Self-assembled monolayers for electrostatic electrocatalysis and enhanced electrode stability in thermogalvanic cells.

Waste heat is ubiquitous; as such, sustainable and long-lasting devices are required to convert it into more useful forms of energy that can make use of this abundant potential resource. Thermogalvanic cells (or thermocells) can use the thermoelectrochemical properties of redox couples to achieve this; entropy-driven redox reactions allow them to act as liquid thermoelectrics. However, excellent electrocatalysis at the electrode surface is required for optimum conversion efficiency. Serendipitous observation of Nafion-based electrocatalysis prompted the exploration of electrostatically charged self-assembled monolayers (SAMs) inside a thermocell. Both electrostatic electrocatalysis and improved electrode stability were observed; in an aqueous K3[Fe(CN)6]/K4[Fe(CN)6]-based cell, modification with (3-trimethylammonium bromide)thiopropane resulted in higher electrical power, and protection against [Fe(CN)6]3-/4--induced gold passivation, relative to bare gold. Molecular-based electrostatic electrocatalysis could be an alternative to precious metal-based nanomaterial electrocatalysis, and could be integrated with (nano)carbon-based electrodes to further enhance the ability of thermogalvanic and other electrochemical energy conversion devices, e.g. redox flow batteries.

High Seebeck coefficient thermogalvanic cells via the solvent-sensitive charge additivity of cobalt 1,8-diaminosarcophagine.

Thermogalvanic devices can chemically convert low grade (<200 °C) waste thermal energy into electrical energy. A temperature gradient across the device drives an entropically favourable electrochemical redox reaction, resulting in continuous current production. The voltage correlates with the entropy change during the redox reaction, which favours high valence metal complexes with high charge densities. Here we investigate cobalt (II/III) sarcophagine ([Co(SAR)]2+/3+) for application in thermogalvanic cells, as a function of solvent; the two uncoordinated amine groups 1,8-diaminosarcophagine are typically protonated to form tetracationic/pentacationic [Co(SARH2)]4+/5+. In water, [Co(SARH2)]4+/5+ gave a thermogalvanic Seebeck coefficient (Se) of +0.43 mV K-1, which is entropically consistent with just the Co2+/3+ core valence, whereas DMSO and ionic liquid solvents gave Se values of +1.84 and +2.04 mV K-1, respectively, in line with the 'Co4+/5+' overall complex. This work proves how the ionic charge on pendant moieties can undergo charge-additivity with the metal core to significantly boost entropically-driven processes, but only in suitably low dielectric and bulky solvents.

Direct measurement of the genuine efficiency of thermogalvanic heat-to-electricity conversion in thermocells.

Harvesting wasted thermal energy could make important contributions to global energy sustainability. Thermogalvanic devices are simple, chemistry-based devices which can convert heat to electricity, through facile redox chemistry. The efficiency of this process is the ratio of electrical energy generated by the cell (in Watts) to the quantity of thermal energy that passes through the cell (also in Watts). Prior work estimated the quantity of thermal energy passed through a thermocell by applying a conductive heat transfer model to the electrolyte. Here, we employ a heat flux sensor to unambiguously quantify both heat flux and electrical power. By evaluating the effect of electrode separation, temperature difference and gelation of the electrolyte, we found significant discrepancy between the estimated model and the quantified reality. For electrode separation, the trend between estimated and measured efficiency went in opposite directions; as a function of temperature difference, they demonstrated the same trend, but estimated values were significantly higher. This was due to significant additional convection and radiation contributions to the heat flux. Conversely, gelled electrolytes were able to suppress heat flux mechanisms and achieve experimentally determined efficiency values in excess of the estimated values (at small electrode separations), with partially gelled systems being particularly effective. This study provides the ability to unambiguously benchmark and assess the absolute efficiency and Carnot efficiency of thermogalvanic electrolytes and even the whole thermocell device, allowing 'total device efficiency' to be quantified. The deviation between the routinely applied estimation methodology and actual measurement will support the rational development of novel thermal energy harvesting chemistries, materials and devices.

Electroanalytical profiling of cocaine samples by means of an electropolymerized molecularly imprinted polymer using benzocaine as the template molecule.

The analysis of 'cutting' or additive agents in cocaine, like benzocaine (BZC), allows police analysts to identify each component of the sample, thus obtaining information like the drugs' provenience. This kind of drug profiling is of great value in tackling drug trafficking. Electropolymerized molecularly imprinted polymers (e-MIPs) on portable screen-printed carbon electrodes (SPCEs) were developed in this study for BZC determination. The MIPs' electropolymerization was performed on a carbon surface using the anaesthetic BZC as the template molecule and 3-amino-4-hydroxybenzoic acid (3,4-AHBA) as the functional monomer. The build-up of this biomimetic sensor was carefully characterized by cyclic voltammetry (CV) and optimized. Cyclic voltammetric investigation demonstrated that BZC oxidation had a complex and pH-dependent mechanism, but at pH 7.4 a single, well-defined oxidation feature was observed. The BZC-MIP interactions were studied by computer-aided theoretical modeling by means of density functional theory (DFT) calculations. The electroanalytical methodology was effectively applied to artificial urine samples; BZC molecular recognition was achieved with a low limit of detection (LOD) of 2.9 nmol L-1 employing square-wave voltammetry (SWV). The e-MIPs were then used to 'fingerprint' genuine cocaine samples, assisted by principal component analysis (PCA), at the central forensic laboratory of the Brazilian Federal Police (BFP) with a portable potentiostat. This electroanalysis provided proof-of-concept that the drugs could be voltammetrically 'fingerprinted' using e-MIPs supported by chemometric analysis.

Gold nanoparticles immobilised in a superabsorbent hydrogel matrix: facile synthesis and application for the catalytic reduction of toxic compounds.

Two methods are reported for the one-pot preparation of high concentrations of gold nanoparticles (AuNPs) embedded throughout sodium polyacrylate hydrogels; this stabilises the AuNP in even extremely high ionic strength environments, and enables them to act as effective catalysts for the hydride-reduction of nitrophenols and of dyes, with zero order kinetics.

Biophysical analysis of cancer stem cell-potent copper(ii) coordination complexes.

Copper(ii) coordination complexes, 1 and 2, containing nonsteroidal anti-inflammatory drugs (NSAIDs) potently kill breast cancer stem cells (CSCs) and bulk breast cancer cells. Although detailed biological studies have been conducted to shed light on their mechanism of cytotoxicity, little is known about their molecular level mechanism of action. This biophysical study, aided by the preparation of a fluorophore-containing analogue, 3, reveals that the complexes operate by undergoing reduction to a copper(i) form and releasing the associated NSAIDs.

Preparation of platinum-based 'cauliflower microarrays' for enhanced ammonia gas sensing.

In amperometric gas sensors, the flux of gas to electrode surfaces determines the analytical response and detection limit. For trace concentration detection, the resulting low current prevents the miniaturisation of such sensors. Therefore, in this study, we have developed repeating arrays of nanostructures which maximise flux towards their surface. Unique platinum 3D cauliflower-shaped deposits with individual floret-shaped segments have been produced in a single step electrodeposition process. The confined walls of recessed microelectrode arrays (10 µm in diameter, 90 electrodes) are utilized to produce these structures with a high surface area. Distinct segments are observed, with the gaps corresponding to electrodes adjacent in the microarray; thus the majority of the deposits face the primary diffusion zones. The sizes and shapes of the deposits are characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM) and the largest structures are found to be 22 ±â€¯1 µm in width and 7.9 ±â€¯0.2 µm in height over the microhole. These modified electrodes are employed to detect ammonia using the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C2mim][NTf2], as an electrolyte. Current responses on the cauliflower arrays were seven times higher for linear sweep voltammetry and ca. 12 times higher for chronoamperometry, relative to the bare microrrays, and limits of detection were less than 1 part per million of ammonia (gas phase concentration). This work highlights the use of modified microarrays with highly accessible 3D structures for enhanced electroanalytical detection of analyte species at ultra low concentrations.

Kamlet-Taft solvent parameters, NMR spectroscopic analysis and thermoelectrochemistry of lithium-glyme solvate ionic liquids and their dilute solutions.

Solvate ionic liquids are a relatively new class of liquids produced by combining a coordinating solvent with a salt. They have a variety of uses and their suitability for such depends upon the ratio of salt to coordinating solvent. This work investigates the Kamlet-Taft solvent parameters of, NMR chemical shifts of nuclei in, and thermoelectrochemistry of a selected set of solvate ionic liquids produced from glymes (methyl terminated oligomers of ethylene glycol) and lithium bis(trifluoromethylsulfonyl)imide at two different compositions. The aim is to improve the understanding of the interactions occurring in these ionic liquids to help select suitable solvate ionic liquids for future applications.

Highlights from the Faraday Discussion on Ionic Liquids: From Fundamental Properties to Practical Applications, Cambridge, UK, September 2017.

For the third time, a Faraday Discussion addressed ionic liquids. Encompassing the wealth of research in this field, the contributions ranged from fundamental insights to the diverse applications of ionic liquids. Lively discussions initiated in the lecture hall and during poster sessions then seamlessly continued during the social program.

Nucleophilic Cleavage of Lignin Model Compounds under Acidic Conditions in an Ionic Liquid: A Mechanistic Study.

A range of lignin model compounds were examined for their reactivity with hydrogen bromide in the ionic liquid N-butylpyridinium triflate. It was found that the ionic liquid enabled rapid reaction at both the hydroxy and methyl ether sites of the model compounds at room temperature. Reactions at the phenyl ether moieties were more complex; rather than facilitating cleavage at these sites, alternate breakdown products that had not been seen in previous studies were observed; these products are consistent with functionalisation of the aromatic components of the model compounds.

Enhancing thermoelectrochemical properties by tethering ferrocene to the anion or cation of ionic liquids: altered thermodynamics and solubility.

Entropic changes inherent within a redox process typically result in significant temperature sensitivity. This can be utilised positively or can be a detrimental process. This study has investigated the thermoelectrochemical properties (temperature-dependant electrochemistry) of the ferrocenium|ferrocene redox couple in an ionic liquid, and in particular the effect of covalently tethering this redox couple to fixed positive or negative charges. As such, the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide was employed to dissolve ferrocene, as well as cationic-tethered ferrocene (the 1-ethyl-3-(methylferrocenyl)imidazolium cation) and anionic-tethered ferrocene (the ferrocenylsulfonyl(trifluoromethylsulfonyl)imide anion). These systems were characterised in terms of their voltammetry (apparent formal potentials, diffusion coefficients and electron transfer rate constants) and thermoelectrochemistry (temperature coefficients of the cell potential or 'Seebeck coefficients', short circuit current densities and power density outputs). The oxidised cationic species behaved like a dicationic species and was thus 6-fold more effective at converting waste thermal energy to electrical power within a thermoelectrochemical cell than unmodified ferrocene. This was almost exclusively due to a significant boost in the Seebeck coefficient of this redox couple. Conversely, the oxidised anionic species was formally a zwitterion, but this zwitterionic species behaved thermodynamically like a neutral species. The inverted entropic change upon going from ferrocene to anion-tethered ferrocene allowed development of a largely temperature-insensitive reference potential based upon a mixture of acetylferrocene and ferricenyl(iii)sulfonyl(trifluoromethylsulfonyl)imide.

Cleavage of ethers in an ionic liquid. Enhancement, selectivity and potential application.

The cleavage of a series of ethers was examined in an ionic liquid containing hydrogen bromide. Reactions that did not proceed in either water or DMSO were found to proceed readily in this system, with notable selectivity between the cleavage of the different ether types examined herein. Increasing the proportion of water in the reaction mixture dramatically decreased the rate constant of ether cleavage; this could, in part, be attributed to a decrease in the solvent stabilisation of the transition state. Through analysis of the electronic requirements of the reaction (using substrates containing substituents with different Hammett parameters) and observation of rate enhancements for an ortho substituted system, the importance of the extent of protonation of the ether prior to nucleophilic attack was demonstrated.

The thermoelectrochemistry of lithium-glyme solvate ionic liquids: towards waste heat harvesting.

Thermoelectrochemistry offers a simple, scalable technique for direct conversion of waste heat into useful electricity. Here the thermoelectrochemical properties of lithium-glyme solvate ionic liquids, as well as their dilute electrolyte analogues, have been investigated using mixtures of tetraglyme (G4, tetraethylene glycol dimethyl ether) and lithium bis(trifluoromethylsulfonyl)imide (Li[NTf2]). The thermoelectrochemical process is entropically-driven by release of the glyme from the lithium-glyme complex cation, due to electrodeposition of lithium metal at the hotter lithium electrode with concomitant electrodissolution at the cooler lithium electrode. The optimum ratio for thermochemical electricity generation is not the solvate ionic liquid (equimolar mixture of Li[NTf2] and glyme), but rather one Li[NTf2] to four G4, due to the mixtures relatively high ionic conductivity and good apparent Seebeck coefficient (+1.4 mV K(-1)). Determination of the lithium-glyme mixture thermal conductivity enabled full assessment of the Figure of Merit (ZT), and the efficiency relative to the Carnot efficiency to be determined. As the lithium electrodeposits are porous, alternating the temperature gradient results in a system that actually improves with repeated use.

Novel Chloroimidazolium-Based Ionic Liquids: Synthesis, Characterisation and Behaviour as Solvents to Control Reaction Outcome.

Novel ionic liquids containing chlorine atoms on the imidazolium cation were synthesised. The physicochemical properties of these ionic liquids were investigated extensively, including glass transition, melting and decomposition temperatures, density, viscosity, miscibility with common solvents and electrochemical window. The behaviour of these ionic liquids as solvents was examined through temperature-dependent kinetic analyses on two reactions: a nucleophilic aromatic substitution (SN Ar) reaction and a bimolecular nucleophilic substitution (SN 2) reaction. The properties and effects on reaction outcome of these new ionic liquids were shown to correlate with the change in the nature of the cation.

Phenazine virulence factor binding to extracellular DNA is important for Pseudomonas aeruginosa biofilm formation.

Bacterial resistance to conventional antibiotics necessitates the identification of novel leads for infection control. Interference with extracellular phenomena, such as quorum sensing, extracellular DNA integrity and redox active metabolite release, represents a new frontier to control human pathogens such as Pseudomonas aeruginosa and hence reduce mortality. Here we reveal that the extracellular redox active virulence factor pyocyanin produced by P. aeruginosa binds directly to the deoxyribose-phosphate backbone of DNA and intercalates with DNA nitrogenous base pair regions. Binding results in local perturbations of the DNA double helix structure and enhanced electron transfer along the nucleic acid polymer. Pyocyanin binding to DNA also increases DNA solution viscosity. In contrast, antioxidants interacting with DNA and pyocyanin decrease DNA solution viscosity. Biofilms deficient in pyocyanin production and biofilms lacking extracellular DNA show similar architecture indicating the interaction is important in P. aeruginosa biofilm formation.