Optimised microwave-assisted synthesis of methylcarbonate salts: a convenient methodology to prepare intermediates for ionic liquid libraries

The reaction of 1-butylpyrrolidine with dimethyl carbonate to yield the ionic liquid precursor, 1-butyl-1-methylpyrrolidinium methylcarbonate, has been investigated under microwave heating conditions and the reaction parameters optimised to achieve 100% yield of the pyrrolidinium salt with no by-products in under 1 h. The reactions of tributylamine, trioctylphosphine, and 1-butylimidazole with dimethyl carbonate under comparable conditions have also been evaluated, yielding the corresponding methylcarbonate salts which can be used as intermediates for the preparation of halide-free ionic liquids without generating any undesirable salt wastes.

Degradation of carbon disulphide (CS2) in soils and groundwater from a CS2 -contaminated site

This study is the first investigation of biodegradation of carbon disulphide (CS₂) in soil that provides estimates of degradation rates and identifies intermediate degradation products and carbon isotope signatures of degradation. Microcosm studies were undertaken under anaerobic conditions using soil and groundwater recovered from CS₂-contaminated sites. Proposed degradation mechanisms were validated using equilibrium speciation modelling of concentrations and carbon isotope ratios. A first-order degradation rate constant of 1.25 × 10-2 h-1 was obtained for biological degradation with soil. Carbonyl sulphide (COS) and hydrogen sulphide (H₂S) were found to be intermediates of degradation, but did not accumulate in vials. A 13C/12C enrichment factor of -7.5 ± 0.8 ‰ was obtained for degradation within microcosms with both soil and groundwater whereas a 13C/12C enrichment factor of -23.0 ± 2.1 ‰ was obtained for degradation with site groundwater alone. It can be concluded that biological degradation of both CS2-contaminated soil and groundwater is likely to occur in the field suggesting that natural attenuation may be an appropriate remedial tool at some sites. The presence of biodegradation by-products including COS and H₂S indicates that biodegradation of CS₂ is occurring and stable carbon isotopes are a promising tool to quantify CS₂ degradation.

Intracellular survival and saprophytic growth of isolates from the Burkholderia cepacia complex in free-living amoebae

Members of the taxonomically diverse Burkholderia cepacia complex have become a major health risk for patients with cystic fibrosis (CF). Although patient-to-patient transmission of B. cepacia strains has been well-documented, very little is known about possible vehicles of transmission and reservoirs for these micro-organisms. In this work, it is shown that strains of the B. cepacia complex can survive within different isolates of the genus Acanthamoeba. Trophozoites containing bacteria developed profuse cytoplasmic vacuolization. Vacuolization was not detected in trophozoites infected with live Escherichia coli or heat-killed B. cepacia, or by incubation of trophozoites with filter-sterilized culture supernatants, indicating that metabolically active intracellular bacteria are required for the formation of vacuoles. Experiments with two different B. cepacia strains and two different Acanthamoeba isolates revealed that bacteria display a low level of intracellular replication approximately 72-96 h following infection. In contrast, extracellular bacteria multiplied efficiently on by-products released by amoebae. The findings suggest that amoebae may be a reservoir for B. cepacia and possibly a vehicle for transmission of this opportunistic pathogen among CF patients.

Improving MTM-UAS to predetermine automotive maintenance times

The preventive knowledge of serviceability times is a critical factor for the quantification of after-sales services costs of a vehicle. Predetermined motion time system are frequently used to set labor rates in industry by quantifying the amount of time required to perform specific tasks. The first such system is known as Methods-time measurement (MTM). Several variants of MTM have been developed differing from each other on their level of focus. Among them MTM-UAS is suitable for processes that average around 1-3 min. However experimental tests carried out by the authors in Elasis (Research Center of FIAT Group) demonstrate that MTM-UAS is not the optimal approach to measure serviceability times. The reason is that it doesn't take into account ergonomic factors. In the present paper the authors propose to correct the MTM-UAS method including in the task analysis the study of human postures and efforts. The proposed approach allows to estimate with an "acceptable" error the time needed to perform maintenance tasks since the first phases of product design, by working on Digital Mock-up and human models in virtual environment. As a byproduct of that analysis, it is possible to obtain a list of maintenance times in order to preventively set after-sales service costs. © 2012 Springer-Verlag.

Effectiveness of the Construction Management Courses

This research assesses the effectiveness of current MSc. Construction Project Management programmes within the UK and Ireland. A review of published prospectuses is used to create questionnaires for universities, graduates and employers. Responses provide an insight into programme creation and their relative success in addressing the needs of industry and in achieving other educational objectives. Since the majority of learning institutions have attained professional accreditation, it is useful to review these awards and to assess their potential value to both graduates and industry alike. Interviews are conducted with representatives from the main professional accrediting bodies to understand their procedures and rigour in enforcing standards of education and training. The results show that project management education could be further enhanced by the inclusion of more practical learning and that current programmes place greater emphasis on hard skills at the expense of the softer human skills. There is clearly a need for a closer working relationship between academics and practitioners to tackle the perceived gap between theoretical learning and construction practice. Learning institutions can use the findings to improve their programmes and address the education deficiencies identified by the industry, by the professional institutions and by graduates.

Coal Combustion Residuals valorisation through the production of compressed masonry brick

The Niger Coal Society (Societé Nigérienne de Charbon – SONICHAR) produces electricity for local consumption in Tefereyre, 75 km north-west from Agadez, Niger. The coal combustion residuals production is about 150,000 tons per year. In order to reduce this environmental burden and to valorize these by-products, a study focusing on their physical and chemical features as well as on the mechanical resistance of compressed brick has been undertaken. Physical characterization of coal slag, chemical and lixiviation tests have been carried out, assessing the material main parameters, verifying the presence of hazardous composites and elements and comparing the obtained results with the findings of an in-deep literary review. Cement powder has been chosen as stabilizing agent as a preliminary option. Four different dosages have been tested and bricks have been produced with a hand-operated press. Compressive strength has been tested at different days of curing. Results show remarkable uniaxial compressive strengths (UCS) for all the mixes after cure, ranging from 4MPa up to more than 20MPa for the highest stabilization ratio. UCS higher than 5MPa have been observed for 20% and 30% cement stabilization ratios after only 7 days of cure, reaching respectively about 11MPa and 13MPa after 45 days. In conclusion obtained bricks show good mechanical resistance and low weight. No health threat has been detected from the obtained sample. Study developments are oriented towards the feasibility of the utilization of low-cost, locally available stabilization means, notably clay and cohesive soils, and on thermal properties assessment.

Marine organisms for bone repair and regeneration

Bioprospecting has led to increased interest in potential applications for marine organisms and their by-products. As a rich source of mineralising porous organisms, our seas and oceans could provide new directions for bone tissue engineering particularly in the supply of biomimetic templates that may enhance in vivo and ex vivo bone formation. In this chapter we examine the history of marine organism use in this field; exploring how these organisms could be utilised, given the problems of sustainability, and reviewing the current evidence to support their use for bone repair and regeneration.

Mechanistic and toxicity studies of the photocatalytic oxidation of microcystin-LR

Cyanobacterial toxins present in drinking water sources pose a considerable threat to human health. Conventional water treatment systems have proven unreliable for the removal of these toxins and hence new techniques have been investigated. Previous work has shown that TiO₂ photocatalysis effectively destroys microcystin-LR in aqueous solutions, however, a variety of by-products were generated. In this paper, we report a mechanistic study of the photocatalytic destruction of microcystin-LR. In particular, the toxicity by-products of the process have been studied using both brine shrimp and protein phosphatase bioassays. 

Hydrogen peroxide enhanced photocatalytic oxidation of microcystin-lR using titanium dioxide

Cyanobacterial toxins present in drinking water sources pose a considerable threat to human health. Conventional water treatment systems have proven unreliable for the removal of these toxins and hence new techniques have been investigated. Previous work has shown that TiO₂ photocatalysis effectively destroys microcystin-LR in aqueous solutions, however non-toxic by-products were detected. It has been shown that photocatalytic reactions are enhanced by utilisation of alternative electron acceptors. We report here enhanced photocatalytic degradation of microcystin-LR following the addition of hydrogen peroxide to the system. It was also found that hydrogen peroxide with UV illumination alone was capable of decomposing microcystin-LR although at a much slower rate than found for TiO₂. No HPLC detectable by-products were found when the TiO₂/UV/H₂O₂ system was used indicating that this method is more effective than TiO₂/UV alone. Results however indicated that only 18% mineralisation occurred with the TiO₂/UV/H₂O₂ system and hence undetectable by-products must still be present. At higher concentrations hydrogen peroxide was found to compete with microcystin-LR for surface sites on the catalyst but at lower peroxide concentrations this competitive adsorption was not observed. Toxicity studies showed that both in the presence and absence of H₂O₂ the microcystin solutions were detoxified. These findings suggest that hydrogen peroxide greatly enhances the photocatalytic oxidation of microcystin-LR.

Semiconductor photocatalysis: an environmentally acceptable alternative production technique and effluent treatment process

New environmentally acceptable production methods are required to help reduce the environmental impact of many industrial processes. One potential route is the application of photocatalysis using semiconductors. This technique has enabled new environmentally acceptable synthetic routes for organic synthesis which do not require the use of toxic metals as redox reagents. These photocatalysts also have more favourable redox potentials than many traditional reagents. Semiconductor photocatalysis can also be applied to the treatment of polluted effluent or for the destruction of undesirable by-products of reactions. In addition to the clean nature of the process the power requirements of the technique can be relatively low, with some reactions requiring only sunlight. 

Unexpected Role for Adaptive αβTh17 Cells in Acute Respiratory Distress Syndrome

Acute respiratory distress syndrome (ARDS) is a devastating disorder characterized by increased alveolar permeability with no effective treatment beyond supportive care. Current mechanisms underlying ARDS focus on alveolar endothelial and epithelial injury caused by products of innate immune cells and platelets. However, the role of adaptive immune cells in ARDS remains largely unknown. In this study, we report that expansion of Ag-specific αβTh17 cells contributes to ARDS by local secretion of IL-17A, which in turn directly increases alveolar epithelial permeability. Mice with a highly restrictive defect in Ag-specific αβTh17 cells were protected from experimental ARDS induced by a single dose of endotracheal LPS. Loss of IL-17 receptor C or Ab blockade of IL-17A was similarly protective, further suggesting that IL-17A released by these cells was responsible for this effect. LPS induced a rapid and specific clonal expansion of αβTh17 cells in the lung, as determined by deep sequencing of the hypervariable CD3RβVJ region of the TCR. Our findings could be relevant to ARDS in humans, because we found significant elevation of IL-17A in bronchoalveolar lavage fluid from patients with ARDS, and rIL-17A directly increased permeability across cultured human alveolar epithelial monolayers. These results reveal a previously unexpected role for adaptive immune responses that increase alveolar permeability in ARDS and suggest that αβTh17 cells and IL-17A could be novel therapeutic targets for this currently untreatable disease.

Effects of LL-37 on Human Gingival Fibroblast Function

Background and Objectives: Gingival fibroblasts play a significant role in the innate immune response of the periodontium to bacterial stimulation. A number of microorganisms and their by-products induce a host response that commonly leads to tissue destruction and periodontal disease progression. LL-37 is an antimicrobial peptide which has multiple roles in host defence including immunomodulation and wound-healing. We have investigated the role of LL-37 on the responsiveness of human gingival fibroblasts to microbial challenge from E. coli lipopolysaccharide (LPS) and P. gingivalis LPS, as well as exploring the direct effects of LL-37 on human gingival fibroblasts. Methods: The effect of LL-37 on bacterial LPS-induced expression of IL-6 and IL-8 by gingival fibroblasts was determined by ELISA. The influence of LL-37 on bacterial LPS-induced IκBα degradation in human gingival fibroblasts was investigated by western blot. The direct effects of LL-37 on modulating gingival fibroblasts gene expression were initially determined by DNA microarray analysis and subsequently confirmed by quantitative polymerase chain reaction (Q-PCR) and ELISA analysis of 9 selected genes. Results: Bacterial LPS-induced IL-8 and IL-6 production by human gingival fibroblasts were significantly reduced in the presence of LL-37 at concentrations in the range of 1-10 µg/ml (p<0.05). The presence of LL-37 at a concentration of 5 µg/ml led to a reduction in LPS-induced IκBα degradation by E. coli LPS (100 ng/ml) and P. gingivalis LPS (10 µg/ml). LL-37 (50 µg/ml) significantly altered the gene expression of 367 genes in human gingival fibroblasts by at least 2-fold. CXCL1, CXCL2, CXCL3, IL-24, IL-8, CCL2, and SOCS3 mRNA were significantly upregulated by LL-37 (p<0.05). LL-37 also significantly stimulated expression of IL-8, hepatocyte growth factor (HGF) and CXCL1 (p<0.05) at the protein level. Discussion: LL-37 plays an important role in the innate immune response due to its broad spectrum antimicrobial and immunomodulatory activity. The ability of LL-37 to directly regulate expression of a range of genes, central to the pathogenesis of periodontitis, identifies multiple roles for the peptide in host homeostasis.

Non-thermal Plasma Exposure Rapidly Attenuates Bacterial AHL-Dependent Quorum Sensing and Virulence.

The antimicrobial activity of atmospheric pressure non-thermal plasma has been exhaustively characterised, however elucidation of the interactions between biomolecules produced and utilised by bacteria and short plasma exposures are required for optimisation and clinical translation of cold plasma technology. This study characterizes the effects of non-thermal plasma exposure on acyl homoserine lactone (AHL)-dependent quorum sensing (QS). Plasma exposure of AHLs reduced the ability of such molecules to elicit a QS response in bacterial reporter strains in a dose-dependent manner. Short exposures (30-60 s) produce of a series of secondary compounds capable of eliciting a QS response, followed by the complete loss of AHL-dependent signalling following longer exposures. UPLC-MS analysis confirmed the time-dependent degradation of AHL molecules and their conversion into a series of by-products. FT-IR analysis of plasma-exposed AHLs highlighted the appearance of an OH group. In vivo assessment of the exposure of AHLs to plasma was examined using a standard in vivo model. Lettuce leaves injected with the rhlI/lasI mutant PAO-MW1 alongside plasma treated N-butyryl-homoserine lactone and n-(3-oxo-dodecanoyl)-homoserine lactone, exhibited marked attenuation of virulence. This study highlights the capacity of atmospheric pressure non-thermal plasma to modify and degrade AHL autoinducers thereby attenuating QS-dependent virulence in P. aeruginosa.

Resistance of alkali activated slag concretes to chloride environments based on chloride penetration measurements

ABSTRACT

One of the binder systems with low environmental footprint is alkali activated slag concretes (AASC), made by adding alkalis such as sodium hydroxide and sodium silicate to industrial by-products such as ground granulated blast furnace slag (GGBS). Whilst they have the similar behaviour as that of traditional cement systems in terms of strength and structural behaviour, AASC do exhibit superior performance in terms of abrasion and acid resistance and fire protection.
In this article, the authors focus their attention on chloride ingress into different grades of AASC. The mix variables in AASC included water-to-binder, binder to aggregate ratio, percentage of alkali and the SiO2/Na2O ratio (silica modulus, Ms). The first challenge is to get mixes for different range of workability (with slump values from 40mm to 240mm) and reasonable early age and long term compressive strength according to each one. Then the chloride diffusion and migration in those mixes were measured and compared with same normal concretes in the existed literature based on chloride penetration depth. Comparing the chloride ingress between tradition concretes and AASCs is worthwhile to prove the possibility of increasing concrete lifetime in proximity to sea and deciding while such concretes are practical for use. Findings show that compared to the PC concretes, the AAS concretes have lower rate of chloride ingress.