RESUMEN
Universal microchip isotachophoresis (µITP) methods were developed for the determination of cationic and anionic macrocomponents (active pharmaceutical ingredients and counterions) in cardiovascular drugs marketed in salt form, amlodipine besylate and perindopril erbumine. The developed methods are characterized by low reagent and sample consumption, waste production and energy consumption, require only minimal sample preparation and provide fast analysis. The greenness of the proposed methods was assessed using AGREE. An internal standard addition was used to improve the quantitative parameters of µITP. The proposed methods were validated according to the ICH guideline. Linearity, precision, accuracy and specificity were evaluated for each of the studied analytes and all set validation criteria were met. Good linearity was observed in the presence of matrix and in the absence of matrix, with a correlation coefficient of at least 0.9993. The developed methods allowed precise and accurate determination of the studied analytes, the RSD of the quantitative and qualitative parameters were less than 1.5% and the recoveries ranged from 98 to 102%. The developed µITP methods were successfully applied to the determination of cationic and anionic macrocomponents in six commercially available pharmaceutical formulations.
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Amlodipino , Isotacoforesis , Isotacoforesis/métodos , Amlodipino/análisis , Reproducibilidad de los Resultados , Tecnología Química Verde/métodos , Control de Calidad , Preparaciones Farmacéuticas/análisis , Preparaciones Farmacéuticas/química , Perindopril/análisis , Límite de Detección , Electroforesis por Microchip/métodos , Fármacos Cardiovasculares/análisisRESUMEN
Propafenone (PPF) belongs to the class 1C antiarrhythmics and can cause electrocardiogram-associated adverse/toxic effects. Cases of PPF intoxication are rarely investigated. We developed a novel and selective GC-MS/MS method for the determination of PPF and its tissue distribution in an intentional fatal poisoning case, which is applicable to PPF quantification in the range of therapeutic to lethal concentrations in complex post-mortem samples. A simple and effective sample pretreatment was applied to all analyzed samples. PPF was determined without the need for dilution, even in highly complex samples containing a wide range of analyte concentrations. Quantification was performed using the standard addition method, developed and validated according to the ICH M10 guidelines. The obtained results indicated that the PPF concentration in the serum from blood taken while alive, before therapy, was the highest ever reported in the literature. Despite the intensive therapy after the patients' admission, the PPF concentrations in the lungs, spleen, femoral blood and cardiac blood were fatal or abnormally high. On the other hand, the concentrations in the liver and skeletal muscle were lower or approximately the same as observed in cases with therapeutic doses. To the best of our knowledge, the distribution of PPF has not been investigated in fatal intoxication cases and can be helpful in clinical or forensic toxicology.
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Propafenona , Humanos , Distribución Tisular , Propafenona/envenenamiento , Masculino , Cromatografía de Gases y Espectrometría de Masas , Espectrometría de Masas en Tándem , Antiarrítmicos/envenenamiento , Resultado Fatal , AdultoRESUMEN
4-Nonylphenol belongs to the alkylphenol group of chemicals, and its high occurrence in the environment can cause an adverse effect on human health. Breast milk can serve as a marker to take measure of human exposure to these chemicals through different routes of exposure. In this work, the influence of selected factors (the kind of water drank by the mothers; the consumption of fish, pork, and beef; wearing gloves; using nail polish, gel nails, vitamins, and medication) on the concentration on 4-nonylphenol in 89 breast milk samples was studied. The concentrations of nonylphenol in breast milk were determined by HPLC with fluorescence detection. The lowest and highest concentrations of 4-nonylphenol in breast milk were 0.97 ng/mL and 4.37 ng/mL, respectively. Statistical significance was observed for the consumption of pork (p = 0.048) and fish (0.041) in relation to the 4-nonylphenol concentration. Certain parameters (use of gel nails, beef consumption, and vitamin supplementation) were at the border of statistical significance (p = 0.06). Other parameters did not show any statistical significance. The results showed that breast milk in Slovakia does not contain a harmful dose of 4-nonylphenol and does not cause health problems. But it is necessary to continue this research and perform extended screening on a larger number of samples.
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Quantitative Structure-Retention Relationships offer a valuable tool for de-risking chromatographic methods in relation to newly formed or hypothetical compounds, arising from synthetic processes or formulation activities. They can also be used to identify optimal separation conditions, or in support of structural elucidation. In this contribution, we provide a systematic study of the relationship between the accuracy of the retention model, the size of the training set and its structural similarity to the predicted compound. We compare structural similarity expressed either on a fingerprint basis (e.g., Tanimoto index), or by Euclidean distance calculated from of subset of molecular descriptors. The results presented indicate that accurate and predictive models can be built from a small dataset containing as few as 25 compounds, provided that the training set is structurally similar to the test compound. When the training set contains compounds selected by minimizing the Euclidean distance calculated from 3 descriptors most correlated with the retention time, root mean square error of 0.48 min and correlation coefficient of 0.9464 were observed for the test sets of 104 compounds. Moreover, these models meet the Tropsha predictivity criteria. These findings potentially bring the prediction of retention times within the practical reach of pharmaceutical analysts involved in chromatographic method development. We also present an optimisation approach to select algorithm settings in order to minimize the prediction error and ensure model predictivity.
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Algoritmos , Relación Estructura-ActividadRESUMEN
Biologically active taxanes, present in small- to medium-sized evergreen conifers of various Taxus species, are widely used for their antioxidant, antimicrobial and anti-inflammatory effects, but mostly for their antitumour effects used in the treatment of solid tumours of the breast, ovary, lung, bladder, prostate, oesophagus and melanoma. More of the substances found in Taxus plant extracts have medical potential. Therefore, at the beginning of this review, we describe the methods of isolation, identification and determination of taxanes in different plant parts. One of the most important taxanes is paclitaxel, for which we summarize the pharmacokinetic parameters of its different formulations. We also describe toxicological risks during clinical therapy such as hypersensitivity, neurotoxicity, gastrointestinal, cardiovascular, haematological, skin and renal toxicity and toxicity to the respiratory system. Since the effect of the drug-form PTX is enhanced by various Taxus spp. extracts, we summarize published clinical intoxications and all fatal poisonings for the Taxus baccata plant. This showed that, despite their significant use in anticancer treatment, attention should also be focused on the risk of fatal intoxication due to ingestion of extracts from these plants, which are commonly found in our surroundings.
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Neoplasias , Taxus , Masculino , Femenino , Humanos , Taxoides/farmacología , Paclitaxel , Extractos Vegetales/farmacología , Neoplasias/tratamiento farmacológicoRESUMEN
An analytical test procedure for the direct determination of trace levels of perchlorate in drinking water by isotachophoresis combined with capillary zone electrophoresis was developed. A capillary electrophoresis analyzer with column coupling technology, capable of combining capillaries with different internal diameters, was employed in combination with conductivity detection. This combination of the capillary electrophoresis techniques facilitated preconcentration of the trace analytes and elimination of potentially interfering macro-components. To eliminate the influence of weak and moderately strong acids on the migration of perchlorate, acidic leading electrolyte (pH 3.2) in the isotachophoresis step and acidic background electrolyte (pH 3.9) in the zone electrophoresis step were chosen. The addition of polyvinylpyrrolidone into the electrolytes enhanced the resolution of perchlorate from other anions, especially remaining anionic macro-components. The developed method is characterized by good repeatability of migration time (relative standard deviation less than 0.2%) as well as peak area (relative standard deviation less than 5.9%), linearity (R = 0.9996), recoveries (100-112%), and sample throughput (90 samples/24 h). The limit of quantitation for perchlorate in drinking water was achieved at 12.5 nmol/L (1.25 µg/L). This approach is more sensitive and more robust than transient isotachophoresis and offers advantages over some more established analytical techniques such as ion chromatography.
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Agua Potable , Isotacoforesis , Aniones , Electrólitos/química , Electroforesis , Electroforesis Capilar/métodos , Isotacoforesis/métodos , PercloratosRESUMEN
An online coupling of microchip isotachophoresis (µITP) with ion mobility spectrometry (IMS) using thermal evaporation interface is reported for the first time. This combination integrates preconcentration power of the µITP followed by unambiguous identification of trace compounds in complex samples by IMS. Short-chain carboxylic acids, chosen as model analytes, were first separated by the µITP in a discontinuous electrolyte system at pH 5-6, and subsequently evaporated at 130 °C during their transfer to the IMS analyzer. Various parameters, affecting the transfer of the separated sample components through the evaporation system, were optimized to minimize dispersion and loss of the analytes as well as to improve sensitivity. The following analytical attributes were obtained for carboxylic acids in the standard solutions: 0.1-0.3 mg L-1 detection limits, 0.4-0.9 mg L-1 quantitation limits, linear calibration range from the quantitation limit to 75 mg L-1, 0.2-0.3% RSD of the IMS response and 98-102% accuracy. The analytical potential of the developed µITP-IMS combination was demonstrated on the analysis of various food, pharmaceutical and biological samples, in which the studied acids are naturally present. These include: apple vinegar, wine, fish sauce, saliva and ear drops. In the real samples, 0.3-0.6% RSD of the IMS response and 93-109% accuracy were obtained.
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Espectrometría de Movilidad Iónica/métodos , Isotacoforesis/métodos , Líquidos Corporales/química , Análisis de los Alimentos , Preparaciones Farmacéuticas/análisisRESUMEN
A novel microchip electrophoresis method with conductivity detection for the determination of nonsteroidal anti-inflammatory drugs (NSAIDs) in several pharmaceutical formulations was developed. The three frequently used NSAIDs - acetylsalicylic acid, diclofenac and ibuprofen were baseline separated on a poly(methyl methacrylate) microchip with coupled separation channels. Elimination of matrix components such as excipients, was realized through online combination of isotachophoresis (ITP) with zone electrophoresis (ZE). ITP-ZE hyphenation can also facilitate preconcentration of target analytes. ITP was carried out in the first separation channel at pH 6.5, while the second channel of the microchip was used for ZE separation and detection of the analytes at pH 7.0. The developed ITP-ZE method was demonstrated to be applicable for direct and reliable determination of NSAIDs in eleven pharmaceutical formulations. The noticeable advantage of this approach is that only simple sample pretreatment (filtration and dilution) is necessary. The method performance parameters, such as linearity (20-250% of nominal concentration of studied NSAIDs in the test samples), accuracy (98-102%) and precision (less than 2% RSD) were obtained. This universal approach is suitable for the determination of frequently used NSAIDs in a single analysis in less than 15 min. In addition to simple sample pretreatment, low running costs and minimal environmental impact could make this method attractive for the analysis of pharmaceutical preparations.
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Antiinflamatorios no Esteroideos , Química Farmacéutica , Electroforesis por Microchip , Preparaciones Farmacéuticas , Antiinflamatorios no Esteroideos/química , Antiinflamatorios no Esteroideos/aislamiento & purificación , Química Farmacéutica/métodos , Conductividad Eléctrica , Isotacoforesis , Preparaciones Farmacéuticas/químicaRESUMEN
Several research disciplines require fast, reliable and highly automated determination of pharmaceutically active compounds and their enantiomers in complex biological matrices. To address some of the challenges of Capillary Electrophoresis (CE), such as low concentration sensitivity and performance degradation linked to the adsorption and interference of matrix components, CE in a hydrodynamically closed system was evaluated using the model compounds Pindolol and Propranolol. Some established validation parameters such as repeatability of injection efficiency, resolution and sensitivity were used to assess its performance, and it was found to be broadly identical to that of hydrodynamically opened systems. While some reduction in separation efficiency was observed, this was mainly due to dispersion caused by injection and it had no impact on the ability to resolve enantiomers of model compounds even when spiked into complex biological matrix such as blood serum. An approximately 18- to 23-fold increase in concentration sensitivity due to the employment of wide bore capillaries was observed. This brings the sensitivity of CE to a level similar to that of liquid chromatography techniques. In addition to this benefit and unlike in hydrodynamically opened systems, suppression of electroosmotic flow, which is essential for hydrodynamically closed systems practically eliminates the matrix effects that are linked to protein adsorption.
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Electroforesis Capilar/métodos , Suero/química , Electroforesis Capilar/instrumentación , Hidrodinámica , Preparaciones Farmacéuticas , Pindolol/análisis , Propranolol/análisis , Reproducibilidad de los Resultados , Sensibilidad y Especificidad , Programas Informáticos , EstereoisomerismoRESUMEN
A novel online coupling of microchip isotachophoresis (µITP) with surface-enhanced Raman spectroscopy (SERS) for the analysis of complex samples is presented. Polymeric microchip with coupled channels was used for µITP-SERS analysis of four structurally similar Raman active synthetic dyes (brilliant black BN, carmoisine, ponceau 4R, and sunset yellow FCF) in pharmaceuticals. The µITP separation and simultaneous pre-concentration of the analytes were performed in the first channel of the microchip at pH 6.0 with the aid of non-Raman active discrete spacers (acetate, butyrate, glutarate, pantothenate, and valerate). Silver nanoparticles used for Raman enhancement were present in the second channel, and individual SERS spectra of the dyes were acquired by a mini Raman spectrometer operating at 532 nm. The analytical enhancement factors for silver nanoparticles were 1-5 × 104. The microchip with coupled channels enabled independent µITP separation and SERS detection, and eliminated any adverse impact of nanoparticles on the separation. The developed approach allowed reliable online SERS identification and detection of dyes with limits of detection ranging from 12 to 62 nM. Synthetic dyes were successfully separated, identified, and quantified in pharmaceutical preparations within 7 min without the need for complex or time-consuming sample pretreatment. The results were in good agreement with those obtained by an independent analytical method reported for studied dyes. Graphical abstract.
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Colorantes/análisis , Electroforesis por Microchip/métodos , Isotacoforesis/métodos , Espectrometría Raman/métodos , Límite de Detección , Nanopartículas del Metal/química , Plata/químicaRESUMEN
Microchip isotachophoresis (µITP) is a miniaturized version of conventional isotachophoresis (ITP) characterized by low sample and buffer consumption and reduced waste production. µITP with universal conductivity detection is suitable for quantitative analysis of relatively simplified samples that contain analyte(s) at relatively high concentration, e.g., pharmaceutical preparations. Here we describe in detail a principle of µITP in terms of reaching highly precise results. A practical use of µITP is shown on the analyses of various pharmaceutical preparations for content of major constituents including active pharmaceutical ingredients as well as pharmaceutical counterions. The pharmaceuticals are treated only minimally prior to the ITP run on a microchip with coupled channels and sample injection channel with 0.9 µL volume. Developed method is suitable for rapid (analysis time up to 10 min), precise (less than 1% RSD of analyte zone length), and accurate (recovery of 98-101%) determination of major pharmaceutical ingredients using a method of internal standard for data evaluation.
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Electroforesis por Microchip/métodos , Isotacoforesis/métodos , Preparaciones Farmacéuticas/análisis , Acetilcisteína/análisis , Buserelina/análisis , Conductividad Eléctrica , Análisis por MicromatricesRESUMEN
Although microchip electrophoresis (MCE) is intended to provide reliable quantitative data, so far there is only limited attention paid to these important aspects. This study gives a general overview of key aspects to be followed to reach high-precise determination using isotachophoresis (ITP) on the microchip with conductivity detection. From the application point of view, the procedure for the determination of acetate, a main component in the pharmaceutical preparation buserelin acetate, was developed. Our results document that run-to-run fluctuations in the sample injection volume limit the reproducibility of quantitation based on the external calibration. The use of a suitable internal standard (succinate in this study) improved the repeatability of the precision of acetate determination from six to eight times. The robustness of the procedure was studied in terms of impact of fluctuations in various experimental parameters (driving current, concentration of the leading ions, pH of the leading electrolyte and buffer impurities) on the precision of the ITP determination. The use of computer simulation programs provided means to assess the ITP experiments using well-defined theoretical models. A long-term validity of the calibration curves on two microchips and two MCE equipments was verified. This favors ITP over other microchip electrophoresis techniques, when chip-to-chip or equipment-to-equipment transfer of the analytical method is required. The recovery values in the range of 98-101 % indicate very accurate determination of acetate in buserelin acetate, which is used in the treatment of hormone-dependent tumors. This study showed that microchip ITP is suitable for reliable determination of main components in pharmaceutical preparations.
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Acetatos/aislamiento & purificación , Buserelina/análisis , Electroforesis por Microchip/métodos , Fármacos para la Fertilidad Femenina/análisis , Isotacoforesis/métodos , Modelos Estadísticos , Calibración , Simulación por Computador , Conductividad Eléctrica , Electroforesis por Microchip/instrumentación , Electroforesis por Microchip/estadística & datos numéricos , Femenino , Análisis de Inyección de Flujo/métodos , Humanos , Concentración de Iones de Hidrógeno , Isotacoforesis/instrumentación , Isotacoforesis/estadística & datos numéricos , Estándares de Referencia , Reproducibilidad de los Resultados , Ácido Succínico/aislamiento & purificaciónRESUMEN
A high-speed DNA fragment separation system based on an on-line combination of capillary ITP with CZE (CITP-CZE) and using UV detection at 260 nm was developed. A novel CITP-CZE buffer system of pH 6.1 was designed for the separation of ten DNA fragments with sizes ranging from 100 to 1000 bp. An effect of underivatized α-, ß- and γ-cyclodextrins on the resolution of DNA fragments in the CZE step of the CITP-CZE combination was systematically investigated. Methylhydroxyethylcellulose present in the BGE was used to eliminate the EOF. DNA ladder fragments were separated within 10 min with LODs in the range of 1-5 ng/µL (S/N = 3). The RSDs of the migration time and peak area of individual DNA fragments were in the range of 1-3 and 3-9%, respectively. The developed CITP-CZE system was further applied to the analysis of digest plasmid DNA samples.
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ADN/análisis , ADN/química , Electroforesis Capilar/métodos , Isotacoforesis/métodos , ADN/aislamiento & purificación , Límite de Detección , Reproducibilidad de los Resultados , Espectrofotometría UltravioletaRESUMEN
In this work, we tested the applicability of a commercial CE instrument (Agilent) for capillary ITP (CITP). The fused silica capillaries were flushed with PVP solution before each sample injection to suppress the EOF. As a dual-detection mode, commercial capacitively coupled contactless conductivity detection and ultraviolet detectors were applied. The experiments showed that the detection gap of the capacitively coupled contactless conductivity detection limits the achievable LOD and the separation resolution when the analyte CITP zones are very narrow, therefore long (120 cm) CE capillary was used and it was largely filled with the sample solution. CITP analyses of several real samples (leather extract, red wine, juice, and fizzy drink) have been demonstrated. In peak mode of CITP when the zone of a chromophore analyte is positioned between nonchromophore zones, excellent sensitivity (in submicromolar concentration range) could be achieved by ultraviolet detection. The hazardous chromate in low concentration was determined in the aqueous extract of tanned leather.
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Electroforesis Capilar/métodos , Isotacoforesis/métodos , Espectrofotometría Ultravioleta/métodos , Calibración , Conductividad Eléctrica , Límite de DetecciónRESUMEN
A novel microchip electrophoresis method for the rapid and high-precision determination of N-acetylcysteine, a pharmaceutically active ingredient, in mucolytics has been developed. Isotachophoresis separations were carried out at pH 6.0 on a microchip with conductivity detection. The methods of external calibration and internal standard were used to evaluate the results. The internal standard method effectively eliminated variations in various working parameters, mainly run-to-run fluctuations of an injected volume. The repeatability and accuracy of N-acetylcysteine determination in all mucolytic preparations tested (Solmucol 90 and 200, and ACC Long 600) were more than satisfactory with the relative standard deviation and relative error values <0.7 and <1.9%, respectively. A recovery range of 99-101% of N-acetylcysteine in the analyzed pharmaceuticals predetermines the proposed method for accurate analysis as well. This work, in general, indicates analytical possibilities of microchip isotachophoresis for the quantitative analysis of simplified samples such as pharmaceuticals that contain the analyte(s) at relatively high concentrations.
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Acetilcisteína/análisis , Electroforesis por Microchip/métodos , Preparaciones Farmacéuticas/análisisRESUMEN
We present a new technique suitable for direct liquid sampling and analysis by ion mobility spectrometry (IMS). The technique is based on introduction of a droplet stream to the IMS reaction region. The technique was successfully used to detect explosives dissolved in methanol and oil as well as to analyze amino acids and dipeptides. One of the main advantages of this technique is its ability to analyze liquid samples without the requirement of any special solution.
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Microchip capillary electrophoresis (MCE) is a relatively new analytical method requiring only small sample amounts, which is very favorable for the analysis of volume-limited biofluids. The practical use of MCE in bioanalysis is still restricted in terms of requirements for simplifying and/or concentrating sample pretreatment techniques. Here, we describe an MCE method for trace analysis of nitrite and nitrate, indicators of various neurological diseases, in cerebrospinal fluid (CSF). The complex CSF samples were simplified by solid-phase microextraction prior to an online combination of isotachophoresis with capillary zone electrophoresis performed on a microchip with coupled channels and a high-volume sample injection channel (9.9 µL). The method is suitable for rapid (total analysis time lasted 20 min), reproducible (0.6-2.4 % RSD for migration time), and sensitive (3-9 nM limits of detection) determinations of nitrite and nitrate in 15-50 times diluted CSF samples.
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Electroforesis Capilar/métodos , Electroforesis por Microchip/métodos , Nitratos/líquido cefalorraquídeo , Nitritos/líquido cefalorraquídeo , HumanosRESUMEN
A new MCE method for the determination of oxalic, citric, glycolic, lactic, and 2- and 3-hydroxybutyric acids, indicators of some metabolic and neurological diseases, in cerebrospinal fluid (CSF) was developed. MCE separations were performed on a PMMA microchip with coupled channels at lower pH (5.5) to prevent proteins interference. A double charged counter-ion, BIS-TRIS propane, was very effective in resolving the studied organic acids. The limits of detection (S/N = 3) ranging from 0.1 to 1.6 µM were obtained with the aid of contact conductivity detector implemented directly on the microchip. RSDs for migration time and peak area of organic acids in artificial and CSF samples were <0.8 and <9.7%, respectively. Recoveries of organic acids in untreated CSF samples on the microchip varied from 91 to 104%. Elimination of chloride interference, a major anionic constituent of CSF, has been reached by two approaches: (i) the use of coupled channels microchip in a column switching mode when approximately 97-99% of chloride was removed electrophoretically in the first separation channel and (ii) the implementation of micro-SPE with silver-form resin prior to the MCE analysis, which selectively removed chloride from undeproteinized CSF samples.
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Ácidos Acíclicos/líquido cefalorraquídeo , Electroforesis por Microchip/métodos , Ácidos Acíclicos/química , Ácidos Acíclicos/aislamiento & purificación , Ácidos Acíclicos/metabolismo , Conductividad Eléctrica , Electroforesis por Microchip/instrumentación , Humanos , Reproducibilidad de los Resultados , Microextracción en Fase SólidaRESUMEN
A new method for the determination of nitrite and nitrate, indicators of various neurological diseases (meningitis, multiple sclerosis, Parkinson's disease) in cerebrospinal fluid (CSF) on an electrophoresis chip was developed. An on-line combination of isotachophoresis (ITP) with capillary electrophoresis (CE) on a poly(methylmethacrylate) chip assembled with coupled separation channels (CC) and contact conductivity detectors was employed. ITP separations performed at low pH (3.6) in the first separation channel enabled a highly selective transfer of the analytes to the second CE stage working under micellar conditions implemented by zwitterionic surfactant, 3-(N,N-dimethyldodecylammonio)-propanesulfonate. The proposed method achieved low limits of detection varied from 0.2 to 0.4µgL(-1) when the sample volume injected onto the chip (9.9µl) was almost the same as the volume of both separation channels. Preferable working conditions on the CC chip (suppressed hydrodynamic and electroosmotic flow) contributed for reproducible migration velocities (intra-day reproducibility up to 2.1% RSD) and determinations of trace concentrations of nitrite and nitrate (intra-day precision up to 3.0% RSD). Huge amount of chloride present in CSF (approx. 4.5gL(-1)) was removed from analyzed CSF samples by microsolid phase extraction performed on silver-form resin prior to the ITP-CE analysis. Developed method provided fast (approx. 20min total analysis time) and reliable determinations of trace nitrite and nitrate and could be fully integrated into the analysis of CSF samples.
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Electroforesis por Microchip/métodos , Nitratos/líquido cefalorraquídeo , Nitritos/líquido cefalorraquídeo , Microextracción en Fase Sólida/métodos , Adolescente , Adulto , Biomarcadores/líquido cefalorraquídeo , Electroforesis por Microchip/instrumentación , Femenino , Humanos , Límite de Detección , Modelos Lineales , Masculino , Persona de Mediana Edad , Enfermedades Neurodegenerativas/líquido cefalorraquídeo , Reproducibilidad de los ResultadosRESUMEN
Adsorption processes on a PMMA chip linked with CZE separations of a group of 13 aliphatic and aromatic mono- and di-amines were studied. Due to the lack of chromophores within aliphatic amines, contact conductivity detection implemented directly onto the chip was used for monitoring of cationic CZE separations. To prevent an adsorption of studied amines to the chip channels, the surface of PMMA chip was modified by dynamic coating. Different surface modifiers, such as aliphatic oligoamines (diethylenetriamine and triethylenetetramine), were added to the BGE solutions filling the chip channels. The effect of various concentrations of surface modifiers on peak profiles and separation parameters of amines was monitored. Of these, mainly, aliphatic di-amines and aromatic mono-amines adversely affected the CZE resolution of a whole group of analytes by their strong adsorption to the chip channels. A propionate BGE with pH 3.2 containing 100 µM triethylenetetramine and 25 mM 18-crown-6-ether was found suitable for CZE resolution of 12 from a total of 13 amines studied. Simple dynamic modification of the surface of PMMA chip enabled fast (analysis time lasted 9 min), sensitive (sub-µM LODs reached) and reproducible (1-3% RSD of the peak areas) CZE analysis of the aliphatic and aromatic amines.