RESUMEN
Because of the "enterohepatic circulation" of bile acid, liver damage can be reflected by monitoring the content of bile acid in the serum of the organism. To monitor the concentration of 15 bile acids in plasma samples, a new technique of PRiME (process, ruggedness, improvement, matrix effect, ease of use) pass-through cleanup procedure combined with high performance liquid chromatography-tandem quadrupole mass spectrometry (HPLC-MS/MS) was developed. The sorbent used in the PRiME pass-through cleanup procedure is a new type of magnetic organic resin composite nano-material modified by C18 (C18-PS-DVB-GMA-Fe3O4), which has high cleanup efficiency of plasma samples. It also shows good performance in the separation and analysis of 15 kinds of bile acids. Under the optimal conditions, the results show higher cleanup efficiency of C18-PS-DVB-GMA-Fe3O4 with recoveries in the range of 82.1-115 %. The limit of quantitative (LOQs) of 15 bile acids were in the range of 0.033 µg/L-0.19 µg/L, and the RSD values of 15 bile acids were in the range of 3.00-11.9 %. Validation results on linearity, specificity, accuracy and precision, as well as on the application to analysis of 15 bile acids in 100 human plasma samples demonstrate the applicability to clinical studies.
Asunto(s)
Ácidos y Sales Biliares , Límite de Detección , Nanocompuestos , Espectrometría de Masas en Tándem , Humanos , Ácidos y Sales Biliares/sangre , Ácidos y Sales Biliares/química , Espectrometría de Masas en Tándem/métodos , Nanocompuestos/química , Cromatografía Líquida de Alta Presión/métodos , Reproducibilidad de los Resultados , Polímeros/química , Nanopartículas de Magnetita/químicaRESUMEN
A rapid and sensitive method based on PRiME (process, robustness, improvements, matrix effects, ease of use) pass-through cleanup procedure and ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) for the simultaneous determination of 12 illicit drugs in human plasma was developed and validated. The clover-shaped nano-titania functionalized covalent organic frameworks (CSTF-COFs) has been evaluated in the PRiME pass-through cleanup procedure to remove blood phospholipids from plasma samples. Ion suppression effects can be dramatically reduced by CSTF-COFs based PRiME pass-through cleanup procedure. Under the optimal conditions, the results showed satisfactory recoveries between 85.8% and 109%. Acceptable precision and accuracy were also obtained with RSD values less than 15.0% and RE values below 13.3%. The limits of detections (LODs) of 12 illicit drugs were in the range of 0.018-0.360 µg/L. Furthermore, the PRiME CSTF-COFs cartridge could be conveniently regenerated and reused for 40-50 cycles. The proposed method was applied to real plasma samples from suspected drug abusers, which was proved to be reliable and robust for drug screening in clinical and forensic toxicology.
Asunto(s)
Drogas Ilícitas , Estructuras Metalorgánicas , Cromatografía Líquida de Alta Presión , Cromatografía Liquida , Humanos , Límite de Detección , Espectrometría de Masas en Tándem/métodosRESUMEN
This work presents a simple, rapid and green chiral analysis method for five triazole fungicides (penconazole, tebuconazole, triadimefon, myclobutanil, and triadimenol) in tobacco, by which the samples were cleaned up by the novel pass-through solid phase extraction and subsequently the stereoisomers were separated and determined by the supercritical fluid chromatography-tandem mass spectrometry (SFC-MS/MS). Optimized separation of the stereoisomers was achieved on an ACQUITY UPC2 Trefoil AMY 1 column within 6 min. Under fortified concentration levels of 0.1, 0.5 and 2.0 mg/kg, the mean recoveries were 82.8-106.6%, the intra-day relative standard deviations (RSDs) were 1.1-6.6%, and the inter-day RSDs were 2.5-5.6%. The correlation coefficient was greater than 0.9926 for all studied analytes within the range of 10-500 ng/mL. The limits of detection (LODs) for all stereoisomers ranged from 0.26 µg/kg to 3.24 µg/kg. The established method was subsequently successfully applied to analyze authentic samples, confirming that this method is a novel, rapid and environmentally friendly method for the stereoselective separation of triazole fungicides in tobacco.
Asunto(s)
Cromatografía con Fluido Supercrítico/métodos , Fungicidas Industriales/análisis , Nicotiana/química , Espectrometría de Masas en Tándem/métodos , Triazoles/análisis , Calibración , Fungicidas Industriales/química , Límite de Detección , Nitrilos/análisis , Nitrilos/química , Reproducibilidad de los Resultados , Extracción en Fase Sólida , Solventes , Estereoisomerismo , Triazoles/químicaRESUMEN
A novel nano-titania modified covalent organic frameworks (NTM-COFs) has been synthesized and characterized by transmission electron microscopy (TEM) and scanning electron micrographs (SEM). Besides, NTM-COFs, as efficient sorbent, has also been evaluated in the on-line pass-through cleanup procedure prior to the analysis of local anesthetic drugs (lidocaine, bupivacaine and tetracaine) in human plasma by liquid chromatography-tandem quadrupole mass spectrometry (LC-MS/MS). Under optimum conditions, the level of matrix effects can be dramatically reduced by the NTM-COFs based on-line pass-through cleanup procedure, with acceptable recoveries ranging from 88.8% to 103%. Satisfactory trueness and precision of the proposed method were also obtained, with the within- and between-run RSDs less than 7.0% and relative error (REs) less than 12%. The limits of detections (LODs) of lidocaine, bupivacaine and tetracaine were 0.029⯵g·L-1, 0.027⯵g·L-1 and 0.016⯵g·L-1, respectively. The analytical method has been successfully applied for the determination of the plasma concentrations of bupivacaine in five parturients who received an epidural administration of bupivacaine hydrochloride during vaginal delivery. Results demonstrate the applicability of the developed NTM-COFs on-line pass-through cleanup procedure coupled with LC-MS/MS method to clinical studies.
Asunto(s)
Anestésicos Locales/sangre , Cromatografía Liquida/métodos , Espectrometría de Masas en Tándem/métodos , Anestésicos Locales/administración & dosificación , Anestésicos Locales/química , Anestésicos Locales/farmacocinética , Femenino , Humanos , Inyecciones Epidurales , Límite de Detección , Modelos Lineales , Nanopartículas del Metal/química , Estructuras Metalorgánicas/química , Reproducibilidad de los Resultados , Titanio/químicaRESUMEN
To develop a rapid, effective, and accurate method for the simultaneous determination of chloramphenicol, thiamphenicol, and florfenicol in human blood by pass-through cleanup solid-phase extraction combined with liquid chromatography-tandem mass spectrometry (LC-MS/MS), novel nano-titania-coated modified magnetic graphene oxide (TiO2-Mag-GO) is used as the PRiME pass-through cleanup solid-phase extraction sorbent for the cleanup of blood phospholipids. The chromatographic separation was performed on an Eclipse Plus C18 column (100 mm×2.1 mm, 1.8 µm) using 0.08% (v/v) aqueous ammonia solution and acetonitrile having aqueous ammonia (0.08%, v/v) as mobile phases. The tandem mass spectrometer was operated using electrospray ion source (ESI) in the multiple reaction monitoring (MRM) mode. The results showed that the linearities were in the range of 0.1-10.0 µg/L with the determination coefficients (r2) greater than 0.9990 for chloramphenicol, thiamphenicol, and florfenicol. The limits of quantification (LOQs) (S/N>10) in the blood samples were between 0.056 and 0.082 µg/L and the recoveries ranged from 90.0% to 105% at three spiked levels. Precision values expressed as relative standard deviations (RSDs) were in the range of 1.2%-6.6%. The developed method can be used for routine analyses to determine chloramphenicol, thiamphenicol, and florfenicol in clinical studies.
Asunto(s)
Cloranfenicol/sangre , Tianfenicol/análogos & derivados , Tianfenicol/sangre , Titanio , Cromatografía Liquida , Residuos de Medicamentos , Grafito , Humanos , Magnetismo , Nanopartículas , Óxidos , Fosfolípidos/sangre , Extracción en Fase Sólida , Espectrometría de Masas en TándemRESUMEN
An enhanced cleanup efficiency hydroxy functionalized-magnetic graphene oxide (EH-Mag-GO) fully covered porous nano-titania as coating has been designed and synthesized. It has been evaluated in PRiME (process, robustness, improvements, matrix effects, ease of use) pass-through cleanup procedure for human plasma prior to analysis of strychnine and brucine by liquid chromatography-tandem quadrupole mass spectrometry (LC-MS/MS). Comparing with the magnetic carboxyl-graphene (Mag-CG), EH-Mag-GO is much more effective for the removal of matrix effect resulted from blood phospholipids. Under optimal conditions, the results show higher cleanup efficiency of EH-Mag-GO with recoveries in the range of 89.4%-118%. The limits of quantification (LOQs) for strychnine and brucine are 0.088⯵g/L and 0.092⯵g/L, respectively. Especially, the EH-Mag-GO is also evaluated for reuse (20 times) without much sacrifice of the cleanup efficiency. Validation results on linearity, specificity, accuracy and precision, as well as on the application to analysis of strychnine and brucine in six cases of suspected semen strychni poisoning demonstrate the applicability to clinical studies.
Asunto(s)
Grafito/química , Óxidos/química , Estricnina/análogos & derivados , Estricnina/sangre , Cromatografía Liquida , Humanos , Fenómenos Magnéticos , Conformación Molecular , Tamaño de la Partícula , Propiedades de Superficie , Espectrometría de Masas en TándemRESUMEN
A novel PRiME (process, robustness, improvements, matrix effects, ease of use) pass-through cleanup procedure has been developed to improve the existing commercially available designs. Carbon nanosorbents, i.e., magnetic modified carboxyl-graphene (Mag-CG) and magnetic modified carboxyl-carbon nanotubes (Mag-CCNTs), have been synthesised and evaluated in PRiME pass-through cleanup procedure for human plasma prior to analysis of 10 selected local anesthetic drugs by liquid chromatography-tandem quadrupole mass spectrometry (LC-MS/MS). The matrix effect, an interesting phenomenon of ion suppression for local anesthetic drugs containing ester group and ion enhancement for other drugs containing acylamino group, has been minimized using carbon nanosorbents PRiME pass-through cleanup procedure. Under the optimal conditions, the obtained results show higher cleanup efficiency of the carbon nanosorbents with recoveries between 70.2% and 126%. Furthermore, the carbon nanosorbents are also evaluated for reuse up to 80-100 times. The limits of quantification (LOQs) for local anesthetic drugs are in the range of 0.024-0.15 µg/L. Validation results on linearity, specificity, accuracy, and precision, as well as the application to the analysis of lidocaine in five patients recruited from the lung cancer demonstrate the applicability to clinical studies.
Asunto(s)
Anestésicos Locales/sangre , Anestésicos Locales/química , Análisis Químico de la Sangre/métodos , Nanotubos de Carbono/química , Grafito/química , Humanos , Imanes/química , Espectrometría de Masas en TándemRESUMEN
We describe a new methodology for the simultaneous determination of the endocrine-disrupting herbicides (acetochlor, alachlor, amitrole, and atrazine), fungicides (carbendazim, triadimefon, penconazole, and propiconazole), and insecticides (carbaryl and carbofuran) in fish samples followed by high-performance liquid chromatography with tandem mass spectrometry. Samples were extracted and purified using the pass-through cleanup approach. The recoveries of the pesticides were in the range 71.8-116.5%, with relative standard deviations lower than 15.28%. Limits of quantitation were in the range of 0.03-2.50 µg/kg. Validation results on linearity, accuracy, and precision, as well as on application to the analysis of the endocrine-disrupting pesticides in 20 fish samples, demonstrated the applicability to screen the presence of pesticides in fish.