Heterogeneous catalysis in an oscillatory baffled flow reactor

The first demonstration of heterogeneous catalysis within an oscillatory baffled flow reactor (OBR) is reported, exemplified by the solid acid catalysed esterification of organic acids, an important prototypical reaction for fine chemicals and biofuel synthesis. Suspension of a PrSOH-SBA-15 catalyst powder is readily achieved within the OBR under an oscillatory flow, facilitating the continuous esterification of hexanoic acid. Excellent semi-quantitative agreement is obtained between OBR and conventional stirred batch reaction kinetics, demonstrating efficient mixing, and highlighting the potential of OBRs for continuous, heterogeneously catalysed liquid phase transformations. Kinetic analysis highlights acid chain length (i.e. steric factors) as a key predictor of activity. Continuous esterification offers improved ester yields compared with batch operation, due to the removal of water by-product from the catalyst, evidencing the versatility of the OBR for heterogeneous flow chemistry and potential role as a new clean catalytic technology. © The Royal Society of Chemistry 2013.

Multi-level genetic algorithm for the resource-constrained re-entrant scheduling problem in the flow shop

The re-entrant flow shop scheduling problem (RFSP) is regarded as a NP-hard problem and attracted the attention of both researchers and industry. Current approach attempts to minimize the makespan of RFSP without considering the interdependency between the resource constraints and the re-entrant probability. This paper proposed Multi-level genetic algorithm (GA) by including the co-related re-entrant possibility and production mode in multi-level chromosome encoding. Repair operator is incorporated in the Multi-level genetic algorithm so as to revise the infeasible solution by resolving the resource conflict. With the objective of minimizing the makespan, Multi-level genetic algorithm (GA) is proposed and ANOVA is used to fine tune the parameter setting of GA. The experiment shows that the proposed approach is more effective to find the near-optimal schedule than the simulated annealing algorithm for both small-size problem and large-size problem. © 2013 Published by Elsevier Ltd.

Measuring the flow properties of small powder samples using an avalanche tester

The feasibility of using a small-scale avalanche tester to measure the flow properties of pharmaceutical lactose powders was examined. The modes of behaviour observed in larger systems were displayed and showed a clear distinction between angular, free-flowing particles and more spherical particles of similar flow characteristics. Angular Lactohale LH100 particles showed slumping behaviour at a rotational frequency of 0.33Hz which disappeared at higher frequencies. Spherical lactose powder with a similar flow function to LH100 only showed rolling behaviour under the same conditions, as did more cohesive powders LH200 and LH300. Further investigation of the LH100 data using Fast Fourier analysis showed that the slumping frequency was 1/10th of the rotational frequency.

Platinum-catalysed cinnamaldehyde hydrogenation in continuous flow

Platinum is one of the most widely used hydrogenation catalysts. Here we describe the translation of batch reactions to continuous flow, affording tunable C=O versus C=C hydrogenation over a Pt/SiO2 catalyst, resulting in high steady state activity and single-pass yields in the selective hydrogenation of cinnamaldehyde to cinnamyl alcohol under mild conditions. Negligible catalyst deactivation occurs under extended flow operation due to removal of reactively-formed poisons from the reaction zone. Process intensification imparts a four-fold enhancement in cinnamyl alcohol productivity.

Benthic Exchange of C, N, and P Along the Estuarine Ecotone of Lower Taylor Slough, Florida (USA): Effect of Seasonal Flows and Phosphorus Availability

The southern Everglades and Florida Bay have experienced a nearly 50 % reduction in freshwater flow resulting in increased salinity and landward expansion of mangrove forest. Given the marine end-member is a natural source of P to this region, it is necessary to understand the interactions between inflows and P availability in controlling the exchange of materials across the mangrove ecotone. From 2007 to 2008, we used sediment core incubations to quantify fluxes of dissolved inorganic N and P and dissolved organic carbon (DOC) in three ecotone areas (dwarf mangrove, pond, and bay). Experiments were repeated seasonally over 2 years involving P-enriched surface water as a factor. We saw consistent uptake of soluble reactive P (SRP), DOC, and nitrate + nitrite (N+N) by the soils/sediments and release of ammonium (NH4 +) from soils/sediments to the water column across all sites and seasons. P enrichment had no discernible effect on DIN or DOC flux, suggesting that rapid P uptake may have been more geochemically mediated. However, uptake of added P occurred across all sites and seasons, reflecting high uptake capacity in this carbonate system and the potential of the mangrove ecotone to sequester P as it becomes more available.

Tracer-based assessment of flow paths, storage and runoff generation in northern catchments : a review

Peer reviewed

Generation of Paramoeba perurans clonal cultures using flow cytometry and confirmation of virulence

Peer reviewed

A Force-Balanced Control Volume Finite Element Method for Multi-Phase Porous Media Flow Modelling

Peer reviewed

Benthic (C. wuellerstorfi) d18O, d13C and Cd/Ca in sediment core NEAP 4K across the last deglaciation

We present evidence that the characteristic chemical signature (based on coupled benthic foraminiferal Cd/Ca and d13C) of Antarctic Intermediate waters (AAIW) penetrated throughout the intermediate depths of the Atlantic basin to the high-latitude North Atlantic during the abrupt cooling events of the last deglaciation: Heinrich 1 and the Younger Dryas. AAIW may play the dynamic counterpart to the "bipolar seesaw" when near-freezing salty bottom waters from the Antarctic (AABW) sluggishly ventilate the deep ocean. Our data reinforce the concept that interglacial circulation is stabilized by salinity feedbacks between salty northern sourced deep waters (NADW) and fresh southern sourced waters (AABW and AAIW). Further, the glacial ocean may be susceptible to the more finely balanced relative densities of NADW and AAIW, due to either freshwater input or a reversal of the salinity gradient, such that the ocean is poised for NADW collapse via a negative salinity feedback. The unstable climate of the glacial period and its termination may arise from the closer competition for ubiquity at intermediate depths between northern and southern sourced intermediate waters.

Source Provenance of Pre-Historic Granitic Grindstones: The Case Study of the Cogotas I Archaeological Site of Arroyo Mucientes/San Lázaro (Castronuño, Valladolid) and a Proposal on the General Methodological Flow Process

The occurrence of hand grindstones at the Cogotas I archaeological sites is considered to be a common feature. Given that a distant-provenance raw material is frequently involved, determination of its source is a basic factor in the search for a better understanding of resource management and for any Political Economy approach. To progress in these directions an overall study should be planned, using selected grindstones with a view to covering diverse sub-zones of the Cogotas I dispersal area, especially because of its considerable distance from the granite basement source. Such a study may today includes diverse analytical procedures combining successive geographic, petrographic, mineralogical and geochemical criteria. To check the plausibility of the proposed methodology, a preliminary test has been carried out on two granite grindstones, obtained at the archaeological excavation at the Castronuño (Valladolid) Cogotian site, which is fifty km away from an inferred source area that was presumably located at Peñausende (Zamora). The result obtained validates the proposed operational process, yielding a generalizable knowledge to other similar situations.

Genetic analyses reveal high levels of seed and pollen flow in hawthorn (Crataegus monogyna Jacq.), a key component of hedgerows

Hedgerows represent important components of agri-environment landscapes that are increasingly coming under threat from climate change, emergent diseases, invasive species and land use change. Given that population genetic data can be used to inform best-practice management strategies for woodland and hedgerow tree species, we carried out a study on hawthorn (Crataegus monogyna Jacq.), a key component of hedgerows, on a regional basis using a combination of nuclear and chloroplast microsatellite markers. We found that levels of genetic diversity were high and comparable to, or slightly higher than, other tree species from the same region. Levels of population differentiation for both sets of markers, however, were extremely low, suggesting extensive gene flow via both seed and pollen. These findings suggest that a holistic approach to woodland management, one which does not necessarily rely on the concept of “seed zones” previously suggested, but which also takes into account populations with high and/or rare chloroplast (i.e. seed-specific) genetic variation, might be the best approach to restocking and replanting.

Continuous flow gas phase photoreforming of methanol at elevated reaction temperatures sensitised by Pt/TiO2

Gas phase photoreforming of methanol using a Pt/TiO2 photocatalyst has been performed under flow conditions at elevated temperatures. Comparing the activity of the reforming process as a function of temperature under dark and irradiated conditions shows a significant enhancement in the rate of H2 production using the photo-assisted conditions at temperatures between 100-140 °C. At higher temperatures, the effect of irradiation is small with the process dominated by the thermal process. Deactivation of the catalyst was observed under irradiation but the catalyst was easily regenerated using an oxygen treatment at 120 °C. Diffuse Reflectance Infra-red Fourier Transform Spectroscopy (DRIFTS) showed that the activity of the catalyst could be correlated with the presence of the photogenerated trapped electrons. In addition, lower amounts of CO adsorbed on Pt, compared to those observed in the dark reaction, were found for the UV-irradiated systems. It is proposed that CO and adsorbed intermediates, such as formate, can act as inhibitors in the photoreforming process and this is further supported by the observation that, before and after the regeneration process in O2, the CO and surface adsorbed organic intermediate products are removed and the activity is recovered.

Catalytic reactions with palladium supported on mesocellular foam : Applications in hydrogenation, isomerization, and C-C bond forming reactions

The major part of this thesis concerns the development of catalytic methodologies based on palladium nanoparticles immobilized on aminopropyl-functionalized siliceous mesocellular foam (Pd0-AmP-MCF). The catalytic activity of the precursor to the nanocatalyst, PdII-AmP-MCF is also covered by this work. In the first part the application of Pd0-AmP-MCF in Suzuki-Miyaura cross-coupling reactions and transfer hydrogenation of alkenes under microwave irradiation is described. Excellent reactivity was observed and a broad range of substrates were tolerated for both transformations. The Pd0-AmP-MCF exhibited high recyclability as well as low metal leaching in both cases. The aim of the second part was to evaluate the catalytic efficiency of the closely related PdII-AmP-MCF for cycloisomerization of various acetylenic acids. The catalyst was able to promote formation of lactones under mild conditions using catalyst loadings of 0.3 - 0.5 mol% at temperatures of up to 50 oC in the presence of Et3N. By adding 1,4-benzoquinone to the reaction, the catalyst could be recycled four times without any observable decrease in the activity. The selective arylation of indoles at the C-2 position using Pd-AmP-MCF and symmetric diaryliodonium salts is presented in the third part. These studies revealed that Pd0-AmP-MCF was more effective than PdII-AmP-MCF for this transformation. Variously substituted indoles as well as diaryliodonium salts were tolerated, giving arylated indoles in high yields within 15 h at 20 - 50 oC in H2O. Only very small amounts of Pd leaching were observed and in this case the catalyst exhibited moderate recyclability. The final part of the thesis describes the selective hydrogenation of the C=C in different α,β-unsaturated systems. The double bond was efficiently hydrogenated in high yields both under batch and continuous-flow conditions. High recyclability and low metal leaching were observed in both cases.

Changes in peak expiratory flow and respiratory strength during the menstrual cycle

This study evaluated the spirometry and respiratory static pressures in 17 young women, twice a week for three successive ovulatory menstrual cycles to determine if such variables changed across the menstrual, follicular, periovulatory, early-tomid luteal and late luteal phases. The factors phases of menstrual cycle and individual cycles had no significant effect on the spirometry variables except for peak expiratory flow (PEF) and respiratory static pressures. Significant weak positive correlations were found between the progesterone:estradiol ratio and PEF and between estrogen and tidal volume (r = 0.37), inspiratory time (r = 0.22), expiratory time (r = 0.19), maximal inspiratory pressure (r = 0.25) and maximal expiratory pressure (r = 0.20) and for progesterone and maximal inspiratory pressure (r = 0.32) during the early-to-mid luteal phase. Although most parameters of the spirometry results did not change during the menstrual cycle, the correlations observed between sexual hormones and respiratory control variables suggest a positive influence of sexual female hormones controlling the thoracic pump muscles in the luteal phase