通过柱切换技术与高效液相色谱联用的限进性柱对盐酸贝那普利的在线富集性能

以自制的限进性填料柱为预处理富集柱,Luna C₁₈柱为分析柱,通过柱切换技术将限进性填料柱与高效液相色谱联用(RAM-HPLC),研究了盐酸贝那普利的在线富集效果。考察了进样体积与峰面积、系统总压力的关系,以及常规进样与大体积进样的差别。当进样体积在100 μL以内时,峰面积随进样体积的增加而增加;当进样体积大于80 μL时,系统总压力变化明显。考虑对整个系统的保护,选择80 μL作为最大进样体积。同一浓度的样品进样20 μL与进样80 μL所得峰面积之间的线性关系良好。RAM柱对盐酸贝那普利具有良好的富集作用,能够有效提高HPLC的灵敏度,而且具有简单、经济的特点。     

The measurement of compositions and the isotopic distribution of released fission gas in the fuel rods of pressurized water reactors (PWR) of Korea

In this work the analysis procedures of fission gas compositions and their isotopic distributions using a gas chromatography (GC) system and/or a quadrupole mass spectrometer (QMS) system were established, and their analysis results were reviewed in order to evaluate their analytical performance. Also, the accumulated data, up to now, regarding fission gas measurement were reviewed to discern any irradiation histories of the punctured fuel rods. A simple gas injection apparatus was designed and fabricated for the quantitative injection of a small volume of fission gas into the GC and the QMS system. With an appropriate temperature controlling of a molecular sieve 5A column, nitrogen, krypton and xenon of a mixture gas was clearly separated within 7 min. According to the analysis results, the relative standard deviation in the determination of fission gas compositions, krypton and xenon, by the GC analysis or by the QMS analysis was about 1%. Based on the review results of the isotopic ratios of krypton and xenon of the released fission gas, it is likely that no abnormally irradiated rods, i.e. defected rods, were included among the punctured rods.     

Factors influencing chromatographic data in fast gas chromatography with on‐column injection

The use of larger volume injection with on‐column injection and fast GC commercial instrumentation was evaluated with the model mixture of n‐alkanes of a broad range of volatility (C₁₀–C₂₈). The presented configuration allows introduction of 40–80‐fold larger sample volumes without any distortion of peak shapes compared to “usual” fast GC set‐ups using narrow‐bore columns. A normal‐bore retention gap (1–5 m×0.32 mm ID) was coupled to a narrow‐bore (5 m×0.1 mm ID×0.4 μm film thickness) analytical column using a standard press‐fit connector. The connection was tight and reliable, and hence suitable for hydrogen as carrier gas. The effect of pre‐column and analytical column connector, injection volume, pre‐column length, column inlet pressure, and analyte volatility on peak shape, peak broadening, and focusing are discussed. The precision of chromatographic data measurements and peak capacity under optimised temperature programmed conditions for fast separations with large volume injection were found to be very good. The presented fast GC set‐up with on‐column injection extends the applicability of the technique to trace analysis.     

气相色谱微体积热导检测器测量氙

气相色谱微体积热导检测器(μTCD)是与毛细管柱相连的浓度型检测器。为提高-TCD测量氙的能力,研究了色谱进样条件、分离条件和检测条件对氙响应影响。结果表明,当柱流量为1.5mL/min,1.0mL样品完全进样所需最短时间为0.4min;等量氙响应值随着柱流量的增加而增大,与色谱柱温度无关;在流量比(q)等于2.3时,等量氙响应值达到最大(0.98-V.s/hPa);且当q=2～3时,其均值为0.97-V.s/hPa;相对标准偏差(RSD)为1.2%。     

Signal enhancement in supercritical fluid chromatography‐diode‐array detection with multiple injection

To circumvent the detrimental effects of large‐volume injection with fixed‐loop injector in modern supercritical fluid chromatography, the feasibility of performing multiple injection was investigated. By accumulating analytes from a certain number of continual small‐volume injections, compounds can be concentrated on the column head, and this leads to signal enhancement compared with a single injection. The signal to noise enhancement of different compounds appeared to be associated with their retention on different stationary phases and with type of sample diluent. The diethylamine column gave the best signal to noise enhancement when acetonitrile was used as sample diluent and the 2‐picolylamine column showed the best overall performance with water as the sample diluent. The advantage of multiple injection over one‐time large‐volume injection was proven with sulfanilamide, with both acetonitrile and water as sample diluents. The multiple injection approach exhibited comparable within‐ and between‐day precision of retention time and peak area with those of single injections. The potential of the multiple injection approach was demonstrated in the analysis of sulfanilamide‐spiked honey extract and diclofenac‐spiked ground water sample. The limitations of this approach were also discussed.     

Gas sorption environments in poly(2,6‐dimethyl‐1,4‐phenylene oxide) by xenon‐129 nuclear magnetic resonance: Effects of processing

One‐ and two‐dimensional xenon‐129 nuclear magnetic resonance (¹²⁹Xe NMR) experiments were performed on a series of poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PXE) samples to characterize the sorption environments and the relative mobility of xenon in the samples. Samples of PXE in sealed NMR tubes pressurized with xenon were studied as a function of temperature, pressure, and processing. In a dense cast film of PXE, the shift relative to the free gas resonance is smaller than that observed for typical glassy polymers, indicating a higher free volume environment. Solubility rises rapidly as temperature decreases. The lower shift and rapid increase in solubility with decreasing temperature are consistent with a relatively high free volume environment for gas sorption. If PXE is antiplasticized, the shift is slightly larger, the increase in signal intensity with decreasing temperature is smaller, and the line widths are greater. This sample is a better packed glass with less free volume and slower diffusion. Samples of PXE produced by rapid precipitation have broad lines and even lower shifts corresponding to a wide distribution of higher free volume environments. The appearance of two lines at low temperatures is consistent with the presence of a bimodal distribution of environments similar to what has been observed with positron annihilation lifetime spectroscopy. The resonance closest to the free gas resonance is associated with very large free volume elements relative to those of traditional glassy polymers. In two‐dimensional experiments, there is a rapid exchange of xenon by diffusion between the two environments, indicating the close spatial proximity of the environments. Two‐dimensional experiments and one‐dimensional progressive saturation experiments reflect a rapid exchange of xenon between the sorbed state and the free gas resonance for the precipitated samples. At low temperatures, the high field peak exchanges more rapidly with the free gas. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1965–1974, 2002     

Large Volume Injection in Fast Gas Chromatography with On‐Column Injector

In this work a fast gas chromatography set‐up with on‐column injection was optimized and evaluated with a model mixture of C₈–C₂₈ n‐alkanes. Usual injection volumes when using narrow‐bore (e. g., 0.1 mm i.d.) analytical columns are ca. 0.1 μL. The presented configuration allows introduction of 10–30‐fold larger sample volumes without any distortion of peak shapes. In the set‐up a normal‐bore retention gap (1 m×0.32 mm i. d.) was coupled to a narrow‐bore (4.8 m×0.1 mm i. d.×0.4 μm film thickness) analytical column using a low dead volume column connector. The effects of the experimental conditions such as inlet pressure, sample volume, initial injection temperature, and oven temperature on a peak focusing are discussed. H‐u curves for helium and hydrogen are used to compare their suitability for high speed gas chromatography and to show the dependence of separation efficiency on the carrier gas velocity at high inlet pressures. In the fast gas chromatography system a baseline separation of C₁₀–C₂₈ n‐alkanes was achieved in less than 3 minutes.     

The use of precolumns for solvent focusing in capillary column gas chromatography

In trace analysis by capillary GC it is often desirable to use larger than normal injection volumes to obtain sufficient sensitivity. This, however, results in a wider solvent peak and tailing, and may reduce column efficiency. This paper describes the use of a short length of a capillary precolumn coated with a stationary phase of polarity similar to that of the sample solvent and a film thickness greater than that of the analytical column; provided the right combination of polarities of injection solvent and liquid phases are used, the precolumn focuses the solvent band, thereby enabling the maximum injection volume to be increased without measurably reducing efficiency. Typical precolumn dimensions are 1 m length, 0.32 mm i.d., and 0.5 μm stationary phase film thickness. Using a precolumn increases the maximum injection volume up to 8 or 10 μl, or three times that appropriate for a conventional analytical column, with little or no loss in efficiency.     

Application of a xenon arc lamp as a light source for evaporative light scattering detection

The standard tungsten-halogen light source used in a commercial evaporative light scattering detector (ELSD) was replaced with a 180 W xenon arc lamp. The xenon arc lamp possesses a broader spectrum in the UV region than the halogen source. The influence of the UV transmittance of five selected solvents was studied with a size-exclusion chromatography column. This solvent parameter was not observed to influence the ELSD response between the two light source settings. With the solvents studied, better sensitivity was obtained with the xenon arc lamp than the halogen lamp. This high-energy source was applied to ceramide III analysis with an octadecyl-grafted silica column and methanol:tetrahydrofuran 97:3 as the mobile phase, and the sensitivity of the quantification of ceramide III increased 16-fold for injected amounts of 14∼140 ng. The molecular species in a sample of naturally occurring ceramides was analyzed using two C18 columns at 40 °C and gradient elution from 100% acetonitrile to 100% isopropanol in 30 min. The increased ELSD sensitivity achieved when using the xenon arc lamp allowed both the minor and major ceramide species to be observed, in contrast to the results achieved when the halogen lamp was used, where the increased photomultiplier voltage needed to observed the signals from the minor species caused the signals from the major ceramide species to occur above the detector response window.     

Volume-load capacity in fast-gradient liquid chromatography effect of sample solvent composition and injection volume on chromatographic performance

We studied the effects of sample solvent composition and injection volumes on the chromatographic performance of ODS-bonded silica columns under fast-gradient running conditions. Chromatographic performance is compromised as a function of both sample injection volume and sample solvent strength, with earlier-eluting analytes being much more affected than later-eluting ones. In general, when injecting samples dissolved in a strong solvent, performance was improved by diluting the strong injection solvent and injecting a proportionally larger volume. Volume loading capacity can be increased by using a longer column, or by using a column of equivalent length, but with a larger inner diameter. Data also suggest that sample solvent strength, not viscosity, is responsible for the noted effects.     

Preparation of a capillary isoelectric focusing column with monolithic immobilized pH gradient and its application on protein separation based on an online capillary isoelectric focusing platform

In the presence of methanol and n‐decanol as porogens, a partially filled capillary monolithic column was prepared by in situ reaction of glycidyl methacrylate and poly (ethylene glycol) diacrylate. Then, Pharmalyte 3–10 was immobilized on this column in order to obtain a capillary isoelectric focusing (cIEF) column with monolithic immobilized pH gradient (M‐IPG). In addition, an online self‐built platform for protein separation was established on account of the introduction of a cross‐shaped unit and two short‐off valves. In this platform, a cross‐shaped unit was not only used to join the M‐IPG column and a six‐way injection valve (1.5 μL sample loop), but also to supply a volume pool of anode buffer so that the process of injection, focusing and mobilization of samples could be sequentially performed. The short‐off valve in the tee unit or cross‐shaped unit could be used to control the direction of the fluid flow. Using this online cIEF platform and under the optimized conditions, 7‐proteins mixture could be separated and a good linear correlation between pI values and migration times was obtained by the M‐IPG column. Meanwhile, based on the online cIEF platform, human serum proteins and a mixture of Hb A and Hb A_1c have been successfully resolved with the newly developed M‐IPG column.     

Simplifying the setup for vacuum‐outlet GC: Using a restriction inside the injection port

The application of vacuum GC has several advantages over pressurized GC. One of the key characteristics is that the optimal gas velocity is very high. Combined with short capillary columns of wide internal diameter, this results in short analysis times using standard GC‐MS equipment. To make vacuum GC possible using a GC‐MS system, a restriction must be positioned at the injection side of the column. This restriction is usually made of deactivated 0.1 mm i.d. fused‐silica tubing which is coupled to the analytical column. Such restrictions will work, but practical challenges are found in coupling, reducing dead volume and robustness. A new way of making restrictions is by incorporating the restriction into the injection port. Using well‐defined short pieces of fused silica with internal diameter of 0.025 mm, one can make a restriction using a Press‐Tight® type connector, and position this inside the injection port. By doing this, the restriction is very short and at high temperature all the time. Activity plays a minimal role, and also leaks will not be an issue as the coupling is in 100% inert gas. Data obtained using this concept is promising as vacuum GC becomes easier and more robust.     

Adsorption and diffusion of Xenon in a granulated nano-NaY zeolite

Henry??s law constant and crystal diffusivity of xenon in the granulated nano-NaY zeolite were measured by the pulse gas chromatography method. For this purpose the moments of response peaks of xenon were analyzed. The effect of extra column parts of the utilized chromatographic system was also considered by analyzing the moments of the response peak which was obtained by pulse injection of inert gas of helium into the carrier gas of nitrogen. In addition, the measurement of average velocity of the carrier gas regarding the pressure drop in the extra column parts of the system attributed to precise results. By carrying out the experiments at various temperatures in the range of 30?C110?°C the heat of adsorption and activation energy of crystal diffusivity were estimated. In order to find the binder effect on the adsorption of and diffusion into granules, the aforementioned parameters were also measured for the binderless granules of macron sized NaY zeolite. Results revealed that although the adsorption of xenon on the binder of bentonite was negligible, the diffusion resistance created by this binder was significant such that the effective crystal diffusivity in the granules with 25?% binder was determined to be 96 percent lower than the granules with no binder.     

Enhancing concentration and mass sensitivities for liquid chromatography trace analysis of clopyralid in drinking water

A theoretical treatment was developed and validated that relates analyte concentration and mass sensitivities to injection volume, retention factor, particle diameter, column length, column inner diameter and detection wavelength in liquid chromatography, and sample volume and extracted volume in solid‐phase extraction (SPE). The principles were applied to improve sensitivity for trace analysis of clopyralid in drinking water. It was demonstrated that a concentration limit of detection of 0.02 ppb (μg/L) for clopyralid could be achieved with the use of simple UV detection and 100 mL of a spiked drinking water sample. This enabled reliable quantitation of clopyralid at the targeted 0.1 ppb level. Using a buffered solution as the elution solvent (potassium acetate buffer, pH 4.5, containing 10% of methanol) in the SPE procedures was found superior to using 100% methanol, as it provided better extraction recovery (70–90%) and precision (5% for a concentration at 0.1 ppb level). In addition, the eluted sample was in a weaker solvent than the mobile phase, permitting the direct injection of the extracted sample, which enabled a faster cycle time of the overall analysis. Excluding the preparation of calibration standards, the analysis of a single sample, including acidification, extraction, elution and LC run, could be completed in 1 h. The method was used successfully for the determination of clopyralid in over 200 clopyralid monoethanolamine‐fortified drinking water samples, which were treated with various water treatment resins.     

Improved analyte detectability of proteins and peptide lysates by means of multiple large‐volume injection in LC‐MS

A ‘multiple (trapping) large‐volume injection’ approach was developed for the analysis of peptides and proteins. In this way, a maximally 10‐fold gain in sensitivity could be achieved. The system involves the use of an automated 10‐port switching valve in combination with a 1 mm i.d. trapping/guard column and a 1 mm i.d.×150 mm analytical column. The optimized multiple injection/loading procedure allows quantitative measurements of peptides and protein lysates. Linear calibration curves (R² ? 0.988) over a minimum of two orders of magnitude were generated for a range of peptide and protein standards with sensitivities equal to or even exceeding, those generally achieved only through increasing miniaturization (quantification limit ?0.5 pmol/mL).     

Understanding the importance of the viscosity contrast between the sample solvent plug and the mobile phase and its potential consequence in two-dimensional high-performance liquid chromatography

The effect of solvent viscosity mismatch on elution performance in reversed-phase HPLC was studied using moment analysis. Two conditions were tested: (1) the mobile phase viscosity was less than the injection plug viscosity, and (2) the mobile phase viscosity was greater than the injection plug viscosity. Under the first condition, retention time and elution performance decreased as the viscosity contrast between the mobile phase and injection plug increased. The effect on performance was more marked as the injection volume increased. A decrease in performance of 12% for compounds with retention factors up to 2.8 was apparent even when the viscosity contrast was only 0.165 cP. In the second set of conditions, elution performance was actually observed to increase, by as much as 25% for a 40 μL injection, as the viscosity contrast between the mobile phase and the solute plug increased. No change in the retention factor was observed. This behaviour was attributed to the shape of an injection plug as it enters into the column, whereby a low viscosity plug permeates away from the wall when the column contains a higher viscosity mobile phase, and vice a versa for a high viscosity plug entering a low viscosity mobile phase. At no stage was either a band splitting or shoulders observed with viscosity contrasts up to 1.283 cP, as could have been expected.     

An automatic gas-chromatographic analyser for the determination of the radioactivity of argon,krypton and xenon

An instrumental procedure for the determination of the amount and the radio-activity of argon, krypton and xenon has been worked out and an automatic analyser has been designed. A sample was taken from the residual gases remaining after absorption in a solution of potassium hydroxide. Oxygen was catalytically combusted and carbon monoxide converted to methane in a stream of hydrogen. Argon and krypton were separated on a 5.5 m long column packed with Porapak Q, and xenon was analyzed on a 0.4 m long column of Synachrom G-5 at 0°. The radioactivity of the pure components was measured with a flow-type proportional counter. The system proposed and the analyser can be simply adapted to run off determinations of other admixtures in the coolants of nuclear power plants.     

Use of a temperature‐programmable injector coupled to gas chromatography–combustion–isotope ratio mass spectrometry for compound‐specific carbon isotopic analysis of polycyclic aromatic hydrocarbons

Compound‐specific isotopic analysis (CSIA) can provide information about the origin of analysed compounds; for instance, polycyclic aromatic hydrocarbons (PAHs) in aerosols. This could be a valuable tool in source apportionment of particulate matter (PM) air pollution. Because gas chromatography–combustion–isotope ratio mass spectrometry (GC‐C‐IRMS) analysis requires an amount of at least 10 ng of an individual PAH, a high concentration of PAHs in the injected extract is needed. When the concentration is low a large volume injector creates the possibility of introducing a satisfactory amount of individual PAHs. In this study a temperature‐programmable injector was coupled to GC‐C‐IRMS and injection parameters (solvent level, transfer column flow, transfers time) were optimised using six solid aromatic compounds (anthracene, fluoranthene, pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene) dissolved in n‐pentane and EPA 610 reference mixture. CSIA results for solid PAHs were compared with results obtained for the single components analysed by elemental analysis–isotope ratio mass spectrometry. The injection method was validated for two sample injection volumes, 50 and 100 µL. This method was also compared with commonly used splitless injection. To be included in the study, measurements had to have an uncertainty lower than 0.5‰ for and a minimum peak height of 200 mV. The lower concentration limits at which these criteria were fulfilled for PAHs were 30 mg/L for 1 µL in splitless injection and 0.3 and 0.2 mg/L for 50 and 100 µL, respectively, in large volume injection. Copyright © 2009 John Wiley & Sons, Ltd.     

Simultaneous determination of peroxydisulfate and conventional inorganic anions by ion chromatography with the column‐switching technique

The application of ion chromatography with the column‐switching technique for the simultaneous analysis of peroxydisulfate and conventional inorganic anions in a single run is described. With this method, conventional inorganic anions were separated by consecutive elution through both the guard column and separation column, but peroxydisulfate that only passed through the guard column had a good peak shape and short retention time. A series of standard solutions consisting of target anions of various concentrations from 0.01 to 75 mg/L were analyzed, with a correlation coefficient (r) ≥ 0.9990. The limits of detection were in the range of 0.49–9.84 μg/L based on the S/N of 3 and a 25 μL injection volume. RSDs for retention time, peak area, and peak height were all <1.77%. A spiking study was performed with satisfactory recoveries between 97.6 and 103.4% for all anions. The quantitative determination of peroxydisulfate and conventional inorganic anions in surface waters was accomplished within 18 min by this column‐switching technique.     

毛细管区带电泳中钴、镍、锌、锰等金属离子的络合富集

提出了CZE络合富集的基本方法。通过络合作用使金属离子在样品区带和背景电解质中具有不同迁移速度而实现富集。以金属离子Co^2 、Zn^2 、Mn^2 和Ni^2 为溶质，4-(2-吡啶偶氮)间苯二酚(PAR)和EDTA为络合剂进行实验研究，探讨了柱容量、样品浓度、络合剂种类及进样方式等参数对富集的影响。在不超出柱容量的情况下，峰高随着进样时间的增加而增大。采用pH8．40、6．25mmol／L硼酸盐分离不同浓度Co^2 、Ni^2 ，进样量可增加约100倍，检测灵敏度增加40倍。