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1.
Artigo em Inglês | MEDLINE | ID: mdl-38460448

RESUMO

This work reports the characterization of the lipidic fraction of seven species of marine organisms gathered along the shoreline of the Po Delta Park of Emilia-Romagna Region (Italy) and of the north Adriatic Sea. Two species of oysters (Crassostrea gigas and Ostrea edulis), two species of clams (Chamelea gallina and Ruditapes philippinarum), one species of mussel (Mytilus galloprovincialis), one species of macroalgae (Ulva rigida), and one species of spiny dogfish (Squalus acanthias) were analyzed to characterize their fatty acids profile and related nutritional value. The lipid fraction was simultaneously extracted and transesterified into fatty acid methyl esters (FAMEs) by using a recently developed one-step microwave-assisted extraction/derivatization (MAED) method. The obtained FAMEs extract was analyzed by a rapid comprehensive multidimensional gas chromatography (GC × GC) method (30 min). The system was equipped with a reverse set of columns (polar × non-polar) connected through a reversed fill/flush flow modulator. The GC × GC system was coupled with a flame-ionization detector (FID) for both qualitative and quantitative purposes. The MAED- GC × GC-FID methodology was suitable in the context of samples containing high percentages of omega-3 PUFA. A total of 82 FAMEs were tentatively identified using standards, literature data, and the two-dimensional plot location. FAME profiles obtained with the proposed approach were comparable with reference methods (AOCS Ce 2b-11), showing no significant differences. Moreover, to determine the food nutritional value of the samples investigated, the most common nutritional indices (index of atherogenicity, index thrombogenicity, hypocholesterolemic/hypercholesterolemic ratio, health-promoting index, unsaturation index, and the fish lipid quality index) were calculated from FAME profiles. Among the samples investigated, Squalus acanthias presented the best nutritional score, while Ruditapes philippinarum had the worst score in 3 out of 6 indices.


Assuntos
Organismos Aquáticos , 60578 , Ácidos Graxos , Ulva , Animais , Ácidos Graxos/análise , Ionização de Chama/métodos , Micro-Ondas , Cromatografia Gasosa/métodos
2.
Methods Mol Biol ; 2789: 75-83, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38506993

RESUMO

Various organic solvents are widely used in the manufacturing, processing, and purification of drug substances, drug products, formulations, excipients, etc. These solvents must be removed to the lowest amount permitted, as they do not possess any therapeutic advantages and may cause undesirable toxicities. Therefore, a rapid and sensitive analytical method for the quantitation of residual solvents is needed. The following chapter presents a static headspace gas chromatographic (HSGC) method for determining the concentration of common residual solvents in various nanoformulations. An efficient and sensitive HSGC method has been developed using PerkinElmer's headspace autosampler/gas chromatographic system with a flame ionization detector (FID) and validated according to the International Conference for Harmonization (ICH) guideline Q3C. The method validation indicates that the method is specific, linear, accurate, precise, and sensitive for the analyzed solvents. The method is suitable for the analysis of 13 residual solvents (methanol, ethanol, acetone, diethyl ether, 2-propanol, acetonitrile, 1-propanol, ethyl acetate, tetrahydrofuran, dichloromethane, chloroform, 1-butanol, and pyridine) and utilizes an Elite 624 Crossbond 6% cyanopropylphenyl, 94% dimethylpolysiloxanes column with helium as a carrier gas.


Assuntos
Etanol , Metanol , Cromatografia Gasosa/métodos , Solventes/química , Ionização de Chama , Metanol/análise
3.
J Agric Food Chem ; 72(13): 7511-7516, 2024 Apr 03.
Artigo em Inglês | MEDLINE | ID: mdl-38517735

RESUMO

The determination of odor threshold values can be performed in various matrices, including air, and serves as a parameter to compare the potencies of odorous compounds. Typically, the odor thresholds in air are determined by gas chromatography-olfactory (GC-O) and referenced to an internal standard, most often (E)-dec-2-enal. Herein, a direct gas chromatography-flame ionization detector-olfactory analysis method for the determination of odor thresholds in air is reported. As model substrates for this novel approach, naturally occurring substances (R)-1-p-menthene-8-thiol as well as (3S,3aS,6R,7aS)-3,6-dimethyl-3a,4,5,6,7,7a-hexahydro-3H-1-benzofuran-2-one were used. The latter compound was synthesized from (-)-isopulegol and exhibited an extremely low odor recognition threshold of 1.9 × 10-6 ng L-1 air, the lowest value reported for a fungal aroma compound thus far.


Assuntos
Odorantes , Compostos Orgânicos Voláteis , Odorantes/análise , Cromatografia Gasosa-Espectrometria de Massas , Olfato , Cromatografia Gasosa , Ionização de Chama , Compostos Orgânicos Voláteis/química
4.
J Forensic Sci ; 69(3): 974-985, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38317608

RESUMO

Ethanol is the psychoactive substance identified most frequently in post-mortem specimens. Unfortunately, interpreting post-mortem ethanol concentrations can be difficult because of post-mortem alcohol redistribution and the possibility of post-mortem alcohol neogenesis. Indeed, in the time interval between death and sample collection, the decedent may be exposed to non-controlled environments for an extended period, promoting microbial colonization. Many authors report that in the presence of carbohydrates and other biomolecules, various species of bacteria, yeast, and fungi can synthesize ethanol and other volatile substances in vitro and in vivo. The aim of this study was to study the impact of several variables on microbial ethanol production as well as develop a mathematical model that could estimate the microbial-produced ethanol in correlation with the most significant consensual produced higher alcohol, 1-propanol. An experimental setup was developed using human blood samples and cadaveric fragments incubated under strictly anaerobic conditions to produce a novel substrate, "cadaveric putrefactive blood" mimicking post-mortem corpse conditions. The samples were analyzed daily for ethanol and 1-propanol using an HS-GC-FID validated method. The formation of ethanol was evaluated considering different parameters such as putrefactive stage, blood glucose concentration, storage temperature, and storage time. Statistical analysis was performed using the Mann-Whitney non-parametric test and simple linear regression. The results indicate that the early putrefactive stage, high blood glucose concentration, high temperature, and time of incubation increase microbial ethanol production. In addition, the developed mathematical equation confirms the feasibility of using 1-propanol as a marker of post-mortem ethanol production.


Assuntos
1-Propanol , Etanol , Mudanças Depois da Morte , Estudo de Prova de Conceito , Humanos , Etanol/análise , Manejo de Espécimes , Cromatografia Gasosa , Biomarcadores/análise , Biomarcadores/metabolismo , Depressores do Sistema Nervoso Central/análise , Toxicologia Forense , Concentração Alcoólica no Sangue , Cadáver , Temperatura , Modelos Teóricos , Ionização de Chama
5.
J Chromatogr A ; 1713: 464501, 2024 Jan 04.
Artigo em Inglês | MEDLINE | ID: mdl-37979511

RESUMO

A quantitative analytical method capable of determining the concentrations of 81 aroma-relevant wine volatiles covering nine orders of magnitude was developed and validated in this study. The method is based on stir bar sorptive extraction (SBSE) of 200 µL of wine diluted with 1.8 mL NaCl brine with pH 3.5. Volatiles thermally desorbed from the stir bars were separated in two runs in a heart-cut multidimensional gas chromatographic system and quantified using either a flame ionization detector (FID) in the first dimension (27 aroma compounds) or a mass spectrometer in the second dimension (54 aroma compounds, transferred to 22 cuts). Typical limits of compound detection lay around 0.02 mg/L by FID or ranged from 0.001 to 0.30 µg/L by mass spectrometry detector, liying below the corresponding odor thresholds in all cases. Linearity, reproducibility, and recovery were considered satisfactory for most compounds, with typical R2 values of 0.989-0.999, relative standard deviation below 10 % for 37 compounds and between 10 and 20 % for 44 compounds, and recovery rates of approximately 100 % (85-109 %) for all but acetaldehyde. An analysis of 20 wine samples completed our validation of the method, showing that a single-sample preparation procedure combined with heart-cut multidimensional two-detector gas chromatography can determine wine volatile concentrations ranging from 350 mg/L of isoamyl alcohol to 3.8 ng/L of 3-isobutyl-2-methoxypyrazine.


Assuntos
Vinho , Vinho/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Odorantes/análise , Ionização de Chama , Reprodutibilidade dos Testes , Espectrometria de Massas
7.
Anal Methods ; 15(44): 6040-6047, 2023 11 16.
Artigo em Inglês | MEDLINE | ID: mdl-37916705

RESUMO

The current well-established chromatography and mass spectrometry based oil spill identification procedures, such as those outlined by the European Committee for Standardization, are highly reliable as methods, highly defensible in the court of law, and widely applicable to the majority of oil spill situations. Nevertheless, the methodology is time consuming and labour intensive, which may not be ideal when dealing with an emergency oil spill situation. In this study, direct analysis in real time time-of-flight mass spectrometry (DART/TOFMS) was used to successfully develop an efficient oil identification method. To confirm the accuracy of this method spilled oil samples were tested from five previous years of blind round robin testing organized by the oil spill identification network of experts (OSINET) under the Bonn Agreement. Heatmap inspection, principal component analysis and finally discriminant analysis of principal components were used to arrive at final predictions regarding the identities of the spilled oil samples. The results were compared with the results of previous gas chromatography flame ionization detection (GC/FID) and gas chromatography triple quadrupole mass spectrometry (GC/MS/MS) analyses of the same oils. While taking only about a tenth of the time, the DART/TOFMS analysis produced results similar to those of classical GC/FID and GC/MS/MS (EI+) procedures. The ability of DART/TOFMS to display this level of validity exemplifies its potential to be a new tool for supplementing classical analyses for oil spill forensics.


Assuntos
Óleos , Espectrometria de Massas em Tandem , Cromatografia Gasosa-Espectrometria de Massas/métodos , Ionização de Chama/métodos , Medicina Legal
8.
Anal Chim Acta ; 1280: 341878, 2023 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-37858543

RESUMO

Simple approach for rapid screening of corona virus disease 2019 (COVID-19) has been developed. This applied gas chromatography-flame ionization detector (GC-FID) analyzing the potential compound marker in sweat samples obtained from COVID-19 positive and negative volunteers in Bangkok, Thailand. The samples were collected by using cotton rods for 15 min, heated at 90 °C for 5 min, and the volatile compounds in the headspace (HS) were injected (5.00 mL) at 150 °C and separated within 13.7 min. The marker peak was tentatively identified as p-cymene by the authentic standard injection and comparison with the GC-mass spectrometry (GC-MS) and comprehensive two-dimensional GC (GC × GC)-MS analysis. Possible mechanisms for the presence of p-cymene were proposed. The marker peak area thresholds were then varied and optimized via construction of the receiver operating characteristic (ROC) curve. With the optimum threshold, the established method offered the accuracy, sensitivity and specificity of 96 %. This method was insignificantly affected (p-value >0.05) by genders, body mass indices, ages, and use of deodorants as well as the p-cymene containing food. However, the performance could be affected by the population with personal hygiene or experiencing the microbiomes producing p-cymene.


Assuntos
COVID-19 , Suor , Masculino , Feminino , Humanos , Ionização de Chama/métodos , Cromatografia Gasosa-Espectrometria de Massas/métodos , COVID-19/diagnóstico , Tailândia
9.
Anal Methods ; 15(35): 4427-4433, 2023 09 14.
Artigo em Inglês | MEDLINE | ID: mdl-37646200

RESUMO

Volatile amines are reagents commonly used in pharmaceutical manufacturing of intermediates, active pharmaceutical ingredients (APIs), and drug products as participating regents for chemical reactions and optimization of product yield. Due to their compound specific daily allowable intake, residual volatile amines are required by regulatory agencies to be monitored and controlled in pharmaceutical products intended for human consumption. However, the accurate quantification of residual volatile amines in pharmaceutical entities can often be challenging as these analytes may chemically react and/or interact with the sample matrix. Herein, we describe a simple and universal headspace gas chromatography with flame ionization detection (HS-GC-FID) method capable of separating 14 commonly used volatile amines. The chemical activity of the volatile amines with the API matrix were mitigated by using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as an additive to reduce matrix effects in conventional high-boiling diluents. The addition of DBU drastically improved the detectability and method accuracy of the residual volatile amines in an acidic API, namely, Ketoprofen®. Additionally, DBU was employed as a GC deactivation reagent to ensure interfacial adsorption of the analytes to GC components were reduced, thereby improving method precision. Method validation showed acceptable linearity, limit of detection, limit of quantitation, solution stability, precision, and robustness. Separation specificity, evaluated by observing the chromatographic resolution of the volatile amines with one-another and against a set of 23 common residual solvents, were shown to be acceptable for most peak pairs.


Assuntos
Aminas , Projetos de Pesquisa , Humanos , Cromatografia Gasosa , Ionização de Chama , Excipientes
10.
J Nat Med ; 77(4): 829-838, 2023 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-37450205

RESUMO

Safranal is one flavor component of saffron, which is used as a spice, food additive, and crude drug. In ISO3632, safranal is defined as the compound that contributes to the quality of saffron, and many quantitative determination methods for safranal have been reported. However, safranal is volatile and degrades easily during storage, and an analytical standard with an exact known purity is not commercially available, making it difficult to quantify accurately the content of safranal in saffron. Here, we developed a method for quantifying safranal using relative molar sensitivity (RMS), called the RMS method, using a GC-flame ionization detector (GC-FID). We determined the RMS of safranal to 1,4-bis(trimethylsilyl)benzene-d4, a certified reference material commercially available, by a combination of quantitative NMR and chromatography. Using two GC-FID instruments made by different manufacturers to evaluate inter-instrument effect, the resultant RMS was 0.770, and the inter-instrument difference was 0.6%. The test solution, with a known safranal concentration, was measured by the RMS method, with an accuracy of 99.4-101%, repeatability of 0.81%, and reproducibility of 0.81-1.3%. Given the ease of degradation, high volatility, and uncertain purity of safranal reagents, the RMS method is a more accurate quantification approach compared to the calibration curve method and methods based on absorption spectrophotometry. Moreover, our findings revealed that the GC-FID makeup gas affected the RMS and quantitative values.


Assuntos
Crocus , Crocus/química , Ionização de Chama , Reprodutibilidade dos Testes , Extratos Vegetais/química , Terpenos/metabolismo , Cicloexenos/análise , Cicloexenos/metabolismo
11.
Food Chem ; 425: 136434, 2023 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-37269638

RESUMO

Yoghurt fermented under sub-lethal high pressure (10, 20, 30 and 40 MPa at 43 °C), and afterward placed under refrigeration (4 °C for 23 days) was studied and compared with yoghurt fermented at atmospheric pressure (0.1 MPa). For a deeper analysis, metabolite fingerprinting by nuclear magnetic resonance (NMR), sugars and organic acids assessment by high performance liquid chromatography (HPLC), total fatty acids (TFA) determination and quantification by gas chromatography with a flame ionization detector (GC-FID) were performed. Metabolomic analyses revealed that only 2,3-butanediol, acetoin, diacetyl and formate vary with the increase of pressure and probable relation with pressure influenced diacetyl reductase, acetoin reductase and acetolactate decarboxylase. Yoghurts fermented at 40 MPa had the lowest content in lactose (39.7 % of total sugar reduction) and the less content in TFA (56.1 %). Further research is of interest to understand more about fermentation processes under sub-lethal high pressure.


Assuntos
Ácidos Graxos , Iogurte , Cromatografia Gasosa , Ácidos , Ionização de Chama , Fermentação
12.
Molecules ; 28(11)2023 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-37298869

RESUMO

The potential of endogenous n-alkane profiling for the assessment of extra virgin olive oils (EVOO) adulteration (blends with cheaper vegetable oils) has been studied by relatively few authors. Analytical methods used for this purpose often involve tedious and solvent-intensive sample preparation prior to analytical determination, making them unattractive. A rapid and solvent-sparing offline solid phase extraction (SPE) gas chromatography (GC) flame ionization detection (FID) method for the determination of endogenous n-alkanes in vegetable oils was, therefore, optimized and validated. The optimized method demonstrated good performance characteristics in terms of linearity (R2 > 0.999), recovery (on average 94%), and repeatability (residual standard deviation, RSD < 11.9%). The results were comparable to those obtained with online high-performance liquid chromatography (HPLC)-GC- FID ( RSD < 5.1%). As an example of an application to prove the potentiality of endogenous n-alkanes in revealing frauds, the data set obtained from 16 EVOO, 9 avocado oils (AVO), and 13 sunflower oils (SFO), purchased from the market, was subjected to statistical analysis and principal component analysis. Two powerful indices, namely (n-C29 + n-C31)/(n-C25 + n-C26) and n-C29/n-C25, were found to reveal the addition of 2% SFO in EVOO and 5% AVO in EVOO, respectively. Further studies are needed to confirm the validity of these promising indices.


Assuntos
Alcanos , Óleos de Plantas , Azeite de Oliva/química , Óleos de Plantas/química , Ionização de Chama/métodos , Cromatografia Gasosa/métodos , Óleo de Girassol , Solventes/análise , Extração em Fase Sólida/métodos
13.
Biomed Chromatogr ; 37(6): e5624, 2023 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-36920060

RESUMO

This study used a liquid-phase microextraction-based effervescent tablet-assisted switchable solvent method coupled to gas chromatography-flame ionization detection as an eco-efficient, convenient-to-use, cost-effective, sensitive, rapid, and efficient method for extracting, preconcentrating, and quantifying trace amounts of diazinon in river water samples. As a switchable solvent, triethylamine (TEA) was used. In situ generation of CO2 using effervescent tablet containing Na2 CO3 and citric acid changed the hydrophobic TEA to the hydrophilic protonated triethylamine carbonate (P-TEA-C). CO2 removal from the specimen solution using NaOH caused P-TEA-C to be converted into TEA and led to phase separation, during which diazinon was extracted into the TEA phase. The salting-out process was helpful in enhancing extraction efficiency. In addition, a number of significant parameters that affect extraction recovery were examined. Under optimum conditions, the limit of detection and limit of quantitation were 0.06 and 0.2 ng/ml, respectively. The extraction recovery percentage and pre-concentration factor were obtained at 95 and 190%, respectively, and the precision (inter- and intra-day, relative standard deviation %, n = 5) was <5%.


Assuntos
Diazinon , Microextração em Fase Líquida , Ionização de Chama/métodos , Solventes/química , Diazinon/análise , Dióxido de Carbono , Cromatografia Gasosa/métodos , Microextração em Fase Líquida/métodos , Água/química , Limite de Detecção
14.
Methods Mol Biol ; 2622: 221-226, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-36781764

RESUMO

Liposomes are composed of different kinds of lipids or lipophilic substances and are used as carriers of bioactive molecules. The characterization of the prepared liposomes consists of the calculation of the drug-to-lipid-molar ratio by measuring the lipids and the encapsulated molecule.The present work describes an analytical methodology for the simultaneous determination of all the lipid ingredients of liposome formulation using thin-layer chromatography coupled with a flame ionization detector (TLC/FID), employing the least possible sample quantity. The method consists of the chromatographic separation of the liposomal ingredients on silica gel scintillated on quartz rods and the subsequent detection of the ingredients by scanning the rods through hydrogen flame. The produced ions are detected by a flame ionization detector, and the signal is converted to a chromatogram.This method may be applied at every step of the liposome preparation for examining the quality of the raw materials, tracking possible errors in the preparation procedure, and finally analyzing the content of the final liposomal composition.


Assuntos
Lipídeos , Lipossomos , Lipossomos/química , Lipídeos/química , Ionização de Chama/métodos , Cromatografia em Camada Delgada/métodos
15.
J Breath Res ; 17(2)2023 01 27.
Artigo em Inglês | MEDLINE | ID: mdl-36634358

RESUMO

Assessing volatile organic compounds (VOCs) as cancer signatures is one of the most promising techniques toward developing non-invasive, simple, and affordable diagnosis. Here, we have evaluated the feasibility of employing static headspace extraction (HS) followed by gas chromatography with flame ionization detector (GC-FID) as a screening tool to discriminate between cancer patients (head and neck-HNC,n= 15; and gastrointestinal cancer-GIC,n= 19) and healthy controls (n= 37) on the basis of a non-target (fingerprinting) analysis of oral fluid and urine. We evaluated the discrimination considering a single bodily fluid and adopting the hybrid approach, in which the oral fluid and urinary VOCs profiles were combined through data fusion. We used supervised orthogonal partial least squares discriminant analysis for classification, and we assessed the prediction power of the models by analyzing the values of goodness of prediction (Q2Y), area under the curve (AUC), sensitivity, and specificity. The individual models HNC urine, HNC oral fluid, and GIC oral fluid successfully discriminated between healthy controls and positive samples (Q2Y = 0.560, 0.525, and 0.559; AUC = 0.814, 0.850, and 0.926; sensitivity = 84.8, 70.2, and 78.6%; and specificity = 82.3; 81.5; 87.5%, respectively), whereas GIC urine was not adequate (Q2Y = 0.292, AUC = 0.694, sensitivity = 66.1%, and specificity = 77.0%). Compared to the respective individual models, Q2Y for the hybrid models increased (0.623 for hybrid HNC and 0.562 for hybrid GIC). However, sensitivity was higher for HNC urine and GIC oral fluid than for hybrid HNC (75.6%) and hybrid GIC (69.8%), respectively. These results suggested that HS-GC-FID fingerprinting is suitable and holds great potential for cancer screening. Additionally, the hybrid approach tends to increase the predictive power if the individual models present suitable quality parameter values. Otherwise, it is more advantageous to use a single body fluid for analysis.


Assuntos
Neoplasias , Compostos Orgânicos Voláteis , Humanos , Ionização de Chama/métodos , Testes Respiratórios , Cromatografia Gasosa/métodos , Compostos Orgânicos Voláteis/análise , Análise dos Mínimos Quadrados , Neoplasias/diagnóstico
16.
Ann Pharm Fr ; 81(1): 64-73, 2023 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-35803334

RESUMO

OBJECTIVE: A simple and robust head space/gas chromatography with flame ionisation sensor (HS/GC/FIS) approach for the trace evaluation of carcinogenic impurity, methyl chloride, in trimetazidine dihydrochloride (TRD) drug ingredient and its formulation is described. METHOD: This HS/GC/FIS approach was based on separation and analysis of CH3Cl content on DB-624 [75.0m - length, 0.53mm - internal diameter, 3.0µm - film thickness] column using nitrogen as carrier gas flowing through the column at 3mL/min stream rate. Detection of eluted CH3Cl was accomplished with flame ionization sensor at a set temperature of 260̊C. RESULTS: The optimised HS/GC/FIS methodological approach was thoroughly validated, demonstrating that it was linear with range of 5.0ppm to 1508.4ppm, sensitive with detection limit of 1.65ppm and quantification limit of 5.01ppm, reproducible with RSD values of 2.10-2.35%, accurate with recoveries of 81.9-99.0%, robust with percent variation of 7.5-12.22% with respect to changes in oven temperature, injector temperature, detector temperature and practical for regular TRD quality control. CONCLUSION: The findings revealed that with this optimised HS/GC/FIS methodological approach, the trace amounts of carcinogenic impurity (methyl chloride) in TRD drug ingredient and formulation could be successfully measured.


Assuntos
Cloreto de Metila , Trimetazidina , Trimetazidina/análise , Cloreto de Metila/análise , Carcinógenos/análise , Cromatografia Gasosa/métodos , Temperatura , Ionização de Chama
17.
J Chromatogr A ; 1687: 463669, 2023 Jan 04.
Artigo em Inglês | MEDLINE | ID: mdl-36463647

RESUMO

Absolute content of terpenes in inflorescences of two strains of Cannabis sativa L., CAT 1 and CAT 3, has been determined. Twenty terpenes commonly present in these samples were quantified by solid phase microextraction combined with gas chromatography and flame ionization detection (SPME/GC-FID). High amounts of ß-myrcene, α-pinene, ß-pinene, limonene, (E)-ß-ocimene, ß-caryophyllene, α-humulene, (E)-nerolidol, and linalool, were found in both strains. Lower concentrations (< 20 µg·g-1) of other terpenes were also determined. Only (E)-ß-ocimene was detected at 50 µg·g-1 in CAT 3 whereas it was below the LOD in CAT 1. Concentrations of other compounds for which standards were not available, were estimated based on a response factor obtained from the calibration curves of compounds with similar chemical structures. Fingerprints of both CAT strains were obtained and the identities of most volatile compounds were assigned using gas chromatography coupled to mass spectrometer detector (GC-MS). Additionally, an assessment of variability of terpenes was achieved by analyzing ten plants of each strain grown under controlled conditions and harvested at the same time. This variability was about 20%, considering terpenes at concentration above 20 µg·g-1.


Assuntos
Cannabis , Terpenos , Terpenos/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Cannabis/química , Ionização de Chama
18.
J Anal Toxicol ; 47(3): 311-316, 2023 Mar 24.
Artigo em Inglês | MEDLINE | ID: mdl-36495201

RESUMO

A comparative evaluation of two methods used for carboxyhemoglobin (COHb) determination in postmortem whole blood was performed: carbon monoxide (CO)-oximetry measuring at 128 wavelengths and headspace gas chromatography with flame ionization detection (HS-GC--FID) where CO was determined after catalytic reduction of CO to CH4 and Fe was determined by atom absorption spectrophotometry (AAS, 248.3 nm). An aliquot of 100 µL whole blood was loaded into the CO-oximetry module. In the HS-GC--FID analysis, to 1.0 mL of whole blood, 3.0 mL of saponin solution was added, mixed and centrifuged. To 20 mL HS vials, 400 µL of the supernatant was added and the vials were immediately sealed. One milliliter of potassium hexacyanoferrat (III) solution was added through the HS septum and mixed. The samples were incubated at 70°C for 5 min. CO was separated using He as carrier gas and a CP-Molsieve 5 Å PLOT capillary column. Fe was determined using 400 µL of the saponin supernatant diluted to 10 mL by water. During a period of ∼3 years, 124 postmortem whole blood samples were analyzed. Bland-Altman method comparison showed satisfactory agreement and no significant bias between the methods for the whole saturation range (5 to 85% COHb). Five samples, all with %COHb >40, showed deviations of more than 10% COHb in absolute terms. One sample, in the lower COHb range <10%, was false negative on the CO-oximetry method. The between-assay accuracy, reported as bias, at 60% COHb was -0.8% and -9.0%, and precision, reported as relative standard deviation, was 1.6% and 7.7%, for the CO-oximetry and HS-GC--FID-AAS methods, respectively. Both methods obtained satisfactory results in proficiency testing rounds, with z-scores <±2 (n = 11). This study showed that the CO-oximetry method based on the 128-wavelength principle and the HS-GC--FID-AAS method are comparable and satisfactory for %COHb determination in postmortem whole blood.


Assuntos
Carboxihemoglobina , Oximetria , Masculino , Humanos , Carboxihemoglobina/análise , Ionização de Chama , Oximetria/métodos , Cromatografia Gasosa , Espectrofotometria Atômica
19.
J Anal Toxicol ; 46(9): e274-e279, 2023 Jan 24.
Artigo em Inglês | MEDLINE | ID: mdl-36346343

RESUMO

Headspace gas chromatography with a flame ionization detector (HS-GC-FID) is a well-established approach for determining blood alcohol concentration, including in cadaveric specimens. Although the integrity of blood specimens can be adequately guaranteed after the sampling, the quantification of ethanol in cadaveric blood can be affected by postmortem fermentative phenomena occurring between the time since death and the sampling of biofluids. The vitreous humor is less affected by putrefactive phenomena allowing compound determination and its use as an alternative biological matrix. The present work aimed to develop and validate a method using the salting-out effect and based on HS-GC-FID for the determination of ethanol in the vitreous humor. The reported analytical method is based on a simple vitreous humor pre-treatment consisting of a dilution (1:9) with a solution of 2.5 mol/L K2CO3 and 0.0012 mol/L tert-butanol (internal standard). After 1 min of incubation, part of the specimen evaporated in the headspace (2,000 µL) is injected into the chromatographic system and analyzed in isothermal mode (40°C), with a chromatographic time of 1.6 min. The method was validated in terms of selectivity, the lowest limit of detection, intraday and total imprecision, and trueness (bias). The determination of ethanol in the vitreous humor and blood was carried out in 75 cases. The correlation between the two matrices was confirmed in 61 cases. However, 14 vitreous humor specimens showed lower ethanol concentrations, and in the related blood specimens, it was possible to identify the signal of n-propanol, a typical product of postmortem microbial fermentation, that justifies the excess of ethanol in the blood specimens.


Assuntos
Etanol , Corpo Vítreo , Humanos , Ionização de Chama , Corpo Vítreo/química , Concentração Alcoólica no Sangue , Cromatografia Gasosa , Cadáver
20.
Drug Test Anal ; 15(4): 470-472, 2023 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-36366778

RESUMO

The original article described difference of total Δ9 -THC contents determined by gas chromatography with flame ionization detection (GC-FID) and high-performance liquid chromatography with ultraviolet detection (HPLC-UV). We presumed that this difference was mainly caused by peak overlapping of Δ9 -THC and presumptive cannabielsoin (CBE) isomer on the GC chromatogram.


Assuntos
Cannabis , Cannabis/química , Dronabinol/análise , Cromatografia Líquida de Alta Pressão/métodos , Ionização de Chama , Flores/química
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