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Liquid chromatographic determination of the adenosine receptor agonist CGS 21680 in blood using on-line solid-phase extraction on a phenylboronic acid support and fluorescence detection.

An analytical method is described for the selective determination of A1 or A2 adenosine receptor agonists in blood. By implementing solid-phase extraction using immobilized-phenylboronic acid (PBA) in sample pretreatment, all adenosine derivatives are retained via their intact cis-diol group. On-line desorption of the analytes from the PBA support to the C18 analytical column is performed by injection of a small plug of perchloric acid. Fluorescence and UV detection are employed for the different adenosine derivatives. The method is applied to the determination of 2-[p-(2-carboxyethyl)phenylethylamino]-5'-N- ethylcarboxyamidoadenosine (CGS 21680, I) in blood using fluorescence detection. The only off-line sample handling step is the extraction of blood with ethyl acetate and subsequent evaporation of the extraction solvent. The detection limit of the method was 0.25 ng (signal-to-noise ratio 3:1) and the determination limit for I in blood (pretreatment of 100 microliters) was 5 ng/ml. The method was validated and used to study the pharmacokinetics of I in rats.

Acetates↗

Quantitative determination of Ecteinascidin 743 in human plasma by miniaturized high-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry.

A method was developed for the bio-analysis of Ecteinascidin 743 (ET-743) using miniaturized liquid chromatography (LC) coupled to an electrospray ionization sample inlet (TurbolonSpray) and two quadrupole mass analyzers (LC/ESI-MS/MS). Solid-phase extraction was used as a sample pretreatment procedure. Ecteinascidin 743 is a very potent anticancer compound and is administered in microgram m-2 dosages, which demands special requirements in terms of sensitivity for the analytical method supporting clinical pharmacokinetic studies. Using conventional LC/UV, a lower limit of quantitation (LLQ) of 1 ng ml-1 plasma was reached using a 500 microliters sample volume, but LC/ESI-MS/MS permitted an LLQ of 10 pg ml-1. The latter method was found to be accurate and precise, and provided a broad linear concentration range of 0.010-2.50 ng ml-1.

Antineoplastic Agents↗

Determination of organic additives in mortars by near-IR spectroscopy. A novel approach to designing a sample set with high-variability components.

Industrial mortars consist primarily of a mixture of cement and an aggregate plus a small amount of additives that are used to modify specific properties. Using too high or too low additive rates usually results in the loss of desirable properties in the end product. This entails carefully controlling the amounts of additives added to mortar in order to ensure correct dosing and/or adequate homogeneity in the final mixture. Near-IR (NIR) spectroscopy has proved effective for this purpose as it requires no sample pretreatment and affords expeditious analyses. The purpose of this work was to determine two organic additives (viz. Ad1 and Ad2) in mortars by using partial least squares regression multivariate calibration models constructed from NIR spectroscopic data. The additives are used to expedite setting and increase cohesion between particles in the mortar. In order to ensure that the sample set contained natural variability in the samples, we used a methodology based on experimental design to construct a representative set of samples. This novel design is based on a hexagonal antiprism that encompasses the concentration ranges spanned by the analytes and the variability inherent in each additive. The D-optimality criterion was used to obtain various combinations between Ad1 and Ad2 additive classes. The partial least squares calibration models thus constructed for each additive provided accurate predictions: the intercept and the slope of the plots of predicted values versus reference values for each additive were close to 0 and 1, respectively, and their confidence ranges included the respective value. The ensuing analytical methods were validated by using an external sample set.

Journal Article↗

A novel ELISA system for selective measurement of human adiponectin multimers by using proteases.

BACKGROUND: Adiponectin, an antiatherogenic adipocyte-derived protein exists in human blood as multiple isoforms--trimeric low molecular weight (LMW), albumin-binding LMW (Alb-LMW), hexameric middle molecular weight (MMW), and high molecular weight (HMW) forms. We developed a novel ELISA system to detect total human adiponectin and the selective level of each adiponectin multimer for investigating the distribution of these levels in human blood. METHODS: Two monoclonal antibodies that were raised against human adiponectin were used to construct a sandwich ELISA to measure adiponectin levels. Adiponectin multimers were selectively measured after sample pretreatment with two proteases that specifically digested the trimeric forms or both the hexameric and trimeric forms. RESULTS: The ELISA had a dynamic range of 0.075-4.8 ng/ml. Intraassay variations (CV) were 5.3% (total adiponectin), 4.1% (MMW+HMW), and 3.3% (HMW). Comparison of the results of ELISA and quantitative western blot analysis of multimeric adiponectin in serum samples revealed good correlation (LMW+Alb-LMW, r=0.873; MMW, r=0.907; HMW, r=0.950). Each of the three forms of adiponectin multimer levels closely correlated with total adiponectin levels in healthy subjects. CONCLUSIONS: This ELISA system can be used to further investigate the physiological roles of human adiponectin multimers.

Adiponectin↗

Direct and sensitive analysis of methamphetamine, ketamine, morphine and codeine in human urine by cation-selective exhaustive injection and sweeping micellar electrokinetic chromatography.

Cation-selective exhaustive injection and sweeping micellar electrokinetic chromatography (CSEI-Sweep-MEKC) was directly used to test some abuse drugs in human urine, including morphine (M), codeine (C), ketamine (K) and methamphetamine (MA). First, phosphate buffer (50 mM, pH 2.5) containing 30% methanol was filled into uncoated fused silica capillary (40 cm, 50 microm I.D.), then high conductivity buffer (100 mM phosphate, 6.9 kPa for 99.9 s) was followed. Electrokinetic injection (10 kV, 500 s) was used to load samples and to enhance sensitivity. The stacking step and separation were performed at -20 kV and 200 nm using phosphate buffer (25 mM, pH 2.5) containing 20% methanol and 100 mM sodium dodecyl sulfate. Using CSEI-Sweep-MEKC, the analytes could be simultaneously analyzed and have a detection limit down to ppb level. It was unnecessary to have sample pretreatments. During method validation, calibration plots were linear (r>or=0.9982) over a range of 150-3,000 ng/mL for M and C, 250-5,000 n g/mL for MA, and 50-1,000 ng/mL for K. The limits of detection were 15 ng/mL for M and C, and 5 ng/mL for MA and K (S/N=3, sampling 500 s at 10 kV). Comparing with capillary zone electrophoresis, the results indicated that this stacking method could increase 6,000-fold sensitivity for analysis of MA. Our method was applied for analysis of 28 real urine samples. The results showed good coincidence with immunoassay and GC-MS. This method was feasible for application to detect trace levels of abused drugs in forensic analysis.

Cations↗

Short-column liquid chromatography with hydride generation atomic fluorescence detection for the speciation of arsenic.

Increasing concerns over human exposure to arsenic and more stringent environmental regulations require rapid determination of trace levels of individual arsenic species, which presents an analytical challenge. We describe a method that is capable of speciating nanogram-per-milliliter levels of arsenite (As(III)), arsenate (As(V)), monomethylarsonic acid (MMAA), and dimethylarsinic acid (DMAA) within 3 min. Speciation of two common inorganic species in drinking water, As(III) and As(V), is complete in 1.5 min. The method is based on a combination of fast high-performance liquid chromatography (HPLC) separation of arsenic species on 3-cm HPLC guard columns and the sensitive detection of arsenic hydride by atomic fluorescence spectrometry. Detection limits for the four arsenic species in urine samples are 0.4-0.8 ng/mL. This simple method allows for the direct speciation of arsenic present in natural water samples and in human urine samples from the general population, with no need of any sample pretreatment. Our results from the determination of arsenic species in urine and water standard reference materials are in good agreement with the certified values of total arsenic concentration. The method has been successfully applied to speciation studies of metabolism of arsenosugars following the consumption of arsenosugar-containing mussels by human volunteers. Speciation of arsenic in urine samples collected from four volunteers after the ingestion of musseles reveals significant increases of DMAA concentration, resulting from the metabolism of arsenosugars. These results suggest that the commonly used biomarkers for assessing human exposure to inorganic arsenic, which are based on the determination of urinary arsenite, arsenate, MMAA, and DMAA, are not reliable when arsenosugar-containing seafood is ingested.

Adult↗

Microparticle-enhanced nephelometric immunoassay of alpha-lactalbumin in human milk.

A microparticle-enhanced nephelometric immunoassay was developed for alpha-lactalbumin quantitation in human milk. It is based on the nephelometric measurement of the light scattered during the competitive immunoagglutination of a microparticle-alpha-lactalbumin conjugate with an anti-alpha-lactalbumin antiserum. This immunoassay is sensitive (detection limit in reaction mixture, 1.5 micrograms/L) and could be performed in high dilution of milk, excluding any interference or sample pretreatment. It allowed the quantification of alpha-lactalbumin on a large range of concentrations (0.5-16.9 g/L) with accuracy (linear recovery in dilution-overloading assay) and precision (within- and between-run coefficients of variation from 1 to 7%). Changes in the alpha-lactalbumin concentration of human milk during lactation were determined in 162 samples. The concentration and ratio of alpha-lactalbumin total protein were found to be significantly lower in colostrum (4.9 g/l, 27%) than in transitional milk (5.2 g/L, 40%), then decreased in mature milk (3.4 g/L, 31%).

Binding, Competitive↗

Cleavage of zearalenone-glycoside, a "masked" mycotoxin, during digestion in swine.

Comparative analyses of cereal samples pretreated with or without beta-glucosidase indicate the presence of zearalenone-glycoside. To examine the stability of zearalenone-glycoside during digestion, mixed feed was artificially contaminated with synthesized zearalenone-4-beta-D-glucopyranoside (395 micrograms/kg) and fed to a pig over a period of 14 days. The metabolites detected in feces and urine samples were zearalenone and alpha-zearalenol. These results demonstrate that zearalenone-4-beta-D-glucopyranoside is decomposed during digestion and the aglucone, zearalenone, is released. Since zearalenone-glycoside is not detected during routine analysis, but hydrolysed during digestion, it seems likely that such "masked mycotoxins" are involved in cases of mycotoxicoses.

Animal Feed↗

Application of a generic fast gradient liquid chromatography tandem mass spectrometry method for the analysis of cytochrome P450 probe substrates.

A liquid chromatography tandem mass spectrometry (LC/MS/MS) method has been developed for the fast routine analysis of selected CYP450 probe substrate metabolites in microsomal incubations, with no sample pretreatment. This has allowed fast and simple assessment of the potential effects which drug candidates may or may not have on the metabolism of specific CYP450 probe substrates, providing information which can then be used to rationalize in vivo interaction studies required in the clinic. This methodology takes advantage of fast gradient chromatography as a generic means of sample separation and analysis. It provides high throughput analysis compared to conventional gradient HPLC, with no significant loss in chromatographic performance.

Chromatography, Liquid↗

Simultaneous quantitative determination of the HIV protease inhibitors amprenavir, indinavir, nelfinavir, ritonavir and saquinavir in human plasma by ion-pair high-performance liquid chromatography with ultraviolet detection.

A reversed-phase high-performance liquid chromatographic assay for the simultaneous quantitative determination of five HIV protease inhibitors (i.e. amprenavir, indinavir, nelfinavir, ritonavir, and saquinavir) in human plasma is described. Sample pretreatment consisted of solid-phase extraction prior to ion-pair, reversed-phase high-performance liquid chromatography with ultraviolet detection at 210 nm (amprenavir, indinavir and nelfinavir) and 239 nm (saquinavir and ritonavir). For amprenavir, indinavir and saquinavir the method has been validated over the range of 25 ng/ml to 25 microg/ml using a 0.6 ml sample volume. For nelfinavir and ritonavir the method has been validated over the range of 50 ng/ml to 25 microg/ml. The method proved to be accurate, with an average accuracy at four concentrations ranging from 90.6 to 109.2%, and precise, with the within-day and between-day precision ranging from 1.8 to 6.7%, and 0.7 to 7.6%, respectively. The protease inhibitors which can be quantified by using this assay proved to be stable under various conditions. This assay can readily be used in a hospital laboratory for the routine monitoring of plasma concentrations of these protease inhibitors.

Anti-HIV Agents↗

A universal HPLC method for the determination of phenolic acids in compound herbal medicines.

A universal method to separate and quantify 13 phenolic acids (gallic acid, chlorogenic acid, gentsic acid, vanillic acid, caffeic acid, syringic acid, sinapic acid, p-coumaric acid, ferulic acid, anisic acid, rosmarinic acid, salicylic acid, and cinnamic acid) in some compound herbal medicines was established by liquid chromatographic (HPLC). On an Agela XBP-C18 (5 microm, 4.6 mm x 150 mm) column, a multistep binary gradient elution program and a simplified sample pretreatment approach were used in the experiment. For all of the phenolic acids, detection limits ranged around 0.01 mg/L. Linear ranges of higher than 2 orders of magnitude were obtained with a correlation coefficient of 0.9991 to 1. Repeatability was 0.39-2.24% (relative standard deviation, RSD) for intraday, 1.17-3.96% (RSD) for interday, and 0.14-5.33% (RSD) for drug sample analysis. Recovery, tested by a standard addition method, ranged from 83.3% to 104.9% for various trace phenolic acids.

Acids, Carbocyclic↗

Simple spectrophotometric flow injection system with an in-valve minicolumn for enhancement during the determination of chromium(III) using EDTA.

A simple spectrophotometric flow injection (FI) procedure for the determination of Cr(III) using ethylenediaminetetraacetic acid (EDTA) was developed. An FI system with a column packed with Amberlite IR-120(H) was employed for sample pretreatment. This leads to the possibility of a single standard calibration. A linear calibration in a range of 10-27 microg Cr(III) was obtained with a detection limit of 1 microg Cr(III) and RSD of 2% (18 microg Cr(III), n=12). The proposed procedure was applied for determination of Cr(III) in leachate and dietary supplement samples. The results agreed with those obtained by the standard methods.

Chromium↗

Direct determination of endogenous melatonin in human saliva by column-switching semi-microcolumn liquid chromatography/mass spectrometry with on-line analyte enrichment.

An analytical method that enables direct and sensitive determination of endogenous melatonin (MLT) in human saliva was developed by means of column-switching semi-microcolumn liquid chromatography (i.d.: 1-2 mm)/mass spectrometry (LC/MS). The system allows direct injection analysis of a 400-microL aliquot of saliva with minimal sample pretreatment (internal standard (IS) addition and vortex mixing) and a relatively short run-time (10 min). The system consists of three columns to attain large volume injection and on-line analyte enrichment. A pre-column packed with a silica-based mixed-functional C8 (4.0 mm i.d. x 20 mm) was used for on-line sample cleanup. MLT and an IS, the d7 isomer of MLT (d7-MLT), were heart-cut by valve switching and enriched at the top of the intermediate trapping column packed with a silica-based C18 (4.0 mm i.d. x 10 mm). Subsequently, the analytes were backflushed into a semi-micro C18 silica column (2.0 mm i.d. x 150 mm) for the final separation. MLT and IS were ascertained by positive electrospray ionization and selected ion monitoring (SIM). MLT was monitored based on its fragment ion at m/z 174.1 by in-source collision-induced dissociation (CID). The validation of this method revealed a detection limit of 2.5 pg mL(-1) at a signal-to-noise (S/N) ratio of 5. The linearity of the method was established in the ranges 5-250 and 100-2500 pg mL(-1) with a coefficient of determination of greater than 0.998. Accuracies, evaluated at five levels in the range 5-1000 pg mL(-1), were between 81 and 108% with a relative standard deviation (RSD) ranging from 1.3-20%. The method was successfully applied for the endogenous saliva MLT monitoring of two healthy subjects.

Adult↗

Direct determination of the ethanol metabolites ethyl glucuronide and ethyl sulfate in urine by liquid chromatography/electrospray tandem mass spectrometry.

A liquid chromatography/electrospray tandem mass spectrometry (LC/ESI-MS/MS) method for the determination in urine samples of two ethanol metabolites, ethyl glucuronide (EtG) and ethyl sulfate (EtS), was developed and validated. Pentadeuterated EtG was used as internal standard for both EtG and EtS. In addition to the surviving ions, two MS/MS reactions were monitored for each analyte, with the deprotonated molecule as precursor ion: m/z 221 --> 75, m/z 221 --> 85 (EtG), and m/z 125 --> 97, m/z 125 --> 80 (EtS). Sample pretreatment, though very simple and rapid (1:50 water dilution and centrifugation of 50 muL of urine), was found to contain the occurrence of matrix effects. The method was accurate and precise over the linear dynamic range (0.05-10 mg/L). The analytes were stable in frozen urine for at least 1 month. The assay was applied to several authentic urine samples from social drinkers and to alcoholic beverages.

Alcoholic Beverages↗

A STORM-based protocol for nanoscale imaging and quantitative analysis of protein-associated and phospholipid-associated structures in natural rubber.

Stochastic Optical Reconstruction Microscopy (STORM) enables nanoscale mapping of molecular components beyond the diffraction limit; however, its reproducible implementation in hydrophobic polymer matrices remains challenging because fluorescence-labeling specificity, fluorophore photoswitching, three-dimensional localization, chromatic registration, and quantitative image analysis must be carefully controlled. This protocol presents a standardized experimental workflow for dual-color labeling, astigmatism-based three-dimensional STORM acquisition, and quantitative analysis of protein-associated and phospholipid-associated structures in natural rubber (NR). The workflow covers sample pretreatment, Cy5 NHS ester labeling of protein-associated primary amines, DiI labeling of phospholipid-rich domains, STORM imaging-buffer preparation, three-dimensional single-molecule localization, dual-channel registration, generation of standardized xy projections, aggregate-size analysis, and projected lateral spatial correlation assessment. Reproducibility is supported by defined acquisition and localization criteria, three independent sample preparations with at least five fields of view analyzed per condition, and unlabeled, single-color, dye-only matrix, and processing-associated Cy5 controls. Mean lateral localization precisions of 11.8 ± 2.3 nm for Cy5 and 13.5 ± 2.9 nm for DiI were obtained, while two-dimensional Fourier ring correlation analysis of the xy projections yielded effective lateral image resolutions of approximately 25 and 28 nm, respectively. Image-based particle segmentation and localization-coordinate-based density-based spatial clustering of applications with noise (DBSCAN) were applied to standardized xy projections as complementary quantitative approaches. Application of the protocol to untreated, centrifuged, and protease-treated NR samples demonstrated treatment-associated changes in the detected abundance and projected size distributions of protein- and phospholipid-associated aggregates, together with a non-monotonic change in their projected lateral spatial correlation. These observations describe alterations in nanoscale organization but do not, by themselves, establish stable protein-phospholipid complex formation. Unlike previous studies that primarily demonstrated the feasibility of STORM imaging in rubber materials, the principal contribution of this work is an end-to-end, step-by-step protocol incorporating defined controls, three-dimensional localization, image-quality metrics, chromatic-registration procedures, and complementary quantitative-analysis pipelines for non-expert users. The workflow may be adaptable to other hydrophobic polymers and soft-material systems after appropriate optimization and validation.

Rubber↗

A phase I study of hydralazine to demethylate and reactivate the expression of tumor suppressor genes.

BACKGROUND: The antihypertensive compound hydralazine is a known demethylating agent. This phase I study evaluated the tolerability and its effects upon DNA methylation and gene reactivation in patients with untreated cervical cancer. METHODS: Hydralazine was administered to cohorts of 4 patients at the following dose levels: I) 50 mg/day, II) 75 mg/day, III) 100 mg/day and IV) 150 mg/day. Tumor biopsies and peripheral blood samples were taken the day before and after treatment. The genes APC, MGMT; ER, GSTP1, DAPK, RARbeta, FHIT and p16 were evaluated pre and post-treatment for DNA promoter methylation and gene expression by MSP (Methylation-Specific PCR) and RT-PCR respectively in each of the tumor samples. Methylation of the imprinted H19 gene and the "normally methylated" sequence clone 1.2 was also analyzed. Global DNA methylation was analyzed by capillary electrophoresis and cytosine extension assay. Toxicity was evaluated using the NCI Common Toxicity Criteria. RESULTS: Hydralazine was well tolerated. Toxicities were mild being the most common nausea, dizziness, fatigue, headache and palpitations. Overall, 70% of the pretreatment samples and all the patients had at least one methylated gene. Rates of demethylation at the different dose levels were as follows: 50 mg/day, 40%; 75 mg/day, 52%, 100 mg/day, 43%, and 150 mg/day, 32%. Gene expression analysis showed only 12 informative cases, of these 9 (75%) re-expressed the gene. There was neither change in the methylation status of H19 and clone 1.2 nor changes in global DNA methylation. CONCLUSION: Hydralazine at doses between 50 and 150 mg/day is well tolerated and effective to demethylate and reactivate the expression of tumor suppressor genes without affecting global DNA methylation.

5-Methylcytosine↗

Quantitative liquid chromatographic-tandem mass spectrometric determination of reserpine in FVB/N mouse plasma using a "chelating" agent (disodium EDTA) for releasing protein-bound analytes during 96-well liquid-liquid extraction.

A sensitive, specific, accurate and reproducible analytical method employing a divalent cation chelating agent (disodium EDTA) for sample treatment was developed to quantitate reserpine in FVB/N mouse plasma. Samples pretreated with 40 microl of 2% disodium EDTA in water were extracted by a semi-automated 96-well liquid-liquid extraction (LLE) procedure to isolate reserpine and a structural analog internal standard (I.S.), rescinnamine, from mouse plasma. The extracts were analyzed by turbo ionspray liquid chromatography-tandem mass spectrometry (LC-MS-MS) in the positive ion mode. Sample preparation time for conventional LLE was dramatically reduced by the semi-automated 96-well LLE approach. The assay demonstrated a lower limit of quantitation of 0.02 ng/ml using 0.1-ml plasma sample aliquots. The calibration curves were linear from 0.02 to 10 ng/ml for reserpine. The intra- and inter-assay precision of quality control (QC) samples ranged from 1.75 to 10.9% for reserpine. The intra- and inter-assay accuracy of QC samples ranged from -8.17 to 8.61%. Reserpine and the I.S. were found to be highly bound to FVB/N mouse plasma protein. This is the first report of disodium EDTA employed as a special protein-bound release agent to recover protein-bound analytes from plasma. These matrix effects and the effects of pH in the HPLC mobile phase on the sensitivities of LC-MS-MS are discussed in this paper.

Animals↗

An automated preconcentration-derivatization system for the determination of cocaine and its metabolites in urine and illicit cocaine samples by gas chromatography/mass spectrometry.

Although gas chromatography/mass spectrometry (GC/MS) is the most powerful technique for analysing cocaine and its hydrolysis products (benzoylecgonine, ecgonine methyl ester and ecgonine) in urine, the sample pretreatment required is rather laborious and involves a large number of steps. This paper reports a continuous method for the separation (based on the retention properties of cocaine and its major metabolites on a reversed phase C18 column), preconcentration (evaporation under nitrogen) and derivatization (collection of the residue in a few microlitres of derivatizing reagent) of cocaine and its metabolites in urine samples for subsequent analysis by GC/MS. Calibration graphs are linear from 5 to 3000 ng/mL; the detection limits are 1 ng/mL (cocaine and ecgonine methyl ester), 20 ng/mL (benzoylecgonine) and 200 ng/mL (ecgonine). The method was applied to illicit cocaine samples and to urine from a drug addict.

Autoanalysis↗