Search

Illicit drug use has become a global issue, posing significant health, socioeconomic, and cultural risks. The study examined essential trace metals: selenium, zinc, and copper in blood concentrations, as well as in serum and scalp hair samples, from 240 male drug-abuse subjects/patients aged 18-45, categorized into three age groups. The study compared 45 healthy subjects of the same age group using an acid digestion method supported by a microwave oven during sample preparation. The technique of atomic absorption spectrometry was employed to identify essential and toxic elements, utilizing certified reference materials for accuracy. According to a recent study, plasma zinc and selenium concentrations in drug abusers are lower than those in referent subjects, potentially increasing vulnerability to infection due to poor nutritional status or other contaminants., (© 2024. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Nitro fatty acids (NO 2 -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 NO 2 -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 (LC‒MS/MS) and gas chromatography tandem mass spectrometry (GC‒MS/MS) for the quantification of NO 2 -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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

The complexity of the drug market and the constant updating of drugs have been challenging issues for drug regulatory authorities. With the emergence of new psychoactive substances (NPS) and the nonmedical use of prescription drugs, forensic and toxicology laboratories have had to adopt new drug screening methods and advanced instrumentation. Using high-performance liquid chromatography coupled with Orbitrap mass spectrometry, we developed a screening method for common NPS and other drugs. Two milliliters of mixed solvent of n-hexane and ethyl acetate (1:1, v:v) were added to 500 μL of blood or urine sample for liquid-liquid extraction, and methanol extraction was used for hair samples. The developed method was applied to 3897 samples (including 332 blood samples, 885 urine samples, and 2680 hair samples) taken from drug addicts in a province of China during 2019-2021. For urine and blood samples, the limits of detection (LODs) ranged from 1.68 pg/mL to 10.7 ng/mL. For hair samples, the LODs ranged from 3.30 × 10 -5 to 4.21 × 10 -3  ng/mg. The matrix effects of urine, blood, and hair samples were in the range of 47.6%-121%, 39.8%-139%, and 6.35%-118%, respectively. And the intra-day precision was 3.5%-6.0% and the inter-day precision was 4.18%-9.90%. Analysis of the actual samples showed an overall positive detection rate of 58.9%, with 5.32% of the samples indicating the use of multiple drugs., (© 2024 American Academy of Forensic Sciences.)

Hypertension is often asymptomatic and can substantially elevate the risk of cardiovascular complications. Olmesartan medoxomil works by competitively blocking the angiotensin II receptors, preventing angiotensin II from constructing the blood vessels and releasing aldosterone. This discussion is focused on the critical analytical methods used to analyze olmesartan medoxomil in pharmaceutical and biological samples. A variety of analytical methods have been employed to both qualitatively and quantitatively determine the analyte, including high-performance thin-layer chromatography (HPTLC), high-performance liquid chromatography (HPLC), voltammetry, capillary zone electrophoresis, UV/Vis spectrophotometry, and 96-microwell assays. The review also includes official methods published in the Indian Pharmacopoeia. Based on existing literature, simple spectrophotometry and liquid chromatography are commonly used to analyze olmesartan medoxomil. These findings provide a solid foundation for future olmesartan medoxomil drug analysis research., (Copyright © 2024 Académie Nationale de Pharmacie. Published by Elsevier Masson SAS. All rights reserved.)

The analysis of biological samples is highly valuable for disease diagnosis and treatment, forensic examination, and public safety. However, the serious matrix interference effect generated by biological samples severely affects the analysis of trace analytes. Sample preparation methods are introduced to address the limitation by extracting, separating, enriching, purifying trace target analytes from biological samples. With the raising demand of biological sample analysis, a review focuses on media for biological sample preparation and analysis over the last 5 years is presented. High-performance media in biological sample preparation are first reviewed, including porous organic frameworks, imprinted polymers, hydrogels, ionic liquids, and bioactive media. Then, application of media for different biological sample preparation and analysis is briefly introduced, including liquid samples of body fluids, solid samples (hair, feces, and tissues), and gas samples of exhale breath gas. Finally, conclusions and outlooks on media promoting biological sample preparation are presented., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The potential pesticide hazard to non-target organisms is a global concern. It is critical to develop the sensitive detection methods of multiple pesticides in various complex matrices. Here, benzene-1,3,5-tricarbaldehyde (BTCA) and 1,3,5-Tri (4-aminophenyl) benzene (TAPB) were employed as precursors for the in-situ growth of COF TAPB-BTCA on the surface of amino-functionalized stainless steel wire (SS) via a solvothermal method. The successful COF TAPB-BTCA bonded fiber exhibited significant enrichment capability of pyrethroids insecticides (PYs), organophosphorus (OPPs), and organochlorine (OCPs), with enrichment factors (EFs) ranging from 1133-7762, 1319-7291, and 734.1-2882, respectively. X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations indicated that various interactions contributed to its high enrichment capacity. Automated detection of PYs, OPPs, and OCPs in water, foods, and biological samples was realized by coupling this fiber with gas chromatography-mass spectrometry (GC-MS). The detection limits were as low as 0.0370-0.657 ng/L, 0.0128-0.400 ng/L, and 0.0329-0.202 ng/L for PYs, OPPs, and OCPs, respectively. In addition, the environmental risks of these samples were assessed based on the above data. This work not only provided a straightforward technique for sensitive monitoring of pesticides in complex matrices but also presented a novel approach for the in-situ controlled growth of versatile adsorbents with broad-spectrum properties., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Background and Aim: Lead (Pb) is a toxic heavy metal and pervasive environmental contaminant, and a class 2 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., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Eletriptan (ETR), a selective pharmaceutical agent agonist of the 5-hydroxytryptamine1 receptor subtype, are primarily used to treat acute migraine attacks. ETR is a triptan-class medication that works by narrowing cerebral blood vessels and reducing chemicals that produce headache pain, light and sound sensitivity, and nausea. Due to its effectiveness in reducing migraine symptoms, it is a worthwhile choice for those looking for quick and efficient treatment. A green, raid, one-pot and straightforward fluorescence spectrometric method was employed to evaluate ETR in tablets and biological samples. By introducing the ETR drug and the fluorescent ligand, Acid red 87, in an acidic buffer, a quenching of the ligand native fluorescent was promptly produced. The quenching action was simply attributed to the selective ion-pair complex generation between the cationic target and the selected ligand. An increase in ETR concentration was linearly proportional to the quenching response in the 50.0 - 500.0 ng/mL range. The optimal configurations for adjusting the system's variable parameters were determined by examining the ETR-Acid red 87 system's response. Additionally, the sensor that was developed met the standards set by the International Council for Harmonisation of Technical Requirements of Pharmaceuticals for Human Use. The sensitivity thresholds of the approach were 13.8 and 42.0 ng/mL for the detection and quantification parameters, respectively, LOD and LOQ. This approach proficiently evaluated the pharmaceutical and biological samples of ETR. Finally, the proposed approach not only simplifies the analysis process but also limits the badimpact on the environment, making it a promising technique for analytical applications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Background: There is widespread interest in the design of portable electrochemical sensors for the selective monitoring of biomolecules. Dopamine (DA) is one of the neurotransmitter molecules that play a key role in the monitoring of some neuronal disorders such as Alzheimer's and Parkinson's diseases. Facile synthesis of the highly active surface interface to design a portable electrochemical sensor for the sensitive and selective monitoring of biomolecules (i.e., DA) in its resources such as human fluids is highly required., Results: The designed sensor is based on a three-dimensional phosphorous and sulfur resembling a g-C 3 N 4 hornet's nest (3D-PS-doped CNHN). The morphological structure of 3D-PS-doped CNHN features multi-open gates and numerous vacant voids, presenting a novel design reminiscent of a hornet's nest. The outer surface exhibits a heterogeneous structure with a wave orientation and rough surface texture. Each gate structure takes on a hexagonal shape with a wall size of approximately 100 nm. These structural characteristics, including high surface area and hierarchical design, facilitate the diffusion of electrolytes and enhance the binding and high loading of DA molecules on both inner and outer surfaces. The multifunctional nature of g-C 3 N 4 , incorporating phosphorous and sulfur atoms, contributes to a versatile surface that improves DA binding. Additionally, the phosphate and sulfate groups' functionalities enhance sensing properties, thereby outlining selectivity. The resulting portable 3D-PS-doped CNHN sensor demonstrates high sensitivity with a low limit of detection (7.8 nM) and a broad linear range spanning from 10 to 500 nM., Significance: The portable DA sensor based on the 3D-PS-doped CNHN/SPCE exhibits excellent recovery of DA molecules in human fluids, such as human serum and urine samples, demonstrating high stability and good reproducibility. The designed portable DA sensor could find utility in the detection of DA in clinical samples, showcasing its potential for practical applications in medical settings., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Rifampicin is a frontline antibiotic in the management of tuberculosis. Since no spectrofluorimetric methods are reported for this drug, this approach was challenged to craft a sensitive, reliable, valid, fast, and green methodology. In recent years, fluorescence spectroscopy has received a lot of interest. Its benefits include ecological greenness and analytical performance. The pharmaceutical industries greatly like this approach because of its low energy and decreased solvent usage, which make it both economical and environmentally friendly. This methodology was based on utilizing the enhanced native fluorescence of the rifampicin at 341 nm after excitation at 241 nm in a beta-cyclodextrin micellar system. Modern developments in analytical chemistry have been applied to reduce risks to the workplace and environment by using distilled water as a dilution solvent for method application and optimization. The method was found excellent green with 97 eco-scale and 0.86 AGREE scores besides an 89.6 overall whiteness score. The range of linearity for rifampicin raw material was 0.2-1.5 μg·mL -1 , and the average recoveries for raw material and spiked plasma were 100.15% and 99.64%, respectively. The suggested technique worked well for the commercial oral syrup of Rimactane® and did not conflict with any common additives., (© 2024 John Wiley & Sons Ltd.)

In this work, electromembrane extraction (EME) was used for the first time to separate aconitine (AC), mesaconitine (Mes-AC) and hypaconitine (Hyp-AC) from biological samples and Chinese herbal medicines. Efficient EME of polar and high molecular weight aconitine alkaloids from different sample matrices was achieved with the solvent of 1-ethyl-2-nitrobenzene (ENB). Under the optimal EME conditions, EME provided recoveries for all targets in the range of 72%-74 %, 85%-103 % and 92%-94 % for whole blood, urine and aqueous samples. The proposed EME systems combined with LC-MS/MS and HPLC-UV were evaluated using different sample matrices, and the methods displayed satisfactory analytical characteristic including negligible matrix effect. The LOD and LOQ of AC, Mes-AC, and Hyp-AC by EME-LC-MS/MS were in the range of 0.002-0.068 ng/mL and 0.005-0.228 ng/mL respectively. The LOD and LOQ of AC, Mes-AC, and Hyp-AC by EME-HPLC-UV were in the range of 0.06-0.26 μg/mL and 0.20-0.86 μg/mL, respectively. The coefficient of determination, R 2 -value was ≥0.9926 for all cases, and the accuracy in the linear ranges was in the range of 91%-111 %. Finally, the method was successfully applied for the qualitative and quantitative analysis of AC and Mes-AC in the whole blood and herbal medicine dreg samples from an actual forensic case, and poisoning by aconitum alkaloids was identified as the cause of death. Therefore, we believe that EME could be a powerful tool to identify poisoning, and EME has great potential for efficient separation of polar and high molecular weight substances. These are of great importance in the fields of but not limited to forensic science, Traditional Chinese Medicine and clinics., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Kynurenic acid (KA) is an active metabolite of tryptophan with notable biological effects, such as antioxidant, neuroprotective, and anti-inflammatory properties. It often undergoes changes of the concentration in biological fluids in chronic diseases. Thus, detecting KA is of great importance for diagnosing inflammatory and neurodegenerative conditions, monitoring disease progression, and assessing responses to pharmacological treatment. This study aimed to design a tailored, flexible platform for sensitive and direct electrochemical detection of KA in biological fluids. Carbon-based electrodes were custom-printed in the lab using specialized inks and flexible substrates. The working electrodes were further functionalized with graphene oxide and subsequently electrochemically reduced to increase the sensitivity toward the analyte. An optimized differential pulse voltammetry protocol was developed for KA detection. The elaborated platform was firstly characterized and then evaluated regarding the analytical performances. It showed a good limit of detection (3 nM and demonstrated the capability to detect KA across a broad concentration range (0.01-500 μM). Finally, the elaborated flexible platform, was succesfully applied for KA determination in serum and saliva samples, in comparison with an optimized HPLC-UV method. The developed platform is the first example of in-lab printed flexible platform reported in literature so far for KA detection. It is also the first study reported in the literature of detection of KA in raw saliva collected from 10 subjects. The sensitivity towards the target analyte, coupled with the adaptability and portability, showcases the potential of this platform for thus illustrating great potential for further development of wearable sensors and biomedical applications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

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., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.)

Capsule phase microextraction (CPME) is an efficient bioanalytical technique that streamlines the sample preparation by integrating the filtration and stirring mechanism directly into the device. A novel composite sorbent designed to be selective towards the target analytes consisting of mixed-mode sorbent chemistry synthesized by sol-gel technology is found promising and superior to the conventional C 18 sorbents. Herein we describe the encapsulation of an ionic liquid (IL)/Carbowax 20M-functionalized sol-gel sorbent (sol-gel IL/Carbowax 20 M) in the lumen of porous polypropylene tubes for the capsule phase microextraction of three phosphodiesterase-5 inhibitors namely avanafil, sildenafil, and tadalafil in human serum and urine samples. The CPME device was characterized by Scanning Electron Microscopy (SEM) and Fourier-Transform Infrared Spectroscopy (FT-IR). The experimental parameters of CPME procedure (e.g. sample pH and ionic strength, extraction time, stirring rate, elution solvent and volume) were carefully optimized to achieve the highest possible extraction efficiency for the analytes. Method validation was conducted in terms of precision, linearity, accuracy, matrix effect, lower limits of quantification, and limits of detection (LOD). The method linearity was investigated in the range of 50-1000 ng mL -1 for all analytes while the precision was less than 11.8 % in all cases. For all analytes, the LOD values were 17 ng mL -1 . The IL/CW 20M-functionalized microextraction capsules could be reused at least 25 times both for urine and serum samples. The green character and the applicability of the proposed method were evaluated using the ComplexGAPI and BAGI indexes. The optimized CPME protocol exhibited reduced consumption of organic solvent and generation of waste, cost-effectiveness, and simplicity. Finally, the proposed method was successfully applied to the analysis of sildenafil in human urine after administration of drug-containing formulation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Background: Sugar phosphates (SPx) play important role in the metabolism of the organism. SPx such as glycerate 3-phosphate, fructose 6-phosphate and glucose 6-phosphate in biological samples have the poor stability, similar structure and low abundance, which make their separation and detection more challenging., Method: UiO-66-NH 2 and ZrO 2 coated SiO 2 (SBA-15) hard-core-shell adsorbents (UiO-66-NH 2 @SBA-15 and ZrO 2 @SBA-15) were synthesized, which were further used for dispersive solid-phase extraction for enriching the SPx in biological samples. The protocol was developed by UiO-66-NH 2 @SBA-15 and ZrO 2 @SBA-15 coupled with gas chromatography-mass spectrometry for the detection of trace SPx. The univariate experiment and response surface methodology were used to optimize the adsorption and desorption conditions., Results: The adsorbents showed excellent adsorption capacity and specificity towards SPx, which were proved by adsorption and selective experiments. Under the optimized conditions, there were good linearity within the range of 5.0-5000.0 ng mL -1 , low limits of detection (0.001-1.0 ng mL -1 ), low limits of quantification (0.005-5.0 ng mL -1 ) and good precision (relative standard deviation less than 14.7 % for intra-day and inter-day). The satisfactory recoveries (89.1-113.8 %) and precision (0.5-14.6 %) were obtained when the sorbents were used to extract SPx from serum, saliva and cell samples. Moreover, UiO-66-NH 2 @SBA-15 was applied to the quantitative analysis of SPx from gastric cancer patients, because of a higher adsorption capacity (169.5-196.1 mg g -1 )., Conclusions: UiO-66-NH 2 @SBA-15 showed great potential in the extraction of SPx in biological samples, which was beneficial to find out the metabolic change of SPx and explain the pathogenesis of the disease., Competing Interests: Declaration of competing interest We declare that we have no financial and personal relationships with other people or organizations that can inappropriately influence our work, there is no professional or other personal interest of any nature or kind in any product, service and/or company that could be construed as influencing the position presented in, or the review of, the manuscript entitled., (Copyright © 2024 Elsevier B.V. All rights reserved.)

A sophisticated electrochemical sensor is presented employing a glassy carbon electrode (GCE) modified with a novel composite of synthesized graphitic carbon nitride (g-C 3 N 4 ) and CoNiO 2 bimetallic oxide nanoparticles (g-C 3 N 4 /CoNiO 2 ). 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-C 3 N 4 /CoNiO 2 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-C 3 N 4 /CoNiO 2 . The synergistic interaction between g-C 3 N 4 and CoNiO 2 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-C 3 N 4 /CoNiO 2 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., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

Metalloproteins binding with trace elements play a crucial role in biological processes and on the contrary, those binding with exogenous heavy metals have adverse effects. However, the methods for rapid, high sensitivity and simultaneous analysis of these metalloproteins are still lacking. In this study, a fast method for simultaneously determination of both essential and toxic metal-containing proteins was developed by coupling size exclusion chromatography (SEC) with inductively coupled plasma tandem mass spectrometry (ICP-MS/MS). After optimization of the separation and detection conditions, seven metalloproteins with different molecular weight (from 16.0 to 443.0 kDa) were successfully separated within 10 min and the proteins containing iron (Fe), copper (Cu), zinc (Zn), iodine (I) and lead (Pb) elements could be simultaneously detected with the use of oxygen as the collision gas in ICP-MS/MS. Accordingly, the linear relationship between log molecular weight and retention time was established to estimate the molecular weight of unknown proteins. Thus, the trace metal and toxic metal containing proteins could be detected in a single run with high sensitivity (detection limits in the range of 0.0020-2.5 μg/mL) and good repeatability (relative standard deviations lower than 4.5 %). This method was then successfully used to analyze metal (e.g., Pb, Zn, Cu and Fe) binding proteins in the blood of Pb-intoxicated patients, and the results showed a negative correlation between the contents of zinc and lead binding proteins, which was identified to contain hemoglobin subunit. In summary, this work provided a rapid and sensitive tool for screening metal containing proteins in large number of biological samples., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Background: Atomic force microscopy (AFM) is one of the main techniques used to characterize the mechanical properties of soft biological samples and biomaterials at the nanoscale. Despite efforts made by the AFM community to promote open-source data analysis tools, standardization continues to be a significant concern in a field that requires common analysis procedures. AFM-based mechanical measurements involve applying a controlled force to the sample and measure the resulting deformation in the so-called force-distance curves. These may include simple approach and retract or oscillatory cycles at various frequencies (microrheology). To extract quantitative parameters, such as the elastic modulus, from these measurements, AFM measurements are processed using data analysis software. Although open tools exist and allow obtaining the mechanical properties of the sample, most of them only include standard elastic models and do not allow the processing of microrheology data. In this work, we have developed an open-source software package (called PyFMLab, as of python force microscopy laboratory) capable of determining the viscoelastic properties of samples from both conventional force-distance curves and microrheology measurements., Methods: PyFMLab has been written in Python, which provides an accessible syntax and sufficient computational efficiency. The software features were divided into separate, self-contained libraries to enhance code organization and modularity and to improve readability, maintainability, testability, and reusability. To validate PyFMLab, two AFM datasets, one composed of simple force curves and another including oscillatory measurements, were collected on HeLa cells., Results: The viscoelastic parameters obtained on the two datasets analysed using PyFMLab were validated against data processing proprietary software and against validated MATLAB routines developed before obtaining equivalent results., Conclusions: Its open-source nature and versatility makes PyFMLab an open-source solution that paves the way for standardized viscoelastic characterization of biological samples from both force-distance curves and microrheology measurements., Competing Interests: No competing interests were disclosed., (Copyright: © 2024 López-Alonso J et al.)

Enrichment and quantification of sugar phosphates (SPx) in biological samples were of great significance in biological medicine. In this work, a series of zirconium-based metal-organic frameworks (MOFs) with different degrees of defects, namely, HP-UiO-66-NH 2 - X , were synthesized using acetic acid as a modulator and were utilized as high-capacity adsorbents for the adsorption of SPx in biological samples. The results indicated that the addition of acetic acid altered the morphology of HP-UiO-66-NH 2 - X , with corresponding changes in pore size (3.99-9.28 nm) and specific surface area (894.44-1142.50 m 2 ·g -1 ). HP-UiO-66-NH 2 -10 showed the outstanding performance by achieving complete adsorption of all four SPx using only 80 μg of the adsorbent. The excellent adsorption efficiency of HP-UiO-66-NH 2 -10 was also obtained with a wide pH range and short adsorption time (10 min). Adsorption experiments demonstrated that the adsorption process involved chemical adsorption and multilayer adsorption. By utilizing X-ray photoelectron spectroscopy and density functional theory to explain the adsorption mechanism, it was found that various interactions (including coordination, hydrogen bonding, and electrostatic interactions) collectively contributed to the exceptional adsorption capability of HP-UiO-66-NH 2 -10. Those results indicated that the defect strategy not only increased the specific surface area and pore size, providing additional adsorption sites, but also reduced the adsorption energy between HP-UiO-66-NH 2 -10 and SPx. Moreover, HP-UiO-66-NH 2 -10 showed a low limit of detection (0.001-0.01 ng·mL -1 ), high precision (<13.77%), and accuracy (80.10-111.83%) in serum, liver, and cells, good stability, high selectivity (SPx/glucose, 1:100 molar ratio), and high adsorption capacity (292 mg·g -1 for SPx). The practical detection of SPx from human serum was also verified, prefiguring the great potentials of defective zirconium-based MOFs for the enrichment and detection of SPx in the biological medicine.

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 × 10 7 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.

Reducing monosaccharides and their phosphates are critical metabolites in the central carbon metabolism pathway of living organisms. Variations in their content can indicate abnormalities in metabolic pathways and the onset of certain diseases, necessitating their analysis and detection. Reducing monosaccharides and their phosphates exhibit significant variations in content within biological samples and are present in many isomers, which makes the accurate quantification of reducing monosaccharides and their phosphates in biological samples a challenging task. Various analytical methods such as spectroscopy, fluorescence detection, colorimetry, nuclear magnetic resonance spectroscopy, sensor-based techniques, chromatography, and mass spectrometry are employed to detect monosaccharides and phosphates. In comparison, chromatography and mass spectrometry are highly favored for their ability to simultaneously analyze multiple components and their high sensitivity and selectivity. This review thoroughly evaluates the current chromatographic and mass spectrometric methods used for detecting reducing monosaccharides and their phosphates from 2013 to 2023, highlighting their efficacy and the advancements in these analytical technologies.

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 1 H 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., (© 2024 The Authors. Magnetic Resonance in Chemistry published by John Wiley & Sons Ltd.)

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 Aβ 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 117 % (recovery), and reproducibility of less than 18 % (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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Herein, a simple, sensitive, and reliable dispersive solid phase extraction was reported for the efficient extraction of sunitinib from biological samples. To facilitate the extraction of the desired analyte from urine and plasma samples, magnetic MIL-101Cr (NH 2 ) @SiO 2 @ NiFe 2 O 4 was synthesized by a hydrothermal method and applied as an effective sorbent during the extraction process. After adsorption of the drug using 10 mg of MIL-101Cr (NH 2 ) @ SiO 2 @ NiFe 2 O 4 nanoparticles through vortexing (1 min), the sorbent was separatedfrom the sample solution using a magnet. To eluate the drug, the sorbent containing the sunitinib was contacted with 100 µL dimethylformamide. The eluent was analyzed by high performance liquid chromatography-tandem mass spectrometry. Reasonable validation data consisting of low limits of detection (0.14, 0.35, and 0.70 ng mL -1 in deionized water, plasma, and urine) and quantification (0.48, 1.2, and 2.4 ng mL -1 in deionized water, plasma, and urine, respectively), a wide linear range of the calibration curve (0.48-200, 1.2-200, and 2.4-100 ng mL -1 in deionized water, plasma, and urine, respectively) good extraction recovery (76 %), and low relative standard deviations for inter- and intra-day precisions (6.9 %) were obtained by the method. Eventually, the proposed procedure was effectively implemented on both plasma and urine samples, yielding successful outcomes., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

This study involved the assessment of 222 Rn 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/m 3 and 3.56 ± 2.31 Bq/m 3 , respectively. While, the mean value of radon concentrations in serum and urine samples for non-smokers was 2.32 ± 0.67 Bq/m 3 and 1.61 ± 1.00 Bq/m 3 , 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 222 Rn 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., Competing Interests: Declaration of competing interest There is no Interest Statement., (Published by Elsevier Ltd.)

Proton magnetic resonance spectroscopy ( 1 H 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 1 H 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 1 H 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.

Poor fluorescence recovery at low analyte dosages and slow ligand binding kinetics are critical challenges currently limiting the use of aptamer-functionalized hydrogels for sensing small molecules. In this paper, we report an adenosine-responsive hydrogel sensor that integrates FRET-signaling aptamer switches into in situ-gelling thin-film hydrogels. The hydrogel sensor is able to entrap a high proportion of the sensing probes (>70% following vigorous washing), delay nucleolytic degradation, stabilize weak aptamer complexes to improve hybridization affinity and suppress fluorescence background, and provide high sensitivity in biological fluids (i.e., undiluted human serum). Furthermore, the developed hydrogel sensors were able to achieve low limits of detection (5.3 μM in buffer and 8.8 μM in serum) within 4 min of exposure to the sample, with signal generation requiring only 20 μL/well of analyte sample. The physical nature of the aptamer encapsulation allows this approach to accommodate virtually any small-molecule aptamer, avoiding the need for covalent anchoring and the complex modification of nucleic acid sequences typically required for effective aptamer-based molecular recognition.

We developed a novel electrochemical sensor for the detection of alfuzosin (AFZ), a drug used to treat benign prostatic hyperplasia, using a double-shelled Co 3 O 4 /NiCo 2 O 4 nanocomposite-modified electrode. The nanocomposites were synthesized using a template-assisted approach, with zeolitic imidazole framework-67 (ZIF-67) as the sacrificial template, involving the formation of uniform ZIF-67/Ni-Co layered double hydroxide (LDH) hollow structures followed by calcination to achieve the final nanocomposite. The nanocomposite was characterized by various techniques and showed high porosity, large surface area, and good conductivity. The nanocomposite-modified electrode exhibited excellent electrocatalytic activity towards AFZ oxidation, with a wide linear range of 5-180 µM and a low limit of detection of 1.37 µM. The sensor also demonstrated good repeatability, reproducibility, and stability selectivity in the presence of common interfering substances. The sensor was successfully applied to determine the AFZ in pharmaceutical tablets and human serum samples, with satisfactory recoveries. Our results suggest that the double-shelled Co 3 O 4 /NiCo 2 O 4 nanocomposite is a promising material for the fabrication of electrochemical sensors for AFZ detection.

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.

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 I 2 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., (© 2024. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

It is a fact that materials contract or expand by changing their temperature. In a certain temperature range, the distance between atoms changes linearly in some materials whereas it changes non-linearly in other materials. X-ray diffraction (XRD) is one of the popular techniques used for understanding the crystal structure of these materials. However, XRD is mostly carried in open air at room temperature or require very expensive high vacuum set-ups and expensive temperature controllers for low temperature studies. Here we propose a design of a variable temperature X-ray diffractometer that can operate in dual modes: heating and cooling in open air. The proposed diffractometer has been used for studying structural phase transition in chromium nitride thin films. The results demonstrated not only the effectiveness of our proposed setup but also its applicability in advancing our understanding of complex material behaviors.•A new design of a variable temperature X-ray diffractometer has been introduced in this paper, which can be used for acquiring XRD data while heating or cooling samples in open air.•As a proof of concept, the newly designed variable temperature X-ray diffractometer is used for studying structural phase transition in CrN thin films., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2024 The Author.)

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 ( R 2 ) 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.

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-CH 3 THF), 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-CH 3 THF (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-CH 3 THF (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.

Chemical attribution is a vital tool to attribute chemicals or related materials to their origins in chemical forensics via various chemometric methods. Current progress related to organophosphorus nerve agents (OPNAs) has mainly focused on the attribution of chemical sources and synthetic pathways. It has not yet been applied in matching exposed biological samples to their sources. This work used chemical attribution to explore organic impurity profiles in biological samples exposed to various OPNAs. Chemical attribution was first used to identify the exposure source of biological samples based on the full-scan data via comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometer (GC × GC-TOFMS). Taking peak area as the only variable, it can quickly match exposed samples to their sources by applying unsupervised or supervised models, screen difference compounds via one-way ANOVA or t-tests, and then identify valuable impurities that can distinguish different types of exposed samples. To further obtain the impurity profile only applicable to a certain weapon' samples, the irrelevant components were removed via conventional methods. The findings showed there were 53 impurities that can promote distinguishing six groups of OPNA exposed samples, as well as 42 components that can be used as valuable impurities to distinguish class G and class V samples. These were all unique impurities that appear in a certain weapon' samples. The outcomes can be a reference for tracing the source for OPNA-exposed samples, which was beneficial to the further development in source matching of forensic samples. Moreover, the chemical attribution for impurity profiles in biological samples after weapons exposure may inspire research into the characteristics of impurity profile in biological samples as well as practical applications of chemical attribution for OPNA-exposed samples, that may expand potential biomarkers and break the limits of existing markers in the future., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

In this research, a sol-gel Carbowax 20M-zwitterionic ionic liquid composite sorbent-based capsule phase microextraction (CPME) device was developed in combination with liquid chromatography-post column derivatization for the first ever reported determination of a somatostatin analogue - lanreotide in human urine. The sol-gel Carbowax 20M-zwitterionic ionic liquid composite sorbent was encapsulated in the lumen of a polypropylene capillary tube and characterized by FT-IR spectroscopy and SEM with energy dispersive X-ray spectroscopy (EDS). The main steps of the CPME workflow were optimized to obtain high extraction efficiency for the target analyte. After the separation of the analyte on a C 8 stationary phase, the peptide was derivatized online with o-phthalaldehyde before the fluorescence detection. The main experimental parameters of CPME and the post-column procedures were systematically investigated and optimized. The method was validated in terms of selectivity, linearity, accuracy, precision, limits of detection (LOD), and limits of quantification (LOQ). The relative bias ranged between 88.8 and 115.6 % for the peptide, while the RSD values for repeatability and intermediate precision were less than 14.3 %. The achieved limit of detection (LOD) was 0.2 μΜ while the limit of quantitation (LOQ) was established as 0.9 μΜ. Finally, the sol-gel Carbowax 20M-zwitterionic ionic liquid composite sorbent-based microextraction capsules were found to be reusable for at least 20 extractions. The developed method presented adequate overall performance, and it could be applied in the analysis of selected peptide in human urine samples., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

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., (© 2024 Wiley-VCH GmbH.)

Dimetridazole (DMZ) is a derivative of nitroimidazole and is a veterinary drug used as an antibiotic to treat bacterial or protozoal infections in poultry. The residues of DMZ cause harmful side effects in human beings. Thus, we have constructed a superior electrocatalyst for DMZ detection. A copper (Cu)-integrated poly(aniline) (PANI) electrocatalyst (PANI-Cu@BSA) was prepared by using a one-step method of biomimetic mineralization and polymerization using bovine serum albumin (BSA) as a stabilizer. Then, the synthesized PANI-Cu@BSA was encapsulated with reduced graphene oxide (rGO) using an ultrasonication method. The PANI-Cu@BSA/rGO nanocomposite had superior water dispersibility, high electrical conductivity, and nanoscale particles. Moreover, a PANI-Cu@BSA/rGO nanocomposite-modified, screen-printed carbon electrode was used for the sensitive electrochemical detection of DMZ. In phosphate buffer solution, the PANI-Cu@BSA/rGO/SPCE displayed a current intensity greater than PANI-Cu@BSA/SPCE, rGO/SPCE, and bare SPCE. This is because PANI-Cu@BSA combined with rGO increases fast electron transfer between the electrode and analyte, and this synergy results in analyte-electrode junctions with extraordinary conductivity and active surface areas. PANI-Cu@BSA/rGO/SPCE had a low detection limit, a high sensitivity, and a linear range of 1.78 nM, 5.96 μA μM -1 cm -2 , and 0.79 to 2057 μM, respectively. The selective examination of DMZ was achieved with interfering molecules, and the PANI-Cu@BSA/rGO/SPCE showed excellent selectivity, stability, repeatability, and practicability.

This study aimed to develop a fast, accurate, and precise high-performance liquid chromatography with UV detection method for simultaneous analysis of underivatized phenylalanine (Phe) and tyrosine (Tyr) in biological samples. Separation of the analytes was accomplished using a Discovery HS F5-3 column, which offered better retention and peak symmetry for the tested analytes. Chromatographic conditions were optimized using central composite experimental design, and three factors were investigated: the concentration of ammonium acetate (A), the acetonitrile proportion in the mobile phase (B) and the column oven temperature (C). The approach was verified using β-expectation tolerance intervals for total error measurement that did not exceed 15%. Optimal settings were A = 50 mm, B = 24% and C = 28°C. The method applicability was determined using human plasma from 75 volunteers. The limits of detection and quantification of the technique were satisfactory at 9 and 29 μm for Phe and 4 and 13 μm for Tyr. The mean analytical bias in spiking levels was acceptable, ranging from -1.649 to +1.659% for both substances, with RSD <5% in all instances. The suggested approach was successfully used to analyze Phe and Tyr in human blood samples and calculate the Phe/Tyr ratio., (© 2023 John Wiley & Sons Ltd.)

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., (© 2023 Wiley Periodicals LLC.)

The Folin-Ciocalteu method is a well-established and widely used assay for measuring total (poly)phenol content in food/plant products. In recent years, there has been growing interest in applying this method to human samples due to its simplicity and efficacy. However, biological matrices such as blood and urine contain several interference substances that must be eliminated beforehand. This mini-review summarizes the current state of knowledge regarding the use of the Folin-Ciocalteu assay to measure total phenolic content in human urine and blood samples, as well as the preceding cleaning methods to remove interferences. Higher total (poly)phenol levels measured by the Folin-Ciocalteu method have been associated with a decrease in mortality and several risk variables. We focus on the application of this sustainable assay as a biomarker of poly(phenol) intake and its potential use as an anti-inflammatory biomarker in clinical laboratories. The Folin-Ciocalteu method, with a clean-up extraction step, is a reliable tool for determining total (poly)phenol consumption. Here, we also recommend using the Folin-Ciocalteu assay as means to measure anti-inflammatory activity.

Lipid peroxidation occurs when substances, such as reactive oxygen species, attack lipids. Polyunsaturated fatty acids are the main targets. Several products are formed, including primary products such as lipid hydroperoxides and secondary products such as malondialdehyde (MDA), the most used lipid peroxidation biomarker. As MDA levels are elevated in several diseases, MDA is an essential indicator for assessing pathological states. The thiobarbituric acid reactive substances assay is the most widely used method for MDA determination. However, it lacks specificity. Capillary Electrophoresis (CE) is a separation technique that has been used to quantify MDA in biological samples. This technique has advantages such as the low amount of biological sample required, absence or low volume of organic solvent, short analysis time, separation of interferents, sample preparation step with only protein precipitation, and the possibility of direct detection of the MDA, without derivatization. To our knowledge, this review article is the first to show the CE background for analyzing MDA in biological samples. Therefore, given the potential of MDA in evaluating pathological states, this article demonstrates the potential of CE to become a reference method for MDA determination in clinical analysis laboratories, which will play a significant role in diagnosing and monitoring diseases.

In light of potential risks of heavy metal exposure, diverse aptasensors have been developed through the combination of aptamers with nanomaterials for the timely and efficient detection of metals in environmental and biological matrices. Aptamer-based sensors can benefit from multiple merits such as heightened sensitivity, facile production, uncomplicated operation, exceptional specificity, enhanced stability, low immunogenicity, and cost-effectiveness. This review highlights the detection capabilities of nanomaterial-based aptasensors for heavy-metal and metalloid ions based on their performance in terms of the basic quality assurance parameters (e.g., limit of detection, linear dynamic range, and response time). Out of covered studies, dendrimer/CdTe@CdS QDs-based ECL aptasensor was found as the most sensitive option with an LOD of 2.0 aM (atto-molar: 10 -18 M) detection for Hg 2+ . The existing challenges in the nanomaterial-based aptasensors and their scientific solutions are also discussed., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Wine has a rich history dating back to 2200 BC, originally recognized for its medicinal properties. Today, with the aid of advanced technologies like metabolomics and sophisticated analytical techniques, we have gained remarkable insights into the molecular-level changes induced by wine consumption in the human organism. This review embarks on a comprehensive exploration of the alterations in human metabolome associated with wine consumption. A great number of 51 studies from the last 25 years were reviewed; these studies systematically investigated shifts in metabolic profiles within blood, urine, and feces samples, encompassing both short-term and long-term studies of the consumption of wine and wine derivatives. Significant metabolic alterations were observed in a wide variety of metabolites belonging to different compound classes, such as phenolic compounds, lipids, organic acids, and amino acids, among others. Within these classes, both endogenous metabolites as well as diet-related metabolites that exhibited up-regulation or down-regulation following wine consumption were included. The up-regulation of short-chain fatty acids and the down-regulation of sphingomyelins after wine intake, as well as the up-regulation of gut microbial fermentation metabolites like vanillic and syringic acid are some of the most important findings reported in the reviewed literature. Our results confirm the intact passage of certain wine compounds, such as tartaric acid and other wine acids, to the human organism. In an era where the health effects of wine consumption are of growing interest, this review offers a holistic perspective on the metabolic underpinnings of this centuries-old tradition.

Bio-SELEX is a revolutionary method for the discovery of novel biomarkers within biological samples, offering profound insights into diagnosing both infectious and non-infectious diseases. This innovative strategy involves three crucial steps: Traditional SELEX, Pull Down, and mass spectrometry. Firstly, Traditional SELEX involves the systematic selection of specific nucleic acid sequences (aptamers) that bind to the target molecules of interest. These aptamers are generated through iterative rounds of selection, amplification, and enrichment, ultimately yielding highly selective ligands. Secondly, the Pull-Down phase employs these aptamers to capture and isolate the target biomarkers from complex biological samples. This step ensures the specificity of the selected aptamers in binding to their intended targets. Lastly, mass spectrometry is utilized to identify and quantify the captured biomarkers, providing precise information about their presence and concentration in the sample. These quantitative data are invaluable in disease diagnosis and monitoring. Bio-SELEX's significance lies in its ability to discover biomarkers for a wide range of diseases, spanning infectious and non-infectious conditions. This approach holds great promise for early disease detection, personalized medicine, and the development of targeted therapies. By harnessing the power of aptamers and mass spectrometry, Bio-SELEX advances our understanding of disease biology and opens new avenues for improved healthcare.

Here, an imine-linked-based spherical covalent organic framework (COF) was prepared at room temperature. The as-synthesized spherical COF served as an adsorbent in dispersive solid-phase extraction (dSPE), by its virtue of great surface area (1542.68 m 2 /g), regular distribution of pore size (2.95 nm), and excellent stability. Therefore, a simple and high-efficiency dispersive solid phase extraction method based on a spherical COF coupled with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was established to determine aryl organophosphate esters in biological samples. This approach displayed favorable linearity in the range of 10.0-1000.0 ng/L (r > 0.9989), a high signal enhancement factor (58.8-181.8 folds) with low limits of detection (0.3-3.3 ng/L). Moreover, it could effectively eliminate complex matrix interference to accurately extract seven aryl organophosphate esters from mouse serum and tissue samples with spiked recoveries of 82.0%-117.4%. The as-synthesized spherical COF has been successfully applied in sample preparation. The dSPE-HPLC-MS/MS method based on a spherical COF has potential application to study the pollutants' metabolism in vivo., (© 2023 Wiley-VCH GmbH.)

Sphingolipids play crucial roles in cellular membranes, myelin stability, and signalling responses to physiological cues and stress. Among them, sphingosine 1-phosphate (S1P) has been recognized as a relevant biomarker for neurodegenerative diseases, and its analogue FTY-720 has been approved by the FDA for the treatment of relapsing-remitting multiple sclerosis. Focusing on these targets, we here report three novel polymeric capture phases for the selective extraction of the natural biomarker and its analogue drug. To enhance analytical performance, we employed different synthetic approaches using a cationic monomer and a hydrophobic copolymer of styrene-DVB. Results have demonstrated high affinity of the sorbents towards S1P and fingolimod phosphate (FTY-720-P, FP). This evidence proved that lipids containing phosphate diester moiety in their structures did not constitute obstacles for the interaction of phosphate monoester lipids when loaded into an SPE cartridge. Our suggested approach offers a valuable tool for developing efficient analytical procedures., (© 2023. The Author(s).)

Electrochemical sensors, due to their excellent and unique features, are of high interest nowadays for the detection and monitoring of several biological compounds. In such a case, serotonin (SRN), an important neurotransmitter, was herein studied for its detection in biological fluids since its presence is more crucial to be monitored and detected in clinical and medical applications. Several study strategies have been used to determine the chemical and physical properties. The crystalline size of the constructed copper sulfide (Cu 2 S) material was measured to be 25.92 nm. The Cu 2 S was fabricated over the working surface and further analyzed for several sensor parameters to be optimized. The charge transfer resistance of the copper sulfide-modified glassy carbon electrode (Cu 2 S/GCE) was determined to be about 277.0 Ω. With the linear range from about 0.029 μM to 607.6 μM for SRN, the limit of detection (LOD) was calculated as 3.2 nM, with a good sensitivity of 13.23 μA μM -1 cm 2 . The sensor experienced excellent repeatability, reproducibility, and long-term stability. The fabricated electrode was selective with the presence of different interfering compounds. The real sample analysis, as determined with the regular addition method with human serum and urine samples, revealed a good recovery percentage. Thus, the employed fabricated electrode material will be highly effective in sensing other analytes of choice.

As a substance present in organisms, nitrite is a metabolite of nitric oxide and can also be ingested. Nitrate is the metabolite of nitrite. Therefore, it is necessary to measure it quickly, easily and accurately to evaluate the health status of humans. Although there have been several reviews on analytical methods for non-biological samples, there have been no reviews focused on both sample preparation and analytical methods for biological samples. First, rapid and accurate nitrite measurement has significant effects on human health. Second, the detection of nitrite in biological samples is problematic due to its very low concentration and matrix interferences. Therefore, the pretreatment plus measuring methods for nitrite and nitrate obtained from biological samples since 2010 are summarized in the present review, and their prospects for the future are proposed. The treatment methods include liquid-liquid microextraction, various derivatization reactions, liquid-liquid extraction, protein precipitation, solid phase extraction, and cloud point extraction. Analytical methods include spectroscopic methods, paper-based analytical devices, ion chromatography, liquid chromatography, gas chromatography-mass spectrometry, electrochemical methods, liquid chromatography-mass spectrometry and capillary electrophoresis. Derivatization reagents with rapid quantitative reactions and advanced extraction methods with high enrichment efficiency are also included. Nitrate and nitrate should be determined at the same time by the same analytical method. In addition, much exploration has been performed on formulating fast testing through microfluidic technology. In this review, the newest developments in nitrite and nitrate processing are a focus in addition to novel techniques employed in such analyses.

Data mining involves the computational analysis of a plethora of publicly available datasets to generate new hypotheses that can be further validated by experiments for the improved understanding of the pathogenesis of neurodegenerative diseases. Although the number of sequencing datasets is on the rise, microarray analysis conducted on diverse biological samples represent a large collection of datasets with multiple web-based programs that enable efficient and convenient data analysis. In this review, we first discuss the selection of biological samples associated with neurological disorders, and the possibility of a combination of datasets, from various types of samples, to conduct an integrated analysis in order to achieve a holistic understanding of the alterations in the examined biological system. We then summarize key approaches and studies that have made use of the data mining of microarray datasets to obtain insights into translational neuroscience applications, including biomarker discovery, therapeutic development, and the elucidation of the pathogenic mechanisms of neurodegenerative diseases. We further discuss the gap to be bridged between microarray and sequencing studies to improve the utilization and combination of different types of datasets, together with experimental validation, for more comprehensive analyses. We conclude by providing future perspectives on integrating multi-omics, to advance precision phenotyping and personalized medicine for neurodegenerative diseases.