Assessing the concentration of conjugated fatty acids within pomegranate seed oil using quantitative nuclear magnetic resonance (qNMR).

INTRODUCTION: Pomegranate seed is rich in oil, and seed oil of pomegranate consists of conjugated fatty acids with different percentages. OBJECTIVES: The current contribution covers how to determine percentages of different isomeric conjugated fatty acids. METHODS: The percentages of these isomers are analysed by quantitative nuclear magnetic resonance (qNMR) using benzoic acid as an internal reference chemical with a well-defined amount. Linear mathematical equations are developed for the quantitative analysis of fatty acids found in pomegranate seed oil. RESULTS: The developed approach is utilised for the pomegranate seed oils prepared in the laboratory and tested for commercial samples. Among the oils derived at the laboratory, the Yeni Hicaz pomegranate cultivar seeds yielded the highest fraction of punicic acid. Among the acids, punicic acid was the one with the highest fraction, while linolenic acid was the one with the lowest percentage. CONCLUSIONS: These results are important in identifying pomegranate seed oils. Among the commercial samples tested with the current approach, only one of them showed similar content analysis as in the laboratory-derived oils.

Quantification of tributyltin in seawater using triple isotope dilution gas chromatography-inductively coupled plasma mass spectrometry achieving high accuracy and complying with European Water Framework Directive limits.

A triple isotope dilution GC-ICPMS method for the determination of tributyltin (TBT) was developed and validated to meet the European Water Framework Directive (WFD) requirements. The validation procedure involved the evaluation of trueness, precision (repeatability, intermediate precision), limit of detection (LOD) and limit of quantification (LOQ), stability, measurement uncertainty and traceability studies. The method is one of the most sensitive methods published to date with good accuracy, 103% average recovery in the range with %RSDs of 2.8-6.7%. A LOD value of 0.015 ng L-1 for the TBT cation was achieved with a sample volume of 12 mL seawater. TBT was derivatized using 20 µL sodium tetraethylborate solution (0.05% NaBEt4) to make volatile for GC-ICPMS. Measurement uncertainty was in the range of 4.8-13% which was achieved through dissolution of tributyltinchloride (TBTCl) in 1-propanol, a low-volatility solvent combined with the use of a triple isotope dilution (ID) calibration technique. Isotope dilution calibration was performed by adding 117Sn isotopically enriched TBT to the seawater samples. The stability test results showed that TBT concentration was stable for three months in seawater samples after passing through a 0.2 µm filter and stored in amber glass bottles at 4°C. The response surface methodology (RSM) approach was successfully implemented to provide optimal conditions for large volume injection (LVI) to obtain the maximum analytical signal. The key variables selected in the experimental design were evaporation time, evaporation temperature, carrier flow, and injection speed. This method was applied to seawater samples collected from the Bay of Izmit, Kocaeli, Turkey, where TBT pollution has not been measured yet.

The BIPM Mycotoxin Metrology Capacity Building and Knowledge Transfer Program: Accurate Characterization of a Pure Aflatoxin B1 Material to Avoid Calibration Errors.

Background: The contamination of food and feed by mycotoxins, Aflatoxin B1 (AfB1) being one of the most prominent examples, is of imminent concern to many countries. Regulatory limits for mycotoxins have been implemented, and these need to be supported by a sound measurement infrastructure for mycotoxin analysis in order to enforce and verify products, protect populations, and avoid technical barriers to trade in food stuffs. Objective: A Capability Building and Knowledge Transfer program on Metrology for Safe Food and Feed in Developing Economies was started at the International Bureau of Weights and Measures to allow National Metrology Institutes or Designated Institutes to work together to strengthen their national mycotoxin metrology infrastructure. Methods: Knowledge transfer to scientists is provided to enable the characterization of selected pure mycotoxin materials and the production of corresponding certified reference material solutions. Results: This higher-order measurement capability can in turn support mycotoxin testing laboratories within their countries through the provision, for example, of standard solutions of critical analytes that are traceable to the International System of Units (SI). Conclusions and Highlights: The purity characterization and value assignment for a high-purity AfB1 material (979.6 ± 2.3 mg/g, k = 2) intended to be used for the gravimetric production of SI traceable calibration solutions for AfB1 is described using an approach combining quantitative NMR and LC-diode array detection-tandem MS for the correction of the mycotoxin-related impurity content.

Analysis of olive oil for authentication and shelf life determination.

High-field proton (1H) nuclear magnetic resonance (NMR) spectroscopy was applied for screening the fatty acyl contents of 33 olive oil samples from five different geographical regions of Turkey to do geographical discrimination analysis. The 1H NMR data were subjected to principal component analysis (PCA) and analysis of variance (ANOVA) to discriminate the origin of olive oils. The combination of discriminative screening by 1H NMR and ANOVA did not require further analysis of olive oil such as gas chromatography (GC). ANOVA was employed for samples from three regions separately: Marmara Region (MR), Aegean Region (AR), and Mediterranean Region (MeR). The best discriminative parameter was the 1H NMR signal of linoleoyl acyl content. Applying both quantitative NMR and statistical analysis indicated that samples from different provinces within each geographical region (MR, AR, and MeR) could be discriminated. Comparing the linoleoyl and oleoyl acyl contents of Turkish olive oils with these of some Mediterranean olive oils showed the possibility of distinguishing the Turkish olive oils. 1H NMR spectra of three olive oil samples with the production years of January 2013, January 2014, and January 2015 were acquired in 2016 for discussing shelf life of olive oil by quantifying fatty acyls content, and determining minor constituents and possible by-products during storage. The effects of altitude and soil quality on fatty acyl contents of olive oil samples from a small olive growing village in Northeastern Turkey were also tested.

The diverse behaviour of the P-Cl bonds in the spiro-cis-ansa spermidine derivative cyclotriphosphazene towards mono-functional nucleophilic reagents.

A number of new spiro-ansa spermidine derivative cyclotriphosphazenes (2-10) is synthesized in order to provide insight into the reaction mechanism for nucleophilic substitution. The structures of the compounds were determined by elemental analysis, mass (MS), (1)H, (19)F (for 9) and (31)P NMR spectroscopies. Compounds (2-8) and 9, 10 can be formed by a proton abstraction-chloride elimination and both the S(N)(1) and S(N)(2) reaction mechanisms, respectively.

Structural investigations of phosphorus-nitrogen compounds. 7. Relationships between physical properties, electron densities, reaction mechanisms and hydrogen-bonding motifs of N3P3Cl(6 - n)(NHBu(t))n derivatives.

A series of compounds of the N3P3Cl(6 - n)(NHBu(t))n family (where n = 0, 1, 2, 4 and 6) are presented, and their molecular parameters are related to trends in physical properties, which provides insight into a potential reaction mechanism for nucleophilic substitution. The crystal structures of N3P3Cl5(NHBu(t)) and N3P3Cl2(NHBu(t))4 have been determined at 120 K, and those of N3P3Cl6 and N3P3Cl4(NHBu(t))2 have been redetermined at 120 K. These are compared with the known structure of N3P3(NHBu(t))6 studied at 150 K. Trends in molecular parameters [phosphazene ring, P-Cl and P-N(HBu(t)) distances, PCl2 angles, and endo- and exocyclic phosphazene ring parameters] across the series are observed. Hydrogen-bonding motifs are identified, characterized and compared. Both the molecular and the hydrogen-bonding parameters are related to the electron distribution in bonds and the derived basicities of the cyclophosphazene series of compounds. These findings provide evidence for a proposed mechanism for nucleophilic substitution at a phosphorus site bearing a PCl(NHBu(t)) group.