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In forensic toxicology, a marker of street heroin use is urgent especially in the absence of urinary 6-monoacetylmorphine. ATM4G, the Glucuronide of Acetylated product of Thebaine compound 4 Metabolite (ATM4), arising from byproducts of street heroin synthesis has been considered as a useful marker in some European studies. However, whether ATM4G is a universal marker particularly in Southeast Asia due to 'street' heroin with high purity, it's still unclear. To investigate putative markers for different regions, ATM4G and other metabolites including the Acetylated product of Thebaine compound 3 Metabolite (ATM3) and thebaol, also originated from thebaine were detected in 552 urine samples from heroin users in Taiwan. Results were compared with that from samples collected in the UK and Germany. Only a sulfo-conjugate of ATM4, ATM4S, was detected in 28 Taiwanese users using a sensitive MS3 method whilst out of 351 samples from the UK and Germany, ATM4G was present in 91. Thebaol-glucuronide was first time detected in 118. No markers were detected in urine following herbal medicine use or poppy seed ingestion. The presence of ATM4S/ATM4G might be affected by ethnicities and heroin supplied in regions. Thebaol-glucuronide is another putative marker with ATM4G and ATM4S for street heroin use.
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Toxicologia Forense/métodos , Glucuronídeos/urina , Heroína/metabolismo , Detecção do Abuso de Substâncias/métodos , Sudeste Asiático , Europa (Continente) , Cromatografia Gasosa-Espectrometria de Massas/métodos , Heroína/urina , Humanos , Derivados da Morfina/urina , Tebaína/urinaRESUMO
This study aimed to develop an automated optical inspection (AOI) system that can rapidly and precisely measure the dimensions of microchannels embedded inside a transparent polymeric substrate, and can eventually be used on the production line of a factory. The AOI system is constructed based on Snell's law. The concept holds that, when light travels through two transparent media (air and the microfluidic chip transparent material), by capturing the parallel refracted light from a light source that went through the microchannel using a camera with a telecentric lens, the image can be analyzed using formulas derived from Snell's law to measure the dimensions of the microchannel cross-section. Through the NI LabVIEW 2018 SP1 programming interface, we programmed this system to automatically analyze the captured image and acquire all the needed data. The system then processes these data using custom-developed formulas to calculate the height and width measurements of the microchannel cross-sections and presents the results on the human-machine interface (HMI). In this study, a single and straight microchannel with a cross-sectional area of 300 µm × 300 µm and length of 44 mm was micromachined and sealed with another polymeric substrate by a solvent bonding method for experimentations. With this system, 45 cross-sectional areas along the straight microchannel were measured within 20 s, and experiment results showed that the average measured error was less than 2%.
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RATIONALE: The presence of α-pyrrolidinovalerophenone (α-PVP) and its metabolites in urine is evidence of the administration of α-PVP. A toxicological challenge is that the metabolites of α-PVP exhibit amphoteric properties, which make them unsuitable for detection using gas chromatography-mass spectrometry (GC/MS). In the study reported, proper derivatization and sample extraction were essential for improving the sensitivity for GC/MS analysis. METHODS: An automated solid-phase extraction (SPE) method has been developed and optimized. The derivatization efficiency was tested using longer reaction time and the addition of polar pyridine into a mixture of N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) with 1% trimethylchlorosilane. Method validation, including linearity, limit of detection, precision, accuracy, and recovery, was evaluated using automatic SPE and GC/MS. RESULTS: The results suggested that adding pyridine to BSTFA (1:1, v/v) significantly improved derivatization efficiency and precision. After optimization, the linear range was from 25 to 1000 ng mL-1 with R2 > 0.9950. The limit of detection was 5 ng mL-1 for α-PVP and 25 ng mL-1 for OH-α-PVP. The recovery for SPE was over 88%. The inter-day and intra-day precisions were less than 15%. A forensic sample has been found containing α-PVP (67.3 ng mL-1 ) and OH-α-PVP (560.2 ng mL-1 ). CONCLUSIONS: This study is the first to validate an auto-SPE-GC/MS method for the quantification and qualification of α-PVP and OH-α-PVP in urine. We have successfully improved the derivatization efficiency and developed a sensitive and semi-automatic approach. This approach is desirable for the detection of synthetic cathinone at trace levels in biological samples.
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Alcaloides/urina , Cromatografia Gasosa-Espectrometria de Massas/métodos , Pirrolidinas/urina , Alcaloides/metabolismo , Drogas Desenhadas/metabolismo , Drogas Desenhadas/farmacocinética , Humanos , Limite de Detecção , Pirrolidinas/metabolismo , Extração em Fase Sólida/métodos , Detecção do Abuso de Substâncias/métodosRESUMO
BACKGROUND/PURPOSE: Although illicit substance use-induced toxicity or complication is a frequent cause of visit to the emergency department (ED), there are limited data on cases confirmed by liquid chromatography tandem-mass spectrometry (LC-MS/MS) analysis. This study aimed to describe clinical presentations of patients who visited the ED because of acute illicit substance-related complications. METHODS: We performed a retrospective study between May 2017 and August 2018 on patients presenting to the ED with positive urine illicit substance analysis by LC-MS/MS. RESULTS: Of 203 patients with at least one illicit substance detected in their urine, 162 (79.8%) showed traditional illicit substances, and 56 (32.0%) showed new psychoactive substances (NPS). Methamphetamine was the most common illicit substance (67.9%). The most common NPS was ketamine (21.7%), followed by synthetic cathinones (14.8%). We divided patients into traditional, NPS and combined (both traditional illicit substance and NPS) groups. Polysubstance use was more common in the NPS group than in the traditional group (P < 0.001). Most patients were men (78.3%), and the average age was lower in the NPS group compared to the traditional group (P < 0.001). Although the chemical structures of cathinones are similar to that of amphetamine, 92.0% of the cathinone use cases without combination with methamphetamine use showed negative immunoassay results. CONCLUSION: Our study provided the acute illicit substance complications at ED by LC-MS/MS analysis in Taiwan. Our study showed that more than one-third cases studied were NPS users. Young adults and polysubstance users were more common among NPS users.
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Drogas Ilícitas , Transtornos Relacionados ao Uso de Substâncias , Cromatografia Líquida , Serviço Hospitalar de Emergência , Feminino , Humanos , Masculino , Estudos Retrospectivos , Detecção do Abuso de Substâncias , Transtornos Relacionados ao Uso de Substâncias/complicações , Transtornos Relacionados ao Uso de Substâncias/epidemiologia , Taiwan/epidemiologia , Espectrometria de Massas em TandemRESUMO
A new up-and-down shaker-assisted dispersive liquid-liquid microextraction (UDSA-DLLME) for extraction and derivatization of five chlorophenols (4-chlorophenol, 4-chloro-2-methylphenol, 2,4-dichlorophenol, 2,4,6-trichloro-phenol, and pentachlorophenol) has been developed. The method requires minimal solvent usage. The relatively polar, water-soluble, and low-toxicity solvent 1-heptanol (12 µL) was selected as the extraction solvent and acetic anhydride (50 µL) as the derivatization reagent. With the use of an up-and-down shaker, the emulsification of aqueous samples was formed homogeneously and quickly. The derivatization and extraction of chlorophenols were completed simultaneously in 1 min. The common requirement of disperser solvent in DLLME could be avoided. After optimization, the linear range covered over two orders of magnitude, and the coefficient of determination (r (2)) was greater than 0.9981. The detection limit was from 0.05 to 0.2 µg L(-1), and the relative standard deviation was from 4.6 to 10.8 %. Real samples of river water and lake water had relative recoveries from 90.3 to 117.3 %. Other emulsification methods such as vortex-assisted, ultrasound-assisted, and manual shaking-enhanced ultrasound-assisted methods were also compared with the proposed UDSA-DLLME. The results revealed that UDSA-DLLME performed with higher extraction efficiency and precision compared with the other methods.
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Clorofenóis/química , Clorofenóis/isolamento & purificação , Cromatografia Gasosa-Espectrometria de Massas/métodos , Microextração em Fase Líquida/métodos , Poluentes Químicos da Água/química , Poluentes Químicos da Água/isolamento & purificação , Água Doce/química , Limite de Detecção , Microextração em Fase Líquida/instrumentaçãoRESUMO
BACKGROUND: High-resolution matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF MS) and nuclear magnetic resonance (NMR) spectroscopy are powerful tools to identify unknown psychoactive substances. However, in complex matrices, trace levels of unknown substances usually require additional fractionation and concentration. Specialized liquid chromatography systems are necessary for both techniques. The small flow rate of nano LC, typically paired with MALDI-TOF MS, often results in prolonged fractionation times. Conversely, the larger flow rate of semi-preparative LC, used for NMR analysis, can be time-consuming and labor-intensive when concentrating samples. To address these issues, we developed an integrated automatic system that integrated to regular LC. RESULT: Automatic spot collector (ASC) and automatic fraction collector (AFC) were present in this study. The ASC utilized in-line matrix mixing, full-contact spotting and real time heating (50 °C), achieving great capacity of 5 µL droplet on MALDI plate, high recovery (76-116%) and rapid evaporation in 2 min. The analytes were concentrated 4-8 times, forming even crystallization, reaching the detection limit at the concentration of 50 µg L-1 for 12 psychoactive substances in urine. The AFC utilizes flexible tubing which flash-tapped the microtube's upper rim (3 mm depth) instead of reaching the bottom. This method prevents sample loss and minimizes the robotic arm's movement, providing a high fractionating speed at 6 s 12 psychoactive compounds were fractionated in a single round analysis (recovery: 81%-114%). Methamphetamine and nitrazepam obtained from drug-laced coffee samples were successful analyzed with photodiode array (PDA) after one AFC round and NMR after five rounds. SIGNIFICANCE: The ASC device employed real-time heating, in-line matrix mixing, and full-contact spotting to facilitate the samples spotting onto the MALDI target plate, thereby enhancing detection sensitivity in low-concentration and complex samples. The AFC device utilized the novel flash-tapping method to achieve rapid fractionation and high recovery rate. These devices were assembled using commercially available components, making them affordable (400 USD) for most laboratories while still meeting the required performance for advanced commercialized systems.
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Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz/métodos , Cromatografia Líquida/métodos , Cristalização , Espectroscopia de Ressonância MagnéticaRESUMO
Amidst far-reaching COVID-19 effects and social constraints, this study leveraged wastewater-based epidemiology to track 38 conventional drugs and 30 new psychoactive substances (NPS) in northern Taiwan. Analyzing daily samples from four Taipei wastewater plants between September 2021 and January 2024-encompassing club reopenings, holidays, Lunar New Year, an outbreak, and regular periods-thirty-one drugs were detected, including 5 NPS. Tramadol, zolpidem tartrate, CMA, and MDPV were newly detected in Taiwanese sewage with frequency of 1.4 %- 89.0 %. Conventional drug use typically increased post-pandemic, aside from benzodiazepines and methadone. Methamphetamine showed 100 % frequency, indicating ongoing daily consumption despite COVID-19 measures. Methamphetamine and morphine's consumption dipped then rose around club reopening, hinting at limited access. The consumption trend of methadone appeared to compensate for the use of morphine. Ketamine and NPS demonstrated similar patterns throughout the entire period. NPS as party drugs seemed influenced by an unstable supply chain and complexities in implementation. Benzodiazepines, commonly abused alongside synthetic cathinones in Taiwan exhibited an opposing trend to NPS while aligned with acetaminophen, suggesting elevated stress and anxiety levels during the pandemic. No significant differences were observed in drug consumption between weekdays and weekends, potentially indicating that COVID-19 measures blurred the traditional distinctions between these timeframes. ENVIRONMENTAL IMPLICATION: New psychoactive substances refer to chemically modified variants of controlled drugs designed to mimic the effects of the original drugs while evading modern detection methods, categorizing them as hazardous materials. The study presents a sewage monitoring project conducted from 2021 to 2024, collecting samples from four WWTPs to analyze NPS and conventional drug trends during and after the COVID-19 pandemic. The findings uncovered connections between drug consumption patterns and pandemic-related policies. In light of the persistent drug abuse and their environmental presence, the results bear critical importance for both environmental and public health. We provide a thorough assessment of these relationships and prioritize areas for future research.
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COVID-19 , Drogas Ilícitas , Águas Residuárias , Taiwan/epidemiologia , COVID-19/epidemiologia , Humanos , Drogas Ilícitas/análise , Psicotrópicos , Vigilância Epidemiológica Baseada em Águas Residuárias , Transtornos Relacionados ao Uso de Substâncias/epidemiologia , SARS-CoV-2 , Poluentes Químicos da Água/análise , Detecção do Abuso de Substâncias/métodosRESUMO
The emergence of new psychoactive substances currently exceeding a thousand is rapidly changing substance prevalence patterns and straining the methods used for detection, most of which are suitable only for a single class of substances. This study presents a rapid and facile dilute-and-shoot system operated in conjunction with an optimized liquid chromatographic separation system for the high-sensitivity detection of substances across a range of substance classes with 3 isotopes used only. The proposed method based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) is able to identify 68 substance and their metabolites in urine samples as small as 50 µL. Optimal chromatographic conditions including 95% water/methanol ratio with 0.1% added formic acid and a prolonged LC gradient run-time (15 min) improved the peak shape of polar compounds and enhanced signal strength by 5%. Under 4-fold dilution, all analytes were within 80-120% of tolerance response levels, indicating that the matrix effect was insignificant. In experiments, the limit of detection (LOD) ranged from 0.05 to 0.5 ng mL-1, while the coefficient of determination (R2) was > 0.9950. The retention time shift of each peak remained at < 2% with an inter-day relative standard deviation (RSD) of 0.9-14.9% and intra-day RSD of 1.1%- 13.8%. The rapid dilute-and-shoot presents a high-sensitivity, significant stability, robustness and reproducibility without serious interference. To demonstrate the effectiveness of the system, 532 urine samples were collected from suspected drug abusers, and the proposed method was used for rapid analysis. Of these samples, 79.5% contained between one and twelve analytes, and 12.4% tested positive for new psychoactive substances, mostly derivatives of amphetamine and synthetic cathinones. The study presents a high-sensitivity analytic system that is capable of detecting substances from multiple classes and can be used for effective monitoring of substance prevalence in urine.
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Fármacos do Sistema Nervoso Central , Espectrometria de Massas em Tandem , Humanos , Cromatografia Líquida/métodos , Espectrometria de Massas em Tandem/métodos , Reprodutibilidade dos Testes , Anfetamina , Limite de Detecção , Cromatografia Líquida de Alta Pressão/métodosRESUMO
Although many phthalates are endocrine-disrupting chemicals that are associated with adverse birth outcomes, the relationship between maternal phthalate exposure and birth outcomes is not yet conclusive. The objective of the present study was to investigate the association between prenatal exposure to phthalates in human maternal and cord blood and birth outcomes of the infants. Sixty-five mother-infant pairs were recruited in Taipei City and New Taipei City, and birth outcomes of the infants were recorded. Twelve phthalate metabolites were measured in maternal and cord blood samples. The mean of mono-ethyl phthalate, mono-isobutyl phthalate (MiBP), mono-n-butyl phthalate (MnBP), and mono-(2-ethylhexyl) phthalate (MEHP) was relatively higher than that of the other metabolites in both maternal and infant blood. There was a significant difference (p < 0.05) for mono-methyl phthalate (MMP) and MnBP between the maternal blood and cord blood of male infants. Mono-benzyl phthalate (MBzP), MMP, MiBP, and ∑di-2-ethylhexyl phthalate (∑DEHP) in maternal blood were inversely correlated with the anogenital index (AGI) of male infants, with a p value between 0.011 and 0.033. Mono-n-octyl phthalate, MMP, MiBP, MnBP, and MBzP were positively correlated with the AGI of female infants, with a p value between 0.001 and 0.034. Cord blood levels of MnBP, mono-(2-ethyl-5-oxohexyl)-phthalate, MEHP, and ∑DEHP were found to be inversely associated with head circumference in all the infants, adjusted for gestational age. Phthalate monoesters are potentially estrogenic and antiandrogenic chemicals. Longitudinal follow-up of the present study population could help clarify the long-term impact of phthalates on growth and the health effects of background exposure levels. Environ Toxicol Chem 2022;41:715-725. © 2022 SETAC.
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Poluentes Ambientais , Ácidos Ftálicos , Efeitos Tardios da Exposição Pré-Natal , Feminino , Humanos , Masculino , Gravidez , Exposição Ambiental , Poluentes Ambientais/efeitos adversos , Poluentes Ambientais/metabolismo , Sangue Fetal/metabolismo , Exposição Materna/efeitos adversosRESUMO
Histone deacetylase (HDAC) inhibitors have emerged as a new class of antitumor agent for various types of tumors. MPT0B291, a novel selective inhibitor of HDAC6, demonstrated significant antiproliferative activity in various human cancer cell types. However, MPT0B291 has very low water solubility, which limits its clinical use for cancer therapy. In the current study, MPT0B291 was encapsulated in human serum albumin (HSA), and its anticancer activities were investigated. Nanoparticles (NPs) were prepared using two-stage emulsification resulting in 100~200-nm NPs with a fine size distribution (polydispersity index of <0.3). The in vitro drug release profiles of MPT0B291-loaded HSA NPs presented sustained-release properties. The cytotoxic effect on MIA PaCa-2 human pancreatic carcinoma cells was found to be similar to MPT0B291-loaded HSA NPs and the free-drug group. The albumin-based formulation provided a higher maximum tolerated dose than that of a drug solution with reduced toxicity toward normal cells. Furthermore, in vivo pharmacokinetic studies demonstrated an effective increase (5~8-fold) in the bioavailability of NPs containing MPT0B291 loaded in HSA compared to the free-drug solution with an extended circulation time (t1/2) leading to significantly enhanced efficacy of anticancer treatment.
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An environmentally friendly thermosensitive nanovesicle-cloud point microextraction technique has been developed with the assistant of ultrasonic waves to determine analgesic drugs with a broad range of polarity in field water and human urine. Based on thin-film hydration, the conformation of nanovesicles formed by a binary mixing system with the nonionic surfactants was evaluated using regular and cryogenic transmission electron microscopy. The multilayered nano-spherical structure was able to capture polar and nonpolar compounds simultaneously. Analgesic drugs (acetaminophen, salicylic acid, ketoprofen, diclofenac, indomethacin, ibuprofen, and mefenamic acid) were detected by ultra-performance liquid chromatography coupled to photodiode array detection. Under optimal conditions including the type and ratio of surfactants, sonication time and sonication temperature, linear calibration curves were obtained over the range of 50-8000⯵g L-1. The coefficient of determination (R2) ranged from 0.9953 to 0.9995, with detection limits of 10-100⯵g L-1. The relative standard deviations ranged from 3.2% to 12.7% for intraday precision (nâ¯=â¯5) and 2.5% to 14.1% for interday precision (nâ¯=â¯15). The relative recoveries obtained from one industrial wastewater sample and two field water samples ranged from 86.1% to 108.1%. In the human urine analysis, three volunteers ingested 1500â¯mg of acetaminophen. After 4â¯h, the concentration of acetaminophen in the urine was found to range from 87.0 to 197.9â¯mg L-1.
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Analgésicos/isolamento & purificação , Analgésicos/urina , Fracionamento Químico/métodos , Nanoestruturas/química , Esgotos/química , Sonicação , Temperatura , Técnicas de Química Sintética , Meio Ambiente , Humanos , Concentração de Íons de Hidrogênio , Nanotecnologia , Reprodutibilidade dos Testes , Cloreto de Sódio/química , Fatores de TempoRESUMO
Programmable surface-patterned functional DNA density is achieved via manipulation of molecular-level defects through chemical lift-off lithography. Artificial SAM defects are well-tunable by a contact-induced reaction, enabling molecular environment guidance and DNA insertion to be spatially and quantitatively addressable. This straightforward molecular density control creates an advanced avenue toward fabricating multiplexed bioactive substrates.
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DNA/química , Impressão , Adenosina/química , Cocaína/química , DNA/genética , Sondas de DNA/química , Sondas de DNA/genética , Fluorescência , Ouro/química , HIV-1/genética , Hibridização de Ácido Nucleico , Propriedades de SuperfícieRESUMO
The classical alkanethiol post-passivation can prevent nonspecific binding of nucleotide bases onto supporting substrates and help aptamers transition from a "lying down" to a "standing up" orientation. However, the surface probes display lower binding affinity towards targets than those in bulk solutions due to unsatisfied hybridization spaces on the alkanethiol passivated substrate. To overcome this challenge, an artificial defect-rich matrix possessing an aptamer "self-standing" property created by chemical lift-off lithography (CLL) is demonstrated. This approach provided artificial defects on a hydroxyl-terminated alkanethiol self-assembled monolayer (SAM), which allowed the insertion of thiolated aptamers. The diluted surface molecular environment assisted aptamers not only to "self-stand" on the surface, but also to separate from each other, providing a suitable surface aptamer density and sufficient space for capturing targets. With this approach, the binding affinity of the aptamer towards a target was comparable to solution-type probes, showing higher recognition efficiency than that in conventional methods.
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Clinicians require a simple quantitative method for the detection of both phenylalanine and tyrosine to facilitate the diagnosis of phenylketonuria, a common inherited disorder of amino acid metabolism. In this study, we developed a novel whole-cell biosensor for the quantification of phenylalanine and tyrosine through the expression of red and green fluorescent proteins. The proposed system responds specifically and sensitively to phenylalanine/tyrosine without interferences from other amino acids. Furthermore, the precision of the biosensor was evaluated using specimens of normal human urine by LC-MS.
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Técnicas Biossensoriais , Fenilalanina/urina , Fenilcetonúrias/diagnóstico , Fatores de Transcrição/genética , Tirosina/urina , Cromatografia Líquida de Alta Pressão , Escherichia coli/metabolismo , Proteínas de Escherichia coli/metabolismo , Humanos , Proteínas Luminescentes/química , Proteínas Luminescentes/metabolismo , Proteínas Repressoras/metabolismo , Espectrometria de Massas por Ionização por Electrospray , Fatores de Transcrição/metabolismoRESUMO
Phthalates are not covalently bound to plastics. They can leach from experimental plastic devices. Due to the development of sensitive techniques, exogenous sources that interfere with the accuracy of phthalate monoester analysis can be easily detected. Here, we propose the simple and rapid dilute-and-shoot method to minimize sample handling and limit contact with laboratory apparatus, which efficiently reduced phthalate interferences mainly from experimental plasticware and improved the accuracy of analysis. Chemical additives in the mobile phase and modifiers in reconstituted solution were evaluated to improve peak shape and liquid chromatography separation. Under optimal conditions, the limit of detection ranged from 0.01 to 0.5â¯ng/mL. No phthalate monoesters were detected above the limit of detection in blank water while the leached concentrations of MMP, MEP, MiBP, MnBP and MEHP from the conventional solid phase extraction procedure were 1.9, 2.7, 0.9, 2.0 and 1.1â¯ng/mL, respectively. In 304 samples collected from primary school- children aged 9-10 years, we observed a positive association between body mass index (BMI) and urinary MMP and MiBP concentrations in boys, while MEOHP and MEHHP were inversely related to BMI in girls. Furthermore, detectable phthalate monoesters may be considered potential chemical obesogens related to BMI in children.
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Poluentes Ambientais/urina , Ácidos Ftálicos/urina , Índice de Massa Corporal , Criança , Exposição Ambiental/análise , Feminino , Humanos , Masculino , Manejo de EspécimesRESUMO
Shaker-assisted dispersive liquid-liquid microextraction (SA-DLLME) and surfactant dispersive liquid-liquid microextraction (SDLLME) have been developed to determine five diphenylether herbicides in water samples using high-performance liquid chromatography with photodiode array detection (HPLC-PDA). For SA-DLLME, an up-and-down shaker-assisted emulsification was used. Extraction was complete in 3 min. Only 30 µL of decyl acetate was required, without a dispersive solvent. The linear range was from 2 to 1000 µg L-1, the coefficient of determination (r2) was better than 0.9992, and the limit of detection (LOD) was from 0.62 to 1.74 µg L-1. The relative recovery (RR) ranged from 90 to 102% for river water, 88 to 104% for lake water, and 93 to 102% for irrigating water. In SDLLME, a microsyringe was used to withdraw and discharge a mixture consisting of an extraction solvent and 1 mg L-1 Tween 60 as a surfactant four times within 10 s to form an emulsified solution. The linear range for the target compounds was from 2 to 1000 µg L-1. The LODs were between 0.72 and 1.38 µg L-1. The RR ranged from 95 to 108% for river water, 96 to 109% for lake water, and 86 to 114% for irrigating water.
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Cromatografia Líquida de Alta Pressão , Herbicidas/análise , Microextração em Fase Líquida , Poluentes Químicos da Água/análise , Água Doce/análise , Limite de Detecção , Solventes , TensoativosRESUMO
Discrimination between street heroin consumption and poppy seed ingestion represents a major toxicological challenge in daily routine work. Several difficulties associated with conventional street heroin markers originate from their versatile occurrence in various poppy seed products and medications, respectively, as well as to small windows of detection. A novel opportunity to overcome these hindrances is represented by the new potential street heroin marker acetylated-thebaine-4-metabolite glucuronide (ATM4G), originating from thebaine during street heroin synthesis followed by metabolic reactions after administration. In this study, urine samples after consumption of different German poppy seed products and urine samples from subjects with suspicion of preceding heroin consumption were tested for ATM4G, 6-AC (6-acetylcodeine), papaverine, noscapine, 6-MAM (6-monoacetylmorphine), morphine, and codeine. Neither 6-AC and 6-MAM nor ATM4G but morphine and codeine could be detected in urine samples following poppy seed ingestion. As well, neither papaverine nor noscapine could be observed even after consumption of poppy seeds containing up to 37 µg noscapine and up to 9.8 µg papaverine, respectively. Concerning the urine samples with suspicion of preceding heroin consumption, ATM4G could be detected in 9 of 43 cases. By contrast, evidence of 6-AC and 6-MAM, respectively, could only be seen in 7 urine samples. In conclusion, ATM4G should be measured additionally in cases requiring discrimination of street heroin consumption from poppy seed intake. Copyright © 2016 John Wiley & Sons, Ltd.
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Analgésicos Opioides/urina , Glucuronídeos/urina , Heroína/urina , Papaver/química , Detecção do Abuso de Substâncias/métodos , Tebaína/uso terapêutico , Cromatografia Gasosa-Espectrometria de Massas/métodos , Humanos , Espectrometria de Massas em Tandem/métodosRESUMO
Phthalates are considered endocrine disruptors. Our study assessed the gender-specific effects of phthalate exposure on thyroid function in children. In total, 189 Taiwanese children were enrolled in the study. One-spot urine and blood samples were collected for analyzing 12 phthalate metabolites in urine and thyroid hormones. The association between urinary phthalate metabolites and serum thyroid hormones was determined using a generalized linear model with a log link function; the children were categorized into groups for analysis according to the 33rd and 66th percentiles. The data were stratified according to gender and adjusted for a priori defined covariates. In girls, a positive association existed between urinary di-2-ethylhexyl phthalate (DEHP) metabolites (mono-(2-ethylhexyl) phthalate, mono-(2-ethyl-5-oxohexyl) phthalate, and mono-(2-ethyl-5-hydroxyhexyl) phthalate) and free thyroxine (T4). In boys, urinary dibutyl phthalate (DBP) metabolites (mono-i-butyl phthalate and mono-n-butyl phthalate) were positively associated with free triiodothyronine (T3). After categorizing each exposure into three groups, urinary DEHP metabolites were positively associated with free T3 levels in boys. Our results suggested that DEHP is associated with free T4 in girls and that DBP is associated with free T3 in boys. Higher DEHP metabolite concentrations exerted larger effects on free T3 in boys. These results reveal the gender-specific relationships between phthalate metabolites and thyroid hormones.
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Disruptores Endócrinos/urina , Exposição Ambiental/efeitos adversos , Poluentes Ambientais/efeitos adversos , Ácidos Ftálicos/metabolismo , Ácidos Ftálicos/urina , Caracteres Sexuais , Glândula Tireoide/efeitos dos fármacos , Hormônios Tireóideos/urina , Criança , Disruptores Endócrinos/análise , Exposição Ambiental/análise , Poluentes Ambientais/análise , Feminino , Humanos , Masculino , Ácidos Ftálicos/análise , Estudos Prospectivos , Taiwan , Testes de Função TireóideaRESUMO
Coupling a two-step liquid-phase microextraction (LPME) with O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine/bis(trimethylsilyl)trifluoroacetamide (PFBHA)/(BSTFA) derivatization was developed to detect hydroxycarbonyls in rainwater samples using gas chromatography-mass spectrometry (GC-MS). LPME provides a fast and inexpensive pre-concentration, and miniaturized extraction to analyze the target compounds rainwater samples. Derivatization techniques offer a clear method to identify target compounds. The hydroxycarbonyls were determined using two-step derivatizations. Dynamic-LPME was applied in the first derivatization, and head-space single drop derivatization was employed in the second reaction. The LODs varied from 0.023 to 4.75 microg/l. The calibration curves were linear for at least two orders of magnitude with R2>or=0.994. The precision was within 6.5-12%, and the relative recoveries in rainwater were more than 89% (the amount added ranged from 0.3 to 15 microg/l). A field sample was found to contain 2.54 microg/l of hydroxyacetone and 0.110 microg/l of 3-hydroxy-2-butanone. Hydroxyacetone was also detected in one of the tested samples at a concentration of 2.39 microg/l.