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Past analyses of sugar and amino acid composition of aphid honeydews have been completed using diverse instrumentation. Here we report the use of hydrophilic interaction liquid chromatography (HILIC) coupled with a triple quadrupole mass spectrometric (MS/MS) detector for the analysis of seven saccharides (xylose, fructose, glucose, sucrose, trehalose, melezitose and raffinose) and five amino acids (glutamic acid, glutamine, aspartic acid, serine, and asparagine). Limits of quantitation ranged from 0.05 mg/L (melezitose) to 1.0 mg/L (fructose) for sugars and from 0.10 mg/L (glutamic acid) to 3.66 mg/L (asparagine) for amino acids. Sample preparation was fast and simple, requiring only the washing of foils used to collect aphid honeydew with hot (80 °C) water and sonication of samples prior to HILIC/MS/MS analysis for both classes of analytes. No analyte derivatization was required and excellent chromatographic characteristics were observed. For those studying honeydew-mediated interactions in the field, this technique allows for rapid characterization of ecologically important amino acids and sugars.•Composition of seven saccharides in Aphis asclepiadis honeydew including xylose, fructose, glucose, sucrose, trehalose, melezitose,and raffinose, and five standard amino acids including glutamic acid, glutamine, aspartic acid, serine, and asparagine, were analyzed using hydrophilic interaction liquid chromatography-mass spectrometry.•All polar analytes were analyzed without derivatization using HILIC-MS with chromatographic run times of 7 min (sugars) and 10 min (amino acids)., Graphical abstract Image, graphical abstract

Ligusticum porteri (osha) is an important wild-harvested medicinal plant. Populations of this plant occur in meadows and forest understories in the subalpine and montane zones of the Rocky Mountains. We examined variation in the bioactive compounds of 44 methanolic extracts of L. porteri roots harvested from eleven populations in Colorado, USA during 2012 and 2015. Populations were found in two distinct regions of Colorado, the Front Range and Western Slope. We also classified population light environment as either meadow or understory based on the mean percent of full-sun photosynthetically active radiation above plants. We used high performance liquid chromatography (HPLC) to quantify variation in five secondary metabolites: Z-ligustilide, trans-ferulic acid, (Z/E)-3-butylidenephthalide, isovanillin and elemicin. Variation between sampling years was found for trans-ferulic acid, elemicin and (E)-3-butylidenephthalide. Root extracts from the Front Range had more than double the mean relative concentrations of (Z)-ligustilide than root extracts from plants on the Western Slope of Colorado. Our results demonstrate distinct chemotypes in L. porteri, and this could have therapeutic effects because (Z)-ligustilide is the major bioactive compound in this species.

Analysis of whiskey samples prepared by a green microextraction technique, dispersive liquid–liquid microextraction (DLLME), before analysis by a qualitative gas chromatography–mass spectrometry (GC/MS) method, is described as a laboratory experiment for an upper division instrumental methods of analysis laboratory course. Here, aroma compounds in whiskey samples (n = 11) were extracted using ultrasound-assisted DLLME with chloroform (as extraction solvent). The chloroform extract was analyzed by GC/MS with data manipulation by AMDIS (automated mass spectral deconvolution and identification system) to allow for comparisons between whiskey samples. Aroma compounds commonly reported in the literature (furfural, isoamyl acetate, 5-methyl furfural, ethyl esters, phenylethyl alcohol, whiskeylactone, and vanillin) were tentatively identified based upon the match to the MS library. This unique laboratory allows students to engage in a real-world analysis of a high-value product and to explore the use of AMDIS to...

The objective of this study was to assess the antibacterial activity and inhibition of biofilm formation of silver nanoparticles (AgNPs) against Escherichia coli (MG1655), Bacillus subtilis, Klebsiella pneumoniae, Pseudomonas aeruginosa, Staphylococcus aureus, and Janthinobacterium lividum. The AgNPs utilized in this study were prepared through one-pot microwave-assisted syntheses guided by principles of green chemistry. The AgNPs were synthesized in three different schemes by reducing Ag+ ions (from AgNO3) with reducing agents dextrose, arabinose, and soluble starch. Formation of AgNPs occurred in less than 15 min, and nanoparticles had diameters of 30 nm or less. Successful synthesis of AgNPs was confirmed using multiple orthogonal approaches, including UV–visible spectroscopy, fluorescence emission spectroscopy, powder X-ray diffraction, and transmission electron microscopy, while size analysis was gathered from transmission electron microscopy images and dynamic light scattering. All AgNPs prepared in...

An accurate method for measuring whole blood total folate using liquid chromatography with tandem mass spectrometry is described and compared to GC/MS and a chemiluminescence assay. Whole blood from normal adults (n = 15) was fortified with a [(13)C(6)]para-aminobenzoic acid (pABA) internal standard and treated with 12.1 N hydrochloric acid at 110 degrees C for 4 h to hydrolyze all folates to pABA. Contaminants in the hydrolysate were adsorbed onto a C18 SPE cartridge. The eluate containing the folate catabolite pABA was partitioned into ethyl acetate and methylesterified with trimethylsilyldiazomethane. The methyl-pABA derivatives were quantified by positive-ion atmospheric pressure chemical ionization (APCI)LC-MS/MS. An isocratic mobile phase of acetonitrile-water (70:30) (v/v) on a C18 analytical column was used with a postcolumn reagent of 0.025% formic acid. The limit of quantitation for folate was 56.6 nmol/L RBC, and the limit of detection was 22.6 nmol/L RBC. Folate levels as determined by LC-MS/MS correlated well with the chemiluminescence assay and a GC/MS method. This new LC-MS/MS method provides enhanced sample throughput (n = 36 per day) as compared to GC/MS methods. LC-MS/MS will enable accurate measurements of red blood cell (RBC) folate in nutrition surveys and clinical trials.

The development of an alternative dispersive liquid–liquid microextraction protocol utilizing a low-density extraction solvent, toluene, is described here for the extraction of the brominated flame retardant, tetrabromobisphenol-A, from dust prior to selected ion monitoring analysis by gas chromatography with mass spectrometry. Method parameters of dispersive solvent type and extraction solvent type were optimized. Excellent recovery (88.9%; n = 5 spike replicates) with good precision was achieved in a spike and recovery study. This developed method was utilized to survey tetrabromobisphenol-A concentrations in dust sampled from a local electronics recycling facility from the ambient environment and 20 computer towers undergoing recycling. Concentrations of tetrabromobisphenol-A from dust in computer towers ranged from not detected (n = 2) up to 64 μg/g with a mean value of 11 μg/g and median of 4.1 μg/g tetrabromobisphenol-A. A composite sample of dust collected from the ambient indoor environment was analyzed with a resulting concentration of 36 μg/g. This is the first application of this novel green method for pre-concentrating flame retardants from dust and the first report of tetrabromobisphenol-A concentrations at a U.S.-based electronics recycling facility.

Background In a marker-trait association study we estimated the statistical significance of 65 single nucleotide polymorphisms (SNP) in 23 candidate genes on HDL levels of two independent Caucasian populations. Each population consisted of men and women and their HDL levels were adjusted for gender and body weight. We used a linear regression model. Selected genes corresponded to folate metabolism, vitamins B-12, A, and E, and cholesterol pathways or lipid metabolism. Methods Extracted DNA from both the Sacramento and Beltsville populations was analyzed using an allele discrimination assay with a MALDI-TOF mass spectrometry platform. The adjusted phenotype, y, was HDL levels adjusted for gender and body weight only statistical analyses were performed using the genotype association and regression modules from the SNP Variation Suite v7. Results Statistically significant SNP (where P values were adjusted for false discovery rate) included: CETP (rs7499892 and rs5882); SLC46A1 (rs37514694; rs739439); SLC19A1 (rs3788199); CD36 (rs3211956); BCMO1 (rs6564851), APOA5 (rs662799), and ABCA1 (rs4149267). Many prior association trends of the SNP with HDL were replicated in our cross-validation study. Significantly, the association of SNP in folate transporters (SLC46A1 rs37514694 and rs739439; SLC19A1 rs3788199) with HDL was identified in our study. Conclusions Given recent literature on the role of niacin in the biogenesis of HDL, focus on status and metabolism of B-vitamins and metabolites of eccentric cleavage of β-carotene with lipid metabolism is exciting for future study.

Tetrabromobisphenol-A (TBBPA) is a brominated flame retardant used worldwide. Despite its widespread use, there are few data concerning environmental concentrations of TBBPA. Thus, the objective of this work was to optimize an ultrasound-assisted dispersed liquid-liquid microextraction (DLLME) method to analyze swabbed surfaces of consumer electronics to determine TBBPA concentrations. Upon sample preparation with DLLME, TBBPA was derivatized with acetic anhydride and then analyzed by gas chromatography–mass spectrometry (GC/MS). Using a 13C12-TBBPA internal standard to improve precision and quantitation, a recovery study was performed. At concentrations of 250–1000 ng/mL, recoveries were 104–106%. Sample preparation with solid phase extraction had comparable recoveries, although overall, improved analyte recovery and precision were achieved with DLLME. In a small survey study, TBBPA concentrations in dust collected from 100 cm2 areas on electronic surfaces (monitor, microwave, refrigerator, and TV) were determined to range from less than the LOQ to 523 ng/mL.

Using linear regression models, we studied the main and 2-way interaction effects of the predictor variables gender, age, BMI, and 64 folate/vitamin B-12/homocysteine (Hcy)/lipid/cholesterol-related single nucleotide polymorphisms (SNP) on log-transformed plasma Hcy normalized by RBC folate measurements (nHcy) in 373 healthy Caucasian adults (50% women). Variable selection was conducted by stepwise Akaike information criterion or least angle regression and both methods led to the same final model. Significant predictors (where P values were adjusted for false discovery rate) included type of blood sample [whole blood (WB) vs. plasma-depleted WB; P < 0.001] used for folate analysis, gender (P < 0.001), and SNP in genes SPTLC1 (rs11790991; P = 0.040), CRBP2 (rs2118981; P < 0.001), BHMT (rs3733890; P = 0.019), and CETP (rs5882; P = 0.017). Significant 2-way interaction effects included gender × MTHFR (rs1801131; P = 0.012), gender × CRBP2 (rs2118981; P = 0.011), and gender × SCARB1 (rs83882; P = 0.003). The relation of nHcy concentrations with the significant SNP (SPTLC1, BHMT, CETP, CRBP2, MTHFR, and SCARB1) is of interest, especially because we surveyed the main and interaction effects in healthy adults, but it is an important area for future study. As discussed, understanding Hcy and genetic regulation is important, because Hcy may be related to inflammation, obesity, cardiovascular disease, and diabetes mellitus. We conclude that gender and SNP significantly affect nHcy.

Though chemical warfare agents (CWAs) have been banned by the Chemical Weapons Convention, the threat that such chemicals may be used, including their deliberate addition to food, remains. In such matrixes, CWAs may hydrolyze to phosphonic acids, which are good surrogate markers of CWA contamination. The method described here details the extraction of five CWA degradation products, including methylphosphonic acid (MPA), ethyl-MPA, isopropyl-MPA, cyclohexyl-MPA, and pinacolyl-MPA, from five different beverages by strata-X solid phase extraction cartridges. Samples were analyzed by liquid chromatography tandem mass spectrometry (LC/MS/MS) with multiple reaction monitoring. The limit of quantitation ranged from 0.05 to 0.5 ng on-column, and the limit of detection was >0.02 ng on-column. Beverages were fortified with the five phosphonic acids at 1 microg/mL and 0.25 microg/mL and quantitated using both an internally standardized method and matrix-matched standards. Reasonable recoveries (>50%) were achieved for ethyl, isopropyl, cyclohexyl, and pinacolyl-MPA for most matrixes.

Tetramethylenedisulfotetramine, commonly known as tetramine, is a highly neurotoxic rodenticide (human oral LD(50) = 0.1 mg/kg) used in hundreds of deliberate and accidental food poisoning events in China. This paper describes a method for the quantitation of tetramine spiked into beverages, including milk, juice, tea, cola, and water, with cleanup by C8 solid phase extraction and liquid-liquid extraction. Quantitation by high-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS) was based upon fragmentation of m/z 347 to m/z 268. The method was validated by gas chromatography-mass spectrometry (GC-MS) operated in selected ion monitoring mode for ions m/z 212, 240, and 360. The limit of quantitation was 0.10 μg/mL by LC-MS/MS versus 0.15 μg/mL for GC-MS. Fortifications of the beverages at 2.5 and 0.25 μg/mL were recovered ranging from 73 to 128% by liquid-liquid extraction for GC-MS analysis, from 13 to 96% by SPE, and from 10 to 101% by liquid-liquid extraction for LC-MS/MS analysis.

Abrine is an alkaloid chemical marker and surrogate analyte of abrin, a group of highly toxic glycoproteins. These toxins can be easily isolated from the seed of the rosary pea plant and distributed in a variety of matrices, including food. A procedure for the cleanup of abrine from various beverages, including milk, cola, juice drink, tea, and water, by C18 Strata-X solid-phase extraction (SPE) cartridges is described with comparison to a previously developed liquid-liquid extraction protocol utilizing acetonitrile and water. Analysis was by liquid chromatography/tandem mass spectrometry. Abrine quantitation was based on fragmentation of m/z 219.2 to product ion m/z 188.2. The method detection limit was 0.025 microg/mL, and the quantitation limit was 0.05 microg/mL. Fortifications of the five beverages at 0.5 and 0.05 microg/mL were recovered ranging from 88 to 111% [relative standard deviation (RSD) < 16%] by SPE and from 48 to 101% (RSD < 19%) by liquid-liquid extraction.

A high-throughput liquid chromatography tandem mass spectrometry (HT LC-MS/MS) method for red blood cell (RBC) folate analysis was developed from a previously described manual (M) LC-MS/MS method. The HT LC-MS/MS method used 96-well plates in which RBC folates were hydrolyzed with concentrated HCl in the presence of the [13C6]pABA internal standard (IS). The pH of the hydrolysate was adjusted to 5.0 before cleanup using 96-well plate OASIS HLB SPE cartridges. The analyte and IS were eluted with ethyl acetate/hexane (95:5, v/v) and methylated with methanol and trimethylsilyldiazomethane. The methylated analyte and IS were quantified with LC-MS/MS as previously described. The HT LC-MS/MS method was validated by determining the recovery of six different folate vitamers, which were quantitatively recovered (84-105% with CV