Perspective on Advancing FDA Regulatory Monitoring for Mycotoxins in Foods using Liquid Chromatography and Mass Spectrometry (Review).

The presence of mycotoxins (such as aflatoxins, deoxynivalenol, fumonisins, and patulin) is routinely monitored by the U.S. Food and Drug Administration (FDA) to ensure that their concentrations in food are below the levels requiring regulatory action or advisories.

Simultaneous determination of cosmetics ingredients in nail products by fast gas chromatography with tandem mass spectrometry.

A rapid and sensitive gas chromatography with tandem mass spectrometry (GC-MS/MS) method has been developed and validated to quantitatively determine cosmetic ingredients, such as toluene, N-methylpyrrolidone, 2,4-dihydroxybenzophenone (benzophenone-1, BP-1), and diethylene glycol dimethacrylate, in nail products. In this procedure, test portions were extracted with acetone, followed by vortexing, sonication, centrifugation, and filtration. During the extraction procedure, BP-1 was derivatized making it amenable to GC-MS analysis, using N,O-​bis(trimethylsilyl)​trifluoroacetamide.

Determination of methylisothiazolinone and methylchloroisothiazolinone in cosmetic products by ultra high performance liquid chromatography with tandem mass spectrometry.

Isothiazolinone biocides are broad-spectrum preservatives that are widely used in cosmetics, household, and industrial products. An increase in the number of cases of allergic contact dermatitis to isothiazolinone preservatives, namely, methylisothiazolinone and methylchloroisothiazolinone, have been recently noticed. The Food and Drug Administration relies on analytical methods to quantify levels of use of cosmetic ingredients and support enforcement action against products that are not in compliance with the law.

Effect of sample dilution on matrix effects in pesticide analysis of several matrices by liquid chromatography-high-resolution mass spectrometry.

This study used two LC columns of different adsorbents and liquid chromatography-electrospray ionization-high-resolution mass spectrometry to study the relationship between matrix effects (ME), the LC separations, and elution patterns of pesticides and those of matrix components. Using calibration standards of 381 pesticides at three dilution levels of 1×, 1/10×, and 1/100×, 108 samples were prepared in solvent and five different sample matrices for the study. Results obtained from principal component analysis and slope ratios of calibration curves provided measurements of the ME and showed the 1/100× sample dilution could minimize suppression ME for most pesticides analyzed.

Sesquiterpenoid tropolone glycosides from Liriosma ovata.

Two new sesquiterpenoid tropolone glycosides, liriosmasides A (1) and B (2), along with two known compounds, secoxyloganin and oplopanpheside C, were isolated from a methanol extract of the roots of Liriosma ovata. The structures of 1 and 2 were elucidated by spectroscopic methods including 1D and 2D NMR and by high-resolution mass spectrometry involving an ultra-high-performance liquid chromatography-quadrupole-orbital ion trap mass spectrometric (UHPLC-Q-Orbitrap MS) method. Compound 1 showed weak inhibitory activity against HIV RNase H.

Mass spectrometric analysis of pharmaceutical adulterants in products labeled as botanical dietary supplements or herbal remedies: a review.

The increased availability and use of botanical dietary supplements and herbal remedies among consumers has been accompanied by an increased frequency of adulteration of these products with synthetic pharmaceuticals. Unscrupulous producers may add drugs and analogues of various classes, such as phosphodiesterase type 5 (PDE-5) inhibitors, weight loss, hypoglycemic, antihypertensive and anti-inflammatory agents, or anabolic steroids, to develop or intensify biological effects of dietary supplements or herbal remedies. The presence of such adulterated products in the marketplace is a worldwide problem and their consumption poses health risks to consumers.

Determining mycotoxins in baby foods and animal feeds using stable isotope dilution and liquid chromatography tandem mass spectrometry.

We developed a stable isotope dilution assay with liquid chromatography tandem mass spectrometry (LC-MS/MS) to determine multiple mycotoxins in baby foods and animal feeds. Samples were fortified with [(13)C]-uniformly labeled mycotoxins as internal standards ([(13)C]-IS) and prepared by solvent extraction (50% acetonitrile in water) and filtration, followed by LC-MS/MS analysis. Mycotoxins in each sample were quantitated with the corresponding [(13)C]-IS.

Determination of prostaglandin analogs in cosmetic products by high performance liquid chromatography with tandem mass spectrometry.

A method was developed and validated for the determination of 16 prostaglandin analogs in cosmetic products. The QuEChERS (Quick, Easy, Cheap, Efficient, Rugged, Safe) liquid-liquid extraction method, typically used for pesticide residue analysis, was utilized as the sample preparation technique. The prostaglandin analogs were chromatographically separated and quantified using high performance liquid chromatography with tandem mass spectrometry (HPLC-MS/MS).

Quantification of aristolochic acids I and II in herbal dietary supplements by ultra-high-performance liquid chromatography-multistage fragmentation mass spectrometry.

A rapid, selective and sensitive ultra-high-performance liquid chromatography-multistage fragmentation mass spectrometry (UHPLC-MS³) method was developed and evaluated for the determination of aristolochic acids I and II (AA I and II) in herbal dietary supplements. A hybrid triple quadrupole/linear ion-trap mass spectrometry was used to monitor MS³ ion transitions m/z 359.2 > 298.

Targeted analysis of multiple pharmaceuticals, plant toxins and other secondary metabolites in herbal dietary supplements by ultra-high performance liquid chromatography-quadrupole-orbital ion trap mass spectrometry.

In this study, an ultra-high performance liquid chromatography-quadrupole-orbital ion trap mass spectrometry (UHPLC-Q-orbitrap MS) method was developed and validated for simultaneous determination of 96 pharmaceuticals, plant toxins, and other plant secondary metabolites in herbal dietary supplements. Target analytes were extracted from samples using the QuEChERS (quick easy cheap effective rugged safe) procedure. The instrument was operated in full MS-data dependent tandem mass spectrometry (full MS-dd-MS/MS) acquisition mode which enabled collection of quantitative high resolution (HR) full mass spectral data and confirmatory HR MS/MS data in a single run.

Determination of multiple mycotoxins in dietary supplements containing green coffee bean extracts using ultrahigh-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS).

An ultrahigh-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method for the determination of 34 mycotoxins in dietary supplements containing green coffee bean (GCB) extracts was developed, evaluated, and used in the analysis of 50 commercial products. A QuEChERS-like procedure was used for isolation of target analytes from the examined matrices. Average recoveries of the analytes were in the range of 75-110%.

Quantitative determination of cucurbitane-type triterpenes and triterpene glycosides in dietary supplements containing bitter melon (Momordica charantia) by HPLC-MS/MS.

Momordica charantia L. (Cucurbitaceae), commonly known as bitter melon, is widely cultivated in many tropical and subtropical areas of the world. It is a common food staple; its fruits, leaves, seeds, stems, and roots also have a long history of use in traditional medicine.

Simultaneous analysis of steviol and steviol glycosides by liquid chromatography with ultraviolet detection on a mixed-mode column: application to Stevia plant material and Stevia-containing dietary supplements.

Simultaneous separation of steviol and steviol glycosides is challenging because of differences in their polarity and chemical structure. In this study, simultaneous analysis of steviol and steviol glycosides was achieved by LC with UV detection using a mixed-mode RP weak anion exchange chromatography column. Steviol and seven steviol glycosides were analyzed on an Acclaim Mixed-Mode Wax-1 (Dionex) column with a linear gradient of deionized water adjusted to pH 3.

Sweeteners from plants--with emphasis on Stevia rebaudiana (Bertoni) and Siraitia grosvenorii (Swingle).

In addition to their widely recognized use as dietary supplement ingredients, plant-derived compounds are increasingly used as natural sweeteners. The search for nonnutritive sweeteners has been stimulated over the last 20-30 years by concern over demonstrated or suspected relationships between consumption of sucrose and high-fructose corn syrups and a variety of health-related conditions. In the USA, there is increased use of plant extracts known to contain highly sweet terpenoids.

Updates on chemical and biological research on botanical ingredients in dietary supplements.

Increased use of dietary supplements is a phenomenon observed worldwide. In the USA, more than 40% of the population recently reported using complementary and alternative medicines, including botanical dietary supplements. Perceptions that such dietary supplements are natural and safe, may prevent disease, may replace prescription medicines, or may make up for a poor diet, play important roles in their increased use.

Comparison of metabolism-mediated effects of pyrrolizidine alkaloids in a HepG2/C3A cell-S9 co-incubation system and quantification of their glutathione conjugates.

1. Toxicity of pyrrolizidine alkaloids (PAs) largely depends on their metabolic activation by hepatic enzymes, including cytochrome P450s, to become chemically reactive pyrrolic derivatives. These then spontaneously release the esterifying acids to generate carbonium ions that form covalent adducts with cellular nucleophiles to exhibit toxicity.

Rapid and simultaneous determination of hexapeptides (Ac-EEMQRR-amide and H2N-EEMQRR-amide) in anti-wrinkle cosmetics by hydrophilic interaction liquid chromatography-solid phase extraction preparation and hydrophilic interaction liquid chromatography with tandem mass spectrometry.

A rapid method for the simultaneous determination of Ac-EEMQRR-amide and H(2)N-EEMQRR-amide in cosmetic products was developed and evaluated. This analytical procedure involved extracting samples with 0.1:0.

Multiresidue pesticide analysis of agricultural commodities using acetonitrile salt-out extraction, dispersive solid-phase sample clean-up, and high-performance liquid chromatography-tandem mass spectrometry.

A multiresidue method analyzing 209 pesticides in 24 agricultural commodities has been developed and validated using the original Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) procedure and high performance liquid chromatography-positive electrospray ionization-tandem mass spectrometry (LC-MS/MS) analysis. Using solvent-only calibration standards (SOCSs) and matrix-matched calibration standards (MMCSs), it was demonstrated that a minimal concentration of 5-10 μg/kg (part per billion, ppb) of analytes in matrix is required for the consistent identification of targeted pesticides with two MRM transitions. Method performance was validated by the precision and accuracy results obtained from fortification studies at 10, 25, 100, and 500 ppb and MMCSs.

Rapid determination of para-phenylenediamine by gas chromatography-mass spectrometry with selected ion monitoring in henna-containing cosmetic products.

A rapid method for the determination of para-phenylenediamine (PPD) in cosmetic products, such as henna tattoos has been developed and evaluated. This analytical procedure involved extracting a 10mg test portion of cosmetic product in 10 mL of ethyl acetate, followed by determination by gas chromatography-mass spectrometry in the selected ion monitoring mode (GC/MS-SIM). 1,4-Phenylenediamine-2,3,5,6-d(4) was selected as an internal standard that was added at the beginning of the extraction procedure and used to correct for recovery and matrix effects.

Emerging pesticide residue issues and analytical approaches.

The 46th Annual Florida Pesticide Residue Workshop of 2009 (FPRW 2009) held in St. Pete Beach, FL, is the latest in an annual tradition drawing scientists from U.S.

Cucurbitane-type triterpenoids from Momordica charantia.

One new cucurbitane-type triterpenoid glycoside, momordicoside U (1), together with five known cucurbitane-type triterpenoids and related glycosides, 3β,7 β,25-trihydroxycucurbita-5,23 (E)-dien-19-al (2), momordicine I (3), momordicine II (4), 3-hydroxycucurbita-5,24-dien-19-al-7,23-di-O-β-glucopyranoside (5), and kuguaglycoside G (6), were isolated from the whole plant of Momordica charantia. Their structures were determined by chemical and spectroscopic methods. Momordicoside U (1) was evaluated for insulin secretion activity in an in vitro insulin secretion assay and displayed moderate activity.

Multiresidue pesticide analysis of ginseng powders using acetonitrile- or acetone-based extraction, solid-phase extraction cleanup, and gas chromatography-mass spectrometry/selective ion monitoring (GC-MS/SIM) or -tandem mass spectrometry (GC-MS/MS).

A multiresidue method for the analysis of 168 pesticides in dried powdered ginseng has been developed using acetonitrile or acetone mixture (acetone/cyclohexane/ethyl acetate, 2:1:1 v/v/v) extraction, solid-phase extraction (SPE) cleanup with octyl-bonded silica (C(8)), graphitized carbon black/primary-secondary amine (GCB/PSA) sorbents and toluene, and capillary gas chromatography-mass spectrometry/selective ion monitoring (GC-MS/SIM) or -tandem mass spectrometry (GC-MS/MS). The geometric mean limits of quantitation (LOQs) were 53 and 6 microg/kg for the acetonitrile extraction and 48 and 7 microg/kg for the acetone-based extraction for GC-MS/SIM and GC-MS/MS, respectively. Mean percent recoveries and standard deviations from the ginseng fortified at 25, 100, and 500 microg/kg using GC-MS/SIM were 87 +/- 10, 88 +/- 8, and 86 +/- 10% from acetonitrile extracts and 88 +/- 13, 88 +/- 12, and 88 +/- 14% from acetone mixture extracts, respectively.

Multiresidue pesticide analysis in fresh produce by capillary gas chromatography-mass spectrometry/selective ion monitoring (GC-MS/SIM) and -tandem mass spectrometry (GC-MS/MS).

A multiresidue method for the analysis of pesticides in fresh produce has been developed using salt-out acetonitrile extraction, solid-phase dispersive cleanup with octadecyl-bonded silica (C(18)), and graphitized carbon black/primary-secondary amine (GCB/PSA) sorbents and toluene, followed by capillary gas chromatography-mass spectrometry in selected ion monitoring mode (GC-MS/SIM) or -tandem mass spectrometry (GC-MS/MS). Quantitation was determined from calibration curves using matrix-matched standards ranging from 3.3 to 6667 ng/mL with r(2) > 0.

Chiral stationary phases for separation of intermedine and lycopsamine enantiomers from Symphytum uplandicum.

Enantioseparation of the pyrrolizidine alkaloid isomers intermedine and lycopsamine, isolated from Symphytum uplandicum, is discussed. The separatory power of two immobilized carbohydrate-based chiral HPLC columns, Chiralpak IA and IC, in different chromatographic conditions is compared. The study demonstrated the importance of solvent and column selection while developing such chiral HPLC separation methods.

Multiresidue pesticide analysis of wines by dispersive solid-phase extraction and ultrahigh-performance liquid chromatography-tandem mass spectrometry.

A multiresidue pesticide method is described for the determination of 72 pesticides in wines. Pesticides were extracted using acetonitrile saturated with magnesium sulfate and sodium chloride, followed by solid-phase dispersive cleanup using primary-secondary amine and graphitized carbon black sorbents. Analysis is performed by ultraperformance liquid chromatography-electrospray ionization-tandem mass spectrometry (UPLC-MS/MS).