Generic Sample Research Articles

Power Amplifier Modeling Framework for Front-End-Aware Next-Generation Wireless Networks

Next-generation wireless systems require increased spectral and energy efficiency in terminals. This can only be achieved if the nonlinear characteristics of the radio front-end, primarily the power amplifier (PA), are known and considered while designing algorithms or optimizing radio links. PA datasheets contain limited information, and wideband PA measurements typically require advanced equipment and software. This paper proposes a measurement and signal processing framework that enables the acquisition of nonlinear PA characteristics using generic complex sample transmitters and receivers, e.g., software-defined radio (SDR). This paper also proposes a multistage signal calibration and synchronization procedure that allows obtaining nonlinear PA characteristics that are non-distorted by other phenomena. The correctness and usefulness of the proposed framework are demonstrated by measuring three PAs, each under varying supply voltage and carrier frequency. At the same time, the high variability of the obtained nonlinear characteristic justifies the need for PA measurements to obtain awareness of nonlinear characteristics.

Development of a generic sample preparation method using dispersive liquid-liquid microextraction for the monitoring of leachable compounds in hospital pharmacy-prepared prefilled drug products.

Performant sample preparation is mandatory in any leachable study to clean and preconcentrate analytes within the sample to offer the best possible extraction recovery as well the best precision for any given substance. The aim consists in developing a sample preparation method for hospital pharmacy-prepared drug products such as long-term storage prefilled syringes, vials and IV bags for the screening of leachable compounds. The Quality Control Laboratory of the Pharmacy of the Lausanne University Hospital (Switzerland) has developed a time- and cost-effective, highly sensitive, robust, and fast method using liquid chromatography coupled with high-resolution mass spectrometry (LC-HRMS) for the analysis of 205 plastic additives. An innovative setup, based on postcolumn infusion (PCI) using 2% ammonium hydroxide in methanol was used to boost the signal intensity of the analytes in MS detection. A database for extractable and leachable trace assessment (DELTA) was built to assist in the screening process of 205 plastic packaging-related compounds. The development of the sample preparation was based on 33 plastic additive candidates in different hospital pharmacy compounding solutions, and their extraction recovery rates as well as their relative standard deviation were taken into consideration. In conclusion, the developed DLLME was assigned with ultrasound assistance and triple extraction, which brought about extraction recovery rates between 67% and 92%, a good RSD <10%, and a preconcentration factor of 50×. Therefore, DLLME could be considered suitable for the semiquantitative screening of leachable additives in simple hospital pharmacy-prepared prefilled drug products.

In vitro quantitative and qualitative analysis of anti-hypertensive tablets and comparison between their generic versus branded formulations

Background: While generic drugs and branded drugs are supposed to be bioequivalent, generic drugs have the additional benefit of being available at a lower cost which can be important in patients with chronic diseases such as hypertension. However, there are some concerns among clinicians that generic drugs may not be as effective as the branded counterparts. Hence, there is a need to generate comparative data between the branded and the generic drugs. Aims and Objectives: The objective of the study was to compare the pharmaceutical parameters and costs of four generic antihypertensive drugs with their branded counterparts. Materials and Methods: Four antihypertensive drugs, namely, Ramipril, atenolol, enalapril, and amlodipine were considered for evaluation for which their generic and branded samples were taken. All the drugs were in tablet form. The costs of these drugs were recorded, and various in vitro tests were conducted to assess and compare their characteristics, including disintegration, dissolution, hardness, weight variation, friability, thickness, diameter, and quantitative analysis using high-performance liquid chromatography and ultraviolet spectrophotometry. These tests were done in accordance with the specifications outlined in the Indian pharmacopoeia 2018. Results: All the branded drugs were more expensive than the generic counterparts. Quantitative assay of the generic sample of ramipril tablets showed a lower amount of the active ingredient than the stated value. Apart from the hardness values of the tablets, all the generic and branded samples fell within the specified normal range for most of the other important parameters. Conclusion: Generic antihypertensive tablets, were less costly than their branded counterparts and generally met the specified standards in in vitro testing. However, there were instances of subpar hardness results and a deficiency in the stated drug amount in the generic (less ramipril content in sample). These findings suggest the importance of rigorous quality control measures for generic medications particularly for those formulations liable for degradation.

Comprehensive characterization of organic compounds in indoor dust after generic sample preparation with SUPRAS and analysis by LC-HRMS/MS

In this study supramolecular solvents (SUPRAS) are employed for the first time to perform a wide screening of organic compounds in indoor dust samples. The potential of SUPRAS to efficiently extract a wide polarity range of compounds, and to simplify and improve the green properties of sample treatment in this area are discussed. SUPRAS made up of inverse aggregates of hexanol in tetrahydrofuran:water mixtures, which have been previously and successfully applied to the target determination of a variety of organic contaminants in different environmental matrices, were employed. Analysis was done with liquid chromatography and high resolution mass spectrometry. Twelve samples from public buildings (six educative buildings, two food stores, two nightclubs, one office and a coffee shop) were collected in South Spain. A total of 146 compounds were detected by target (∼33 %), suspect (∼55 %) and non-target screening (∼12 %). Around 86 % of all the compounds were identified (or tentatively identified) with levels of confidence equal or higher than 3. Novel designer drugs of abuse, unreported organophosphorus compounds and well-known organic contaminants, such as bisphenols, parabens, phthalates and flame retardants are reported. Differences with previous studies on wide screening of indoor dust reveal the influence of the employed databases for data processing and of the extraction method together with the different contamination profiles given by the sample location.

Non-targeted analysis of lipidic extracts by high-resolution mass spectrometry to characterise the chemical exposome: Comparison of four clean-up strategies applied to egg

Biota samples are used to monitor chemical stressors and their impact on the ecosystem and to describe dietary chemical exposure. These complex matrices require an extraction step followed by clean-up to avoid damaging sensitive analytical instruments based on chromatography coupled to mass spectrometry. While interest for non-targeted analysis (NTA) is increasing, there is no versatile or generic sample preparation for a wide range of contaminants suitable for a diversity of biotic matrices. Among the contaminants’ variety, persistent contaminants are mostly hydrophobic (mid- to non-polar) and bio-magnify through the lipidic fraction. During their extraction, lipids are generally co-extracted, which may cause matrix effect during the analysis such as hindering the acquired signal. The aim of this study was to evaluate the efficacy of four clean-up methods to selectively remove lipids from extracts prior to NTA. We evaluated (i) gel permeation chromatography (GPC), (ii) Captiva EMR-lipid cartridge (EMR), (iii) sulphuric acid degradation (H2SO4) and (iv) polydimethyl siloxane (PDMS) for their efficiency to remove lipids from hen egg extracts. Gas and liquid chromatography coupled with high-resolution mass spectrometry fitted with either electron ionisation or electrospray ionisation sources operating in positive and negative modes were used to determine the performances of the clean-up methods. A set of 102 chemicals with a wide range of physico-chemical properties that covers the chemical space of mid- to non-polar contaminants, was used to assess and compare recoveries and matrix effects. Matrix effects, that could hinder the mass spectrometer signal, were lower for extracts cleaned-up with H2SO4 than for the ones cleaned-up with PDMS, EMR and GPC. The recoveries were satisfactory for both GPC and EMR while those determined for PDMS and H2SO4 were low due to poor partitioning and degradation/dissociation of the compounds, respectively. The choice of the clean-up methods, among those assessed, should be a compromise that takes into account the matrix under consideration, the levels and the physico-chemical properties of the contaminants.

Enteric-coating film effect on the delayed drug release of pantoprazole gastro-resistant generic tablets.

Background: Enteric coating films in acidic labile tablets protect the drug molecule from the acidic environment of the stomach. However, variations in the excipients used in the coating formulation may affect their ability to provide adequate protection. This study is the first to investigate the potential effects of coating materials on the protective functionality of enteric coating films for pantoprazole (PNZ) generic tablets after their recall from the market. Methods: A comparative analysis was conducted between generic and branded PNZ products, using pure drug powder for identification. The in vitro release of the drug was evaluated in different pH media. The study also utilized various analytical and thermal techniques, including differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier-transform infrared (FTIR), and confocal Raman microscopy. Results: The in vitro assessment results revealed significant variations in the release profile for the generic product in acidic media at 120 min. DSC and TGA thermal profile analyses showed slight variation between the two products. XRD analysis exhibited a noticeable difference in peak intensity for the generic sample, while SEM revealed smaller particle sizes in the generic product. The obtained spectra profile for the generic product displayed significant variation in peaks and band intensity, possibly due to impurities. These findings suggest that the excipients used in the enteric coating film of the generic product may have affected its protective functionality, leading to premature drug release in acidic media. Additionally, the presence of polysorbate 80 (P-80) in the brand product might improve the properties of the enteric coating film due to its multi-functionality. Conclusions: In conclusion, the excipients used in the brand product demonstrated superior functionality in effectively protecting the drug molecule from acidic media through the enteric coating film, as compared to the generic version.

Diverse Sample Generation: Pushing the Limit of Generative Data-Free Quantization.

Generative data-free quantization emerges as a practical compression approach that quantizes deep neural networks to low bit-width without accessing the real data. This approach generates data utilizing batch normalization (BN) statistics of the full-precision networks to quantize the networks. However, it always faces the serious challenges of accuracy degradation in practice. We first give a theoretical analysis that the diversity of synthetic samples is crucial for the data-free quantization, while in existing approaches, the synthetic data completely constrained by BN statistics experimentally exhibit severe homogenization at distribution and sample levels. This paper presents a generic Diverse Sample Generation (DSG) scheme for the generative data-free quantization, to mitigate detrimental homogenization. We first slack the statistics alignment for features in the BN layer to relax the distribution constraint. Then, we strengthen the loss impact of the specific BN layers for different samples and inhibit the correlation among samples in the generation process, to diversify samples from the statistical and spatial perspectives, respectively. Comprehensive experiments show that for large-scale image classification tasks, our DSG can consistently quantization performance on different neural architectures, especially under ultra-low bit-width. And data diversification caused by our DSG brings a general gain to various quantization-aware training and post-training quantization approaches, demonstrating its generality and effectiveness.

A Novel Part in the Swiss Army Knife for Linking Biodiversity Data: The digital specimen identifier service

Digital specimens are new information objects on the internet, which act as digital surrogates of the physical objects they represent. They are designed to be extended with data derived from the specimen like genetic, morphological and chemical data, and with data that puts the specimen in context of its gathering event and the environment it was derived from. This requires linking the digital specimens and their related entities to information about agents, locations, publications, taxa and environmental information. To establish reliable links and (re-)connect data to specimens, a new framework is needed, which creates persistent identifiers (PIDs) for the digital specimen and its related entities. These PIDs should be actionable by machines but also can be used by humans for data citation and communication purposes. The framework that enables this is a new PID infrastructure, produced by the European Commission-funded BiCIKL project (Biodiversity Community Integrated Knowledge Library), creates persistent and actionable identifiers. It is a generic PID infrastructure that will be used by the Distributed System for Scientific Collections research infrastructure (DiSSCo), but it can also be used by other infrastructures and institutions. PIDs minted by DiSSCo will be linked to the digital specimens and samples provided through DiSSCo. The new PIDs are a key element in enabling the concept of Digital Extended Specimens (Webster et al. 2021) and provide unique and resolvable references to enable bidirectional linking. DiSSCo has done extensive work to select the most appropriate PID scheme (Hardisty et al. 2021) and to design a PID infrastructure for the pan-European specimens. The draft design has been discussed with technical specialists in the joint DiSSCo and Consortium of European Taxonomic Facilities (CETAF) community, with international stakeholders like the Global Biodiversity Information Facility (GBIF) and Integrated Digitized Biocollections (iDigBio) and was discussed at the 2022 conference of the Society for the Preservation of Natural History Collections (SPNHC). A first implementation was demonstrated in the Biodiversity Information Standards (TDWG) annual conference in 2022 and illustrated key elements in the design. To be able to provide digital specimen identifiers as DOIs (Digital Object Identifiers), a pilot project was started in 2023 with DataCite to investigate if Digital Specimen DOIs in the new PID infrastructure can be created using the DataCite service. The pilot aim was to create metadata crosswalks to the DataCite schema in consultation with the DataCite Metadata Working Group, to evaluate synergies with the IGSN (International Generic Sample Number) metadata schema, to develop and test PID kernel metadata registration, and to evaluate performance and the impact of using DataCite services. There are around two billion specimens and creating PIDs for them as DOIs requires creating DOIs at an unprecedented scale. Also, PID kernel metadata registration is new for DOIs. The included metadata for specimens will complement existing Biodiversity Information Standards such as Darwin Core, and supports the new MIDS (Minimum Information about a digital specimen) standard that is under development. The design, development and testing of the new PID infrastructure is being done as part of the BiCIKL project that aims to foster collaboration between infrastructures and develop bidirectional connections (Penev et al. 2022). In the session, we will demonstrate the results in development of the PID infrastructure as part of the BiCIKL toolbox to link biodiversity data and to discuss the progress with creating digital specimen DOIs.

Intelligent automatic operational modal analysis

Operational modal analysis methods have been proven especially useful to identify existing structures and infrastructures under serviceability conditions. However, the installation of sensing systems for monitoring continuously an ever larger number of existing constructions has motivated significant efforts towards the automation of the available methods.Within this framework, the present paper introduces a new paradigm for the automatic output-only modal identification of linear structures under ambient vibrations, namely the intelligent automatic operational modal analysis (i-AOMA). It exploits the covariance-based stochastic subspace (SSI-cov) algorithm for the output-only identification of the modal parameters and its workflow consists of two main phases. Initially, quasi-random samples of the control parameters for the SSI-cov algorithm are generated. Once the SSI-cov algorithm is performed for each sample, the corresponding stabilization diagrams are processed in order to prepare a database for training the intelligent core of the i-AOMA method. This is a machine learning technique (namely a random forest algorithm) that predicts which combination of the control parameters for the SSI-cov algorithm is able to provide good modal estimates. Afterward, new quasi-random samples of the control parameters for the SSI-cov algorithm are generated repeatedly until a statistical convergence criterion is achieved. If the generic sample is classified as feasible by the intelligent core of the i-AOMA method, then the SSI-cov algorithm is performed. Finally, stable modal results are distilled from the stabilization diagrams and relevant statistics are computed to evaluate the uncertainty level due to the variability of the control parameters.The proposed i-AOMA method has been applied to identify the modal features of the Al-Hamra Firduos Tower, an iconic 412.6 m tall building located in Kuwait City (Kuwait). The final results well agree with a previous experimental study, and it was also possible to identify two new vibration modes of the structure. The implemented open-source Python code is made freely available.

Automated Proteomics Workflows for High-Throughput Library Generation and Biomarker Detection Using Data-Independent Acquisition.

Sequential window acquisition of all theoretical mass spectra-mass spectrometry underpinned by advanced bioinformatics offers a framework for comprehensive analysis of proteomes and the discovery of robust biomarkers. However, the lack of a generic sample preparation platform to tackle the heterogeneity of material collected from different sources may be a limiting factor to the broad application of this technique. We have developed universal and fully automated workflows using a robotic sample preparation platform, which enabled in-depth and reproducible proteome coverage and characterization of bovine and ovine specimens representing healthy animals and a model of myocardial infarction. High correlation (R2 = 0.85) between sheep proteomics and transcriptomics datasets validated the developments. The findings suggest that automated workflows can be employed for various clinical applications across different animal species and animal models of health and disease.

Improved pseudo-force approach for Monte Carlo Simulation of non-linear fractional oscillators under stochastic excitation

This paper presents a step-by-step procedure for the numerical integration of the fractional differential equation governing the response of single-degree-of-freedom (SDOF) non-linear systems endowed with fractional derivatives subjected to stochastic excitation. The procedure, labeled improved pseudo-force method (IPFM), is developed by extending a step-by-step integration scheme proposed by the second author for the numerical solution of classical differential equations. The IPFM relies on the following main steps: i) to use the Grünwald–Letnikov (GL) approximation of the fractional derivative; ii) to treat terms depending on the unknown values of the response, which result from the GL approximation as well as from the non-linear restoring forces, as pseudo-forces; iii) to handle non-linearities by performing iterations at each time step. The IPFM provides accurate solutions by using time steps of larger size compared to classical step-by-step integration schemes. In this paper, the IPFM is applied within the framework of classical Monte Carlo Simulation (MCS) to evaluate the time domain dynamic response of non-linear fractional systems subjected to the generic sample of a stochastic excitation.

Use of ion chromatographic pulsed amperometric method (IC-PAD) for measuring aqueous sulfide in synthetic and real domestic wastewater

Sulfide detection in domestic wastewater is widely demanded, as sulfide induces odour nuisance and wastewater assets corrosion. However, traditional sulfide detection methods are usually plagued by the limited detection range or interference from impurities. To address these constraints, this study improved the ion chromatographic pulsed amperometric method (IC-PAD) and tested its validity for use in domestic wastewater. Prior to sulfide detection, sulfide-containing sample collection usually requires the use of sulfide antioxidant buffers (SAOB) to minimize sulfide loss. Different sample matrixes require different SAOB recipes, which increases complexity and uncertainty when measuring different environmental samples. Therefore, this study also developed a more convenient and generic sample collection method without the addition of SAOB. The results indicated that the proposed SAOB-free sample collection method could minimize the sulfide loss during sample collection. The IC-PAD method showed a wide linear detection range up to 10 mg-S/L. The detection limit was 3 μg-S/L. Matrix effect studies showed that 1 g/L glucose, formate, acetate, methanol, ethanol, propionate, butyrate, lactate, or sulfate had no evident interference on sulfide measurement. However, 5 mM phosphate buffer led to interference, but reducing the KOH eluent concentration from 62 to 30 mM avoid this interference. Wolfe's vitamin mixture and Wolfe's modified mineral mixture could cause diminutive interference equivalent to 2.53 ± 1.32 μg-S/L sulfide. Moreover, the interference caused by chloride indicated that the IC-PAD method is more applicable for measuring sulfide in low-chloride wastewater. To this end, the IC-PAD method showed high accuracy and precision in the real domestic wastewater samples with chloride concentration of 68 mg/L. The recovery was higher than 97% and the relative standard deviation (RSD) was lower than 1.2%. This study demonstrated the potential use of IC-PAD method for measuring sulfide in real domestic wastewater and possible interference from the solution matrix to be considered.

Assessment of contaminants of emerging concern in European apex predators and their prey by LC-QToF MS wide-scope target analysis

Apex predators are good indicators of environmental pollution since they are relatively long-lived and their high trophic position and spatiotemporal exposure to chemicals provides insights into the persistent, bioaccumulative and toxic (PBT) properties of chemicals. Although monitoring data from apex predators can considerably support chemicals’ management, there is a lack of pan-European studies, and longer-term monitoring of chemicals in organisms from higher trophic levels. The present study investigated the occurrence of contaminants of emerging concern (CECs) in 67 freshwater, marine and terrestrial apex predators and in freshwater and marine prey, gathered from four European countries. Generic sample preparation protocols for the extraction of CECs with a broad range of physicochemical properties and the purification of the extracts were used. The analysis was performed utilizing liquid (LC) chromatography coupled to high resolution mass spectrometry (HRMS), while the acquired chromatograms were screened for the presence of more than 2,200 CECs through wide-scope target analysis. In total, 145 CECs were determined in the apex predator and their prey samples belonging in different categories, such as pharmaceuticals, plant protection products, per- and polyfluoroalkyl substances, their metabolites and transformation products. Higher concentration levels were measured in predators compared to prey, suggesting that biomagnification of chemicals through the food chain occurs. The compounds were prioritized for further regulatory risk assessment based on their frequency of detection and their concentration levels. The majority of the prioritized CECs were lipophilic, although the presence of more polar contaminants should not be neglected. This indicates that holistic analytical approaches are required to fully characterize the chemical universe of biota samples. Therefore, the present survey is an attempt to systematically investigate the presence of thousands of chemicals at a European level, aiming to use these data for better chemicals management and contribute to EU Zero Pollution Ambition.

Advanced throughput analytical strategies for the comprehensive HRMS screening of organic micropollutants in eggs of different bird species

Raptors are ideal indicators for biomonitoring studies using wildlife in order to assess the environmental pollution in the terrestrial ecosystem, since they are placed in the highest trophic position in the food webs and their life expectancy is relatively long. In this study, 26 eggs of 4 bird species (Peregrine falcon, Eurasian curlew, Little owl and Eagle owl) collected in Germany, were investigated for the presence of persistent organic pollutants (POPs) and thousands of contaminants of emerging concern (CECs). Generic sample preparation protocols were followed for the extraction of the analytes and the purification of the extracts, and the samples were analyzed both by liquid (LC) and gas chromatography (GC) coupled to high resolution mass spectrometry (HRMS), for capturing a wide range of organic micropollutants with different physicochemical properties. State-of-the-art screening methodologies were applied in the acquired HRMS data, including wide-scope target analysis of 2448 known pollutants and suspect screening of over 65,000 environmentally relevant compounds. Overall, 58 pollutants from different chemical classes, such as plant protection products, per- and polyfluoroalkyl substances and medicinal products, as well as their transformation products, were determined through target analysis. Most of the detected compounds were lipophilic (logP>2), although the presence of (semi)polar contaminants should not be overlooked, underlying the need for holistic analytical approaches in environmental monitoring studies. p,p’-DDE, PCB 153 and PCB138, PFOS and methylparaben were the most frequently detected compounds. 50 additional substances were identified and semi-quantified through suspect screening workflows, including mainly compounds of industrial use with high production volume.

A Generic Sample Preparation Approach for Different Microfluidic Labs-on-Chips

Sample preparation refers to the task of generating fluids with a specified target concentration. Generally, this is achieved by performing a set of mixing operations between biochemical fluids with a given volumetric ratio. Sample preparation plays a crucial role in several medical applications. Microfluidic devices or labs-on-chips (LoCs) got established as a suitable solution to realize this task in a miniaturized, integrated, and automatic fashion. Over the years, a variety of different microfluidic platforms emerged, which all have their respective pros and cons. Accordingly, numerous approaches aiming at the sample preparation problem have been proposed—each specialized on a single platform only. More precisely, sample preparation methods introduced thus far provide solutions for a particular platform only, i.e., they are platform specific. In this work, we propose a generic approach that generalizes the constraints of the different microfluidic platforms and, by this, provides a platform-independent sample preparation method. This allows designers to quickly check what existing platform is most suitable for the considered task and to easily support upcoming and future microfluidic platforms as well. We evaluated the performance of the proposed method with a wide range of test cases and concluded (from the evaluations) that the proposed generic approach is capable of efficiently generating results for various platforms with a quality that is close to results from dedicated approaches presented thus far.

Germanium-Tin (GeSn) Metal-Semiconductor-Metal (MSM) Near-Infrared Photodetectors.

Narrow-bandgap germanium–tin (GeSn) is employed to fabricate metal–semiconductor–metal (MSM) near-infrared photodetectors with low-dark currents and high responsivity. To reduce the dark current, the SiO2 layer is inserted in between the metal and semiconductor to increase the barrier height, albeit at the expense of photocurrent reduction. To couple more incident light into the absorption layer to enhance the responsivity, the distributed Bragg reflectors (DBRs) are deposited at the bottom of the GeSn substrate while placing the anti-reflection layer on the surface of the absorption layer. With the interdigital electrode spacing and width, both set at 5 µm and with 1 V bias applied, it is found the responsivities of the generic MSM control sample detector, the MSM with DBR, and the MSM with AR layer are 0.644 A/W, 0.716 A/W, and 1.30 A/W, respectively. The corresponding specific detectivities are 8.77 × 1010, 1.11 × 1011, and 1.77 × 1011 cm·Hz1/2/W, respectively. The measurement data show that these designs effectively enhance the photocurrent and responsivity. At 1 V bias voltage, normalized responsivity evinces that the photodetection range has been extended from 1550 nm to over 2000 nm, covering the entire telecommunication band. Incorporating GeSn as a sensing layer offers one of the new alternative avenues for IR photodetection.

Probing for peptidic drugs (2-10kDa) in doping control blood samples.

Bioactive peptides with a molecular mass between 2 and 10kDa represent an important class of substances banned in elite sports, which has been recognized with an increasing number and variety of substances by anti-doping organizations. Also, the annually renewed list of prohibited substances of the World Anti-Doping Agency (WADA) explicitly mentions more and more of these peptides, and efficient testing procedures are required. Even under simplified sample preparation conditions, liquid chromatography coupled to high-resolution mass spectrometry (with resolution properties>100,000 full width at half maximum) offers suitable conditions for this task and can therefore be used as an initial testing procedure. In contrast to urine, blood analysis essentially relies on the detection of intact peptide hormones, and the expected concentrations are commonly higher in blood samples than in urine. This facilitates the analysis, and a generic sample preparation by means of mixed-mode solid-phase extraction could be realized in this study. Co-extraction and analysis of several different peptides such as insulins (human, lispro, aspart, glulisine, tresiba, detemir, glargine, bovine insulin and porcine insulin), growth hormone releasing hormones (sermorelin, CJC-1295 and tesamorelin), insulin-like growth factors (long-R3-IGF-I, R3-IGF-I and Des1-3-IGF-I) and mechano growth factors (human MGF and MGF-Goldspink) with criteria that fulfil the requirements of the WADA documents (TD2022 MRPL) for doping controls. The proof of principle was shown by the analysis of post administration samples after treatment with synthetic insulin analogues.

Validation of the QuEChERSER mega-method for the analysis of pesticides, veterinary drugs, and environmental contaminants in tilapia (Oreochromis Niloticus)

ABSTRACT Diverse food safety programmes around the world are designed to help ensure production of safe food. To meet this need, the development and implementation of more efficient and effective analytical methods to monitor residues (pesticides and veterinary drugs) and contaminants in food is important. In this study, we report the validation results for a simple high-throughput mega-method for residual analysis of 213 pesticides and veterinary drugs, including 15 metabolites, plus 12 environmental contaminants (polychlorinated biphenyls) in tilapia muscle for implementation in routine laboratory analyses. The generic sample preparation method and analytical approach are known as QuEChERSER (more than QuEChERS). A small portion of the initial extract (204 µL) is taken for analysis by ultrahigh-performance liquid chromatography (UHPLC) tandem mass spectrometry (MS/MS) covering 145 analytes, and the remaining extract undergoes a salting out step followed by an automated robotic instrument top sample preparation (ITSP) cleanup, also known as micro-solid-phase extraction (µSPE), plus fast low-pressure gas chromatography LPGC-MS/MS for 134 analytes (66 pesticides are targeted in both UHPLC-MS/MS and LPGC-MS/MS). The mega-method was validated in spiked tilapia samples at 5, 10, 15, and 20 ng/g with 10 replicates per level over two days (n = 80 overall), and 70–140% recoveries with RSDs ≤20% were achieved for 92% of the analytes in LC and 82% in GC. No significant matrix effects were observed for the analytes in LPGC-MS/MS, and only 5% of the analytes exceeded ±20% matrix effect in UHPLC-MS/MS. Analysis of standard reference materials (NIST SRMs 1946 and 1947) for contaminants in freeze-dried fish showed acceptable results, further demonstrating that the QuEChERSER mega-method can be implemented to expand analytical scope and increase laboratory efficiency compared to the QuEChERS method.

Supramolecular solvent-based microextraction probe for fast detection of bisphenols by ambient mass spectrometry

In this study, we investigated for the first time the suitability of supramolecular solvent (SUPRAS)-based microextraction probe for the development of generic and fast sample treatment prior to qualitative analysis by ambient mass spectrometry (AMS) based on ASAP (atmospheric solids analysis probe). SUPRAS are nanostructured liquids formed by the self-assembly of amphiphilic aggregates with multiple binding sites and microenvironments of different polarity for the efficient extraction of multiple compounds. Different types of SUPRAS were evaluated as a simple and single step sample treatment for ASAP. The method was applied to the screening of bisphenol A and structural analogues in thermal paper. Optimal results were achieved with SUPRAS synthesized with 1-decanol in mixtures of ethanol:water. SUPRAS (1.1–2 μL) were loaded onto glass probes and placed in contact with samples for 10 s before ASAP analysis. AMS signal peaks (width: 0.2–0.5 min) were easily integrated and normalized with internal standards (RSD: 2–25%). The method was applied to 62 samples of thermal paper. BPA and BPS were the most widely used, this highlighting the progressive industrial replacement of BPA by BPS.

Multi-analyte gas chromatography-mass spectrometry method to monitor bisphenols, musk fragrances, ultraviolet filters, and pesticide residues in seafood

A gas chromatography-mass spectrometry method for the analysis of thirty-six anthropogenic contaminants in the edible portion of four distinct seafood items is reported. Considering the heterogeneous composition of algae, mussels, and lean/fatty fish muscles, a generic sample preparation based on the QuEChERS procedure combined with dispersive liquid-liquid microextraction (DLLME) with in situ acetylation was successfully applied for quantification of pesticide residues, bisphenols, musk fragrances and UV-filters. Matrix effects were influenced by the type of seafood, with the lowest effects being observed with EMR-lipid and graphitized carbon black sorbents in dispersive solid-phase extraction cleanup step. Method performance features were successful evaluated in the different seafood samples – algae, mussel, lean and fatty fish muscles, following the criteria established by SANTE/12682/2019 for analytical methods for pesticide residues analysis. The detection and quantification of bisphenol F, musk fragrances (galaxolide and tonalide), UV-filters (2-ethylhexyl salicylate, 2-ethylhexyl 4-methoxycinnamate, and isoamyl 4-methoxycinnamate), and residues of permethrin in commercial samples of algae, mussel and fish collected in a Portuguese estuary support the suitability of the proposed method for future seafood monitoring by food safety authorities.