Concept: Water softening
In this study, the efficiency of six ion exchange resins to reduce the dissolved organic matter (DOM) from a biologically treated newsprint mill effluent was evaluated and the dominant removal mechanism of residual organics was established using advanced organic characterisations techniques. Among the resins screened, TAN1 possessed favourable Freundlich parameters, high resin capacity and solute affinity, closely followed by Marathon MSA and Marathon WBA. The removal efficiency of colour and lignin residuals was generally good for the anion exchange resins, greater than 50% and 75% respectively. In terms of the DOM fractions removal measured through liquid chromatography-organic carbon and nitrogen detector (LC-OCND), the resins mainly targeted the removal of humic and fulvic acids of molecular weight ranging between 500 and 1000gmol(-1), the portion expected to contribute the most to the aromaticity of the effluent. For the anion exchange resins, physical adsorption operated along with ion exchange mechanism assisting to remove neutral and transphilic acid fractions of DOM. The column studies confirmed TAN1 being the best of those screened, exhibited the longest mass transfer zone and maximum treatable volume of effluent. The treatable effluent volume with 50% reduction in dissolved organic carbon (DOC) was 4.8 L for TAN1 followed by Marathon MSA - 3.6L, Marathon 11 - 2.0L, 21K-XLT - 1.5L and Marathon WBA - 1.2L. The cation exchange resin G26 was not effective in DOM removal as the maximum DOC removal obtained was only 27%. The resin capacity could not be completely restored for any of the resins; however, a maximum restoration up to 74% and 93% was achieved for TAN1 and Marathon WBA resins. While this feasibility study indicates the potential option of using ion exchange resins for the reclamation of paper mill effluent, the need for improving the regeneration protocols to restore the resin efficiency is also identified. Similarly, care should be taken while employing LC-OCND for characterising resin-treated effluents, as the resin degradation is expected to contribute some organic carbon moieties misleading the actual performance of resin.
Living in a hard water area is associated with an increased risk of atopic dermatitis (AD). Greater skin barrier impairment following exposure to surfactants in wash products combined with high calcium, and/or chlorine, levels in hard water is a compelling mechanism for this increase. The purpose of this study was to investigate this mechanism in individuals with and without a predisposition to skin barrier impairment. We recruited 80 subjects; healthy controls and AD patients with and without FLG mutations. The skin of each participant was washed with sodium lauryl sulfate (SLS) in water of varying hardness and chlorine concentration, rinsed and covered with chambers to determine the effects of surfactant residues. Sites washed with hard water exhibited significantly increased SLS deposits. These deposits increased transepidermal water loss and caused irritation, particularly in AD patients carrying FLG mutations. A clear effect of chlorine was not observed. Water softening by ion-exchange mitigated the negative effects of hard water. Barrier impairment resulting from the interaction between hard water and surfactants is a contributory factor to the development of AD. Installation of a water softener in early life may be able to prevent AD development. An intervention study is required to test this hypothesis.
Post-synthestic chemical transformations of colloidal nanocrystals, such as ion-exchange reactions, provide an avenue to compositional fine tuning or to otherwise inaccessible materials and morphologies. While cation-exchange is facile and commonplace, anion-exchange reactions have not received substantial deployment. Here we report fast, low-temperature, deliberately partial or complete anion-exchange in highly luminescent semiconductor nanocrystals of cesium lead halide perovskites (CsPbX3, X=Cl, Br, I). By adjusting the halide ratios in the colloidal nanocrystal solution, the bright photoluminescence can be tuned over the entire visible spectral region (410-700 nm) while maintaining high quantum yields of 20-80% and narrow emission linewidths of 10-40 nm (from blue to red). Furthermore, fast inter-nanocrystal anion-exchange is demonstrated, leading to uniform CsPb(Cl/Br)3 or CsPb(Br/I)3 compositions simply by mixing CsPbCl3, CsPbBr3 and CsPbI3 nanocrystals in appropriate ratios.
Herein, we successfully devised a novel photoelectrochemical (PEC) platform for ultrasensitive detection of adenosine by target-triggering cascade multiple cycle amplification based on the silver nanoparticles-assisted ion-exchange reaction with CdTe quantum dots (QDs). In the presence of target adenosine, DNA s1 is released from the aptamer and then hybridizes with hairpin DNA (HP1), which could initiate the cycling cleavage process under the reaction of nicking endonuclease. Then the product (DNA b) of cycle I could act as the “DNA trigger” of cycle II to further generate a large number of DNA s1, which again go back to cycle I, thus a cascade multiple DNA cycle amplification was carried out to produce abundant DNA c. These DNA c fragments with the cytosine ©-rich loop were captured by magnetic beads, and numerous silver nanoclusters (Ag NCs) were synthesized by AgNO3and sodium borohydride. The dissolved AgNCs released numerous silver ions which could induce ion exchange reaction with the CdTe QDs, thus resulting in greatly amplified change of photocurrent for target detection. The detection linear range for adenosine was 1.0 fM ~10 nM with the detection limit of 0.5 fM. The present PEC strategy combining cascade multiple DNA cycle amplification and AgNCs-induced ion-exchange reaction with QDs provides new insight into rapid, and ultrasensitive PEC detection of different biomolecules, which showed great potential for detecting trace amounts in bioanalysis and clinical biomedicine.
Desalination and softening of sea, brackish, and ground water are becoming increasingly important solutions to overcome water shortage challenges. Various technologies have been developed for salt removal from water resources including multi-stage flash, multi-effect distillation, ion exchange, reverse osmosis, nanofiltration, electrodialysis, as well as adsorption. Recently, removal of solutes by adsorption onto selective adsorbents has shown promising perspectives. Different types of adsorbents such as zeolites, carbon nanotubes (CNTs), activated carbons, graphenes, magnetic adsorbents, and low-cost adsorbents (natural materials, industrial by-products and wastes, bio-sorbents, and biopolymer) have been synthesized and examined for salt removal from aqueous solutions. It is obvious from literature that the existing adsorbents have good potentials for desalination and water softening. Besides, nano-adsorbents have desirable surface area and adsorption capacity, though are not found at economically viable prices and still have challenges in recovery and reuse. On the other hand, natural and modified adsorbents seem to be efficient alternatives for this application compared to other types of adsorbents due to their availability and low cost. Some novel adsorbents are also emerging. Generally, there are a few issues such as low selectivity and adsorption capacity, process efficiency, complexity in preparation or synthesis, and problems associated to recovery and reuse that require considerable improvements in research and process development. Moreover, large-scale applications of sorbents and their practical utility need to be evaluated for possible commercialization and scale up.
Electrocatalytic CO2conversion at near ambient temperatures and pressures offers a potential means of converting waste greenhouse gases into fuels or commodity chemicals (e.g., CO, formic acid, methanol, ethylene, alkanes, and alcohols). This process is particularly compelling when driven by excess renewable electricity because the consequent production of solar fuels would lead to a closing of the carbon cycle. However, such a technology is not currently commercially available. While CO2electrolysis in H-cells is widely used for screening electrocatalysts, these experiments generally do not effectively report on how CO2electrocatalysts behave in flow reactors that are more relevant to a scalable CO2electrolyzer system. Flow reactors also offer more control over reagent delivery, which includes enabling the use of a gaseous CO2feed to the cathode of the cell. This setup provides a platform for generating much higher current densities ( J) by reducing the mass transport issues inherent to the H-cells. In this Account, we examine some of the systems-level strategies that have been applied in an effort to tailor flow reactor components to improve electrocatalytic reduction. Flow reactors that have been utilized in CO2electrolysis schemes can be categorized into two primary architectures: Membrane-based flow cells and microfluidic reactors. Each invoke different dynamic mechanisms for the delivery of gaseous CO2to electrocatalytic sites, and both have been demonstrated to achieve high current densities ( J > 200 mA cm-2) for CO2reduction. One strategy common to both reactor architectures for improving J is the delivery of CO2to the cathode in the gas phase rather than dissolved in a liquid electrolyte. This physical facet also presents a number of challenges that go beyond the nature of the electrocatalyst, and we scrutinize how the judicious selection and modification of certain components in microfluidic and/or membrane-based reactors can have a profound effect on electrocatalytic performance. In membrane-based flow cells, for example, the choice of either a cation exchange membrane (CEM), anion exchange membrane (AEM), or a bipolar membrane (BPM) affects the kinetics of ion transport pathways and the range of applicable electrolyte conditions. In microfluidic cells, extensive studies have been performed upon the properties of porous carbon gas diffusion layers, materials that are equally relevant to membrane reactors. A theme that is pervasive throughout our analyses is the challenges associated with precise and controlled water management in gas phase CO2electrolyzers, and we highlight studies that demonstrate the importance of maintaining adequate flow cell hydration to achieve sustained electrolysis.
In recent papers we have discussed the optimization of design and operating conditions for cuboid packed-bed device for chromatographic separations. The efficiency metrics used in these studies included the number of theoretical plates per unit bed height as well as attributes of flow-through and eluted peaks. These studies were carried out using equivalent columns as benchmarks. The cuboid packed-bed devices consistently outperformed the columns in terms of the above metrics. The current study examines how well, or indeed if at all these superior efficiency metrics translate to superiority in multi-component protein separation. Cation exchange resin was examined in the current study using appropriate multi-component model protein system which was chosen with close isoelectric points to make the separation challenging. Effects of operating and experimental parameters such as flow rate, loop size and linear gradient length on separation performance were systematically investigated. Separation metrics examined included peak width, tailing factor, asymmetry factor and resolution of separated protein peaks. The results obtained showed that the cation exchange cuboid packed-bed device significantly outperformed its equivalent commercial column (e.g., the number of theoretical plates per unit bed height was 8636/m for the cuboid packed-bed device as opposed to 1480/m for the column at a flow rate of 0.5 mL/min). The difference in efficiency was particularly high at lower flow rate and when shorter gradients were employed. The results suggest that the cuboid packed-bed devices could potentially have promising application in preparative separations such as biopharmaceutical purifications.
The unification of tunable band edge (BE) emission and strong Mn2+ doping luminescence in all-inorganic cesium lead halide perovskite nanocrystals (NCs) CsPbX3 (X = Cl and Br) is of fundamental importance in fine tuning their optical properties. Herein, we demonstrate that, benefiting from the differentiation of the cation/anion exchange rate, ZnBr2 and preformed CsPb1-xCl3:xMn NCs can be used to obtain high Br content Cs(Pb1-x-zZnz)(ClyBr1-y)3:xMn2+ perovskite NCs with strong Mn2+ emission, and Mn2+ substitution ratio can reach about 22%. More specifically, the fast anion ex-change could be realized by the soluble halide precursors leading to anion exchange within a few seconds as observed from the strong BE emission evolution, while the cation exchange instead generally required at least a few hours, moreover, their exchange mechanism and dynamics process have been evaluated. The Mn2+ emission intensity could be further varied by controlling the replacement of Mn2+ by Zn2+ with prolonged ion exchange reaction time. White light emission of the doped perovskite NCs via this cation/anion synergistic exchange strategy has been realized, which also successfully demonstrated in a prototype white LED device based on a commercially available 365 nm LED chip.
Caramel enriched in di-D-fructose dianhydrides (DFAs, a family of prebiotic cyclic fructodisaccharides) is a functional food with beneficial properties for health. The aim of this work was to study the conversion of fructose into DFAs catalyzed by acid ion-exchange resin, in order to establish a simplified mechanism of the caramelization reaction and a kinetic model for DFA formation. Batch reactor experiments were carried out in a 250 mL spherical glass flask and afforded up to 50%DFA yields. The mechanism proposed entails order 2 reactions that describe fructose conversion on DFAs or formation of by-products such as HMF or melanoidins. A third order 1 reaction defines DFA transformation into fructosyl-DFAs or fructo-oligosaccharides. The influence of fructose concentration, resin loading and temperature was studied to calculate the kinetic parameters necessary to scale up the process.
An integrated all flow-through technology platform for the purification of therapeutic monoclonal antibodies (mAb), consisting of activated carbon and flow-through cation and anion exchange chromatography steps, can replace a conventional chromatography platform. This new platform was observed to have excellent impurity clearance at high mAb loadings with overall mAb yield exceeding 80%. Robust removal of DNA and host cell protein was demonstrated by activated carbon and a new flow-through cation exchange resin exhibited excellent clearance of mAb aggregate with high monomer recoveries. A ten-fold improvement of mAb loading was achieved compared to a traditional cation exchange resin designed for bind and elute mode. High throughput 96-well plate screening was used for process optimization, focusing on mAb loading and solution conditions. Optimum operating windows for integrated flow-through purification are proposed based on performance characteristics. The combination of an all flow-through polishing process presents significant opportunities for improvements in facility utilization and process economics.