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OBJECTIVES: The study aimed to analyze the effect of BNT162b2 vaccination among Polish healthcare workers in terms of serologic response and adverse events. MATERIAL AND METHODS: A questionnaire survey covered data in the period January 1-March 31, 2021 gathered in 2 hospitals in Wielkopolska, Poland. Additionally, serological analysis (SARS-CoV-2 anti-S protein IgG) was performed. RESULTS: A total of 617 medical workers were vaccinated with BNT162b2 (Comirnaty, Pfizer). Data from the questionnaires were received from all of the staff after the first and the second dose. No severe side effects were observed. The most common side effect following the first and second doses of vaccination was pain at the injection site. After the first dose, 3 (1.4 %) women aged 18-55 years, 5 women (3.9 %), and 3 men (8.3 %) aged >55 years had negative SARS-CoV-2 anti-S protein IgG result. After the second dose, all those who agreed to have antibodies tested responded to vaccination with positive SARS-CoV-2 anti-S protein IgG results. CONCLUSIONS: Vaccination tolerance was good in the studied population; no severe side effects were observed. After the second dose, all tested healthcare workers responded to vaccination with antibody production. Int J Occup Med Environ Health. 2022;35(6):761-66.
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COVID-19 , Efeitos Colaterais e Reações Adversas Relacionados a Medicamentos , Masculino , Feminino , Humanos , Vacina BNT162 , Polônia , Soroconversão , SARS-CoV-2 , Anticorpos Antivirais , Imunoglobulina G , Pessoal de SaúdeRESUMO
Ionic liquids (ILs) such as imidazole can be used to prevent the sorption of analytes onto the quartz walls of the capillary. Coating the capillary wall with a cation layer increases its surface stability, consequently improving the repeatability of separation process. Currently, examining the effects of dynamic coatings on the capillary wall is an emerging trend in capillary electrophoresis (CE) research. This study uses micellar electrokinetic chromatography (MEKC) to evaluate how ILs in the background electrolyte (BGE) affect the separation efficiency of biogenic amines (BAs). Specifically, this research focuses on 12 ILs built from cations containing an imidazole ring with different alkyl substituents and anions, as well as one IL containing a pyridinium cation with tetrafluoroborate anion. All analyzed ILs, which were added to the BGE in concentrations ranging from 1 to 20 mM, were tested for their ability to improve the electrophoretic separation of selected BAs, namely: homovanillic acid (HVA), vanililmandelic acid (VMA), dihydroxyphenylglicol (DHPG), 3-metoxy-4-hydroxyphenyl glicol (MHPG), normetanephrine (NM), metanephrine (M), and dihydroxyphenylacetic acid (DOPAC). The results showed that the most effective ILs added to the BGE were those with a chloride anion (1-hexyl-3-methylimidazolium chloride [HMIM+Cl-] and 1-ethyl-3-methylimidazolium chloride [EMIM+Cl-]) and those with a tetrafluoroborate anion (1-hexyl-3-methylimidazolium tetrafluoroborate [HMIM + BF4-]). Improved separation efficiency was also obtained for the BGE containing 1-hexyl-3-methylimidazolium hexafluorophosphate [HMIM + PF6-]. On the other hand, ILs with trifluoromethanesulfonate [OTf-] or bis(trifluoromethylsulfonyl)imide [NTf2-] anions, even at low concentrations in the BGE, disturbed the flow of current through the capillary and worsened the separation process. Overall, this study provides a critical evaluation of the impact of different types and concentrations of ILs on the performance of the MEKC method during the analysis of selected BAs.
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Cromatografia Capilar Eletrocinética Micelar , Líquidos Iônicos , Aminas Biogênicas , Eletroforese Capilar , MicelasRESUMO
BACKGROUND: L-tryptophan is an essential amino acid necessary for the human body to function. Its degradation occurs through two metabolic pathways. Approximately 95 % of the Ltryptophan available in the body is converted via the kynurenine pathway, while the remainder is degraded via the serotonin pathway. Properly maintained balance between the concentrations of individual small molecular metabolites is extremely important to maintain homeostasis in the human body, and its disruption could lead to the development of numerous neurological, neurodegenerative, neoplastic, as well as cardiovascular diseases. Recent reports have suggested that by controlling the levels of selected L-tryptophan metabolites (potential biomarkers), it is possible to diagnose numerous diseases, monitor their course, and assess patient prognosis. OBJECTIVE: The aim of this paper is to review the currently important clinical applications of selected biomarkers from the L-tryptophan metabolism pathways that would be helpful in early diagnosis, monitoring the course and treatment of serious diseases of affluence, which ultimately could improve the patients' quality of life, as well as support targeted therapy of the aforementioned diseases. CONCLUSION: Since the biochemical biomarkers determination in body fluids presents the ideal minimally invasive tool in the patents' diagnosis and prognostication, this study emphasizes the current trends and perspectives of application of analysis of selected L-tryptophan metabolites named kynurenine and serotonin-derived small compounds in the routine medical procedures.
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Cinurenina , Triptofano , Biomarcadores , Humanos , Cinurenina/metabolismo , Qualidade de Vida , Serotonina/metabolismo , Triptofano/metabolismoRESUMO
A high-performance version of in-line, three-phase direct immersion-single drop microextraction (DI-SDME) coupled with capillary electrophoresis (CE) was demonstrated using a commercial CE instrument, and all the major and minor details were described to provide an easy-to-follow and user-friendly protocol. The excellent sample cleanup and enrichment power of this method was demonstrated with nonsteroidal anti-inflammatory drugs (NSAIDs) in human urine. The only preparation of urine samples was the addition of HCl to acidify the urine sample to pH 2. The acidic NSAIDs in the acidified urine sample were extracted into a basic acceptor drop covered with a thin organic layer attached to the inlet tip of a capillary immersed in the sample. A simple but powerful DI-SDME-CE method could be carried out automatically without any modification of the existing CE instrument. For improved performance, sample agitation and heating were employed by installing a microstirrer and a thermostating jacket in the sample tray. With 10 min of DI-SDME at 35°C with stirring, NSAIDs such as ketoprofen, ibuprofen, and naproxen in urine were enriched 340-970-fold with intraday and interday RSDs of 0.8-2.4% and 1.1-3.6%, respectively. The LODs obtained with in-line coupled CE/UV were 10-50 nM (2-10 µg/L). The performance of DI-SDME-CE/UV was also demonstrated by determining the naproxen level in human urine collected 24 h after taking a single oral dose of the drug. The spike recovery of naproxen from a single-point standard addition to the urine sample was 80%. Our high-performance three-phase DI-SDME-CE method is quite promising for the analysis of ionizable trace analytes in a complex sample matrix.
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Eletroforese Capilar , Cetoprofeno , Anti-Inflamatórios não Esteroides , Humanos , Ibuprofeno , NaproxenoRESUMO
Lead (Pb) was revealed for its role as a neurodevelopmental toxin. The determination of neurotransmitters (NTs) in particular brain regions could ameliorate the precise description and optimization of therapeutic protocols able to restore the harmony of signaling pathways in nervous and immune systems. The determination of selected analytes from the group of NTs based on the liquid chromatography (LC)-based method was carried out to illustrate the changes of amino acid (AA) and biogenic amine (BA) profiles observed in chosen immune and nervous systems rat tissues after Pb intoxication. Also, a protective combination of AA was proposed to correct the changes caused by Pb intoxication. After the administration of Pb, changes were observed in all organs studied and were characterized by a fluctuation of NT concentrations in immune and nervous systems (hypothalamus samples). Using a protective mixture of bioactive compounds prevented numerous changes in the balance of NT. The combined analysis of the immune and nervous system while the normalizing effect of curative agents on the level of differentially secreted NTs and AA is studied could present a new approach to the harmonization of those two essential systems after Pb intoxication.
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Chumbo/toxicidade , Substâncias Protetoras/farmacologia , Animais , Biomarcadores/sangue , Encéfalo/efeitos dos fármacos , Fígado/efeitos dos fármacos , Fígado/metabolismo , Linfócitos/efeitos dos fármacos , Linfócitos/metabolismo , Masculino , Ratos , Baço/metabolismoRESUMO
A new approach for the sensitive, robust and rapid determination of idarubicin (IDA) in human plasma and urine samples based on liquid chromatography with fluorescence detection (LC-FL) was developed. Satisfactory chromatographic separation of the analyte after solid-phase extraction (SPE) was performed on a Discovery HS C18 analytical column using a mixture of acetonitrile and 0.1% formic acid in water as the mobile phase in isocratic mode. IDA and daunorubicin hydrochloride used as an internal standard (I.S.) were monitored at the excitation and emission wavelengths of 487 and 547 nm, respectively. The method was validated according to the FDA and ICH guidelines. The linearity was confirmed in the range of 0.1-50 ng/mL and 0.25-200 ng/mL, while the limit of detection (LOD) was 0.05 and 0.125 ng/mL in plasma and urine samples, respectively. The developed LC-FL method was successfully applied for drug determinations in human plasma and urine after oral administration of IDA at a dose of 10 mg to a patient with highly advanced alveolar rhabdomyosarcoma (RMA). Moreover, the potential exposure to IDA present in both fluids for healthcare workers and the caregivers of patients has been evaluated. The present LC-FL method can be a useful tool in pharmacokinetic and clinical investigations, in the monitoring of chemotherapy containing IDA, as well as for sensitive and reliable IDA quantitation in biological fluids.
Assuntos
Monitoramento de Medicamentos/métodos , Idarubicina/sangue , Idarubicina/urina , Antibióticos Antineoplásicos/sangue , Antibióticos Antineoplásicos/normas , Antibióticos Antineoplásicos/urina , Cromatografia Líquida/métodos , Daunorrubicina/sangue , Daunorrubicina/normas , Daunorrubicina/urina , Monitoramento de Medicamentos/normas , Monitoramento de Medicamentos/estatística & dados numéricos , Fluorescência , Humanos , Idarubicina/normas , Limite de Detecção , Padrões de Referência , Reprodutibilidade dos Testes , Sensibilidade e Especificidade , Extração em Fase SólidaRESUMO
The tumor microenvironment (TME) consists of numerous biologically relevant elements. One of the most important components of the TME is the extracellular matrix (ECM). The compounds of the ECM create a network that provides structural and biochemical support to surrounding cells. The most important substances involved in the regulation of the ECM degradation process are matrix metalloproteinases (MMPs) and their endogenous inhibitors (tissue inhibitors of metalloproteinases, TIMPs). The disruption of the physiological balance between MMP activation and deactivation could lead to progression of various diseases such as cardiovascular disease, cancer, fibrosis arthritis, chronic tissue ulcers, pathologies of the nervous system (such as stroke and Alzheimer's disease), periodontitis, and atheroma. MMP-TIMP imbalance results in matrix proteolysis associated with various pathological processes such as tumor invasion. The present review discusses the involvement of two MMPs, MMP-2 and MMP-7, in cancer pathogenesis. These two MMPs have been proven in several studies, conducted mostly on adults, to make an important contribution to cancer development and progression. In the current review, several studies that indicate the importance of MMP-TIMP balance determination for the pediatric population are also highlighted. The authors of this review believe that carrying out biochemical and clinical studies focused on metalloproteinases and their inhibitors in tumors in children will be of great relevance for future patient diagnosis, determination of a prognosis, and monitoring of therapy.
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The broad spectrum of the mechanism of action of immune-boosting natural compounds as well as the complex nature of the food matrices make researching the health benefits of various food products a complicated task. Moreover, many routes are involved in the action of most natural compounds that lead to the inhibition of chronic inflammation, which results in a decrease in the ability to remove a pathogen asymptomatically and is connected to various pathological events, such as cancer. A number of cancers have been associated with inflammatory processes. The current review strives to answer the question of whether plant-derived sulfur compounds could be beneficial in cancer prevention and therapy. This review focuses on the two main sources of natural sulfur compounds: alliaceous and cruciferous vegetables. Through the presentation of scientific data which deal with the study of the chosen compounds in cancer (cell lines, animal models, and human studies), the discussion of food processing's influence on immune-boosting food content is presented. Additionally, it is demonstrated that there is still a need to precisely demonstrate the bioavailability of sulfur-containing compounds from various types of functional food, since the inappropriate preparation of vegetables can significantly reduce the content of beneficial sulfur compounds. Additionally, there is an urgent need to carry out more epidemiological studies to reveal the benefits of several natural compounds in cancer prevention and therapy.
Assuntos
Glucosinolatos/uso terapêutico , Inflamação/prevenção & controle , Neoplasias/prevenção & controle , Extratos Vegetais/uso terapêutico , Plantas/química , Compostos de Enxofre/uso terapêutico , Animais , HumanosRESUMO
The prominent biological effects of adrenaline (A), noradrenaline (NA) and dopamine (DA) as well as the clinical importance of their metabolites (such as dihydroxyphenylacetic acid (DOPAC), methoxy4-hydroxyphenyl glycol (MHPG), dihydroxyphenylglycol (DHPG), metanephrine (M), normetanephrine (NM), vanillylmandelic acid (VMA), homovanillic acid (HVA)) have forced researchers to evaluate new analytical methodologies for their isolation and preconcentration from biological samples. For this reason, the three most popular extraction techniques (dispersive liquid-liquid microextraction (DLLME), solid-phase extraction (SPE), solid-phase microextraction (SPME)) were tested. Micellar electrokinetic chromatography (MEKC) - a mode of capillary electrophoresis - with a diode array detector (DAD) was applied to assess the extraction efficiency. Next, the enrichment factor (EF) of each applied method was calculated in respect to standard mixtures of the analytes at the same concentration levels. The EF results of seven selected metabolites of biogenic amines (BAs) from urine after sample preparation procedures based on twenty-five different protocols (one DLLME, thirteen SPE and eleven SPME) were calculated and compared using hierarchical cluster analysis (HCA). The SPE as well as SPME procedures were proved to be the most effective approaches for the simultaneous extraction of the chosen compounds. Moreover, an ionic liquid (IL) - 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide - added to methanol in SPME additionally could successfully improve the extraction efficiency. It was also confirmed that the HCA approach could be considered a supportive tool in the selection of a suitable sample preparation procedure for that group of endogenous substances.
Assuntos
Cromatografia Capilar Eletrocinética Micelar/métodos , Redes e Vias Metabólicas , Tirosina/análise , Aminas Biogênicas , Soluções Tampão , Análise por Conglomerados , Eletrólitos/química , Humanos , Reprodutibilidade dos Testes , Extração em Fase Sólida , Tirosina/química , Tirosina/urinaRESUMO
The aim of the work was to develop a simple, sensitive and accurate liquid chromatography with fluorescence detection (LC-FL) method for the determination of epirubicin in human urine and plasma. Solid phase extraction with HLB cartridges and mixture of dichloromethane:2-propanol:methanol (2:1:1, v/v/v) as the eluent, was used to prepare the samples. The chromatographic analysis was carried out on a Synergi Hydro-RP column with a mobile phase consisting of 40 mM phosphate buffer (pH 4.1) and acetonitrile (69:31, v/v). Epirubicin was monitored at 497 nm and 557 nm for excitation and emission wavelengths, respectively. Validation data confirmed that the limit of detection and limit of quantification was 0.25 ng/mL and 0.5 ng/mL in both matrices. Next, the optimized LC-FL method was applied to determine the level of epirubicin in real samples taken from a 19-year-old patient with metastatic alveolar rhabdomyosarcoma (RMA) to create a drug profile. Plasma and urine samples were collected for 24 h after the end of a 6-hour infusion of epirubicin. The obtained results confirmed that the optimized and validated LC-FL method can be successfully used in drug monitoring therapy, pharmacokinetic and clinical studies. Moreover, the current work is also drawing attention to the relatively high level of epirubicin in the patient urine, which requires compliance with the safety rules in contact with this biological fluid by both medical staff and others, e.g. family members.
Assuntos
Cromatografia Líquida de Alta Pressão/métodos , Monitoramento de Medicamentos/métodos , Epirubicina/sangue , Epirubicina/urina , Espectrometria de Fluorescência/métodos , Adulto , Antibióticos Antineoplásicos/sangue , Antibióticos Antineoplásicos/farmacocinética , Antibióticos Antineoplásicos/uso terapêutico , Antibióticos Antineoplásicos/urina , Estabilidade de Medicamentos , Epirubicina/farmacocinética , Epirubicina/uso terapêutico , Humanos , Limite de Detecção , Modelos Lineares , Masculino , Neoplasias/tratamento farmacológico , Reprodutibilidade dos Testes , Extração em Fase Sólida , Adulto JovemRESUMO
Multiple reviews have been published on various aspects of carotenoid extraction. Nevertheless, none of them focused on the discussion of recent green chemistry extraction protocols, especially for the carotenoids extraction from Daucus carota L. This group of bioactive compounds has been chosen for this review since most of the scientific papers proved their antioxidant properties relevant for inflammation, stress-related disorders, cancer, or neurological and neurodegenerative diseases, such as stroke and Alzheimer's Disease. Besides, carrots constitute one of the most popular sources of carotenoids. In the presented review emphasis has been placed on the supercritical carbon dioxide and enzyme-assisted extraction techniques for the relevant tetraterpenoids. The detailed descriptions of these methods, as well as practical examples, are provided. In addition, the pros and cons of each method and comparison with the standard solvent extraction have been discussed.
Assuntos
Dióxido de Carbono/química , Carotenoides/isolamento & purificação , Cromatografia com Fluido Supercrítico/métodos , Daucus carota/química , Química Verde/métodos , Carotenoides/química , Hidrolases/administração & dosagem , Extração Líquido-Líquido , Polissacarídeo-Liases/administração & dosagem , Solventes/químicaRESUMO
Matrix metalloproteinases are a class of enzymes, which degrade extracellular matrix components such as collagens, elastin, laminin or fibronectin. So far, four matrix metalloproteinases have been shown to degrade elastin and its precursor tropoelastin, namely matrix metalloproteinase-2, -7, -9 and -12. This study focuses on investigating the elastinolytic capability of membrane-type 1 matrix metalloproteinase, also known as matrix metalloproteinase-14. We digested recombinant human tropoelastin and human skin elastin with matrix metalloproteinase-14 and analyzed the peptide mixtures using complementary mass spectrometric techniques and bioinformatics tools. The results and additional molecular docking studies show that matrix metalloproteinase-14 cleaves tropoelastin as well as elastin. While tropoelastin was well degraded, fewer cleavages occurred in the highly cross-linked mature elastin. The study also provides insights into the cleavage preferences of the enzyme. Similar to cleavage preferences of matrix metalloproteinases-2, -7, -9 and -12, matrix metalloproteinase-14 prefers small and medium-sized hydrophobic residues including Gly, Ala, Leu and Val at cleavage site P1'. Pro, Gly and Ala were preferably found at P1-P4 and P2'-P4' in both tropoelastin and elastin. Cleavage of mature skin elastin by matrix metalloproteinase-14 released a variety of bioactive elastin peptides, which indicates that the enzyme may play a role in the development and progression of cardiovascular diseases that go along with elastin breakdown.
Assuntos
Elastina/metabolismo , Metaloproteinase 14 da Matriz/metabolismo , Proteólise , Tropoelastina/metabolismo , Humanos , Simulação de Acoplamento Molecular/métodosRESUMO
Biogenic amines (BAs) are bioactive endogenous compounds which play a significant physiological role in many cell processes like cell proliferation and differentiation, signal transduction and membrane stability. Likewise, they are important in the regulation of body temperature, the increase/decrease of blood pressure or intake of nutrition, as well as in the synthesis of nucleic acids and proteins, hormones and alkaloids. Additionally, it was confirmed that these compounds can be considered as useful biomarkers for the diagnosis, therapy and prognosis of several neuroendocrine and cardiovascular disorders, including neuroendocrine tumours (NET), schizophrenia and Parkinson's Disease. Due to the fact that BAs are chemically unstable, light-sensitive and possess a high tendency for spontaneous oxidation and decomposition at high pH values, their determination is a real challenge. Moreover, their concentrations in biological matrices are extremely low. These issues make the measurement of BA levels in biological matrices problematic and the application of reliable bioanalytical methods for the extraction and determination of these molecules is needed. This article presents an overview of the most recent trends in the quantification of BAs in human samples with a special focus on liquid chromatography (LC), gas chromatography (GC) and capillary electrophoresis (CE) techniques. Thus, new approaches and technical possibilities applied in these methodologies for the assessment of BA profiles in human samples and the priorities for future research are reported and critically discussed. Moreover, the most important applications of LC, GC and CE in pharmacology, psychology, oncology and clinical endocrinology in the area of the analysis of BAs for the diagnosis, follow-up and monitoring of the therapy of various health disorders are presented and critically evaluated.
RESUMO
The analysis of biogenic amines (BAs) and their metabolites is helpful for the diagnosis of central nervous system disorders and other neuroendocrine and cancer disturbances. In the study, a developed micellar electrokinetic chromatography method, coupled with diode array detection (MEKC-DAD), was validated to monitor levels of adrenaline (A), noradrenaline (NA), dopamine (DA), L-Tryptophan (L-Tryp) and L-Tyrosine (L-Tyr) in real human urine samples. These neurotransmitters were isolated from urine samples using solid-phase microextraction (SPME) and methanol containing 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid as the desorption phase. The method was linear for DA, A and L-Tyr in the range of 0.5-20 µg/mL and for NA and L-Tryp in the range of 0.25-20 µg/mL. The good linearity for BAs was confirmed by the correlation coefficient (R2) from 0.9989 for A to 0.9997 for NA and L-Tryp, respectively. The validation assays for accuracy, precision, limit of detection, limit of quantification, absolute recovery, and stability of the analytes were consistent with the requirements recommended by the FDA and ICH guidelines. Next, the validated SPME-MEKC method was successfully used for the quantification of A, NA, DA, L-Tryp and L-Tyr in real human urine samples collected from pediatric patients suffering from neuroblastoma, ganglioneuroblastoma, Wilms' tumor, rhabdoid tumor and lipoblastomatosis, as well as from healthy volunteers. Finally, the levels of BAs in cancer patients were evaluated as to whether they can be used as biomarkers of various health disturbances.
Assuntos
Aminas Biogênicas/urina , Cromatografia Capilar Eletrocinética Micelar/métodos , Líquidos Iônicos/química , Neoplasias/diagnóstico , Microextração em Fase Sólida/métodos , Aminas Biogênicas/isolamento & purificação , Aminas Biogênicas/metabolismo , Biomarcadores Tumorais/isolamento & purificação , Biomarcadores Tumorais/metabolismo , Biomarcadores Tumorais/urina , Criança , Pré-Escolar , Feminino , Voluntários Saudáveis , Humanos , Lactente , Limite de Detecção , Masculino , Neoplasias/urinaRESUMO
In this study, a field amplified sample injection (FASI) and hydrophobic interaction electrokinetic chromatography (HIEKC) method has been developed for the separation of five macrolide antibiotics: spiramycin, ivermectin, tylosin, josamycin, rapamycin, and one ansamycin drug - rifamycin. By the manipulation of both the sample and separation buffer compositions, their pH values and molarity, a systematic approach has been achieved to maximize analyte differential electrophoretic mobility and signal amplification. The impact of the sample solution composition and the injection mode on the signal amplification effect of the six tested antibiotics was also investigated. Moreover, the influence of the injection of the sample and the water plug on the quantity, symmetry and height of the analyte signal was demonstrated. All the analytes were completely resolved in less than 8â¯min in an uncoated fused-silica capillary of 75⯵m internal diameter (I.D.) x 50â¯cm length. The electrophoretic separations were performed in a 60% (v/v) acetonitrile and 20â¯mM phosphate electrolyte system (pH 7.1) with an applied voltage of 25â¯kV. The established method was validated and confirmed to be applicable for the determination of the active ingredients in a quality control analysis.
Assuntos
Antibacterianos/análise , Cromatografia Capilar Eletrocinética Micelar , Interações Hidrofóbicas e Hidrofílicas , Compostos Macrocíclicos/análiseRESUMO
Extraction of endogenous compounds and drugs and their corresponding metabolites from complex matrices, such as biofluids and solid tissues, requires adequate analytical approach facilitating qualitative and quantitative analysis. To this end, solid-phase microextraction has been introduced as modern technology that is capable of efficient and high-throughput extraction of compounds due to its ability to amalgamate sampling, extraction, and pre-concentration steps, while requiring minimal use of organic solvents. The ability of solid-phase microextraction to enable analyses on small-volume biological samples and growing availability of biocompatible solid-phase microextraction coatings make it a highly useful technology for variety of applications. For example, solid-phase microextraction is particularly useful for identifying biomarkers in metabolomics studies, and it can be successfully applied in pharmaceutical and toxicological studies requiring the fast and sensitive determination of drug levels, especially those that are present at low levels in biological matrices such as plasma, urine, saliva, and hair. Moreover, solid-phase microextraction can be directly applied in in vivo studies because this extraction technique is non-exhaustive and its biocompatible probes offer minimal invasiveness to the analyzed system. In this article, we review recent progress in well-established solid-phase microextraction technique for in vitro and in vivo analyses of various metabolites and drugs in clinical, pharmaceutical, and toxicological applications.
Assuntos
Pesquisa Biomédica , Preparações Farmacêuticas/análise , Microextração em Fase Sólida , Biomarcadores/análise , Biomarcadores/metabolismo , Metabolômica , Preparações Farmacêuticas/metabolismoRESUMO
Simultaneous electrokinetic and hydrodynamic injection of rapamycin (sirolimus) with off-line and online sample preconcentration techniques and using MEKC has been studied. Compared to conventional hydrodynamic injection, a 168-fold improvement in the signal was obtained with a combination of simultaneous electrokinetic and hydrodynamic injectionand field enhanced sample injection in conjunction with a sweeping technique called sequential stacking featuring sweeping. However, the coupling of the developed electrophoretic method and solid-phase microextraction allowed the signal intensity to increase more than 231 times. In this approach, the injection of the sample at negative polarity (anode at the detector end) into the capillary and the MEKC separation was achieved within 5 min using an electrolyte (composed of 10 mM sodium tetraborate and 40 mM SDS) when ultraviolet (UV) detection was performed at 280 nm. Thus, by combining the application of the sequential stacking featuring sweeping supported by the solid-phase microextraction clean-up procedure, the detection limit (LOD) for rapamycin in a serum sample was significantly decreased, and was set at 25 ng/mL. The proposed combined simultaneous electrokinetic and hydrodynamic injection with field enhanced sample injection -sweeping technique following MEKC separation of sirolimus in human serum could be an effective tool in biomedical and clinical applications.
Assuntos
Cromatografia Capilar Eletrocinética Micelar/métodos , Sirolimo/sangue , Humanos , Limite de Detecção , Pressão , Microextração em Fase SólidaRESUMO
The determination of neurotransmitters (NTs) as relevant potential biomarkers in the study of various central nervous system (CNS) pathologies has been demonstrated. Knowing that NTs-related diseases mostly occupy individual regions of the nervous system, as observed, for instance, in neurodegenerative diseases (Alzheimer's and Parkinson's Diseases), the analysis of brain slices is preferred to whole-brain analysis. In this report, we present sample preparation approaches, such as solid-phase extraction, solid-phase microextraction, and dispersive liquidâ»liquid microextraction, and discuss the pitfalls and advantages of each extraction method. The ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate)-assisted solid-phase microextraction (IL-SPME) is found to be, in our research, the relevant step towards the simultaneous determination of six NTs, namely, dopamine (DA), adrenaline (A), noradrenaline (NA), serotonin (5-HT), l-tryptophan (l-Trp), l-tyrosine (l-Tyr) in rat brain samples. The development of a novel bioanalytical technique for the evaluation of biomarkers in the context of green chemistry might be accelerated just with the use of IL, and this approach can be considered an advantageous strategy.
Assuntos
Encéfalo/metabolismo , Microextração em Fase Líquida/métodos , Neurotransmissores/isolamento & purificação , Extração em Fase Sólida/métodos , Microextração em Fase Sólida/métodos , Animais , Ratos Wistar , Processamento de Sinais Assistido por ComputadorRESUMO
A simple, rapid, reliable and sensitive method based on liquid chromatography with fluorescence detection (LC-FL) for the quantification of doxorubicin (DOX) in human plasma and urine samples was developed. The assay was carried out after the solid-phase extraction procedure (SPE) with hydrophilic-lipophilic balance (HLB) cartridges, and with daunorubicin hydrochloride (DAU) used as the internal standard. Chromatographic separation was performed on a Discovery HS C18 column in isocratic elution mode, and the detection of the analytes set at excitation and emission wavelengths of 487 and 555â¯nm, respectively. The developed LC-FL method has been validated for accuracy, precision, selectivity, linearity, recovery and stability. The limits of detection and quantification for DOX were 0.5 and 1â¯ng/mL in both biological fluids, respectively. Linearity was confirmed in the range of 1-1000â¯ng/mL and 0.001-25⯵g/mL in plasma and urine samples, respectively, with a correlation coefficient greater than 0.9994. The proposed LC-FL method is selective, precise and accurate, and has been successfully applied for drug monitoring in pediatric cancer patients treated with DOX as a component of OEPA (Oncovin (Vincristine)-Etoposide-Prednisone-Adriamycin) and IOA (Ifosfamide-Oncovin-Adriamycin) chemotherapeutic schemes. Moreover, real exposure of hospital personnel to the anthracycline drugs in plasma and urine was evaluated in clinical practice.
Assuntos
Antibióticos Antineoplásicos/análise , Protocolos de Quimioterapia Combinada Antineoplásica/uso terapêutico , Doxorrubicina/análise , Monitoramento de Medicamentos/métodos , Neoplasias/tratamento farmacológico , Adolescente , Antibióticos Antineoplásicos/uso terapêutico , Antibióticos Antineoplásicos/toxicidade , Cromatografia Líquida de Alta Pressão/instrumentação , Cromatografia Líquida de Alta Pressão/métodos , Daunorrubicina/análise , Doxorrubicina/farmacocinética , Doxorrubicina/uso terapêutico , Doxorrubicina/toxicidade , Etoposídeo/uso terapêutico , Fluorescência , Humanos , Limite de Detecção , Masculino , Neoplasias/sangue , Neoplasias/urina , Exposição Ocupacional/efeitos adversos , Recursos Humanos em Hospital , Prednisona/uso terapêutico , Reprodutibilidade dos Testes , Extração em Fase Sólida , Vincristina/uso terapêuticoRESUMO
Nowadays, ionic liquids (ILs) are receiving more attention in various fields of analytical chemistry. Their contribution to the enhancement of the clean-up, extraction, separation and determination of trace amounts of various biologically important compounds in distinct matrices is well documented. Moreover, their importance as "green chemistry" solvents has been pointed out. Advanced analytical methods based on the IL-assisted microextraction and electrophoretic determination of minute concentrations of neurotransmitters (NTs) in samples are presented here for the first time. In this paper, experimental data showed the usefulness of the chosen imidazolium-based ILs in solid-phase microextraction (SPME), followed by the micellar electrokinetic chromatography (MEKC) determination of three biogenic amines: dopamine, noradrenaline and adrenaline together with such amino acids as L-tyrosine and L-tryptophan. A significant increase in SPME yields, using 1-ethyl-3-methylimidazolium tetrafluoroborate as a component of the desorbent, allowing from 9 to 21 times the signal enhancement for the selected NTs, has been achieved. The elaborated IL-based SPME procedures might serve as a straightforward analytical platform for the unbiased analysis of NTs as biomarkers of various diseases where an unbalanced secretion of NTs is registered.