Fast and Environmentally Friendly Microfluidic Technique for the Fabrication of Polymer Microspheres.

This paper reports on a novel microfluidic technique for the fabrication of microspheres of synthetic polymers including poly(vinyl chloride) (PVC), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), poly(lactic acid) (PLA), and polystyrene (PS). The polymers are dissolved in tetrahydrofuran (THF) and the method is based on the diminished solubility of THF in a 20% (w/v) NaCl solution which allows the formation of droplets of the polymer solution. These polymer solution droplets are generated in a microfluidic system and their desolvation is accomplished within seconds by allowing the droplets to rise by buoyancy through a NaCl solution with a concentration lower than 15%. The size and morphology of the resultant polymer microspheres have been investigated by optical and scanning electron microscopy. Apart from the elimination of the use of highly toxic solvents as in conventional methods for manufacturing of polymer microspheres, the newly developed technique has the advantages of providing faster desolvation of the polymer solution droplets and a higher yield of microspheres compared to emulsification-based techniques.

Development of a passive sampler based on a polymer inclusion membrane for total ammonia monitoring in freshwaters.

A passive sampler for determining the time-weighted average total ammonia (i.e. molecular ammonia and the ammonium cation) concentration (C TWA) in freshwaters, which incorporated a polymer inclusion membrane (PIM) as a semi-permeable barrier separating the aqueous source solution from the receiving solution (i.e. 0.8 mol L(-1) HCl), was developed for the first time. The PIM was composed of dinonylnaphthalene sulfonic acid (DNNS) as a carrier, poly (vinyl chloride) (PVC) as a base polymer and 1-tetradecanol as a modifier. Its optimal composition was found to be 35 wt% commercial DNNS, 55 wt% PVC and 10 wt% 1-tetradecanol. The effect of environmental variables such as the water matrix, pH and temperature were also studied using synthetic freshwaters. The passive sampler was calibrated under laboratory conditions using synthetic freshwaters and exhibited a linear response within the concentration range 0.59-2.8 mg L(-1) NH4(+) (0.46-2.1 mg N L(-1)) at 20 °C. The performance of the sampler was further investigated under field conditions over 7 days. A strong correlation between spot sampling and passive sampling was achieved, thus providing a proof-of-concept for the passive sampler for reliably measuring the C(TWA) of total ammonia in freshwaters, which can be used as an indicator in tracking sources of faecal contamination in stormwater drains.

The determination of zinc using flow injection and continuous flow analysis combined with a polymer inclusion film-coated column: Application to the determination of zinc in alloys and commercial lithium chloride.

A column coated with a polymer inclusion film (PIF) containing Aliquat 336 as carrier cast on glass beads packed in a glass tube is described for the separation, preconcentration, and determination of zinc(II) in flow injection analysis (FIA) and continuous flow analysis (CFA) systems. In the FIA method, 200 µL of a sample solution containing 2 mol/L lithium chloride is injected into a 2 mol/L lithium chloride stream. This converts zinc(II) ion into its anionic chlorocomplexes which are then extracted into the Aliquat 336-based PIF by anion exchange. The extracted zinc(II) is then back-extracted into a stream of 1 mol/L sodium nitrate solution and determined spectrophotometrically using 4-(2-pyridylazo)resorcinol as the color reagent. The limit of detection (LOD, S/N = 2) was determined as 0.017 mg/L. The usability of the PIF-based FIA method was demonstrated by the determination of zinc in alloys. The PIF-coated column was also employed successfully in the CFA determination of zinc(II) as an impurity in commercial lithium chloride samples. For this, 2 mol/L commercial lithium chloride solution was passed through the column for a predetermined time period followed by stripping in a stream of 1 mol/L sodium nitrate solution.

Microfluidic Fabrication of Micropolymer Inclusion Beads for the Recovery of Gold from Electronic Scrap.

A composite material, referred to as micropolymer inclusion beads (µPIBs), was fabricated for the first time using a microfluidic technique and applied successfully for the recovery of Au(III) from simulated digests of electronic scrap. Best results for the extraction of Au(III) were achieved with µPIBs consisting of 55% (m/m) poly(vinyl chloride) as the base polymer, 35% (m/m) Aliquat 336 as the extractant, and 10% (m/m) 1-tetradecanol as a modifier. The size and surface morphology of the µPIBs were examined using optical microscopy and scanning electron microscopy, respectively. A batch of 200 mg µPIBs allowed the complete and selective extraction of Au(III) (2.85 mg) from 50 mL of a simulated digest of electronic scrap containing other metal ions, including 1365 mg Cu(II). The extracted Au(III) was quantitatively stripped from the µPIBs into 50 mL of 0.1 mol L-1 solution of thiourea. No Cu(II) and only sub-microgram levels of Cd(II) and Zn(II) were detected in this solution, thus confirming the suitability of the µPIBs for the efficient recovery of Au(III) from digests of electronic scrap. The microfluidic method used in this study is expected to be applicable for the fabrication of µPIBs for the selective separation of other chemical species by varying the composition of the beads.

A cross-linked polymer inclusion membrane for enhanced gold recovery from electronic waste.

A cross-linked polymer inclusion membrane (CL-PIM) incorporating the extractant trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl) phosphinate (Cyphos® IL 104) was developed for the first time for the enhanced Au(III) recovery from aqua regia digests of electronic waste (discarded mobile phones). Cellulose triacetate (CTA), poly(vinyl chloride) (PVC) and poly(vinylidene fluoride-co-hexafluropropylene) (PVDF-HFP) were examined as base polymers. The suitability of poly(ethylene glycol) dimethylacrylate (PEGDMA), poly(ethylene glycol) divinyl ether (PEGDVE) and N-ethylmaleimide (NEM) as cross-linking agents, and the possibility of using triarylsulfonium hexafluorophosphate (TASHFP) and 2,2-dimethoxy-2-phenylacetophenone (DMPA) as initiators were investigated. It was demonstrated that the CL-PIMs composed of Cyphos® IL 104 (30 wt%), PVDF-HFP, PEGDMA (base polymer to cross-linking agent ratio 6:4) and DMPA (1 wt%) or TASHFP (2 wt%) transported Au(III) from 2.5 mol L-1 hydrochloric acid solutions twice as fast as their non-CL-PIM counterpart, showing excellent stability over five successive transport experiments. However, in aqua regia feed solutions (6 mol L-1 acidity) only the CL-PIM containing TASHFP was able to achieve complete Au(III) recovery. AFM studies revealed that the PVDF-HFP-based CL-PIMs had a much higher surface contact area when compared to their non-CL counterpart, and this is proposed to be the reason for their superior transport performance. The CL-PIM that showed good transport efficiency in aqua regia was also applied to aqua regia digests of electronic waste from two mobile phones, and Au(III) was selectively recovered in less than 24 h, while other metals present in significantly higher concentrations were not transported.

Voltammetric ion-selective electrodes for the selective determination of cations and anions.

A general theory has been developed for voltammetric ion sensing of cations and anions based on the use of an electrode coated with a membrane containing an electroactive species, an ionophore, and a supporting electrolyte dissolved in a plasticizer. In experimental studies, a membrane coated electrode is fabricated by the drop coating method. In one configuration, a glassy carbon electrode is coated with a poly(vinyl chloride) based membrane, which contains the electroactive species, ionophore, plasticizer and supporting electrolyte. In the case of a cation sensor, ionophore facilitated transfer of the target cation from the aqueous solution to the membrane phase occurs during the course of the reduction of the electroactive species present in the membrane in order to maintain charge neutrality. The formal potential is calculated from the cyclic voltammogram as the average of the reduction and oxidation peak potentials and depends on the identity and concentration of the ion present in the aqueous solution phase. A plot of the formal potential versus the logarithm of the concentration exhibits a close to Nernstian slope of RT/F millivolts per decade change in concentration when the concentration of K(+) and Na(+) is varied over the concentration range of 0.1 mM to 1 M when K(+) or Na(+) ionophores are used in the membrane. The slope is close to RT/2F millivolts for a Ca(2+) voltammetric ion-selective electrode fabricated using a Ca(2+) ionophore. The sensor measurement time is only a few seconds. Voltammetric sensors for K(+), Na(+), and Ca(2+) constructed in this manner exhibit the sensitivity and selectivity required for determination of these ions in environmentally and biologically important matrixes. Analogous principles apply to the fabrication of anion voltammetric sensors.

Automatic determination of arsenate in drinking water by flow analysis with dual membrane-based separation.

The sequential application of a polymer inclusion membrane (PIM), composed of poly(vinylidenefluoride-co-hexafluoropropylene) and the anionic extractant Aliquat 336, and a microporous polytetrafluoroethylene (PTFE) gas-permeable membrane was utilized for the first time to develop a flow analysis (FA) system, for the automatic determination of trace levels of arsenate (As(V)) in drinking water as arsine. The system incorporated a flow-through extraction cell for separation and preconcentration of arsenate and a gas-diffusion cell for the separation of arsine prior to its spectrophotometric determination based on the discoloration of a potassium permanganate solution. Under optimal conditions the FA system is characterized by a limit of detection of 3.0 µg L-1 As(V) and repeatability of 1.8% (n = 5, 25 µg L-1 As(V)) and 2.8% (n = 5, 50 µg L-1 As(V)). The newly developed FA method was successfully applied to the determination of arsenate in drinking water samples in the µg L-1 concentration range.

A novel polymer inclusion membrane based method for continuous clean-up of thiocyanate from gold mine tailings water.

Thiocyanate is present in gold mine tailings waters in concentrations up to 1000mgL-1 and this has a serious environmental impact by not allowing water reuse in the flotation of gold ore. This significantly increases the consumption of fresh water and the amount of wastewater discharged in tailings dams. At the same time thiocyanate in tailings waters often leads to groundwater contamination. A novel continuous membrane-based method for the complete clean-up of thiocyanate in concentrations as high as 1000mgL-1 from its aqueous solutions has been developed. It employs a flat sheet polymer inclusion membrane (PIM) of composition 70wt% PVC, 20wt% Aliquat 336 and 10wt% 1-tetradecanol which separates counter-current streams of a feed thiocyanate solution and a 1M NaNO3 receiving solution. The PIM-based system has been operated continuously for 45days with 99% separation efficiency. The volume of the receiving solution has been drastically reduced by recirculating it and continuously removing thiocyanate by precipitating it with in-situ generated Cu(I). The newly developed PIM-based thiocyanate clean-up method is environmentally friendly in terms of reagent use and inexpensive with respect to both equipment and running costs.

The Effect of Surface Confined Gold Nanoparticles in Blocking the Extraction of Nitrate by PVC-Based Polymer Inclusion Membranes Containing Aliquat 336 as the Carrier.

Clusters of gold nanoparticles (AuNPs) formed on the surface of PVC-based polymer inclusion membranes (PIMs) with a liquid phase containing Aliquat 336 as the carrier and in some cases 1-dodecanol or 2-nitrophenol octyl ether as plasticizers were found to inhibit the extraction of nitrate by the PIMs. This observation was based on gradually increasing the mass of AuNPs on the membrane surface and testing the ability of the membrane to extract nitrate after each increase. In this way, it was possible to determine the so-called "critical AuNP masses" at which the studied membranes ceased to extract nitrate. On the basis of these results, it can be hypothesized that the surfaces of these PIMs are not homogeneous with respect to the distribution of their membrane liquid phases, which are present only at certain sites. Extraction takes place only at these sites, and at the "critical AuNP mass" of a PIM, all these extraction sites are blocked and the membrane loses its ability to extract.

Flow injection spectrophotometric determination of V(V) involving on-line separation using a poly(vinylidene fluoride-co-hexafluoropropylene)-based polymer inclusion membrane.

A poly(vinylidene fluoride-co-hexafluoropropylene)-based polymer inclusion membrane (PIM) using Cyphos® IL 101 (i.e. trihexyl(tetradecyl)phosphonium chloride) as the carrier and 2-nitrophenyl octyl ether as a plasticizer in a mass ratio of 55/35/10 was employed for the on-line extractive separation of V(V) prior to its spectrophotometric determination in a flow injection analysis (FIA) system using xylenol orange as the colorimetric reagent. The selectivity of the membrane allowed the determination of V(V) in sulfate solutions in the presence of a variety of cations and anions. The interference of molybdenum(VI) was eliminated by off-line extraction using the same PIM. A univariate sequential optimization of the newly developed FIA system was conducted and under optimal conditions the system is characterized by a linear concentration range of 0.5-8.0mgL-1, detection limit of 0.08mgL-1 and sample throughput of 4h-1. The relative standard deviation at the 3mgL-1 level of V(V) was 2.9% based on 8 replicate determinations. The membrane was stable, which was reflected by the standard deviation value for determinations over three consecutive days (24 determinations of 3mgL-1 V(V)) of 3.6%. The newly developed FIA system was applied to the determination of V(V) in water and dietary supplements samples and a good agreement with inductively coupled plasma optical emission spectrometry was observed.

Polymer inclusion membranes (PIMs) in chemical analysis - A review.

This review highlights the increasing interest in polymer inclusion membranes (PIMs) in analytical chemistry as they are adapted to new and novel applications. PIMs are polymer-based liquid membranes and were first introduced 50 years ago as the sensing membranes in ion-selective electrodes and optodes. More recently however, PIMs have been used for other applications in analytical chemistry such as for sample separation, sample pre-concentration, electro-driven extraction, and passive sampling, and have also been incorporated into on-line and automated analysis systems. The present review provides a general overview of the analytical chemistry applications of PIMs reported in the literature to date and illustrates their versatility for solving challenging chemical analysis problems.

Improvement of Chromium(VI) Extraction from Acidic Solutions Using a Poly(vinyl chloride)-based Polymer Inclusion Membrane with Aliquat 336 as the Carrier.

An important reason for the inefficient extraction of Cr(VI) from its acidic solutions into polymer inclusion membranes (PIMs), consisting of poly(vinyl chloride) as the base-polymer and Aliquat 336 as the carrier, was found to be associated with the leaching of Aliquat 336 from the PIMs into the solutions, where it subsequently reduced the anionic Cr(VI) species to cationic Cr(III) species. The PIM extraction efficiency for Cr(VI) was significantly improved by the addition of NaNO3 to the solutions, which suppressed the leaching of Aliquat 336 and the reduction of Cr(VI) to Cr(III).

Colorimetric detection based on localised surface plasmon resonance of gold nanoparticles: Merits, inherent shortcomings and future prospects.

Localised surface plasmon resonance (LSPR) of gold nanoparticles (AuNPs) has been exploited for two decades in analytical science and has proven to be a powerful tool for the detection of various kinds of substances including small molecules, ions, macro biomolecules and microbes. Detection can be performed by visual colour change observations, photometry or resonance light scattering. A wide range of applications have been studied in the areas of environmental, pharmaceutical and biological analysis and clinical diagnosis. In this article, some fundamental aspects and important applications involving LSPR of AuNPs are reviewed. Several inherent shortcomings of these techniques and possible strategies to circumvent them are discussed.

Extraction of Gold(III) from Hydrochloric Acid Solutions with a PVC-based Polymer Inclusion Membrane (PIM) Containing Cyphos(®) IL 104.

Poly(vinyl chloride) (PVC) based polymer inclusion membranes (PIMs), with different concentrations of Cyphos® IL 104 as the membrane extractant/carrier, were studied for their ability to extract Au(III) from hydrochloric acid solutions. Some of the PIMs also contained one of the following plasticizers or modifiers: 2-nitrophenyloctyl ether, dioctylphthalate, 1-dodecanol, 1-tetradecanol, or tri(2-ethylhexyl) phosphate. The best performance, in terms of extraction rate and amount of Au(III) extracted, was exhibited by a PIM consisting of 25 wt% Cyphos(®) IL 104, 5 wt% 1-dodecanol, and 70 wt% PVC. An almost complete back-extraction of the Au(III) extracted from this membrane was achieved by using a 0.10 mol L(-1) Na2SO3 receiver solution at pH 8. The stoichiometry of the extracted Au(III)/Cyphos® IL 104 adduct was determined as [P]⁺ [AuCl4](-) H⁺ [PO2](-) where [P]⁺ and [PO2](-) represent trihexyl(tetradecyl) phosphonium and bis(2,4,4-trimethylpentyl) phosphinate ions, respectively. Back-extraction of Au(III) is suggested to occur by reduction of Au(III) to Au(I), with the formation of the species [Au(SO3)2](3-) in the aqueous receiver solution. Loss of 1-dodecanol from the newly developed PIM to the aqueous solutions in contact with it was observed, which indicated that this membrane was suitable for single use in the efficient recovery of Au(III) from hydrochloric acid solutions of electronic scrap or recycled jewelry.

Development of a passive sampler for Zinc(II) in urban pond waters using a polymer inclusion membrane.

The use of a polymer inclusion membrane (PIM) in a novel passive sampler to measure the time-weighted average concentration of Zn(II) in urban waters is described. The passive sampler consists of a compartment containing an acidic receiving solution, which is separated from the external source solution by a PIM consisting of 40 wt% di-2-(ethylhexyl) phosphoric acid as the extractant, and 60 wt% poly-(vinyl chloride) as the base polymer. Two laboratory passive sampling techniques were tested. One involved immersion of the passive sampler into a source solution ("dip-in" approach) for a predetermined period of time while in the other one the source solution was flown past the membrane of the sampler ("flow-through" approach). The latter approach was found to be more suitable for the calibration of the passive sampler under laboratory conditions. A successful application using the "dip-in" sampling approach in urban waters has been conducted for proof of concept.

The use of a polymer inclusion membrane as a sorbent for online preconcentration in the flow injection determination of thiocyanate impurity in ammonium sulfate fertilizer.

A polymer inclusion membrane (PIM) is used for the first time as a sorbent in the construction of a preconcentration column to enhance the sensitivity in flow injection analysis (FIA). The PIM-coated column is readily prepared by coating the PIM containing poly(vinyl chloride), Aliquat 336, and 1-tetradecanol onto glass beads packed in a glass tube. The determination of trace amounts of thiocyanate in ammonium sulfate fertilizer demonstrates the potential of the proposed PIM-coated column in FIA. Thiocyanate standards or samples of relatively large volume (e.g. up to 2000 µL) are injected into a nitrate carrier stream. The sample zone passes through the proposed preconcentration column where thiocyanate is concentrated in a smaller volume of a carrier solution thus resulting in up to 7.4 fold increase in sensitivity. Thiocyanate is detected spectrophotometrically after its reaction with Fe(III) downstream of the preconcentration column. The limits of detection of thiocyanate in the absence and presence of 20 g L(-1) ammonium sulfate (S/N=2) are 0.014 and 0.024 mg L(-1), respectively. Thiocyanate was successfully determined in several samples of ammonium sulfate fertilizer.

Imaging chemical extraction by polymer inclusion membranes using fluorescence microscopy.

Polymer inclusion membranes (PIMs) transport chemicals between bodies of liquid by simultaneously performing chemical extraction and back-extraction. The internal chemical and physical mechanisms by which this transport occurs are, however, poorly understood. Also, some PIMs, which are otherwise optimal for their task, age and lose function after only days, limiting their feasibility for industrial upscaling. Through the application of fluorescence imaging methods we are able for the first time to see where chemical extraction occurs in the membrane. Extraction of fluorescein from solution by PIMs demonstrates inhomogeneities that do not correlate to surface morphology. Fluorescence lifetime imaging demonstrates that regions of increased extraction have distinctly different fluorescence lifetimes to that of the surrounding PIM indicating localized chemical environments, and this is observed to change with membrane age. Fluorescence imaging is shown to allow probing and novel understanding of PIM internal chemical morphology.

The use of a polymer inclusion membrane for separation and preconcentration of orthophosphate in flow analysis.

A highly sensitive flow analysis system has been developed for the trace determination of reactive phosphate in natural waters, which uses a polymer inclusion membrane (PIM) with Aliquat 336 as the carrier for on-line analyte separation and preconcentration. The system operates under flow injection (FI) and continuous flow (CF) conditions. Under optimal FI conditions the system is characterised by a linear concentration range between 0.5 and 1000 µg L(-1)P, a sampling rate of 10h(-1), a limit of detection of 0.5 µgL(-1)P and RSDs of 3.2% (n = 10, 100 µg L(-1)) and 7.7% (n = 10, 10 µg L(-1)). Under CF conditions with 10 min stop-flow time and sample solution flow rate of 1.32 mL min(-1) the flow system offers a limit of detection of 0.04 µg L(-1)P, a sampling rate of 5h(-1) and an RSD of 3.4% (n=5, 2.0 µg L(-1)). Interference studies revealed that anions commonly found in natural waters did not interfere when in excess of at least one order of magnitude. The flow system, operating under CF conditions, was successfully applied to the analysis of natural water samples containing concentrations of phosphate in the low µg L(-1)P range, using the multipoint standard addition method.

The use of a polymer inclusion membrane in a paper-based sensor for the selective determination of Cu(II).

A disposable paper-based sensor (PBS) is described for the determination of Cu(II) in natural and waste waters at approximately 2 cents per measurement. The device makes use of a polymer inclusion membrane (PIM) to provide the selectivity for Cu(II). The PIM consists of 40 wt% di(2-ethlyhexyl) phosphoric acid (D2EHPA) as the carrier, 10 wt% dioctyl phthalate (DOP) as a plasticizer, 49.5 wt% poly(vinyl chloride) (PVC) as the base polymer and 0.5 wt% (mm(-1)) 1-(2'-pyridylazo)-2-naphthol (PAN) as the colourimetric reagent. High selectivity under mildly acidic conditions (HCl, pH 2.0) is achieved for Cu(II) in the presence of frequently encountered metal ions in natural and waste waters such as Fe(III), Al(III), Zn(II), Cd(II), Pb(II), Ca(II), Mg(II), and Ni(II). The laminated PBS consists of a PIM sensing disc (2mm in diameter) attached to the centre of a circular hydrophilic zone (7 mm in diameter) pretreated with 0.01 M HCl. This hydrophilic zone separates the sample port (a circular hole in the plastic cover) from the PIM sensing disc. After introducing 19.2 µL of a sample/standard solution to the sample port, Cu(II) diffuses across the hydrophilic zone and is extracted into the PIM disc as the Cu(II)-D2EHPA complex which subsequently reacts with PAN to produce the red-purple coloured Cu(II)-PAN complex. The colour intensity of the PIM disc is measured 15 min after sample/standard introduction by scanning using a flatbed scanner. Under optimal conditions the device is characterized by a limit of detection (LOD) and limit of quantitation (LOQ) of 0.06 and 0.21 mg L(-1) Cu(II), respectively, with two linear ranges together covering the Cu(II) concentration range from 0.1 to 30.0 mg L(-1). The PBS was successfully applied to the determination of Cu(II) in hot tap water and mine tailings water.

On-line extractive separation in flow injection analysis based on polymer inclusion membranes: a study on membrane stability and approaches for improving membrane permeability.

The effect of temperature on the sensitivity and sampling rate is studied for a flow injection analysis (FIA) system that uses a membrane separation cell fitted with a polymer inclusion membrane (PIM) for the determination of Zn(II). A temperature of 50 °C for the flowing donor and acceptor solutions and the membrane separation cell improves the sensitivity and the sampling rate relative to 20 °C up to 10-fold and 2-fold, respectively. Studies on the stability of the PIM are reported that show a limited loss of the membrane liquid phase into the aqueous phases used in the FIA system but this has exhibited a negligible effect on the amount of Zn(II) transported across the membrane. Most importantly, the extent of leaching of the PIM components is shown to depend on the nature of the aqueous phase with the membrane eventually reaching a stable composition. It is also shown that the application of ultrasound to the membrane separation cell leads to a slight increase in sensitivity without affecting the long term membrane stability.