Phase-Transfer Catalysis in Segmented Flow in a Microchannel: Fluidic Control of Selectivity and Productivity

Precise control over the interfacial area of aqueous and organic slugs in segmented flow in a microchannel reactor provides an attractive means to optimize the yield and productivity of a phase-transfer-catalyzed reaction. Herein, we report the selective alkylation of phenylacetonitrile to the monoalkylated product in a microchannel of 250-mu m internal diameter operated in a continuous and solvent-free manner in the slug-flow regime. The conversion of phenylacetonitrile increased from 40% to 99% as a result of a 97% larger slug surface-to-volume ratio when the volumetric aqueous-to-organic phase flow ratio was raised from 1.0 to 6.1 at the same residence time. The larger surface-to-volume ratio significantly promoted catalyst phase transfer but decreased selectivity because of the simultaneous increase of the rate of the consecutive reaction to the dialkylated product. There exists all Optimum flow ratio with a maximum productivity. Conversion and selectivity in the microchannel reactor were both found to be significantly larger than in a stirred reactor.

Socio-economic inequalities in cerebral palsy prevalence in the United Kingdom: a register-based study

Evidence is unclear as to whether there is a socio-economic gradient in cerebral palsy (CP) prevalence beyond what would be expected from the socio-economic gradient for low birthweight, a strong risk factor for CP. We conducted a population-based study in five regions of the UK with CP registers, to investigate the relationship between CP prevalence and socio-economic deprivation, and how it varies by region, by birthweight and by severity and type of CP. The total study population was 1 657 569 livebirths, born between 1984 and 1997. Wards of residence were classified into five quintiles according to a census-based deprivation index, from Q1 (least deprived) to Q5 (most deprived). Socio-economic gradients were modelled by Poisson regression, and region-specific estimates combined by meta-analysis.

The prevalence of postneonatally acquired CP was 0.14 per 1000 livebirths overall. The mean deprivation gradient, expressed as the relative risk in the most deprived vs. the least deprived quintile, was 1.86 (95% confidence interval [95% CI 1.19, 2.88]). The prevalence of non-acquired CP was 2.22 per 1000 livebirths. For non-acquired CP the gradient was 1.16 [95% CI 1.00, 1.35]. Evidence for a socio-economic gradient was strongest for spastic bilateral cases (1.32 [95% CI 1.09, 1.59]) and cases with severe intellectual impairment (1.59 [95% CI 1.06, 2.39]). There was evidence for differences in gradient between regions. The gradient of risk of CP among normal birthweight births was not statistically significant overall (1.21 [95% CI 0.95, 1.54]), but was significant in two regions. There was non-significant evidence of a reduction in gradients over time.

The reduction of the higher rates of postneonatally acquired CP in the more socioeconomically deprived areas is a clear goal for prevention. While we found evidence for a socio-economic gradient for non-acquired CP of antenatal or perinatal origin, the picture was not consistent across regions, and there was some evidence of a decline in inequalities over time. The steeper gradients in some regions for normal birthweight cases and cases with severe intellectual impairment require further investigation.

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.

The role of infrequent and extraordinary deep dives in leatherback turtles (Dermochelys coriacea)

Infrequent and exceptional behaviours can provide insight into the ecology and physiology of a particular species. Here we examined extraordinarily deep (300-1250 m) and protracted (>1h) dives made by critically endangered leatherback turtles (Dermochelys coriacea) in the context of three previously suggested hypotheses: predator evasion, thermoregulation and exploration for gelatinous prey. Data were obtained via satellite relay data loggers attached to adult turtles at nesting beaches (N=11) and temperate foraging grounds (N=2), constituting a combined tracking period of 9.6 years (N=26,146 dives) and spanning the entire North Atlantic Ocean. Of the dives, 99.6% (N=26,051) were to depths <300 m with only 0.4% (N=95) extending to greater depths (subsequently termed 'deep dives'). Analysis suggested that deep dives: (1) were normally distributed around midday; (2) may exceed the inferred aerobic dive limit for the species; (3) displayed slow vertical descent rates and protracted durations; (4) were much deeper than the thermocline; and (5) occurred predominantly during transit, yet ceased once seasonal residence on foraging grounds began. These findings support the hypothesis that deep dives are periodically employed to survey the water column for diurnally descending gelatinous prey. If a suitable patch is encountered then the turtle may cease transit and remain within that area, waiting for prey to approach the surface at night. If unsuccessful, then migration may continue until a more suitable site is encountered. Additional studies using a meta-analytical approach are nonetheless recommended to further resolve this matter.

School-related predictors of smoking, drinking and drug use: Evidence from the Belfast Youth Development Study

Objective

To examine whether students’ school engagement, relationships with teachers, educational aspirations and involvement in fights at school are associated with various measures of subsequent substance use.
Methods

Data were drawn from the Belfast Youth Development Study (n = 2968). Multivariate logistic models examined associations between school-related factors (age 13/14) and substance use (age 15/16).
Results

The two factors which were consistently and independently associated with regular substance use among both males and females were student–teacher relationships and fighting at school: positive teacher-relationships reduced the risk of daily smoking by 48%, weekly drunkenness by 25%, and weekly cannabis use by 52%; being in a fight increased the risk of daily smoking by 54%, weekly drunkenness by 31%, and weekly cannabis use by 43%. School disengagement increased the likelihood of smoking and cannabis use among females only.
Conclusion

Further research should focus on public health interventions promoting positive relationships and safety at school.

A kinetic study of the liquid-phase hydrogenation of citral on Au/TiO2 and Pt-Sn/TiO2 thin films in capillary microreactors

The kinetics of the liquid-phase hydrogenation of citral (3,7-dimethyl-2,6-octadienal) on Au/TiO2 and Pt-Sn/TiO2 thin films was studied in the temperature range 313-353 K and citral concentrations of 0.25-10.0 mol m(-3). The thin films were deposited onto the inner walls of silica capillaries with internal diameter of 250 mu m. First-order dependence on hydrogen pressure and near zero order dependence on citral concentration were observed for the initial rate of citral hydrogenation over the Pt-Sn/TiO2 and Au/TiO2 thin films. The Au/TiO2 catalyst prevents citronellal formation. The highest yield of unsaturated alcohols was obtained on the Pt-Sn/TiO2 film at a reaction temperature of 343 K, liquid residence time of 30 min and a citral conversion of 99%. (C) 2011 Elsevier B.V. All rights reserved.

Theoretical and experimental correlations of gas dissolution, diffusion, and thermodynamic properties in determination of gas permeability and selectivity in supported ionic liquid membranes

Supported ionic liquid membranes (SILMs) has the potential to be a new technological platform for gas/organic vapour separation because of the unique non-volatile nature and discriminating gas dissolution properties of room temperature ionic liquids (ILs). This work starts with an examination of gas dissolution and transport properties in bulk imidazulium cation based ionic liquids [C_nmim][NTf2] (n = 2.4, 6, 8.10) from simple gas H₂, N₂, to polar CO₂, and C₂H₆, leading to a further analysis of how gas dissolution and diffusion are influenced by molecular specific gas-SILMs interactions, reflected by differences in gas dissolution enthalpy and entropy. These effects were elucidated again during gas permeation studies by examining how changes in these properties and molecular specific interactions work together to cause deviations from conventional solution–diffusion theory and their impact on some remarkably contrasting gas perm-selectivity performance. The experimental perm-selectivity for all tested gases showed varied and contrasting deviation from the solution–diffusion, depending on specific gas-IL combinations. It transpires permeation for simpler non-polar gases (H₂, N₂) is diffusion controlled, but strong molecular specific gas-ILs interactions led to a different permeation and selectivity performance for C₂H₆ and CO₂. With exothermic dissolution enthalpy and large order disruptive entropy, C₂H₆ displayed the fastest permeation rate at increased gas phase pressure in spite of its smallest diffusivity among the tested gases. The C₂H₆ gas molecules “peg” on the side alkyl chain on the imidazulium cation at low concentration, and are well dispersed in the ionic liquids phase at high concentration. On the other hand strong CO₂-ILs affinity resulted in a more prolonged “residence time” for the gas molecule, typified by reversed CO₂/N₂ selectivity and slowest CO₂ transport despite CO₂ possess the highest solubility and comparable diffusivity in the ionic liquids. The unique transport and dissolution behaviour of CO₂ are further exploited by examining the residing state of CO₂ molecules in the ionic liquid phase, which leads to a hypothesis of a condensing and holding capacity of ILs towards CO₂, which provide an explanation to slower CO₂ transport through the SILMs. The pressure related exponential increase in permeations rate is also analysed which suggests a typical concentration dependent diffusion rate at high gas concentration under increased gas feed pressure. Finally the strong influence of discriminating and molecular specific gas-ILs interactions on gas perm-selectivity performance points to future specific design of ionic liquids for targeted gas separations.

School Neighborhood Disadvantage as a Predictor of Long-Term Sick Leave Among Teachers: Prospective Cohort Study

This ongoing prospective study examined characteristics of school neighborhood and neighborhood of residence as predictors of sick leave among school teachers. School neighborhood income data for 226 lower-level comprehensive schools in 10 towns in Finland were derived from Statistics Finland and were linked to register-based data on 3,063 teachers with no long-term sick leave at study entry. Outcome was medically certified (> 9 days) sick leave spells during a mean follow-up of 4.3 years from data collection in 2000-2001. A multilevel, cross-classified Poisson regression model, adjusted for age, type of teaching job, length and type of job contract, school size, baseline health status, and income level of the teacher's residential area, showed a rate ratio of 1.30 (95% confidence interval: 1.03, 1.63) for sick leave among female teachers working in schools located in low-income neighborhoods compared with those working in high-income neighborhoods. A low income level of the teacher's residential area was also independently associated with sick leave among female teachers (rate ratio = 1.50, 95% confidence interval: 1.18, 1.91). Exposure to both low-income school neighborhoods and low-income residential neighborhoods was associated with the greatest risk of sick leave (rate ratio = 1.71, 95% confidence interval: 1.27, 2.30). This study indicates that working and living in a socioeconomically disadvantaged neighborhood is associated with increased risk of sick leave among female teachers.

Hydrodynamic cavitation in micro channels with channel sizes of 100 and 750 micrometers

Decreasing the constriction size and residence time in hydrodynamic cavitation is predicted to give increased hot spot temperatures at bubble collapse and increased radical formation rate. Cavitation in a 100 x 100 mu m(2) rectangular micro channel and in a circular 750 mu m diameter milli channel has been investigated with computational fluid dynamics software and with imaging and radical production experiments. No radical production has been measured in the micro channel. This is probably because there is no spherically symmetrical collapse of the gas pockets in the channel which yield high hot spot temperatures. The potassium iodide oxidation yield in the presence of chlorohydrocarbons in the milli channel of up to 60 nM min(-1) is comparable to values reported on hydrodynamic cavitation in literature, but lower than values for ultrasonic cavitation. These small constrictions can create high apparent cavitation collapse frequencies.

Pre-Retirement Age Migration to Remote Rural Areas

Recent literature suggests that the increasingly blurred relationship between paid employment and retirement facilitates a retirement transition period, a life course stage, which may involve a change of residence. The role of such pre-retirement age mobility in the repopulation of rural areas has, however, received relatively little academic scrutiny. This paper draws upon findings from a two-year study conducted in three UK case study areas. It examines the extent of pre-retirement age (aged 50–64) migration into remote rural communities and the impacts this type of movement has upon economic activity, social and community engagement and service provision. It is argued that while this under-researched cohort offers opportunities to support the social and economic sustainability of rural communities (at least in the short and medium term), there are notable challenges which are likely to emerge as it ages in situ. The findings are particularly relevant given national trends on population ageing.

The removal of patients who live outside the practice boundary:a study of outside-area removals in Northern Ireland in 2001-2002

It has been suggested that there are significant overlaps between removals due to deregistration and removals arising because patients live outside the practice area. If this is true, it would mean that the current estimates of deregistration would need to be revised upwards. All outside-area removals for the calendar years 2001 and 2002 were reviewed and characterised by age, sex and Jarman score of the enumeration district of the patients' residence and distance from the practice. The average outside-area removal rate was just over one removal per practice per year. Removal rates were highest between the ages of 18 and 44 years; there were no significant differences between the sexes. Rates of removal increased exponentially with distance, although even at marked distances from the practice there were about 10 patients remaining on the list for each one removed. Residents in deprived areas were more likely to be removed, although because areas most distal to the practice tend to be affluent, overall there was a predominance of affluent patients among those who are removed. In Northern Ireland rates of outside-area removal are only slightly higher than those of deregistration. It is evident that GPs are exercising some discretion as to which of the outside-area patients they retain on their list. This has the potential to cause some misunderstanding and resentment among patients, as has been reported previously.

THE MARINE RADIOCARBON BOMB PULSE ACROSS THE TEMPERATE NORTH ATLANTIC: A COMPILATION OF Delta C-14 TIME HISTORIES FROM ARCTICA ISLANDICA GROWTH INCREMENTS

Marine radiocarbon bomb-pulse time histories of annually resolved archives from temperate regions have been underexploited. We present here series of Delta C-14 excess from known-age annual increments of the long-lived bivalve mollusk Arctica islandica from 4 sites across the coastal North Atlantic (German Bight, North Sea; Tromso, north Norway; Siglufjordur, north Icelandic shelf; Grimsey, north Icelandic shelf) combined with published series from Georges Bank and Sable Bank (NW Atlantic) and the Oyster Ground (North Sea). The atmospheric bomb pulse is shown to be a step-function whose response in the marine environment is immediate but of smaller amplitude and which has a longer decay time as a result of the much larger marine carbon reservoir. Attenuation is determined by the regional hydrographic setting of the sites, vertical mixing, processes controlling the isotopic exchange of C-14 at the air-sea boundary, C-14 content of the freshwater flux, primary productivity, and the residence time of organic matter in the sediment mixed layer. The inventories form a sequence from high magnitude-early peak (German Bight) to low magnitude-late peak (Grimsey). All series show a rapid response to the increase in atmospheric Delta C-14 excess but a slow response to the subsequent decline resulting from the succession of rapid isotopic air-sea exchange followed by the more gradual isotopic equilibration in the mixed layer due to the variable marine carbon reservoir and incorporation of organic carbon from the sediment mixed layer. The data constitute calibration series for the use of the bomb pulse as a high-resolution dating tool in the marine environment and as a tracer of coastal ocean water masses.

Using temporal analysis of products and flux response technology to determine diffusion coefficients in catalytic monoliths

The importance of accurately measuring gas diffusivity in porous materials has led to a number of methods being developed. In this study the Temporal Analysis of Products (TAP) reactor and Flux Response Technology (FRT) have been used to examine the diffusivity in the washcoat supported on cordierite monoliths. Herein, the molecular diffusion of propane within four monoliths with differently prepared alumina/CeZrOx washcoats was investigated as a function of temperature. Moment-based analysis of the observed TAP responses led to the calculation of the apparent intermediate gas constant, Kp, that characterises adsorption into the mesoporous network and apparent time delay, tapp, that characterises residence time in the mesoporous network. Additionally, FRT has been successfully adapted as an extensive in situ perturbation technique in measuring intraphase diffusion coefficients in the washcoats of the same four monolith samples. The diffusion coefficients obtained by moment-based analysis of TAP responses are larger than the coefficients determined by zero length column (ZLC) analysis of flux response profiles with measured values of the same monolith samples between 20 and 100 °C ranging from 2–5×10^-9 m² s^-1 to 4–8×10^-10 m² s^-1, respectively. The TAP and FRT data, therefore, provide a range of the lower and upper limits of diffusivity, respectively. The reported activation energies and diffusivities clearly correlate with the difference in the washcoat structure of different monolith samples.

Methylation using dimethylcarbonate catalysed by ionic liquids under continuous flow conditions

The ionic liquid, tributylmethylammonium methylcarbonate, has been employed as a catalytic base for clean N-methylation of indole with dimethylcarbonate. The reaction conditions were optimised under microwave heating to give 100% conversion and 100% selectivity to N-methylindole, and subsequently transferred to a high temperature/high pressure (285 degrees C/150 bar) continuous flow process using a short (3 min) residence time and 2 mol% of the catalyst to efficiently methylate a variety of different amines, phenols, thiophenols and carboxylic acid substrates. The extremely short residence times, versatility, and high selectivity have significant implications for the synthesis of a wide range of pharmaceutical intermediates, as high product throughputs can be obtained via this scalable continuous flow protocol. It has also been shown that the ionic liquid can be generated in situ from tributylamine, which has the net effect of transforming an ineffective stoichiometric base into a highly efficient catalyst for this broad class of reactions.

Methane to higher hydrocarbons via halogenation

Activation of methane with a halogen followed by the metathesis of methyl halide is a novel route from methane to higher hydrocarbons or oxygenates. Thermodynamic analysis revealed that bromine is the most suitable halogen for this goal. Analysis of the published data on the reaction kinetics in a CSTR enabled us to judge on the effects of temperature, reactor residence time and the feed concentrations of bromine and methane to the conversion of methane and the selectivity towards mono or dibromomethane. The analysis indicated that high dibromomethane selectivity is attainable (over 90%) accompanied by high methane conversions. The metathesis of dibromomethane can provide an alternative route to the conversion of methane (natural gas) economically with smaller installations than the current syn-gas route. (c) 2005 Elsevier B.V. All rights reserved.