On-column ion-exchange preconcentration of inorganic anions in open tubular capillary electrochromatography with elution using transient-isotachophoretic gradients. 3. Implementation and method development

A solid-phase extraction method based on an ion-exchange retention mechanism has been used for in-line preconcentration of inorganic anions prior to their separation by capillary electrophoresis (CE). A single capillary containing a preconcentration and a separation zone has been used in a commercial CE instrument without instrumental modification. Analyte anions were retained on a preconcentration zone comprising an adsorbed layer of cationic latex particles, while separation was achieved in a separation zone comprising fused silica modified by adsorption of a cationic polymer. Elution of the adsorbed analytes was achieved using an eluotropic gradient formed by a transient isotachophoretic boundary between a fluoride electrolyte and a naphthalenedisulfonate electrolyte. Optimization of the electrolyte concentrations, sample injection times, and back-flushing times allowed the successful separation of sub-ppb levels of inorganic anions using a 100-min injection at 2 bar pressure, introducing over 40 capillary volumes of sample. A method based on a 10-min injection allowed a 100-fold increase in sensitivity over conventional hydrodynamic injection for Br-, I-, NO3-, CrO4(2-), and MoO4(2-) with a total analysis time of 25 min. Detection limits were dependent on the injection time but were in the range 2.2-11.6 ppb for a 10-min injection time. This approach was used to determine NO3- in Antarctic ice cores where the analysis could be performed using a sample volume 100 times less than that used for ion chromatography.     

One-step concentration of analytes based on dynamic change in pH in capillary zone electrophoresis

A novel strategy for one-step concentration of analytes during capillary electrophoresis (CE) is presented. A short platinum wire was inserted into the 75-microm-i.d. separation capillary. When a high voltage was applied for CE separation, a sharp pH gradient along the capillary was created dynamically by the electrolysis of water in the running buffer. Concentration of a large volume of injected analytes was accomplished by the change in analyte charge due to the dynamic pH gradient. Depending on the polarity of the applied potential and the direction of electroosmotic flow, either anions or cations can be concentrated. Several hundredfold concentration factors were achieved. Fluorescence imaging by a CCD camera was used to monitor 10 cm of the capillary near the platinum wire during the concentration process. The observations are consistent with a sweeping mechanism.     

Latex-coated polymeric monolithic ion-exchange stationary phases. 2. Micro-ion chromatography

Latex-coated monolithic polymeric stationary phases are used for micro-ion chromatography (mu-IC) of inorganic anions. Monolithic columns were prepared by the in situ polymerization of butyl methacrylate, ethylene dimethacrylate, and 2-acrylamido-2-methyl-1-propanesulfonic acid within fused-silica capillaries of varying internal diameters. Introduction of ion-exchange sites was achieved by coating the anionic polymeric monolith with either Dionex AS10 or Dionex AS18 quaternary ammonium functionalized latex particles to give total ion-exchange capacities in the range 9-24 nequiv for a 30-cm column. The resultant mu-IC columns were used for the separation of anionic analytes using chloride or acetate as the eluent-competing ion and direct UV spectrophotometric detection at 195 nm or using hydroxide as the eluent-competing ion and suppressed or nonsuppressed contactless conductivity detection. Separation efficiencies of 13,000 plates/m were observed (for iodate), and separation efficiency was maintained for large increases in flow rate (up to 42 microL/min, corresponding to a linear flow velocity of 18.5 mm/s), enabling highly reproducible, rapid separations to be achieved (seven analyte anions in less than 2 min). Use of a hollow fiber micromembrane suppressor enabled effective suppression of hydroxide eluents over the range 0.5-5.0 mM, thereby permitting suppressed conductivity detection to be performed. However, the relatively large size of the suppressor resulted in reduced separation efficiencies (e.g., 5400 plates/m for iodate). Detection limits obtained with suppressed conductivity detection were in the range 0.4-1.2 microM.     

Hydrophilic interaction chromatography using methacrylate-based monolithic capillary column for the separation of polar analytes

A porous zwitterionic monolith was prepared by thermal copolymerization of N,N-dimethyl-N-methacryloxyethyl-N-(3-sulfopropyl)ammonium betaine and ethylene dimethacrylate inside a 100-mum-i.d. capillary. The resulting monolith was evaluated as a hydrophilic liquid chromatography (HILIC) stationary phase. No evidence of swelling or shrinking of the monolith in different polarity solvents was observed. A typical HILIC mechanism was observed at higher organic solvent content (ACN% > 60%). The poly(SPE-co-EDMA) monolith showed very good selectivity for neutral, basic, and acidic polar analytes. For charged analytes, both hydrophilic interactions and electrostatic interactions contributed to their retention, which provide chromatographers more choice to optimize the separations.     

Hydrophobic,pellicular, monolithic capillary columns based on cross-linked polynorbornene for biopolymer separations

Monolithic capillary columns were prepared by transition metal-catalyzed ring-opening metathesis copolymerization of norborn-2-ene and 1,4,4a,5,8,8a-hexahydro-1,4,5,8-exo,endo-dimethanonaphthalene inside a silanized 200-microm-i.d. fused-silica capillary using a mixture of toluene and 2-propanol as porogen and Cl2(PCy3)2Ru(=CHPh) as initiator. The synthesized columns allowed the rapid and highly efficient separation of single- and double-stranded nucleic acids by ion-pair reversed-phase high-performance liquid chromatography and of proteins by reversed-phase high-performance liquid chromatography. Compared to 3-mm-i.d. analytical columns synthesized from an identical polymerization mixture, a considerable improvement in the peak widths at half-height of oligonucleotides in the order of 60-80% was obtained. Significant differences in morphology between the capillary column, where the surface of the monolith was rather soft and rugulose, and the analytical column, where the surface was very sharp and smooth, were observed, most probably due to differences in polymerization kinetics. The synthesized monoliths were successfully applied to the separation of the diastereomers of phosphorothioate oligodeoxynucleotides. To confirm the identity of the eluting compounds on the basis of their intact molecular masses, the chromatographic separation system was on-line hyphenated to electrospray ionization mass spectrometry.     

Efficient polymer monolith for strong cation-exchange capillary liquid chromatography of peptides

A stable poly[2-acrylamido-2-methyl-1-propanesulfonic acid-co-poly(ethylene glycol) diacrylate] monolith was synthesized inside a 75-microm-i.d. capillary by photoinitiated copolymerization with water, methanol, and ethyl ether as porogens. The resulting monolith was evaluated for strong cation-exchange capillary liquid chromatography of both synthetic and natural peptides. Although the monolith possessed relatively strong hydrophobicity due to the use of 2-acrylamido-2-methyl-1-propanesulfonic acid as one monomer, the monolith had a high dynamic binding capacity of 157 microequiv of peptide/mL, or 332 mg of cytochrome c/mL. Exceptionally high resolution resulting from extremely narrow peaks was obtained, resulting in a peak capacity of 179 when using a shallow salt elution gradient. Although a second, naturally formed gradient might contribute to the sharp peaks obtained, high efficiency was mainly due to the use of poly(ethylene glycol) diacrylate as a biocompatible cross-linker.     

On-capillary ion-exchange preconcentration of inorganic anions in open-tubular capillary electrochromatogrpahy with elution using transient-isotachophoretic gradient. 2. Characterization of the isotachophoretic gradient

Diffuse transient-isotachophoretic boundaries can be used as an elution gradient of increasing eluotropic strength to elute inorganic anions that have been preconcentrated on an open-tubular ion-exchange stationary phase prior to electrophoretic separation. The generation and characteristics of these gradients for elution after preconcentration have been investigated. The gradients are generated by placing a low-mobility, weak ion-exchange competing anion in the capillary (weak electrolyte, WE), and a high-mobility, strong ion-exchange competing anion in the electrolyte vials (strong electrolyte, SE). Application of voltage establishes a diffuse boundary with the composition changing from the weak anion to the strong anion. Comparison of elution gradients generated with different electrolyte systems was accomplished by comparing the eluotropic strength (a function of eluent concentration, ion-exchange selectivity coefficient, and charge) and the shape of the profile as it changes from WE to SE. The ion-exchange selectivity coefficient of the SE competing anion is important in establishing a sharp change in elution strength. A large difference in mobility between the WE and SE competing anions gives an SE with a higher final eluotropic strength, but the slope of the gradient is shallower. This results in a reduction in the efficiency of analyte focusing. To ensure maximum focusing efficiency, the WE and SE electrolytes should be selected such that the SE has the highest possible eluotropic strength for a given concentration of WE. The SE competing anion should also have a sufficiently low electrophoretic mobility to ensure focusing for the maximum number of analytes, and the mobility difference between the WE and SE competing anions should be as small as possible.     

On-line preconcentration in capillary electrochromatography using a porous monolith together with solvent gradient and sample stacking

Preconcentration effects of solvent gradient and sample stacking are investigated on a photopolymerized sol-gel (PSG) in capillary electrochromatography. The porous PSG monolith has a high mass-transfer rate. This characteristic promotes preconcentration of dilute samples. Plugs of samples more than 2 cm in length prepared in the separation solution (nongradient condition) are injected onto the PSG column. The extent of preconcentration is quite significant, showing up to a 100-fold increase in peak heights of the separated analytes. Even larger preconcentrations are achieved under gradient conditions by dissolving the sample in a matrix with a higher concentration of noneluting solvent (water). For eight alkyl phenyl ketones and four polycyclic aromatic hydrocarbons that serve as neutral test analytes, improvements in peak heights obtained under gradient conditions can be more than a 1000-fold. Indeed, injection of a 91.2-cm plug, which is more than 3 times the total length of the capillary, was possible with only a minor loss in resolution. Five peptides serve as charged test analytes. Nongradient conditions in which the sample is hydrodynamically injected onto the PSG column show sizable preconcentration because of sample stacking. The use of a solvent gradient with the same ionic strength, however, does not appear to have practical value because of destacking caused by the changing organic composition that affects the conductivity. As an alternative preconcentration method, we demonstrate that electric field-enhanced sample injection on the PSG yielded up to a 1000-fold improvement in detection sensitivity for the test peptides.     

Fabrication of graphene oxide nanosheets incorporated monolithic column via one-step room temperature polymerization for capillary electrochromatography

Graphene oxide (GO) has received great interest for its unique properties and potential diverse applications. Here, we show the fabrication of GO nanosheets incorporated monolithic column via one-step room temperature polymerization for capillary electrochromatography (CEC). GO is attractive as the stationary phase for CEC because it provides not only ionized oxygen-containing functional groups to modify electroendoosmotic flow (EOF) but also aromatic macromolecule to give hydrophobicity and π-π electrostatic stacking property. Incorporation of GO into monolithic column greatly increased the interactions between the tested neutral analytes (alkyl benzenes and polycyclic aromatics) and the stationary phase and significantly improved their CEC separation. Baseline separation of the tested neutral analytes on the GO incorporated monolithic column was achieved on the basis of typical reversed-phase separation mechanism. The precision (relative standard deviation (RSD), n = 3) of EOF was 0.3%, while the precision of retention time, peak area, and peak height for the tested neutral analytes were in the range of 0.4-3.0%, 0.8-4.0%, and 0.8-4.9%, respectively. In addition, a set of anilines were well separated on the GO incorporated monolith. The GO incorporated monolithic columns are promising for CEC separation.     

100,000-fold concentration of anions in capillary zone electrophoresis using electroosmotic flow controlled counterflow isotachophoretic stacking under field amplified conditions

An electroosmotic flow (EOF) controlled counterflow isotachophoretic stacking boundary (cf-ITPSB) system under field amplified conditions has been examined as a way to improve the sensitivity of anions separated by capillary zone electrophoresis. The system comprised a high concentration of a high-mobility leading ion (100 mM chloride) and a low concentration of low-mobility terminating ion (1-3 mM MES or CHES) added to the sample in an unmodified fused-silica capillary at pH 8.05, buffered with Tris. Computer simulation studies using the software GENTRANS showed an increase in sensitivity of at least 10-fold over the previous cf-ITPSB system for simple inorganic ions, nitrite and nitrate. The simulations also suggested that the cf-ITPSB became stationary within the capillary and that its stationary position was not adversely affected by the concentration of MES. This was in contrast to experimental results that showed a slow and continual movement of the cf-ITPSB. This was more pronounced at lower concentrations of terminator (i.e., <3 mM) and resulted in a loss of resolution due to the cf-ITPSB being closer to the detector upon separation. This discrepancy was attributed to the change in pH across the capillary due to electrolysis and low buffering capacity in the sample, a phenomenon that cannot be simulated by the GENTRANS software. Replacement of MES with CHES as a lower mobility ion with increased buffer capacity failed to reduce the movement of the cf-ITPSB but did provide a further 3-fold improvement in sensitivity. The potential of this approach for sensitivity enhancement was demonstrated for the co-EOF separation of a mixture of six inorganic and small organic ions, with detection limits at the single-figure nanogram per liter level. These detection limits are 100,000 times better than can be achieved by normal hydrodynamic injection (ions prepared in water) and 250 times better than has been achieved by other online preconcentration approaches. The application of the EOF-controlled cf-ITPSB with counter-EOF separation of two pharmaceutical pollutants, naproxen and diflunisal, was also demonstrated with an improvement in sensitivity of 1000 giving detection limits of 350 ng/L in sewage treatment wastewater without any offline pretreatment.     

Large-volume sample stacking in acidic buffer for analysis of small organic and inorganic anions by capillary electrophoresis

This paper describes a straightforward approach for stacking extremely large volumes of sample solutions containing small organic and inorganic anions in capillary electrophoresis. The methodology involves the stacking of large sample volumes and the separation of the stacked anions in an acidic buffer (pH <4) without intermediate polarity switching. More than 300-fold enrichment was readily attained in a few minutes in the stacking of two similar organic (maleic and fumaric acids) and two inorganic (bromide and nitrate) anions. The applicability of the technique was tested in the determination of trace amounts of nitrate anion (analyte-to-matrix ratio being 1:2 × 10(4) and 1:2.5 × 10(6)) in analytical-grade potassium bromide and boric acid.     

Identification of inorganic improvised explosive devices by analysis of postblast residues using portable capillary electrophoresis instrumentation and indirect photometric detection with a light-emitting diode

A commercial portable capillary electrophoresis (CE) instrument has been used to separate inorganic anions and cations found in postblast residues from improvised explosive devices (IEDs) of the type used frequently in terrorism attacks. The purpose of this analysis was to identify the type of explosive used. The CE instrument was modified for use with an in-house miniaturized light-emitting diode (LED) detector to enable sensitive indirect photometric detection to be employed for the detection of 15 anions (acetate, benzoate, carbonate, chlorate, chloride, chlorite, cyanate, fluoride, nitrate, nitrite, perchlorate, phosphate, sulfate, thiocyanate, thiosulfate) and 12 cations (ammonium, monomethylammonium, ethylammonium, potassium, sodium, barium, strontium, magnesium, manganese, calcium, zinc, lead) as the target analytes. These ions are known to be present in postblast residues from inorganic IEDs constructed from ammonium nitrate/fuel oil mixtures, black powder, and chlorate/perchlorate/sugar mixtures. For the analysis of cations, a blue LED (470 nm) was used in conjunction with the highly absorbing cationic dye, chrysoidine (absorption maximum at 453 nm). A nonaqueous background electrolyte comprising 10 mM chrysoidine in methanol was found to give greatly improved baseline stability in comparison to aqueous electrolytes due to the increased solubility of chrysoidine and its decreased adsorption onto the capillary wall. Glacial acetic acid (0.7% v/v) was added to ensure chrysoidine was protonated and to enhance separation selectivity by means of complexation with transition metal ions. The 12 target cations were separated in less than 9.5 min with detection limits of 0.11-2.30 mg/L (calculated at a signal-to-noise ratio of 3). The anions separation system utilized a UV LED (370 nm) in conjunction with an aqueous chromate electrolyte (absorption maximum at 371 nm) consisting of 10 mM chromium(VI) oxide and 10 mM sodium chromate, buffered with 40 mM tris(hydroxymethyl)aminomethane at pH 8.05. All 15 target anions were baseline separated in less than 9 min with limits of detection ranging from 0.24 to 1.15 mg/L (calculated at a signal-to-noise ratio of 3). Use of the portable instrumentation in the field was demonstrated by analyzing postblast residues in a mobile laboratory immediately after detonation of the explosive devices. Profiling the ionic composition of the inorganic IEDs allowed identification of the chemicals used in their construction.     

Sol-gel monolithic columns with reversed electroosmotic flow for capillary electrochromatography

Sol-gel chemistry was used to prepare porous monolithic columns for capillary electrochromatography. The developed sol-gel approach proved invaluable and generates monolithic columns in a simple and rapid manner. Practically any desired column length ranging from a few tens of centimeters to a few meters may be readily obtained. The incorporation of the sol-gel precursor, N-octadecyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride, into the sol solution proved to be critical as this reagent possesses an octadecyl moiety that allows for chromatographic interactions of analytes with the monolithic stationary phase. Additionally, this reagent served to yield a positively charged surface, thereby providing the relatively strong reversed electroosmotic flow (EOF) in capillary electrochromatography. The enhanced permeability of the monolithic capillaries allowed for the use of such columns without the need for modifications to the commercial CE instrument. There was no need to pressurize both capillary ends during operation or to use high pressures for column rinsing. With the developed procedure, no bubble formation was detected during analysis with the monolithic capillaries when using electric field strengths of up to 300 V cm(-1). The EOF in the monolith columns was found to be dependent on the percentage of organic modifier present in the mobile phase. Separation efficiencies of up to 1.75 x 10(5) plates/m (87,300 plates/column) were achieved on a 50 cm x 50 microm i.d. column using polycyclic aromatic hydrocarbons and aromatic aldehydes and ketones as test solutes.     

In-line valve injection for capillary electrophoresis

Direct in-line injection is successfully demonstrated for capillary electrophoresis using a commercially available injection valve designed for liquid chromatographic applications. The internal, fluid-contacting materials in this valve injector are composed of ceramics and PEEK (polyetheretherketone). In studies up to 20 kV, this materials design provides a sufficient dielectric interface to insulate the high-voltage buffer from the metal valve body. Partial-loop injections from 6 to > 60 nL are shown to be highly reproducible and generally consistent with direct electrokinetic injections under the same experimental conditions. The small extracolumn variance contributed by the valve injection system is symmetrical, and the measured theoretical plates for 75-microm- and 100-microm-i.d. separation capillaries are 1.6 x 10(5) and 2.5 x 10(5), respectively. As a result, the separation performance is quite good, demonstrating the viability of in-line valve injection for capillary electrophoresis. This development in capillary electrophoretic instrumentation has important implications for the advancement of electrophoretic applications as well as for the design of completely integrated analysis systems.     

Factors affecting the temporal stability of semipermanent bilayer coatings in capillary electrophoresis prepared using double-chained surfactants

Surfactants such as didodecyldimethylammonium bromide (DDAB) adsorb onto fused-silica capillaries to form semipermanent bilayer coatings. However, such coatings must be regenerated between runs to maintain efficiency and reproducibility. In this paper, chemical and physical factors affecting the stability of DDAB coatings are investigated. Chemical factors such as ionic strength and the nature of the buffer anion (e.g., from acetate to phosphate), which decrease the critical micelle concentration of DDAB, improve the coating stability. Increasing buffer pH also increases the coating stability. Finally, reducing the capillary diameter and reducing the volume of buffer flushed through the capillary enhance the coating stability. Using 50 mM acetate, pH 5.0, in a 25-microm-i.d. capillary, cationic proteins were separated with efficiencies of 1.05 million plates/m and a run-to-run migration time reproducibility of 0.6-0.8% RSD for 10 successive runs without regeneration of the DDAB coating between runs.     

Enhanced stability self-assembled coatings for protein separations by capillary zone electrophoresis through the use of long-chained surfactants

Semipermanent coatings were generated within fused-silica capillaries by flushing the capillary with a 0.1 mM solution of the double-chained cationic surfactants didodecyldimethylammonium bromide, dimethylditetradecylammonium bromide (2C(14)DAB), dihexadecyldimethylammonium bromide, and dimethyldioctadecylammonium bromide (2C(18)DAB) and the triple-chained surfactant tridodecylmethylammonium iodide. All of these coatings were semipermanent, whereby the coating remained intact after the unadsorbed surfactant was removed from the capillary. The separation efficiencies for four model cationic proteins ranged from 1.2 to 1.4 million plates/m for the 2C(14)DAB coating to 0.3-0.4 million plates/m for the 2C(18)DAB coatings. The stability of the coating increased with increasing hydrophobicity of the surfactant (i.e., increasing chain length and decreasing cmc). Over 60 successive separations were performed on a 2C(18)DAB-coated capillary over 12 days, without any regeneration of the coating. The migration times varied by less than 2.3% over this period with no loss in efficiency.     

Low-attomole electrospray ionization MS and MS/MS analysis of protein tryptic digests using 20-microm-i.d. polystyrene-divinylbenzene monolithic capillary columns

This work explores the use of 20-microm-i.d. polymeric polystyrene-divinylbenzene monolithic nanocapillary columns for the LC-ESI-MS analysis of tryptic digest peptide mixtures. In contrast to the packing of microparticles, capillary columns were prepared, without the need of high pressure, in fused-silica capillaries, by thermally induced in situ copolymerization of styrene and divinylbenzene. The polymerization conditions and mobile-phase composition were optimized for chromatographic performance leading to efficiencies over 100000 plates/m for peptide separations. High mass sensitivity (approximately 10 amol of peptides) in the MS and MS/MS modes using an ion trap MS was found, a factor of up to 20-fold improvement over 75-microm-i.d. nanocolumns. A wide linear dynamic range (approximately 4 orders of magnitude) was achieved, and good run-to-run and column-to-column reproducibility of isocratic and gradient elution separations were found. As samples, both model proteins and tissue extracts were employed. Gradient nano-LC-MS analysis of a proteolytic digest of a tissue extract, equivalent to a sample size of approximately 1000 cells injected, is presented.     

Micro-SPE method for sample introduction in capillary HPLC/MS

A new solid-phase extraction on-line device for micro-HPLC is presented. This device optimizes the injection of very dilute samples into a packed capillary column. It consists of two capillary, reversed-phase, HPLC columns of different length that can be linked together as a single chromatographic column. The first segment, only 2 cm long is connected to the HPLC injector. When disconnected from the longer column, several milliliters of an aqueous sample can be passed through at a high flow rate for fast trapping. On the basis of the retention mechanism, all suitable compounds are focused on the short column head in a sharp band. As soon as the chromatographic column is recomposed, the trapped analytes are eluted and separated at the optimal flow rate and gradient conditions. Due to the high preconcentration factor, trace-level analysis can be performed successfully. Different classes of analytes of various polarities and molecular weights can be determined, depending on the stationary phase and on the detector used. Some pesticides belonging to different classes were chosen to evaluate the performance of the device using an electron ionization mass spectrometer as HPLC detector. A fungicide in an irrigation canal water was determined at a concentration level of 4.5 microg x L(-1).     

Ultratrace LC/MS proteomic analysis using 10-microm-i.d. Porous layer open tubular poly(styrene-divinylbenzene) capillary columns

In this paper, the preparation and performance of long, high-efficiency poly(styrene-divinylbenzene) (PS-DVB), 10-microm-i.d. porous layer open tubular (PLOT) capillary columns are described. PLOT capillaries ( approximately 3% RSD column-to-column retention time), with relatively high permeability, were prepared by in-situ polymerization. Relatively high loading capacities, approximately 100 fmol for angiotensin I and approximately 50 fmol for insulin, were obtained with a 4.2 m x 10-microm-i.d. PLOT column. Low detection levels (attomole to sub-attomole) were achieved when the column was coupled on-line with a linear ion trap MS (LTQ). Analysis of human epidermal growth factor receptor (EGFR), a large transmembrane tyrosine kinase receptor with heterogeneous phosphorylation and glycosylation structures, was obtained at the 25 fmol level. The PLOT column yielded a peak capacity of approximately 400 for the separation of a complex tryptic digest mixture when the sample preparation included a 50-microm-i.d. PS-DVB monolithic precolumn and ESI-MS detection. As an example of the power of the column, 3046 unique peptides covering 566 distinct Methanosarcina acetivorans proteins were identified from a 50 ng in-gel tryptic digest sample combining five cuts in a single LC/MS/MS analysis using the LTQ. The results demonstrate the potential of the PLOT column for high-resolution LC/MS at the ultratrace level.     

Identification of inorganic improvised explosive devices using sequential injection capillary electrophoresis and contactless conductivity detection

A simple sequential injection capillary electrophoresis (SI-CE) instrument with capacitively coupled contactless conductivity detection (C(4)D) has been developed for the rapid separation of anions relevant to the identification of inorganic improvised explosive devices (IEDs). Four of the most common explosive tracer ions, nitrate, perchlorate, chlorate, and azide, and the most common background ions, chloride, sulfate, thiocyanate, fluoride, phosphate, and carbonate, were chosen for investigation. Using a separation electrolyte comprising 50 mM tris(hydroxymethyl)aminomethane, 50 mM cyclohexyl-2-aminoethanesulfonic acid, pH 8.9 and 0.05% poly(ethyleneimine) (PEI) in a hexadimethrine bromide (HDMB)-coated capillary it was possible to partially separate all 10 ions within 90 s. The combination of two cationic polymer additives (PEI and HDMB) was necessary to achieve adequate selectivity with a sufficiently stable electroosmotic flow (EOF), which was not possible with only one polymer. Careful optimization of variables affecting the speed of separation and injection timing allowed a further reduction of separation time to 55 s while maintaining adequate efficiency and resolution. Software control makes high sample throughput possible (60 samples/h), with very high repeatability of migration times [0.63-2.07% relative standard deviation (RSD) for 240 injections]. The separation speed does not compromise sensitivity, with limits of detection ranging from 23 to 50 μg·L(-1) for all the explosive residues considered, which is 10× lower than those achieved by indirect absorbance detection and 2× lower than those achieved by C(4)D using portable benchtop instrumentation. The combination of automation, high sample throughput, high confidence of peak identification, and low limits of detection makes this methodology ideal for the rapid identification of inorganic IED residues.