Redetermination of the O-O bond length in the dioxygen-adduct of Vaska’s complex

Solid state structural studies were performed with (Ph₃P)₂IrCl(CO)(O₂) and the O-O length redetermined to be 1.47(1) Å in contrast to results reported earlier.     

Crystal structure,vibrational spectra and thermal decomposition study of a new,dicationic, acidic pyrophosphate: KHMgP<Subscript>2</Subscript>O<Subscript>7</Subscript>⋅2H<Subscript>2</Subscript>O

Colourless crystals of a new, dicationic, hydropyrophosphate dihydrate salt, KHMgP₂O₇⋅ 2H₂O, are formed, when a mixture of aqueous equimolar solutions of MgCl₂⋅4H₂O and K₄P₂O₇, at pH 2.12, are left to stand at ambient temperature for 4 days. The new pyrophosphate salt has been characterized by single-crystal X-ray diffraction, IR and Raman spectra, and DSC-TG thermal analysis. The structure consists of alternating layers of [HP₂O₇]³⁻ groups and MgO₆ octahedra, joined by K⁺ ions and bridging hydrogen bonds. The [P₂O₇]⁴⁻ anions exhibit a bent eclipsed conformation. The absence of coincidences for the majority of the IR and Raman bands is in accord with the centrosymmetric structure of the material. The ³¹P chemical shift tensor components have been determined from the solid-state MAS NMR spectra. The structural changes occurring during thermal decomposition have been examined by TG-DSC, X-ray powder diffraction (XRD) and IR spectroscopy. When the new pyrophosphate salt is heated gradually, it first becomes amorphous and then condenses to chain metaphosphates.     

Crystal structure and solid-state31P CP-MAS NMR spectrum of the bis(trifluoroacetato) (triphenylphosphine)mercury(II) dimer [Hg(CF3CO2)2PPh3]2

The title compound belongs to the monoclinic space groupP2₁/c,a=20.29(1),b=12.644(8),c=18.25(1), Å,=95.76(5)°. The unit cell contains two dimeric [Hg(CF₃CO₂)₂PPh₃]₂ molecules in which each Hg atom forms strong primary bonds to a PPh₃ molecule and an oxygen of a monodentate trifluoroacetate ligand. These two Hg atoms are bridged by two extra trifluoroacetate ligands, one providing a single oxygen to a Hg-O-Hg bridge, the other including both carboxylate oxygens in a Hg-O-C-O-Hg bridging moiety. This unusual type of bridging makes the two halves of the molecule symmetry independent, leading to distinct signals at 31.5 and 29.9 ppm for the phosphines in the³¹P CP-MAS NMR spectrum of the solid complex.     

Geographical variation in residence and risk of multiple nonmelanoma skin cancers in US women and men

Residence in high ultraviolet (UV) locations is associated with increased risk for incident nonmelanoma skin cancer (NMSC). However, the effect of geographic location on multiple NMSC development has not been well studied. We evaluated the association between state of residence at birth, age 15 and 30 and risk of multiple NMSCs among 80275 women and men. After adjusting for age, gender, hair color, number of sunburns, tanning ability, family history of melanoma and nevus count, the cumulative relative risks (RRs) of developing ≥1 NMSC for those consistently residing in medium- and high-UV index states were 1.20 (95% CI 1.14-1.27) and 1.42 (95% CI 1.32-1.53) respectively. We found that compared to individuals with one lifetime NMSC, the multivariate cumulative RRs of developing ≥2 NMSCs for those who stayed in medium- and high-UV index states at all three timepoints were 1.09 (95% CI 1.00-1.19) and 1.15 (95% CI 1.02-1.30) respectively. These results cannot account for migration during the interval period and seasonal changes in residence; further, as BCC is the predominant NMSC, the results may be BCC-driven. In conclusion, we found that consistent residence in medium- or high-UVR locations was significantly associated an incremental risk of ≥2 NMSCs later in life.     

Synthesis of a new fluorinated fluorescent β-cyclodextrin sensor

The synthesis of a new fluorescent sensor incorporating a fluorinated indolizine unit bound to 6-amino-β-cyclodextrin by two different synthetic ways is described. Its sensing ability toward adamantanol has been demonstrated.     

Thermal characterization of mangaba-based films

The purpose of this study was to evaluate the physical–chemical properties of starch (SF), mangaba (MF), and mangaba/starch-based films (MSF), using differential thermal analysis, thermogravimetry/derivative thermogravimetry, infrared spectroscopy, mechanical profile, and scanning electron microscopy. The films were prepared by casting process using sucrose and propyleneglycol as plasticizers. The thermal profiles of MF and MSF were similar and showed increased thermal stability. The mechanical properties of MF and MSF presented decreases of tensile strength and elastic modulus when compared with SF. The MSF showed the best thermal and mechanical characteristics.     

Symbiotic signaling in actinorhizal symbioses

Actinorhizal symbioses are mutualistic associations between plants belonging to eight angiosperm families and soil bacteria of the genus Frankia. These interactions lead to the formation of new root organs, actinorhizal nodules, where the bacteria are hosted and fix atmospheric nitrogen thus providing the plant with an almost unlimited source of nitrogen for its nutrition. It involves an elaborate signaling between both partners of the symbiosis. In recent years, our knowledge of this signaling pathway has increased tremendously thanks to a series of technical breakthroughs including the sequencing of three Frankia genomes [1] and the implementation of RNA silencing technology for two actinorhizal species. In this review, we describe all these recent advances, current researches on symbiotic signaling in actinorhizal symbioses and give some potential future research directions.     

Nineteenth century roots of quasideterminants

In this expository paper I provide a complete record of the nineteenth century publications that bear on the development of quasideterminants in the twentieth century. Two important recursive feasible algorithms, Sylvester’s from 1851 and Dodgson’s from 1866 are discussed, and the antecedents of both are traced back to work by Jacobi.