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Stir-bar sorptive extraction (SBSE) is a popular solvent-less sample preparation method, which is widely applied for the sampling and preconcentration of a wide range of non-polar solutes. A typical stir-bar for SBSE is composed of a polydimethylsiloxane (PDMS) film, coated onto a glass jacket with an incorporated magnet core. Sampling is carried out by direct immersion or by exposing the stir-bar to the headspace of the sample. To-date the majority of reported SBSE devices have used PDMS as the sorbent, with a few alternative commercially SBSE coatings available (such as polyethylene glycol and polyacrylate), which limits the applicability of SBSE to more polar and hydrophilic solutes. The interest in more selective extraction has been the driving force behind the recent development of novel SBSE coatings, particularly those exhibiting selectivity towards more polar solutes. During the last decade, a significant number of novel SBSE coatings were introduced utilising different fabrication approaches, including surface adhesion, molecular imprinting, sol-gel technology, immobilised monoliths, and solvent exchange processes. A range of nano- and micro-carbon-based materials, functional polymers, metal organic frameworks (MOFs), and inorganic nanoparticles have been employed for this purpose. Some of these SBSE coatings have exhibited higher thermal and chemical stability and delivered wider selectivity profiles. This review aims to summarise these significant developments, reported over the past six years, with specific attention to novel materials and selectivity for extending the potential applications of SBSE.

Electrochemical (EC) detection techniques in flow-based analytical systems such as flow injection analysis (FIA), capillary electrophoresis (CE), and liquid chromatography (LC) have attracted continuous interest over the last three decades, leading to significant advances in EC detection of a wide range of analytes in the liquid phase. In this context, the unique advantages of pulsed amperometric detection (PAD) in terms of high sensitivity and selectivity, and electrode cleaning through the application of pulsed potential for noble metal electrodes (e.g. Au, Pt), have established PAD as an important detection technique for a variety of electrochemically active compounds. PAD is especially valuable for analytes not detectable by ultraviolet (UV) photometric detection, such as organic aliphatic compounds and carbohydrates, especially when used with miniaturised capillary and chip-based separation methods. These applications have been accomplished through advances in PAD potential waveform design, as well as through the incorporation of nanomaterials (NMs) employed as microelectrodes in PAD. PAD allows on-line pulsed potential cleaning and coupling with capillary or standard separation techniques. The NMs are largely employed in microelectrodes to speed up mass and electron transfer between electrode surfaces and to perform as reactants in EC analysis. These advances in PAD have improved the sensitive and selective EC detection of analytes, especially in biological samples with complex sample matrices, and detection of electro-inactive compounds such as aliphatic organic compounds (i.e., formic acid, acetic acid, maleic acids, and β-cyclodextrin complexes). This review addresses the fundamentals of PAD, the role of pulsed sequences in AD, the utilisation of different EC detectors for PAD, technological advancements in PAD waveforms, utilisation of microelectrodes in PAD techniques, advances in the use of NMs in PAD, the applications of PAD, and prospects for EC detection, with emphasis on PAD in flow-based systems.

A new high sensitivity deep-UV LED photometric detector with a z-type flow cell (45 nL or 180 nL) for miniaturised and portable capillary liquid chromatography (LC) was designed and fabricated to overcome sensitivity limitations due to short pathlength in on-capillary detectors. The new detector has a 10 mm geometric pathlength and uses high intensity light-emitting diodes (LED) as light sources in the deep-UV range (254 nm and 280 nm). No optical reference was necessary due to the low drift in the signal. Stray light was minimized by the use of an adjustable slit with a 0.5 mm pinhole. The direct relationship between absorbance and concentration was obtained using dichromate to evaluate the sensitivity and the linearity range of the detector. Performance of the miniaturised version was compared with that obtained from a commercial benchtop detector for capillary LC under the same conditions using the same optical z-cell. The miniaturised version exhibited a superior performance across all parameters, including 3 times higher effective pathlength, 4 times higher upper limit of detector linearity, and 2–5 times lower stray light levels. An application of the new detector was shown with the detection of l -dopa, l -tyrosine, norfenefrine, phenylephrine and tyramine, separated using capillary LC. The baseline noise level recorded was as low as 3.9 μAU. Further, the detector was applied in a miniaturised capillary LC for the indirect detection of common inorganic anions. In comparison to an on-capillary LED detector applied under similar chromatographic conditions, there was a 50 times higher signal to noise (S/N) ratio.

A simple and highly efficient method for the determination of highly toxic arsenic species using non-covalently aminated silica is proposed. The polyamines including poly(hexamethyleneguanidine), poly(4,9-dioxadodecane-1,12-guanidine), hexadimethrine, and poly(diallyldimethylammonium) were tested as silica modifiers. The prepared adsorbents allow effective preconcentration of anionic species of arsenic from aqueous solutions. It was found that As(V) can be quantitatively extracted from solutions at pH 4.5–7.0 by the anion exchange mechanism in less than 5 min, while neutral at this pH As(III) was not adsorbed at these conditions. A reaction with 2,3-dimercapto-1-propanesulphonic acid, which resulted in the formation of the negatively charged complex of As(III) with adsorbents was used for its quantitative extraction from solutions with a pH of 3.5–6.5. A system of two cartridges filled with poly(diallyldimethylammonium) modified silica and the on-line reaction of As(III) with 2,3-dimercapto-1-propanesulphonic acid proceeding between the cartridges was used for separate preconcentration and determination of As(V) and As(III) at pH 5. The proposed method was used for four-year monitoring of natural water pollution by arsenic in the area of residence of the indigenous peoples of Tyva Republic (Russia).

CE methods have been developed for the analysis of organic and peroxide-based explosives. These methods have been developed for deployment on portable, in-field instrumentation for rapid screening. Both classes of compounds are neutral and were separated using micellar electrokinetic chromatography (MEKC). The effects of sample composition, separation temperature, and background electrolyte composition were investigated. The optimised separation conditions (25mM sodium tetraborate, 75mM sodium dodecyl sulfate at 25°C, detection at 200nm) were applied to the separation of 25 organic explosives in 17min, with very high efficiency (typically greater than 300,000 platesm-1) and high sensitivity (LOD typically less than 0.5mgL-1; around 1-1.5μM). A MEKC method was also developed for peroxide-based explosives (10mM sodium tetraborate, 100mM sodium dodecyl sulfate at 25°C, detection at 200nm). UV detection provided LODs between 5.5 and 45.0mgL-1 (or 31.2-304μM), which is comparable to results achieved using liquid chromatography. Importantly, no sample pre-treatment or post-column reaction was necessary and the peroxide-based explosives were not decomposed to hydrogen peroxide. Both MEKC methods have been applied to pre-blast analysis and for the detection of post-blast residues recovered from controlled, small scale detonations of organic and peroxide-based explosive devices. Refereed/Peer-reviewed

A simple, high-performance counter-current chromatography method with sequential UV absorbance (254 nm) and evaporative light scattering detection (ELSD) was developed for the quantification of pre-extracted low molecular weight dissolved organic matter (DOM) extracted from natural waters. The method requires solid-phase extraction (SPE) extraction of only small volumes of water samples, here using poly(styrenedivinylbenzene)-based extraction cartridges (Varian PPL). The extracted and concentrated DOM was quantified using reversed-phase high-performance counter-current chromatography (HPCCC), with a water/methanol (5:5) mobile phase and hexane/ethyl acetate (3:7) stationary phase. The critical chromatographic parameters were optimised, applying a revolution speed of 1900 rpm and a flow-rate of 1 mL min(-1). Under these conditions, 50 μL of extracted DOM solution could be injected and quantified using calibration against a reference natural dissolved material (Suwannee River), based upon UV absorbance at 254 nm and ELSD detection. Both detection methods provided excellent linearity (R(2) 0.995) for DOM across the concentration ranges of interest, with limits of detection of 4 μg ml(-1) and 7 μg ml(-1) for ELSD and UV absorbance, respectively. The method was validated for peak area precision (5%), and accuracy and recovery based upon spiking seawater samples prior to extraction, together with DOM solutions post-extraction (95% recovery). The developed method was applied to the determination of the concentration of DOM in seawater, based upon initial sample volumes as small as 20 mL.

A new polymer flow-cell for chemiluminescence detection (CLD) has been designed and developed by diverging multiple linear channels from a common centre port in a radial arrangement. The fabrication of radial flow-cell by 3D PolyJet printing and fused deposition modeling (FDM) has been evaluated, and compared with a similarly prepared spiral flow-cell design commonly used in chemiluminescence detectors. The radial flow-cell required only 10 h of post-PolyJet print processing time as compared to ca. 360 h long post-PolyJet print processing time required for the spiral flow-cell. Using flow injection analysis, the PolyJet 3D printed radial flow-cell provided an increase in both the signal magnitude and duration, with an average increase in the peak height of 63% and 58%, peak area of 89% and 90%, and peak base width of 41% and 42%, as compared to a coiled-tubing spiral flow-cell and the PolyJet 3D printed spiral flow-cell, respectively. Computational fluid dynamic (CFD) simulations were applied to understand the origin of the higher CLD signal obtained with the radial flow-cell design, indicating higher spatial coverage near the inlet and lower linear velocities in the radial flow-cell. The developed PolyJet 3D printed radial flow-cell was applied in a new ion chromatography chemiluminescence based assay for the detection of H2O2 in urine and coffee extracts.

A 3D printed photometric detector body with integrated slit was fabricated to position a LED and photodiode either side of capillary tubing using a fused deposition modelling (FDM) printer. To make this approach suitable for capillaries down to 50 μm i.d. the dimension of the in-built slit is the critical element of the printed housing. The spatial orientation of the model for printing was found to significantly impact on the resolution of the structures and voids that can be printed. By designing a housing with a slit positioned in the XY plane in parallel with the print direction, the narrowest void (slit) that could be printed was 70 μm. The potential use of the 3D printed slit for photometric detection was characterised using tubing and capillary from 500 down to 50 μm i.d, demonstrating a linear response from 632 to 40 mAU. The effective pathlength and stray light varied from 383 to 22 μm and 3.8% - 50% for 500- 50 μm i.d tubing and capillary. The use of a V-shaped alignment feature allowed for easy and reliable positioning of the tubing inside the detector, as demonstrated by a RSD of 1.9% (n = 10) in peak height when repositioning the tubing between measurements using flow injection analysis (FIA). The performance of the 3D printed housing and 70 μm slit was benchmarked against a commercially available interface using the CE separation of Zn2+ and Cu2+ complexes with PAR. The limit of detection with the 3D printed slit was 6.8 and 4.5 μM and is 2.8 and 1.6 μM with the commercial interface.

A range of organic solvents (ethanol, isopropanol and acetone) has been investigated as alternatives to acetonitrile and methanol when used in conjunction with Corona Charged Aerosol Detection (Corona CAD). These solvents have been evaluated with regard to their effect on the response of the Corona CAD. Three dimensional response surfaces were constructed using raw data showing the relationship between detector response, analyte concentration and percentage of organic solvent in the mobile phase, using sucralose or quinine as the test analyte. The detector response was non-linear in terms of analyte concentration for all solvents tested. However, detector response varied in an approximately linear manner with percentage of organic solvent over the range 0–40% for ethanol or isopropanol and 0–80% for acetone and methanol. The chromatographic performance of the various solvents when used as aqueous–organic mobile phases was evaluated for isocratic and gradient separations of sugars and sugar alcohols by hydrophilic interaction liquid chromatography (HILIC) using an Asahipak NH2P-504E column coupled with Corona CAD detection. It was found that whilst acetonitrile provided the highest column efficiencies and lowest detection limits of the solvents studied, acetone also performed well and could be used to resolve the same number of analytes as was possible with acetonitrile. Typical efficiencies and detection limits of 5330 plates m−1 and 1.25 μg mL−1, respectively, were achieved when acetone was used as the organic modifier. Acetone was utilised successfully as an organic modifier in the HILIC separation of carbohydrates in a beer sample and also for a partially digested dextran sample.

In this work, hydrolysis of three different hexafluorophosphate salts in purified water was investigated. Aqueous samples of lithium hexafluorophosphate (LiPF(6)), sodium hexafluorophosphate (NaPF(6)) and potassium hexafluorophosphate (KPF(6)) were prepared and stored for different times. Ion chromatography (IC) with UV as well as non-suppressed and suppressed conductivity detection was used for the analysis of the reaction products. For the detection and identification of the formed decomposition products, an IC method using IonPac AS14A 250 mm × 4.0 mm i.d. column and 2.5 mM KHCO(3)-2.5 mM K(2)CO(3) eluent was established. Besides hexafluorophosphate, four other anionic species were detected in fresh and matured aqueous solutions. The hydrolysis products fluoride (F(-)), monofluorophosphate (HPO(3)F(-)), phosphate (HPO(4)(2-)) and difluorophosphate (PO(2)F(2)(-)) were found and were unambiguously identified by means of standards or electrospray ionization mass spectrometry (ESI-MS). It was shown that stability of hexafluorophosphate solutions depends on the nature of the counter ion and decreases in the order potassium>sodium>lithium.

Examination of the chemiluminescence reactions of dihydroxybenzenes, aminophenols and phenylenediamines with acidic potassium permanganate has provided a new understanding of the relationships between analyte structure, reaction conditions, kinetics of the light-producing pathway and emission intensity, with broad implications for this widely utilised chemiluminescence detection system. Using a permanganate reagent prepared in a polyphosphate solution and adjusted to pH 2.5, large differences in the rate of reaction with different positional isomers were observed, with the meta-substituted forms reacting far slower and therefore exhibiting much lower chemiluminescence intensities in flow analysis systems. The preliminary partial reduction of permanganate to form significant concentrations of Mn(III) increased the rate of reaction with all analytes tested, resulting in comparable or (in the case of aminophenol and phenylenediamine) even greater emission intensities for the meta-isomers, demonstrating the opportunity to tune the selectivity of the reagent towards certain classes of compound or even specific positional isomers of the same compound. Using more acidic permanganate reagents, in which polyphosphates are not required, the discrepancy between the chemiluminescence intensities was still observed, but was less prominent due to the generally faster rates of reaction. The enhancement of these chemiluminescence reactions by on-line addition of formic acid or formaldehyde can in part also be attributed to the generation of significant pools of the key Mn(III) precursor to the emitting species.

Significant advances within the field of ion chromatography (IC) have often had their roots in research focussed on the development of new phase technologies, aimed to both simultaneously increase efficiency and vary selectivity. To increase selectivity it is necessary to develop new selective ion-exchangers, achieved by varying the nature of functional groups and the matrix of the stationary phase. In this comprehensive review, developments over the past decade in the production and application of zwitterionic and amphoteric ion-exchangers are presented and discussed. Zwitterionic and amphoteric ion-exchangers, where positive and negative charges are located in close proximity, exhibit alternative ion selectivity to standard anion and cation ion-exchangers, such as those traditionally used in IC, and have the potential for selectivity optimisation in IC due to control of the ratio of electrostatic attraction/repulsion forces between analyte ions and ion-exchange groups. This can result in the ability to utilise relatively dilute eluents, which increases detector sensitivity, with further advantages of zwitterionic ion-exchangers including their possible application to the simultaneous separation of cationic and anionic species.

The potential of 3D selective laser melting (SLM) technology to produce compact, temperature and pressure stable titanium alloy chromatographic columns is explored. A micro bore channel (0.9 mm I.D. × 600 mm long) was produced within a 5 × 30 × 30 mm titanium alloy (Ti–6Al–4V) cuboid, in form of a double handed spiral. A poly(butyl methacrylate-co-ethyleneglycoldimethacrylate) (BuMA-co-EDMA) monolithic stationary phase was thermally polymerised within the channel for application in reversed-phase high-performance liquid chromatography. The prepared monolithic column was applied to the liquid chromatographic separation of intact proteins and peptides. Peak capacities of 69–76 (for 6–8 proteins respectively) were observed during isothermal separation of proteins at 44 °C which were further increased to 73–77 using a thermal step gradient with programmed temperature from 60 °C to 35 °C using an in-house built direct-contact heater/cooler platform based upon matching sized Peltier thermoelectric modules. Rapid temperature gradients were possible due to direct-contact between the planar metal column and the Peltier module, and the high thermal conductivity of the titanium column as compared to a similar stainless steel printed column. The separation of peptides released from a digestion of E.coli was also achieved in less than 35 min with ca. 40 distinguishable peaks at 210 nm.

Trends towards portable analytical instrumentation of the last decades have not been equally reflected in developments of portable liquid chromatography (LC) instrumentation for rapid on-site measurements. A miniaturised medium pressure capillary LC (MPLC) system with gradient elution capability has been designed based on a flexible modular microfluidic system using primarily off-the-shelf low cost components to ensure wide accessibility to other analysts. The microfluidic platform was assembled on a breadboard and contained microsyringe pumps and switch valves, complemented with an injection valve and on-capillary detectors, all controlled by a PC. Four miniaturised microsyringe pumps, with 5, 20 and 100 μL syringe volume options, formed the basis of the pumping system. Two pairs of pumps were used for each mobile phase to create gradient elution capability. The two microsyringe pumps in each pairs were linked by two electrically operated microfluidic switching valves and both pairs of pumps were connected through a zero void volume cross-connector, thus providing a low hold-up volume for gradient formation. Sample was injected by a 20 nL nano-LC sampling valve, directly connected to a 18 cm long 100 μm i.d. Chromolith CapRod RP-18 monolithic capillary column. On-capillary LED-based UV-vis photometric detection was conducted through a piece of equal diameter fused silica capillary connected after the column. The performance of the portable LC system was evaluated theoretically and experimentally, including the maximum operating pressure, gradient mixing performance, and the performance of the detectors. The 5 μL microsyringe pump offered the best performance, with typical maximum operating pressures up to 11.4 ± 0.4 MPa (water) and gradient pumping repeatability of between 4 and 9% for gradients between 0.10% s(-1) and 0.33% s(-1). Test analytes of charged and uncharged dyes and pharmaceuticals of varying hydrophobicity showed typical RSD values of 0.7-1.4% and 3.3-4.8% in isocratic mode and 1.2-4.6% and 3.2-6.4% in gradient mode, respectively for retention time and peak area repeatability.

The high-performance separation of alkaline earth and transition metal ions on a bare porous silica 10.0 cm × 0.46 cm monolith (Merck Chromolith Si) was achieved using solvent enhanced ion chromatography. Using acetonitrile or methanol based ammonium and sodium acetate buffered mobile phases, the effect upon cation retention of mobile phase ionic strength, organic content and pH were evaluated. Increasing mobile phase acetonitrile concentration from 60 to 80% acetonitrile resulted in 10–15-fold increases in cation retention due to reduced hydration of the metal ions and hence enhanced ion-exchange interactions with surface silanol groups. The optimised conditions for the separation of Cu(II), Cd(II), Ni(II), Co(II) and Mn(II) were found to be 80% MeCN with 10.3 mM ammonium acetate (pH 4.6). Detection of transition metal ions was obtained using post-column reaction with 4-(2-pyridylazo) resorcinol and absorbance at 510 nm. Under elevated flow conditions (up to 5 mL/min), total runs times could be reduced to under 4 min. Optimum peak efficiencies were seen at flow rates of between 1.5 and 2 mL/min and were equivalent to an average efficiency of 25,000 N/m.

There has recently been increased interest in coupling ion chromatography (IC) to high resolution mass spectrometry (HRMS) to enable highly sensitive and selective analysis. Herein, the first comprehensive study focusing on the direct coupling of suppressed IC to HRMS without the need for post-suppressor organic solvent modification is presented. Chromatographic selectivity and added HRMS sensitivity offered by organic solvent-modified IC eluents on a modern hyper-crosslinked polymeric anion-exchange resin (IonPac AS18) are shown using isocratic eluents containing 5-50 mM hydroxide with 0-80% methanol or acetonitrile for a range of low molecular weight anions (

Sodium polyphosphate is commonly used to enhance chemiluminescence reactions with acidic potassium permanganate through a dual enhancement mechanism, but commercially available polyphosphates vary greatly in composition. We have examined the influence of polyphosphate composition and concentration on both the dual enhancement mechanism of chemiluminescence intensity and the stability of the reagent under analytically useful conditions. The average chain length (n) provides a convenient characterisation, but materials with similar values can exhibit markedly different distributions of phosphate oligomers. There is a minimum polyphosphate chain length (∼6) required for a large enhancement of the emission intensity, but no further advantage was obtained using polyphosphate materials with much longer average chain lengths. Providing there is a sufficient average chain length, the optimum concentration of polyphosphate is dependent on the analyte and in some cases, may be lower than the quantities previously used in routine detection. However, the concentration of polyphosphate should not be lowered in permanganate reagents that have been partially reduced to form high concentrations of the key manganese(III) co-reactant, as this intermediate needs to be stabilised to prevent formation of insoluble manganese(IV).

An ODS reversed-phase column has been used in conjunction with an aqueous mobile phase containing methylthymol blue for the separation and visible detection of metal ions. Retention is due to the formation of a dynamically coated chelating stationary phase and is dependent upon mobile phase pH and ligand concentration. Post-column addition of a buffer solution enables the sensitive visible detection of the metal ions as methylthymol blue complexes at 600 nm. The developed method resulted in improved peak efficiencies and a differing selectivity for certain metal ions, when compared to a pre-coated methylthymol blue chelating column (where the ligand was first used to modify the stationary phase, but was not included as a component of the mobile phase). The isocratic separation and visible detection of 12 metal ions was possible, including a number of the lanthanide series metals.

The nature and extent of mixed-mode retention mechanisms evident for three structurally related, agglomerated, particle-based stationary phases were evaluated. These three agglomerated phases were Thermo Fisher ScientificIon PacAS11-HC – strong anion exchange, Thermo Fisher Scientific IonPac CS10 – strong cation-exchange PS-DVB, and the Thermo Fisher Scientific Acclaim Trinity P1silica-based substrate, which is commercially marketed as a mixed-mode stationary phase. All studied phases can exhibit zwitterionic and hydrophobic properties, which contribute to the retention of charged organic analytes. A systematic approach was devised to investigate the relative ion-exchange capacities and hydrophobicities for each of the three phases, together with the effect of eluent pH upon selectivity, using a specifically selected range of anionic, cationic and neutral aromatic compounds. Investigation of the strong anion-exchange column and the Trinity P1 mixed-mode substrate, in relation to ion-exchange capacity and pH effects, demonstrated similar retention behaviour for both the anionic and ampholytic solutes, as expected from the structurally related phases. Further evaluation revealed that the ion-exchange selectivity of the mixed-mode phase exhibited properties similar to that of the strong anion-exchange column, with secondary cation-exchange selectivity, albeit with medium to high anion-exchange and cation-exchange capacities, allowing selective retention for each of the anionic, cationic and ampholytic solutes. Observed mixed-mode retention upon the examined phases was found to be a sum of anion- and cation-exchange interactions, secondary ion-exchange and hydrophobic interactions, with possible additional hydrogen bonding. Hydrophobic evaluation of the three phases revealed log P values of 0.38–0.48, suggesting low to medium hydrophobicity. These stationary phases were also benchmarked against traditional reversed-phase substrates namely, octadecylsilica YMC-Pac Pro C18 and neutral μPS-DVB resin IonPac NS1-5u, yielding log P values of 0.57 and 0.52, respectively.

Picolinic acid was used as an on-column chelating agent for the reversed-phase liquid chromatographic separation of manganese(II), copper(II), nickel(II), cobalt(II), cadmium(II) and zinc(II). The effects of picolinic acid concentration, pH and type and content of organic solvent on the retention of transition metal ions have been studied. The possibility of sensitive UV detection of complexes at 235 nm is demonstrated. Data on the use of studied system for the determination of some metal ions in a galvanic bath waste water are presented.