Ionic liquids are not always green: hydrolysis of 1-butyl-3-methylimidazolium hexafluorophosphate

1-Butyl-3-methylimidazolium fluoride hydrate has been identified crystallographically as a decomposition product created during purification of the hydrophobic ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate. This highlights the need to treat ionic liquids much as one would any other research chemical with potentially hazardous properties, unknown toxicity and/or stability, particularly when searching for 'green solvents'.

Rational design of a dual-mode optical and chemical prodrug

Purpose. The purpose of this study is to demonstrate the rational design and behaviour of the first dual mode optical and chemical prodrug, exemplified by an acetyl salicylic acid-based system. Methods. A cyclic 1,4-benzodioxinone prodrug was synthesised by reaction of 3,5-dimethoxybenzoin and acetyl salicoyl chloride with pyridine. After purification by column chromatography and recrystallization, characterization was achieved using infrared and NMR spectroscopies, mass spectrometry, elemental analysis and single crystal X-ray diffraction. Light-triggered drug liberation was characterised via UV-visible spectroscopy following low-power 365 nm irradiation for controlled times. Chemical drug liberation was characterised via UV-visible spectroscopy in pH 5.5 solution. Results. The synthetic method yielded pure prodrug, with full supporting characterisation. Light-triggered drug liberation proceeded at a rate of 8.30 10j2 sj1, while chemical, hydrolytic liberation proceeded independently at 1.89 10j3 sj1. The photochemical and hydrolytic reactions were both quantitative. Conclusions. This study demonstrates the first rational dual-mode optical and chemical prodrug, using acetyl salicylic acid as a model, acting as a paradigm for future dual-mode systems. Photochemical drug liberation proceeds 44 times faster than chemical liberation, suggesting potential use in drug-eluting medical devices where an additional burst of drug is required at the onset of infection.

Mass spectrometry-based metabolomics applied to the chemical safety of food

Mass spectrometry (MS)-based metabolomics is emerging as an important field of research in many scientific areas, including chemical safety of food. A particular strength of this approach is its potential to reveal some physiological effects induced by complex mixtures of chemicals present at trace concentrations. The limitations of other analytical approaches currently employed to detect low-dose and mixture effects of chemicals make detection very problematic. Besides this basic technical challenge, numerous analytical choices have to be made at each step of a metabolomics study, and each step can have a direct impact on the final results obtained and their interpretation (i.e. sample preparation, sample introduction, ionization, signal acquisition, data processing, and data analysis). As the application of metabolomics to chemical analysis of food is still in its infancy, no consensus has yet been reached on defining many of these important parameters. In this context, the aim of the present study is to review all these aspects of MS-based approaches to metabolomics, and to give a comprehensive, critical overview of the current state of the art, possible pitfalls, and future challenges and trends linked to this emerging field. (C) 2010 Elsevier Ltd. All rights reserved.

A quantitative research on S- and SO2-poisoning Pt/Vulcan carbon fuel cell catalyst

A quantitative research on S and SO2 poisoning Pt/Vulcan carbon (Pt/VC) catalysts for fuel cells was conducted by the three-electrode method. Pt/VC electrodes were contaminated by submersion in a SO2- containing solution made up of 0.2 mM Na2SO3 and 0.5 M H2SO4 for different periods of time, and held at 0.05 V (vs. RHE) in 0.5 M H2SO4 solutions in order to gain zero-valence sulfur (S0) poisoned electrodes. The sulfur coverage of Pt was determined from the total charge consumed as the sulfur was oxidized from S0 at 0.05 V (vs. RHE) to sulfate at >1.1 V (vs. RHE). The summation of initial coverage of S0 (S) and coverage of H (H) are approximately equal to 1 (H + S = 1) when 0.5

Chemical and mechanical stability of sodium sulfate activated slag after exposure to elevated temperature

The chemical and mechanical stability of slag activated with two different concentrations of sodium sulfate (Na₂SO₄) after exposure to elevated temperatures ranging from 200 to 800 °C with an increment of 200 °C has been examined. Compressive strengths and pH of the hardened pastes before and after the exposure were determined. The various decomposition phases formed were identified using X-ray diffraction, thermogravimetric analysis and scanning electron microscopy. The results indicated that Na₂SO₄ activated slag has a better resistance to the degradation caused by exposure to elevated temperature up to 600 °C than Portland cement system as its relative strengths are superior. The finer slag and higher Na₂SO₄ concentration gave better temperature resistance. Whilst the pH of the hardened pastes decreased with an increase in temperature, it still maintained a sufficiently high pH for the protection of reinforcing bar against corrosion.

A comparison of nitogen fate and transport in catchments underlain by high and low permeability aquifers using chemical and isotopic tools.

Variability in nitrogen fate and transport in different catchments types is often not considered. This research considers the importance of such nitrogen processes within groundwater pathways in two agricultural catchments in Ireland; a well drained catchment, underlain by karstified Carboniferous limestone, and a poorly drained catchment, underlain by Silurian greywacke.
Depth specific low-flow groundwater sampling was used to evaluate the hydrochemical stratification in groundwater. Groundwater samples, as well as surface water samples, along river courses were analysed for nitrogen species (NO3, NH4 and NO2) and nitrate isotopes (d15N and d18O) as well as field parameters and major ions
.
The dominant nitrate (NO3) groundwater pathway in the poorly drained greywacke catchment is through the shallow weathered bedrock, as indicated by transmissivity values and the ionic and isotopic signatures, and a clear reduction in NO3 concentration is observed with depth. A similar chloride trend would suggest dilution is a major factor, however d15N and d18O isotopic values producing an enrichment ratio of 1.8 indicate that denitrification is also an important process involved in the fate of the NO3 within the groundwater flow system. This consistent trend with depth is in contrast to the stratification pattern observed in the karstified catchment. NO3 was not detected in the shallow groundwater pathway; the dominant groundwater pathway is in the deeper groundwater where there is little change in the nitrate isotope values with depth (d15N values range between 4.1 and 4.6 ‰). This deeper groundwater contributes the dominant proportion of the river flow through a number of springs. As a result, the deeper groundwater, springs and river have a similar ionic signature and NO3 concentration range (23 ± 3 mg/l). Despite this pattern, the NO3 isotopes show a distinct difference in isotopic values between the deeper groundwater in the diffuse karst and the springs indicating some denitrification is occurring during groundwater discharge into the river. Furthermore the isotopes give an indication of the variability of the spatial extent of the springs and the complexities of the fissures through which they are fed. The results of this study clearly show the importance of the geology in the fate and transport of NO3 in agricultural catchments.

Chemical Exposures of Women Workers in the Plastics Industry with Particular Reference to Breast Cancer and Reproductive Hazards.

Despite concern about the harmful effects of substances contained in various
plastic consumer products, little attention has focused on the more heavily
exposed women working in the plastics industry. Through a review of the
toxicology, industrial hygiene, and epidemiology literatures in conjunction
with qualitative research, this article explores occupational exposures in producing
plastics and health risks to workers, particularly women, who make up
a large part of the workforce. The review demonstrates that workers are
exposed to chemicals that have been identified as mammary carcinogens and
endocrine disrupting chemicals, and that the work environment is heavily
contaminated with dust and fumes. Consequently, plastics workers have a
body burden that far exceeds that found in the general public.

Characterization of physio-chemical processes and hydration kinetics in concretes containing supplementary cementitious materials using electrical property measurements

The current study monitors both the short- and long-term hydration characteristics of concrete using discretized conductivity measurements from initial gauging, through setting and hardening, the latter comprising both the curing and post-curing periods. In particular, attention is directed to the near-surface concrete as it is this zone which protects the steel from the external environment and has a major influence on durability, performance and service-life. A wide range of concrete mixes is studied comprising both plain Portland cement concretes and concretes containing fly-ash and ground granulated blast furnace slag. The parameter normalised conductivity was used to identify four distinct stages in the hydration process and highlight the influence of supplementary cementitious materials (SCM) on hydration and hydration kinetics. A relationship has been presented to account for the temporal decrease in conductivity, post 10-days hydration. The testing procedure and methodology presented lend itself to in-situ monitoring of reinforced concrete structures. (c) 2013 Elsevier Ltd. All rights reserved.

Removal of microorganisms and their chemical metabolites from water using semiconductor photocatalysis

Semiconductor photocatalysis has been applied to the remediation of an extensive range of chemical pollutants in water over the past 30 years. The application of this versatile technology for removal of micro-organisms and cyanotoxins has recently become an area that has also been the subject of extensive research particularly over the past decade. This paper considers recent research in the application of semiconductor photocatalysis for the treatment of water contaminated with pathogenic micro-organisms and cyanotoxins. The basic processes involved in photocatalysis are described and examples of recent research into the use of photocatalysis for the removal of a range of microorganisms are detailed. The paper concludes with a review of the key research on the application of this process for the removal of chemical metabolites generated from cyanobacteria.