Determination of nickel in alloys and plant leaves with salicylaldehyde 3-oxobutanoylhydrazone by spectrophotometry.

A simple and highly sensitive reagent of salicylaldehyde 3-oxobutanoylhydrazone (salicylaldehyde acetoacetic acid hydrazone, SAAH) was synthesized and studied for the spectrophotometric determination of nickel in detail. In the pH range 6, which greatly increased the selectivity, nickel reacted with SAAH to form a 1:1 yellow complex, having a sensitive absorption peak at 405 nm. Under the optimal conditions, Beer's law was obeyed over the range from 0.0117 to 0.1174 microg cm(-3). The apparent molar absorptivity was 3.025 x 10(5) dm3 mol(-1) cm(-1). The detection limit and the variation coefficient were found to be 1.752 ng cm(-3) and 1.0%, respectively. The method has been applied to the quantitative determination of nickel in different alloys and leaves.     

Thermophoresis in laminar flow over cold inclined plates with variable properties

This paper deals with the analysis of two dimensional laminar thermophoretic flow over inclined plates. Cold wall conditions are assumed and the governing equations are solved by a finite difference marching technique. Results for the hydrodynamic, thermal and particle concentration boundary layers are obtained over a wide range of parameters. Special emphasis is placed on the external aerosol particle deposition process.     

Model reduction for parametric instability analysis in shells conveying fluid

Flexible pipes conveying fluid are often subjected to parametric excitation due to time-periodic flow fluctuations. Such systems are known to exhibit complex instability phenomena such as divergence and coupled-mode flutter. Investigators have typically used weighted residual techniques, to reduce the continuous system model into a discrete model, based on approximation functions with global support, for carrying out stability analysis. While this approach is useful for straight pipes, modelling based on FEM is needed for the study of complicated piping systems, where the approximation functions used are local in support. However, the size of the problem is now significantly larger and for computationally efficient stability analysis, model reduction is necessary. In this paper, model reduction techniques are developed for the analysis of parametric instability in flexible pipes conveying fluids under a mean pressure. It is shown that only those linear transformations which leave the original eigenvalues of the linear time invariant system unchanged are admissible. The numerical technique developed by Friedmann and Hammond (Int. J. Numer. Methods Eng. Efficient 11 (1997) 1117) is used for the stability analysis. One of the key research issues is to establish criteria for deciding the basis vectors essential for an accurate stability analysis. This paper examines this issue in detail and proposes new guidelines for their selection.     

Spin coupling in distorted high-valent Fe(IV)-porphyrin radical complexes

In order to study structural influences on the interaction of Fe(IV) (S=1) and porphyrin cation radical (S=1/2) in high-valent iron porphyrin complexes of the type ¦X-(TMP)Fe=O¦⁺(Cl^–), X=I, Br₂, Br₄ were generated by mCPBA oxidation of corresponding Fe(III) porphyrins. The halogen substitution at the peripheral positions of the porphyrin leads to distortion of the planar porphyrin ring of ¦(TMP)Fe=O¦⁺. The new species have beeen investigated by temperature-dependent EPR and field-dependent Mössbauer spectroscopy; for the evaluation of spectra, we adopted the spin-Hamiltonian formalism including exchange interaction explicitly. As in ¦(TMP)Fe=O¦⁺, strong ferromagnetic spin coupling was observed with|J₀|D=0.9–1 and a zero-field spltting ofD32 cm^–1. For consistent parametrization of EPR and Mössbauer results, anisotropic coupling had to be introduced. Compared to ¦(TMP)Fe=O¦⁺ [1], analysis of the spectroscopic data shows that zero-field splitting and spin coupling is only slightly affected by the halogen distortion of the porphyrin structure.     

N-porphyrinylamino and -amido compounds by addition of an amino or amido nitrogen to a porphyrin meso position

This report describes the synthesis and characterization of a series of octaethylporphyrin derivatives in which the porphyrin pi-network is connected to phenyl, 3-fluoranthenyl, or 1-pyrenyl aromatic systems through a meso amino or amido nitrogen. Metal-free bases and zinc(II) and iron(III) complexes have been obtained. These compounds represent the first examples of linkages between porphyrins and extended pi-networks through a nitrogen atom directly attached to a porphyrin meso position. 1H NMR studies of the metal-free bases and zinc complexes showed that in the amido-linked adducts, the plane containing the aryl substituent was oriented perpendicular to the plane of the porphyrin. Linkage through the secondary amino nitrogen, however, allowed the aryl plane to rotate toward coplanarity with the porphyrin plane, resulting in conjugation of the highest occupied aryl and porphyrin molecular orbitals through the nitrogen lone pair. In developing routes to the amino-linked compounds, the facile formation of fused azaaryl chlorins via an oxidative intramolecular cycloaddition was observed. An aryl carbon ortho to the meso linkage attacked the beta-carbon of an adjacent pyrrole ring, accompanied by 1,2-migration of a pyrrole beta-ethyl substituent and a two-electron oxidation of the initially formed macrocycle. The resulting structures are analogous to benzochlorins. The electronic spectra of the metal-free bases are characterized by intense, long-wavelength bands in the visible region. Molecular structures of the chloroferric complexes of the azabenzofluorantheno- and azabenzpyrenoporphyrin macrocycles (derived from fusion of the fluoranthenyl and pyrenyl substituents, respectively) were obtained by X-ray diffraction. The porphyrin moiety in the azabenzofluoranthenoporphyrin adopted a gable structure, with a 22 degrees fold along a diagonal including the pyrrole-ring C4 and C16 alpha-carbons. By contrast, the azabenzpyrenoporphyrin was virtually planar.     

Synthesis of poly(alkyl aryl ether) dendrimers

Poly(alkyl aryl ether) dendrimers of up to four generations composed of a phloroglucinol core, branching components, and pentamethylene spacers are synthesized by a divergent growth methodology. A repetitive synthetic sequence of phenolic O-alkylation and O-benzyl deprotection reactions are adopted for the synthesis of these dendrimers. The peripheries of the dendrimers contain 6, 12, 24, and 48 phenolic hydroxyl groups, either in the protected or unprotected form, for the first, second, third, and fourth generations, respectively. Because of the presence of hydrophilic exterior and relatively hydrophobic interior regions, alkaline aqueous solutions of these dendrimers are able to solubilize an otherwise insoluble pyrene molecule and these supramolecular complexes precipitate upon neutralization of the aqueous solutions.     

Facile and Sensitive Spectrophotometric Determination of Propoxur in Formulations and Environmental Samples

A facile, rapid, and sensitive spectrophotometric method for the determination of propoxur in insecticidal formulations, fortified water, vegetables, agricultural wastewater, and agricultural soil samples has been elaborated. The proposed method is based on the hydrolysis of propoxur under basic conditions, followed by instantaneous azo coupling of the resulting 2‐isopropoxyphenol with the anilines 2a – c . This yielded the orange‐red chromophore 3a (λ_max=at 470 nm), the pale‐red coupling product 3b (490 nm), or the red derivative 3c (478 nm), which are stable for 46 h, 38 h, and 24 h, respectively, and could be readily analyzed spectrophotometrically.     

Synthesis, fluorescence and photoisomerization studies of azobenzene-functionalized poly(alkyl aryl ether) dendrimers

A series of azobenzene-functionalized poly(alkyl aryl ether) dendrimers have been synthesized and their photochemical and photophysical properties in solution and as thin films have been investigated. Although the photochemical behavior of the azodendrimers in solution indicated that the azobenzene units behave independently, very similar to the constituent monomer azobenzene unit, the properties of thin solid films of the dendrimers were distinctly different. The azodendrimers, AzoG1, AzoG2, and AzoG3 were observed to form stable supercooled glasses, which showed long-wavelength absorption and red emission characteristics of J-aggregates of the azobenzene chromophores. Reversible photoinduced isomerization of the azodendrimers in the glassy state is described.     

Determination of rhodium in water samples using cloud point extraction (CPE) coupled with flame atomic absorption spectrometry (FAAS)

Cloud point extraction was applied as a method for preconcentration of rhodium after formation of a complex with 2-propylpiperidine-1-carbodithioate (2-PPC), and later determined by flame atomic absorption spectrometry using TritonX-114 as surfactant. Rhodium was complexed with 2-PPC in an aqueous phase and kept for 15 min in a thermostatted bath at 40 °C. Separation of the two phases was accomplished by centrifugation for 15 min at 4000 rpm. The chemical variables affecting the cloud point extraction were optimized and successfully applied to rhodium determination in various water samples. Under optimized conditions, the preconcentration system (100 mL sample) permitted an enhancement factor of 50. The detection limits obtained under optimal conditions was 0.052 ng mL⁻¹. The extraction efficiency was investigated at different rhodium concentrations (7.0–42.0 μg mL⁻¹), and good recoveries (96.42–99.14%) were obtained using this method. It has been applied to the determination of rhodium in water and was compared with reported methods in terms of Student’s ‘t’-test and variance ratio ‘f’-test.