Combining Bio- and Chemo-catalysis for the Conversion of Bio-Renewable Alcohols

The use of biomass as a source of fuel is on the sharp increase. In parallel with this expansion, new chemical processes and technologies are required to improve efficiency, sustainability, and profitability.
Biocatalytic and chemocatalytic methods can be combined to affect the conversion of bio-alcohols, and convert them to valuable chemical targets in an atom efficient and environmentally benign manor. Fermentation offers a useful first step in biomass conversion, as whole cell biocatalysts can provide sustained activity when fed with crude biomass. Coupling this with homogeneous and/or heterogeneous catalysis enables the preparation of a diverse product range. The transition between biocatalytic and chemocatalytic steps can be assisted by utilising ionic liquids.
Ionic liquids have potential roles in biorefineries that generate alcohols; as an extractant, reaction medium, and catalytic reagent. Underpinning the potential of ionic liquids in this area is: 1. the ability of ionic liquids to solubilize polyols and alcohols; 2. the facility to functionalise ionic liquids and tune properties; 3. the low volatility of ionic liquids.
The FP7 project GRAIL will be highlighted; this project focusses on the utilisation of glycerol formed as a by-product in biodiesel synthesis.

The use of binary mixtures of 1-butyl-1-methylpyrrolidinium bis{(trifluoromethyl)sulfonyl}imide and aliphatic nitrile solvents as electrolyte for supercapacitors

Abstract The development of high voltage electrolytes is one of the key aspects for increasing both energy and power density of electrochemical double layer capacitors (EDLCs). The usage of blends of ionic liquids and organic solvents has been considered as a feasible strategy since these electrolytes combine high usable voltages and good transport properties at the same time. In this work, the ionic liquid 1-butyl-1-methylpyrrolidinium bis{(trifluoromethyl)sulfonyl}imide ([Pyrr14][TFSI]) was mixed with two nitrile-based organic solvents, namely butyronitrile and adiponitrile, and the resulting blends were investigated regarding their usage in electrochemical double layer capacitors. Both blends have a high electrochemical stability, which was confirmed by prolonged float tests at 3.2 V, as well as, good transport properties. In fact, the butyronitrile blend reaches a conductivity of 17.14 mS·cm−1 and a viscosity of 2.46 mPa·s at 20 °C, which is better than the state-of-the-art electrolyte (1 mol·dm−3 of tetraethylammonium tetrafluoroborate in propylene carbonate).

Binary Mixtures of 1-Butyl-1-Methylpyrrolidinium Bis{(trifluoromethyl)Sulfonyl}Imide and Aliphatic Nitrile Solvents As Electrolyte for Electrochemical Double Layer Capacitors (Invited).

Electrochemical double layer capacitors (EDLCs), also known as supercapacitors, are promising energy storage devices, especially when considering high power applications [1]. EDLCs can be charged and discharged within seconds [1], feature high power (10 kW·kg-1) and an excellent cycle life (>500,000 cycles). All these properties are a result of the energy storage process of EDLCs, which relies on storing energy by charge separation instead of chemical redox reactions, as utilized in battery systems. Upon charging, double layers are forming at the electrode/electrolyte interface consisting of the electrolyte’s ions and electric charges at the electrode surface.In state-of-the-art EDLC systems activated carbons (AC) are used as active materials and tetraethylammonium tetrafluoroborate ([Et4N][BF4]) dissolved in organic solvents like propylene carbonate (PC) or acetonitrile (ACN) are commonly used as the electrolyte [2]. These combinations of materials allow operative voltages up to 2.7 V - 2.8 V and an energy in the order of 5 Wh·kg-1[3]. The energy of EDLCs is dependent on the square of the operative voltage, thus increasing the usable operative voltage has a strong effect on the delivered energy of the device [1]. Due to their high electrochemical stability, ionic liquids (ILs) were thoroughly investigated as electrolytes for EDLCs, as well as, batteries, enabling high operating voltages as high as 3.2 V - 3.5 V for the former [2]. While their unique ionic structure allows the usage of neat ILs as electrolyte in EDLCs, ILs suffer from low conductivity and high viscosity increasing the intrinsic resistance and, as a result, a lower power output of the device. In order to overcome this issue, the usage of blends of ionic liquids and organic solvents has been considered a feasible strategy as they combine high usable voltages, while still retaining good transport properties at the same time.In our recent work the ionic liquid 1-butyl-1-methylpyrrolidinium bis{(trifluoromethyl)sulfonyl}imide ([Pyrr14][TFSI]) was combined with two nitrile-based organic solvents, namely butyronitrile (BTN) and adiponitrile (ADN), and the resulting blends were investing regarding their usage in electrochemical double layer capacitors [4,5]. Firstly, the physicochemical properties were investigated, showing good transport properties for both blends, which are similar to the state-of-the-art combination of [Et4N][BF4] in PC. Secondly, the electrochemical properties for EDLC application were studied in depth revealing a high electrochemical stability with a maximum operative voltage as high as 3.7 V. In full cells these high voltage organic solvent based electrolytes have a good performance in terms of capacitance and an acceptable equivalent series resistance at cut-off voltages of 3.2 and 3.5 V. However, long term stability tests by float testing revealed stability issues when using a maximum voltage of 3.5 V for prolonged time, whereas at 3.2 V no such issues are observed (Fig. 1).Considering the obtained results, the usage of ADN and BTN blends with [Pyrr14][TFSI] in EDLCs appears to be an interesting alternative to state-of-the-art organic solvent based electrolytes, allowing the usage of higher maximum operative voltages while having similar transport properties to 1 mol∙dm-3 [Et4N][BF4] in PC at the same time.

Efficient and Selectable Production of Reactive Species Using a Nanosecond Pulsed Discharge in Gas Bubbles in Liquid

A plasma gas bubble-in-liquid method for high production of selectable reactive species using a nanosecond pulse generator has been developed. The gas of choice is fed through a hollow needle in a point-to-plate bubble discharge, enabling improved selection of reactive species. The increased interface reactions, between the gas-plasma and water through bubbles, give higher productivity. H₂O₂ was the predominant species produced using Ar plasma, while predominantly  and NO₂ were generated using air plasma, in good agreement with the observed emission spectra. This method has nearly 100% selectivity for H₂O₂, with seven times higher production, and 92% selectivity for , with nearly twice the production, compared with a plasma above the water.

Utilisation of ionic liquid solvents for the synthesis of Lily-of-the-Valley fragrance {beta-Lilial (R); 3-(4-t-butylphenyl)-2-methylpropanal}

The Heck arylation of 2-methylprop-2-en- I -ol in ionic liquids and organic solvents is reported using a range of homogeneous and heterogeneous palladium catalysts. Higher activity is observed in the ionic liquid media compared with N-methyl pyrrolidinone and under solventless conditions. The ionic liquid-catalyst system may be recycled easily with little loss in activity, although significant palladium leaching from the heterogeneous catalyst was observed. In the case of Trans-bis(2,3-dihydro-3-methylbenzothiazole-2-ylidene)diiodopalladium (11) reported to be highly active for this transformation, significant induction petiods were observed indicating that nanoparticles may be responsible for the catalysis. Using the ionic liquid Heck reaction, a recyclable synthesis for the fragrance beta-Lilial((R)) has been developed. (c) 2004 Elsevier B.V. All rights reserved.

Lanthanide-doped luminescent ionogels

Ionogels are solid oxide host networks con. ning at a meso-scale ionic liquids, and retaining their liquid nature. Ionogels were obtained by dissolving lanthanide(III) complexes in the ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide, [C(6)mim][Tf2N], followed by confinement of the lanthanide-doped ionic liquid mixtures in the pores of a nano-porous silica network. [C(6)mim][Ln(tta)(4)], where tta is 2-thenoyltrifluoroacetonate and Ln = Nd, Sm, Eu, Ho, Er, Yb, and [choline](3)[Tb(dpa)(3)], where dpa = pyridine-2,6-dicarboxylate (dipicolinate), were chosen as the lanthanide complexes. The ionogels are luminescent, ion-conductive inorganic-organic hybrid materials. Depending on the lanthanide(III) ion, emission in the visible or the near-infrared regions of the electromagnetic spectrum was observed. The work presented herein highlights that the confinement did not disturb the first coordination sphere of the lanthanide ions and also showed the excellent luminescence performance of the lanthanide tetrakis beta-diketonate complexes. The crystal structures of the complexes [C(6)mim][Yb(tta)(4)] and [choline](3)[Tb(dpa)(3)] are reported.

Transport Properties of Self-Consolidating Concrete

The permeability of concrete is influenced by the porosity and the interconnectivity of the pores in the cement paste and the microcracks in concrete, especially in the interface of paste-aggregate. The movements of gases, liquids, and ions through concrete is important because of their interactions with concrete constituents, including pore water, which can alter the integrity of concrete directly and indirectly, leading to the deterioration of structures. This study reports the findings from an investigation carried out to study the effect of the mixture variations on the durability of medium- and high-strength self-consolidating concrete (SCC). The mixture variations studied include the type of mineral admixtures, such as limestone powder (LSP) and pulverized fuel ash (PFA), and viscositymodifying admixtures (VMA) for both medium- and high-strength SCC. Air permeability, water permeability, capillary absorption, and chloride diffusivity were used to assess the durability of SCC mixtures in comparison with normal, vibrated concretes. The results showed that SCC mixtures, for medium- and high-strength grades using PFA followed by LSP, have lower permeability properties compared with normal concretes. SCC made with VMA had a higher sorptivity, air permeability, and water permeability compared with other SCC mixtures, which can be attributed to higher watercement ratio (w/c) and lack of pore filling effect. An in-place migration coefficient was obtained using the in-place ion migration test. This was used to compare the potential diffusivity of different concretes. The results indicated that SCC, for both grades of strength, made with PFA showed much lower diffusivity values in comparison with other mixtures, whereas the SCC mixtures with VMA showed higher diffusivity.

Selective oxidation of a pyrimidine thioether using supported tantalum catalysts

Ta2O5-SiO2 catalysts were prepared by a sol-gel method using tetraethyl orthosilicate (TEOS) and tantalum (V) ethoxide as the sources of silicon and tantalum, and two families of quaternary ammonium salts, [CnH(2n+1)(CH3)(3)N]Br (n = 14, 16, 18) and [(CnH(2n+1))(4)N]Br (n = 10, 12, 16, 18) as surfactants. The catalysts were compared for the selective suffoxidation of 4,6-dimethyl-2-thiomethylpyrimidine using peroxide as an oxidising agent in a range of ionic liquids and organic solvents. The sol-gel catalysts were also compared with tantalum on MCM-41 prepared by grafting. The catalysts were characterized from adsorption-desorption isotherms of N-2, XRD patterns, small-angle X-ray scattering, IR spectra from adsorbed pyridine and CDCl3, XPS spectra, and Si-29 magic angle spinning (MAS) NNIR experiments. The effect of recycling on the catalyst leaching and selectivity/activity was also studied. High activities and selectivities were found in [NTf2](-) based ionic liquids and organic solvents with good recyclability of the catalyst. Tantalum was found in the solution after reaction; however, this was determined to be due to entrapment of catalyst particulates, as opposed to leaching of the active metal. (c) 2005 Elsevier Inc. All rights reserved.

Controlled fragrance delivery in functionalised ionic liquid-enzyme systems

It is often believed that both ionic liquids and surfactants generally behave as non-specific denaturants of proteins. In this paper, it is shown that amphiphilic ionic liquids bearing a long alkyl chain and a target molecule, where the target molecule is appended via a carboxylic ester functionality, can represent super-substrates that enable the catalytic activity of an enzyme, even at high concentrations in solution. Menthol has been chosen as the target molecule for slow and controlled fragrance delivery, and it was found that the rate of the menthol release can be controlled by the chemical structure of the ionic liquid. At a more fundamental level, this study offers an insight into the complex hydrophobic, electrostatic, and hydrogen bond interactions between the enzyme and substrate.

Soil conditioning for EPBMs

Nowadays, the Earth Pressure Balanced (EPB) shields are used more and more caused by both the mechanical development of the machines and the more effective use of additives such as foams and polymers. These additives are used to condition spoil in the screw conveyor. A crucial component of EPB tunnelling applications is ground conditioning. Thus, in order to permit quantitative measurements of the conditioned ground behavior, it is necessary to develop and use a test able to simulate the extraction of earth from the chamber with a screw conveyor. This reliable test procedure can provide quantitative parameters that can really describe the conditioned soil behavior.

Interactions of a non-thermal atmospheric pressure plasma effluent with PC-3 prostate cancer cells

The effect of a radio-frequency driven, microscale non thermal atmospheric pressure plasma jet operated in helium with vol. 0.3% molecular oxygen gas admixture, on PC-3 prostate cancer cells has been investigated. The viability of cells exposed to the plasma was found to decrease with increasing plasma exposure time, with apoptosis through caspase and PARP cleavage being observed. High concentrations of nitrite and nitrate were detected in growth media exposed to the plasma and were found to increase in a time dependent manner post exposure. This indicates a slow release of reactive nitrogen species into the growth media, which is likely to influence cellular response to plasma exposure.

On the Performances of Ionic Liquid-Based Electrolytes for Li-NMC Batteries

Herein, the N-butyl-N-methylpyrrolidinium bis(fluorosulfonyl)amide and the N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)amide room temperature ionic liquids, combined with the lithium bis(trifluoromethanesulfonyl)amide salt, are investigated as electrolytes for Li/LiNi1/3Mn1/3Co1/3O2 (Li/NMC) batteries. To conduct this study, volumetric properties, ionic conductivity and viscosity of the pure ionic liquids and selected electrolytes were firstly determined as a function of temperature and composition in solution. These data were then compared with those measured in the case of the standard alkyl carbonate-based electrolyte: e.g. the EC/PC/3DMC + 1 mol·L−1 LiPF6. The compatibility of the selected electrolytes with the lithium electrode was then investigated by following the evolution of Li/electrolyte interfaces through impedance measurements. Interestingly, the impedances of the investigated Li/electrolyte interfaces were found to be more than three times lower than that measured using the standard electrolyte. Finally, electrochemical performances of the ionic liquid-based electrolytes were investigated using galvanostatic charge and discharge and cyclic voltammetry of each Li/NMC cell. Using these electrolytes, each tested Li cell reaches up to 145 mA·h·g−1 at C/10 and 110 mA·h·g−1 at C with a coulombic efficiency close to 100 %.

Engineering Simulations

Over recent years, ionic liquids have emerged as a class of novel fluids that have inspired the development of a number of new products and processes. The ability to design these materials with specific functionalities and properties means that they are highly relevant to the growing philosophy of chemical-product design. This is particularly appropriate in the context of a chemical industry that is becoming increasingly focussed on small-volume, high-value added products with relatively short times to market. To support such product and process development, a number of tools can be utilised. A key requirement is that the tool can predict the physical properties and activity coefficients of multi-component mixtures and, if required, model the process in which the materials will be used. Multi-scale simulations that span density functional theory (DFT) to process-engineering computations can address the relevant time and length scales and have increased in usage with the availability of cheap and powerful computers. Herein we will discuss the area of engineering calculations relating to the design of ionic liquid processes, that is, the computational tools that bridge this gap and allow for process simulation tools to utilise and assist in the design of ionic liquids. It will be shown that, at present, it is possible to use available tools to estimate many important properties of ionic liquids and mixtures containing them with a sufficient level of accuracy for preliminary design and selection.

Carbon Dioxide Uptake from Natural Gas by Binary Ionic Liquid-Water mixtures

Carbon dioxide solubility in a set of carboxylate ionic liquids formulated with stoicheiometric amounts of water is found to be significantly higher than for other ionic liquids previously reported. This is due to synergistic chemical and physical absorption. The formulated ionic liquid/water mixtures show greatly enhanced carbon dioxide solubility relative to both anhydrous ionic liquids and aqueous ionic liquid solutions, and are competitive with commercial chemical absorbers, such as activated N-methyldiethanolamine or monoethanolamine.

Dual functional ionic liquids as plasticisers and antimicrobial agents for medical polymers

Contamination of medical devices with bacteria such as Meticillin resistant Staphylococcus aureus (MRSA) is of great clinical concern. Poly(vinyl chloride) is widely used in the production of medical devices, such as catheters. The flexibility of catheter tubing is derived from the addition of plasticisers. Here, we report the design of two dual functional ionic liquids, 1-ethylpyridinium docusate and tributyl(2-hydroxyethyl)phosphonium docusate, which uniquely provide a plasticising effect, and exhibit antimicrobial and antibiofilm-forming activity to a range of antibiotic resistant bacteria. The plasticisation of poly(vinyl chloride) was tailored as a function of ionic liquid concentration. The effective antimicrobial behaviour of both ionic liquids originates from the chemical structure of the anion or cation and is not limited to the length of the alkyl chain on the anion/cation. The design approach adopted will be useful in developing ionic liquids as multi-functional additives for polymers.