PHTHALOCYANINE-INDUCED PHOTOHEMOLYSIS: STRUCTURE-ACTIVITY RELATIONSHIP AND THE EFFECT OF FLUORIDE

Abstract— Phthalocyanine (Pc) containing AI, Ga or Zn as central metal ligand and substituted with a varying number of sulfonic acid residues as well as additional benzene rings were synthesized and their photodynamic activity was assayed using photohemolysis of human erythrocytes as an endpoint. The Pc derivatives vaned > 300-fold in their photodynamic activity. Activity corrclated with binding of the dye to the cell, with the exception of some of the amphiphilic dyes where cell uptake was an order of magnitude higher than expected from the observed activity. Fluoride was shown to inhibit AIPcS_n-induccd photohemolysis. This effect occurred also with other AlPc and GaPc derivatives, but the concentration of F required to slow photohemolysis by a factor of two (K_i) varied between 4 μ M and 10 mM. Fluorescence spectral studies indicated complex formation between F⁻ and the dye, which was stronger for AlPc than GaPc derivatives. Ultrastructural studies using scanning electron microscopy showed that the photosensitized cells were converted to spherocytes and that F⁻ prevented this to a large extent.     

Thermal synthesis and characterisation of N,N'-di(chlorobenzyl) ureas

The thermal stability of the Schiff base ethylacetoacetate-o-chlorobenzylamine (bdII), N-o-chlorobenzyl-C-benzoyl acetamide (bdIII), and N-p-chlorobenzyl-C-benzoyl acetamide (bdIV) were studied by thermogravimetric analysis. II Gave N,N'-di(o-chlorobenzyl) urea (bdIa) at 60° C, whereas the thermogravimetric curves of III and IV indicate that reactions other than formation of I may occur. The urea derivatives (I) have also been prepared from benzylamines and the corresponding β-ketoester and identified.     

Nitroxide mediated living radical polymerization of styrene onto poly (vinyl chloride)

Nitroxide‐mediated ‘living’ free radical polymerisation (LREP) was employed for the first time to prepare graft copolymer by having arylated poly (vinyl chloride) (PVC‐Ph) as a backbone and polystyrene (PS) as branches. The graft copolymerization of styrene was initiated by arylated PVC carrying 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO) groups as a macroinitiator. Thus, the arylated PVC was prepared in the mild conditions and these reaction conditions could overcome the problem of gelation and crosslinking in polymers. Then, 1‐hydroxy TEMPO was synthesized by the reduction of TEMPO with sodium ascorbate. This functional nitroxyl compound was coupled with brominated arylated PVC (PVC‐Ph‐Br). The resulting macro‐initiator (PVC‐Ph‐TEMPO) for ‘living’ free radical polymerization was then heated in the presence of styrene to form graft copolymer. DSC, GPC, ¹HNMR, and FT‐IR spectroscopy were employed to investigate the structure of the polymers. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis, Characterization, and Biological Activity of n-Tributyltin Derivatives of Pharmaceutically Active Carboxylates

Summary.  Tributyltin(IV) derivatives of six different pharmaceutically active carboxylates were synthesized. The complexes were characterized by different analytical techniques (elemental analysis; infrared, NMR, and mass spectroscopy). ¹¹⁹Sn NMR data were also recorded in six different coordinating and non-coordinating solvents. The antibacterial activities of the compounds were tested using ten different bacteria relative to the reference drugs ampicillin and cephalexin. Received September 20, 2001. Accepted (revised) December 6, 2001     

Microbial transformation of prednisone

The microbial transformation of prednisone (17alpha,21-dihydroxy-pregna-1,4-diene-3,11,20-trione) (1) by Cunninghamella elegans afforded two metabolites, 17alpha,21-dihydroxy-5alpha-pregn-1-ene-3,11,20-trione (2) and 17alpha,20S,21-trihydroxy-5alpha-pregn-1-ene-3,11-dione (3), while the fermentation of 1 with Fusarium lini, Rhizopus stolonifer and Curvularia lunata afforded a metabolite 1,4-pregnadiene-17alpha,20S,21-triol-3,11-dione (4). Compound 3 was found to be a new metabolite. Their structures were elucidated on the basis of spectroscopic techniques. Compound 3 showed inhibitory activity against lipoxygenase enzyme.     

Polarographic behaviour of salicylaldehyde-2-pyridylhydrazone and its copper(II) complex

The polarographic behaviour of salicylaldehyde-2-pyridylhydrazone (SAPH) has been studied in aqueous buffer solution containing 40% ethanol using DC and DP polarographic methods. In the pH range 1.8–7.5 the observed single irreversible reduction wave is assigned to the splitting of the N-N bond and reduction of C=N centre. In alkaline medium, a second wave appears at a more negative potential due to the reduction of the salicylaldehyde which is formed by hydrolytic decomposition of the SAPH molecule. The effect of pH on the limiting current andE _1/2 as well as the reduction mechanism are discussed and compared with similar compounds. The kinetic parameters of the electrode reaction have been calculated.The analytical properties of the copper(II)-SAPH system is described. The complex gave rise to a single irreversible well-defined wave (E _1/2=–0.58 V at pH=5.2). The reaction process is diffusion controlled. A method is suggested for the determination of Cu(II) in presence of different metal ions as the difference in theirE _1/2 values is sufficient for the purpose.This work is taken partly from the M. Sc. Thesis of Jamal S. Shalabi     

Syntheses, characterization and study of the use of cobalt (II) Schiff-base complexes as catalysts for the oxidation of styrene by molecular oxygen

Schiff-Base complexes of bis-5-phenylazosalicylaldehyde ethylenediimine and bis-5-phenylazosalicylaldehyde-O-phenylenediimine ligands with Co(II) (I and II) have been synthesized and characterized by their IR spectra and elemental analyses. These complexes catalyze the oxidation of styrene in the presence of dioxygen and excess pyridine. The effect of the reaction conditions on the oxidation of styrene was studied by varying solvent, nature and amount of the catalyst and substrate. The catalytic behavior of the studied complexes was shown to be dependent on the conditions applied. In all reactions, acetophenone and 1- phenylethanol were the only observed products.     

Determination of percolation threshold electroactivity and phase behavior study on conducting blends of thermotropic polyesters and polyaniline

The new thermotropic polyester/polyaniline (PIn/PAni) blends have been prepared by solution blend of synthesized liquid crystalline poly[4,4′‐bis (ω‐alkoxy) biphenylisophthalate]s having four and six methylene units in spacer (PI4 and PI6) with PAni doped with camphorsolfonic acid (CSA). The percolation threshold electroactivity of prepared blend films has been determined by cyclic voltammetry. The effect of the PAni concentration, solvent nature and polyester structure on the electroactivity of the blends has been investigated. The extremely low percolation threshold of prepared PIn/PAni‐CSA blends from dimethylformamide (DMF) and m‐cresol solution was 3% weight of PAni‐CSA. The amount of conducting polymer necessary to retard the formation of the liquid crystalline (LC) phase is up to 45% by weight. Phase behavior studies by differential scanning calorimetry and polarizing microscopy show that blends with 45% of conducting polymer are both liquid crystal and conductive. The morphology of the blends has been investigated by scanning electron microscopy. Copyright © 2004 John Wiley & Sons, Ltd.     

Parametric study of catalytic reforming process?

Summary A parametric study of catalytic reforming process in a pilot plant was carried out by varying the pressure, H₂/HC ratio, and space velocity. The results show that lower aromatics and higher hydrogen yields can be accomplished by increasing the space velocity in existing reformers, which will also result in better C₅⁺yield.     

Potentiodynamic and cyclic voltammetric behaviour of a lead electrode in NaOH solution

Summary The electrochemical behaviour of lead in NaOH solution was studied by potentiodynamic and cyclic voltammetric techniques in combination with X-ray diffraction analysis. The active dissolution of lead involves a small shoulderA1 followed by a peakA1 prior to a passive region. The shoulderA1 is assigned to the electroformation of a Pb(OH)₂ film, whereas peakA1 is due to the formation of PbO. Beyond the passive region, the current density increases again, forming a small shoulderA2 and a peakA2 prior to the oxygen evolution potential. The shoulderA2 and the peakA2 are correlated to the electrooxidation of PbO to Pb₃O₄ and PbO₂, respectively. The intensity of the anodic peaks increases with increasing alkali concentration, temperature and scan rate. In cyclic voltammetry, the reverse scan shows two cathodic peaksC1 andC2 which are correlated to the electroreduction of PbO and PbO₂ respectively, to Pb.

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Potentiodynamisches und cyclovoltammetrisches Verhalten einer Bleielektrode in NaOH-Lösung

Zusammenfassung Das elektrochemische Verhalten von Blei in NaOH wurde mittels potentiodynamischer und cyclovoltammetrischer Techniken unter Zuhilfenahme der Röntgenbeugungsanalyse untersucht. Die aktive Auflösung von Blei verläuft über eine SchulterA1, die von einem einer passiven Region vorgelagerten PeakA1 gefolgt wird. Die SchulterA1 wird der elektrochemischen Bildung eines Pb(OH)₂-Films, der PeakA1 der Bildung von PbO zugeschrieben. Jenseits der passiven Region steigt die Stromdichte wieder an, und vor Erreichen des Sauerstoffpotentials treten eine kleine SchulterA2 und ein PeakA2 auf, die mit der Elektrooxidation von PbO zu Pb₃O₄ und PbO₂ korrelieren. Analog dazu beobachtet man in der cyclischen Voltammetrie zwei kathodische PeaksC1 undC2, die der Elektroreduktion von PbO und PbO₂ zu Pb entsprechen. Die Intensität der anodischen Peaks steigt mit steigender Alkalikonzentration, Temperatur und Scangeschwindigkeit.