New Ni(II), Pd(II) and Pt(II) complexes coordinated to azo pyrazolone ligand with a potent anti‐tumor activity: Synthesis,characterization, DFT and DNA cleavage studies

The absolute necessity to fight some class of tumor is perceived as serious health concerns, so the discovery and development of effective anticancer agents are urgently needed. (E)‐4‐((2‐hydroxyphenyl)diazenyl)‐3‐phenyl‐1H‐pyrazol‐5(4H)‐one, HL, and its Ni(II), Pd(II) and Pt(II) complexes were synthesized and the biological activity was evaluated for antitumor, antioxidant and antimicrobial activity as well as DNA cleavage. Their structures were assigned depending on the elemental analysis, conductivity, magnetic moment, spectral measurements (IR, ¹HNMR, mass and UV–Vis) and thermal analysis. 3D molecular modeling using DFT method confirmed that the geometrical structures agree well with the suggested experimental ones. The antitumor activity was evaluated against four different cell lines using MTT assay. The ligand HL showed a potent cytotoxic activity compared to 5‐fluorouracil as a reference drug. For metal complexes, the order of activity was: Pd(II) > Ni(II) > Pt(II). A remarkable antioxidant activity for the ligand HL was recorded. It was higher than that of the metal complexes. Results of antimicrobial experiments revealed that all compounds were moderate to highly active against selected bacterial strains but inactive as antifungal except Pd(II) which showed a moderate antifungal activity. Gel electrophoresis showed insignificant nucleases activity for the ligand or its metal complexes even in the presence of H₂O₂ providing protection of DNA from damage. The antitumor activity of our compounds may be not due to DNA cleavage but may be referred to a mechanism similar to that of 5‐fluorouracil which interfere with DNA replication. The present work suggests the use of this ligand in the design and development of new anticancer drugs.     

Exact analytical solution for a thermal boundary layer in a saturated porous medium

The forced convection thermal boundary layer in a porous medium as an analytically tractable special case of a mixed convection problem is considered. It is shown that some general features of the mixed convection solutions reported recently by other authors [B. Brighi, J.-D. Hoernel, On the concave and convex solutions of mixed convection boundary layer approximation in a porous medium, Appl. Math. Lett. (published online, 2005); M. Guedda, Multiple solutions of mixed convection boundary layer approximations in a porous medium, Appl. Math. Lett. (published online, 2005)] can already be recovered from this exactly solvable case.     

Biotransformation of soy flour isoflavones by Aspergillus niger NRRL 3122 β-glucosidase enzyme

β-glucosidase enzyme produced from Aspergillus niger NRRL 3122 has been partially purified and characterised. Its molecular weight was 180 KDa. The optimal pH and temperature were 3.98 and 55 °C, respectively. It promoted the hydrolysis of soy flour isoflavone glycosides to their aglycone. Two-level Plackett–Burman design was applied and effective variables for genistein production were determined. Reaction time had a significant positive effect, and pH had a significant negative effect. They were further evaluated using Box–Behnken model. Accordingly, the optimal combination of the major reaction affecting factors was reaction time, 5 h and pH, 4. The concentration of genistein increased by 11.73 folds using this optimal combination. The antioxidant activity of the non-biotransformed and biotransformed soy flour extracts was determined by DPPH method. It was found that biotransformation increased the antioxidant activity by four folds.     

Energy transfer pathways in dinuclear heteroleptic polypyridyl complexes: through-space vs through-bond interaction mechanisms

A series of homo- and heteronuclear ruthenium and osmium polypyridyl complexes with the bridging ligands 1,3-bis(5-(2-pyridyl)-1H-1,2,4-triazol-3-yl)benzene (H(2)mL) and 1,4-bis(5-(2-pyridyl)-1H-1,2,4-triazol-3-yl)benzene (H(2)pL) are reported. The photophysical properties of these compounds are investigated, and particular attention is paid to the heteronuclear (RuOs) compounds, which exhibit dual emission. This is in contrast to phenyl-bridged polypyridine Ru-Os complexes with a similar metal-metal distance, in which the Ru emission is strongly quenched because the nature of the bridging ligand allows for an efficient through-bond coupling. The results obtained for the compounds reported here suggest that energy transfer is predominantly taking place via a dipole-dipole, F?rster type, mechanism, that may dominate when through-bond coupling is weak. This is in stark contrast to ground state interaction, which is found to be critically dependent on the nature of the bridging unit employed.     

Monitoring photodynamic therapy of localized infections by bioluminescence imaging of genetically engineered bacteria

The increasing occurrence of multi-antibiotic resistant microbes has led to the search for alternative methods of killing pathogens and treating infections. Photodynamic therapy (PDT) uses the combination of non-toxic dyes and harmless visible light to produce reactive oxygen species that can kill mammalian and microbial cells. Although the photodynamic inactivation of bacteria has been known for over a hundred years, its use to treat infections has not been much developed. This may be partly due to the difficulty of monitoring the effectiveness of PDT in animal models of infection. In order to facilitate this monitoring process, we have developed a procedure that uses bioluminescent genetically engineered bacteria and a light sensitive imaging system to allow real-time visualization of infections. When these bacteria are treated with PDT in vitro, the loss of luminescence parallels the loss of colony-forming ability. We have developed several models of infections in wounds and soft-tissue abscesses in mice that can be followed by bioluminescence imaging. The size and intensity of the infection can be sequentially monitored in a non-invasive fashion in individual mice in real-time. When photosensitizers are introduced into the infected tissue followed by illumination with red light, a light-dose dependent loss of luminescence is seen. If the bacterium is invasive, the loss of luminescence correlates with increased survival of the mice, whilst animals in control groups die of sepsis within five days. Healing of the PDT treated wounds is not impaired and may actually be improved. This approach can allow many animal models of localized infections to be accurately monitored for efficacy of treatment by PDT.     

Accurate Ab Initio Calculations for LiH and its Ions, LiH+ and LiH−

Ab initio calculations were performed for LiH using a pseudopotential approach with CPP corrections and huge basis sets on both atoms. A wide range of ^1,3Σ⁺ electronic adiabatic states have been investigated, from the ground state up to those dissociating into Li(5p)+H. Permanent and transition electric dipole moments are also considered for the first few excited states. Comparison with experiments and recent all-electron calculations, reveals an excellent global accuracy, only the bottom of the ground state being better described by all-electron approaches. Using almost identical basis sets, coupled cluster all-electron calculations are performed for the ground states of LiH⁺, LiH⁻ and LiH. High care has been given to the correct relative position of the asymptotes, allowing for this rather complete set of accurate ab initio data to be useful for further molecular physics studies.     

3-[2-(3,5-dimethylpyrazolyl)] succinic anhydride: Synthone for the synthesis of some heterocycles with potential pharmaceutical activity

Summary Aminolysis of 3-[2-(3,5-dimethylpyrazolyl)] succinic anhydride (1) leads to5. Hydrazine hydrate reacts with1a to give 4-(3,5-dimethylpyrazolyl)-1,2,4,5-tetrahydro-3,6-pyridazindione. The structures were confirmed by IR, MS,¹H and¹³C NMR.

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3-[2-(3,5-Dimethylpyrazolyl)]-succinanhydrid, ein Synthon für die Synthese einiger Heterocyclen mit potentieller pharmazeutisch nutzbarer Aktivität

Zusammenfassung Die Aminolyse von 3-[2-(3,5-Dimethylpyrazolyl)]-succinanhydrid (1) führt zu5. Hydrazinhydrat reagiert mit1a zu 4-(3,5-Dimethylpyrazolyl)-1,2,4,5-tetrahydro-3,6-pyridazindion. Die Strukturen wurden mittels IR, MS,¹H-NMR und¹³C-NMR überprüft.

     

Solid catalysts for the production of fine chemicals: the use of natural phosphate alone and doped base catalysts for the synthesis of unsaturated arylsulfones

The inexpensive natural phosphate, both alone and doped with potassium fluoride, is a new basic catalyst for the synthesis of α,β-unsaturated arylsulfones. Activation by water and benzyltriethylammonium chloride has also been investigated. When using an ammonium salt, natural phosphate doped with potassium fluoride is an excellent solid support for the synthesis of α,β-unsaturated arylsulfones, leading to excellent yields in a few minutes.