Electrochemical synthesis of Co,Ni, and Zn complexes with 2-Pyrrole-[N-(o-hydroxyphenyl)methylimines]: The crystal structure of 2,2′-Bipyridine bis{2-[(2-pyrrole)methylimino]5-methylphenolato}nickel(II)

The electrochemical oxidation of anodic cobalt, nickel, and zinc in acetonitrile containing both 2-pyrrole-[N-(o-hydroxyphenyl)methylimines] (H₂L) and a bidentate ligand (1, 10-phenanthroline(phen) or 2,2′-bipyridine(bipy)) yielded compounds of general formula M(HL)₂ · phen and M(HL)₂ · bipy (M = Co, Ni, Zn). The crystal structure of 2,2′-bipyridine bis{2-[(2-pyrrole)methylimino]5-methylphenolato}nickel(II) was determined by X-ray diffraction. This compound crystallizes in the orthorhombic space group Pccn with a = 19.430(2), b = 28.488(2), c = 17.567(1) Å. The nickel atom has a distorted octahedral geometry, and the pyrrole nitrogen is not coordinated. The IR, ¹H-NMR and UV-visible spectra of the complexes are discussed and related to the structure.     

Synthesis of an Azasteroid Using an Acyl Iminium Ion-Initiated Tandem Cyclization

An acyl iminium ion-initiated tandem cyclization gave an unexpected dienone product, a seco-azasteroid (2). The factors governing the formation of 2 were investigated in an attempt to optimize its formation. The reaction was applied to a more elaborate system, resulting in the synthesis of the full steroid skeleton of 13-azaandrosta-1,4-diene-3,17-dione (3), which contains the unusual substitution of a chlorine atom for the axial 19-methyl.     

Viscoelastic and thermal characterization of crosslinked PVC

Soft PVC is employed for the manufacturing of a wide range of products with different properties and a relatively low cost. The utilization of soft PVC is restricted by the poor thermal, chemical and mechanical resistance properties. Also, plasticizer migration can modify the properties or can make useless the materials for some applications because of toxicity or a general loss of properties. PVC crosslinking is the most effective way to improve mechanical and transport properties of rigid or flexible PVC at high temperatures, but at the same time the thermal stability of PVC may be significantly reduced. In this work, the crosslinking reaction of plasticized poly(vinyl chloride) (PVC) through difunctional amines was studied. The mechanisms involved in the crosslinking reaction were explained by Fourier transform infrared (FTIR) analysis. The thermal activated crosslinking reaction was studied by cone and plate rheometry, analyzing the evolution of viscoelastic properties of the suspension as a function of time and temperature. The effect of the addition of crosslinking agents on the thermal stability of the polymer was studied by thermogravimetric analysis (TGA), which revealed that crosslinking reactions promote thermal degradation phenomena in the polymer matrix. This is attributed to the formation of HCl and other species promoting polymer degradation during crosslinking, thus leading to higher weight loss during thermal treatment with respect to unmodified PVC plastisols. This was also confirmed by an evident yellowing after crosslinking, especially at higher temperatures.     

Flow-injection spectrophotometric determination of arylamines and sulphonamides by diazotization and coupling in a micellar medium

In a sodium dodecyl sulphate (SDS) micellar solution, the rate of coupling of a diazonium ion with N-(1- naphthyl)ethylenediamine (NED) increases greatly, the protonation of the resulting azo dyes takes place at higher pH values and the dyes are more soluble. These favourable features were applied to the development of a simple flow-injection spectrophotometric procedure for the determination of diazotizable substances of pharmaceutical interest. Limits of detection in the range 0.2–0.5 μg ml^?1 (signal-to-noise ratio=3), with relative standard deviation of 0.7–3% (n=3) for 5 μg ml^?1 standards, were obtained.     

Ferromagnetism and chirality in two-dimensional cyanide-bridged bimetallic compounds

The combination of hexacyanoferrate(III) anions, [Fe(CN)(6)](3)(-), with nickel(II) complexes derived from the chiral ligand trans-cyclohexane-1,2-diamine (trans-chxn) affords the enantiopure layered compounds [Ni(trans-(1S,2S)-chxn)(2)](3)[Fe(CN)(6)](2).2H(2)O (1) and [Ni(trans-(1R,2R)-chxn)(2)](3)[Fe(CN)(6)](2).2H(2)O (2). These chiral systems behave as ferromagnets (T(c) = 13.8 K) with a relatively high coercive field (H(c) = 0.17 T) at 2 K. They also exhibit an unusual magnetic behavior at low temperatures that has been attributed to the dynamics of the magnetic domains in the ordered phase.     

Fourier Transform Infrared Spectroscopy and Solid Phase Extraction Applied to the Determination of Oil and Grease in Water Matrices

 The solid phase extraction as a solvent-free method for the analysis of oil and grease in waters was studied. The use of a PTFE surface as a solid phase allows the retention of the volatile fraction of oil and grease, and further analysis of carbon–hydrogen bonds using infrared spectroscopy can be done on the surface. Various oils and grease samples were tested: n-hexadecane, n-tetradecane, n-nonadecane, n-docosane, isooctane, diesel oil and gasoline. Temperatures from 25° to 90 °C and a range of heating times were checked for extraction. Precision tests showed relative standard deviation values of around 10% in several samples of the same concentration. Calibration lines of n-hexadecane showed high correlation coefficients from 0.9 to 30 mg/l. Recoveries for the various oils using different calibration lines showed values from 90 to 110%. The method described here is fast and clean, and allows reproducible measurements of oil and grease in water that do not require the use of a solvent. Received March 1, 2001; accepted August 15, 2001; published online July 15, 2002