Continuous flow hydroformylation using supported ionic liquid phase catalysts with carbon dioxide as a carrier.

A supported ionic liquid phase (SILP) catalyst prepared from [PrMIM][Ph2P(3-C6H4SO3)] (PrMIM = 1-propyl-3-methylimidazolium), [Rh(CO)(2)(acac)] (acacH = 2,4-pentanedione) [OctMIM]NTf2 (OctMIM = 1-n-octyl-3-methylimidazolium, Tf = CF3SO2) and microporous silica has been used for the continuous flow hydroformylation of 1-octene in the presence of compressed CO2. Statistical experimental design was used to show that the reaction rate is neither much affected by the film thickness (IL loading) nor by the syngas: substrate ratio. However, a factor-dependent interaction between the syngas: substrate ratio and film thickness on the reaction rate was revealed. Increasing the substrate flow led to increased reaction rates but lower overall yields. One of the most important parameters proved to be the phase behaviour of the mobile phase, which was studied by varying the reaction pressure. At low CO2 pressures or when N-2 was used instead of CO2 rates were low because of poor gas diffusion to the catalytic sites in the SILP. Furthermore, leaching of IL and Rh was high because the substrate is liquid and the IL had been designed to dissolve in it. As the CO2 pressure was increased, the reaction rate increased and the IL and Rh leaching were reduced, because an expanded liquid phase developed. Due to its lower viscosity the expanded liquid allows better transport of gases to the catalyst and is a poorer solvent for the IL and the catalyst because of its reduced polarity. Above 100 bar (close to the transition to a single phase at 106 bar), the rate of reaction dropped again with increasing pressure because the flowing phase becomes a better and better solvent for the alkene, reducing its partitioning into the IL film. Under optimised conditions, the catalyst was shown to be stable over at least 40 h of continuous catalysis with a steady state turnover frequency (TOF, mol product (mol Rh)(-1)) of 500 h(-1) at low Rh leaching (0.2 ppm). The selectivity of the catalyst was not much affected by the variation of process parameters. The linear: branched (1:b) ratios were ca. 3, similar to that obtained using the very same catalyst in conventional organic solvents.

The RET mutation E768D confers a late-onset Familial medullary thyroid carcinoma - only phenotype with incomplete penetrance: Implications for screening and management of carrier status

Objective: We describe a 4-generation family with familial medullary thyroid carcinoma (FMTC) - a variant of multiple endocrine neoplasia type 2 (MEN 2) without extra-thyroid features. RET mutation analysis confirmed an E768D mutation in exon 13 in 8 family members, 3 affected with medullary thyroid cancer alone while the other 5 were detected to be mutation carriers. This mutation has been described in very few families worldwide and the spectrum of disease and natural history is unclear. Results: Three affected members had medullary thyroid cancer (MTC) confirmed histologically at ages 25, 50 and 56 years, respectively. The E768D mutation appears to have a less aggressive clinical course compared to other high risk RET mutations with no evidence of clinical recurrence up to I I years after initial therapy. Of five gene carriers identified, two are asymptomatic at the age of 70 and 61, and three had raised calcitonin levels at 46, 39, and 45 years. Following total thyroidectomy, one gene carrier had a histologically normal thyroid at age 46, following a mildly elevated calcitonin, one had C-cell hyperplasia at the age of 39, and one had a frank focus of carcinoma in the left thyroid lobe at the age of 45. No members had evidence of phaeochromocytoma or parathyroid disease on screening. Conclusion: The RET E768D mutation is associated with MTC with a later age at presentation, incomplete penetrance and less aggressive course compared with other high risk RET mutations. To date in this family the E768D mutation has not been associated with either phaeochromocytoma or hyperparathyroidism. The appropriate screening strategy for and management of E768D carriers is difficult reflecting the phenotypic heterogeneity.

Travelling Images, Images of Travel in Nicolas Bouvier's L'Usage du monde

Sketches and photographs are a familiar tool of the traveller-writer, who commonly draws on them when transforming experience into a textual narrative. The verbal thus displaces the visual — the latter retained, if at all, as mere illustration — in ways that echo James Heffernan's definition of ekphrasis as the ‘verbal description of visual representation’. Yet Nicolas Bouvier's 1963 travel narrative L'Usage du monde challenges conventional conceptions of ekphrasis. Juxtaposing the stark ink drawings of Thierry Vernet — Bouvier's travelling companion — with Bouvier's textual narrative, L'Usage du monde shifts representation away from a hierarchical relationship between verbal and visual; it offers instead an account of other cultures that is grounded in polyphony and exchange. This article applies Bouvier's own image of travel as a mosaic to the dual narrative form (or ‘iconotext’, to use Michael Nerlich's term) in order to consider a range of fluid relationships between Bouvier's text and Vernet's drawings. In examining these relationships of amplification, reduction, and absence, the article argues that the plurality of the narrative prompts a rethinking of conventional, binary paradigms of intercultural contact. Ultimately, the iconotextual nature of L'Usage du monde can be interpreted as a metaphor for the processes of cultural translation and transculturation that are central to Bouvier's travelling ethos.

Low-complexity iterative method of equalization for single carrier with cyclic prefix in doubly selective channels

Orthogonal frequency division multiplexing (OFDM) requires an expensive linear amplifier at the transmitter due to its high peak-to-average power ratio (PAPR). Single carrier with cyclic prefix (SC-CP) is a closely related transmission scheme that possesses most of the benefits of OFDM but does not have the PAPR problem. Although in a multipath environment, SC-CP is very robust to frequency-selective fading, it is sensitive to the time-selective fading characteristics of the wireless channel that disturbs the orthogonality of the channel matrix (CM) and increases the computational complexity of the receiver. In this paper, we propose a time-domain low-complexity iterative algorithm to compensate for the effects of time selectivity of the channel that exploits the sparsity present in the channel convolution matrix. Simulation results show the superior performance of the proposed algorithm over the standard linear minimum mean-square error (L-MMSE) equalizer for SC-CP.

Travelling wave chirped pulse amplified transient pumping for collisional excitation lasers

A similar to 3 ps travelling wave chirped pulse amplified pulse at 6 x 10(14) W cm(-2) superimposed on similar to 300 ps background pulses is shown to be an efficient method to pump transient collisional excitation X-ray lasers in both Ni-like and Ne-like ions. Measurements of X-ray laser output as a function of plasma length are fitted with results of an amplified spontaneous emission model of the laser output taking account of travelling wave pumping effects. A small signal gain coefficient similar to 42 cm(-1) and a effective gain length product of similar to 18 are measured for the Ni-like Sn laser at 120 Angstrom. Simulations from a hydrodynamic and atomic physics code (EHYBRID) coupled to a ray trace code show that a spatially averaged small signal gain similar to 65 cm(-1) can be obtained in Ne-like Ge provided the optimum pumping pulse arrangement is used. (C) 1999 Elsevier Science B.V. All rights reserved.