Comparison of direct analysis in real-time mass spectrometry, atmospheric solids analysis probe-mass spectrometry, and ion mobility spectrometry for ensuring food safety by rapid screening of poppy seeds.

The opium poppy (Papaver somniferum) is a global commercial crop that has been historically valued for both medicinal and culinary purposes. Naturally occurring opium alkaloids including morphine, codeine, thebaine, noscapine, and papaverine are found primarily in the latex produced by the plant. If the plant is allowed to fully mature, poppy seeds that do not contain the opium alkaloids will form within the pods and may be used in the food industry. It is possible for the seeds to become contaminated with alkaloids by the latex during harvesting, posing a potential health risk for consumers. In the USA, there have been more than 600 reported adverse events including 19 fatalities that may be linked to the consumption of a contaminated poppy-containing product such as home-brewed poppy seed tea. Unwashed poppy seeds and pods may be purchased over the Internet and shipped worldwide. The Forensic Chemistry Center, US Food and Drug Administration (FDA) has evaluated several mass spectrometers (MS) capable of rapid screening to be used for high-throughput analysis of samples such as poppy seeds. These include a direct analysis in real-time (DART) ambient ionization source coupled to a single-quadrupole MS, an atmospheric solids analysis probe (ASAP) ionization source coupled to the same MS, and ion mobility spectrometers (IMS). These instruments have been used to analyze 17 poppy seed samples for the presence of alkaloids, and the results were compared to data obtained using liquid chromatography with mass spectral detection (LC-MS/MS). Results from the 17 poppy seed samples indicate that the DART-MS, ASAP-MS, and IMS devices detect many of the same alkaloids confirmed during the LC-MS/MS analyses, although both the false-positive and false-negative rates are higher, possibly due to the non-homogeneity of the samples and the lack of chromatographic separation.

Sustainable chromatographic purification of milbemectin: Application of high-speed countercurrent chromatography coupled with off-line atmospheric pressure solid analysis probe-high resolution mass spectrometry.

Isolation of valuable chemicals is an important process in reagent manufacturing for the pharmaceutical and food science industries. This process is traditionally time-consuming, expensive, and consumes vast amounts of organic solvents. Considering green chemistry and sustainability concerns, we sought to develop a sustainable chromatographic purification methodology for obtaining antibiotics by focusing on the reduction of organic solvent waste generation. Milbemectin (mixture of milbemycin A3 and milbemycin A4) was successfully purified using high-speed countercurrent chromatography (HSCCC) and pure fractions (>98% purity, HPLC) could be identified using the organic solvent fee atmospheric pressure solid analysis probe mass spectrometry (ASAP-MS). The organic solvents required for HSCCC could be redistilled and recycled for continued HSCCC purification, thus reducing the consumption of organic solvent (n-hexane/ethyl acetate) by 80+%. Optimization of the two-phase solvent system (n-hexane/ethyl acetate/methanol/water, 9/1/7/3, v/v/v/v) for HSCCC was assisted computationally, thereby reducing solvent waste from an experimental determination. Our proposal application of HSCCC and offline ASAP-MS provides proof of concept for a sustainable, preparative scale, chromatographic purification methodology for obtaining antibiotics in high purity.

First report on quality and purity assessment of sweet almond oil in Brazilian body oils by gas chromatography and mass spectrometry.

Sweet almond oil is a raw material with high-added value used in different products. Then, the aim of this study is to evaluate the quality and purity of 10 body oils based on sweet almond oils currently available in the Brazilian market. Fatty acid composition and triacylglycerol (TAG) profile were determined by gas chromatography with flame ionization detector (GC-FID) and atmospheric solids analysis probe mass spectrometry (ASAP-MS), respectively. The authenticity of samples was assessed using an analytical curve equation. Soybean oil was chosen as the adulterant because it is the cheapest vegetable oil commercialized in Brazil. Hierarchical clustering analysis (HCA) in conjunction with ASAP-MS classified product samples according to the type of vegetable oil (soybean and sweet almond oils). The addition of soybean oil (8.79% to 99.70%) was confirmed in samples. However, only two samples stated in their label the presence of soybean oil as an ingredient. These findings highlight the need for better oversight by regulatory bodies to ensure that consumers acquire high quality and authentic products based on equally high quality and purity of sweet almond oils.

Fast and eco-friendly method using atmospheric solids analysis probe mass spectrometry to characterize orange varieties.

Orange fruit is one of the most popular types of fruit in the world, and its juice is the main product of its processing. This study aimed to evaluate a simple, fast, and eco-friendly methodology, atmospheric solids analysis probe mass spectrometry (ASAP-MS), to assess the chemical profile of four oranges varieties (Valencia, Folha Murcha, Pera, and Iapar). The oranges' varieties were evaluated for the physicochemical composition (extraction yield, pH, total titratable acidity, total soluble solids [TSS], °Brix), ratio (TSS/TA), and bioactive compounds (ASAP-MS analysis). The characterization of oranges resulted in great values of oranges yield according to the varieties (44.00-48.10% [w/w], adequate and characteristic acidity [0.73-1.35%], soluble solids content (10.24-13.80°Brix), pH (3.30-3.96), and ratio (7.59-19.90) level for this fruit. This powerful method showed that all analysis procedures were simple, fast, and easy because there is no need to prepare the sample and the analysis time lasted 2 min. Besides, results obtained exhibited a vast array of chemical groups. Principal component analysis (PCA) defined and distinguished the varieties of the orange. Therefore, ASAP-MS and PCA showed that they are very attractive candidates for routine analysis to monitor the varieties of the orange with its pronounced advantages, besides being contributing to the environment because it does not use any quantities of organic solvents. This methodology was applied for the first time to this type of sample.

Application of Atmospheric Solids Analysis Probe Mass Spectrometry (ASAP-MS) in Petroleomics: Analysis of Condensed Aromatics Standards, Crude Oil, and Paraffinic Fraction.

Atmospheric solids analysis probe mass spectrometry (ASAP-MS) is a powerful tool for analysis of solid and liquid samples. It is an excellent alternative for crude oil analysis without any sample preparation step. Here, ASAP-MS in positive ion mode, ASAP(+)-MS, has been optimized for analysis of condensed aromatics (CA) standards, crude oil, and paraffinic fraction samples using a Synapt G2-S HDMS. Initially, two methodologies were used to access the chemical composition of samples: (1) using a temperature gradient varying from 150 to 600 °C at a heating rate of 150 °C min-1, and (2) with constant temperature of 300 and 400 °C. ASAP(+)-MS ionized many compounds with a typical petroleum profile, showing a greater signals range of m/z 250-1300 and 200-1400 for crude oil and paraffin samples, respectively. Such performance, mainly related to the detection of high molecular weight compounds (>1000 Da), is superior to that of other traditional ionization sources, such as ESI, APCI, DART, and DESI. Additionally, the CA standards were identified in both forms: radicals, [M]+•, and protonated cations, [M + H]+, with minimum fragmentation. Therefore, ASAP was more efficient in accessing the chemical composition of nonpolar and polar compounds. It is promising in its application with ultrahigh resolution MS instruments, such as FT-ICR MS and Orbitrap, since molecular formulas with greater resolution and mass accuracy (<1 ppm) would be assigned. Graphical Abstract ᅟ.

Direct Analysis of Amphetamine Stimulants in a Whole Urine Sample by Atmospheric Solids Analysis Probe Tandem Mass Spectrometry.

Amphetamine-type stimulants (ATS) are among illicit stimulant drugs that are most often used worldwide. A major challenge is to develop a fast and efficient methodology involving minimal sample preparation to analyze ATS in biological fluids. In this study, a urine pool solution containing amphetamine, methamphetamine, ephedrine, sibutramine, and fenfluramine at concentrations ranging from 0.5 pg/mL to 100 ng/mL was prepared and analyzed by atmospheric solids analysis probe tandem mass spectrometry (ASAP-MS/MS) and multiple reaction monitoring (MRM). A urine sample and saliva collected from a volunteer contributor (V1) were also analyzed. The limit of detection of the tested compounds ranged between 0.002 and 0.4 ng/mL in urine samples; the signal-to-noise ratio was 5. These results demonstrated that the ASAP-MS/MS methodology is applicable for the fast detection of ATS in urine samples with great sensitivity and specificity, without the need for cleanup, preconcentration, or chromatographic separation. Thus ASAP-MS/MS could potentially be used in clinical and forensic toxicology applications.

A fast and reliable detection of indigo in historic and prehistoric textile samples.

We present a method requiring no sample preparation for the direct identification of indigoid colorants in tiny amounts in ancient historic fabrics using ASAP®-MS. Exact determinations were completed in less than 1 min. Copyright © 2015 John Wiley & Sons, Ltd.