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See detailValidation of a nonaqueous capillary electrophoretic method for the enantiomeric purity determination of R-flurbiprofen using a single-isomer amino cyclodextrin derivative
Rousseau, Anne ULg; Chiap, Patrice ULg; Ivanyi, Robert et al

in Journal of Chromatography. A (2008), 1204(2), 219-225

Nonaqueous capillary electrophoresis (NACE) was successfully applied to the enantiomeric purity determination of R-flurbiprofen using 6-monodeoxy-6-mono(2-hydroxy)propylamino-beta-cyclodextrin (IPA-beta ... [more ▼]

Nonaqueous capillary electrophoresis (NACE) was successfully applied to the enantiomeric purity determination of R-flurbiprofen using 6-monodeoxy-6-mono(2-hydroxy)propylamino-beta-cyclodextrin (IPA-beta-CD) as chiral selector. The nonaqueous BGE was made up of 20 mM IPA-beta-CD, 20 mM ammonium camphorsulfortate and 40 mM ammonium acetate in methanol. Flufenamic acid was selected as internal standard. The CE method was carefully optimized in order to prevent the adsorption of the cationic CD onto the capillary wall, and therefore, to avoid loss of peak efficiency and enantioresolution. To achieve this goal, the addition of ammonium camphorsulfonate was found to be necessary. In the selected conditions, the determination of 0.1% of S-flurbiprofen in R-flurbiprofen could be performed using the method of standard additions. The NACE method was then fully validated by applying a novel strategy using accuracy profiles. (c) 2008 Elsevier B.V. All rights reserved. [less ▲]

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See detailRisk-Based Approach for the Transfer of Quantitative Methods: Bioanalytical Applications
Rozet, Eric ULg; Dewé, Walthère ULg; Morello, R. et al

in Journal of Chromatography. A (2008), 1189

The transfer of analytical methods from a sending laboratory to a receiving one requires to guarantee that this last laboratory will obtain accurate results. Undeniably method transfer is the ultimate ... [more ▼]

The transfer of analytical methods from a sending laboratory to a receiving one requires to guarantee that this last laboratory will obtain accurate results. Undeniably method transfer is the ultimate step before routine implementation of the method at the receiving site. The conventional statistical approaches generally used in this domain which analyze separately the trueness and precision characteristics of the receiver do not achieve this. Therefore, this paper aims first at demonstrating the applicability of two recent statistical approaches using total error-based criterion and taking into account the uncertainty of the true value estimate of the sending laboratory, to the transfer of bioanalytical methods. To achieve this, they were successfully applied to the transfer of two fully automated liquid chromatographic method coupled on-line to solid-phase extraction. The first one was dedicated to the determination of three catecholamines in human urine using electrochemical detection, and the second one to the quantitation of N-methyl-laudanosine in plasma using fluorescence detection. Secondly, a risk-based evaluation is made in order to understand why classical statistical approaches are not sufficient to provide the guarantees that the analytical method will give most of the time accurate results during its routine use. Finally, some recommendations for the transfer studies are proposed. [less ▲]

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See detailLiquid chromatographic determination of enrofloxacin in nasal secretions and plasma of healthy pigs using restricted access material for on-line sample clean-up
Bimazubute, M. A.; Rozet, Eric ULg; Dizier, Isabelle ULg et al

in Journal of Chromatography. A (2008), 1189(1-2), 456-466

A new fully automated method was developed for the quantitative analysis of an antibacterial drug, enrofloxacin (ENRO), in both nasal secretions and plasma samples of healthy pigs. The method is based on ... [more ▼]

A new fully automated method was developed for the quantitative analysis of an antibacterial drug, enrofloxacin (ENRO), in both nasal secretions and plasma samples of healthy pigs. The method is based on the use of a pre-column packed with restricted access material (RAM), namely RP-18 ADS (alkyl diol silica), for on-line sample clean-up coupled to a liquid chromatographic (LC) column containing octadecyl silica. The only off-line sample preparation was the 50-fold dilution of nasal secretions and plasma samples in the washing liquid composed of 25 mM phosphate buffer of pH 7.4. A 10 μl diluted sample volume was injected directly onto the pre-column and washed for 7 min. By rotation of a switching valve, the analyte of interest was eluted in the back-flush mode with the LC mobile phase which consisted in a mixture of 25 mM phosphate buffer of pH 3.0 and acetonitrile according to a segmented gradient elution. By a new rotation of the switching valve, the pre-column and the analytical column were equilibrated for 3 min with the initial mobile phases. The flow-rate was 0.8 ml min−1 for the washing liquid and 1.5 ml min−1 for the LC mobile phase. ENRO was detected by fluorescence at excitation and emission wavelengths of 278 and 445 nm, respectively. Finally, the developed method was validated using an original strategy based on total measurement error and accuracy profiles as a decision tool. The limits of quantitation of ENRO in plasma and in nasal secretions were 30.5 and 91.6 ng/ml, respectively. The validated method was then applied successfully to the determination of ENRO in healthy pigs treated by intramuscular injection at different doses (2.5, 10 and 30 mg/kg bodyweight) for a pilot study. This method could be also used for the simultaneous analysis of ENRO and its main metabolite, ciprofloxacin (CIPRO). [less ▲]

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See detailNonaqueous electrokinetic chromatography-electrospray ionization mass spectrometry using anionic cyclodextrins
Mol, Roelof; Servais, Anne-Catherine ULg; Fillet, Marianne ULg et al

in Journal of Chromatography. A (2007), 1159(1-2), 51-57

The set-up of an on-line method for coupling nonaqueous electrokinetic chromatography (NAEKC) and electrospray ionization mass spectrometry (ESI-MS) is presented. It allows the use of the single-isomer ... [more ▼]

The set-up of an on-line method for coupling nonaqueous electrokinetic chromatography (NAEKC) and electrospray ionization mass spectrometry (ESI-MS) is presented. It allows the use of the single-isomer derivative anionic cyclodextrins heptakis(2,3-di-O-methyl-6-O-sulfo)-beta-cyclodextrin (HDMS-beta-CD) and heptakis(2.3-di-O-acetyl-6-O-sulfo)-beta-cyclodextrin (HDAS-beta-CD) for chiral and achiral separations of positively charged analytes. The effect of the cyclodextrins (CDs) on the MS signal intensities of model compounds was studied. When a voltage is applied over the CE capillary, the overall mobility of the CDs is towards the inlet vial preventing CDs from entering the ion source. However, the sodium counter ions of the CDs still enter the ion source and appeared to cause ionization suppression. Nevertheless, significant analyte signals could still be detected with detection limits in the sub-mu g/ml. System parameters such as sheath liquid composition and flow rate, nebulizing gas pressure, capillary position in the sprayer and the drying gas flow and temperature were studied and optimized. The selection of a relatively low nebulizing gas pressure appeared to be important to achieve optimum sensitivity. The chiral selectivity of the NAEKC-ESI-MS system could be improved by addition of camphorsulfonate to the background electrolyte. Using mixtures of drugs and drug-related compounds, the NAEKC-ESI-MS system is shown to offer potential for (chiral) drug profiling. (c) 2007 Elsevier B.V. All rights reserved. [less ▲]

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See detailUsing tolerance intervals in pre-study validation of analytical methods to predict in-study results - The fit-for-future-purpose concept
Rozet, Eric ULg; Hubert, Cédric ULg; Ceccato, Attilio ULg et al

in Journal of Chromatography. A (2007), 1158(1-2), 126-137

It is recognized that the purpose of validation of analytical methods is to demonstrate that the method is suited for its intended purpose. Validation is not only required by regulatory authorities, but ... [more ▼]

It is recognized that the purpose of validation of analytical methods is to demonstrate that the method is suited for its intended purpose. Validation is not only required by regulatory authorities, but is also a decisive phase before the routine use of the method. For a quantitative analytical method the objective is to quantify the target analytes with a known and suitable accuracy. For that purpose, first, a decision about the validity of the method based on prediction is proposed: a method is declared proper for routine application if it is considered that most of the future results generated will be accurate enough. This can be achieved by using the "beta-expectation tolerance interval" (accuracy profile) as the decision tool to assess the validity of the analytical method. Moreover, the concept of "fit-for-purpose" is also proposed here to select the most relevant response function as calibration curve, i.e. choosing a response function based solely on the predicted results this model will allow to obtain. This paper reports four case studies where the results obtained with quality control samples in routine were compared to predictions made in the validation phase. Predictions made using the "beta-expectation tolerance interval" are shown to be accurate and trustful for decision making. It is therefore suggested that an adequate way to conciliate both the objectives of the analytical method in routine analysis and those of the validation step consists in taking the decision about the validity of the analytical method based on prediction of the future results using the most appropriate response function curve, i.e. the fit-for-future-purpose concept. [less ▲]

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See detailDevelopment and validation of a multi-residue method for pesticide determination in honey using on-column liquid-liquid extraction and liquid chromatography-tandem mass spectrometry
Pirard, Catherine; Widart, Joëlle ULg; Nguyen, Bach Kim ULg et al

in Journal of Chromatography. A (2007), 1152(1-2), 116-123

We report on the development and validation under ISO 17025 criteria of a multi-residue confirmatory method to identify and quantify 17 widely chemically different pesticides (insecticides: Carbofuran ... [more ▼]

We report on the development and validation under ISO 17025 criteria of a multi-residue confirmatory method to identify and quantify 17 widely chemically different pesticides (insecticides: Carbofuran, Methiocarb, Pirimicarb, Dimethoate, Fipronil, Imidacloprid; herbicides: Amidosulfuron, Rimsulfuron, Atrazine, Simazine, Chloroturon, Linuron, Isoxaflutole, Metosulam; fungicides: Diethofencarb) and 2 metabolites (Methiocarb sulfoxide and 2-Hydroxytertbutylazine) in honey. This method is based on an on-column liquid liquid extraction (OCLLE) using diatomaceous earth as inert solid support and liquid chromatography (LC) coupled to mass spectrometry (MS) operating in tandem mode (MS/MS). Method specificity is ensured by checking retention time and theoretical ratio between two transitions from a single precursor ion. Linearity is demonstrated all along the range of concentration that was investigated, from 0.1 to 20 ng g(-1) raw honey, with correlation coefficients ranging from 0.921 to 0.999, depending on chemicals. Recovery rates obtained on home-made quality control samples are between 71 and 90%, well above the range defined by the EC/657/2002 document, but in the range we had fixed to ensure proper quantification, as levels found in real samples could not be corrected for recovery rates. Reproducibility is found to be between 8 and 27%. Calculated CC alpha and CC beta (0.0002-0.943 mg g(-1) for CC alpha, and 0.0002-1.232 ng g(-1) for CCP) show the good sensitivity attained by this rnulti-residue analytical method. The robustness of the method has been tested in analyzing more than 100 raw honey samples collected from different areas in Belgium, as well as some wax and bee samples, with a slightly adapted procedure. (C) 2007 Elsevier B.V. All rights reserved. [less ▲]

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See detailNonaqueous capillary electrophoretic behavior of 2-aryl propionic acids in the presence of an achiral ionic liquid - A chemometric approach
Francois, Yannis; Varenne, Anne; Juillerat, Emilie et al

in Journal of Chromatography. A (2007), 1138(1-2), 268-275

Ionic liquids (ILs) appear really attractive as electrolyte additives in nonaqueous capillary electrophoresis (NACE). These salts may offer new possibilities of interactions to modulate analyte effective ... [more ▼]

Ionic liquids (ILs) appear really attractive as electrolyte additives in nonaqueous capillary electrophoresis (NACE). These salts may offer new possibilities of interactions to modulate analyte effective mobilities. The presence of 1-n-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMIM NTf2) in acetonitrile/alcohol background electrolytes (BGEs) was investigated in this work. The aim of this study was to elucidate the influence of the IL concentration on the electrophoretic behavior of four arylpropionic acids and to identify the interactions between the analytes and the 1L cation. The influence on mobility of the IL concentration, the nature and the proportion of the organic solvents, and the concentration of the ionic components of the BGE was first studied by a univariate approach. A four-factor D-optimal experimental design was then applied to provide a deeper insight into analyte interaction with IL cation present both free in BGE and adsorbed onto the capillary wall. (c) 2006 Elsevier B.V. All rights reserved. [less ▲]

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See detailDevelopment of a mass spectrometry method for the determination of a melanoma biomarker, 5-S-cysteinyldopa, in human plasma using solid phase extraction for sample clean-up.
Martin, Gaëlle ULg; Chiap, Patrice ULg; Paquet, Philippe ULg et al

in Journal of Chromatography. A (2007), 1156(1-2), 141-8

5-S-cysteinyldopa is a well-known pigment intermediate and analysis of its plasma concentration is interesting for the early diagnosis, as well as for evaluation of treatment and follow-up of malignant ... [more ▼]

5-S-cysteinyldopa is a well-known pigment intermediate and analysis of its plasma concentration is interesting for the early diagnosis, as well as for evaluation of treatment and follow-up of malignant melanoma. A determination method of 5-SCD in human plasma was developed using solid phase extraction (SPE) on disposable cartridges and liquid chromatography electrospray mass spectrometry (LC-ESI-MS-MS). Compound's sensitivity to light and oxidation requires the addition of anti-oxidative agents (AO), to work in acidic media at 4 degrees C and to avoid light exposure of samples since blood collection. Different solid phases involving covalent binding to phenylboronic groups or dual retention mechanisms were evaluated and extraction cartridges containing both hydrophobic and strong cation exchange functionalities were finally selected. The LC separation of 5-SCD from endogenous catecholamines was achieved by gradient elution on a C18 stationary phase. 5-SCD was detected by multiple reaction monitoring (MRM) performed on ES(+) generated ions. Finally, the method was prevalidated in the lower ng/ml range. Good results with respect to accuracy, trueness and precision were obtained. [less ▲]

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See detailDevelopment of an absolute quantification method targeting growth hormone biomarkers using liquid chromatography coupled to isotope dilution mass spectrometry.
Kirsch, Stéphanie ULg; Widart, Joëlle ULg; Louette, Joel et al

in Journal of Chromatography. A (2007), 1153(1-2), 300-6

A method to perform absolute quantification of two biomarkers (IGF-1 and IGFBP-3) of growth hormone abuse has been developed. Isotope dilution is used with synthetically labelled peptides as internal ... [more ▼]

A method to perform absolute quantification of two biomarkers (IGF-1 and IGFBP-3) of growth hormone abuse has been developed. Isotope dilution is used with synthetically labelled peptides as internal standards. Peptide selection and multiple reaction monitoring design are discussed. A simple sample preparation based on the reduction and alkylation of cysteine residues followed by tryptic digestion provides a sufficient digestion of proteins. Serum samples fortified with increasing amounts of target proteins are analysed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) on a triple quadrupole mass spectrometer. Specificity is ensured by the selection of sequences with no homology in BLAST, as well as retention time deviation check, and ion ratio monitoring. Linearity is studied in terms of calibration curves. These curves for IGFBP-3 and IGF-1 are generated with mean slopes of 0.055 and 0.065, intercepts of 0.107 and -0.011, and with coefficients of correlation of 0.95 and 0.98, respectively. These curves result from the addition of proteins to the serum. Risks of variations related to potential matrix effects are therefore reduced, as well as probable variations related to the digestion steps. The working concentration ranges are 4-10 ng/microl for IGFBP-3 and 2-8 ng/microl for IGF-1. Preliminary data regarding repeatability show that relative standard deviations (RSDs) range between 13 and 32% for IGFBP-3 and between 7 and 29% for IGF-1. [less ▲]

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See detailAnalysis of recent pharmaceutical regulatory documents on analytical method validation.
Rozet, Eric ULg; Ceccato, Attilio ULg; Hubert, Cédric ULg et al

in Journal of Chromatography. A (2007), 1158(1-2), 111-25

All analysts face the same situations as method validation is the process of proving that an analytical method is acceptable for its intended purpose. In order to resolve this problem, the analyst refers ... [more ▼]

All analysts face the same situations as method validation is the process of proving that an analytical method is acceptable for its intended purpose. In order to resolve this problem, the analyst refers to regulatory or guidance documents, and therefore the validity of the analytical methods is dependent on the guidance, terminology and methodology, proposed in these documents. It is therefore of prime importance to have clear definitions of the different validation criteria used to assess this validity. It is also necessary to have methodologies in accordance with these definitions and consequently to use statistical methods which are relevant with these definitions, the objective of the validation and the objective of the analytical method. The main purpose of this paper is to outline the inconsistencies between some definitions of the criteria and the experimental procedures proposed to evaluate those criteria in recent documents dedicated to the validation of analytical methods in the pharmaceutical field, together with the risks and problems when trying to cope with contradictory, and sometimes scientifically irrelevant, requirements and definitions. [less ▲]

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See detailHigh-throughput biomonitoring of dioxins and polychlorinated biphenyls at the sub-picogram level in human serum
Focant, Jean-François ULg; Eppe, Gauthier ULg; Massart, Anne-Cécile ULg et al

in Journal of Chromatography. A (2006), 1130(1), 97-107

We report on the use of a state-of-the-art method for the measurement of selected polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and polychlorinated biphenyls in human serum specimens ... [more ▼]

We report on the use of a state-of-the-art method for the measurement of selected polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and polychlorinated biphenyls in human serum specimens. The sample preparation procedure is based on manual small size solid-phase extraction (SPE) followed by automated clean-up and fractionation using multi-sorbent liquid chromatography columns. SPE cartridges and all clean-up columns are disposable. Samples are processed in batches of 20 units, including one blank control (BC) sample and one quality control (QC) sample. The analytical measurement is performed using gas chromatography coupled to isotope dilution high-resolution mass spectrometry. The sample throughput corresponds to one series of 20 samples per day, from sample reception to data quality cross-check and reporting, once the procedure has been started and series of samples keep being produced. Four analysts are required to ensure proper performances of the procedure. The entire procedure has been validated under International Organization for Standardization (ISO) 17025 criteria and further tested over more than 1500 unknown samples during various epidemiological studies. The method is further discussed in terms of reproducibility, efficiency and long-term stability regarding the 35 target analytes. Data related to quality control and limit of quantification (LOQ) calculations are also presented and discussed. (c) 2006 Elsevier B.V. All rights reserved. [less ▲]

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See detailSuitability of tandem-in-time mass spectrometry for polybrominated diphenylether measurement in fish and shellfish samples: Comparison with high resolution mass spectrometry
Pirard, Catherine; De Pauw, Edwin ULg; Focant, Jean-François ULg

in Journal of Chromatography. A (2006), 1115(1-2), 125-132

The first part of the present study focused on the development of an alternative automated sample preparation method for the measurement of selected polybrominated diphenyl ethers (PBDEs) in fish and ... [more ▼]

The first part of the present study focused on the development of an alternative automated sample preparation method for the measurement of selected polybrominated diphenyl ethers (PBDEs) in fish and shellfish. A previously developed automated method has been further optimized and simplified to decrease blank levels and cost. Sorbent and solvent quantities have been significantly reduced without altering extract quality. The second part of the study consisted of comparing tandem-in-time quadrupole ion storage mass spectrometry (QISTMS/MS) to high resolution mass spectrometry (HRMS) for the isotope dilution (ID) measurement step after gas chromatography (GC) separation. Both mass spectrometric methods performed similarly in terms of accuracy but better precision was observed for HRMS. Although better sensitivity can be attained with the high resolution sector instrument, method limits of quantification (mLOQs) were very similar for both approaches as they were dependent on the procedural blanks levels. The mLOQ values ranged between 0.04 and 3.56 ng/g fat, depending on the congener. They allowed the unambiguous identification and quantification of all target analytes, except for BDE-183, in most considered fish extracts. An analytical procedure based on rapid automated sample preparation and QISTMS/MS appeared to be suitable for the measurement of PBDEs in fish and shellfish speciment under quality assurance/quality control (QA/QC) criteria. (c) 2006 Elsevier B.V. All rights reserved. [less ▲]

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See detailValidation of a high-performance thin-layer chromatography/densitometry method for the quantitative determination of glucosamine in a herbal dietary supplement
Esters, Virginie ULg; Angenot, Luc ULg; Brandt, V. et al

in Journal of Chromatography. A (2006), 1112(1-2), 156-164

A quantitative densitometric high-performance thin-layer chromatography (HPTLC) method was developed for the determination of glucosamine in a dietary supplement containing dried extracts of the main ... [more ▼]

A quantitative densitometric high-performance thin-layer chromatography (HPTLC) method was developed for the determination of glucosamine in a dietary supplement containing dried extracts of the main plants traditionally used for rheumatic disorders. The HPTLC method was chosen in order to circumvent the tedious and time-consuming sample preparation steps necessarily performed before using HPLC methods when analysing complex matrixes. Glucosamine was separated from the plant extracts on a silica gel 60 F(254) HPTLC plate using a saturated mixture of 2-propanol-ethyl acetate-ammonia solution (8%) (10:10:10, v/v/v). The plates were developed vertically up to a distance of 80 mm. For visualization, the plate was dipped into a modified anisaldehyde reagent and heated at 120 degrees C for 30 min in a drying oven. Glucosamine appeared as brownish-red chromatographic zones on a colourless background. Densitometric quantification was performed at lambda = 415 nm by reflectance scanning. The HPTLC method was successfully validated by applying the novel validation protocol proposed by a commission of the "Societe Francaise des Sciences et Techniques Pharmaceutiques" (SFSTP). In the pre-validation phase, the appropriate response function was determined, while in the validation phase the method showed good performance thereby fulfilling its objective of quantifying accurately. The relative standard deviations for repeatability and intermediate precision were between 4.9 and 8.6%. Moreover, the method was found to be accurate, as the two-sided 95% beta-expectation tolerance interval did not exceed the acceptance limits of 85 and 115% on the whole analytical range (800-1,200 ng of glucosamine). [less ▲]

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See detailNonaqueous capillary electrophoresis method for the enantiomeric purity determination of S-timolol using heptakis(2,3-di-O-methyl-6-O-sulfo)-beta-cyclodextrin: validation using the accuracy profile strategy and estimation of uncertainty.
Marini Djang'Eing'A, Roland ULg; Servais, Anne-Catherine ULg; Rozet, Eric ULg et al

in Journal of Chromatography. A (2006), 1120(1-2), 102-11

Nonaqueous capillary electrophoresis (NACE) was successfully applied to the enantiomeric purity determination of S-timolol maleate using heptakis(2,3-di-O-methyl-6-O-sulfo)-beta-cyclodextrin (HDMS-beta-CD ... [more ▼]

Nonaqueous capillary electrophoresis (NACE) was successfully applied to the enantiomeric purity determination of S-timolol maleate using heptakis(2,3-di-O-methyl-6-O-sulfo)-beta-cyclodextrin (HDMS-beta-CD) as chiral selector. With a background electrolyte made up of a methanolic solution of 0.75 M formic acid, 30 mM potassium camphorsulfonate and containing 30 mM HDMS-beta-CD, the determination of 0.1% of R-timolol in S-timolol could be performed with an enantiomeric resolution of 8.5. Pyridoxine was selected as internal standard. The NACE method was then fully validated by applying a novel strategy using accuracy profiles. It is based on beta-expectation tolerance intervals for the total measurement error which includes trueness and intermediate precision. The uncertainty of measurements derived from beta-expectation tolerance intervals was estimated at each concentration level of the validation standards. To confirm the suitability of the developed and validated method, several real samples of S-timolol maleate containing R-timolol maleate at different concentrations were analysed and the results were compared to those obtained by liquid chromatography. [less ▲]

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See detailInfluence of the nature of the electrolyte on the chiral separation of basic compounds in nonaqueous capillary electrophoresis using heptakis(2,3-di-O-methyl-6-O-sulfo)-beta-cyclodextrin
Servais, Anne-Catherine ULg; Fillet, Marianne ULg; Chiap, Patrice ULg et al

in Journal of Chromatography. A (2005), 1068(1), 143-150

The influence on the enantiomeric resolution of the nature of the cationic BGE component (sodium, ammonium or potassium) and that of the anionic component (chloride, formate, methanesulfonate or ... [more ▼]

The influence on the enantiomeric resolution of the nature of the cationic BGE component (sodium, ammonium or potassium) and that of the anionic component (chloride, formate, methanesulfonate or camphorsulfonate) as well as the concentration of heptakis(2,3-di-O-methyl-6-O-sulfo)-beta-cyclodextrin (HDMS-beta-CD), the selected chiral selector, was studied in nonaqueous capillary electrophoresis (NACE). For this purpose, two D-optimal designs with 33 and 26 experimental points were applied. Three beta-blockers (atenolol, celiprolol and propranolol) and three local anesthetics (bupivacaine, mepivacaine and prilocaine) were selected as basic model compounds. Both cationic and anionic BGE components were found to have a deep impact on the enantiomeric resolution of the investigated analytes but it is the cationic component that has shown the strongest influence. Indeed, in some cases, the change of the latter led to a complete loss of enantioresolution. Based on the observed results, two NACE systems were recommended, namely ammonium formate and potassium camphorsulfonate in a methanolic solution containing HDMS-beta-CD and acidified with formic acid, in order to separate efficiently the enantiomers of basic drugs. (c) 2004 Elsevier B.V. All rights reserved. [less ▲]

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See detailRecent advances in mass spectrometric measurement of dioxins
Focant, Jean-François ULg; Pirard, Catherine; Eppe, Gauthier ULg et al

in Journal of Chromatography. A (2005), 1067(1-2), 265-275

Past years, many efforts have been dedicated to the development of alternative analytical methods for the measurement of dioxins in various types of matrices. Polychlorinated dibenzo-p-dioxins (PCDDs ... [more ▼]

Past years, many efforts have been dedicated to the development of alternative analytical methods for the measurement of dioxins in various types of matrices. Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) are compounds that are present in samples at part-per-billion (ppb) or part-per-trillion (ppt) level. Their measurement requires the use of very sensitive analytical methods. Gas chromatography (GC) coupled to quadrupole ion storage mass spectrometry (QISTMS), fast GC (FGC) coupled to time-of-flight mass spectrometry (TOFMS) and comprehensive two-dimensional gas chromatography (GC x GC) coupled to TOFMS are the more promising tools challenging the reference GC high resolution mass spectrometry (HRMS) based on sector instruments. We report herein some of the advances we achieved in the past years in our laboratory on the development of alternative measurement methods for those compounds. (c) 2004 Elsevier B.V. All rights reserved. [less ▲]

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See detailComprehensive two-dimensional gas chromatography with isotope dilution time-of-flight mass spectrometry for the measurement of dioxins and polychlorinated biphenyls in foodstuffs - Comparison with other methods
Focant, Jean-François ULg; Eppe, Gauthier ULg; Scippo, Marie-Louise ULg et al

in Journal of Chromatography. A (2005), 1086(1-2), 45-60

A comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC x GC-TOF-MS) experimental setup was tested for the measurement of seven 2,3,7,8-substituted polychlorinated dibenzo ... [more ▼]

A comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC x GC-TOF-MS) experimental setup was tested for the measurement of seven 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs), ten 2,3,7,8-substituted polychlorinated dibenzofurans (PCDFs), four non-ortho-polychlorinated biphenyls (PCBs), eight mono-ortho-PCBs, and six indicator PCBs (Aroclor 1260) in foodstuff samples. A 40 m RTX-500 (0.18 mm I.D., 0.10 mu m df) was used as the first dimension (D-1) and a 1.5 nn BPX-50 (0.10 mm I.D., 0.10 mu m df) as the second dimension (2 D). The GC x GC chromatographic separation was completed in 45 min. Quantification was performed using C-13-label isotope dilution (11)). Isotope ratios of the selected quantification ions were checked against theoretical values prior to peak assignment and quantification. The dynamic working range spanned three orders of magnitude. The lowest detectable amount of 2,3,7,8-TCDD was 0.2 pg. Fish, pork, and milk samples were considered. On a congener basis, the GC x GC-ID-TOF-MS method was compared to the reference GC-ID high resolution mass spectrometry (HRMS) method and to the alternative GC-ID tandem-in-time quadrupole ion storage mass spectrometry (QIST-MS/MS). PCB levels ranged from low picogram (pg) to low nanogram (ng) per gram of sample and data compared very well between the different methods. For all matrices, PCDD/Fs were at a low pg level (0.05-3 pg) on a fresh weight basis. Although congener profiles were accurately described, RSDs of GC x GC-ID-TOF-MS and GC-QIST-MS/MS were much higher than for GC-ID-HRMS, especially for low level pork and milk. On a toxic equivalent (TEQ) basis, all methods, including the dioxin-responsive chemically activated luciferase gene expression (DR-CALUX) assay, produced similar responses. A cost comparison is also presented. (c) 2005 Elsevier B.V. All rights reserved. [less ▲]

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See detailFully automated method for the liquid chromatographic-tandem mass spectrometric determination of cyproterone acetate in human plasma using restricted access material for on-line sample clean-up
Christiaens, B.; Fillet, Marianne ULg; Chiap, Patrice ULg et al

in Journal of Chromatography. A (2004), 1056(1-2), 105-110

A new automated method for the quantitative analysis of cyproterone acetate (CPA) in human plasma has been developed using on-line solid phase extraction (SPE) prior to the LC-MS/MS determination. The ... [more ▼]

A new automated method for the quantitative analysis of cyproterone acetate (CPA) in human plasma has been developed using on-line solid phase extraction (SPE) prior to the LC-MS/MS determination. The method was based on the use of a pre-column packed with internal-surface reversed-phase material (LiChrospher RP-4 ADS, 25 mm x 2 mm) for sample clean-up coupled to LC separation on an octadecyl silica stationary phase by means of a column switching system. A 30 microl plasma sample volume was injected directly onto the pre-column using a mixture of water, acetonitrile and formic acid (90:10:0.1 (v/v/v)) adjusted to pH 4.0 with diluted ammonia as washing liquid. The analyte was then eluted in the back-flush mode with the LC mobile phase consisting of water, methanol and formic acid (10:90:0.1 (v/v/v)). The dispensing flow rates of the washing liquid and the LC mobile phase were 300 microl min(-1). Medroxyprogesterone acetate (MPA) was used as internal standard. The MS ionization of the analytes was achieved using electrospray (ESI) in the positive ion mode. The pseudomolecular ionic species of CPA and MPA (417.4 and 387.5) were selected to generate daughter ions at 357.4 and 327.5, respectively. Finally, the developed method was validated according to a new approach using accuracy profiles as a decision tool. Very good results with respect to accuracy, detectability, repeatability, intermediate precision and selectivity were obtained. The LOQ of cyproterone acetate was 300 pg ml(-1). [less ▲]

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See detailImproved separation of the 209 polychlorinated biphenyl congeners using comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry
Focant, Jean-François ULg; Sjödin, Andreas; Patterson, Donald G.

in Journal of Chromatography. A (2004), 1040(2), 227-238

The separation of the 209 polychlorinated biphenyl (PCB) congeners has been studied using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC x GC-TOFMS). Four ... [more ▼]

The separation of the 209 polychlorinated biphenyl (PCB) congeners has been studied using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC x GC-TOFMS). Four column combinations based on thermally stable phases, DB-1/HT-8, DB-XLB/HT-8, DB-XLB/BPX-50, and HT-8/BPX-50, have been investigated. The HT-8/BPX-50 set produced the best separation. The distribution of the 100 to 150 ms wide peaks was highly structured in the chromatographic space and based on the degree of ortho-substitution within each separated homologue series. A total of 192 congeners were resolved in 146 min (1.3 analyte per min) using this column set. Eight coelutions involved 17 congeners. Among them, seven congeners were present in Aroclors at levels >1.0 wt.% (CBs 33, 47, 48, 95, 97, 163, 187). Except for CBs 47 and 48, none of the major constituents of commercial mixtures were coeluting. CB 138 was well separated from CBs 163 and 164 in the second dimension. For all column sets, CBs 20, 33, and 109 always coeluted with other PCBs. The 12 toxic dioxin-like congeners (CBs 77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169, 189), and the seven European Union marker PCBs (CBs 28, 52, 101, 118, 138, 153, 180) were separated from any interfering congeners. This was not the case for the other investigated column sets. [less ▲]

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See detailEvaluation of a novel anion-exchange restricted-access sorbent for on-line sample clean-up prior to the determination of acidic compounds in plasma by liquid chromatography
Rbeida, O.; Christiaens, B.; Hubert, Philippe ULg et al

in Journal of Chromatography. A (2004), 1030(1-2), 95-102

A new kind of silica-based restricted-access material (RAM) with anionic properties has been tested in pre-columns for on-line solid-phase extraction of acidic compounds from directly injected plasma ... [more ▼]

A new kind of silica-based restricted-access material (RAM) with anionic properties has been tested in pre-columns for on-line solid-phase extraction of acidic compounds from directly injected plasma samples prior to their determination by reversed-phase liquid chromatography (LC), using the column-switching technique. The outer surface of the porous RAM particles contains hydrophilic diol groups while diethylaminoethyl (DEAE) groups are bound to the internal surface which gives the sorbent the properties of a weak anion exchanger towards low-molecular-mass compounds. Due to an appropriate pore diameter (about 6 nm), macromolecules, such as proteins, are physically excluded from the pores and flushed directly out during the sample clean-up process, while small compounds have access to the inner surface and can be retained mainly by electrostatic interactions. The retention capability of this novel packing material has been tested for some hydrophilic acidic compounds such as aspartic acid, glutamic acid, ascorbic acid and acetylcysteine as well as for some more hydrophobic drugs such as naproxen, ibuprofen and diclofenac, used as model compounds. The influence of the composition of the washing liquid on the retention of the analytes in the pre-column has been investigated. The efficiency of the sorbent to clean-up complex matrices was also tested using human plasma and urine samples. A generic washing liquid composition was then selected in order to obtain efficient and selective sample clean-up as well as a high recovery of the acidic analytes. (C) 2003 Elsevier B.V. All rights reserved. [less ▲]

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