Sensitive determination of styrene and related compounds in human body fluids by headspace capillary gas chromatography with cryogenic oven trapping

Summary A simple and sensitive method is presented for determination of styrene, toluene, ethylbenzene, isopropylbenzene andn-propylbenzene in human body fluids by capillary gas chromatography (GC) with cryogenic oven trapping. After heating a blood or urine sample containing each compound andp-diethylbenzene (internal standard, IS) in a 7.0-mL vial at 60°C for 20 min, 5 mL of headspace vapor was drawn into a glass syringe and injected into a GC. All vapor was introduced into an Rtx-Volatile middle bore capillary column in splitless mode at oven temperature of 20°C to trap entire analytes, and the oven temperature then programmed to 280°C for GC measurements by flame ionization detection. The present conditions gave sharp peaks of each compound and IS, and low background noises for whole blood or urine samples.     

Sensitive determination of n-hexane and cyclohexane in human body fluids by capillary gas chromatography with cryogenic oven trapping

A sensitive method was developed for determination of n-hexane and cyclohexane in human body fluids by headspace capillary gas chromatography (GC) with cryogenic oven trapping. Whole blood and urine samples containing n-hexane and cyclohexane were heated in a 7.5 mL vial at 70 degrees C for 15 min, and 5 mL of the headspace vapor was drawn into a glass syringe. All vapor was introduced through an injection port of a GC instrument in the splitless mode into an Rtx-Volatiles middle-bore capillary column at an oven temperature of -40 degrees C for trapping volatile compounds. The oven temperature was programmed to 180 degrees C for GC with flame ionization detection. These conditions gave sharp peaks for both n-hexane and cyclohexane, a good separation of each peak, and low background impurities for whole blood and urine. The extraction efficiencies of n-hexane and cyclohexane were 13.2-30.3% for whole blood and 12.7-20.7% for urine. The coefficients of within-day variation in terms of extraction efficiency of both compounds were 5.0-9.5% for whole blood and 3.8-10.8% for urine; those of day-to-day variation for the compounds were not greater than 16.6%. The regression equations for n-hexane and cyclohexane showed good linearity in the range of 5-500 ng/0.5 mL for whole blood and urine. The detection limits (signal-to-noise ratio = 3) for both compounds were 1.2 and 0.5 ng/0.5 mL for whole blood and urine, respectively. The data on n-hexane or cyclohexane in rat blood after inhalation of each compound are also presented.     

Simple Analysis of Amphetamines in Human Whole Blood and Urine by Headspace Capillary Gas Chromatography with Large Volume Injection

Summary A very simple method for the analysis of methamphetamine and amphetamine in human whole blood and urine by headspace gas chromatography (GC) has been presented. It neither needs solid-phase microextraction nor cryogenic trapping devices, but only a conventional capillary GC instrument with flame ionization detection (FID). The two special points to be mentioned in this method are the in-matrix derivatization of amphetamines for vaporization and the capability of injection of as large as 5 mL of the headspace vapor into a GC instrument in the splitless mode for sensitive detection. After heating a whole blood or urine sample containing amphetamines, -methylbenzylamine (internal standard, IS) and heptafluoro-n-butyryl chloride under alkaline conditions in a 7.0-mL vial at 90 °C for 20 min, 5 mL of the headspace vapor was drawn with a glass syringe and injected into the gas chromatograph. During injection the column was at 40 °C to trap the analytes, and then the oven temperature was programmed up to 320 °C. Sharp peaks were obtained for each analyte and IS, and only a relatively small number of background impurity peaks for the whole blood and urine samples. The detection limits for each amphetamine were estimated to be 0.1 g mL^–1 for whole blood and 0.03 g mL^–1 for urine. Precision and linearity were also tested to confirm the reliability. Methamphetamine and amphetamine could be determined from whole blood and urine obtained at autopsy in three methamphetamine poisoning cases. The identity of each peak appearing in the gas chromatograms was confirmed by GC/mass spectrometry.     

Detection of organophosphate pesticides in human body fluids by headspace solid-phase microextraction (SPME) and capillary gas chromatography with nitrogen-phosphorus detection

Summary Organosphosphate pesticides have been found extractable by headspace solid-phase microextraction (SPME), and the best conditions of their extraction from human whole blood and urine samples have been investigated. The body fluid samples containing nine pesticides (IBP, methyl parathion, fenitrothion, malathion, fenthion, isoxathion, ethion, EPN and phosalone) were heated at 100°C in a septum-capped vial in the presence of various combinations of acid and salts, and SPME fiber was exposed to the headspace of the vial to allow adsorption of the pesticides before capillary gas chromatography (GC) with nitrogen-phosphorus detection. The heating with distilled water/HCl/(NH₄)₂SO₄/NaCl and with distilled water/HCl gave the best results for urine and whole blood, respectively. Recoveries of the nine pesticides were 0.8–10.6% except for phosalone (0.03%) for whole blood, and 3.8–40.2% for urine. The calibration curves for the pesticides showed linearity in the range of 50–400 ng/0.5 mL for whole blood except for malathion (100–400 ng/0.5 mL whole blood) and 7.5–120 ng/0.5 mL for urine except for phosalone (15–120 ng/0.5 mL urine) with detection limits of 2.2–40 ng/0.5 mL for whole blood and 0.8–12 ng/0.5 mL for urine.     

Cold-surface photochemistry of primary and tertiary alkyl nitrites

Reflection-absorption infrared spectroscopy (RAIRS) is used to explore the photochemistry of primary and tertiary alkyl nitrites deposited on a gold surface. The primary alkyl nitrites examined for this study were n-butyl, isobutyl, and isopentyl nitrite. These compounds showed qualitatively similar spectra to those observed in previous condensed-phase measurements. The photolysis of the primary nitrites involved the initial formation of an alkoxy radical and NO, followed by production of nitroxyl (HNO) and an aldehydic species. In addition, the formation of nitrous oxide, identified from its distinctive transition near 2230 cm(-1), was observed to form from the self-reaction of nitroxyl. The reaction rates for cis and trans conformer decay, as tracked through their intense N═O stretching modes, were found to be significantly different, potentially due to a structural bias that favors HNO formation for the initial trans conformer photoproducts over recombination. Tert-butyl nitrite demonstrates only the trans conformer in the RAIRS spectra prior to photolysis; however, recombination of the initial NO and RO(?) photoproducts was observed to produce the cis conformer in the photolyzed samples. The primary photoproducts from tert-butyl nitrite can also react to form acetone and nitrosomethane, but the absence of HNO prohibits the formation of N(2)O that was observed for the primary alkyl nitrites. Additionally, the RAIRS spectrum of isobutyl nitrite co-deposited with water was measured to examine the photolysis of this species on a water-ice surface. No change in the identity of the photoproducts was observed in this experiment, and minimal frequency shifting (1-3 cm(-1)) of the vibrational modes occurred. In addition to being a known atmospheric source of NO and various aldehydes, our results point to cold surface processing of alkyl nitrites as a potential environmental source of nitrous oxide.     

Rapid determination of amino acids in neonatal blood samples based on derivatization with isobutyl chloroformate followed by solid-phase microextraction and gas chromatography/mass spectrometry

The purpose of this study was to develop a simple, rapid and sensitive analytical method for determination of amino acids in neonatal blood samples. The developed method involves the employment of derivatization and a solid-phase microextraction (SPME) technique together with gas chromatography/mass spectrometry (GC/MS). Amino acids in blood samples were derivatized by a mixture of isobutyl chloroformate, methanol and pyridine, and the N(O,S)-alkoxycarbonyl alkyl esters thus formed were headspace extracted by a SPME fiber. Finally, the extracted analytes on the fiber were desorbed and detected by GC/MS in electron impact (EI) mode. L-Valine, L-leucine, L-isoleucine, L-phenylanaline and L-tyrosine in blood samples were quantitatively analyzed by measurement of the corresponding N(O,S)-alkoxycarbonyl alkyl esters using an external standard method. SPME conditions were optimized, and the method was validated. The method was applied to diagnosis of neonatal phenylkenuria (PKU) and maple syrup urine disease (MSUD) by the analyses of five amino acids in blood samples. The results showed that the proposed method is a potentially powerful tool for simultaneous screening for neonatal PKU and MSUD.     

Determination of nerve agent metabolites in human urine by isotope-dilution gas chromatography-tandem mass spectrometry after solid phase supported derivatization

A simple and sensitive method has been developed and validated for determining ethyl methylphosphonic acid (EMPA), isopropyl methylphosphonic acid (IMPA), isobutyl methylphosphonic acid (iBuMPA), and pinacolyl methylphosphonic acid (PMPA) in human urine using gas chromatography-tandem mass spectrometry (GC-MS/MS) coupled with solid phase derivatization (SPD). These four alkyl methylphosphonic acids (AMPAs) are specific hydrolysis products and biomarkers of exposure to classic organophosphorus (OP) nerve agents VX, sarin, RVX, and soman. The AMPAs in urine samples were directly derivatized with pentafluorobenzyl bromide on a solid support and then extracted by liquid–liquid extraction. The analytes were quantified with isotope-dilution by negative chemical ionization (NCI) GC-MS/MS in a selected reaction monitoring (SRM) mode. This method is highly sensitive, with the limits of detection of 0.02 ng/mL for each compound in a 0.2 mL sample of human urine, and an excellent linearity from 0.1 to 50 ng/mL. It is proven to be very suitable for the qualitative and quantitative analyses of degradation markers of OP nerve agents in biomedical samples.     

Biomarkers of alcohol abuse in racehorses by liquid chromatography/tandem mass spectrometry

A rapid and sensitive method was developed for the screening, quantification and confirmation of ethyl glucuronide (EG) and ethyl sulfate (ES) as biomarkers for alcohol administration to racehorses using liquid chromatography coupled on-line with triple quadrupole tandem mass spectrometry. Urine sample aliquots (0.1 mL) were pre-treated by protein precipitation. Separation of EG and ES was achieved on an Ultra PFP column. Isocratic elution with a flush step was performed using 0.1% formic acid in water (A) and 0.1% formic acid in acetonitrile (B). Analysis was performed by negative electrospray ionization in multiple reaction monitoring mode. The retention times for EG and ES were 1.7 +/- 0.30 and 3.4 +/- 0.30 min, respectively. The internal standard used was d(5)-ethyl glucuronide with a retention time of 1.7 +/- 0.30 min. The entire separation was completed in <5 min. The limit of detection (LOD) and of quantification (LOQ) for both analytes were 100 ng/mL (S/N > or =3) and 500 ng/mL, respectively. The limit of confirmations (LOC) for EG and ES were 500 ng/mL and 1.0 microg/mL, respectively. The assay was linear over a concentration range of 0.5-100 microg/mL (r(2) > 0.995). Intra- and inter-day accuracy and precision were less than 15%. The analytes were stable in urine for 24 h at room temperature, 10 days at 4 degrees C and 21 days at -20 degrees C and -70 degrees C. Ion suppression or enhancement due to matrix effect was negligible. The measurement uncertainty was <14% for EG and <25% for ES. This method was successfully used for the quantification of EG and ES in urine samples following alcohol administration to research horses and for screening and confirmation of EG and ES in urine samples obtained from racehorses post-competition. The method is simple, rapid, inexpensive, and reliably reproducible.     

Poly(methacrylic acid-ethylene glycol dimethacrylate) monolith in-tube solid phase microextraction coupled to high performance liquid chromatography and analysis of amphetamines in urine samples

In-tube solid-phase microextraction (SPME) based on a poly(methacrylic acid-ethylene glycol dimethacrylate) monolithic capillary column was investigated for the extraction of amphetamine, methamphetamine and their methylenedioxy derivatives. The monolithic capillary column showed high extraction efficiency towards target analytes, which could be attributed to its larger loading amount of extraction phase than conventional open-tubular extraction capillaries and the convective mass transfer procedure provided by its monolithic structure. The extraction mechanism was studied, and the results indicated that the extraction process of the target analytes was involved with hydrophobic interaction and ion-exchange interaction. The polymer monolith in-tube SPME-HPLC system with UV detection was successfully applied to the determination of amphetamine, methamphetamine and their methylenedioxy derivatives in urine samples, yielding the detection limits of 1.4 - 4.0 ng/mL. Excellent method reproducibility (RSD < 2.9%) was found over a linear range of 0.05-5 microg/mL, and the time for the whole analysis was only approximately 25 min. The monolithic capillary column was reusable in coping with the complicated urine samples.     

在线固相萃取/液相色谱-线性离子阱质谱法同时定性定量检测全血和尿液中7种抗凝血杀鼠药

建立了同时测定全血和尿液样品中7种抗凝血杀鼠药的在线固相萃取/液相色谱-线性离子阱质谱(on-line SPE/LC-LIT/MS)分析方法。用乙腈沉淀样品中的蛋白质,于稀释、离心、过滤后直接进样。经在线固相萃取柱富集纯化;以C18柱为分析柱,甲醇-乙酸铵水溶液(0.02 mol/L)为流动相进行梯度洗脱;在电喷雾电离(ESI)负离子模式下,记录目标母离子在锁定保留时间窗口内的二级全扫描信号,通过自建数据库进行定性确证,挑选高灵敏度与专属性的二级子离子进行定量,从而实现7种杀鼠药的同时定性和定量分析。7种杀鼠药在各自质量浓度范围内线性关系良好,相关系数为0.9946~0.9997,检出限和定量限分别为0.02~1.00 ng/mL和0.10~4.00 ng/mL, 3个添加水平的回收率为81.0%~113.9%,相对标准偏差为0.1%~6.2% (n=6)。该方法简单方便,灵敏度高,能够满足全血和尿液样品中7种抗凝血杀鼠药的快速筛查和准确定量。     

Determination of pentazocine in human whole blood and urine by gas chromatography/surface ionization organic mass spectrometry

Pentazocine has been found to be measurable with much higher sensitivity by gas chromatography (GC)/surface ionization (SI) organic mass spectrometry (OMS) than by the conventional GC/electron ionization (EI) mass spectrometry. The compound was extracted from human whole blood and urine with Sep-Pak C(18) cartridges before analysis by GC/SIOMS; recoveries were > 96.6% for both samples. The calibration curves were linear in the range 6.25-100 ng ml(-1) and the detection limits were 500 pg ml(-1) of a sample by selected ion monitoring (SIM) with GC/SIOMS. The intra- and inter-day relative standard deviations for the determination of pentazocine in whole blood and urine were not greater than 9.6%. The sensitivity for pentazocine obtained by SI-SIM was about 60 times higher than that obtained by EI-SIM. To validate the present GC/SIOMS method for pentazocine, whole blood and urine samples collected from two volunteers 1-6 h after intramuscular injection of 15 mg of pentazocine were analyzed. The concentrations were 13.5-59.3 ng ml(-1) for whole blood and 0.39-4.00 microg ml(-1) for urine.     

Determination of the angiotensin-converting enzyme inhibitor quinapril and its metabolite quinaprilat in pharmaceuticals and urine by capillary zone electrophoresis and solid-phase extraction

Quinapril is an antihypertensive drug commonly used in the treatment of hypertension and congestive heart failure. In this work, a capillary zone electrophoresis system is optimized for the analysis of quinapril and its active metabolite quinaprilat in urine, as well as for the determination of the drug and its combination with hydrochlorothiazide in pharmaceuticals. The separation takes place in a fused-silica capillary. The running electrolyte consists of a 60 mM borate buffer solution, pH 9.5. The analysis of urine samples requires a previous extraction step using C8 solid-phase cartridges. Under the optimum experimental conditions, the separation of the two analytes and the internal standard takes less than 5 min. The detection limits obtained (75 and 95 ng/mL for quinapril and quinaprilat, respectively) allow the application of the electrophoretic method to the determination of the drug and its metabolite in urine samples obtained from four patients treated with quinapril.     

Determination of curcumol in rat plasma by capillary gas chromatography with a hydrogen flame ionization detector

A simple and sensitive capillary gas chromatography with a hydrogen flame ionization detector (GC‐FID) method was developed for the determination of curcumol in rat plasma. From a variety of compounds and solvents tested, buagafuran was selected as the internal standard (IS) and acetonitrile was found to be the best protein precipitation agent and solvent for extracting curcumol from plasma and tissues samples. (Buagafuran was used as an internal standard. Curcumol was extracted by a protein precipitation with acetonitrile.) The samples were determined by GC on an HP‐5 column (30.0 m × 0.32 mm, 0.25 μm); inlet volume 2 μL; split ratio 10 : 1; inlet temperature 250°C; oven temperature 180°C; flow 1.0 mL/·min; FID 250°C; carrier gas N₂. The resulting retention times of curcumol and IS were 6.0 and 9.5 min. There was good linearity over the range 0.133–133.3 μg/mL (r = 0.9999) in plasma samples. The method recoveries were 97.7–102.0% in plasma, and the intra‐ and inter‐day variances (RSD) were less than 15% in all cases. The GC method was applied to develop a pharmacokinetics study in which experimental rats received a single administration of curcumol by intravenous injection. Copyright © 2009 John Wiley & Sons, Ltd.     

Rapid determination of three anticoagulant rodenticides in whole blood by liquid chromatography coupled with electrospray ionization mass spectrometry

A rapid, sensitive and selective method for the simultaneous determination of bromadiolone, flocoumafen and brodifacoum in whole blood using warfarin as internal standard (IS) by high-performance liquid chromatography coupled with electrospray ionization mass spectrometry (HPLC/ESI-MS) has been developed and validated. The target compounds were extracted from the whole blood with ethyl acetate and separated on an XDB C18 column (150 mm x 2.1 mm i.d. x 5 microm) by using a mobile phase consisting of 0.2% acetic acid/methanol (12/88, v/v) at a constant flow rate of 0.50 mL/min. The analytes were detected using negative ESI-MS in the selected ion monitoring (SIM) mode. The molecular ions [M-H]- of m/z 527, 541,523 and 307 were selected for the quantification for bromadiolone, flocoumafen, brodifacoum and the IS, respectively. The calibration curves were linear (r2 > 0.995) in the concentration range of 0.50-100.00 ng/mL. The method showed a satisfactory sensitivity (0.05-0.5 ng/mL using 200 microL blood), precision (RSD < 11.9%), accuracy (recovery: 82.0-96.1%) and selectivity. This method was successfully applied to the determination of the analytes for the diagnoses of poisoned human beings and animals.     

Detection of ethanol in human body fluids by headspace solid-phase micro extraction (SPME)/capillary gas chromatography

Summary Ethanol has been found extractable from human whole blood and urine samples by headspace solid-phase micro extraction (SPME) with a Carbowax/divinylbenzene-coated fiber. After heating a vial containing the body fluid sample with ethanol, and isobutanol as internal standard (IS) at 70°C in the presence of (NH₄)₂SO₄, a Carbowax/divinylbenzene-coated SPME fiber was exposed in the headspace of the vial to allow adsorption of the compounds. The fiber needle was then injected into a middle-bore capillary gas chromatography (GC) port. The headspace SPME-GC gave intense peaks for both compounds; a small amount of background noises appeared, but did not interfere with the detection of the compounds. Recoveries of ethanol and IS were 0.049 and 0.026% for whole blood, respectively, and 0.054 and 0.085% for urine, respectively. The calibration curves for ethanol showed excellent linearity in the range of 80–5000 mg L^–1 for whole blood and 40–5000 mg L^–1 for urine; the detection limits for both samples were 20 and 10 mg L^–1, respectively. The data on actual determination of ethanol after the drinking of beer are also presented for two subjects.     

Improvement in steroid screening for doping control with special emphasis on stanozolol

The Medical Commission of the International Olympic Committee forbids the use of anabolic androgenic steroids and beta2-agonists to improve athletic performance. In this work we have selected examples of anabolic androgenic compounds and their metabolites to evaluate the GC-MS analysis of some trimethylsilyl derivatives. The aim is to set the best GC conditions to improve the detection within the whole range of analyte elution temperatures. The initial column temperature was changed to 105 or 140 degrees C followed by 40 degrees C min(-1) to 200 degrees C and then 15 degrees C min(-1) to 300 degrees C. Using 140 degrees C as the initial oven temperature it was possible to obtain narrower initial analyte distributions for the compounds that elutes at the beginning of the chromatogram as clenbuterol, mabuterol, epimethylenediol and norandrosterone, without loss of derivatized metabolites signal. Later. eluting analytes, such as the stanozolol metabolites, furazabol and oxandrolone were not affected. Temperatures below 140 degrees C. resulted in partial derivatization for some analytes mainly stanozolol related structures. Therefore evaluation of derivatization conditions as occurring in three steps, the vial, vaporization chamber and capillary column, was thoroughly assessed. The new program temperature improves the signal-to-noise ratio for some compounds and shows adequate resolution for endogenous compounds. Some of the difficult key separations necessary for doping control enforcement were also obtained with the proposed method.     

Use of short chain alkyl imidazolium ionic liquids for on‐line stacking and sweeping of methotrexate,flinic acid and folic acid: Their application to biological fluids

Methotrexate (MTX) is widely used for the treatment of many types of cancer. Folinic acid (FNA) and folic acid (FA) were usually simultaneously supplemented with MTX to reduce the side effects of a folate deficiency. This study, for the first time, included on‐line sample preconcentration by stacking and sweeping techniques under reduced or enhanced electric conductivity in the sample region using short chain alkyl imidazolium ionic liquids (ILs) as micelle forming agents for analyte focusing. Both analyte focusing by micelle collapse (AFMC) and sweeping‐MEKC had been investigated for the comparison of their effectiveness to examine simultaneously MTX, FNA and FA in plasma and urine under physiological conditions. In sweeping‐MEKC, the sample solution without micelles was hydrodynamically injected as a long plug into a fused‐silica capillary pre‐filled with phosphate buffer containing 3.0 mol/L of 1‐butyl‐3‐methylimidazolium bromide (BMIMBr). Using AFMC, the analytes were prepared in BMIMBr micellar matrix and hydrodynamically injected into the phosphate buffer without IL micelles. The conductivity ratio between BGE and sample (γ, BGE/sample) was optimized to be 3.0 in sweeping‐MEKC and 0.33 in AFMC resulting the adequate separation of analytes within 4.0 min. To reduce the possibility of BMIMBr adsorption, an appropriate rinsing protocol was used. The limits of detection were calculated as 0.1 ng/mL MTX, 0.05 ng/mL FNA and 0.05 ng/mL FA by sweeping‐MEKC and 0.5 ng/mL MTX, 0.3 ng/mL FNA and 0.3 ng/mL FA by AFMC. The accuracy was tested by recovery in plasma and urine matrices giving values ranging between 90 and 110%. Both stacking and sweeping by BMIMBr could be successfully used for the rapid, selective and sensitive determination of pharmaceuticals in complex matrices due to its fascinating properties, including high conductivity, good thermal stability and ability to form different types of interactions by electrostatic, hydrophobic, hydrogen bonding and π–π interactions. In sweeping‐MEKC, the using of BMIMBr enhanced the γ factor, k retention factor and the injected amount of sample. Consequently, this technique offers particular potential for higher sensitivity by giving 22‐ and 5‐fold sensitivity enhancement factors (SEFs) of MTX compared to CZE and AFMC, respectively.     

Determination of amphetamines in human urine by liquid chromatography with fluorimetric detection using a solid-phase extraction procedure

A precise and feasible HPLC method has been developed for the analysis of amphetamine (AMPH), methamphetamine (MAMPH) and methylenedioxymethamphetamine (MDMA, ecstasy) in human urine. A chromatographic run on a C8 Genesis (150 mm x 4.6 mm, 5 microm) column maintained at 30 degrees C lasts about 17 min, using a mobile phase composed of ACN (12%) and a pH 2.5 phosphate buffer (88%) containing 0.3% triethylamine. Mirtazapine was used as the internal standard. Good linearity was found in the 100-2000 ng/mL concentration range for AMPH and MAMPH and in the 12-2000 ng/mL concentration range for MDMA. The pretreatment of urine samples was carried out by means of a careful SPE procedure on C2 cartridges. The extraction yields were very satisfactory for all analytes, with average values greater than 97%. The leading conditions allowed the determination of AMPH, MAMPH and MDMA with satisfactory precision and accuracy. The method has been successfully applied to the determination of the analytes in urine of AMPH users.     

基于整体柱的固相萃取-高效液相色谱法测定尿液中4种羟基多环芳烃

建立了基于聚合物整体柱的固相萃取-高效液相色谱测定尿液中4种羟基多环芳烃（OH-PAHs）的分析方法。在注射器管中合成聚（甲基丙烯酸丁酯-乙二醇二甲基丙烯酸酯）整体柱（poly （BMA-co-EDMA））,并将其用于尿液中4种羟基多环芳烃的前处理,同时考察了上样浓度、淋洗液、洗脱液和洗脱体积对萃取效率的影响。结合高效液相色谱-荧光分析,4种羟基多环芳烃在各自的范围内线性关系良好（r≥0.9991）;方法的检出限和定量限分别为0.06~0.09 ng/mL和0.20~0.30 ng/mL;日内（n=5）和日间（n=3）精密度分别为1.4%~5.3%和2.6%~7.3%。对焦炉工人尿液样品进行加标（3 ng/mL）回收试验,回收率为78.2%~117.0%。该固相萃取柱能够有效萃取和净化尿液中4种羟基多环芳烃,并且可以重复使用。该法简单、准确,可应用于尿液中羟基多环芳烃的分析。     

Micellar electrokinetic chromatographic method for the determination of letrozole, citalopram and their metabolites in human urine

A new micellar electrokinetic chromatographic method has been developed to analyse human urine samples containing a combination of a drug used for the treatment of breast cancer (letrozole), an antidepressant (citalopram) and their main metabolites. Best results were obtained by using 15 mM borate buffer (pH 9.2) containing 20 mM sodium dodecyl sulphate and 12% (v/v) 2-propanol as the background electrolyte. The separation was performed through a fused silica capillary at 40 degrees C with the application of 6s (3.45 kPa) of hydrodynamic injection and 30 kV of separation voltage. Detection wavelength was 240 nm. Under these conditions, the migration times for all the studied compounds were ranged between 3.0 and 8.0 min. Linearity ranges were determined as 0.4-5.0 microg/mL for all the compounds. Detection limits between 12.5 and 25 ng/mL were determined in urine samples. According to the validation study, the developed method has been proven to be accurate, precise, sensitive, specific, rugged and robust. This method has been used to determine letrozole, citalopram and their metabolites in human urine at clinical levels. Prior to determination, the samples are purified and enriched by means of an extraction-preconcentration step with a preconditioned C(18) cartridge and by eluting the compounds with methanol. The developed method was applied to the determination of these analytes in three urine samples from patients undergoing treatment with letrozole or citalopram.