Exploring zinc coordination in novel zinc battery electrolytes

The coordination of zinc ions by tetraglyme has been investigated here to support the development of novel electrolytes for rechargeable zinc batteries. Zn(2+) reduction is electrochemically reversible from tetraglyme. The spectroscopic data, molar conductivity and thermal behavior as a function of zinc composition, between mole ratios [80 : 20] and [50 : 50] [tetraglyme : zinc chloride], all suggest that strong interactions take place between chloro-zinc complexes and tetraglyme. Varying the concentration of zinc chloride produces a range of zinc-chloro species (ZnClx)(2-x) in solution, which hinder full interaction between the zinc ion and tetraglyme. Both the [70 : 30] and [50 : 50] mixtures are promising electrolyte candidates for reversible zinc batteries, such as the zinc-air device.

Oleocanthal, a phenolic derived from virgin olive oil: a review of the beneficial effects on inflammatory disease

Virgin olive oil (VOO) is credited as being one of many healthful components of the Mediterranean diet. Mediterranean populations experience reduced incidence of chronic inflammatory disease states and VOO is readily consumed as part of an everyday dietary pattern. A phenolic compound contained in VOO, named oleocanthal, shares unique perceptual and anti-inflammatory characteristics with Ibuprofen. Over recent years oleocanthal has become a compound of interest in the search for naturally occurring compounds with pharmacological qualities. Subsequent to its discovery and identification, oleocanthal has been reported to exhibit various modes of action in reducing inflammatory related disease, including joint-degenerative disease, neuro-degenerative disease and specific cancers. Therefore, it is postulated that long term consumption of VOO containing oleocanthal may contribute to the health benefits associated with the Mediterranean dietary pattern. The following paper summarizes the current literature on oleocanthal, in terms of its sensory and pharmacological properties, and also discusses the beneficial, health promoting activities of oleocanthal, in the context of the molecular mechanisms within various models of disease.

Structure of the electrical double layer at aqueous gold and silver interfaces for saline solutions

We report the structure of the electrical double layer, determined from molecular dynamics simulations, for a range of saline solutions (NaCl, KCl, MgCl2 and CaCl2) at both 0.16 and 0.60molkg(-1) on different facets of the gold and silver aqueous interfaces. We consider the Au/Ag(111), native Au/Ag(100) and reconstructed Au(100)(5×1) facets. For a given combination of metallic surface and facet, some variations in density profile are apparent across the different cations in solution, with the corresponding chloride counterion profiles remaining broadly invariant. All density profiles at the higher concentration are predicted to be very similar to their low-concentration counterparts. We find that each electrolyte responds differently to the different metallic surface and facets, particularly those of the divalent metal ions. Our findings reveal marked differences in density profiles between facets for a given metallic interface for both Mg(2+) and Ca(2+), with Na(+) and K(+) showing much less distinction. Mg(2+) was the only ion for which we find evidence of materials-dependent differences in interfacial solution structuring between the Ag and Au.

Recycling textiles : The use of ionic liquids in the separation of cotton polyester blends

Textiles are commonly made from intimate blends of polyester and cotton, which makes recycling very difficult. We report for the first time the use of ionic liquid in the separation of polyester cotton blends. By selective dissolution of the cotton component, the polyester component can be separated and recovered in high yield. This finding presents an environmentally benign approach to recycling textile waste. © 2014 The Royal Society of Chemistry.

3D-printed and CNC milled flow-cells for chemiluminescence detection

Herein we explore modern fabrication techniques for the development of chemiluminescence detection flow-cells with features not attainable using the traditional coiled tubing approach. This includes the first 3D-printed chemiluminescence flow-cells, and a milled flow-cell designed to split the analyte stream into two separate detection zones within the same polymer chip. The flow-cells are compared to conventional detection systems using flow injection analysis (FIA) and high performance liquid chromatography (HPLC), with the fast chemiluminescence reactions of an acidic potassium permanganate reagent with morphine and a series of adrenergic phenolic amines.

Chemiluminescence detection with water-soluble iridium(III) complexes containing a sulfonate-functionalised ancillary ligand

The chemiluminescence from four cyclometalated iridium(III) complexes containing an ancillary bathophenanthroline-disulfonate ligand exhibited a wide range of emission colours (green to red), and in some cases intensities that are far greater than the commonly employed benchmark reagent, [Ru(bpy)3](2+). A similar complex incorporating a sulfonated triazolylpyridine-based ligand enabled the emission to be shifted into the blue region of the spectrum, but the responses with this complex were relatively poor. DFT calculations of electronic structure and emission spectra support the experimental findings.

Enhancing permanganate chemiluminescence detection for the determination of glutathione and glutathione disulfide in biological matrices

Acidic potassium permanganate chemiluminescence enables direct post-column detection of glutathione, but its application to assess the redox state of a wider range of biological fluids and tissues is limited by its sensitivity. Herein we show that the simple on-line addition of an aqueous formaldehyde solution not only enhances the sensitivity of the procedure by two orders of magnitude, but also provides a remarkable improvement in the selectivity of the reagent towards thiols such as glutathione (compared to phenols and amino acids that do not possess a thiol group). This enhanced mode of detection was applied to the determination of glutathione and its corresponding disulfide species in homogenised striatum samples taken from both wild type mice and the R6/1 transgenic mouse model of Huntington's disease, at both 8 and 12 weeks of age. No significant difference was observed between the GSH/GSSG ratios of wild type mice and R6/1 mice at either age group, suggesting that the early disease progression had not significantly altered the intracellular redox environment.

Red-green-blue electrogenerated chemiluminescence utilizing a digital camera as detector

Exploiting the distinct excitation and emission properties of concomitant electrochemiluminophores in conjunction with the inherent color selectivity of a conventional digital camera, we create a new strategy for multiplexed electrogenerated chemiluminescence detection, suitable for the development of low-cost, portable clinical diagnostic devices. Red, green and blue emitters can be efficiently resolved over the three-dimensional space of ECL intensity versus applied potential and emission wavelength. As the relative contribution ratio of each emitter to the photographic RGB channels is constant, the RGB ECL intensity versus applied-potential curves could be effectively isolated to a single emitter at each potential.

Protein electrochemistry using graphene-based nano-assembly: an ultrasensitive electrochemical detection of protein molecules via nanoparticle-electrode collisions

We describe a new electrochemical detection approach towards single protein molecules (microperoxidase-11, MP-11), which are attached to the surface of graphene nanosheets. The non-covalently functionalized graphene nanosheets exhibit enhanced electroactive surface area, where amplified redox current is produced when graphene nanosheets collide with the electrode.

Ethanol as an alternative to formaldehyde for the enhancement of manganese(IV) chemiluminescence detection.

Previous applications of manganese(IV) as a chemiluminescence reagent have required the use of formaldehyde to enhance the emission intensity to analytically useful levels. However, this known human carcinogen (by inhalation) is not ideal for routine application. A wide range of alternative enhancers have been examined but to date none have been found to provide the dramatic increase in chemiluminescence intensities obtained using formaldehyde. Herein, we demonstrate that ethanol offers a simple, safe and inexpensive alternative to the use of formaldehyde for manganese(IV) chemiluminescence detection, without compromising signal intensity or sensitivity. For example, chemiluminescence signals for opiate alkaloids using 50-100% ethanol were 0.8-1.6-fold those using 2M formaldehyde. This innocuous alternative enhancer is shown to be a particularly effective for the direct detection of thiols and disulfides by manganese(IV) chemiluminescence, which we have applied to a simple HPLC procedure to determine a series of biomarkers of oxidative stress.

Synthesis and preliminary investigations into norbornane-based amphiphiles and their self-assembly

A range of norbornane based amphiphiles, which possess a rigid 'kink' in the centre of amphiphiles, were accessed via a concise four step synthesis. The self-assembly properties of these novel compounds were then investigated and the critical aggregation concentration (CAC), hydrodynamic diameter (DH) by dynamic light scattering (DLS) and their morphology by cryogenic transmission electron microscopy (cryoTEM) and negatively stained transmission electron microscopy (TEM) were determined. These compounds while possessing similar CAC values (50-70 μM) exhibited a wide variety of particle size (60-140 nm) and morphologies, including vesicles, cigar-shaped aggregates and rod-like micelles. Considering the similarities in molecular structure we have proposed that the unique nature of the molecular 'kink' is affecting molecular assembly in which subtle changes in molecular structure have large ramifications on aggregate size and morphology.

Photostability of wool fabrics coated with pure and modified TiO2 colloids

The surface of wool fabrics was coated with TiO2 and TiO2-based nanocomposite colloids and the impact of this coating on the photostability of wool was investigated. TiO2 along with TiO2/Metal and TiO2/Metal/SiO2 sols were synthesized through a low-temperature sol-gel method and applied to fabrics. Composite colloids were synthesized through integrating the silica and three noble metals of silver (Ag), gold (Au) and platinum (Pt) into the synthesis process of sols. Four different molar ratios of Metal to TiO2 (0.01%, 0.1%, 0.5% and 1%) were used to elucidate the role of metal type and amount on the obtained features. Photostability and UV protection features of fabrics were evaluated through measuring the photo-induced chemiluminescence (PICL), photoyellowing rate and ultraviolet protection factor (UPF) of fabrics. PICL and photoyellowing tests were carried out under UVA and UVC light sources, respectively. PICL profiles demonstrated that the presence of pure and modified TiO2 nanoparticles on fabrics reduced the intensity of PICL peak indicating a lower amount of polymer free radicals in coated wool, compared to that of pristine fabric. Moreover, a higher PICL peak intensity as well as photoyellowing rate was observed on fabrics coated with modified colloids in comparison with pure TiO2. The surface morphology of fabrics was further characterized using FESEM images.

Design, characterization and application of a novel mono-layer pin-microvalve for microfluidic devices

Valves are one of the key components in microfluidic devices to control the fluid flow. In this paper we introduce a novel manual pin-valve which can operate in both analogue (partially close) and digital (on/off) states. We also demonstrate implementation of this pin-valve in a hydrodynamic flow focusing (HFF) device. © The Royal Society of Chemistry 2014.

Ultrafine PDMS fibers: Preparation from in situ curing-electrospinning and mechanical characterization

Polydimethylsiloxane (PDMS) fibers with unexpected elasticity were prepared by a modified core-shell electrospinning method using a commercially-available liquid PDMS precursor (Sylgard 184) and polyvinylpyrrolidone (PVP) as core and sheath materials, respectively. The liquid PDMS precursor was crosslinked in situ to form a solid core when the newly-electrospun core-sheath nanofibers were deposited onto a hot-plate electrode collector. After dissolving the PVP sheath layer off the fibers, net PDMS fibers showed larger average diameter than core-sheath fibers, with an average diameter around 1.35 μm. The tensile properties of both single fibers and fibrous mats were measured. Single PDMS fibers had a tensile strength and elongation at break of 6.0 MPa and 212%, respectively, which were higher than those of PDMS cast film (4.9 MPa, 93%). The PDMS fiber mat had larger elongation at break than the single PDMS fibers, which can be drawn up to 403% their original length. Cyclic loading tests indicated a Mullin effect on the PDMS fiber mats. Such a superior elastic feature was attributed to the PDMS molecular orientation within fibers and the randomly-orientated fibrous structure. Highly-elastic, ultrafine PDMS fibers may find applications in strain sensors, biomedical engineering, wound healing, filtration, catalysis, and functional textiles. © The Royal Society of Chemistry 2014.

Characterization of structure and energy of TixCy cluster at early formation stage in iron matrix by molecular dynamics

The structure, energy and bonding property of TixCy clusters formed in iron matrix were studied through molecular dynamics (MD) simulation method. The initial clusters with 1D-linear, 2D-ring, and 3D-tetrahedral structures were determined and their stability was calculated. The effect of temperature on the stability of the clusters was also discussed. In addition, the dissociation path of TiC clusters in iron matrix and the corresponding energy variation were analyzed. © 2014 Elsevier B.V. All rights reserved.