Aromatic amine antioxidants (AAs) and p-phenylenediamines-quinones (PPD-Qs) in e-waste recycling industry park: Occupational exposure and liver X receptors (LXRs) disruption potential.

Recently, evidence of aromatic amine antioxidants (AAs) existence in the dust of the electronic waste (e-waste) dismantling area has been exposed. However, there are limited studies investigating occupational exposure and toxicity associated with AAs and their transformation products (p-phenylenediamines-quinones, i.e., PPD-Qs). In this study, 115 dust and 42 hand wipe samples collected from an e-waste recycling industrial park in central China were analyzed for 19 AAs and 6 PPD-Qs. Notably, the median concentration of ∑6PPD-Qs (1,110 ng/g and 1,970 ng/m2) was significantly higher (p < 0.05, Mann-Whitney U test) than that of ∑6PPDs (147 ng/g and 34.0 ng/m2) in dust and hand wipes. Among the detected analytes, 4-phenylaminodiphenylamine quinone (DPPD-Q) (median: 781 ng/g) and 1,4-Bis(2-naphthylamino) benzene quinone (DNPD-Q) (median: 156 ng/g), were particularly prominent, which were first detected in the e-waste dismantling area. Occupational exposure assessments and nuclear receptor interference ability, conducted through estimated daily intake (EDI) and molecular docking analysis, respectively, indicated significant occupational exposure to PPD-Qs and suggested prioritized Liver X receptors (LXRs) disruption potential of PPDs and PPD-Qs. The study provides the first evidence of considerable levels of AAs and PPD-Qs in the e-waste-related hand wipe samples and underscores the importance of assessing occupational exposure and associated toxicity effects.

Effects of seasoning addition and cooking conditions on the formation of free and protein-bound heterocyclic amines and advanced glycation end products in braised lamb.

The accumulation of heterocyclic amines (HAs) and advanced glycation end products (AGEs) in thermally processed meats has been arising safety concerns. The effects of cooking conditions and seasoning addition on the formation of HAs and AGEs in Chinese traditional braised lamb were investigated by UPLC-MS/MS analysis. Soy sauce significantly increased the formation of HAs and AGEs, among which light soy sauce had the greatest promoting effect (69.45-15300.62 %). Conversely, spices inhibited HAs and AGEs formation, the inhibition rate of free HAs and AGEs reached 22.06-34.72 % when using 70 % ethanol extract. Hot blanching treatment and adding soy sauce and spices at a later stage could significantly suppress HAs and AGEs production. Flavonoids, including galangin, hesperidin, narirutin, etc., were identified as key effectors in spices. These findings help to promote awareness of the formation of HAs and AGEs in braised lamb and provide valuable insights for optimizing processing techniques to minimize their production.

Structural elucidation of derivatives of polyfunctional metabolites after methyl chloroformate derivatization by high-resolution mass spectrometry gas chromatography. Application to microbiota metabolites.

Metabolomics has become an essential discipline in the study of microbiome, emerging gas chromatography coupled to mass spectrometry as the most mature, robust, and reproducible analytical technique. Silylation is the most widely used chemical derivatization strategy, although it has some limitations. In this regard, alkylation by alkyl chloroformate offers some advantages, such as a rapid reaction, milder conditions, better reproducibility, and the generation of more stable derivatives. However, commercial spectral libraries do not include many of the alkyl derivatives, mainly for polyfunctional metabolites, which can form multiple derivatives. That introduces a huge bias in untargeted metabolomics leading to common errors such as duplicates, unknowns, misidentifications, wrong assignations, and incomplete results from which non-reliable findings and conclusions will be retrieved. For this reason, the purpose of this study is to overcome these shortcomings and to expand the knowledge of metabolites in general and especially those closely related to the gut microbiota through the thorough study of the reactivity of the different functional groups in real matrix derivatized by methyl chloroformate, a common representative alkylation reagent. To this end, a systematic workflow has been developed based on exhaustive structural elucidation, along with computational simulation, and taking advantage of the high sensitivity and high-resolution gas chromatography-mass spectrometry. Several empirical rules have been established according to chemically different entities (free fatty acids, amino acids, polyols, sugars, amines, and polyfunctional groups, etc.) to predict the number of derivatives formed from a single metabolite, as well as their elution order and structure. In this work, some methyl chloroformate derivatives not previously reported as well as the mechanisms to explain them are given. Extremely important is the interconversion of E- and Z- geometric isomers of unsaturated dicarboxylic acids (case of fumaric-maleic and case of citraconic-mesaconic acids), or the formation of cycled derivatives for amino acids, as well as common metabolites, as in the case of serine and cysteine, and many others.

GC-MS Analysis of Primary Aromatic Amines Originated From Azo Dyes in Commercial Textile or Leather Products Using Helium Alternative Carrier Gases.

BACKGROUND: In recent years, due to the global shortage of helium gas, the development of gas chromatography (GC) analytical methods using alternatives to helium carrier gases is necessary. OBJECTIVE: The objective of this study was to examine the applicability of hydrogen and nitrogen as alternative carrier gases using the test method for azo compounds in the Act on Control of Household Products Containing Harmful Substances of Japan. METHOD: The gas chromatograph mass spectrometer (GC-MS) analytical method using hydrogen and nitrogen as alternative carrier gases was compared with a method using helium for 26 primary aromatic amines (PAAs) originated from azo dyes. RESULTS: When hydrogen and nitrogen were used as carrier gases under the same conditions used during analysis using helium (same column, gas flow rate, oven temperature conditions, etc.), sufficient peak separation of 26 PAAs was obtained. The sensitivities of the methods using helium and hydrogen were comparable, whereas the sensitivity was lower when nitrogen was used, with the detection limits ranging from 1/220 to 1/25. However, all carrier gases achieved quantification at concentrations below the standard value (30 µg/g) of the Act on Control of Household Products Containing Harmful Substances, and the results were in agreement with the standard value for the target product. CONCLUSIONS: Our results indicated that hydrogen or nitrogen can be used as alternative carrier gases to helium for GC-MS analysis of azo compounds producing specific aromatic amines. HIGHLIGHTS: Using hydrogen or nitrogen as an alternative carrier gas to helium, azo compounds could be quantified with excellent accuracy.

Mechanism of aroma enhancement methods in accelerating Congou black tea acidification subjected to room temperature storage.

Acidification of aroma-enhanced black tea during storage was studied. UPLC-Q-TOF/MS (Ultra Performance Liquid Chromatography and Quadrupole-Time of Flight Mass Spectrometer) and HPLC (High-Performance Liquid Chromatography) analysis of non-volatile substances and organic acids revealed a decrease of soluble sugars and amino acids in aroma-enhanced black tea, while an increase in organic acids such as oxalic acid, malic acid and quinic acid. Further in vitro experiments indicated that the acidification of aroma-enhanced tea during storage can be attributed to decomposition of sugars and amino acids by heating, oxidation of aromatic aldehydes. Meanwhile, the amino acids, catechins, soluble sugars and flavonoids that constitute the taste of black tea are further reduced, changing the taste composition of tea infusion and further increasing its acidity. This study revealed the reasons for black tea acidification during aroma enhancement and storage and provided a theoretical basis for improving black tea quality.

Integrating Post-Ionization Separation via Differential Mobility Spectrometry into Direct Analysis in Real Time Mass Spectrometry for Toy Safety Screening.

Direct analysis in real time (DART) enables direct desorption and ionization of analytes, bypassing the time-consuming chromatographic separation traditionally required for mass spectrometry (MS) analysis. However, DART-MS suffers from matrix interference of complex samples, resulting in compromised detection sensitivity and quantitation accuracy. In this study, DART-MS was combined with differential mobility spectrometry (DMS) to provide an additional dimension of post-ionization ion mobility separation within a millisecond time scale, compensating for the lack of separation in DART-MS analysis. As proof-of-concept, primary aromatic amines (PAAs), a class of potentially hazardous chemicals, were analyzed in various toy products, including bubble solutions, finger paints, and plush toys. In addition to commercial Dip-it glass rod and metal mesh sampling tools, a customized rapid extractive evaporation device was designed for the accelerated extraction and sensitive analysis of solid toy samples. The incorporation of DMS in DART-MS analysis enabled the rapid separation and differentiation of isomeric analytes, leading to improved accuracy and reliability. The developed protocols were optimized and validated, achieving good linearity with correlation coefficients greater than 0.99 and acceptable repeatability with relative standard deviations less than 10%. Moreover, satisfactory sensitivity was realized with limits of detection and quantitation ranges of 0.2-5 and 1-20 µg/kg (µg/L) for the 11 PAA analytes. The established methodology was applied for the analysis of real toy samples (n = 18), which confirmed its appealing potential for toy safety screening and consumer health protection.

Selenium content, chemical composition and volatile components of essential oil and hydrosol from flowers of Cardamine violifolia.

Cardamine violifolia is a unique selenium hyperaccumulating vegetable in China, but its flowers are commonly wasted in large-scale cultivation. To better utilize this resource, this study explored the selenium content, chemical composition, and volatile organic compounds (VOCs) of hydro-distilling essential oil (EO) and hydrosol from C. violifolia flowers. ICP-MS results indicated that the EO and hydrosol contained selenium reaching 13.66±2.82 mg/kg and 0.0084±0.0013 mg/kg, respectively. GC-MS analysis revealed that organic acids, hydrocarbons, and amines were the main components of EO. Additionally, benzyl nitrile, benzaldehyde, benzyl isothiocyanate, benzyl alcohol, megastigmatrienone, and 2-methoxy-4-vinylphenol also existed in considerable amounts. The hydrosol extract had fewer components, mainly amines. HS-SPME-GC-MS corresponded to the composition analysis and aromatic compounds were the prevalent VOCs, while HS-GC-IMS primarily identified C2-C10 molecular alcohols, aldehydes, ethers, and sulfur-containing compounds. This study first described the chemical composition and VOC profiles of EO and hydrosol from selenium hyperaccumulating plant.

Effects of volatile organic compounds of smoke from different woods on the heterocyclic amine formation and quality changes in pork patty.

This study investigated the effects of smoke derived from cypress (CY), mulberry (MU), metasequoia (ME), pine (PI), and camphor (CA) on the heterocyclic aromatic amines (HAs), flavor, and sensory attributes of smoked pork patty. The results showed that the smoke derived from the five kinds of wood and the flavor of the corresponding smoked meat were classified into three types. Moreover, the smoke of CY and PI, and the smoke of MU and ME can be classified into one category respectively, which significantly improved the flavor of the smoked meat. Both free and protein-bound HAs were detected in smoked meat, while the smoking process significantly increased the HAs content, especially free Norharman (3.26 ng/g in control meat, and 82.24 ng/g in meat smoked with CY). Correlation analysis showed that various volatile organic compounds (VOCs) and HAs were closely associated. Future research should pay attention to the VOCs in smoked meat including vanillin, Close attention should be paid to tridecane and crotonic acid, as well as tetradecane and α-Dehydro-ar-himachalene in smoke, which were consistently correlated with various HAs and may participate in HAs formation. These results may reveal how the smoking process influences the formation of HAs and which factors should be targeted to inhibit HAs in smoked meat products.

Effects of soy protein and its hydrolysates on the formation of heterocyclic aromatic amines in roasted pork.

This study investigated the influence mechanism of soy protein and its hydrolysates (under three different degree of hydrolysis) on formation of heterocyclic aromatic amines (HAAs) formation in roasted pork. The results showed that 7S and its hydrolysates significantly inhibited the formation of quinoxaline HAAs, and the maximum inhibitory rate of MeIQx, 4,8-MeIQx, and IQx was 69%, 79%, and 100%, respectively. However, soy protein and its hydrolysates could promote the formation of pyridine HAAs (PhIP, and DMIP), its content increased significantly with the increase in the degree of hydrolysis of the protein. The content of PhIP increased 41, 54, and 165 times with the addition of SPI, 7S, and 11S at 11% degree of hydrolysis, respectively. In addition, they promoted the formation of ß-carboline HAAs (Norharman and Harman), in a manner similar with that of PhIP, especially the 11S group. The inhibitory effect on quinoxaline HAAs was probably correlated with DPPH radical scavenging capacity. Nevertheless, the promotive effect on other HAAs might be related to the high levels of free amino acids and reactive carbonyls. This research may provide recommendation for the application of soy protein in high-temperature meat products.

Solvent-free automated thermal desorption-gas chromatography/mass spectrometry for direct screening of hazardous compounds in consumer textiles.

The global production of textiles utilizes numerous large-volume chemicals that may remain to some extent in the finished garments. Arylamines, quinolines, and halogenated nitrobenzene compounds are possible mutagens, carcinogens and/or skin sensitizers. For prevention, control of clothing and other textiles must be improved, especially those imported from countries without regulations of textile chemicals. An automated analytical methodology with on-line extraction, separation, and detection would largely simplify screening surveys of hazardous chemicals in textiles. Automated thermal desorption-gas chromatography/mass spectrometry (ATD-GC/MS) was developed and evaluated as a solvent-free, direct chemical analysis for screening of textiles. It requires a minimum of sample handling with a total run time of 38 min including sample desorption, chromatographic separation, and mass spectrometric detection. For most of the studied compounds, method quantification limit (MQL) was below 5 µg/g for 5 mg of textile sample, which is sufficiently low for screening and control of quinoline and arylamines regulated by EU. Several chemicals were detected and quantified when the ATD-GC/MS method was applied in a limited pilot screening of synthetic fiber garments. A number of arylamines were detected, where some of the halogenated dinitroanilines were found in concentrations up to 300 µg/g. This is ten times higher than the concentration limit for similar arylamines listed by the EU REACH regulation. Other chemicals detected in the investigated textiles were several quinolines, benzothiazole, naphthalene, and 3,5-dinitrobromobenzene. Based on the present results, we suggest ATD-GC/MS as a screening method for the control of harmful chemicals in clothing garments and other textiles.

Assessment of physicochemical properties of sorbent materials in passive and active sampling systems towards gaseous nitrogen-containing compounds.

The adsorption and desorption behavior of volatile nitrogen-containing compounds in vapor phase by solid-phase microextraction Arrow (SPME-Arrow) and in-tube extraction (ITEX) sampling systems, were investigated experimentally using gas chromatography-mass spectrometry. Three different SPME-Arrow coating materials, DVB/PDMS, MCM-41, and MCM-41-TP and two ITEX adsorbents, TENAX-GR and MCM-41-TP were compared to clarify the selectivity of the sorbents towards nitrogen-containing compounds. In addition, saturated vapor pressures for these compounds were estimated, both experimentally and theoretically. In this study, the adsorption of nitrogen-containing compounds on various adsorbents followed the Elovich model well, while a pseudo-first-order kinetics model best described the desorption kinetics. Pore volume and pore sizes of the coating sorbents were essential parameters for the determination of the adsorption performance for the SPME-Arrow sampling system. MCM-41-TP coating with the smallest pore size gave the slowest adsorption rate compared to that of DVB/PDMS and MCM-41 in the SPME-Arrow sampling system. Both adsorbent and adsorbate properties, such as hydrophobicity and basicity, affected the adsorption and desorption kinetics in SPME-Arrow system. The adsorption and desorption rates of studied C6H15N isomers in the MCM-41 and MCM-41-TP sorbent materials of SPME-Arrow system were higher for dipropylamine and triethylamine (branched amines) than for hexylamine (linear chain amines). DVB/PDMS-SPME-Arrow gave fast adsorption rates for the aromatic-ringed pyridine and o-toluidine. All studied nitrogen-containing compounds demonstrated high desorption rates with DVB/PDMS-SPME-Arrow. Chemisorption and physisorption were the sorption mechanisms in MCM-41- and MCM-41-TP- SPME-Arrow, but additional experiments are needed to confirm this. An active sampling technique ITEX gave comparable adsorption and desorption rates on the selective MCM-41-TP and universal TENAX-GR sorbent materials for all the compounds studied. Vapor pressures of nitrogen-containing compounds were experimentally estimated by using retention index approach and these values were compared with the theoretical ones, calculated using the COnductor-like Screening MOdel for Real Solvent (COSMO-RS) model. Both values agreed well with those found in the literature proving that these methods can be successfully used in predicting VOC's vapor pressures, e.g. for the formation of secondary organic aerosols.

The Flexibility of ß-Content, γ-Confidence Tolerance Intervals to Qualimetry a Simultaneous 22 Aromatic Amines Derived from Azo Dyes in Fabric Using a Sensitive GC-MS Technique.

BACKGROUND: Azo dyes are among the most widely used dyes in the textile industry, releasing a series of carcinogenic aromatic amines that can be absorbed through the skin. OBJECTIVE: This work aims to show that 22 azo dye amines in a textile matrix can be quantified using a GC-MS method. METHODS: Based on the notion of total error and ß-content, γ-confidence tolerance intervals (ß,γ-CCTI), a chemometric approach known as the "uncertainty profile" has been used to completely validate a GC-MS method for the simultaneous assay of 22 azo amines in fabrics. According to International Organization for Standardization (ISO) in ISO 17025 guidelines, analytical validation and measurement uncertainty estimates have evolved to be two main principles for ensuring the accuracy of analytical results and controlling the risk associated with their use. RESULTS: The calculated tolerance intervals allowed for the determination of the uncertainty limits at each concentration level. These limits when compared to the acceptable limits show that a significant portion of the expected outcomes is in conformity. Additionally, the relative expanded uncertainty values, calculated with a proportion of 66.7% and a 10% risk, do not exceed 27.7, 12.2, and 10.9% for concentration levels 1, 15, and 30 mg/L, respectively. CONCLUSION: The capability and flexibility of the ß-content, γ-confidence intervals have been established through the use of this innovative approach to carrying out qualimetry of the GC-MS method depending on the behavior, required conformity proportion, and acceptable tolerance limits of each amine. HIGHLIGHTS: An efficient GC-MS technique for the simultaneous determination of 22 azo amines in a textile matrix has been developed. Analytical validation using a new strategy based on the uncertainty concept is reported, uncertainty associated to measurement results is estimated, and the applicability of our approach to the GC-MS method is investigated.

Quantification of hetero-cyclic amines from different categories of braised beef by optimized UPLC-TQ-XS/ESI method.

This research work has developed and optimized a sensitive analytical method for separation and quantification of heterocyclic amines (HCAs) mainly including PhIP, Harman, Norharman, IQ, MeIQ, AαC, MeAαC and Trp-P-2 by optimizing UPLC-TQ-XS using electrospray ionization source (ESI+) on ACQUITY UPLC® BEH C18 column in <7 min, from braised beef sample matrix. Meanwhile, modified HCAs extraction by modifying QuEChERS (quick, easy, cheap, efficient, rugged and safe) technique and revisited with solid phase extraction (SPE) for HCAs purification, instead using traditional QuEChERS salts. Moreover, optimized pH conditions of HCA extracts before purification, for better extraction recoveries. Furthermore, this method was validated in terms of method validation parameters. Lastly, simulation of real braised beef model provided the minimum formation of HCAs by optimizing cooking parameters and precursors in a cooking system. Therefore, this method could be applied simultaneously on braised beef matrix either marketed or home cooked for HCAs analysis.

Quantification of Serum Metabolites in Early Colorectal Adenomas Using Isobaric Labeling Mass Spectrometry.

A major challenge in reducing the death rate of colorectal cancer is to screen patients using low-invasive testing. A blood test shows a high compliance rate with reduced invasiveness. In this work, a multiplex isobaric tag labeling strategy coupled with mass spectrometry is adopted to relatively quantify primary and secondary amine-containing metabolites in serum for the discovery of metabolite level changes of colorectal cancer. Serum samples from patients at different risk statuses and colorectal cancer growth statuses are studied. Metabolite identification is based on accurate mass matching and/or retention time of labeled metabolite standards. We quantify 40 metabolites across all the serum samples, including 18 metabolites validated with standards. We find significantly decreased levels of threonine and asparagine in the patients with growing adenomas or high-risk adenomas (p < 0.05). Glutamine levels decrease in patients with adenomas of unknown growth status or high-risk adenomas. In contrast, arginine levels are elevated in patients with low-risk adenoma. Receiver operating characteristic analysis shows high sensitivity and specificity of these metabolites for detecting growing adenomas. Based on these results, we conclude that a few metabolites identified here might contribute to distinguishing colorectal patients with growing adenomas from normal individuals and patients with unknown growth status of adenomas.

Development and evaluation of a novel fluorescent chiral derivatization reagent DBD-S-M-Pro: first observation of four chiral amino acids in human hair.

This study reports a novel fluorescent chiral derivatization reagent, 4-(N,N-dmethylaminosulfonyl)-2,1,3-benzoxadiazole-(2-succinimidoxy)-trans-2-methyl-L-proline (DBD-S-M-Pro), with a benzoxadiazole structure containing an N-hydroxysuccinimide activation group. DBD-S-M-Pro targets chiral amino-functional compounds under alkaline conditions without a condensation agent. Gradient elution was performed on a BEH C18 (100 × 2.1 mm, 1.7 µm) column with a mobile phase of 0.05% formic acid (FA) in 10 mM ammonium acetate (CH3COONH4) and 0.1% FA in acetonitrile or methanol. The efficiency of the chiral resolution was evaluated under excitation and emission wavelengths of 450 nm and 560 nm, respectively. The 19 chiral amino acids were separated in the range of 1.45-14.84. The resolutions of almost all DL-amino acids exceeded 1.5; the exceptions were serine (Ser) and lysine (Lys), with resolutions of 1.45 and 1.46, respectively. In addition, a new approach was devised for the simultaneous analysis of four chiral amino acids (DL-Glu, DL-Ala, DL-Val, and DL-Phe) in human hair. These amino acids were analyzed in the range of 12.5-400 pmol, with R2 ≥ 0.9990, limits of detection (S/N = 3) of 4-10 pmol, and intraday and interday precisions of 0.57-6.23%. The average spikes in the hair recoveries were 89.76-111.54%, and the matrix effects were 92.47-102.40%. Next, the contents of free chiral amino acids in the hair samples of 10 healthy volunteers (five males and five females) were analyzed with this method, and the differences were compared. The developed DBD-S-M-Pro provides a novel strategy for the sensitive determination of free chiral amino acids in living organisms.

Sensory acceptability of antioxidant-based formulations dedicated to mitigate heterocyclic aromatic amines in cooked meat.

In a previous work, we studied the inhibition of heterocyclic aromatic amine formation by natural ingredients rich in antioxidants: caper, oregano, wine and green tea. This present work aimed to assess the sensory impact of the addition of these ingredients in ground beef patties. The best liked formulations were determined by a hedonic scoring. Caper and oregano were not significantly different from the standard, the most appreciated, due to their congruency with cooked meat. Direct dissimilarity assessment was performed to evaluate the overall, gustative and odor differences between formulations. Olfactive differences were evidenced as key drivers of these differences. Standard and caper were close while oregano was found significantly different from them. A fast sensory profiling permitted to evidence that aromatic plant note was discriminant for oregano formulation. Gas chromatography-mass spectrometry/multibooth olfactometry identified the distinctive odor-active compounds of the formulations as pyrazines and sulfide for oregano formulation and ester for caper formulation.

The effect of PhIP precursors on the generation of particulate matter in cooking oil fumes at high cooking temperatures and the inflammation response in human lung cells.

Cooking Oil Fumes (COFs) contain carcinogenic organic substances such as polycyclic aromatic hydrocarbons (PAHs) and heterocyclic amines (HCAs), of which 2-Amino-1-methyl-6-phenylimidazo(4,5-b)pyridine (PhIP) is known as mainly meat-borne carcinogens. In this work, to identify the mechanisms to induce the inflammation response in human lung cells (A549) exposed to COFs, we investigated the physicochemical and biological characteristics of COFs generated with PhIP precursors (L-phenylalanine, creatinine, and glucose) at high cooking temperatures (300 °C and 600 °C). Interestingly, we found that PhIP was not formed both at 300 °C and 600 °C, while a large number of carbon nanoparticles were generated from soybean oil containing the PhIP precursors at 600 °C. From the biological analysis, COFs generated with the PhIP precursors at 600 °C induced the most significant pro-inflammatory cytokine (IL-6). This result indicates that the particulate matter in COFs generated with the PhIP precursors above the smoke temperature is the primary factor directly affecting the lung inflammatory response rather than PhIP. This study demonstrates for the first time a novel principle of the inflammatory response that the PhIP precursors can aggravate lung injury by affecting the physical properties of COFs depending on cooking temperature. Therefore, our finding is a significant result of overcoming the bias in previous studies focusing only on the chemical toxicity of PhIP in the inflammatory response of COFs.

Raw to charred: Changes of precursors and intermediates and their correlation with heterocyclic amines formation in grilled lamb.

This work aimed to investigate the changes and correlations of precursors, intermediates and heterocyclic amines (HCAs) in lamb during charcoal grilling. 28 chemical compounds were detected by high-performance liquid chromatography and gas chromatography-mass spectrometry in grilled lamb from raw to charred. Results demonstrated the types and contents of HCAs were increased during grilling, of which 2-amino-1-methyl-6-phenylimidazo [4,5-b] pyridine (PhIP) was dominant and accounted for 61% at the end of grilling (42 min). Glucose and creatine (P < 0.05) decreased with grilling time, creatinine (P < 0.05) and total free amino acid increased. The types and contents of four intermediates (formaldehyde, acetaldehyde, phenylacetaldehyde, 2,5-dimethylpyrazine) increased during grilling. Glucose, creatine, creatinine, ten free amino acids and four intermediates showed significant correlation to HCAs. Also, the ratios of four precursors were significantly correlated with HCAs (P < 0.05), besides creatine/glucose ratio. These results suggested that the time of charcoal grilling should not exceed 14 min at 145 °C in order to reduce the formation of harmful compounds in lamb meat.

Extraction of heterocyclic amines and polycyclic aromatic hydrocarbons from pork jerky and the effect of flavoring on formation and inhibition.

Heterocyclic amines (HAs) and polycyclic aromatic hydrocarbons (PAHs)are widely distributed in foods.This study aims to extract PAHs and HAs from pork jerky simultaneously by QuEChERS for analysis by GC-MS/MS and UPLC-MS/MS, respectively. Also,the effects of flavoring materials and processing temperature on the formation of PAHs and HAswere studied. Acetonitrile containing 1% acetic acid possessed the highest extraction efficiency, with high accuracy and precision being attained forHAs and PAHs. Pork jerky roasted at 220℃ generated a higherPAHs content than180℃, but unaffected the HAs formation.Addition of sugarreduced formation ofboth HAs and PAHs during roasting, while soy sauce reduced somePAHs and promotedHAs formation. Incorporation of 0.5% curcumaorcinnamon powderinhibited HA formation with amore pronounced effect being shown by the latter,but neither inhibitedPAH formation. The correlation between HA and PAH formation was assessed by principle component analysis.

Development of a diphenyl sulfide structure derivatization reagent for amino acid enantiomers analysis: Application of dynamic monitoring in human urine after drinking wine.

We developed a novel chiral mass spectrometry derivatization reagent (S)-(3-(4-carboxythiazolidin-3-yl)-3-oxopropyl) diphenylsulfonium (CTOD) with a positively charged sulfur-containing structure for high-sensitivity detection of the chiral resolution of amino acid enantiomers. CTOD reacted with DL-amino acids at 60oC for 60 min to generate the corresponding diastereomers, fifteen chiral amino acid-derived products were separated. Resolution (Rs) values were of the range 1.54-4.36, except Asn 1.07, achieving good separation. A highly sensitive and selective UHPLC-MS/MS method for the simultaneous determination and chiral separation of five chiral amino acids (Pro, Ala, Glu, Asp, and Phe) based on CTOD derivatization was established and applied to the detection of chiral amino acids in different wines. The diastereomeric resolution of the five amino acids was 1.71-5.42, and an excellent linear relationship was obtained in the range of 0.25-500 pmol (R2 ≥0.9993). The detection limit was 0.05-0.25 pmol. The intra- and inter-day precisions were 0.51-5.76% and 0.78-5.18%, respectively, and the average recovery was 90.03-99.99%. In addition, the metabolic concentration of chiral amino acids was monitored after drinking red wine and white wine, and the fitting curve of metabolic concentration was drawn.