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Cytokines are compounds that belong to a special class of signaling biomolecules that are responsible for several functions in the human body, being involved in cell growth, inflammatory, and neoplastic processes. Thus, they represent valuable biomarkers for diagnosing and drug therapy monitoring certain medical conditions. Because cytokines are secreted in the human body, they can be detected in both conventional samples, such as blood or urine, but also in samples less used in medical practice such as sweat or saliva. As the importance of cytokines was identified, various analytical methods for their determination in biological fluids were reported. The gold standard in cytokine detection is considered the enzyme-linked immunosorbent assay method and the most recent ones have been considered and compared in this study. It is known that the conventional methods are accompanied by a few disadvantages that new methods of analysis, especially electrochemical sensors, are trying to overcome. Electrochemical sensors proved to be suited for the elaboration of integrated, portable, and wearable sensing devices, which could also facilitate cytokines determination in medical practice.
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Técnicas Biosensibles , Dispositivos Electrónicos Vestibles , Humanos , Sudor/química , Saliva/química , Técnicas Biosensibles/métodosRESUMEN
Nitro fatty acids (NO2-FAs) are biologically active compounds produced from the reaction of unsaturated fatty acids with reactive nitrogen species (RNS). Due to their electrophilic nature, these endogenously produced metabolites can react with nucleophilic targets, producing a spectrum of modulatory and protective effects. Determination of NO2-FAs in biological samples is challenging due to their low nanomolar to picomolar endogenous concentrations, indistinct metabolism, and distribution in many tissues and biofluids. Several attempts have been made to develop precise, standardized, and efficient methodologies for assessing physiological and pathophysiological processes to overcome the difficulties associated with their measurement. This review discusses those approaches utilizing liquid chromatography tandem mass spectrometry (LCâMS/MS) and gas chromatography tandem mass spectrometry (GCâMS/MS) for the quantification of NO2-FAs, in addition to a summary of their laboratory synthesis and extraction from biological samples. Clinical associations with different pathological conditions, including hyperlipidaemia, cardiac ischemia and herpes simplex type 2 viral infection (HSV-2), are also discussed.
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Ácidos Grasos , Espectrometría de Masas en Tándem , Humanos , Ácidos Grasos/análisis , Espectrometría de Masas en Tándem/métodos , Cromatografía Liquida/métodos , Cromatografía de Gases y Espectrometría de Masas/métodos , Animales , Nitrocompuestos/análisis , Nitrocompuestos/químicaRESUMEN
Sample preparation in an analytical sequence increases the number of errors, is highly time-consuming, and involves the manipulation of hazardous reagents. Therefore, when an improvement in an analytical method is required, the sample preparation step needs to be optimised or redesigned. Moreover, this step can involve significant toxic reagents and a high volume of waste. In that regard, this study proposes a new procedure based on microwave-assisted wet digestion combining two green strategies: a miniaturised system (with a few microlitres of volume) and the only use of hydrogen peroxide. Three biological samples (human serum, urine, and plant in vitro material) were chosen due to their high potential for disease monitoring, toxicological studies, and biotechnology applications. Several trace elements (Ca, Cd, Co, Cu, Fe, Mg, Mn, Mo, Ni, Se, and Zn) were determined by inductively coupled plasma optical emission spectroscopy and inductively coupled plasma mass spectrometry. For human serum and urine, a certified reference material was used to check for accuracy; the recovery ranged from 72% (Cd, ICP-MS) to 105% (Mg, ICP OES) for serum, while for urine, they varied from 82% (Ni, ICP-MS) to 122% (Zn, ICP-MS). For the soybean callus sample (in vitro plant material), a comparison between the proposed method and the acid digestion method was conducted to evaluate the accuracy, and the results agreed. The detection limits were 0.001-60 µg L-1 (lowest for Cd), thus demonstrating a suitable sensitivity. Moreover, the decomposition efficiency was demonstrated by determining the residual carbon, and a low amount was found in the final product digested (below 0.8% w v-1). A green metric approach was calculated for the proposed method, and according to AGREEprep software, it was found to be around 0.4. Finally, the method was applied to urine samples collected in patients with COVID-19 and soybean callus cultivated with silver nanoparticles. This sample preparation method is a new acidless and miniaturised alternative for elemental analysis involving biological samples.
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This paper introduces an enhanced technique for analyzing iron isotopes in complex marine and biological samples. A dedicated iron purification method for biological marine matrices, utilizing three ion exchange columns, is validated. The MC-ICPMS in pseudo-high-resolution mode determines precise iron isotopic ratios, with sensitivity improved through the DSN-100 desolvating nebulizer system and Apex-IR. Only 2 µg of iron on DSN versus 1 µg on Apex is needed for six replicates (30-60 times improvement) while 10 to 20 µg is required for a single measurement on a wet system considering the resolution power (Rp) is maintained at 11,000-13,000. The Ni-doping method with a Fe/Ni ratio of 1 yields more accurate isotopic ratios than standard-sample bracketing alone. Measurement reproducibility of triplicate samples from marine biological experiments on MC-ICPMS is ± 0.03 (2SD) for δ56Fe and ± 0.07 for δ57Fe (2SD). This study introduces a novel iron purification process specifically designed for marine and biological samples, enhancing sensitivity and enabling more reliable measurements with smaller sample sizes and reduced uncertainties. It proposes iron isotopic compositions for biological reference materials, offering a valuable reference dataset in diverse scientific disciplines.
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Isótopos de Hierro , Espectrometría de Masas , Isótopos de Hierro/análisis , Espectrometría de Masas/métodos , Animales , Reproducibilidad de los Resultados , Agua de Mar/química , Hierro/análisisRESUMEN
Liquid chromatography-mass spectrometry (LC-MS) has emerged as a powerful analytical technique for analyzing complex biological samples. Among various chromatographic stationary phases, porous graphitic carbon (PGC) columns have attracted significant attention due to their unique properties-such as the ability to separate both polar and non-polar compounds and their stability through all pH ranges and to high temperatures-besides the compatibility with LC-MS. This review discusses the applicability of PGC for SPE and separation in LC-MS-based analyses of human biological samples, highlighting the diverse applications of PGC-LC-MS in analyzing endogenous metabolites, pharmaceuticals, and biomarkers, such as glycans, proteins, oligosaccharides, sugar phosphates, and nucleotides. Additionally, the fundamental principles underlying PGC column chemistry and its advantages, challenges, and advances in method development are explored. This comprehensive review aims to provide researchers and practitioners with a valuable resource for understanding the capabilities and limitations of PGC columns in LC-MS-based analysis of human biological samples, thereby facilitating advancements in analytical methodologies and biomedical research.
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A novel ferrofluid prepared from a hydrophobic deep eutectic solvent (DES) and Fe3O4@graphite composite materials was introduced as a green microextraction medium for the separation and enrichment of trace estrogens in real samples. It was found that the ferrofluid greatly improved the capacity and selectivity of target analytes, benefiting from the enrichment of both DES and Fe3O4@graphite composite materials. Using a combination of high-performance liquid chromatography-fluorescence detection (HPLC-FLD) and vortex-assisted liquid-liquid microextraction (VALLME), a new method was established for simultaneous rapid processing and accurate determination of three estrogens (estradiol [E2], estriol [E3], and ethinyl estradiol [EE2]) in environmental water and urine samples. Key parameters affecting the extraction efficiency were optimized using a single-factor approach and response surface methodology. Under optimal conditions, this method yielded a low limit of detection (1.01 ng L-1, 3.03 ng L-1, and 25.0 ng L-1 for EE2, E2, and E3, respectively), wide linear range (3-200,000 ng L-1), high enrichment factors (9.81-47.2), and satisfactory recovery (73.8-129.0%). Compared with traditional analytical techniques, this method avoids the use of volatile toxic organic extraction solvents and cumbersome phase separation operations.
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Estrógenos , Interacciones Hidrofóbicas e Hidrofílicas , Límite de Detección , Microextracción en Fase Líquida , Contaminantes Químicos del Agua , Estrógenos/orina , Estrógenos/análisis , Contaminantes Químicos del Agua/orina , Contaminantes Químicos del Agua/análisis , Microextracción en Fase Líquida/métodos , Cromatografía Líquida de Alta Presión/métodos , Disolventes Eutécticos Profundos/química , HumanosRESUMEN
Understanding and comparing the applicability of electromembrane extraction (EME) and liquid-phase microextraction (LPME) is crucial for selecting an appropriate microextraction approach. In this work, EME and LPME based on supported liquid membranes were compared using biological samples, including whole blood, urine, saliva, and liver tissue. After optimization, efficient EME and LPME of clozapine from four biological samples were achieved. EME provided higher recovery and faster mass transfer for blood and liver tissue than LPME. These advantages were attributed to the electric field disrupting clozapine binding to interfering substances. For urine and saliva, EME demonstrated similar recoveries while achieving faster mass transfer rates. Finally, efficient EME and LPME were validated and evaluated combined with liquid chromatography-tandem mass spectrometry (LC-MS/MS). The coefficient of determination of all methods was greater than 0.999, and all methods showed acceptable reproducibility (≤14%), accuracy (90%-110%), and matrix effect (85%-112%). For liver and blood with high viscosity and complex matrices, EME-LC-MS/MS provided better sensitivity than LPME-LC-MS/MS. The above results indicated that both EME and LPME could be used to isolate non-polar basic drugs from different biological samples, although EME demonstrated higher recovery rates for liver tissue and blood.
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Clozapina , Microextracción en Fase Líquida , Cromatografía Liquida , Reproducibilidad de los Resultados , Espectrometría de Masas en Tándem , Microextracción en Fase Líquida/métodos , Membranas ArtificialesRESUMEN
Benchtop NMR provides improved accessibility in terms of cost, space, and technical expertise. In turn, this encourages new users into the field of NMR spectroscopy. Unfortunately, many interesting samples in education and research, from beer to whole blood, contain significant amounts of water that require suppression in 1H NMR in order to recover sample information. However, due to the significant reduction in chemical shift dispersion in benchtop NMR systems, the sample signals are much closer to the water resonance compared to those in a corresponding high-field NMR spectrum. Therefore, simply translating solvent suppression experiments intended for high-field NMR instruments to benchtop NMR systems without careful consideration can be problematic. In this study, the effectiveness of several popular water suppression schemes was evaluated for benchtop NMR applications. Emphasis is placed on pulse sequences with no, or few, adjustable parameters making them easy to implement. These fall into two main categories: (1) those based on Pre-SAT including Pre-SAT, PURGE, NOESY-PR, and g-NOESY-PR and (2) those based on binomial inversion including JRS and W5-WATERGATE. Among these schemes, solvent suppression sequences based on Pre-SAT offer a general approach for easy solvent suppression for samples with higher analyte concentrations (sucrose standard and Redbull™). However, for human urine, binomial-like sequences were required. In summary, it is demonstrated that highly efficient water suppression approaches can be implemented on benchtop NMR systems in a simple manner, despite the limited spectral dispersion, further illustrating the potential for widespread implementation of these approaches in education and research.
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A sophisticated electrochemical sensor is presented employing a glassy carbon electrode (GCE) modified with a novel composite of synthesized graphitic carbon nitride (g-C3N4) and CoNiO2 bimetallic oxide nanoparticles (g-C3N4/CoNiO2). The sensor's electrocatalytic capabilities for Sunitinib (SUNI) oxidation were demonstrated exceptional performance with a calculated detection limit (LOD) of 52.0 nM. The successful synthesis and integrity of the composite were confirmed through meticulous characterization using various techniques. FT-IR analysis affirmed the successful synthesis of g-C3N4/CoNiO2 by providing insights into its molecular structure. XRD, FE-SEM, SEM-EDX, and BET analyses collectively validated the material's structural integrity, surface morphology, and electrocatalytic performance. Optimization of key analytical parameters, such as loading volume, concentration, electrolyte solution type, and pH, enhanced the electrocatalytic sensing capabilities of g-C3N4/CoNiO2. The synergistic interaction between g-C3N4 and CoNiO2 bimetallic oxide nanoparticles executed the sensor highly effective in the electrical oxidation of SUNI. Across a concentration range of 0.1-83.8 µM SUNI, the anodic peak current exhibited a linear increase with good precision. Application of the newly developed g-C3N4/CoNiO2 system to detect SUNI in a variety of samples, including urine, human serum, and capsule dosage forms, obtained satisfactory recoveries ranging from 97.1 to 103.0%. This methodology offers a novel approach to underscore the potential of the developed sensor for applications in biological and pharmaceutical monitoring.
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Técnicas Electroquímicas , Electrodos , Grafito , Límite de Detección , Compuestos de Nitrógeno , Sunitinib , Grafito/química , Humanos , Sunitinib/química , Sunitinib/análisis , Sunitinib/sangre , Sunitinib/orina , Técnicas Electroquímicas/métodos , Técnicas Electroquímicas/instrumentación , Compuestos de Nitrógeno/química , Nanopartículas del Metal/química , Carbono/química , Óxidos/química , Oxidación-Reducción , Nitrilos/químicaRESUMEN
A reliable, rapid, and inexpensive nano-sized chemosensor is presented for methamidophos (MET) - an insecticide. Poly(lactic acid) (PLA)-stabilized gold nanoparticles (AuNPs) were synthesized by a simple one-pot, two-phase chemical reduction method. The synthesized PLA-AuNPs were subsequently employed for selective, efficient, and quantitative detection of MET. MET is one of the highly toxic pesticides used for eradication of agricultural and urban insects. Upon the addition of MET, the wine-red color of PLA-AuNPs swiftly transformed into greyish-blue, further corroborated by a significant bathochromic and hyperchromic shift in the SPR band. The presence of other interfering insecticides, metal salts, and drugs did not have any pronounced effect on quantitative MET detection. The detection limit, the quantification limit, and linear dynamic range of MET utilizing PLA-AuNPs were 0.0027 µM, 0.005 µM, and 0.005-1000 µM, respectively. The PLA-AuNP-based assay renders an efficient, rapid, accurate, and selective quantification of MET in food, biological, and environmental samples. The proposed sensor provides an appropriate platform for fast and on-the-spot determination of MET without requiring a well-equipped lab setup.
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Insecticidas , Nanopartículas del Metal , Compuestos Organotiofosforados , Oro , Insecticidas/análisis , Colorimetría/métodos , PoliésteresRESUMEN
One-carbon folate metabolites and one-carbon-related amino acids play an important role in human physiology, and their detection in biological samples is essential. However, poor stability as well as low concentrations and occurrence in different species in various biological samples make their quantification very challenging. The aim of this study was to develop a simple, fast, and sensitive ultra-high-performance liquid chromatography MS/MS (UHPLC-MS/MS) method for the simultaneous quantification of various one-carbon folate metabolites (folic acid (FA), tetrahydrofolic acid (THF), p-aminobenzoyl-L-glutamic acid (pABG), 5-formyltetrahydrofolic acid (5-CHOTHF), 5-methyltetrahydrofolic acid (5-CH3THF), 10-formylfolic acid (10-CHOFA), 5,10-methenyl-5,6,7,8-tetrahydrofolic acid (5,10-CH+-THF), and 4-α-hydroxy-5-methyltetrahydrofolate (hmTHF)) and one-carbon-related amino acids (homocysteine (Hcy), methionine (Met), S-ade-L-homocysteine (SAH), and S-ade-L-methionine (SAM)). The method was standardized and validated by determining the selectivity, carryover, limits of detection, limits of quantitation, linearity, precision, accuracy, recovery, and matrix effects. The extraction methods were optimized with respect to several factors: protease-amylase treatment on embryos, deconjugation time, methanol precipitation, and proteins' isoelectric point precipitation on the folate recovery. Ten one-carbon folate metabolites and four one-carbon-related amino acids were detected using the UHPLC-MS/MS technique in various biological samples. The measured values of folate in human plasma, serum, and whole blood (WB) lay within the concentration range for normal donors. The contents of each analyte in mouse plasma were as follows: pABG (864.0 nmol/L), 5-CH3THF (202.2 nmol/L), hmTHF (122.2 nmol/L), Met (8.63 µmol/L), and SAH (0.06 µmol/L). The concentration of each analyte in mouse embryos were as follows: SAM (1.09 µg/g), SAH (0.13 µg/g), Met (16.5 µg/g), 5,10-CH+THF (74.3 ng/g), pABG (20.6 ng/g), and 5-CH3THF (185.4 ng/g). A simple and rapid sample preparation and UHPLC-MS/MS method was developed and validated for the simultaneous determination of the one-carbon-related folate metabolites and one-carbon-related amino acids in different biological samples.
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Carbono , Espectrometría de Masas en Tándem , Humanos , Ratones , Animales , Cromatografía Líquida de Alta Presión/métodos , Espectrometría de Masas en Tándem/métodos , Ácido Fólico/metabolismo , Metionina , Racemetionina , Ácido Glutámico , HomocisteínaRESUMEN
The levels of the MMPs in the biological samples of confirmed patients with gastric cancer are significantly elevated compared to those found in healthy people. Therefore, a novel 3D stochastic microsensor based on graphene oxide, modified with gold nanoparticles and (Z)-N-(pyridin-4-yl-methyl) octadec-9-enamide (namely N2-AuNP/GO), was designed for the determination of MMP-2 in biological samples, and validated for the screening tests of biological samples in order to be used for the early diagnosis of gastric cancer. The proposed sensor presents a low limit of quantification (1.00 × 10-22 g mL-1), high sensitivity (1.84 × 107 s-1 g-1 mL), and a wide working concentration range (1.00 × 10-22-1.00 × 10-7 g mL-1). Recovery values higher than 99.15% were recorded for the assay of MMP-2 in whole blood, gastric tissue tumors, saliva, and urine samples.
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Oro , Grafito , Metaloproteinasa 2 de la Matriz , Nanopartículas del Metal , Grafito/química , Humanos , Metaloproteinasa 2 de la Matriz/sangre , Metaloproteinasa 2 de la Matriz/orina , Metaloproteinasa 2 de la Matriz/metabolismo , Nanopartículas del Metal/química , Oro/química , Neoplasias Gástricas/diagnóstico , Neoplasias Gástricas/sangre , Técnicas Biosensibles/métodosRESUMEN
Proton magnetic resonance spectroscopy (1H MRS) presents a powerful tool for revealing molecular-level metabolite information, complementary to the anatomical insight delivered by magnetic resonance imaging (MRI), thus playing a significant role in in vivo/in vitro biological studies. However, its further applications are generally confined by spectral congestion caused by numerous biological metabolites contained within the limited proton frequency range. Herein, we propose a pure-shift-based 1H localized MRS method as a proof of concept for high-resolution studies of biological samples. Benefitting from the spectral simplification from multiplets to singlet peaks, this method addresses the challenge of spectral congestion encountered in conventional MRS experiments and facilitates metabolite analysis from crowded NMR resonances. The performance of the proposed pure-shift 1H MRS method is demonstrated on different kinds of samples, including brain metabolite phantom and in vitro biological samples of intact pig brain tissue and grape tissue, using a 7.0 T animal MRI scanner. This proposed MRS method is readily implemented in common commercial NMR/MRI instruments because of its generally adopted pulse-sequence modules. Therefore, this study takes a meaningful step for MRS studies toward potential applications in metabolite analysis and disease diagnosis.
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Encéfalo , Espectroscopía de Protones por Resonancia Magnética , Animales , Porcinos , Espectroscopía de Protones por Resonancia Magnética/métodos , Encéfalo/metabolismo , Encéfalo/diagnóstico por imagen , Imagen por Resonancia Magnética/métodos , Vitis/química , Fantasmas de ImagenRESUMEN
OBJECTIVE: Aim: This article is aimed at raising awareness and stimulating scientific discussion on the necessity of involving qualified medical professionals in conducting criminal procedural actions that involve intervention in human somatic rights, in order to further improve the legal instruments ensuring compliance with the European Court of Human Rights (hereinafter referred to as the ECHR) standards in this field. PATIENTS AND METHODS: Materials and Methods: In preparing the article, the following issues were worked out: the provisions of international legal acts; legal positions of the ECHR related to the use of medical knowledge in the criminal process; scientific studies of various aspects of the use of medical knowledge in the criminal process. The methodological basis of the research is dialectical, comparative-legal, systemic-structural, analytical, synthetic, complex research methods. CONCLUSION: Conclusions: The use of medical knowledge in the criminal process generally takes two forms: (a) expert and (b) ancillary. The expert form, particularly forensic medical examination, must adhere to a set of criteria reflected in the practice of the ECHR. Personal searches involving penetration into human body cavities generally align with the requirements of the he European Convention on Human Rights (hereinafter referred to as the Convention), provided certain conditions are met, including medical considerations. The criterion for the admissibility of coercive collection of biological samples for examination is the existence of samples independent of the individual's will.
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Derechos Humanos , Humanos , Derechos Humanos/legislación & jurisprudencia , Europa (Continente) , Medicina Legal/legislación & jurisprudencia , Testimonio de Experto/legislación & jurisprudencia , Derecho Penal/legislación & jurisprudenciaRESUMEN
For the simultaneous determination of monoamine neurotransmitters (NTs) like dopamine, serotonin, noradrenaline, and epinephrine, and their metabolites (metanephrine, normetanephrine, 3-methoxytyramine, vanillylmandelic acid, 3,4-dihydroxyphenylacetic acid, homovanillic acid, and 5-hydroxyindoleacetic acid), a robust liquid chromatography method coupled with tandem mass spectrometry (LC-MS/MS) was introduced as the analytical method. This analytical method proved to be accurate for the simultaneous measurement of the amounts of 11 NTs and their metabolites in biological samples. The method proved to be more efficient and better than the previously reported method in terms of precision, recovery, sample requirement, and extraction procedure. The reported method requires only 100 µL of blood and 200 µL of urine, and the extraction procedure requires acetonitrile precipitation, filtration, drying, and reconstitution in water. The separation of all analytes was performed on an C18 column (4.6 mm × 150 mm and 1.8 µm). A 10 min gradient elution program with a mobile phase consisting of phase A (0.2% formic acid in water) and phase B (methanol) was used. The positive ionization mode was used for the detection of all analytes in multiple reaction monitoring (MRM). The proposed method was validated with an internal standard and yielded lower limits of detection and quantification ranges of 0.0182-0.0797 ng/mL and 0.0553-0.2415 ng/mL, respectively, with a good linearity (R2) between 0.9959 and 0.9994. The recoveries ranged from 73.37% to 116.63% in blood and from 80.9% to 115.33% in urine. For the NTs and metabolites, the intra- and interday % CV were 0.24-9.36 and 0.85-9.67, respectively. The developed LC-MS/MS method was successfully used for the determination of trace amounts of endogenous compounds in human blood and urine samples.
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Cromatografía Líquida con Espectrometría de Masas , Espectrometría de Masas en Tándem , Humanos , Cromatografía Liquida/métodos , Espectrometría de Masas en Tándem/métodos , Neurotransmisores/análisis , Agua , Cromatografía Líquida de Alta Presión/métodos , Extracción en Fase SólidaRESUMEN
Ovarian cancer, which affects the female reproductive organs, is one of the most common types of cancer. Since this type of cancer has a high mortality rate from gynaecological cancers, the scientific community shows great interest in studies on its treatment. Chemotherapy, radiotherapy, and surgical treatment methods are used in its treatment. In the absence of targeted treatments in these treatment methods, side effects occur in patients, and patients show resistance to the drug. In addition, the underlying causes of ovarian cancer are still not fully known. The scientific world thinks that genetic factors, environmental conditions, and consumed foods may cause this cancer. The most important factor in the treatment of ovarian cancer is early diagnosis. Therefore, the drugs used in the treatment of ovarian cancer are platinum-based anticancer drugs. In addition to these drugs, the most preferred treatment method recently is targeted treatment approaches using poly(adenosine diphosphate ribose) polymerase (PARP) inhibitors. In this review, studies on the sensitive analysis of the treatment methods of these new-generation drugs used in the treatment of ovarian cancer have been comprehensively examined. In addition, the basic features, structural aspects, and biological data of analytical methods used in treatments with new-generation drugs are explained. Analytical studies carried out in the literature in recent years aim to show future developments in how these new-generation drugs are used today and to guide future studies by comprehensively examining and explaining the structure-activity relationship, mechanism of action, toxicity, and pharmacokinetic studies. Finally, in this study, the methods used in the analysis of drugs used in the treatment of ovarian cancer and the studies conducted between 2015 and 2023 were discussed in detail.
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Mass spectrometry is characterized by its high sensitivity, ability to measure very low analyte concentrations, specificity to distinguish between closely related compounds, availability to generate high-throughput methods for screening, and high multiplexing capacity. This technique has been used as a platform to analyze fluid biomarkers for Alzheimer's disease. However, more effective sample preparation procedures, preferably antibody-independent, and more automated mass spectrometry platforms with improved sensitivity, chromatographic separation, and high throughput are needed for this purpose. This short communication discusses the development of a fiber-in-tube SPME-CapLC-MS/MS method to determine Aß peptides in cerebrospinal fluid obtained from Alzheimer's disease patients. To obtain the fiber-in-tube SPME capillary, we longitudinally packed 22 nitinol fibers coated with a zwitterionic polymeric ionic liquid into the same length of the PEEK tube. In addition, this communication compares this fiber-in-tube SPME method with the conventional HPLC scale (HPLC-MS/MS) and when directly coupled to CapESI-MS/MS without chromatographic separation, and, as a case study, discusses the benefits and challenges inherent in miniaturizing the flow scale of the sample preparation technique (fiber-in-tube SPME) to the CapLC-MS/MS system. Fiber-in-tube SPME-CapLC-MS/MS provided LLOQ ranging from 0.09 to 0.10 ng mL-1, accuracy ranging from 91 to 117â¯% (recovery), and reproducibility of less than 18â¯% (RSD). Analysis of the cerebrospinal fluid samples obtained from Alzheimer's disease patients evidenced that the method is robust. At the capillary scale (10 µL min-1), this innovative method presented higher analytical sensitivity than the conventional HPLC-MS/MS scale. Although fiber-in-tube SPME directly coupled to CapESI-MS/MS offers advantages in terms of high throughput, the sample was dispersed and non-quantitatively desorbed from the capillary at low flow rate. These results highlighted that chromatographic separation is important to decrease the matrix effect and to achieve higher detectability, which is indispensable for bioanalysis.
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Enfermedad de Alzheimer , Péptidos beta-Amiloides , Microextracción en Fase Sólida , Espectrometría de Masas en Tándem , Enfermedad de Alzheimer/líquido cefalorraquídeo , Humanos , Espectrometría de Masas en Tándem/métodos , Microextracción en Fase Sólida/métodos , Péptidos beta-Amiloides/líquido cefalorraquídeo , Péptidos beta-Amiloides/análisis , Cromatografía Líquida de Alta Presión/métodos , Límite de Detección , Biomarcadores/líquido cefalorraquídeo , Biomarcadores/análisis , Reproducibilidad de los ResultadosRESUMEN
This study involved the assessment of 222Rn concentrations in liquid samples (namely serum and urine) obtained from individuals who were smokers and non-smokers across five distinct age groups in the Najaf Governorate of Iraq. The measurements were conducted using a portable digital Air Things device commonly employed for detecting radon gas in residential environments. This device was placed in a container that is placed in liquid samples, which makes it work to capture the existing radon. The mean value of radon concentrations in serum and urine samples for smokers was 5.64 ± 2.80 Bq/m3 and 3.56 ± 2.31 Bq/m3, respectively. While, the mean value of radon concentrations in serum and urine samples for non-smokers was 2.32 ± 0.67 Bq/m3 and 1.61 ± 1.00 Bq/m3, respectively. By comparing the radon concentrations for serum and urine samples with age and smoking groups, the value of P-Value (p < 0.01) was increased significantly statistically. Also, it is found that a positive and good correlation for radon concentrations between serum and urine. Although the levels of radon were found to be under the globally accepted thresholds, the results of 222Rn in all samples of serum and urine in smokers were higher than in non-smokers. Thus, it may be concluded that cigarette smoking is used as a biomarker of the presence of radon gas.
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Contaminantes Radiactivos del Aire , Contaminación del Aire Interior , Monitoreo de Radiación , Radón , Humanos , Radón/análisis , Contaminación del Aire Interior/análisis , Vivienda , Contaminantes Radiactivos del Aire/análisis , Ambiente , Monitoreo de Radiación/métodosRESUMEN
Arsenic (As) is an environmental pollutant with carcinogenic effects and breast cancer (BC) is a prevalent malignant tumor in women. The goal of this meta-analysis was to establish a connection between biological sample As levels and the risk of developing BC. Pub Med, Web of Science, Scopus, and Elsevier were used to systematically screen the literature published between 1990 and 2023. The Newcastle-Ottawa scale was also used in assessing the quality of publications. A random-effects model was used to assess the pertinent data that was gleaned from these articles. Using the I2 index the heterogeneity of studies was performed. Egger's test and funnel plots were used to look at publication bias. We identified 16 epidemiologic studies that included 2713 women with BC and 5347 healthy individuals. The results showed that the difference between the case group and the control group was 0.72 [95% confidence interval (CI) 0.30 to 1.14]. According to subgroup analysis, the value for blood was 0.18 [95% CI 0.01 to 0.35], whereas the value for hair was 3.08 [95% CI 0.19 to 5.97]. The present meta-analysis suggested that As levels were significantly higher in BC patients than in controls. This systematic review and meta-analysis provide evidence supporting a positive relationship between arsenic levels in biological media and BC risk. These findings highlight the importance of further research to investigate the mechanisms of this association and explore potential preventive strategies to reduce the adverse effects of arsenic exposure on BC.
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BACKGROUND AND AIM: Lead (Pb) is a toxic heavy metal and pervasive environmental contaminant, and a class 2â¯A carcinogen according to the IARC classification, yet its link with cancer at several body sites remains uncertain. Here, we aimed at summarizing the scientific evidence regarding its association with cancer risk and mortality, focusing on studies that carried out Pb measurements in biological samples. METHODS: We reviewed articles published in PubMed and EMBASE until January 2nd, 2024, that quantified the epidemiological association between Pb measured in blood, urine, nails, and other biological media, and cancer risk and mortality (overall and by cancer site/type). RESULTS: We included 46 articles (out of 8022 screened) published in 1995-2023 and reporting on investigations conducted in fifteen countries. In terms of design, 20 were prospective, 24 were retrospective case-control studies, and 2 were cross-sectional. Pb levels were determined in blood in the majority of studies (n=28). The most consistent evidence was for the association of Pb with cancer of the gastrointestinal tract, particularly the oesophagus, stomach (RR ranging from 0.80 to 2.66), colon-rectum, and pancreas; and of the bladder and urinary tract (RR from 1.10 to 2.89). For other specific malignancies, the data were conflicting or too limited to draw reliable conclusions. Finally, increased Pb concentration in blood and urine was consistently associated with higher overall cancer incidence and mortality. CONCLUSIONS: Lead is a widespread and highly persistent environmental pollutant associated with cancer at multiple body sites. Comprehensive primary prevention interventions aiming at reducing opportunities for Pb exposure need to be continuously promoted and implemented.