Selenite Downregulates STAT3 Expression and Provokes Lymphocytosis in the Liver of Chronically Exposed Syrian Golden Hamsters

Arsenic is considered a worldwide pollutant that can be present in drinking water. Arsenic exposure is associated with various diseases, including cancer. Antioxidants as selenite and α-tocopherol-succinate have been shown to modulate arsenic toxic effects. Since changes in STAT3 and PSMD10 gene expression have been associated with carcinogenesis, the aim of this study was to evaluate the effect of arsenic exposure and co-treatments with selenite or α-tocopherol-succinate on the expression of these genes, in the livers of chronically exposed Syrian golden hamsters. Animals were divided into six groups: (i) control, (ii) chronically treated with 100 ppm arsenic, (iii) treated with 6 ppm α-tocopherol-succinate (α-TOS), (iv) treated with 8.5 ppm selenite, (v) treated with arsenic + α-TOS, and (vi) treated with arsenic + selenite. Urine samples and livers were collected after 20 weeks of continuous exposure. The urine samples were analyzed for arsenic species by atomic absorption spectrophotometry, and real-time RT-qPCR analysis was performed for gene expression evaluation. A reduction in STAT3 expression was observed in the selenite-treated group. No differences in PSMD10 expression were found among groups. Histopathological analysis revealed hepatic lymphocytosis in selenite-treated animals. As a conclusion, long-term exposure to arsenic does not significantly alter the expression of STAT3 and PSMD10 oncogenes in the livers of hamsters; however, selenite down-regulates STAT3 expression and provokes lymphocytosis.     

Synthesis and properties of [NiCp*(2,5-tBu2PC4H2)], a 20-valence-electron phosphanickelocene

The reaction of the bulky phospholide salt Li(2,5-tBu2PC4H2) x 2THF (1; THF = tetrahydrofuran) with [NiCp*(acac)] (HCp* = pentamethylcyclopentadiene, Hacac = acetylacetone) gives the green air-sensitive phosphanickelocene [NiCp*(2,5-tBu2PC4H2)] (2) in yields of about 85%. An X-ray structural determination of 2 shows long Ni-ring bonds and "delocalised" ring P-C and C-C bonds characteristic of a classical 20-valence-electron (ve) nickelocene. The electronic structure of 2 has been clarified through a combined Amsterdam density functional (ADF) and photoelectron spectroscopic study, which indicates that the higher lying semi-occupied molecular orbital (SOMO) (-5.82 eV) has a' symmetry and that the phosphorus "lone pair" is energetically low-lying (-8.15 eV). Oxidation of phosphanickelocene 2 by AgBF4 occurs quantitatively to give the corresponding air-sensitive orange phosphanickelocenium salt [NiCp*(2,5-tBu2PC4H2)][BF4] (3). This complex has also been characterised by an X-ray crystallographic study, which reveals long Ni-C(alpha) and short C(alpha)-C(beta) bonds in the phospholyl ligand indicative of a SOMO having a' symmetry. PMe3 reacts with 2 at room temperature to provoke a ring-slip reaction that gives the 18ve complex [NiCp*eta1-(2,5-tBu2PC4H2)(PMe3)] (4), but shows no reaction with the phosphanickelocenium salt 3 under the same conditions.     

Dibenzo[a,d]cycloheptenyl dibenzophosphole palladium dichloride: synthesis, X-ray-crystal structure and application in the Suzuki-Miyaura coupling

A highly rigid dibenzo[a,d]cycloheptenyl dibenzophosphole with a pre-organized concave shaped binding site acts as an efficient ligand in the palladium catalyzed Suzuki-Miyaura coupling process between halogenoaromatics and phenylboronic acid.     

A sigma 4, lambda 5-phosphinine palladium complex: a new type of phosphorus ligand and catalyst. Application to the Pd-catalyzed formation of arylboronic esters

A palladium(II) complex of a S-P-S pincer ligand featuring a metallated ylidic P-atom efficiently catalyzes the coupling between pinacolborane and various iodoaryls to yield the corresponding arylboronic esters (TON between 5100 and 76,500).     

Preparation of polymer-bound 1,2 - and 1,3 - diamines

Two modified copolymers were used for the preparation of polymer bound symmetrical aliphatic diamines using phase transfer catalysis (P.T.C.). These compounds are potential ligands for transition metal ions.     

The role of photodarkening and Auger recombination in the dynamics of the optical response for Cd(S,Se) nanoparticles

We first recall the main linear optical properties of semiconductor-doped glasses in the strong confinement regime. We then discuss the origin of the photodarkening effect and its consequences on the luminescence and absorption spectra. Photodarkening and, at high excitation intensity, Auger processes strongly modify carrier recombination as studied by time-resolved luminescence measurements. This is further supported by using nonlinear optical techniques such as optical phase conjugation. We finally recall the origin of the nonlinear response of such media in the resonant regime and the size dependence of the corresponding figure of merit.     

Synthesis and resolution of the planar chirality of ester-functionalised phospharuthenocenes

Menthyl phospholide ester anions provide an operationally simple and high yielding entry to the first planar chiral enantiopure phospharuthenocene derivatives.     

Diphosphines with expandable bite angles: highly active ethylene dimerisation catalysts based on upper rim, distally diphosphinated calix[4]arenes

The binding properties of two large diphosphines, cone-5,17-dibromo-11,23-bis(diphenylphosphino)-25,26,27,28-tetrapropoxycalix[4]arene (1) and cone-5,17-bis(diphenylphosphino)-25,26,27,28-tetrapropoxycalix[4]arene (2) toward Ni(II) centres have been investigated. Whatever the starting complex, NiBr2 or [NiCp]BF4, quantitative formation of a chelate complex was observed, illustrating the preorganisation of the ligands. An X-ray structure determination was carried out for [NiCp1]BF4 which revealed that the nickel atom is positioned to one side of the calixarene axis, the PNiP plane being roughly parallel to the calixarene reference plane. The molecule has C(1) symmetry in the solid state, a feature which is also observed in solution at low temperature. As shown by variable-temperature 1H and 31P NMR studies, the complex undergoes two distinct motions: 1) a fan-like swinging of the coordination plane which displaces the metal from one side of the calixarene axis to the other, a motion during which the PNiP angle is likely to undergo a significant enlargement; 2) a rapid oscillation of each PPh2 unit about the corresponding Ni--P bond. In the latter dynamics the two endo-oriented PPh rings alternately occupy the calixarene entry. The two flexible ligands were assessed in ethylene oligomerisation. Activation with methylaluminoxane of the paramagnetic complexes [NiBr2.(1 or 2)] afforded highly active ethylene dimerisation catalysts, with turnover frequencies up to 10(6) (mol C2H4) (mol Ni)(-1) h(-1). The selective formation of 1-butene can be rationally controlled by using low catalyst concentrations.