Antitumor Pentamethylcyclopentadienyl Rhodium Complexes of Maltol and Allomaltol: Synthesis, Solution Speciation and Bioactivity

The reaction of the dimer [RhIII(pentamethylcyclopentadienyl)(m-Cl)Cl]2 ([RhIII(Cp*)(m- Cl)Cl]2) with the hydroxypyrone ligands maltol and allomaltol affords complexes of the general formula [RhIII(Cp*)(L)Cl] under standard and microwave conditions. The organometallic compounds were characterized by standard analytical methods and in the case of the allomaltol derivative in the solid state by single-crystal X-ray diffraction analysis. The complexes showed similar cytotoxicity profiles and were proved to be moderately active against various human cancer cell lines. The stoichiometry and stability of these complexes were determined in aqueous solution by pH-potentiometry, 1H NMR spectroscopy and UVvisible spectrophotometry. Speciation was studied in the presence and in the absence of chloride ions. Hydrolysis of [RhIII(Cp*)(H2O)3]2+ gave dimeric mixed hydroxido species [(RhIII(Cp*))2(m-OH)3]+ and [(RhIII(Cp*))2(m-OH)2Z2] (Z = H2O/Cl‒). Formation of the mononuclear complexes [RhIII(Cp*)(L)Z] of maltol and allomaltol with similar and moderate stability was found. These species predominate at physiological pH and decompose only partially at micromolar concentrations. In addition, hydrolysis of the aqua complex or the chlorido/hydroxido co-ligand exchange resulted in the formation of the mixed-hydroxido species [RhIII(Cp*)(L)(OH)] in the basic pH range. Replacement of the chlorido by an aqua ligand in the complex [RhIII(Cp*)(L)Cl] was monitored and with the help of the equilibrium constants the extent of aquation at various chloride concentrations of the extra- and intracellular milieu can be predicted. Complexation of these RhIII complexes was compared to analogous [RuII(h6-p-cymene)] species and higher conditional stabilities were found in the case of the RhIII compounds at pH 7.4

Influence of temperature and applied potential on the permeability of polyphenol films prepared on vitreous carbon in acid and alkaline media

The electrochemical polymerization of phenol is known to rapidly produce a thin insulating film at the anode surface. This film generally blocks further polymerization. The objective of this study is to show that, depending on the operating conditions, polymeric films resulting from phenol oxidation present different properties and that certain films can be so porous that they allow the oxidation of phenol to continue. The deposition of polyphenol films with improved permeability could be attractive in the removal of phenol from polluted solutions. Polyphenol films were prepared in aqueous solution on a vitreous carbon anode either by cyclic voltammetry or by electro-oxidation at constant potential. The apparent permeability P (%) of the films prepared by these techniques was evaluated by monitoring changes in the electrode response towards phenol and potassium ferricyanide at 25 and 85°C and as a function of the potential applied during electropolymerization performed either in acidic (1 mol L-¹H₂SO₄) or in alkaline (1 mol L-¹ NaOH) aqueous solution. It was shown that: (1) the polyphenol film electrosynthesized in alkaline medium was more permeable than that prepared in acidic medium, (2) the apparent permeability was higher when the polyphenol film was electrosynthesized with simultaneous oxygen evolution and (3) the use of a high temperature in the polyphenol film preparation, especially in the presence of a concomitant oxygen evolution, significantly enhanced its apparent permeability (P ≥ 100 %). These results are interpreted in terms of a mixed-transport mechanism involving both pore and membrane diffusion. The effect of the permeability of the polymeric film on the removal of phenol from aqueous solution by electropolymerization is discussed

Influence of temperature and applied potential on the permeability of polyphenol films prepared on vitreous carbon in acid and alkaline media

The electrochemical polymerization of phenol is known to rapidly produce a thin insulating film at the anode surface. This film generally blocks further polymerization. The objective of this study is to show that, depending on the operating conditions, polymeric films resulting from phenol oxidation present different properties and that certain films can be so porous that they allow the oxidation of phenol to continue. The deposition of polyphenol films with improved permeability could be attractive in the removal of phenol from polluted solutions. Polyphenol films were prepared in aqueous solution on a vitreous carbon anode either by cyclic voltammetry or by electro-oxidation at constant potential. The apparent permeability P (%) of the films prepared by these techniques was evaluated by monitoring changes in the electrode response towards phenol and potassium ferricyanide at 25 and 85°C and as a function of the potential applied during electropolymerization performed either in acidic (1 mol L-¹H₂SO₄) or in alkaline (1 mol L-¹ NaOH) aqueous solution. It was shown that: (1) the polyphenol film electrosynthesized in alkaline medium was more permeable than that prepared in acidic medium, (2) the apparent permeability was higher when the polyphenol film was electrosynthesized with simultaneous oxygen evolution and (3) the use of a high temperature in the polyphenol film preparation, especially in the presence of a concomitant oxygen evolution, significantly enhanced its apparent permeability (P ≥ 100 %). These results are interpreted in terms of a mixed-transport mechanism involving both pore and membrane diffusion. The effect of the permeability of the polymeric film on the removal of phenol from aqueous solution by electropolymerization is discussed

Bis(1H+-pyrazinium N4-oxide) Dichromate

2C₄H₅N₂O⁺.Cr₂O²₇⁻, Mᵣ=410∙2, monoclinic, P2₁, a=8∙(2), b=6∙132 (2), c=14∙493 (4) Å, β=94∙50 (2)°, V=708∙8 (3) ų, Z=2, Dₓ=1∙92 g cm⁻³, Mο Κα, λ=0∙71069 Å, μ=15∙5 cm⁻¹, F(000)=412, T=293 K, R=0∙0602 for 1980 unique observed reflections with F≥3σ(F). The structure consists of discrete dinegative dichromate anions hydrogen bonded to monopositive pyrazinium N-oxide cations (N―H∙∙∙O=2∙724, 2∙644 Å). A strong hydrogen bond to the bridging O atom in the Cr₂O²₇⁻ anion leads to significant lengthening of the bridging Cr―O bonds. A short C―H∙∙∙O interaction (3∙180 Å) is also observed