Formation and retention of aroma compounds in pigeons roasted by circulating non-fried roast technique by means of UHPLC-HRMS and GC-O-MS.

Lipids are key aroma contributors in meat products. However, the role of different lipids in the presence of aroma compounds in roasted pigeons has not been studied. The formation of aroma compounds and lipids during the circulating non-fried roasting of pigeons was investigated. The results presented that 18 aroma compounds, including 5-methy-2,3-diethylpyrazine, were identified as key aroma compounds. A total of 6324 lipids were classed into 47 categories, such as phosphatidylcholine (PC), phosphatidylethanolamine (PE), and triglyceride (TG). Nine lipids, containing PA(P-20:0/22:4(7Z,10Z,13Z,16Z)) and LPC 16:0-SN1, showed promise as potential biomarkers for discriminating differential pigeons using OPLS-DA. PC (13.76%), TG (13.58%), and their products were major lipids, among which TG 16:0 16:0 18:2, LPC 18:2-SN1, and PC 18:1_18:1 played a crucial role in the presence of aroma compounds. Interestingly, the linoleic acid, an important aroma contributor, was predominantly bonded to the sn-2 position of phospholipid and sn-3 position of neutral lipids.

Novel compound heterozygous mutations of the NPC1 gene associated with Niemann-pick disease type C: a case report and review of the literature.

BACKGROUND: Niemann-Pick Disease type C is a fatal autosomal recessive lipid storage disorder caused by NPC1 or NPC2 gene mutations and characterized by progressive, disabling neurological deterioration and hepatosplenomegaly. Herein, we identified a novel compound heterozygous mutations of the NPC1 gene in a Chinese pedigree. CASE PRESENTATION: This paper describes an 11-year-old boy with aggravated walking instability and slurring of speech who presented as Niemann-Pick Disease type C. He had the maternally inherited c.3452 C > T (p. Ala1151Val) mutation and the paternally inherited c.3557G > A (p. Arg1186His) mutation using next-generation sequencing. The c.3452 C > T (p. Ala1151Val) mutation has not previously been reported. CONCLUSIONS: This study predicted that the c.3452 C > T (p. Ala1151Val) mutation is pathogenic. This data enriches the NPC1 gene variation spectrum and provides a basis for familial genetic counseling and prenatal diagnosis.

Understanding the role of lipids in aroma formation of circulating non-fried roasted chicken using UHPLC-HRMS-based lipidomics and heat transfer analysis.

The role of lipids in aroma formation of circulating non-fried roasted (CNR) chicken with different roasting times was studied using ultra-high performance liquid chromatography high-resolution mass spectrometry (UHPLC-HRMS)-based lipidomics and heat transfer analysis. Thirteen odorants were confirmed as important aroma compounds of CNR chicken, including dimethyl trisulfide, 3,5-dimethyl-2-ethylpyrazine, nonanal, and 1-octen-3-ol. A comprehensive lipidomics analysis identified 1254 lipids in roasted chickens, classified into 23 distinct lipid categories that included 281 phosphatidylcholines (PC), 223 phosphatidylethanolamines (PE), and 202 triglycerides (TG). Using OPLS-DA analysis, the lipid PG (18:1_18:1) showed promise as a potential biomarker for distinguishing between chickens subjected to CNR treatments with varying roasting times. The lipids PC, PE, and their derivatives are likely to play a crucial role in the formation of aroma compounds. In addition, TGs that contributed to the retention of key odorants in roasted chicken included TG (16:0_16:0_18:1), TG (16:0_16:0_18:0), and TG (16:0_18:1_18:1). Findings further showed that lower water activity and specific heat capacity promoted the formation and retention of aroma compounds during the CNR process. This study contributed to a better understanding of the formation of aroma compounds through lipid oxidation in roasted chicken.

Nano-Voids in Ultrafine Explosive Particles: Characterization and Effects on Thermal Stability.

Ultrafine explosives show high safety and reliable initiation and have been widely used in aerospace, military, and industrial systems. The outstanding performance of ultrafine explosives is largely given by the unique void defects according to the simulation results. However, the structures and effects of internal nano-voids in ultrafine explosive particles have been rarely investigated experimentally. In this work, contrast-variation small angle X-ray scattering was verified to reliably measure the structures of internal nano-voids in ultrafine explosive 2,6-diamino-3,5-dinitropyrazine-1-oxide (LLM-105) and 2,2',4,4',6,6'-hexanitro diphenylethylene (HNS). The size of nano-voids is around 10 nm, and the estimated number of nano-voids in a single particle is considerable. Moreover, the thermal stability of ultrafine LLM-105 was improved via changing the structures of nano-voids. This work provides a methodology for the study of nano-void defects in ultrafine organic particles and may pave the path to enhance the performance of ultrafine explosives via defect engineering.

Wide-Scope Multi-residue analysis of pesticides in beef by gas chromatography coupled with quadrupole Orbitrap mass spectrometry.

Increasing pesticide contamination in foods of animal origin has made the wide-scope multi-residue analysis of pesticides an international concern. By using 191 pesticides, this study investigates a sensitive and reliable method for multi-residue analysis of pesticides in beef to determine the extent of the application of this method. The QuEChERS method was employed to extract and purify the pesticides as C18 was utilized as the absorbents. Then, the purified pesticides were analysed using gas chromatography - quadrupole orbitrap mass spectrometry (GC-Q-Orbitrap-MS). The validation test results revealed that this method was satisfactorily sensitive since its screening detection limit (SDL) ranged from 0.2 to 100 µg∙kg-1. The recovery tests implemented at three spiking levels, namely 100, 200, and 500 µg∙kg-1, generated the results of 71.95 %-113.97 %, while the intra- and inter-day precisions were 0.27 %-17.94 %, indicating that this method had excellent accuracy and precision.

Identification of oxidosqualene cyclases associated with saponin biosynthesis from Astragalus membranaceus reveals a conserved motif important for catalytic function.

INTRODUCTION: Triterpenoids and saponins have a broad range of pharmacological activities. Unlike most legumes which contain mainly oleanane-type scaffold, Astragalus membranaceus contains not only oleanane-type but also cycloartane-type saponins, for which the biosynthetic pathways are unknown. OBJECTIVES: This work aims to study the function and catalytic mechanism of oxidosqualene cyclases (OSCs), one of the most important enzymes in triterpenoid biosynthesis, in A. membranaceus. METHODS: Two OSC genes, AmOSC2 and AmOSC3, were cloned from A. membranaceus. Their functions were studied by heterologous expression in tobacco and yeast, together with in vivo transient expression and virus-induced gene silencing. Site-directed mutagenesis and molecular docking were used to explain the catalytic mechanism for the conserved motif. RESULTS: AmOSC2 is a ß-amyrin synthase which showed higher expression levels in underground parts. It is associated with the production of ß-amyrin and soyasaponins (oleanane-type) in vivo. AmOSC3 is a cycloartenol synthase expressed in both aerial and underground parts. It is related to the synthesis of astragalosides (cycloartane-type) in the roots, and to the synthesis of cycloartenol as a plant sterol precursor. From AmOSC2/3, conserved triad motifs VFM/VFN were discovered for ß-amyrin/cycloartenol synthases, respectively. The motif is a critical determinant of yield as proved by 10 variants from different OSCs, where the variant containing the conserved motif increased the yield by up to 12.8-fold. Molecular docking and mutagenesis revealed that Val, Phe and Met residues acted together to stabilize the substrate, and the cation-π interactions from Phe played the major role. CONCLUSION: The study provides insights into the biogenic origin of oleanane-type and cycloartane-type triterpenoids in Astragalus membranaceus. The conserved motif offers new opportunities for OSC engineering.

Untargeted Profiling and Differentiation of Volatiles in Varieties of Meat Using GC Orbitrap MS.

Volatile compounds play vital roles in food sensory attributes and food quality. An analysis of volatile compounds could illustrate the sensory attributes at the microscale level. Here, untargeted profiling approaches for volatiles in five most-consumed meat species were established using headspace SPME-GC/high resolution Orbitrap MS. An extended high-resolution database of meat volatile compounds was established to enhance the qualification accuracy. Using sulfur-containing compounds, aldehydes, and ketones as the research model, the parameters including fiber coating types, extraction temperature, extraction time, and desorbing time were optimized. Principle component analysis, volcano analysis and partial least squares discriminant analysis were applied to run the classification and the selection of discriminant markers between meat varieties, respectively. Different varieties could be largely distinguished according to the volatiles' profiles. 1-Octen-3-ol, 1-octen-3-one, 2-pentyl furan and some other furans degraded from n-6 fatty acids would contribute to distinguishing duck meat from other categories, while methyl esters mainly from oleic acid as well as dimethyl sulfoxide and carbon disulfide possibly produced from the sulfur-containing amino acids contributed to the discrimination of beef. Therefore, volatiles' profiling not only could interpret the aroma style in meat but also could be another promising method for meat differentiation and authentication.

Effects of Grain Refinement and Thermal Aging on Atomic Scale Local Structures of Ultra-Fine Explosives by X-ray Total Scattering.

The atomic scale local structures affect the initiation performance of ultra-fine explosives according to the stimulation results of hot spot formation. However, the experimental characterization of local structures in ultra-fine explosives has been rarely reported, due to the difficulty in application of characterization methods having both high resolution in and small damage to unstable organic explosive materials. In this work, X-ray total scattering was explored to investigate the atomic scale local distortion of two widely applicable ultra-fine explosives, LLM-105 and HNS. The experimental spectra of atomic pair distribution function (PDF) derived from scattering results were fitted by assuming rigid ring structures in molecules. The effects of grain refinement and thermal aging on the atomic scale local structure were investigated, and the changes in both the length of covalent bonds have been identified. Results indicate that by decreasing the particle size of LLM-105 and HNS from hundreds of microns to hundreds of nanometers, the crystal structures remain, whereas the molecular configuration slightly changes and the degree of structural disorder increases. For example, the average length of covalent bonds in LLM-105 reduces from 1.25 Å to 1.15 Å, whereas that in HNS increases from 1.25 Å to 1.30 Å, which is possibly related to the incomplete crystallization process and internal stress. After thermal aging of ultra-fine LLM-105 and HNS, the degree of structural disorder decreases, and the distortion in molecules formed in the synthesis process gradually healed. The average length of covalent bonds in LLM-105 increases from 1.15 Å to 1.27 Å, whereas that in HNS reduces from 1.30 Å to 1.20 Å. The possible reason is that the atomic vibration in the molecule intensifies during the heat aging treatment, and the internal stress was released through changes in molecular configuration, and thus the atomic scale distortion gradually heals. The characterization method and findings in local structures obtained in this work may pave the path to deeply understand the relationship between the defects and performance of ultra-fine explosives.

Non-targeted analysis of unknown volatile components in scented stationery via headspace GC-Orbitrap MS.

This paper reports the non-targeted analysis of unknown volatile components in scented stationery based on headspace gas chromatography-Orbitrap high-resolution mass spectrometry. The volatiles released from the samples (22 scented erasers and 17 scented pens) under specific headspace conditions were analyzed. A qualitative analysis of unknown substances was carried out according to four identification steps (step 1: comprehensive score and retention index, step 2: identification of molecular ion peaks by chemical ionization, step 3: fragment ion detail comparison for distinguishing isomers, step 4: verification by chemical standards). A total of 101 volatile substances were identified in the scented erasers, and 86 volatile substances were identified in the scented pens. The identified substances were divided into eight categories. Aliphatic hydrocarbons, aromatic hydrocarbons, esters, and alcohols were the top four groups of substances identified in scented erasers and pens. The identified substances were further filtered and screened according to their detection rate, toxicity, and response intensity. Finally, 14 high-risk volatile chemicals in scented stationery were listed. This study can be used as a reference for identifying unknown substances and as a guide for monitoring volatile chemicals in products and assessing their possible risks to consumers.

Accurate Determination of 12 Lactones and 11 Volatile Phenols in Nongrape Wines through Headspace-Solid-Phase Microextraction (HS-SPME) Combined with High-Resolution Gas Chromatography-Orbitrap Mass Spectrometry (GC-Orbitrap-MS).

This paper clarifies the contribution of lactones and volatile phenols to the aroma of nongrape wine. A target method for the simultaneous determination of these two kinds of volatiles in nongrape wines was developed using headspace-solid-phase microextraction (HS-SPME) combined with high-resolution gas chromatography-Orbitrap mass spectrometry (GC-Orbitrap-MS). A high-resolution mass spectrometry database including 12 lactones and 11 volatile phenols was established for qualitative accuracy. Different matrix-matched calibration standards should be prepared for specific samples due to the matrix effects. The method was successfully validated and applied in three nongrape wines. Hawthorn wine contained more lactones (δ/γ-hexalactone, δ/γ-nonalactone, δ/γ-decalactone, γ-undecalactone, δ/γ-dodecalactone, C10 massoia lactone, and whiskey lactone), while blueberry wine contained more volatile phenols (especially 4-vinylguaiacol and 4-ethylguiaiacol). Goji berry wines contained certain concentrations of δ-nonalactone, γ-nonalactone, δ-hexalactone, and 3-ethyl phenol. This study demonstrated that HS-SPME-GC-Orbitrap-MS can be applied for the accurate quantification of trace aroma compounds such as lactones and volatile phenols in fruit wines.

Non-targeted analysis of unknown volatile chemicals in medical masks.

This paper reports the non-targeted analysis of unknown volatile chemicals in medical masks through headspace gas chromatography-Orbitrap high-resolution mass spectrometry. In view of the difficulties that may be encountered in the qualitative analysis of unknown substances, several typical cases and the corresponding reliable solutions are given from the perspective of comprehensive score and retention index, chemical ionization identification molecular formula, fragment ion detail comparison for distinguishing isomers, and identification of alkanes. With this method, 69 volatile substances were identified in 60 masks. The identified substances were divided into nine categories. Alkanes, esters, benzenes, and alcohols were the top four groups of substances identified in masks and accounted for 34.8%, 15.9%, 10.1%, and 7.2% of the total substances, respectively. In addition, ketones, ethers, phenolics, amides, and other substances were identified. Ethanol, 1,4-dichlorobenzene, toluene, m-xylene, dimethyl glutarate, and N,N-dimethylacetamide had high detection rates. The identified substances were further filtered and screened according to their detection rate, toxicity, and response intensity. Finally, 12 high-risk volatile chemicals in medical masks were listed. This study could serve as a reference for identifying unknown substances and a guide for monitoring volatile chemicals in masks and promoting chemical safety improvements in products.

Non-targeted identification of unknown chemical hazardous substances in infant teether toys by gas chromatography-Orbitrap high resolution mass spectrometry.

Chemical hazardous substances in teethers may migrate into infant's body through oral exposure, resulting in a potential health risk. In recent years, researchers have performed a series of studies for detecting target chemicals in teethers and other toys, but the presence of unknown chemicals has not been systematically investigated yet. This paper reports the non-targeted identification of unknown chemical hazards that may have migrated from teethers to infants based on gas chromatography-Orbitrap high resolution mass spectrometry. In view of the difficulties that may be encountered in the qualitative analysis of substances, several typical cases and the corresponding reliable solutions are given from the perspective of comprehensive score and retention index, isotope-aided qualitative analysis, chemical ionization identification formula, and fragment ion detail comparison for distinguishing isomers. Finally, 28 substances are identified in 10 teether samples. Among them, phenol, N-methylaniline, 1,6-dioxacyclododecane-7,12-dione and cyclohexanone have higher detection rates. This study not only has valuable reference for the identification of unknown substances, but also has positive guiding role in monitoring potential chemical hazards in toys and promoting the safety of products.

[Determination of 2,4,6-trichloroanisole in wine by head-space solid phase micro-extraction and gas chromatography-mass spectrometry].

OBJECTIVE: To establish a method of combining gas chromatography-mass spectrometry (GC-MS) with head-space solid phase micro-extraction (HS-SPME) for the detection of 2,4,6-trichloroanisole (2,4,6-TCA) in wine. METHODS: 2,4,6-TCA in wine were extracted by polydimethylsiloxane (PDMS,100 microm) fiber for 15 min under 35 degrees C in a water bath. The fiber was then transferred into the injection port of the GC-MS and separated by a CP-SIL 8CB-MS capillary column (30m x 0.25mm x 0.25 microm), and detected by mass spectrometry using d5-2,4,6-TCA as an internal standard. RESULTS: The linear range for 2,4,6-TCA was 5 (60ng/L, the detection limit was 0.06ng/L. The recovery of standard addition (5, 10, 20ng/L) was in the range of 79.8% (101.6% with relative standard deviations (RSD, n=5) < or = 7%. CONCLUSION: Organic solvents were avoided and the selection was sensitive for the method, which is suitable for the determination of 2,4,6-TCA in wine.