A bacteria-specific 2[4Fe-4S] ferredoxin is essential in Pseudomonas aeruginosa

<p>Abstract</p> <p>Background</p> <p>Ferredoxins are small iron-sulfur proteins belonging to all domains of life. A sub-group binds two [4Fe-4S] clusters with unequal and extremely low values of the reduction potentials. These unusual properties are associated with two specific fragments of sequence. The functional importance of the very low potential ferredoxins is unknown.</p> <p>Results</p> <p>A bioinformatic screening of the sequence features defining very low potential 2[4Fe-4S] ferredoxins has revealed the almost exclusive presence of the corresponding <it>fdx </it>gene in the <it>Proteobacteria </it>phylum, without occurrence in <it>Archaea </it>and <it>Eukaryota</it>. The transcript was found to be monocistronic in <it>Pseudomonas aeruginosa</it>, and not part of an operon in most bacteria. Only <it>fdx </it>genes of bacteria which anaerobically degrade aromatic compounds belong to operons. As this pathway is not present in all bacteria having very low potential 2[4Fe-4S] ferredoxins, these proteins cannot exclusively be reductants of benzoyl CoA reductases. Expression of the ferredoxin gene did not change in response to varying growth conditions, including upon macrophage infection or aerobic growth with 4-hydroxy benzoate as carbon source. However, it increased along the growth curve in <it>Pseudomonas aeruginosa </it>and in <it>Escherichia coli</it>. The sequence immediately 5' upstream of the coding sequence contributed to the promotor activity. Deleting the <it>fdx </it>gene in <it>Pseudomonas aeruginosa </it>abolished growth, unless a plasmid copy of the gene was provided to the deleted strain.</p> <p>Conclusions</p> <p>The gene of the very low potential 2[4Fe-4S] ferredoxin displays characteristics of a housekeeping gene, and it belongs to the minority of genes that are essential in <it>Pseudomonas aeruginosa</it>. These data identify a new potential antimicrobial target in this and other pathogenic <it>Proteobacteria</it>.</p

Structurally Diverse Metal Coordination Compounds, Bearing Imidodiphosphinate and Diphosphinoamine Ligands, as Potential Inhibitors of the Platelet Activating Factor

Metal complexes bearing dichalcogenated imidodiphosphinate [R2P(E)NP(E)R2′]− ligands (E = O, S, Se, Te), which act as (E,E) chelates, exhibit a remarkable variety of three-dimensional structures. A series of such complexes, namely, square-planar [Cu{(OPPh2)(OPPh2)N-O, O}2], tetrahedral [Zn{(EPPh2)(EPPh2)N-E,E}2], E = O, S, and octahedral [Ga{(OPPh2)(OPPh2)N-O,O}3], were tested as potential inhibitors of either the platelet activating factor (PAF)- or thrombin-induced aggregation in both washed rabbit platelets and rabbit platelet rich plasma. For comparison, square-planar [Ni{(Ph2P)2N-S-CHMePh-P, P}X2], X = Cl, Br, the corresponding metal salts of all complexes and the (OPPh2)(OPPh2)NH ligand were also investigated. Ga(O,O)3 showed the highest anti-PAF activity but did not inhibit the thrombin-related pathway, whereas Zn(S,S)2, with also a significant PAF inhibitory effect, exhibited the highest thrombin-related inhibition. Zn(O,O)2 and Cu(O,O)2 inhibited moderately both PAF and thrombin, being more effective towards PAF. This work shows that the PAF-inhibitory action depends on the structure of the complexes studied, with the bulkier Ga(O,O)3 being the most efficient and selective inhibitor

A Molecular Tetrahedral Cobalt-Seleno-Based Complex as an Efficient Electrocatalyst for Water Splitting

The cobalt-seleno-based coordination complex, [Co{(SePiPr2)2N}2], is reported with respect to its catalytic activity in oxygen evolution and hydrogen evolution reactions (OER and HER, respectively) in alkaline solutions. An overpotential of 320 and 630 mV was required to achieve 10 mA cm-2 for OER and HER, respectively. The overpotential for OER of this CoSe4-containing complex is one of the lowest that has been observed until now for molecular cobalt(II) systems, under the reported conditions. In addition, this cobalt-seleno-based complex exhibits a high mass activity (14.15 A g-1) and a much higher turn-over frequency (TOF) value (0.032 s-1) at an overpotential of 300 mV. These observations confirm analogous ones already reported in the literature pertaining to the potential of molecular cobalt-seleno systems as efficient OER electrocatalysts

The novel [Ni{(Ph2P)2N(CH2)3Si(OCH3)3-P,P´}I2] complex: Structural features and catalytic reactivity in the oligomerization of ethylene

The novel [Ni{(Ph2P)2N(CH2)3Si(OCH3)3-P,P´}I2] complex (1) was synthesized and investigated by a variety of spectroscopic methods (IR, 1H and 31P NMR). The molecular structure of 1, determined by single crystal X-ray diffraction, was compared with those of the analogue [Ni{(Ph2P)2N(CH2)3Si(OCH3)3-P,P´}Cl2] complex (2) and the recently reported [Ni{iCPrP)2NH-P,P´}I2] complex. Complexes 1 and 2 were tested as homogeneous catalysts for the oligomerization of ethylene, leading to the formation of C4 and, to a smaller extent, C6 products, in moderate yields

Some Unsymmetrical Metal 1,2-Dithiolenes Based on Palladium, Platinum and Gold

The unsymmetrical complexes Pd(dpedt)(dddt). Pt(dpedt)(dddt), Pd(dpedt)(dmit), and Au(dpedt)-(dddt) (where dpedt is diphenyl-ethylenedithiolate, dddt is 5,6-dihydro-1,4-dithin-2,3-dithiolate and dmit is 1,3-dithiol-2-thione-4,5-dithiolate) were prepared and characterized. The study of their chemical and electrochemical behavior showed that they are stable in air and could be candidate materials for fabrication of field-effect transistors and other devices

A Molecular Tetrahedral Cobalt–Seleno-Based Complex as an Efficient Electrocatalyst for Water Splitting

The cobalt–seleno-based coordination complex, [Co{(SePiPr2)2N}2], is reported with respect to its catalytic activity in oxygen evolution and hydrogen evolution reactions (OER and HER, respectively) in alkaline solutions. An overpotential of 320 and 630 mV was required to achieve 10 mA cm−2 for OER and HER, respectively. The overpotential for OER of this CoSe4-containing complex is one of the lowest that has been observed until now for molecular cobalt(II) systems, under the reported conditions. In addition, this cobalt–seleno-based complex exhibits a high mass activity (14.15 A g−1) and a much higher turn-over frequency (TOF) value (0.032 s−1) at an overpotential of 300 mV. These observations confirm analogous ones already reported in the literature pertaining to the potential of molecular cobalt–seleno systems as efficient OER electrocatalysts