The undesirable acetylation of cellulose by the acetate ion of 1-ethyl-3-methylimidazolium acetate

The ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([C2mim]OAc) is considered to be an inert solvent of cellulose and lignocellulosic biomass. Acetylation (1.7 % mol, or DS 0.017) of cellulose after dissolution in [C2mim]OAc (150 °C for 20 min), is demonstrated by compositional analysis, FTIR analysis and 13C NMR spectroscopy (in [C2min]OAc with 13C enriched acetate). This acetylation, in the absence of added acylating agents, has not been reported before and may limit [C2mim]OAc utility in industrial scale biomass processing, even at this low extent. For example, cellulose acetylation may contribute to IL loss in processes where the IL is recovered and reused and inhibit enzyme saccharification of cellulose in lignocellulosic biofuel production processes based on saccharification and fermentation.

The philosophy and practice of water sensitive urban design : is it consistent with a whole system approach

This paper provides a critique of the Water Sensitive Urban Design (WSUD) paradigm by discussing its congruence with an established sustainable design principle called 'whole system design'. It was found that WSUD is congruent with the whole system design approach as a philosophy, but not in practice. Future improvement of WSUD practice may depend on the adoption of a front-loaded, teamwork-based design and planning process that is embedded in the principle of whole system design.

Three-dimensional geological modelling and multivariate statistical analysis of water chemistry data to analyse and visualise aquifer structure and groundwater composition in the Wairau Plain, Marlborough District, New Zealand

Concerns regarding groundwater contamination with nitrate and the long-term sustainability of groundwater resources have prompted the development of a multi-layered three dimensional (3D) geological model to characterise the aquifer geometry of the Wairau Plain, Marlborough District, New Zealand. The 3D geological model which consists of eight litho-stratigraphic units has been subsequently used to synthesise hydrogeological and hydrogeochemical data for different aquifers in an approach that aims to demonstrate how integration of water chemistry data within the physical framework of a 3D geological model can help to better understand and conceptualise groundwater systems in complex geological settings. Multivariate statistical techniques(e.g. Principal Component Analysis and Hierarchical Cluster Analysis) were applied to groundwater chemistry data to identify hydrochemical facies which are characteristic of distinct evolutionary pathways and a common hydrologic history of groundwaters. Principal Component Analysis on hydrochemical data demonstrated that natural water-rock interactions, redox potential and human agricultural impact are the key controls of groundwater quality in the Wairau Plain. Hierarchical Cluster Analysis revealed distinct hydrochemical water quality groups in the Wairau Plain groundwater system. Visualisation of the results of the multivariate statistical analyses and distribution of groundwater nitrate concentrations in the context of aquifer lithology highlighted the link between groundwater chemistry and the lithology of host aquifers. The methodology followed in this study can be applied in a variety of hydrogeological settings to synthesise geological, hydrogeological and hydrochemical data and present them in a format readily understood by a wide range of stakeholders. This enables a more efficient communication of the results of scientific studies to the wider community.

Effects of cold water immersion on knee joint position sense in healthy volunteers

The purpose of this study was to determine the effects of cryotherapy, in the form of cold water immersion, on knee joint position sense. Fourteen healthy volunteers, with no previous knee injury or pre-existing clinical condition, participated in this randomized cross-over trial. The intervention consisted of a 30-min immersion, to the level of the umbilicus, in either cold (14 ± 1°C) or tepid water(28 ± 1°C). Approximately one week later, in a randomized fashion, the volunteers completed the remaining immersion. Active ipsilateral limb repositioning sense of the right knee was measured, using weight-bearing and non-weight bearing assessments, employing video-recorded 3D motion analysis. These assessments were conducted immediately before and after a cold and tepid water immersion. No significant differences were found between treatments for the absolute (P = 0.29), relative (P = 0.21) or variable error (P = 0.86). The average effect size of the outcome measures was modest (range –0.49 to 0.9) and all the associated 95% confidence intervals for these effect sizes crossed zero. These results indicate that there is no evidence of an enhanced risk of injury, following a return to sporting activity, after cold water.

Recycling endosome membrane incorporation into the leading edge regulates lamellipodia formation and macrophage migration

In comparison to our knowledge of the recycling of adhesion receptors and actin assembly, exactly how the cell controls its surface membrane to form a lamellipodium during migration is poorly understood. Here, we show the recycling endosome membrane is incorporated into the leading edge of a migrating cell to expand lamellipodia membrane. We have identified the SNARE complex that is necessary for fusion of the recycling endosome with the cell surface, as consisting of the R-SNARE VAMP3 on the recycling endosome partnering with the surface Q-SNARE Stx4/SNAP23, which was found to translocate and accumulate on the leading edge of migrating cells. Increasing VAMP3-mediated fusion of the recycling endosome with the surface increased membrane ruffling, while inhibition of VAMP3-mediated fusion showed that incorporation of the recycling endosome is necessary for efficient lamellipodia formation. At the same time, insertion of this recycling endosome membrane also delivers its cargo integrin α5β1 to the cell surface. The loss of this extra membrane for lamellipodia expansion and delivery of cargo in cells resulted in macrophages with a diminished capacity to effectively migrate. Thus, the recycling endosome membrane is incorporated into the leading edge and this aids expansion of the lamellipodia and simultaneously delivers integrins necessary for efficient cell migration.

Modeling perceived collision risk in port water navigation

An increase in the likelihood of navigational collisions in port waters has put focus on the collision avoidance process in port traffic safety. The most widely used on-board collision avoidance system is the automatic radar plotting aid which is a passive warning system that triggers an alert based on the pilot’s pre-defined indicators of distance and time proximities at the closest point of approaches in encounters with nearby vessels. To better help pilot in decision making in close quarter situations, collision risk should be considered as a continuous monotonic function of the proximities and risk perception should be considered probabilistically. This paper derives an ordered probit regression model to study perceived collision risks. To illustrate the procedure, the risks perceived by Singapore port pilots were obtained to calibrate the regression model. The results demonstrate that a framework based on the probabilistic risk assessment model can be used to give a better understanding of collision risk and to define a more appropriate level of evasive actions.

Modelling port water collision risk using traffic conflicts

Navigational collisions are one of the major safety concerns for many seaports. Despite the extent of work recently done on collision risk analysis in port waters, little is known about the influencing factors of the risk. This paper develops a technique for modeling collision risks in port waterways in order to examine the associations between the risks and the geometric, traffic, and regulatory control characteristics of waterways. A binomial logistic model, which accounts for the correlations in the risks of a particular fairway at different time periods, is derived from traffic conflicts and calibrated for the Singapore port fairways. Estimation results show that the fairways attached to shoreline, traffic intersection and international fairway attribute higher risks, whereas those attached to confined water and local fairway possess lower risks. Higher risks are also found in the fairways featuring higher degree of bend, lower depth of water, higher numbers of cardinal and isolated danger marks, higher density of moving ships and lower operating speed. The risks are also found to be higher for night-time conditions.

A study of ionic liquids for dissolution of sugarcane bagasse

Over the last decade, Ionic Liquids (ILs) have been used for the dissolution and derivatization of isolated cellulose. This ability of ILs is now sought for their application in the selective dissolution of cellulose from lignocellulosic biomass, for the manufacture of cellulosic ethanol. However, there are significant knowledge gaps in the understanding of the chemistry of the interaction of biomass and ILs. While imidazolium ILs have been used successfully to dissolve both isolated crystalline cellulose and components of lignocellulosic biomass, phosphonium ILs have not been sufficiently explored for the use in dissolution of lignocellulosic biomass. This thesis reports on the study of the chemistry of sugarcane bagasse with phosphonium ILs. Qualitative and quantitative measurements of biomass components dissolved in the phosphonium ionic liquids (ILs), trihexyltetradecylphosphonium chloride ([P66614]Cl) and tributylmethylphosphonium methylsulphate ([P4441]MeSO4) are obtained using attenuated total reflectance-Fourier Transform Infra Red (FTIR). Absorption bands related to cellulose, hemicelluloses and lignin dissolution monitored in situ in biomass-IL mixtures indicate lignin dissolution in both ILs and some holocellulose dissolution in the hydrophilic [P4441]MeSO4. The kinetics of lignin dissolution reported here indicate that while dissolution in the hydrophobic IL [P66614]Cl appears to follow an accepted mechanism of acid catalysed β-aryl ether cleavage, dissolution in the hydrophilic IL [P4441]MeSO4 does not appear to follow this mechanism and may not be followed by condensation reactions (initiated by reactive ketones). The quantitative measurement of lignin dissolution in phosphonium ILs based on absorbance at 1510 cm-1 has demonstrated utility and greater precision than the conventional Klason lignin method. The cleavage of lignin β-aryl ether bonds in sugarcane bagasse by the ionic liquid [P66614]Cl, in the presence of catalytic amounts of mineral acid. (ca. 0.4 %). The delignification process of bagasse is studied over a range of temperatures (120 °C to 150 °C) by monitoring the production of β-ketones (indicative of cleavage of β-aryl ethers) using FTIR spectroscopy and by compositional analysis of the undissolved fractions. Maximum delignification is obtained at 150 °C, with 52 % of lignin removed from the original lignin content of bagasse. No delignification is observed in the absence of acid which suggests that the reaction is acid catalysed with the IL solubilising the lignin fragments. The rate of delignification was significantly higher at 150 °C, suggesting that crossing the glass transition temperature of lignin effects greater freedom of rotation about the propanoid carbon-carbon bonds and leads to increased cleavage of β-aryl ethers. An attempt has been made to propose a probable mechanism of delignifcation of bagasse with the phosphonuim IL. All polymeric components of bagasse, a lignocellulosic biomass, dissolve in the hydrophilic ionic liquid (IL) tributylmethylphosphonium methylsulfate ([P4441]MeSO4) with and without a catalytic amount of acid (H2SO4, ca. 0.4 %). The presence of acid significantly increases the extent of dissolution of bagasse in [P4441]MeSO4 (by ca. 2.5 times under conditions used here). The dissolved fractions can be partially recovered by the addition of an antisolvent (water) and are significantly enriched in lignin. Unlike acid catalysed dissolution in the hydrophobic IL tetradecyltrihexylphosphonium chloride there is little evidence of cleavage of β-aryl ether bonds of lignin dissolving in [P4441]MeSO4 (with and without acid), but this mechanism may play some role in the acid catalysed dissolution. The XRD of the undissolved fractions suggests that the IL may selectively dissolve the amorphous cellulose component, leaving behind crystalline material.

The effect of light intensity and temperature on photocatalytic water splitting

Photocatalytic water splitting is a process which could potentially lead to commercially viable solar hydrogen production. This thesis uses an engineering perspective to investigate the technology. The effect of light intensity and temperature on photocatalytic water splitting was examined to evaluate the prospect of using solar concentration to increase the feasibility of the process. P25 TiO2 films deposited on conducting glass were used as photocatalyst electrodes and coupled with platinum electrodes which were also deposited on conducting glass. These films were used to form a photocatalysis cell and illuminated with a Xenon arc lamp to simulate solar light at intensities up to 50 suns. They were also tested at temperatures between 20°C and 100°C. The reaction demonstrated a sub-linear relationship with intensity. Photocurrent was proportional to intensity with an exponential value of 0.627. Increasing temperature resulted in an exponential relationship. This proved to follow an Arrhenius relationship with an activation energy of 10.3 kJ mol-1 and a pre-exponential factor of approximately 8.7×103. These results then formed the basis of a mathematical model which extrapolated beyond the range of the experimental tests. This model shows that the loss of efficiency from performing the reaction under high light intensity is offset by the increased reaction rate and efficiency from the associated temperature increase. This is an important finding for photocatalytic water splitting. It will direct future research in system design and materials research and may provide an avenue for the commercialisation of this technology.

Two SusD-like proteins encoded within a polysaccharide utilisation locus of an uncultured ruminant bacteroidetes bind strongly to cellulose

We demonstrate that two characteristic Sus-like proteins encoded within a Polysaccharide Utilisation Locus (PUL) bind strongly to cellulosic substrates and interact with plant primary cell walls. This shows associations between uncultured Bacteroidetes-affiliated lineages and cellulose in the rumen, and thus presents new PUL-derived targets to pursue regarding plant biomass degradation.

Analysis of involved parties in port water conflicts

With increasing rate of shipping traffic, the risk of collisions in busy and congested port waters is expected to rise. However, due to low collision frequencies it is difficult to analyze such risk in a sound statistical manner. This study aims at examining the occurrence of traffic conflicts in order to understand the characteristics of vessels involved in navigational hazards. A binomial logit model was employed to evaluate the association of vessel attributes and the kinematic conditions with conflict severity levels. Results show a positive association for vessels of small gross tonnage, overall vessel length, vessel height and draft with conflict risk. Conflicts involving a pair of dynamic vessels sailing at low speeds also have similar effects.

Statistical analysis of conflict involvements in port water navigation

With increasing rate of shipping traffic, the risk of collisions in busy and congested port waters is likely to rise. However, due to low collision frequencies in port waters, it is difficult to analyze such risk in a sound statistical manner. A convenient approach of investigating navigational collision risk is the application of the traffic conflict techniques, which have potential to overcome the difficulty of obtaining statistical soundness. This study aims at examining port water conflicts in order to understand the characteristics of collision risk with regard to vessels involved, conflict locations, traffic and kinematic conditions. A hierarchical binomial logit model, which considers the potential correlations between observation-units, i.e., vessels, involved in the same conflicts, is employed to evaluate the association of explanatory variables with conflict severity levels. Results show higher likelihood of serious conflicts for vessels of small gross tonnage or small overall length. The probability of serious conflict also increases at locations where vessels have more varied headings, such as traffic intersections and anchorages; becoming more critical at night time. Findings from this research should assist both navigators operating in port waters as well as port authorities overseeing navigational management.