Synthesis and Photochemistry of Novel 3,5-Diacetyl-1,4-dihydropyridines. II [1]

In continuation of previous work some novel 3,5-diacetyl-1,4-dihydropyridine derivatives were synthesized and their photochemical behavior was studied under oxygen and argon atmosphere. Oxidation of the dihydropyridine ring and formation of pyridine derivatives was the result of the reaction. The presence of oxygen affects not only on the rate of oxidation, but also the formation of some unidentified by-products was observed on irradiation under this atmosphere.     

Spin dynamics investigated by EPR in the paramagnetic regime of La2/3Ca1/3Mn1−x Me x O3 (Me = Al, In) manganites

We report an electron paramagnetic resonance (EPR) investigation of the spin dynamics in the paramagnetic regime of the colossal magnetoresistive manganites La_2/3Ca_1/3Mn_1?x Me _x O₃ (Me=Al, In;x≤0.05). The temperature dependences of the EPR linewidth and integral intensity have been analyzed in terms of the bottleneck spin relaxation and small-polaron hopping models. The exchange coupling integral between Mn³⁺ and Mn⁴⁺ ions and the polaron activation energy decrease with increasing doping level. A discussion is given concerning the factors which could explain the observed changes.     

Highly selective PVC-membrane electrodes based on Co(II)-Salen for determination of nitrite ion.

A cobalt(II) derivative was used as a suitable ionophore for the preparation of a polymeric membrane nitrite-selective electrode. The electrode reveals a Nemstian behavior over a very wide NO2- ion concentration range (1.0 x 10(-6)-1.0 x 10(-1) M) and a very low detection limit (5.0 x 10(-7) M). The potentiometric response is independent of the pH of solution in the pH range 4.0-9.5. The electrode shows advantages such as low resistance, fast response and, most importantly, good selectivity relative to a wide variety of inorganic and organic anions. In fact, the selectivity behavior of the proposed NO2- ion-selective electrode shows great improvements compared to the previously reported electrodes for nitrite ion. The proposed electrodes could be used for at least 2 months without any significant changes in potentials. The electrode was successfully applied to the determination of nitrate ion concentrations in sausage and milk samples.     

Uncharged encapsulated iron(II) complexes: transfer chemical potentials and solvation in water-methanol and water-t-butanol mixtures

Summary Transfer chemical potentials have been determined from measured solubilities for four uncharged encapsulated iron(II) complexes containing three diimine ligating moieties and O₃BOBu-n and O₃BF capping groups, in H₂O–MeOH andt-BuOH–H₂O solvent mixtures, The trends in transfer chemical potentials are discussed in terms of the natures of the encapsulating ligands, and are compared with those for a selection of other iron(II)-diimine complexes.     

A neutron polarization analysis study of Ce2Fe17 in its paramagnetic phase

Spin-flip (paramagnetic) scattering and neutron depolarization studies were performed on Ce₂Fe₁₇ in its paramagnetic phase on the Dhruva neutron polarization analysis spectrometer. The absence of normalQ dependence of the scattered spin flip intensity shows that Ce₂Fe₁₇ is not a normal paramagnetic and there exist superparamagnetic clusters of sufficiently large dimensions (～100Å). The observed neutron depolarization gives an indication of the dynamics of these Ce₂Fe₁₇ superparamagnetic clusters.     

Efficient synthesis of ferrocenylenones by Friedel-Crafts acylation with EtAlCl2-Me3Al

Efficient synthesis of ferrocenylenones using a Friedel-Crafts acylation reaction is described. Acryloyl, methacryloyl, crotonoyl, cinnamoyl, and β-methylcrotonoyl chlorides react with ferrocene in the presence of a Lewis acid (EtAlCl₂ or EtAlCl₂-Me₃Al) to give the corresponding ferrocenylenones (acryloyl, methacryloyl, crotonoyl, cinnamoyl, and methylcrotonoylferrocenes) in good isolated yields. Besides ferrocenylenones, chloroactylferrocene is also synthesised by this method.     

Novel monohydrogenphosphate sensor based on vanadyl salophen

A novel PVC-based membrane sensor based on vanadyl salophen (VNSP) for determination of trace amounts of monohydrogenphosphate (MHP) ions is introduced. The electrode revealed Nernstian response towards monohydrogenphosphate over the wide concentration range from 1.0×10⁻¹ to 1.0×10⁻⁶ M at the pH of 8.2. The effect of solvent mediator, cationic additives and amount of ion-carrier on the behavior of the sensor was investigated. The sensor shows a short response time (<20 s) in the whole concentration ranges. The selectivity of the electrode is very high, and it can be used for detection of trace amounts of monohydrogenphosphate in the presence of large amounts of other anions. The detection limit of the electrode was 5.0×10⁻⁷ M (48 ng/ml) and it could be used for 14 weeks without any measurable changes in the slope. The potentiometric selectivity coefficients data revealed negligible interference from 16 common anions. It was successfully applied for the direct determination of monohydrogenphosphate in fertilizer samples and, as an indicator electrode, in potentiometric titration of HPO₄²⁻ ion with barium nitrate.