GC-MS Method Research Articles

Hydroxy Fatty Acids as Novel Markers for Authenticity Identification of the Honey Entomological Origin Based on the GC-MS Method.

The authenticity of honey is generally a worldwide concern, and there is a pressing need to establish a suitable entomological method to identify the authenticity of Apis cerana cerana (A. cerana) and Apis mellifera ligustica (A. mellifera) honey. Hydroxy fatty acids as bee-derived components are known to widely exist in honey and other biosamples. Herein, we present an identification strategy for hydroxy fatty acids based on the relative quantification with reference to royal jelly and targeted quantification combined with multivariate statistical analysis to identify the honey entomological origin. Multivariate statistical analysis was used to further determine differential hydroxy fatty acids between A. cerana honey and A. mellifera honey. Results showed that 8-hydroxyoctanoic acid (96.20-253.34 versus 0-32.46 mg kg-1) and 3,10-dihydroxydecanoic acid (1.96-6.56 versus 0-0.35 mg kg-1) could be used as markers for accurate identification of the honey entomological origin, while the three fraud honey samples were recognized using this method. This study provides the novel marker hydroxy fatty acids to identify A. cerana honey and A. mellifera honey from the perspective of bee-derived component differences.

Cellulose Paper Sorptive Extraction (CPSE) Combined with Gas Chromatography–Mass Spectrometry (GC–MS) for Facile Determination of Lorazepam Residues in Food Samples Involved in Drug Facilitated Crimes

Reports related to incidences of drug facilitated crimes (DFCs) have notably increased in recently. In such cases, victims report being assaulted or robbed while under the influence of drugs. Lorazepam (LZ) is frequently used in DFCs as it can easily make victims docile owing to its potent numbing effect. Therefore, a straightforward and green analytical method to analyze LZ in spiked food matrices in connection with criminal acts becomes important. The current study reports a simple, green, and high sample throughput analytical method for determining LZ in food and drink matrices commonly encountered in DFCs, based on recently introduced cellulose paper sorptive extraction (CPSE). For the extraction of LZ from food matrices, pristine cellulose paper (CP, commonly used laboratory filter paper) was used as a sorptive medium. Five pieces of CP (1.5″ × 1.5″ each) were dipped into diluted food matrices (cream biscuits and tea) and stirred on a rotary shaker for 30 min at 200 rpm. The CPs were then dried, and the adsorbed LZ was back-extracted into 2 mL of methanol. The extract was then subjected to GC–MS analysis in selected ion monitoring (SIM) mode. Several parameters, including CP size and number, back-extraction solvent type and volume, sample volume, extraction time and stirring speed, pH, ionic strength, elution time and speed, were thoroughly screened and optimized. Under the optimized conditions, the method was found to be linear in the range of 0.2–10 µg·mL−1 (or µg·g−1) with a coefficient of determination (R2) ranging from 0.996–0.998. The limit of detection and limit of quantification for cream biscuits were 0.054 and 0.18 µg·g−1 whereas they were 0.05 and 0.16 µg·mL−1 for tea samples. For all measurements, the relative standard deviations (%RSD) were always below 10%. Two mL of methanol per sample was used during the entire sample preparation process. The greenness of the proposed procedure was evaluated using Analytical Eco-Scale and GAPI greenness assessment tools. Finally, the CPSE–GC–MS method has been applied for the determination of LZ in forensic food samples which were used in DFCs.

Comparison between Hydroalcoholic (Ethanolic and Methanolic) of Broccoli Floret (Brassica Oleracea) Extract by GC-MS Method and its Antioxidant Effect by DPPH Method

Introduction: The amount of active ingredients in natural medicines depends on the method and solvent of the extractor. Therefore, the aim of this study was to compare the antioxidant activity of aqueous ethanolic and aqueous methanolic extracts of broccoli.
 Methods: In this observational-analytical study, after preparing broccoli from farms of Lorestan City, Iran and approval of the herbarium center, ethanolic and methanolic extracts were obtained by maceration and vacuum concentrating. Then it was analyzed using a GC-MS device. Moreover, the total phenol, flavonoids, and anti-radical properties of the extracts were measured. The results were statistically analyzed using SPSS version 16 software and independent t-test and regression coefficient. A significance level of P<0.05 was considered.
 Results: The total phenol content of hydroalcoholic (ethanolic and methanolic) extracts was 41.52 ±5.40 and 33.03±0. 37 (mg GAE / g dw), respectively, but this difference was not significant (P <0.05). The total flavonoid content in aqueous methanolic and aqueous ethanolic extracts was 40.36 ± 1.93 and 28.79 ± 1.49 (mg Q/g dw), respectively, and this difference was significant (P <0.05). The result of inhibition of DPPH free radicals by broccoli extracts showed an increase, and in terms of effective concentration, a significant difference was seen between ethanolic and methanolic extracts (P<0.05). Moreover, the highest free radical scavenging activity was 92.1% in aqueous methanolic extract and 72.8% in aqueous ethanolic extract. The mean values ​​of the active chemical compounds of sulforaphane in GC-MS analysis of different extracts of broccoli were significant (P <0.01). The percentage of sulforaphane in the aqueous methanolic extract was 14.86 and in the aqueous ethanolic extract was 1.41.
 Conclusion: According to the results, broccoli aqueous methanolic extract can be recommended in vivo for experimental studies with strong antioxidant potential.

Pyrolysis GC-MS Characterization of Plastic Debris from the Northern Gulf of Alaska Shorelines

Plastics and their breakdown components are accumulating at alarming rates in global ecosystems, including the Gulf of Alaska. Obtaining knowledge of the chemical composition of plastics is important because different types of plastics are manufactured using different types of polymers and copolymers for specialized applications. We employed pyrolysis GC-MS for the chemical characterization of 115 plastic debris samples of different physical and optical properties nonrandomly collected from shorelines in the northern Gulf of Alaska. A two-tier approach of peak fingerprinting and mass spectral data of marker peaks provided higher confidence in the data. The analyses did not appear to be compromised by the physical properties, optical properties, or weathering conditions of the debris. Polyethylene and polypropylene, the low-density floating plastics possibly of oceanic origins, were some of the most frequently detected polymers in the Katmai National Park and Preserve and Kenai Fjords National Park. Interestingly, a more diverse composition of polyethylene, polypropylene, polystyrene, poly(ethylene terephthalate), and poly(vinyl chloride) was detected in Western Prince William Sound shorelines, possibly of oceanic as well as terrestrial origins. Additional benefits of the pyrolysis GC-MS method included the detection of copolymers and plastic additives in the same analytical runs.

Chemical composition, nutritional values, elemental analysis and biological properties of Prunus mahaleb L.: From waste to new potential sources for food, cosmetic and drug industry

Prunus mahaleb L. seeds are widely used in the baking industry as spice for flavouring. While achieving the mahaleb powder for commercial use in local companies, the seeds are sometimes mixed unintentionally with their kernels (stony shell) during sieving procedure. As the chemical and biological properties of the kernel of seeds are not well known, the kernel, seeds and the market sample obtained from a local supplier are decided to investigate individually. The antioxidant capacity and the trace element analyses of the seeds and kernels were performed by TEAC and CUPRAC assays and ICP-MS. The market sample was analysed for nutrient and oil composition. Fatty acid composition of the oil was determined with GC-FID and GC-MS methods. The chemical composition of the methanol extract of the seeds and kernels was studied by LC-MS/MS. Trace elements Mn, Co, Ni, Cu, Zn and Se were determined in the methanol extracts, ethyl acetate and water fractions. Mushroom tyrosinase enzyme inhibitions of 33 different extracts and fractions of various waste parts of the plant (kernel, fruit, twigs, flos, leaves) were investigated. The nutritional values showed that the market sample had high nutritious properties. The fatty acid content of the oil was found to be valuable in remedying dysfunctions of the body. Kernel ethylacetate fraction showed the highest tyrosinase enzyme inhibition. The role of copper element on enzyme activity was determined. The kernels are accepted as a waste material may also be evaluated as a good promising choice for food, cosmetic and drug industry.

A new JECFA method for GC-MS determination of propylene chlorohydrine residues in hydroxypropylated starches.

Propylene chlorohydrins (PCH) are formed as byproducts in the reaction between starch and propylene oxide (PO). For hydroxypropylated starch (HP-starch) applications in food, JECFA set the maximum allowed total propylene chlorohydrin (PHC-t) residues level at 1 mg/kg. To develop an improved analytical method for the determination of the PCH-t content in starches in the low mg/kg range to replace the outdated JECFA method. A new GC-MS method that utilizes aqueous methanol as extraction medium for PCH. The GC-MS system is equipped with a programmable temperature vaporization injector and Stabilwax-DA column using helium as carrier gas. The quantitative detection is achieved in the selected ion monitoring mode. This single laboratory validation (SLV) study showed good linear calibrations for both 1-chloro-2-propanol (PCH-1) and 2-chloro-1-propanol (PCH-2) in the concentration range of 0.5-4 mg/kg in dry starch. The lower limit of quantitation of PCH-1 and PCH-2 was 0.2-0.3 mg/kg in dry starch, the relative standard deviation reproducibility (RSDR) at the concentration level of 1-2 mg/kg in dry starch was 3-5%, and the recovery values for both PCH-1 and PCH-2 were in the range of 78-112% at a concentration level of about 0.6 mg/kg in dry starch.Compared with the current, outdated JECFA method, the new GC-MS method is more sustainable, less laborious and therefore more economical. The analytical capacity of the new method is 4-5 times higher than the analytical capacity of the old JECFA method. The GC-MS method is fit for a Multi Laboratory Trial (MLT). Based on the results of this SLV and the MLT (will be published in a second paper), the Joint FAO/WHO Expert Committee on Food Additives has recently decided to replace the outdated GC-FID JECFA method for the new GC-MS method for the determination of PCH-t content in starches.

Profile and Bioactivity of Bioactive Compounds of Beauveria bassiana Fungi Entomopathogens of Endophytes as Plant Growth Boosters

The purpose of this study was to identify bioactive compounds of Beauveria bassiana entomopathogenic fungi derived from insect isolates of Leptocorisa oratorius and endophytic fungi B. bassiana from cocoa plants that have bioactivity as growth boosters. The research was conducted in the laboratory of Biological Control, Faculty of Agriculture, Andalas University. The study was conducted for 4 months, using the GCMS method. From the results of the study, bioactive compounds identified as growth boosters of B. bassiana endofyt fungi from cocoa plants are compounds Acetic acid, Ethanoic acid, Ethylic acid, Glacial acetic acid, CH 3 COOH; n- Hexadecanoic acid Hexadecanoic acid, Palmitic acid; 9-Octadecenoic acid (2)-(CAS), Oleic acid, Red oil, Oelsaure; octadecanoic acid (CAS) Stearic acid, n-Octadecanoicacid, vanilla; Ergosta-5,7,22-trien-3-ol, (3.,beta.,22 E) – (CAS), Ergosterol (CAS); while from the entomopathogenic B. bassiana fungus from L. oratorius insects are Acetic acid (CAS), Ethylic acid, vinegar acid, Ethanoic acid, CH3COOH, Dianhydromannitol; Isosorbide, D-Glucitol,1,4-3,6-dianhydro-(+)-D-Isosorbide Devicoran; Hexadecanoic acid, methyl ester (CAS), Methyl palmitate, Uniphat A60; n-Hexadecanoic acid Hexadecanoic acid, n- Hexadecanoic acid, Palmitic acid; 9-octadecenoic acid, methyl ester, (E)-elaidic acid; 9-octadecanoic acid (Z)-(CAS) , oleic acid, Red oil, Oelsauere; octadecanoic acid, stearic acid, -n-octadecanoic acid, Humko Industrene R; Ergosta-5,7,22-trien-3-ol, (3.beta.,22E)-CAS, Ergosterol (CAS )

Influence of original and additive AAEMs on the migration and transformation of N by pyrolysis in Fushun oil shale

Oil shale contains a large amount of nitrogen compounds during pyrolysis, which will lead to a decline in the quality of shale oil and produce a large number of PM2.5 precursors. To study the migration and transformation of N during the pyrolysis, fixed-bed pyrolysis experiments were conducted on oil shale with different pyrolysis temperatures (500 ℃、600 ℃、700 ℃、800 ℃) and residence times (20 min、40 min), meanwhile, the migration and transformation of single AAEMs on the N of oil shale pyrolysis, the acid-wash samples were loaded with the original and higher concentrations of metals (K2CO3, CaCO3, Na2CO3, MgCO3) according to the ICP results and subjected to experiments at 600 °C - 20 min, the obtained products were analyzed by XPS、GC-MS and solution absorption method. The results revealed that higher temperatures promoted the enrichment of nitrogen-containing molecules in tar, and longer residence durations also led to an increase. Some mineral components in oil shale facilitated the conversion of semi-coke nitrogen to oil-phase nitrogen. An elevated loading concentration caused the catalytic cleavage of macromolecular nitrides. With an increase in temperature, NH3 and HCN exhibited two distinct peaks, respectively. AAEMs encouraged the production of NH3 but limited the content of HCN, where Ca played a more important function than K. The N transformation route was identified by contrasting the effects of reaction temperatures、residence times and AAEMs on N distribution.

A smartphone-based fluorospectrophotometer and ratiometric fluorescence nanoprobe for on-site quantitation of pesticide residue

Cost-effective and user-friendly quantitation at points-of-need plays an important role in food safety inspection, environmental monitoring, and biomedical analysis. This study reports a stand-alone smartphone-based fluorospectrophotometer (the SBS) installed with a custom-designed application (the SBS-App) for on-site quantitation of pesticide using a ratiometric sensing scheme. The SBS can collect fluorescence emission spectra in the wavelength range of 380-760nm within 5s. A ratiometric fluorescence probe is facilely prepared by directly mixing the blue-emissive carbon nanodots (the Fe3+-specific fluorometric indicator) and red-emissive quantum dots (the internal standard) at a ratio of 11.6 (w/w). Based on the acetylcholinesterase/choline oxidase dual enzyme-mediated cascade catalytic reactions of Fe2+/Fe3+ transformation, a ratiometric fluorescence sensing scheme is developed. The practicability of the SBS is validated by on-site quantitation of chlorpyrifos in apple and cabbage with a comparable accuracy to the GC-MS method, offering a scalable solution to establish a cost-effective surveillance system for pesticide pollution.

Isolation and characterization of sex specific cuticular hydrocarbons in non-Drosophila, Phorticella striata (Sajjan and Krishnamurthy, 1975) (Diptera, Drosophilidae)

Cuticular hydrocarbons are the major organic compounds synthesized by oenocytes. The CHCs act as sex pheromones, cell communicators, inhibits dissection, and chemotaxonomic cues. The CHCs were isolated from non-Drosophila species Phorticella striata (Sajjan and Krishnamurthy, 1975) (Diptera, Drosophilidae) by employing whole body extract through GCMS method. Among the identified organic compounds, a total of 38 compounds were obtained from male flies and 68 organic compounds were isolated from female flies, Majority of the CHCs identified were methyl branched alkanes, some of them were esters and alcohols. Male flies exhibit 15 specific CHCs in which tetradecane, 2, 6, 10-trimethylwas dominant with a relative abundance (15.60%) and cyclopropane tetradecanoic acid was the least found CHCs with a relative abundance (RA) of 0.75 per cent. The flies exhibit 28 female specific CHC‘s, among them tetradecane was dominant (r value of 19.20%) and Iodomethyl undecane was the least (RA=0.70%). Both male and female flies shared 23 CHCs, but the ratio among them showed great variance. Among the shared CHCs 3-Trifluoroacetoxy dodecane was dominant in female (RA=14.50%), the male exhibited RA of 4.66 per cent. In male flies 3-Trifluoroacetoxy pentadecane was most abundant CHC (RA=10.90%), than female (4.31%).

Development of qualitative GC MS method for simultaneous identification of PM-CCM a modified illicit drugs preparation and its modern-day application in drug-facilitated crimes

Prescriptions for psychoactive substances such as Pregabalin, Methamphetamine, Caffeine, Clonazepam and Mirtazapine (PM-CCM) are common in the treatment of a variety of disorders. Indeed, the PM-CCM has been used in different therapeutic areas, including insomnia, anxiety, seizure disorders, etc. Unfortunately, these psychoactive substances are present in the illegal street market, leading to a lot of drug abuse among some addicted users, road insecurity and suicide. Hence, it has become essential to validate and develop a rapid and effective method to analyze the PM-CCM, a modified illicit drug, for drug abuse in the forensic sciences. A simple, rapid, specific and sensitive Gas Chromatography-Mass Spectrometry(GC-MS) method has been developed for the identification of Pregabalin, Methamphetamine, Caffeine, Clonazepam and Mirtazapine (PM-CCM) in forensic exhibits. At room temperature, the sample was ultrasonicated for 5 minutes before being extracted with methanol. A highly precise auto-injector is used to inject a very small quantity of samples for analysis. Helium is used as a carrier gas with a flow rate of 1 ml/min. The separation of PM-CCM was performed on SH-RXi-5 MS, ID.25 mm, film thickness. 25 µm, length of 30 m column. The constituents of PM-CCM were identified by the mass-to-charge ratio (m/z ratio) of fragments of the parent compound by comparing them with the NIST-17 MS Library. Separation and identification of PM-CCM were achieved within a 15-minute run. The proposed method has been successfully used for the routine analysis of PM-CCM in complex illicit drug preparations and in forensic exhibits as well. The application of above discussed qualitative analysis method and screening of PM-CCM, modified illicit drug samples demonstrates the potential and applicability of the technique to the fast chemical profiling of illicit samples.

Assessment of Cytotoxic Effects of Latex from <i>Cascabela thevetia</i> (L.) Lippold and <i>Plumeria alba</i> L. via <i>In vitro</i> and <i>In silico</i> Approaches

Plant latex has been found to occur in more than 40 families and among them, Apocynaceae is one. Two plants of this family i.e., Cascabela thevetia (L.) Lippold and Plumeria alba L. had been chosen for the current experimental work. The aqueous and methanolic latex extracts were evaluated for their phytochemical constituents and cytotoxic activities. To determine the cytotoxic effects of the latex extracts, MTT [3-[4,5-dimethylthiazol-2-yl]-2,5- diphenyltetrazolium bromide] assay was performed by using cell lines A549 Human Lung Cancer and MCF-7 Human Breast Cancer. Further, for confirmation of the cytotoxic effects apoptosis assay was conducted. The richness of the latex extracts was determined by GC-MS and HPTLC methods. The preliminary phytochemical analysis of the latex extracts was conducted using GC-MS methodology. The presence of cardiac glycosides was analyzed using High-Performance Thin Layer Chromatography. Here, Digoxin was used as the standard. Studies have revealed that Na+ K+-ATPase can serve as a powerful target for developing anticancer drugs and cardiac glycosides have exhibited anticancer effects via inhibition of the Na+ K+-ATPase. Hence, molecular docking studies were conducted in which 6KPX served as the target and the compounds evaluated by the NIST library in GC-MS served as the ligands. Further, Molecular docking studies confirmed the best among the compounds based on their RF score, binding affinity, and as a binder whether these compounds were good or bad. These methodologies altogether helped in evaluating the richness of the plant latex extracts, and the potent cytotoxic molecules present in them.

Enhanced removal of organic matter from oxygen-pressure leaching solution by modified anode slime

Organic matter has become a typical harmful impurity, posing a serious problem and catastrophic effects in the hydrometallurgical extraction of zinc. The highly efficient and inexpensive method for the removal of organics from the leaching solution is of great practical significance for the efficient operation of zinc hydrometallurgy. For this reason, the removal of organic matter from oxygen-pressure leaching solution using modified anode slime was investigated by TOC analysis, FTIR spectroscopy, XRD, GCMS, and other characterization methods, and its mechanism was also discussed. The results show that the removal of organic matter using anode slime modified with sulfuric acid was significantly improved, and the removal of TOC reached 57.83% for anode slime modified at a temperature of 80 °C with a ratio of sulfuric acid to anode slime of 14 mL/100 g, which was more than 2.7 times that of untreated anode slime. The good removal effect of organic matter using the modified anode slime could be attributed to the transformation of inert α-MnO2 to active MnOOH by concentrated sulfuric acid-mediated modification. It was also found that the acid–solid ratio and temperature exhibited a significant effect on the modification of anode slime. The XPS analysis results of Mn 2p, Mn 3s, and O 1s, combined with the XRD patterns of the modified products indicated that the modification of anode slime led to the conversion of MnO2 in anode slime to MnOOH in the presence of H2SO4. However, MnO2 was further converted into high crystallinity MnOOH, even MnSO4 when the temperature exceeded 80 °C or the acid–solid ratio exceeded 18 mL/100 g, resulting in the decreased degradation performance for organic matter. The characterization results of FTIR spectroscopy and GCMS show that modified anode slime does not exhibit a degradation effect on all types of organic substances in leaching solution; however, it is very effective for some alcohols, olefins, and esters.

STUDY OF THE CHEMICAL COMPOSITION OF STACHYS PALUSTRIS L. ESSENTIAL OIL PRODUCING IN THE ASTRAKHAN REGION

Samples of essential oil from the ground part of Stachys palustris L., which grows wild in the Astrakhan region, were obtained by hydrodistillation, and the dependence of its yield on the growing season of the plant was studied. The duration of the hydrodistillation process was set experimentally to study the dynamics of changes in the results of essential oil over time. The yield of essential oil is observed in % when converted to the weight of absolutely dry raw materials. The highest yield of essential oil was obtained from plants in the flowering phase (0.19–0.20%). Quantitative analysis of the main components of Stachys palustris L. essential oil was carried out by GC-MS method. The quantitative content of essential oil components was calculated from the areas of gas chromatographic peaks without using correction factors. It was found that the composition of the essential oil of Stachys palustris L. was very specific. 47 compounds belonging to various classes have been identified. It has been established that the composition of the essential oil of the Stachys palustris L. is very specific. 47 compounds corresponding to the class were identified. Compound classes include fatty acids and acid esters (36.23%), carbonyl compounds (14.25%) and oxygenated basic sesquiterpenes (12.90%), phenols (5.85%). Among the sesquiterpenoids, the predominant component of the essential oil is hexahydrofarnesylacetone (7.5%). The oil also contains (Z)-phytol (6.78%), thymol (4.2%), β-ionone (3.36%) and β-caryophyllene (2.87%). Nonspecific components of the essential oil of the taxon Stachys palustris growing in the Astrakhan region are coumarin (10.27%) and coumaran (0.36%).

Metabolites of Mangrove Sediment Bacteria from Semarang and Karimunjawa as Anti-Fungal and Antibacterial

Pathogenic bacteria are microorganisms that cause disease in humans because bacteria grow cosmopolitan with human life, both on land and underwater. This research aimed to obtain mangrove sediment bacteria that have the potential as antibacterial and antifungal bacteria from mangrove sediments in Semarang and Karimunjawa waters. Mangrove sediment bacteria that have the potential as antibacterial and antifungal bacteria from Semarang and Karimunjawa waters, as well as identification of their compounds using the GCMS method. Sediment samples were collected from Semarang and Karimunjawa, and bacterial screening and isolation were then carried out. Bacterial isolates were tested with pathogenic fungi Malassezia furfur and Candida albicans. As well as the pathogenic bacteria Staphylococcus aureus, Escherichia coli, and Staphylococcus typhi. Then, the potential bacteria were identified by the molecular DNA method and analyzed by the GC-MS method to determine the secondary metabolite compounds that act as antifungal and antibacterial. The results showed that the bacterial isolation of mangrove sediments from Karimunjawa and Semarang that had antibacterial activity against pathogenic bacteria E. coli, S. aureus, and S. typhi were 3 isolates, namely SKK 1 MA, SKS 2 ISP, and SKS 4 ISP. The 3 isolates also had antifungal activity against the fungal pathogens Malassezia furfur and Candida albicans. The molecular identification showed that the 3 potential isolates, namely SKK 1 MA, SKS 2 ISP, and SKS 4 ISP, were Bacillus sp., Bacillus cereus, and Alcaligenes faecalis, respectively. Results of the analysis of the content of bacteria as antifungal and antibacterial showed that the bacteria were dominated by the content of unsaturated fatty acids (omega 9) and saturated fatty acids. HIGHLIGHTS Pathogenic fungal infections are difficult to treat besides infections caused by pathogenic bacteria Natural substances produced by microorganisms are very diverse in structure and are an essential source in the search for new drugs for various diseases in humans, including infections by pathogenic fungi and pathogenic bacteria The mangrove sediment bacteria were found to have potential as antifungal and antibacterial and were proven to contain fatty acids Bacteria found to be useful as antifungal and antibacterial agents for various bio-industrial activities GRAPHICAL ABSTRACT

Investigation of Solid Phase Microextraction Gas Chromatography–Mass Spectrometry, Fourier Transform Infrared Spectroscopy and 1H qNMR Spectroscopy as Potential Methods for the Authentication of Baijiu Spirits

The baijiu spirit is often the focus of fraudulent activity due to the widely varying prices of the products. In this work, Solid Phase Microextraction Gas Chromatography (SPME GCMS), Fourier Transform Infrared (FTIR) Spectroscopy and 1H qNMR spectroscopy were evaluated as potential methods to authenticate baijiu samples. Data were collected for 30 baijiu samples produced by seven different distilleries. The data from the SPME GCMS and FTIR methods were treated by a Principal Component Analysis to identify clusters that would suggest chemical differences in the products from different distilleries. The results suggest that SPME GCMS has the potential to be a fully portable method for baijiu authentication. FTIR did not appear suitable for authentication but can be used to find the %ABV range of the sample. 1H quantitative NMR (1H qNMR) was utilized to quantify the ethanol concentrations and calculate the observable congener chemistry comprising ester, ethanol, methanol, fusel alcohol, and organic acids. Discrepancies in ethanol content were observed in three samples, and a lack of major congeners in two samples indicates the possible presence of a counterfeit product. Detailed and quantitative congener chemistry is obtainable by NMR and provides a possible fingerprint analysis for the authentication and quality control of baijiu style, producer, and the length of the ageing process.

Synthesis, crystal structure, Hirshfeld surface analysis, DFT and antihyperglycemic activity of 9-allyl-2,3,9,10a-tetrahydrobenzo[b]cyclopenta[e][1,4]diazepin-10(1H)-one

In this work, a novel benzodiazepine-2-one derivative (4) was synthesized by N-allylation of cyclopenta[e][1,5]benzodiazepine-2-one. The chemical structure of the target compound was confirmed by FT-IR, UV-Vis, 1H & 13C-NMR, GC-MS and single-crystal X-ray diffraction methods. Structural, topological, electronic and reactivity of new molecule were studied by using B3LYP/6-311++G** calculations in ethanol and in gas phase. Studies on charges, molecular electrostatic potentials, atoms in molecules (AIM), natural bond orbital (NBO), and frontier orbitals have evidenced that the seven membered diazepine ring play a very important role in the properties of (4) increasing its reactivity in ethanol. Good concordances are observed when the predicted IR, 1H-NMR, 13C-NMR and UV-Vis spectra are compared with the corresponding experimental ones. Complete vibrational assignments together with the scaled force constants are reported. The new compound was evaluated in vitro for their antihyperglycemic activity against α-amylase and α-glucosidase enzymes. Compound 4 was found to be more potent with IC50 value of 30.63 μM against α-glucosidase enzyme, compared to the reference drug “Acarbose” (IC50 = 113.60 μM) and exhibited good inhibitory activity against α-amylase enzyme with IC50 value of 133.8 μM as compared with the reference drug “Acarbose” (IC50 = 124.5 μM). Additionally, in silico molecular docking studies were carried out to confirm the experimental observations and investigate the efficacy of the title compound.

Quantitative analysis of ethanolamine plasmalogen species in red blood cells using liquid chromatography tandem mass spectrometry for diagnosing peroxisome biogenesis disorders

Plasmalogens are glycerophospholipids characterized by a vinyl-ether bond with a fatty alcohol at the sn-1 position, a polyunsaturated fatty acid at the sn-2 position, and a polar head at the sn-3 position, commonly phosphoethanolamine. Plasmalogens play crucial roles in several cellular processes. Reduced levels have been associated with Alzheimer’s and Parkinson’s disease progression. Markedly reduced plasmalogens are a classic feature of peroxisome biogenesis disorders (PBD) because plasmalogen synthesis requires functional peroxisomes. Particularly, severe plasmalogen deficiency is the biochemical hallmark of rhizomelic chondrodysplasia punctata (RCDP). Traditionally, plasmalogens are evaluated in red blood cells (RBCs) by gas-chromatography/mass-spectrometry (GC–MS), which cannot distinguish individual species. We developed a liquid-chromatography/tandem mass-spectrometry (LC-MS/MS) method to quantify eighteen phosphoethanolamine plasmalogens in RBCs to diagnose PBD patients, especially RCDP. Validation results showed a specific, robust, and precise method with broad analytical range. Age-specific reference intervals were established; control medians were used to assess plasmalogen deficiency in patients’ RBCs. Clinical utility was also confirmed in Pex7 deficient mouse models recapitulating severe and milder RCDP clinical phenotypes. To our knowledge, this is the first attempt to replace the GC–MS method in the clinical laboratory. In addition to diagnosing PBDs, structure-specific plasmalogen quantitation could help understand disease pathogenesis and monitor therapy.

A novel method for the therapeutic drug monitoring of biperiden in plasma by GC-MS using salt-assisted liquid–liquid microextraction

Biperiden is an anticholinergic agent with central effects. It is used in Parkinson's syndromes and in the treatment of extrapyramidal symptoms that occur with the use of various agents (neuroleptics, antipsychotics). It causes anticholinergic syndrome in high doses. For this reason, therapeutic drug monitoring of biperiden is important. This study, it was aimed to develop a validated GC-MS method for the therapeutic monitoring of biperiden in human plasma. Biperiden and internal standard biperiden-d5 were extracted from plasma using the salt-assisted liquid–liquid extraction method. The method was validated according to the European Medicines Agency (EMA), Bioanalytical method validation guidelines. The lower limit of quantification of the developed method was chosen as 0.5 ng/mL. The calibration curve of biperiden for the method was validated between 0.5 and 15 ng/mL, showing correlation coefficients >0.99. In addition, the developed method was used for the therapeutic drug monitoring of biperiden in real patient plasma.

Analytical Method Cluster Development for Comprehensive Characterisation of Suberinic Acids Derived from Birch Outer Bark.

Suberin is a complex polyester biopolymer, and it is practically impossible to estimate the real content of suberin in suberised plant tissues. This indicates the importance of the development of instrumental analytical methods for the comprehensive characterisation of suberin derived from plant biomass for the successful integration of suberinic products into biorefinery production chains. In this study, we optimised two GC-MS methods-one with direct sylilation, and the second with additional depolymerisation, using GPC methods with RI detector and polystyrene calibration and with a three-angle light scattering detector and an eighteen-angle light scattering detector. We also performed MALDI-Tof analysis for non-degraded suberin structure determination. We characterised suberinic acid (SA) samples obtained from birch outer bark after alkaline depolymerisation. The samples were particularly rich in diols, fatty acids and their esters, hydroxyacids and their corresponding esters, diacids and their corresponding esters, as well as extracts (mainly betulin and lupeol) and carbohydrates. To remove phenolic-type admixtures, treatment with ferric chloride (FeCl3) was used. The SA treatment with FeCl3 allows the possibility to obtain a sample that has a lower content of phenolic-type compounds and a lower molecular weight than an untreated sample. It was possible to identify the main free monomeric units of SA samples by GC-MS system using direct silylation. By performing an additional depolymerisation step before silylation, it was possible to characterise the complete potential monomeric unit composition in the suberin sample. For the molar mass distribution determination, it is important to perform GPC analysis. Even though chromatographic results can be obtained using a three- laser MALS detector, they are not fully correct because of the fluorescence of the SA samples. Therefore an 18-angle MALS detector with filters was more suitable for SA analysis. MALDI-Tof analysis is a great tool for the polymeric compound structural identification, which cannot be done using GC-MS. Using the MALDI data, we discovered that the main monomeric units that makes up the SA macromolecular structure are octadecanedioic acid and 2-(1,3-dihydroxyprop-2-oxy)decanedioic acid. This corresponds with GC-MS results, showing that after depolymerisation hydroxyacids and diacids were the dominant type of compounds found in the sample.