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.

Help or hindrance? Supplier involvement and causal ambiguity within inter-organisational NPD teams

Suppliers are increasingly involved in buyer firms’ interorganizational new product development (NPD) teams. Yet the transfer of knowledge within this context may be subject to varying degrees of causal ambiguity, potentially limiting the effect of supplier involvement on performance. We develop a theoretical model exploring the effect of supplier involvement practices on the level of causal ambiguity within interorganizational NPD teams, and the subsequent impact on competitor imitation, new product advantage, and project performance. Our model also serves as a test of the paradox that causal ambiguity both inhibits imitation by competitors, but also adversely affects organisational outcomes. Results from an empirical study of 119 R&D intensive manufacturing firms in the United Kingdom largely support these hypotheses. Results from structural equation modeling show that supplier involvement orientation and long-term commitment lower causal ambiguity within interorganizational NPD teams. In turn, this lower causal ambiguity generates a new product advantage and increases project performance for the buyer firm, but has no significant effect on competitor imitation. Instead, competitor imitation is delayed by the extent to which the firm develops a new product advantage within the market. These results shed light on the causal ambiguity paradox showing that lower causal ambiguity during interorganizational new product development increases both product and project performance, but without reducing barriers to imitation. Product development managers are encouraged to utilize supplier involvement practices to minimise ambiguity in the NPD project, and to target their supplier involvement efforts on solving causally ambiguous technological problems to sustain a competitive advantage.

Tracking leatherback turtles (Dermochelys coriacea) during consecutive inter-nesting intervals: Further support for direct transmitter attachment

Over recent years there have been substantial efforts to record and interpret the post-nesting movements of leatherback turtles (Dermochelys coriacea) breeding in tropical regions. Less well documented are the movements undertaken by individual turtles during the breeding season itself, or more specifically between sequential nesting events. Such movements are of interest for two reasons: (1) gravid female leatherbacks may range extensively into the territorial waters and nesting beaches of neighbouring countries, raising questions for conservationists and population ecologists; and (2) the magnitude of movements themselves help elucidate underlying reproductive strategies (e.g. whether to rest near to the nesting or forage extensively). Here, satellite relay data loggers are used (SRDLs) to detail the movements and behaviour of two female leatherback turtles throughout three consecutive inter-nesting intervals in the Commonwealth of Dominica, West Indies. Both near-shore residence and extensive inter-nesting movements were recorded, contrasting previous studies, with movements away from the nesting beach increasing towards the end of the nesting season. Using this behavioural study as a backdrop, the suitability of attaching satellite transmitters directly to the carapace was additionally explored as an alternative approach to conventional harness deployments. Specifically, the principal aims were to (1) gather empirical data on speed of travel and (2) assess dive performance (aerobic dive limit) to enable comparisons with turtles previously fitted with harnesses elsewhere in the Caribbean (n = 6 turtles; Grenada, WI). This produced mixed results with animals bearing directly attached transmitters travelling significantly faster (55.21 km day(-1): SD 6.68) than harnessed individuals (39.80 km day(-1); SD 6.19); whilst no discernable difference in dive performance could be found between the two groups of study animals. (C) 2009 Elsevier B.V. All rights reserved.

Distribution, extent of inter-annual variability and diet of the bloom-forming jellyfish Rhizostoma in European waters

Jellyfish (Cnidaria: Scyphozoa) are increasingly thought to play a number of important ecosystem roles, but often fundamental knowledge of their distribution, seasonality and inter-annual variability is lacking. Bloom forming species, due to their high densities, can have particularly intense trophic and socio-economic impacts. In northern Europe it is known that one particularly large (up to 30 kg wet weight) bloom forming jellyfish is Rhizostoma spp. Given the potential importance, we set out to review all known records from peer-reviewed and broader public literature of the jellyfish R. octopus (Linnaeus) and R. pulmo (Macri) (Scyphozoa: Rhizostomae) across western Europe. These data revealed distinct hotspots where regular Rhizostoma spp. aggregations appeared to form, with other sites characterized by occasional abundances and a widespread distribution of infrequent observations. Surveys of known R. octopus hotspots around the Irish Sea also revealed marked inter-annual variation with particularly high abundances forming during 2003. The location of such consistent aggregations and inter-annual variances are discussed in relation to physical, climatic and dietary variations.

Double-Electron Above-Threshold Ionization Resonances as Interference Phenomena

We report calculations of double ionization energy spectra and momentum distributions of laser-driven helium due to few-cycle pulses of wavelength 195 nm. The results are obtained from full-dimensional numerical integration of the two electron time-dependent Schr¨odinger equation. A momentum-space analysis of doubly ionizing wavepackets shows that the concentric-ring structure of above-threshold double ionization, together with the associated structure of peaks in the total kinetic energy spectrum, may be attributed to wavepacket interference effects, where at least two doubly-ionizing wavepackets from different recollision events populate the same spatial hemisphere.

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.

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.

Approaching near-capacity on a multi-antenna channel using successive decoding and interference cancellation receivers

In this paper, we address the problem of designing multirate codes for a multiple-input and multiple-output (MIMO) system by restricting the receiver to be a successive decoding and interference cancellation type, when each of the antennas is encoded independently. Furthermore, it is assumed that the receiver knows the instantaneous fading channel states but the transmitter does not have access to them. It is well known that, in theory, minimum-mean-square error (MMSE) based successive decoding of multiple access (in multi-user communications) and MIMO channels achieves the total channel capacity. However, for this scheme to perform optimally, the optimal rates of each antenna (per-antenna rates) must be known at the transmitter. We show that the optimal per-antenna rates at the transmitter can be estimated using only the statistical characteristics of the MIMO channel in time-varying Rayleigh MIMO channel environments. Based on the results, multirate codes are designed using punctured turbo codes for a horizontal coded MIMO system. Simulation results show performances within about one to two dBs of MIMO channel capacity.