilamellar vesicles is more than 2 times faster than in supported phospholipid bilayers under identical conditions

The lateral diffusion coefficients of a BODIPY tail-labeled lipid in two model systems, namely, free-standing giant unilamellar vesicles (GUVs) and supported phospholipid bilayers (SPBs), were determined by fluorescence correlation spectroscopy (FCS) using the Z-scan approach. For the first time, the performed measurements on 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) bilayers maintain exactly the same experimental conditions for both systems, which allows for a quantitative comparison of lipid diffusion in these two commonly used model membranes. The results obtained revealed that the lipid mobility in free-standing bilayers (D=7.8+/-0.8 microm2 s-1) is significantly higher than in the bilayer created on the solid support (mica) (D=3.1+/-0.3 microm2 s-1).     

Investigating the spectrum of biological activity of substituted quinoline-2-carboxamides and their isosteres

In this study, a series of thirty-five substituted quinoline-2-carboxamides and thirty-three substituted naphthalene-2-carboxamides were prepared and characterized. They were tested for their activity related to the inhibition of photosynthetic electron transport (PET) in spinach (Spinacia oleracea L.) chloroplasts. Primary in vitro screening of the synthesized compounds was also performed against four mycobacterial species. N-Cycloheptylquinoline-2-carboxamide, N-cyclohexylquinoline-2-carboxamide and N-(2-phenylethyl)quinoline-2-carboxamide showed higher activity against M. tuberculosis than the standards isoniazid or pyrazinamide and 2-(pyrrolidin-1-ylcarbonyl)quinoline and 1-(2-naphthoyl)pyrrolidine expressed higher activity against M. kansasii and M. avium paratuberculosis than the standards isoniazid or pyrazinamide. The most effective antimycobacterial compounds demonstrated insignificant toxicity against the human monocytic leukemia THP-1 cell line. The PET-inhibiting activity expressed by IC(50) value of the most active compound N-benzyl-2-naphthamide was 7.5 μmol/L. For all compounds, the structure-activity relationships are discussed.     

Voltammetric determination of dinitronaphthalenes using a silver solid amalgam paste electrode

The electrochemical behavior and application of a new sensor, a silver solid amalgam paste electrode (AgSA-PE), based on the mixture of a fine silver solid amalgam powder (60:40 (w(Hg)/w(Ag))) and a suitable organic pasting liquid (Paraffin oil) in a ratio of 20:1 (w/w), was investigated in an aqueous-methanolic media (1:1). This alternative working electrode provides simple preparation and handling, adequate mechanical stability, easily renewable electrode surface, sufficiently wide cathodic potential window (up to -1200 mV within a pH range of 2.7-12.3), and sufficient sensitivity without any necessary pretreatment. The practical usability of the AgSA-PE was verified by the development of voltammetric methods for the determination of selected environmentally important pollutants (1,3-, 1,5-, and 1,8-dinitronaphthalenes) in an aqueous-methanolic media (1:1). The differential pulse voltammetric methods at AgSA-PE give linear concentration dependences in the range of 1-100 μmol l(-1) with limits of detection of about 1 μmol l(-1) in a mixture of Britton-Robinson buffer of appropriate pH and methanol (1:1).     

Non-hydrolytic synthesis of titanosilicate xerogels by acetamide elimination and their use as epoxidation catalysts

Novel non-hydrolytic syntheses of titanosilicate xerogels by polycondensation of silicon acetate, Si(OAc)₄, with titanium (IV) dimethylamide or diethylamide, Ti(NR₂)₄ (R?=?Me, Et), are presented. The reactions are based on acetamide elimination and yield gels with a high content of Si?CO?Ti bonds in comparison with the ester elimination route. Although a ligand exchange was observed, it was interestingly not followed by homo-condensation and during the synthesis the phase separation to SiO₂ and TiO₂ was avoided. The degree of condensation reached up to 68?%. The xerogels prepared for a comparison by ester elimination from Si(OAc)₄ and titanium (IV) isopropoxide featured a significantly lower content of the Si?CO?CTi bonds. The initial tests in the epoxidation of cyclohexene by cumyl hydroperoxide (CHP) indicated a high selectivity and moderate activity of the xerogels. The catalytic properties were significantly improved by combining non-hydrolytic and hydrolytic methods yielding mesoporous and homogeneous Si/Ti mixed oxides. The catalysts prepared by these methods provided a complete epoxidation of cyclohexene in 2?h at?65?°C.     

Theoretical assessment of the Ni–Sn system

Abstract  

A new theoretical assessment of the Ni–Sn system has been performed by use of the CALPHAD method. Recent experimental results were significantly different from older experimental data and, therefore, a new reassessment of older theoretical work was necessary. The theoretical models for some intermetallic phases were changed to make them consistent with other binary systems in the thermodynamic database developed in the scope of COST action MP0602. Very good agreement was reached both with new experimental phase equlibrium data and older thermodynamic data.     

Etching of polyethylene terephthalate thin films by neutral oxygen atoms in the late flowing afterglow of oxygen plasma

Films of polyethylene terephthalate were deposited on quartz crystals and exposed to oxygen atoms to study their etching characteristics and quantify the etching rate. Oxygen (O) atoms were created by passing molecular oxygen through plasma created in a microwave discharge. The discharge power was fixed at 250 W, while the pressure of oxygen was 50 Pa. Before exposure to oxygen atoms, a thin polymer film of polyethylene terephthalate (PET) was deposited uniformly over a crystal with a diameter of 12 mm. The crystal was mounted on a quartz crystal microbalance to accurately determine the thickness of the polymer film. The polymer film was exposed to O atoms in the flowing afterglow. The density of O atoms was measured with a cobalt catalytic probe mounted next to the sample and was determined to be 1.2 × 10²¹ m^–3. Samples were treated with O atoms for different periods of up to 120 min. The thickness of the film decreased linearly with treatment time. After 90 min of treatment, a 65‐nm‐thick polymer film was completely removed. Therefore, the etching rate was 0.5 nm/min, so the interaction probability between an O atom and an atom in the sample was extremely low, just 1.4 × 10^–6. Samples treated for different periods were investigated by atomic force microscopy and X‐ray photoelectron spectroscopy to examine the etching characteristics of O atoms in the flowing afterglow. Copyright © 2012 John Wiley & Sons, Ltd.