Influence of colourants on environmental degradation of plastic litter.

Plastic degradation and the resultant production of microplastics has an important effect on the environment and fauna across the world. This paper shows that the colourant incorporated into plastic formulations has a significant effect on the stability of plastics. A static experimental exposure of differently coloured polypropylene bottle tops from the same manufacturer to a moderate climate over 3 years showed that black, white and silver plastics were almost unaffected whereas the specific blue, green and especially red pigments used in this study were significantly degraded. The second part of the study collected littered HDPE plastic containers from a remote South African beach and analysed their condition as a function of the given manufacturing date stamp. Most items were black or white and samples up to 45 years old were found with relatively little environmental degradation other than mild abrasion. It appears that carbon and titanium dioxide colourants protect the HDPE polymer from photolytic degradation. While anthraquinone, phthalocyanine and diketopyrrolopyrrole pigments were found to enable UV light to degrade the polymer leading to brittle plastics, promoting the formation of microplastics, it is likely that other pigments that do not strongly absorb in the UV will result in similar degradation.

A mechanistic study identifying improved technology critical metal delamination from printed circuit boards at lower power sonications in a deep eutectic solvent.

Deep eutectic solvents (DESs) are an emerging class of ionic liquids that offer a solution to reclaiming technology critical metals (TCMs) from electronic waste, with potential for improved life cycle analysis. The high viscosities typical of DESs, however, impose mass transport limitations such that passive TCM removal generally requires immersion over extended durations, in some cases in the order of hours. It is postulated that, through the targeted application of power ultrasound, delamination of key structures in electronic components immersed in DESs can be significantly accelerated, thereby enabling rapid recovery of TCMs. In this paper, we fully characterise cavitation in a Choline Chloride-Ethylene Glycol DES as a function of sonotrode input power, by the acoustic detection of the bubble collapse shockwave content generated during sonications at more than 20 input powers over the available range. This justifies the selection of two powers for a detailed study of ultrasonically enhanced TCM-delamination from printed circuit boards (PCBs). Dual-perspective high-speed imaging is employed, which facilitates simultaneous observation of TCM removal, and the cavitation evolution and interaction with the PCB surface. Bubble jetting is identified as a key contributor to initial pitting of the TCM layers, exposing the larger underlying copper layer, with the contributions of additional inertial cavitation-mediated phenomena such as bubble-collapse shockwaves also demonstrated as important for delamination. Optimal cavitation activity throughout the sonication then promotes etching of the copper base layer of the PCB structure targeted by the DES, liberating the overlaying TCMs in sections as large as 0.79 mm2. We report a thirtyfold improvement in processing time compared to passive delamination, with sonications at the lower power outperforming those at the higher power. The results demonstrate the potential for industrially scalable recovery of TCMs from the growing quantities of global e-waste, using combined power ultrasonics and DESs.

A novel method for extracting metals from asteroids using non-aqueous deep eutectic solvents.

Extra-terrestrial mining and metal processing are vital for access to strategic metals for space exploration. This study demonstrates for the first time the catalytic dissolution of metals from meteorite proxies of metal-rich asteroids using a deep eutectic solvent (DES). DESs are of particular interest for extra-terrestrial mining as they can be designed to have relatively low vapour pressures and could potentially be made from organic waste products created in extra-terrestrial settlements. Three types of meteorites were investigated: two chondrites (H3, H5) and one iron (IAB-MG) meteorite. Chondrite samples were composed of silicates (olivine, pyroxene) with metal-rich phases occurring as native metal alloys, sulphides and oxides. Metallic Fe-Ni and troilite (FeS) are the most abundant metal-bearing phases in all three samples, particularly in the iron-rich meteorite. The samples were subjected to chemical micro-etching experiments with iodine and iron(III) chloride as oxidising agents in a DES formed from the mixture of choline chloride and ethylene glycol. Micro-etching experiments demonstrated that Fe-Ni rich phases are effectively leached out in this system, while other mineral phases remain unreactive.

Concentrated Ionic Fluids: Is There a Difference Between Chloride-Based Brines and Deep Eutectic Solvents?

Deep Eutectic Solvents (DESs) have been lauded as novel solvents, but is there really a difference between them and concentrated aqueous brines? They provide a method of adjusting the activity of water and chloride ions which can affect mass transport, speciation and reactivity. This study proposes a continuum of properties across concentrated ionic fluids and uses metal processing as an example. Charge transport is shown to be governed by fluidity and there is no discontinuity between molar conductivity and fluidity irrespective of cation, charge density or ionic radius. Diffusion coefficients of iron(III) and copper(II) chloride in numerous concentrated ionic fluids show the same linear correlation between diffusion coefficient and fluidity. These oxidising agents were used to etch copper, silver and nickel and while the etching rate increased with fluidity for copper, etching of silver and nickel only occurred at high chloride and low water activity as passivation occurred when water activity increased. Overall, brines provide a high chloride content at a lower viscosity than DESs, but unlike DESs, brines are unable to prevent passivation due to their high water content. The results show how selective etching of mixed metal waste streams can be achieved by tuning chloride and water activity.

Anion effect on the redox properties of copper ions in ionic liquids and deep eutectic solvents.

It has long been claimed that the anion of the DES or IL is critical for controlling the redox properties of metal ions. In this study we investigate the effect of different salt anions on the copper redox properties and speciation, and compare that with the effect of the different solvent anions, when a single copper salt is used in a range of solvents. It is shown that the effect of the solvent anion is much more significant than that of the salt anion on the redox properties. It is also found that copper species remain the same copper tetrachloride species despite the starting salt. An exception is seen for the copper(I) salt, which makes linear dichloride species, as well as the copper(II) acetate system, which displays concentration dependence. When the anion of the ionic liquid is changed, the copper species change correspondingly with the coordinating strength of the solvent anion, leading to a greater difference in redox response, which is due to the different species present. Thus, these speciation differences can be used to modify the redox potentials in the solution.

Iodine speciation in deep eutectic solvents.

Iodine has been shown to act as a good electrocatalyst for metal digestion in deep eutectic solvents (DESs) but little is known about its speciation or reactivity in these high chloride containing media. Extended X-ray absorption fine structure (EXAFS) spectroscopy measurements were made at the iodine K-edge in a range of DESs with different glycolic or acidic hydrogen bond donors (HBDs), along with examining the effect of iodine concentration between 0.01 and 0.5 mol dm-3. Three groups of speciation were detected: mixed I2Cl-/I3- (glycol and lactic acid systems), mixed I3-/I2 (oxalic acid and urea systems), and singular I3- (levulinic acid system). UV-vis spectroscopy was used to confirm the speciation. Electrochemistry showed that iodine redox behaviour was unaffected by the changing speciation. Leaching data showed that metal oxidation was related not only to changing iodine speciation, but also the reactivity and coordination ability of the HBD.

Controlled release of pharmaceutical agents using eutectic modified gelatin.

Deep eutectic solvent (DES) is a class of ionic liquids, consisting of a mixture generally formed by combining hydrogen bond donors (HBDs) such as alcohols, amides and carboxylic acids with various quaternary ammonium salts. The decrease in melting points of the constituents is due to the charge delocalization during formation of hydrogen bonding between the hydrogen bond acceptor with the hydrogen bond donor. This can be considered one of the main reasons for increasing solubility and absorption of DESs. Most active pharmaceutical ingredients (APIs) have polar functional groups containing amide, carboxylic acid, alcohol or quaternary ammonium groups. These tend to increase the melting point of the compounds, but they can be used to form eutectic mixtures. While this concept has previously used, the combination of quaternary ammonium salts with amides, carboxylic acids and alcohols can result in large depressions of freezing points and so-called deep eutectic solvents are formed. DESs mix readily with water and so could increase the uptake of APIs. In this study, pharmaceutical deep eutectic solvents (PDESs) are formulated from 3 APIs: imipramine HCl, ascorbic acid and catechol. These PDESs were used to plasticise gelatine. It is shown that the materials formed can be used to increase the rate of API uptake via both oral and transdermal delivery modes. Thus, the concentration of the PDESs in solution reaches the maximum before the pure drugs. Particularly for catechol, after 1 s, the dissolution of the PDESs was more than twice that of the pure drug. Moreover, the transdermal delivery mode uptake of the PDES based on imipramine HCl from the patch after 15 min was found to be 65% compared with just imipramine HCl which released only 20%.

Deep eutectic solvents-The vital link between ionic liquids and ionic solutions.

When selecting a solvent for a given solute, the strongly held idiom "like dissolves like", meaning that polar solvents are used for polar solutes, is often used. This idea has resulted from the concept that most molecular solvents are homogeneous. In a deep eutectic solvent (DES), however, both components can be ionic or non-ionic, polar or non-polar. By tuning the components, DESs can solubilize a wide variety of solutes, often mixing hydrophobic and hydrophilic components, and the mixture can be designed to control phase behavior. The liquids often contain significant short-length order, and preferential solvation of one component often occurs. The addition of small polar molecules such as water or alcohols results in non-homogeneous liquids, which have significantly decreased viscosity and increased ionic conductivity. Accordingly, the areas covered in this special issue focus on structure and dynamics, solvation, the mobility of charged species, and the ability to obtain controllable phase behavior by adding polar diluents or using hydrophobic DESs.

Amidine-based ionic liquid analogues with AlCl3: a credible new electrolyte for rechargeable Al batteries.

Here we demonstrate the generation of novel ionic liquid analogue (ILA) electrolytes for aluminium (Al) electrodeposition that are based on salts of amidine Lewis bases. The electrolytes exhibit reversible voltammetric plating/stripping of Al, good ionic conductivities (10-14 mS cm-1), and relatively low viscosities (50-80 cP). The rheological properties are an improvement on analogous amide-based ILAs and make these liquids credible alternatives to ILAs based on urea or acetamide, or conventional chloroaluminate ionic liquids (IL) for Al battery applications.

23Na NMR T1 relaxation measurements as a probe for diffusion and dynamics of sodium ions in salt-glycerol mixtures.

Mixtures of sodium salts with oxygen-containing molecules are useful from the perspective of applications such as sodium ion batteries because they fill the gap between deep eutectic solvents and molten salt hydrates. In a previous work, the physical properties (such as diffusion coefficients, conductivity, viscosity, and glass transition temperature) of four salts, namely, Na2B4O7 · 10H2O, NaOAc · 3H2O, NaBr, and NaOAc, were measured with glycerol. Pulsed-field gradient (PFG) nuclear magnetic resonance (NMR) was also used to measure self-diffusion coefficients of 1H-bearing species. However, the technique was not able to measure diffusion of sodium ions due to the very fast NMR relaxation rate of such species, resulting in loss of the PFG NMR signal. In the current work, this study is expanded using 23Na T1 relaxation measurements which, under certain assumptions, can be translated into diffusion coefficients. Analysis of the physical properties is then correlated with self-diffusion coefficient measurements to elucidate information about structure and ionic mobility. It is shown that NaOAc · 3H2O, NaBr, and NaOAc fit models for ionic conductivity and diffusion, which are consistent with ionic liquids where charge transport is limited by ionic mobility rather than the number of charge carriers. The waters of hydration of NaOAc · 3H2O do not appear to form a separate phase but are instead strongly coordinated to the cation. In contrast, Na2B4O7 · 10H2O appears to form a water-rich phase with enhanced sodium mobility.

Mechanical properties of 3-D printed polyvinyl alcohol matrix for detection of respiratory pathogens.

Polyvinyl alcohol is used to 3D print (fused deposition modelling) sampling matrices for bacterial detection. A specific configuration was designed using Computer-Aided Design software. The mechanical properties of the printed samples were studied using uniaxial tensile testing, and compared to those of the original Polyvinyl alcohol filament, with and without heat treatment. The effects of different factors such as UV treatment, printing speed, infill density and printing direction on the mechanical properties of the printed samples including strength, strain and modulus of elasticity were studied. The results show that the effect of the fused deposition modelling process on the mechanical properties of the printed Polyvinyl alcohol cannot be explained by its exposure to heat. UV treatment reduced the strength, characteristic strains and Young's modulus. It makes Polyvinyl alcohol samples brittle. The effects of printing speed and the infill density on the mechanical properties of printed samples can be no linear. An unexpected relation between printing direction and mechanical properties was demonstrated by the studied specimens that needs further theoretical understanding. There is a huge scatter in strength of PVA samples compared with typical engineering materials, and in the fracture strain of original PVA filament, the 3D printing process can reduce the scatter but only by a limited extent. To summarise, there is a sophisticated relation between printing parameters and the mechanical properties of the printed Polyvinyl alcohol.

3-D printed polyvinyl alcohol matrix for detection of airborne pathogens in respiratory bacterial infections.

Novel sampling matrices were manufactured using 3D printing for the detection of respiratory pathogens in expired air. A specific configuration of the matrices was designed using Computer-Aided Design software. Polyvinyl alcohol (PVA) was printed using fused deposition modelling to create a multilayer matrix to enhance the capture of bacteria. The performance of these matrices was compared with gelatine filters that have been used for this work to date. PVA matrices (60 mm diameter) were contaminated with bacteria either by direct inoculation, or by aerosol exposure using an Omron A3 nebuliser. Rough and smooth morphotypes of Mycobacterium abscessus, M. smegmatis and M. bovis BCG, were used in this study to contaminate the matrices. PVA matrices and gelatine sampling filters were contaminated to compare recovery rates for quantitative analyses. These were dissolved in water, bacteria pelleted and DNA extracted followed by a Mycobacterium-specific quantitative Polymerase Chain Reaction (qPCR).The results showed that 3D printed PVA matrices are very effective to capture the bacteria. 3D printed PVA matrix and gelatine filters yielded results of the same order of magnitude for mycobacterial analyses, however, PVA matrix offers several advantages over the latter material. 3D printed PVA is considered as an economic and time-effective matrix as it is cheaper than gelatine filters. PVA is sufficiently robust to be handled and loaded into the surgical masks for sampling, compared to the brittle gelatine filters that required supportive frames. PVA is a synthetic material and it is suitable for DNA-based analyses, whilst gelatine is derived from animal collagen, and carries a high bacterial DNA background that interferes with the target DNA analysis. Furthermore, PVA dissolves in distilled water without requiring chemicals or enzymes, such as the case for gelatine hydrolysis. To summarise, 3D printed PVA sampling matrix is considered a promising tool used for microbiological diagnostic purposes.

Separation of iron(iii), zinc(ii) and lead(ii) from a choline chloride-ethylene glycol deep eutectic solvent by solvent extraction.

Deep eutectic solvents (DESs) were used as alternatives to the aqueous phase in solvent extraction of iron(iii), zinc(ii) and lead(ii). The selective extraction of iron(iii) and zinc(ii) was studied from a feed of ethaline (1 : 2 molar ratio of choline chloride : ethylene glycol) and lactiline (1 : 2 molar ratio of choline chloride : lactic acid), with the former DES being more selective. A commercial mixture of trialkylphosphine oxides (Cyanex 923, C923) diluted in an aliphatic diluent selectively extracted iron(iii) from a feed containing also zinc(ii) and lead(ii). The subsequent separation of zinc(ii) from lead(ii) was carried out using the basic extractant Aliquat 336 (A336). The equilibration time and the extractant concentration were optimized for both systems. Iron(iii) and zinc(ii) were stripped using 1.2 mol L-1 oxalic acid and 0.5 mol L-1 aqueous ammonia, respectively. An efficient solvometallurgical flowsheet is proposed for the separation and recovery of iron(iii), lead(ii) and zinc(ii) from ethaline using commercial extractants. Moreover, the process was upscaled in a countercurrent mixer-settler set-up resulting in successful separation and purification.

Recovery of yttrium and europium from spent fluorescent lamps using pure levulinic acid and the deep eutectic solvent levulinic acid-choline chloride.

A solvometallurgical approach for the recovery of rare-earth elements from lamp phosphor waste was developed. The solubility of individual phosphors in different deep-eutectic solvents (DESs) was measured. The DES levulinic acid-choline chloride (x ChCl = 0.33) showed high solubility of the YOX phosphor (Y2O3:Eu3+) and low solubility of the HALO phosphor (Sr,Ca)10(PO4)(Cl,F)2:Sb3+,Mn2+, which does not contain any rare-earth element. This DES was selected for further investigation. When the DES was compared to pure levulinic acid, very similar leaching behaviour was observed, showing that the proton activity is more important than the chloride as a metal ligand. The leaching of YOX and HALO using levulinic acid-choline chloride (x ChCl = 0.33) or pure levulinic acid was optimised in terms of water content, temperature and leaching time. The optimised parameters were validated in a synthetic mixture of phosphors and in real lamp phosphor waste. The co-dissolution of HALO is higher in the real waste than in the synthetic mixture. The real waste was also leached with an aqueous solution of hydrochloric acid, which was non-selective against dissolution of YOX, and with the functionalised ionic liquid betainium bis(trifluoromethylsulfonyl)imide. The ionic liquid gave a similar selectivity as levulinic acid, but is much more expensive. The recovery of the metals from the pregnant leach solution was tested via precipitation with oxalic acid and solvent extraction. Oxalic acid precipitation was not suitable for the DES system. The metals could be extracted via solvent extraction with the acidic extractant bis(2-ethylhexyl)phosphoric acid (D2EHPA) and stripped by an aqueous hydrochloric acid solution. Pure levulinic acid was found to be more suitable than the corresponding ChCl-based DES for the selective recovery of YOX.

Globular and Fibrous Proteins Modified with Deep Eutectic Solvents: Materials for Drug Delivery.

Proteinaceous materials have numerous structures, many of which aid in the roles they perform. Some need to impart strength while others need elasticity or toughness. This study is the first to investigate the modification of both globular and fibrous protein, namely, zein, soy protein and gelatin, using deep eutectic solvents (DES) to form bioplastics, which may have application in drug delivery systems. The effects of DES content on the thermal and mechanical properties of the material were determined. Zein and soy are globular proteins, which both showed a significant change in the properties by the addition of DES. Both of these materials were, however, weaker and less ductile than the starch based materials previously reported in the literature. The material made from gelatin, a fibrous protein, showed variable properties depending on how long they were in contact with each other before pressing. Conductivity and NMR measurements indicate the existence of a continuous liquid phase, which are useful in the demonstrated application of transdermal drug delivery systems. It is shown that pharmaceutical DESs can be gelled with gelatin and this method is three times faster at delivering a pharmaceutical active ingredient across the skin barrier than from a corresponding solid formulation.

Potential Dependence of Surfactant Adsorption at the Graphite Electrode/Deep Eutectic Solvent Interface.

Atomic force microscopy and cyclic voltammetry are used to probe how ionic surfactant adsorbed layer structure affects redox processes at deep eutectic solvent (DES)/graphite interfaces. Unlike its behavior in water, sodium dodecyl sulfate (SDS) in DESs only adsorbs as a complete layer of hemicylindrical hemimicelles far above its critical micelle concentration (CMC). Near the CMC it forms a tail-to-tail monolayer at open-circuit potential (OCP) and positive potentials, and it desorbs at negative potentials. In contrast, cetyltrimethylammonium bromide (CTAB) adsorbs as hemimicelles at low concentrations and remains adsorbed at both positive and negative potentials. The SDS horizontal monolayer has little overall effect on redox processes at the graphite interface, but hemimicelles form an effective and stable barrier. The stronger solvophobic interactions between the C16 versus C12 alkyl chains in the DES allow CTAB to self-assemble into a robust coating at low concentrations and illustrate how the structure of the DES/electrode interface and electrochemical response can be engineered by controlling surfactant structure.

Nanostructure of the deep eutectic solvent/platinum electrode interface as a function of potential and water content.

The interfacial nanostructure of the three most widely-studied Deep Eutectic Solvents (DESs), choline chloride:urea (ChCl:Urea), choline chloride:ethylene glycol (ChCl:EG), and choline chloride:glycerol (ChCl:Gly) at a Pt(111) electrode has been studied as a function of applied potential and water content up to 50 wt%. Contact mode atomic force microscope (AFM) force-distance curves reveal that for all three DESs, addition of water increases the interfacial nanostructure up to ∼40 wt%, after which it decreases. This differs starkly from ionic liquids, where addition of small amounts of water rapidly decreases the interfacial nanostructure. For the pure DESs, only one interfacial layer is measured at OCP at 0.5 nm, which increases to 3 to 6 layers extending ∼5 nm from the surface at 40 or 50 wt% water. Application of a potential of ±0.25 V to the Pt electrode for the pure DESs increases the number of near surface layers to 3. However, when water is present the applied potential attenuates the steps in the force curve, which are replaced by a short-range exponential decay. This change was most pronounced for ChCl:EG with 30 wt% or 50 wt% water, so this system was probed using cyclic voltammetry, which confirms the interfacial nanostructure is akin to a salt solution.

Redox fusion of metal particles using deep eutectic solvents.

Alternating anodic and cathodic current pulses have been applied to a metal powder on an electrode surface to fuse the particles together. It is shown that homogeneous films can be electroformed with different morphologies depending on the size of the powder and the experimental conditions.

Brønsted acidity in deep eutectic solvents and ionic liquids.

Despite the importance of ionic liquids in a variety of fields, little is understood about the behaviour of protons in these media. The main difficulty arises due to the unknown activity of protons in non-aqueous solvents. This study presents acid dissociation constants for nine organic acids in deep eutectic solvents (DESs) using standard pH indicator solutes. The pKIn value for bromophenol blue was found by titrating the DES with triflic acid. The experimental method was developed to understand the acid-base properties of deep eutectic solvents, and through this study it was found that the organic acids studied were slightly less dissociated in the DES than in water with pKa values between 0.2 and 0.5 higher. pKIn values were also determined for two ionic liquids, [Bmim][BF4] and [Emim][acetate]. The anion of the ionic liquid changes the pH of the solution by acting as a buffer. [Emim][acetate] was found to be more basic than water. It is also shown that water significantly affects the pH of ionic liquids. This is thought to arise because aqueous mixtures with ionic liquids form heterogeneous solutions and the proton partitions into the aqueous phase. This study also attempted to develop an electrochemical pH sensor. It was shown that a linear response of cell potential vs. ln aH+ could be obtained but the slope for the correlation was less than that obtained in aqueous solutions. Finally it was shown that the liquid junction potential between two reference electrodes immersed in different DESs was dependent upon the pH difference between the liquids.

Bright metal coatings from sustainable electrolytes: the effect of molecular additives on electrodeposition of nickel from a deep eutectic solvent.

Organic and inorganic additives are often added to nickel electroplating solutions to improve surface finish, reduce roughness and promote uniform surface morphology of the coatings. Such additives are usually small molecules and often referred to as brighteners or levellers. However, there have been limited investigations into the effect of such additives on electrodeposition from ionic liquids (ILs) and deep eutectic solvents (DESs). Here we study the effect of four additives on electrolytic nickel plating from an ethyleneglycol based DES; these are nicotinic acid (NA), methylnicotinate (MN), 5,5-dimethylhydantoin (DMH) and boric acid (BA). The additives show limited influence on the bulk Ni(ii) speciation but have significant influence on the electrochemical behaviour of Ni deposition. Small concentrations (ca. 15 mM) of NA and MN show inhibition of Ni(ii) reduction whereas high concentrations of DMH and BA are required for a modest difference in behaviour from the additive free system. NA and MN also show that they significantly alter the nucleation and growth mechanism when compared to the additive free system and those with DMH and BA. Each of the additive systems had the effect of producing brighter and flatter bulk electrodeposits with increased coating hardness but XRD shows that NA and MN direct crystal growth to the [111] orientation whereas DMH and BA direct crystal growth to the [220] orientation.