Evaluation of glycerol core aldehydes formation in edible oils under restaurant deep frying.

Glycerol core aldehydes (GCAs) are potentially toxic lipid oxidation products characterized by aldehydic acids bonded to glycerol via acyl groups. This study investigated the profile and change of GCAs in rapeseed oil (RO), high-oleic sunflower oil (HOSO) and cottonseed oil (CO) after frying chicken nuggets (CNs), fish nuggets (FNs) and French fries (FFs) for 60 h in real restaurant frying systems. Three GCAs (8-oxo, 9-oxo, and 10-oxo-8) were identified, with the GCAs (9-oxo) accounting for the highest value (60%), followed by GCAs (10-oxo-8) and GCAs (8-oxo). The total GCAs increased from 1.12 to 2.02 mg/g with frying time from 0 to 60 h in RO used for frying FNs. The FN frying systems produced the largest amount of GCAs, whereas the FF frying systems produced the least. RO contained more GCAs than CO and HOSO owing to its higher unsaturated fatty acid content (91.81%). Furthermore, the GCAs showed a high correlation with polymerized and oxidized products, indicating that the formation of GCAs were related to the oxidative stability of oils. These results may provide insight into the formation of GCAs and their control during frying.

Occupational exposure limits of methyl t-butyl ether in workplace air / 中国职业医学

OBJECTIVE: To establish the occupational exposure limits for methyl t-butyl ether(MTBE) in the air of workplace in China. METHODS: According to the GBZ/T 210.1-2008 Guide for Establishing Occupational Health Standards--Part 1: Occupational Exposure Limits for Airborne Chemicals in the Workplace, we collected and analyzed data on physical and chemical properties, toxicology, occupational epidemiology and foreign occupational exposure limits related to MTBE by literature search. A total of 180 occupational workers exposed to MTBE were selected as exposure group, and 155 workers and administrative logistics personnel without exposure to MTBE were selected as the control group. Occupational hygiene investigation and occupational physical examination were carried out. We deduced the occupational exposure limits for MTBE in workplace air in China by combining literature data. RESULTS: The time-weighted average(TWA) of MTBE in the workplace air developed by the United States of America and Britain is 180.00 mg/m~3. The short-term exposure limit(STEL) of MTBE in the workplace air developed by Australia and New Zealand is 270.00 mg/m~3. The concentration of TWA(C_(TWA)) of MTBE in the exposure group was less than 0.08-4.90 mg/m~3. The concentration of short term exposure was less than 0.10-14.28 mg/m~3, and the C_(TWA) was less than 0.02-83.66 mg/m~3, in parts of workplaces. There was no statistically significant difference on the self-conscious discomfort and the abnormality in physical examination between these two groups(P>0.05). CONCLUSION: It's recommended that the permissible concentration-TWA of MTBE should be set at 180.00 mg/m~3, and the permissible concentration-STEL should be set at 270.00 mg/m~3 in China.

Influence of heat and moisture treatment on carotenoids, phenolic content, and antioxidant capacity of orange maize flour.

The aim of this work was to study the effect of heat and moisture treatment (HMT) on carotenoids, phenolic content and antioxidant capacity of ground, orange maize. Total carotenoid content (TCC) of untreated sample (53.39 mg/kg) was 2.2 times higher than measured in treated orange maize f (24.61 mg/kg). The rates of degradation with HMT were in the following order: ß-carotene > ß-cryptoxanthin > zeaxanthin > lutein. There was a significant interaction between longer heating time and higher moisture content on carotenoid degradation (p < .05). Total phenolic content (TPC) in raw sample (1664.74 mg/kg) was two-fold higher than in treated orange maize (827.89 mg/kg). Ferulic acid was the most abundant and stable phenolic acid in raw and treated orange maize. The antioxidant capacity of orange maize was higher in methanol than in butanol extracts. The highest correlation (0.924) was observed between TPC and ABTS+ scavenging capacity of methanol extracts.

Provitamin A potential of landrace orange maize variety (Zea mays L.) grown in different geographical locations of central Malawi.

The provitamin A potential of landrace orange maize from different locations (A, B, C and D) of central Malawi has been evaluated. Physicochemical compositions, color, total carotenoid content (TCC), carotenoid profiles, and oxygen radical absorbance capacity (ORAC) and 2,2-diphenyl-1-picryhydrazyl (DPPH) free radical scavenging activity as antioxidant capacities of maize were determined. Color values of orange maize had correlations with ß-cryptoxanthin (r>0.36). TCC of white and orange maize averaged 2.12 and 59.5 mg/kg, respectively. Lutein was the most abundant carotenoid (47.8%) in orange maize, followed by zeaxanthin (24.2%), ß-carotene (16.4%) and ß-cryptoxanthin (11.6%). Location D showed the highest levels of lutein, zeaxanthin and antioxidant capacity. Provitamin A content of orange maize met the target level (15 µg/g) of biofortification. Retinol activity equivalent (RAE) from ß-cryptoxanthin and ß-carotene in orange maize averaged 81.73 µg/100g. In conclusion, orange maize has the potential to be a natural source of provitamin A.

Hypothesis-driven weight of evidence analysis to determine potential endocrine activity of MTBE.

Endocrine-related endpoints in animals have been reported to respond to high doses of methyl tertiary-butyl ether (MTBE), however, a systematic and transparent evaluation of endocrine potential has not been published. Resolving whether MTBE exhibits endocrine activity is important given regulatory and public interest in endocrine disrupting substances and their potential for causing adverse effects in humans or wildlife. A weight-of-evidence (WoE) analysis was conducted, focusing on hypotheses related to the potential for MTBE to interact with estrogen, androgen, and thyroid pathways, and steroidogenesis. To reach scientifically justified conclusions based on the totality of evidence, this WoE procedure involved a semi-quantitative relevance weighting of each endpoint for each hypothesis and systematic consideration of each endpoint in various study designs. This procedure maximized use of an extensive body of relevant and reliable literature on MTBE with evidence supporting or opposing a given mode of action hypothesis. Evaluating the strength and consistency of observations from many MTBE studies also provided a way to assess whether high doses used in experiments with MTBE confound identification of direct endocrine system responses. Based on results of studies using mammalian and fish models and in vitro screening assays, this WoE assessment reveals that MTBE lacks direct endocrine activity.

Adduct formation in liquid chromatography-triple quadrupole mass spectrometric measurement of bryostatin 1.

Bryostatin 1, a potential anti-Alzheimer drug, is effective at subnanomolar concentrations. Measurement is complicated by the formation of low m/z degradation products and the formation of adducts with various cations, which make accurate quantitation difficult. Adduct formation caused the sample matrix or mobile phase to partition bryostatin 1 into products of different mass. Degradation of the 927 [M+Na](+) ion to a 869m/z product was strongly influenced by ionization conditions. We validated a bryostatin 1 assay in biological tissues using capillary column HPLC with nanospray ionization (NSI) in a triple-quadrupole mass spectrometer in selected reaction monitoring (SRM) mode. Adduct formation was controlled by adding 1mM acetic acid and 0.1mM sodium acetate to the HPLC buffer, maximizing the formation of the [M+Na](+) ion. Efficient removal of contaminating cholesterol from the sample during solvent extraction was also critical. The increased sensitivity provided by NSI and capillary-bore columns and the elimination of signal partitioning due to adduct formation and degradation in the ionization source enabled a detection limit of 1×10(-18)mol of bryostatin 1 and a LLOQ of 3×10(-18)mol from 1µl of sample. Bryostatin 1 at low pmol/l concentrations enabled measurement in brain and other tissues without the use of radioactive labels. Despite bryostatin 1's high molecular weight, considerable brain access was observed, with peak brain concentrations exceeding 8% of the peak blood plasma concentrations. Bryostatin 1 readily crosses the blood-brain barrier, reaching peak concentrations of 0.2nM, and specifically activates and translocates brain PKCɛ.

Quantitation of leukotriene B(4) in human sputum as a biomarker using UPLC-MS/MS.

Leukotriene B4 (LTB4) is a potent mediator of inflammation and has been recognized as an important target for therapeutic intervention for treatment of diseases such as asthma. In the current work, a highly selective and sensitive UPLC-MS/MS assay was developed for quantitation of LTB4 in human sputum as a biomarker for LTB4 biosynthesis inhibition. A fit-for-purpose strategy for method development, assay qualification, and study support was adopted for this biomarker project. A surrogate matrix (protein buffer) was used for preparation of calibration samples and certain levels of quality control (QC) samples to avoid interference from endogenous analyte, while the low QC was prepared in authentic matrix, human sputum. The analytical methodology utilized a liquid-liquid extraction procedure in 96-well plate format. Chromatographic separation was achieved with a reversed-phase ultra high pressure liquid chromatography (UPLC) column using gradient elution, and the run time was 4.5min per sample. The lower limit of quantitation (LLOQ) was 0.2ng/mL, and the calibration curve range was 0.2-20ng/mL. Acceptable accuracy, precision, linearity, specificity, recovery, and matrix effect was obtained. Bench-top stability (6h), freeze-thaw stability (3 cycles at -20°C), and autosampler stability (97h at ambient temperature) all met acceptance criteria. Frozen long-term stability for 166 days at -20°C in sputum did not meet acceptance criteria by showing only ≥75% of nominal concentration and the information was taken into consideration for study support. Two important observations in the current work were: (1) LTB4 was unstable in sputum in the presence of liquification reagent dithiothreitol (DTT). Therefore, a non-DTT treatment method for sputum processing was developed and applied to the bioanalytical assay and clinical study support; and (2) chromatographic separation of LTB4 from its three non-enzymatically derived isomers, i.e. 6-trans-LTB4, 12-epi-LTB4, and 6-trans-12-epi-LTB4, was achieved. This assay was successfully applied to a Phase II clinical study for proof-of-concept of a LTA4 hydrolase inhibitor for treatment of asthma.