Solventless continuous flow homogeneous hydroformylation of 1-octene

The hydroformylation of 1-octene under continuous flow conditions is described. The system involves dissolving the catalyst, made in situ from [ Rh(acac)(CO)(2)] (acacH = 2,4- pentanedione) and [RMIM][TPPMS] ( RMIM = 1-propyl (Pr), 1-pentyl (Pn) or 1-octyl (O)-3-methyl imidazolium, TPPMS = Ph2P(3-C6H4SO3)), in a mixture of nonanal and 1-octene and passing the substrate, 1-octene, together with CO and H-2 through the system dissolved in supercritical CO2 (scCO(2)). [PrMIM][TPPMS] is poorly soluble in the medium so heavy rhodium leaching (as complexes not containing phosphine) occurs in the early part of the reaction. [PnMIM][ PPMS] affords good rates at relatively low catalyst loadings and relatively low overall pressure (125 bar) with rhodium losses <1 ppm, but the catalyst precipitates at higher catalyst loadings, leading to lower reaction rates. [OMIM][ TPPMS] is the most soluble ligand and promotes high reaction rates, although preliminary experiments suggested that rhodium leaching was high at 5-10 ppm. Optimisation aimed at balancing flows so that the level within the reactor remained constant involved a reactor set up based around a reactor fitted with a sight glass and sparging stirrer with the CO2 being fed by a cooled head HPLC pump, 1-octene by a standard HPLC pump and CO/H-2 through a mass flow controller. The pressure was controlled by a back pressure regulator. Using this set up, [OMIM][ TPPMS] as the ligand and a total pressure of 140 bar, it was possible to control the level within the reactor and obtain a turnover frequency of ca. 180 h(-1). Rhodium losses in the optimised system were 100 ppb. Transport studies showed that 1-octene is preferentially transported over the aldehydes at all pressures, although the difference in mol fraction in the mobile phase was less at lower pressures. Nonanal in the mobile phase suppresses the extraction of 1-octene to some extent, so it is better to operate at high conversion and low pressure to optimise the extraction of the products relative to the substrate. CO and H2 in the mobile phase also suppress the extraction effciency by as much as 80%.

Psychological status of patients referred for orthognathic correction of skeletal II and III discrepancies

Objective: To establish the extent of psychological problems among patients who require orthognathic treatment. Materials and Methods: Five aspects of psychological functioning were assessed for 162 patients who required orthognathic treatment and compared with 157 control subjects.

Results: Analysis of variance did not detect any significant difference in the five psychological scores recorded for the skeletal II, skeletal III, and control groups. The proportion of subjects with one or more psychological measure beyond the normal range was 27% for skeletal II subjects, 25% for skeletal III subjects, and 26% for control subjects. One skeletal II subject (1.5%), three skeletal III subjects (3%), and five control subjects (3%) required referral for psychological counseling.

Conclusions: The orthognathic patients did not differ significantly from the control subjects in their psychological status. © 2010 by The EH Angle Education and Research Foundation, Inc.

Cue Competition Effects and Young Children's Causal and Counterfactual Inferences

The authors examined cue competition effects in young children using the blicket detector paradigm, in which objects are placed either singly or in pairs on a novel machine and children must judge which objects have the causal power to make the machine work. Cue competition effects were found in a 5- to 6-year-old group but not in a 4-year-old group. Equivalent levels of forward and backward blocking were found in the former group. Children's counterfactual judgments were subsequently examined by asking whether or not the machine would have gone off in the absence of I of 2 objects that had been placed on it as a pair. Cue competition effects were demonstrated only in 5- to 6-year-olds using this mode of assessing causal reasoning.

Breit-Pauli R-matrix calculation of fine-structure effective collision strengths for the electron impact excitation of Mg V

Context. Electron-impact excitation collision strengths are required for the analysis and interpretation of stellar observations.
Aims. This calculation aims to provide effective collision strengths for the Mg V ion for a larger number of transitions and for a greater temperature range than previously available, using collision strength data that include contributions from resonances.
Methods. A 19-state Breit-Pauli R-matrix calculation was performed. The target states are represented by configuration interaction wavefunctions and consist of the 19 lowest LS states, having configurations 2s22p4, 2s2p5, 2p6, 2s22p33s, and 2s22p33p. These target states give rise to 37 fine-structure levels and 666 possible transitions. The effective collision strengths were calculated by averaging the electron collision strengths over a Maxwellian distribution of electron velocities.
Results. The non-zero effective collision strengths for transitions between the fine-structure levels are given for electron temperatures in the range = 3.0 - 7.0. Data for transitions among the 5 fine-structure levels arising from the 2s22p4 ground state configurations, seen in the UV range, are discussed in the paper, along with transitions in the EUV range – transitions from the ground state 3P levels to 2s2p5?3P levels. The 2s22p4?1D–2s2p5?1P transition is also noted. Data for the remaining transitions are available at the CDS.

Activation of the epidermal growth factor receptor (EGFR) by a novel metalloprotease pathway

Neutrophil Elastase (NE) is a pro-inflammatory protease present at higher than normal levels in the lung during inflammatory disease. NE regulates IL-8 production from airway epithelial cells and can activate both EGFR and TLR4. TACE/ADAM17 has been reported to trans-activate EGFR in response to NE. Here, using 16HBE14o-human bronchial epithelial cells we demonstrate a new mechanism by which NE regulates both of these events. A high molecular weight soluble metalloprotease activity detectable only in supernatants from NE-treated cells by gelatin and casein zymography was confirmed to be meprin alpha by Western immunoblotting. In vitro studies demonstrated the ability of NE to activate meprin alpha, which in turn could release soluble TGFa and induce IL-8 production from 16HBE14o- cells. These effects were abrogated by actinonin, a specific meprin inhibitor. NE-induced IL-8 expression was also inhibited by meprin alpha siRNA. Immunoprecipitation studies detected EGFR/TLR4 complexes in NE-stimulated cells overexpressing these receptors. Confocal studies confirmed colocalization of EGFR and TLR4 in 16HBE14o- cells stimulated with meprin alpha. NF?B was also activated via MyD88 in these cells by meprin alpha. In bronchoalveolar lavage fluid from NE knock-out mice infected intra-tracheally with Pseudomonas aeruginosa meprin alpha was significantly decreased compared with control mice, and was significantly increased and correlated with NE activity, in bronchoalveolar lavage fluid from individuals with cystic fibrosis but not healthy controls. The data describe a previously unidentified lung metalloprotease meprin alpha, and its role in NE-induced EGFR and TLR4 activation and IL-8 production.

The Low Density Transiting Exoplanet WASP-15b

We report the discovery of a low-density exoplanet transiting an 11th magnitude star in the Southern hemisphere. WASP-15b, which orbits its host star with a period P = 3.7520656 ± 0.0000028 d, has a mass M p = 0.542 ± 0.050 M J and radius R p = 1.428 ± 0.077 R J, and is therefore one of the least dense transiting exoplanets so far discovered (?p = 0.247 ± 0.035 g cm-3). An analysis of the spectrum of the host star shows it to be of spectral type around F5, with an effective temperature T eff = 6300 ± 100 K and [Fe/H] = -0.17 ± 0.11.

FKBPL regulates estrogen receptor signaling and determines response to endocrine therapy

The HSP90 chaperone and immunophilin FKBPL is an estrogen-responsive gene that interacts with estogen receptor a (ERa) and regulates its levels. In this study, we explored the effects of FKBPL on breast cancer proliferation. Breast cancer cells stably overexpressing FKBPL became dependent on estrogen for their growth and were dramatically more sensitive to the antiestrogens tamoxifen and fulvestrant, whereas FKBPL knockdown reverses this phenotype. FKBPL knockdown also decreased the levels of the cell cycle inhibitor p21WAF1 and increased ERa phosphorylation on Ser118 in response to 17ß-estradiol and tamoxifen. In support of the likelihood that these effects explained FKBPL-mediated cell growth inhibition and sensitivity to endocrine therapies, FKBPL expression was correlated with increased overall survival and distant metastasis-free survival in breast cancer patients. Our findings suggest that FKBPL may have prognostic value based on its impact on tumor proliferative capacity and sensitivity to endocrine therapies, which improve outcome.

Migration, human capital accumulation and economic development

We study how the possibility of migration changes the composition of human capital in sending countries, and how this affects development. In our model, growth is driven by productivity growth, which occurs via imitation or innovation. Both activities use the same types of skilled labour as input, albeit with different intensities. Heterogenous agents accumulate skills in response to economic incentives. Migration distorts these incentives, and the accumulation of human capital. This slows down, or even hinders, economic development. The effect is stronger, the farther away the country is from the technological frontier. (C) 2008 Elsevier B.V. All rights reserved.