METALLOPURPURINS and LIGHT: EFFECT ON TRANSPLANTABLE RAT BLADDER TUMORS and MURINE SKIN

Purpurins are modified chlorins with photodynamic properties. Their strong absorption in the red region of the visible spectrum makes them candidates for use in photodynamic cancer therapy. A series of metal derivatives of the free base purpurins have been synthesized and shown to cause tumor necrosis in transplantable tumors when exposed to visible light. In the following set of experiments, the effects of two metallo-derivatives (tin and zinc) of two purpurins, octaethylpurpurin (NT2) and etiopurpurin (ET2), and light on the N-[4-(5-nitro-2-furyl)-2-thiazolyl] formamide transplantable tumors in Fischer CDF(F344)/CrlBr rats were studied. The photodynamic activity was assessed by a short term assay using tumor dry weight 12 days after purpurin-PDT as a criterion of response. From these experiments it appears that SnET2 greater than SnNT2 greater than ZnET2 greater than ZnNT2 in photodynamic activity. SnET2 was further characterized by attempting to determine the time interval after systemic injection at which maximum therapeutic effect occurred. These studies shown that 24 h after metallopurpurin injection was the optimum time for treatment of tumors with visible light. In a final set of experiments, the effect of solar light on the skin of hairless mice injected with SnET2 was found to be much less injurious than with hematoporphyrin derivative.     

Solvatochromism and piezochromism of pentacyanoferrate(II) complexes in binary aqueous solvent media

Summary The solvatochromic behaviour of a number of pentacyano-ferrates (II), [Fe^II(CN)₅L] ^n-, is described, for solutions in H₂O-alcohol, -Me₂CO and -DMSO mixtures. The strong dependence of solvent sensitivity on the nature of the ligand L is particularly fully documented for H₂OMeOH mixtures (0–100% MeOH). The piezochromic behaviour of seven pentacyanoferrates(II) has been established, in aqueous solution. The connection between piezochromism and solvatochromism is detailed, and the solvatochromic results discussed in terms of (preferential) solvation.     

Growth factors and gangliosides: a possible new perspective in neuronal growth control.

For many permanent cell lines the transition from a growing (P) to a resting (R) state is reversibly controlled by growth factors present in serum. This P-to-R transition was studied in a neuronal cell line (B104) with respect to the action of serum, dibutyryl cyclic AMP (DBcAMP), gangliosides, and a glioma cell-produced growth factor GGF. In this cell system gangliosides seem to act as differentiation and survival factors. The kinetics of uptake of radioactively labeled gangliosides and survival experiments both support the idea of the stable incorporation of exogenously added gangliosides into the cells. Based on the experimental evidence a new model of cell development is proposed. Thus in addition to the R or Go state, which in this cell system is rather unstable and probably regulated by cyclic nucleotides, we postulate a differentiated D state, which is controlled by gangliosides and which is characterized by its stability (survival time). This D compartment seems to be closer to the in vivo differentiated neuron than does the R or P state. tthe possible mechanisms for the action of gangliosides are discussed.     

The diffraction of a shock wave by an inclined body of revolution

Summary The interaction between a plane normal shock wave of arbitrary strength and a slender body of revolution, held with its axis at a small angle to the direction of propagation of the shock, is considered. The pressure field is determined by using the method of matched asymptotic expansions and the general results are applied to the problem of diffraction by an inclined circular cone.

---

Zusammenfassung Es wird die Beeinflussung einer ebenen Stosswelle beliebiger Stärke durch einen schlanken Rotationskörper untersucht, dessen Achse einen kleinen Winkel mit der Ausbreitungsrichtung des Stosses bildet. Das Druckfeld wird mit Hilfe der abgestimmten asymptotischen Entwicklungen bestimmt, und die allgemeinen Resultate werden auf das Problem der Diffraktion durch einen angestellten Kreiskegel angewendet.

     

Phosphoryl‐Rich Flame‐Retardant Ions (FRIONs): Towards Safer Lithium‐Ion Batteries

The functionalized catecholate, tetraethyl (2,3‐dihydroxy‐1,4‐phenylene)bis(phosphonate) (H₂‐DPC), has been used to prepare a series of lithium salts Li[B(DPC)(oxalato)], Li[B(DPC)₂], Li[B(DPC)F₂], and Li[P(DPC)₃]. The phosphoryl‐rich character of these anions was designed to impart flame‐retardant properties for their use as potential flame‐retardant ions (FRIONs), additives, or replacements for other lithium salts for safer lithium‐ion batteries. The new materials were fully characterized, and the single‐crystal structures of Li[B(DPC)(oxalato)] and Li[P(DPC)₃] have been determined. Thermogravimetric analysis of the four lithium salts show that they are thermally stable up to around 200 °C. Pyrolysis combustion flow calorimetry reveals that these salts produce high char yields upon combustion.     

Polymer complexes. LXX. Synthesis,spectroscopic studies,thermal properties and antimicrobial activity of metal(II) polymer complexes

The monomer 3‐allyl‐5‐(phenylazo)‐2‐thioxothiazolidine‐4‐one (HL) was prepared by the reaction of allyl rhodanine with aniline through diazo‐coupling reaction. Reaction of HL with Ni(II) or Co(II) salts gave polymer complexes ( 1 – 8 ) with general stoichiometries [M(HL)(Cl)₂(OH₂)₂]_n, [M(HL)(O₂SO₂)(OH₂)₂]_n, [M(L)(O₂NO)(H₂O)₂]_n and [M(L)(O₂CCH₃)(H₂O)₂]_n (where M = Ni(II) or Co(II)). The structures of the polymer complexes were identified using elemental analysis, infrared and electronic spectra, molar conductance, magnetic susceptibility, X‐ray diffraction and thermogravimetric analysis. The interaction between the polymer complexes and calf thymus DNA showed a hypochromism effect. HL and its polymer complexes were tested against bacterial and fungal species. Co(II) polymer complex 2 is the most effective against Klebsiella pneumoniae and is more active than penicillin. The results showed that Ni(II) polymer complex 5 is a good antibacterial agent against Staphylococcus aureus and Pseudomonas aeruginosa. Molecular docking was used to predict the binding between the monomer with the receptors of prostate cancer (PDB code: 2Q7L Hormone) and breast cancer (PDB code: 1JNX Gene regulation). Coats–Redfern and Horowitz–Metzger methods were applied for calculating the thermodynamic parameters of HL and its polymer complexes. The thermal activation energy of decomposition for HL is higher than that for the polymer complexes.     

Polymer complexes. LXXVI. Synthesis,characterization, CT‐DNA binding,molecular docking and thermal studies of sulfoxine polymer complexes

Novel polymer complexes of 8‐hydroxyquinoline‐5‐sulfonic acid hydrate ( H ₂ L ) with Cu²⁺, Co²⁺ and Ni²⁺ chloride were prepared and characterized. Microanalysis, magnetic susceptibility, IR spectra, electron spin resonance, mass spectra, X‐ray, molar conductance, thermal, and UV–Vis spectra studies have been used to confirm the structure of the prepared polymer complexes. The molecular and electronic structures of the hydrogen bond conformers for ligand ( H ₂ L ) were optimized theoretically and the quantum chemical parameters were calculated. On the basis of elemental and IR data, the chemical structure of metal chelates commensurate that the tri‐dentate (H₂L) coordinate to metal chlorides through oxygen atom of phenolic OH and oxygen atom of SO₃‐H group by replacing H atoms and nitrogen of the quinoline ring. The magnetic studies suggested the octahedral geometrical structure for all produced polymer complexes with general formula {[ML (OH₂)₃] .xH₂O}_n (M = Cu²⁺, x = 1.; Co²⁺, x = 2 and Ni²⁺, x = 2) in molar ratio (1:1). Coats–Redfern and Horowitz–Metzger methods have been used for calculating the activation thermodynamic parameters of the thermal decomposition for H ₂ L and its polymer complexes. The interaction between H ₂ L and its transition metal complexes with the calf thymus DNA (CT‐DNA) was determined by UV–Vis spectra. Binding efficiency between H ₂ L with the receptors of the prostate cancer (PDB code 2Q7L Hormone) and the breast cancer (PDB code 1JNX Gene regulation) was studied by molecular docking. The inhibition behaviour of H ₂ L against the corrosion of carbon steel / HCl (2 M) solution was studied by weight loss, Tafel polarisation, electrochemical impedance spectroscopy (EIS) and electrochemical frequency modulation (EFM) techniques. The adsorption isotherm was found to be Friendlish isotherm. The morphology of inhibited carbon steel? s surface was studied using scanning electron microscope (SEM) and energy dispersive X‐ray spectroscopy (EDS).     

Synthesis,characterization of Schiff base metal complexes and their biological investigation

A new Schiff base ligand named (E)‐2‐(((3‐aminophenyl)imino)methyl)phenol (HL) was prepared through condensation reaction of m‐phenylenediamine and 2‐hydroxybenzaldehyde in 1:1 molar ratio. The new ligand was characterized by elemental analysis and spectral techniques. The coordination behavior of a series of transition metal ions named Cr (III), Mn (II), Fe (III), Co (II), Ni (II), Cu (II), Zn (II) and Cd (II) with the newly prepared Schiff base ligand (HL) is reported. The nature of bonding and the stereochemistry of the complexes have been deduced from elemental analyses, IR, UV–Vis, ¹H NMR, mass, electronic spectra, magnetic susceptibility and conductivity measurements and further their thermal stability was confirmed by thermogravimetric analysis (TG). From IR spectra, it was observed that the ligand is a neutral tridentate ligand coordinates to the metal ions through protonated phenolic oxygen, azomethine nitrogen and nitrogen atom of NH₂ group. The existence, the number and the position of the water molecules was studied by thermal analysis. The molecular structures of the Schiff base ligand (HL) and its metal complexes were optimized theoretically and the quantum chemical parameters were calculated. The synthesized ligand and its complexes were screened for antimicrobial activities against bacterial species (Staphylococcus aureus and Bacillis subtilis, (gram positive bacteria)), (Salmonella SP., Escherichia coli and Pseudomonas aeruginosa, (gram negative bacteria)) and fungi (Aspergillus fumigatus and Candida albicans). The complexes were found to possess high biological activities against different organisms. Molecular docking was used to predict the efficiency of binding between Schiff base ligand (HL) and both receptors of Escherichia coli (3 T88) and Staphylococcus aureus (3Q8U). The receptor of Escherichia coli (3 T88) showed best interaction with Schiff base ligand (HL) compared to receptor of Staphylococcus aureu (3Q8U).