Porous Layer Open Tubular Columns Research Articles

Preparation of UiO-66 MOF-Bonded Porous-Layer Open-Tubular Columns Using an In Situ Growth Approach for Gas Chromatography.

The thermally stable zirconium-based MOF, UiO-66, was employed for the preparation of bonded porous-layer open-tubular (PLOT) GC columns. The synthesis included the in situ growth of the UiO-66 film on the inner wall of the capillary through a one-step solvothermal procedure. SEM-EDX analysis revealed the formation of a thin, continuous, uniform, and compact layer of UiO-66 polycrystals on the functionalized inner wall of the column. The average polarity (ΔIav = 700) and the McReynolds constants reflected the polar nature of the UiO-66 stationary phase. Several mixtures of small organic compounds and real samples were used to evaluate the separation performance of the fabricated columns. Linear alkanes from n-pentane to n-decane were baseline separated within 1.35 min. Also, a series of six n-alkylbenzenes (C3-C8) were separated within 3 min with a minimum resolution of 3.09, whereas monohalobenzene mixtures were separated at 220 °C within 14s. UiO-66 PLOT columns are ideally suited for the isothermal separation of chlorobenzene structural isomers at 210 °C within 45 s with Rs ≥ 1.37. The prepared column featured outstanding thermal stability (up to 450 °C) without any observed bleeding or significant impact on its performance. This feature enabled the analysis of various petroleum-based samples.

Development of a gas chromatography system coupled to a metal-oxide semiconductor (MOS) sensor, with compensation of the temperature effects on the column for the measurement of ethene

Abstract. A possible way to reduce the size and complexity of common gas chromatography (GC) systems is the economization of the column temperature regulation system. To this end, a temperature compensation method was developed and validated on a benchtop GC-PDD (pulsed discharge detector) with ethene. An in-house-developed algorithm correlates the retention index of a test gas to the retention index of a previously selected reference gas. To investigate further methods of cost reduction, commercial gas sensors were tested as cheap, sensitive, and versatile detectors. Therefore, CO2 was chosen as a naturally occurring reference gas, while ethene was chosen as a maturity marker for climacteric fruits and hence as a test gas. A demonstrator, consisting of a simple syringe injection system, a PLOT (porous layer open tubular) column boxed in a polystyrene-foam housing, a commercial MOS (metal-oxide semiconductor) sensor for the test gas, and a CO2-specific IR (infrared) sensor, was used to set up a simple GC system and to apply this method on test measurements. Sorption parameters for ethene and CO2 were determined via a van 't Hoff plot, where the entropy S was −11.982 J mol−1 K−1 ΔSEthene0 and 1.351 J mol−1 K−1 ΔSCarbondioxide0, and the enthalpy H was −20.622 kJ mol−1 ΔHEthene0 and −14.792 kJ mol−1 ΔHCarbondioxide0, respectively. Ethene (100 ppm) measurements revealed a system-specific correction term of 0.652 min. Further measurements of ethene and interfering gases revealed a mean retention time for ethene of 3.093 min; the mean predicted retention time is 3.099 min. The demonstrator was able to identify the test gas, ethene, as a function of the reference gas, CO2, in a first approach, without a column heating system and in a gas mixture by applying a temperature compensation algorithm and a system-specific holdup time correction term.

Valve-based comprehensive two-dimensional gas chromatography with quadrupole mass spectrometry detection using a porous layer open tubular column in the first dimension

A comprehensive two-dimensional gas chromatography instrument with quadrupole mass spectrometry (GC×GC-qMS) is developed and evaluated, by retrofitting a commercial GC-qMS instrument with a high temperature diaphragm valve (HT-DV) modulator. A porous layer open tubular (PLOT) column in the first dimension (1D), and a more polar wall coated open tubular (WCOT) column in the second dimension (2D) were used. The HT-DV can modulate analytes of any volatility and the combination of the PLOT and WCOT columns provides ample separation selectivity for samples containing an extended range of volatility from highly volatile analytes to analytes of more moderate volatility. In addition to instrument development, we describe data visualization considerations when upgrading from GC-qMS to GC×GC-qMS. Unlike time-of-flight mass spectrometry (TOFMS), the mass spectrum cycle time for qMS (defined as the sum of scan time and interscan delay) is a linear function of the range of mass channels (m/z) analyzed. If the cycle time does not divide evenly into the modulation period, PM, visual distortions will appear in the GC×GC chromatogram. We present two approaches to address this GC×GC chromatogram distortion issue. The first method does not require post-run computations; however, care must be taken in selecting an appropriate mass range to minimize the visual distortion issue. A half of the modulation period of total shift in the 2D separations with a PM of 2 s was determined tolerable for a 15 min separation, with 44 mass ranges (and their accompanying scan rate) deemed suitable out of 350 possible mass ranges. Also, a computational “resampling” method, which can be used to correct any qMS scan rate used was implemented. Figures-of-merit for the HT-DV modulated GC×GC-qMS instrument were also examined. Reproducible peak height (average RSDheight = 9.2%, s = 3.5%) and areas (average RSDarea = 9.3%, s = 2.8%) were obtained with low LODs (average LOD = 4.2 mg/L, s = 2.5 mg/L).

Retention performance of alumina porous layer open-tubular column coated with γ–alumina nanoparticles in the highly volatile hydrocarbons separation

An alumina porous layer open-tubular (Al2O3 PLOT) column coated with γ–alumina nanoparticles (20 nm) for highly volatile hydrocarbons (C1 to C5) separation was described. Relative to the coating of bulk alumina, this column was easily coated with dynamic method under 0.4 or 0.6 MPa for 0.53 mm or 0.32 mm capillary, respectively. And the thickness of coating layer could be tuned by repeating the coating process after column was dried and activated at 300 °C for 3 h. The effect of deactivation agents on the physicochemical properties of nano γ–alumina was characterized by X–ray diffraction (XRD) measurement and nitrogen adsorption–desorption isotherms. The influences of deactivation agents, film thickness, conditioning and column dimensions on the inertness, polarity, selectivity and elution order of C1 to C5 separation were investigated in detail. The crystallite structure and size of nano alumina were not affected by the deactivation agents and remained constant during the column making processes, whereas specific surface area, pore volume and average half pore width altered significantly. The specific surface area decreased to 125.4 m2 g–1 or 174.0 m2 g–1 and the average half pore size distributions decreased to 1.6–8.4 nm or 2.4–14.3 nm when it was deactivated with potassium chloride or sodium sulfate solution, respectively. The deactivation agents and its concentrations impacted significantly on the retention performance of column. The column deactivated with sodium sulfate solution exhibited stronger polarity and lower selectivity than which deactivated with potassium chloride solution although both columns showed good inertness. The length, internal diameter and film thickness of the column had less influence on the selectivity and resolution for C1 to C5 hydrocarbons separation, whereas the conditioning temperature and time had an obvious influence. The column had distinguished polarity and selectivity which was different from either bulk or commercial alumina columns. Typically, the hydrocarbons were baseline separated with resolutions ranging from 1.65 to 15.33 within 9 min under programmed temperature below 100 °C, and the tailing factors ranging from 1.02 to 1.07.

Practical aspects of preparation, optimization, and evaluation of poly(styrene-divinylbenzene)porous-layer open tubular (PLOT) columns for capillary liquid chromatography

Using open tubular (OT) capillary columns in the nano and micro liquid chromatography scales has several advantages over conventional large-bore packed columns. Among the open tubular columns, those of the PLOT (porous layer open tubular) type are more suitable for liquid chromatography due to the porous character of the stationary phase that provides more significant interaction with the analytes. In addition, recent instrumental advances in capillaryLC coupled with mass spectrometry (MS) have opened up new avenues for developing and applying OT-LC-MS. This work discusses the possibility of applying PLOT columns in the capillary LC flow range (0.5–2 μL min−1) and describes the preparation, optimization, and evaluation of those columns. Poly(styrene-divinylbenzene) (PS-DVB) was used as the stationary phase, and the internal diameter of the columns discussed in this work was 10 and 25 μm. A comparison between these diameters is presented regarding fabrication and practical aspects of the operation. Additionally, for the 25 μm PLOT column, the gradient window and the flow rate effects on the system's performance were investigated. Flow rates of 1 μL min−1 and a gradient window of 60% (from 20 to 80% of acetonitrile) were the best conditions to work on this column in capillary LC conditions.

Selection of gas standards, gas chromatography column and adsorbents for the measurement of very volatile organic compounds (C1–C6) in indoor air

The ISO 16000-6 standard gives directions to adapt the analysis of volatile organic compounds (VOCs) in indoor and test chamber air to very volatile organic compounds (VVOCs). The same techniques with sorbent-based active sampling, thermal desorption and gas chromatography coupled with mass spectrometry (TD-GC/MS) should be used. However, VVOCs require gaseous standards, an adapted GC column and a reliable sampling adsorbent. This work presents experimental results to tackle those three experimental gaps. A stable standard gas mixture containing 47 VVOCs, 13 VOCs and an internal standard was successfully generated. It was employed to study the suitability of seven types of chromatography columns. The use of PLOT (Porous Layer Open Tubular) columns such as PoraBOND Q is well suitable for VVOC analysis. The recoveries of the 60 analytes on a total of 16 adsorbents and their combinations were determined: A combination of the graphitized carbon black Carbograph 5TD 40/60 and the carbon molecular sieve Carbosieve™ SII showed great recoveries for all analytes. Carbon molecular sieves adsorb water which can impair the analysis. A dry purge of the multi-sorbent in the sampling direction led to a complete water removal and promising recoveries of the analytes.

Application of Porous Layer Open Tubular Columns: Beyond Permanent Gases

Porous layer open tubular (PLOT) columns are traditionally built with particles that are adhered to the tubing walls. These columns have unique selectivity and provide a great alternative when gaseous samples need to be separated, but these columns also have been used to separate higher boiling point analytes. There are many different commercially available stationary phases of PLOT columns, including alumina-based columns, molecular sieves, and porous polymers. Alumina-based columns have an aluminum oxide stationary phase that is then deactivated with different salts. These columns have high capacity, superior loading ability, and produce symmetrical peaks. Molecular sieve columns are designed specifically for permanent gas separations because the columns have high retention. Porous polymer columns are highly hydrophobic, making them more applicable to analyzing a wider range of samples.

Porous layer open tubular nano liquid chromatography directly coupled to electron ionization mass spectrometry

A 25 µm i.d x 1.2 m length PS-DVB porous layer open tubular column (PLOT) was prepared and assessed in the configuration of a nano liquid chromatography coupled to an electron ionization mass spectrometry system (OT-nanoLC-EI-Ms), via the direct insertion of the column outlet into the ionization source. The developed system's operational parameters were comprehensively studied, and the setup performance was investigated employing both unidimensional and column switching configurations. As a result, the OT-nanoLC-EI-MS system demonstrated competitive applicability in separating non-amenable ESI compounds, such as polyaromatic hydrocarbons (PAHs) and non-amenable GC compounds such as thermolabile pesticides. Furthermore, with excellent chromatographic performance, the PLOT columns can work under more compatible EI-detection conditions — such as the elution with 100% organic solvent. For example, PAHs retention factors ranged between 1.5 and 2.2 for 100% MeCN mobile phase, and more than 33,000 plates per meter for naphthalene at 50 nL/min flow rate. In analyzing thermolabile pesticides, the column switching PLOT-nanoLC-EI-MS system provided LODs of 25 µg/L, demonstrating suitable intra e interday reproducibility (% RSD < 13%, n = 3), and possibilities the direct injection of raw samples with suitable robustness.

Methodology of quantitative comparison of practically achievable kinetic performance of differently structured liquid chromatography columns

Previously introduced structural quality factor (qmax) of LC column is a measure of its potential kinetic performance – the larger is qmax the proportionally larger is peak capacity (nc) of isothermal and gradient analysis with the same analysis time (tanal) and pressure (Δp). However, the best practically achievable column performance depends not only on qmax, but is limited by the narrowest practically achievable widths of the flow-through channels in the column internal support structure. These widths can be represented by the smallest practically achievable column permeability (Kmin). Large Kmin might result in unnecessarily high nc in prohibitively long tanal. Structure-independent methodology of evaluation of these effects on a column performance limits and relevant equations are developed. The best performance (the shortest tanal at a given nc) is achieved when a column operates at its highest acceptable Δp (Δpmax) even if (for reducing tanal) the column has to operate under non-optimal conditions. To demonstrate the methodology, three column types with substantially different qmax - the solid-core particle columns (SCPCs), qmax=0.4; the pillar-array columns (PACs), qmax=0.65, inter-pillar distance 1.25 µm; and the porous-layer open-tubular columns (PLOTCs), qmax=0.97, 4.6 µm ID - were compared. It is shown that, because practically available Kmin of SCPCs is much smaller than that in evaluated PLOTCs or PACs, the latter two cannot outperform contemporary SCPCs with dp≤4μm in applications with practically acceptable tanal, although SCPCs have the lowest qmax. Factors affecting Kmin, and the effect of Δpmax on a column performance limit were also evaluated and discussed.

Column Overload in PLOT Columns

Injecting too much sample onto a chromatographic system will eventually overload the column. Analytical chemists are concerned about column overloading because it reduces column efficiency, and, as a result, the resolution is sacrificed. Surprisingly, there is little data in the literature about the overloading of the porous layer open tubular (PLOT) columns. This month’s article looks at the basic types of column overload, volume and mass, and defines the variables that most affect the sample loading capacity in PLOT column chromatography.

Preparation and properties of GC capillary column with hypercrosslinked stationary phase.

For the first time, highly porous hypercrosslinked polystyrene layer was synthesized within a gas chromatography capillary column and successfully deposited onto the capillary walls generating porous layer open-tubular capillary column. Elaborated three steps synthetic procedure provides tightly bonded porous polymeric layer and ensues complete elimination of particle shedding and the needs for particle traps. Due to highly developed surface area, porous layer open-tubular column provides strong solute retention that is useful for the separation of various volatile solvents and light gas compounds including ethane, ethylene, ethyne. Aqueous injections will not harm the column.

Porous layer open-tubular column with styrene and itaconic acid-copolymerized polymer as stationary phase for capillary electrochromatography-mass spectrometry.

Enhancing the specific surface area of stationary phase is important in chromatographic science, especially in open-tubular column in which the coating only exists on the inner surface. In this work, a porous layer open-tubular (PLOT) column with stationary phase of styrene and itaconic acid-copolymerized polymer was developed. Thermal-initiated polymerization method with strategies like controlling the ratio of reaction reagents to solvents and reaction time, confinement by the narrow inner diameter of capillary were used for preparing the stationary phase with uniform structure and relatively thick layer. Due to the high separation efficiency and capacity, the PLOT column was used for capillary electrochromatography (CEC) separation of multiple groups of analytes like alkylbenzenes, phenyl amines, phenols, vanillins, and sulfonamides with theoretical plates (N) up to 1,54,845 N/m. In addition, due to high permeability of the CEC column and large electroosmotic flow mobility generated by abundant carboxyl groups in the coating material, the PLOT-CEC column was successfully coupled with mass spectrometry (MS) through a sheath flow interface. The developed PLOT-CEC-MS method was used for the analysis of antiseptics like parabens and herbicides like pyridines.

Baseline correction method for dynamic pressure gradient modulated comprehensive two-dimensional gas chromatography with flame ionization detection

A baseline correction method is developed for comprehensive two-dimensional (2D) chromatography (GC × GC) with flame-ionization detection (FID) using dynamic pressure gradient modulation (DPGM). The DPGM-GC × GC-FID utilized porous layer open tubular (PLOT) columns in both dimensions to focus on light hydrocarbon separations. Since DPGM is nominally a stop-flow modulation technique, a rhythmic baseline disturbance is observed in the FID signal that cycles with the modulation period (PM). This baseline disturbance needs to be corrected to optimize trace analysis. The baseline correction method has three steps: collection of a background “blank” chromatogram and multiplying it by an optimized normalization factor, subtraction of the normalization-optimized background chromatogram from a sample chromatogram, and application of Savitzky-Golay smoothing. An alkane standard solution, containing pentane, hexane and heptane was used for method development, producing linear calibration curves (r2 > 0.991) over a broad concentration range (7.8 ppm – 4000 ppm). Further, the limit-of-detection (LOD) and limit-of-quantification (LOQ) were determined for pentane (LOD = 2.5 ppm, LOQ = 8.2 ppm), hexane (LOD = 0.9 ppm, LOQ = 3.0 ppm), and heptane (LOD = 1.9 ppm, LOQ = 6.4 ppm). A natural gas sample separation illustrated method applicability, whereby the DPGM produced a signal enhancement (SE) of 30 for isopentane, where SE is defined as the height of the tallest 2D peak in the modulated chromatogram for the analyte divided by the height of the unmodulated 1D peak. The 30-fold SE resulted in about a 10-fold improvement in the signal-to-noise ratio (S/N) for isopentane. Additional versatility of the baseline correction method for more complicated samples was demonstrated for an unleaded gasoline sample, which enabled the detection (and visual appearance) of trace components.

A Gas Chromatography Method for Simultaneous Quantification of Inorganic Gases and Light Hydrocarbons Generated in Thermochemical Processes

This paper reports a method for simultaneous determination of H2, O2, N2, CO, CO2, CH4, C2H2, C2H4, C2H6, C3H4 (propadiene and propyne), C3H6, C3H8 and C4H10 (n-butane and iso-butane) by gas chromatography using thermal conductivity and flame ionization detectors. A single porous layer open tubular column (0.53 mm internal diameter × 30 m length × 30 μm thick) was applied and no catalytic converter was needed to convert CO and CO2 into CH4 to enable identification by a flame ionization detector. The most appropriate chromatographic conditions were defined for the method and it was validated according to the recommendations of the National Health Surveillance Agency and the National Institute of Metrology, Standardization and Industrial Quality. Chromatographic conditions defined for the target gases presented satisfactory linearity (r &gt; 0.99), and limits of detection ranged between 0.0916 and 2.75 ppm. High accuracy (98-101%) obtained for the gas chromatography/thermal conductivity detector/flame ionization detector method associated to low relative standard deviation (&lt; 2%) confirmed its applicability in routine quantification of target gases formed during the pyrolysis of municipal refuse-derived fuel.

A porous layer open-tubular capillary column supported with pepsin and zeolitic imidazolate framework for enantioseparation of four basic drugs in capillary electrochromatography

New material zeolitic imidazolate framework-4, 5-imidazoledicarboxylic acid (ZIF-IMD) located on the pore surface of porous layer open-tubular (PLOT) column previously functionalized with N-(3-aminopropyl)-imidazole have been prepared via a layer-by-layer self-assembly strategy. This new ZIF-IMD coating hybrids are used as solid-phase carriers for chiral selector pepsin immobilization. The ZIF-IMD material was characterized by scanning electron microscopy, energy-dispersive spectroscopy, transmission electron microscope and X-ray diffraction. The synthesized pepsin@ZIF-IMD@POLT column achieved the baseline separation of hydroxychloroquine (HCQ), chloroquine (CHQ) and hydroxyzine (HXY) (the resolution of HCQ: 2.19; CHQ: 1.84; HXY: 1.53). Compared with the pepsin@PLOT column (without ZIF-IMD material), the chiral separation capability of the pepsin@ZIF-IMD@POLT column can be remarkably improved. Several key parameters including concentration of chiral selector, buffer pH, applied voltage and buffer concentration were systematically evaluated to provide the optimal enantioseparation condition. The relative standard deviations (RSDs) of intra-day, inter-day, column-to-column and inter-batch of migration time and Rs of the HCQ were evaluated in detail, respectively (RSD < 7.21%). Additionally, the potential mechanism of increased resolution was discussed in the article.

Identifying an unknown compound in flue gas of semiconductor industry – Forensics of a perfluorocarbon

This study investigated the source of a false positive signal in the measurement of total non-methane organic compounds (TNMOCs) by an on-line analyzer based on flame ionization detection (FID) in the flue gas released from a semiconductor fabrication plant. Since no release of volatile organic compounds (VOCs) into the waste gas stream in acid/base ventilation was assured by the plant authority, the positive detection of VOCs became a subject of dispute. In addition to the TNMOC analysis of 5 samples, the investigation used the method that coupled thermal desorption (TD) with gas chromatography mass spectrometry (GC/MS), dubbed TD-GC/MS, to identify the substance that produced the FID signals of TNMOCs. The waste gas was collected with sampling canisters and analyzed by in-laboratory TD-GC/MS. However, mass scanning from 45 to 250 m/z to remove interference from air matrix of O2, N2 and CO2 forbid detecting any ion fragments smaller than 45 m/z and, thus, led to poor match in mass (MS) library search. As a result, a highly retentive porous layer open tubular (PLOT) capillary column was employed to separate the unknown away from the air peak. The success of acquiring all key ion fragments of 31, 50, 69, and 131 m/z resulted in an excellent match with octafluorocyclobutane (C4F8) in the NIST database. A gas standard was then prepared and injected to confirm the identity of C4F8 by the identical mass spectrum and GC retention time. The concentrations of C4F8 found in the 5 flue gas samples varying from 3.32 to 6.21 ppmv were very close to the NMOC range of 3.48–6.62 ppmv as reported by the TNMOC analyzer, proving that the FID signals observed from TNMOC method were mostly produced from C4F8. Consequently, the method of TD-GC/MS would be an ideal method to pre-screen the presence of PFCs before a non-distinguishable TNMOC analyzer is applied to approximate the VOC level as part of the integrated effort to monitor VOC in flue gas.

Multiple-open-tubular column enabling transverse diffusion. Part 1: Band broadening model for accurate mass transfer predictions

We derive a model of band broadening in multiple-open-tubular columns enabling transverse diffusion (MOTTD). In MOTTD columns, the flow channels are straight, parallel, cylindrical tubes arranged in a hexagonal compact array. A mesoporous material or stationary phase (130 Å bridged-ethyl hybrid (BEH) silica support) is filling the volume between the flow channels. The model is based on Giddings’ random-walk theory of non-equilibrium chromatography. It is calibrated for the unknown configuration factor, qs, related to the specific geometry of the stationary phase in MOTTD columns. qs values are found based on the best fit of the model to simulated dispersion data obtained by the lattice-Boltzmann method for modelling fluid flow and a random-walk particle-tracking technique to address advective–diffusive transport of the analytes. For the model calibration, simulations are performed for different ratios, ρ, of the average inner diameter of the flow channels to their closest center-to-center distance under retained and non-retained conditions.The model is successfully validated (average relative errors below 10%) under both retained and non-retained conditions. For the same column format (4.6 mm i.d. × 150 mm), external porosity, zone retention factor, and relative standard deviation of the distribution of the inner diameters of the flow channels, the derived model reveals the intrinsic advantage of MOTTD columns (center-to-center distance between flow channels of 5 µm and ρ = 0.62) over a conventional column packed with 5 µm 130 Å BEH silica particles and the same multiple porous-layer open-tubular column (MPLOT) disabling transverse dispersion. MOTTD columns are weakly affected by the polydispersity of the inner diameter of the flow channels. Provided MOTTD columns could be prepared at a small feature size of 5 µm or less, they are expected to deliver a significant improvement in column technology relative to current particulate and silica monolithic columns.

Development and evaluation of a novel analyser for ISO14687 hydrogen purity analysis

Standards ISO14687 and EN17124 set stringent limits for numerous gaseous impurities and particulates that may damage the fuel cell system in a hydrogen vehicle, as it is highly sensitive to the presence of even very low levels of impurities. However, performing the whole set of analyses is both technically challenging and time-consuming for any laboratory and will require a combination of several analytical techniques or instruments. In this study, we discussed the selection of analytical techniques for hydrogen purity testing in order to optimize the CAPEX (capital expenditure) and OPEX (operational expenditure), while ensuring the quality of the results and the compliance of the analytical methods with ISO21087. Among the individual impurities to be analysed in ISO14687, spectroscopy techniques are suitable for ammonia, carbon dioxide, carbon monoxide, formaldehyde, formic acid, oxygen and water. Spectroscopy techniques are even suitable for some impurities belonging to the three total species such as hydrogen sulphide, hydrogen chloride and methane. However, helium and argon, which are monoatomic, do not exhibit response in the infrared region. Therefore, any spectroscopic analysis method must be completed by another method in order to simultaneously analyse all individual gaseous impurities from ISO14687. In this study, we constructed and demonstrated the feasibility of an instrument composed of a gas chromatograph having three columns (two packed columns and a PLOT (Porous Layer Open Tubular) column and two detectors (FID and TCD) coupled in parallel to two OFCEAS instruments using reference gas mixtures. Finally, we also proposed an extended configuration that will allow performing the whole set of analyses for gaseous species from ISO14687.

Application of porous layer open tubular capillary columns with narrow inner diameter in nanoflow-high performance liquid chromatography for N-derivatized amino acid enantiomers

Porous layer open tubular capillary columns with a narrow inner diameter (NPLOT) have potential in life science, especially in single-cell analysis. In this work, quinidine-based chiral NPLOT columns were prepared by in-situ thermal-initiated polymerization. The porous layer of the organic polymer was prepared with a 6 μm i. d capillary by in-situ thermal-initiated polymerization, following which the thickness and morphology of the NPLOT column were observed for different durations (3 h, 6 h, and 9 h) of polymerization. The thicknesses of the porous layer were 103±51 nm and 210±51 nm when polymerization was conducted for 3 h and 6 h, respectively. Subsequently, the columns prepared under 3 h of polymerization were applied in nanoflow-high performance liquid chromatography for the enantioseparation of N-derivatized amino acid enantiomers. Baseline separation was achieved in 2 min. The sample volume consumed was of the picoliter level, which would provide a means of research for single-cell analysis.

Ionic liquid-copolymerized monolith based porous layer open tubular column for CEC-MS analysis

Developing novel capillary electrochromatography (CEC) column with high separation efficiency and capacity is an essential work in CEC. In this work, porous layer open tubular (PLOT) column has been developed by co-polymerization of quaternary ammonium typed ionic liquid (IL), 1-allyl-methylimidazolium chloride (AlMeIm+Cl−) with styrene (IL-styrene) and ethylene dimethacrylate (EDMA) for CEC-MS analysis. The PLOT-CEC column possesses high separation efficiency and capacity while keeping the inherent advantages of open tubular (OT) column unaltered, which is suitable for CEC analysis. Due to the uniform branch-like structure with large specific surface area, the IL-styrene based PLOT-CEC column showed excellent separation efficiency towards multiple kinds of analytes with theoretical plates up to N = 322,277 N/m for phloroglucinol. And thanks to the high permeability and large EOF mobility generated by positively charged ionic liquid, the PLOT-CEC column showed good performance in CEC-MS analysis of parabens, amino acids and peptides with stable separation and ESI spray. Good repeatability with relative standard deviations for intra-day, inter-day runs and between tubes less than 4.94% was obtained.