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- Green zero-valent iron nanoparticles from Cistus ladanifer by-products for glyphosate remediation in water and soilPublication . Fernandes, Filipe; Paíga, Paula; Freitas, Maria; Pinho, Cláudia; Oliveira, Ana Isabel; Delerue-Matos, Cristina; Grosso, Clara; Pinho, Cláudia; Oliveira, Ana IsabelFood and agricultural sectors produce large quantities of waste that present high potential for valorization. Cistus ladanifer L., used in the perfume and essential oil industries, produces post-distillation residues rich in phenolic compounds (PCs). These residues can be exploited for the green synthesis of nano zero-valent iron (nZVI), widely studied for environmental remediation. The aim of this study was to develop green synthesized nZVI using Abbreviations: AAE, Ascorbic acid equivalents; ABTS•+, 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid; AES, Analytical Eco-scale; AGREE, Analytical Greenness Calculator; AMPA, Aminomethylphosphonic acid; C-nZVI, Chemically synthesized nZVI; CLL, C. ladanifer leaves; CLS, C. ladanifer stems; DPPH•, 1,1- diphenyl-2-picrylhydrazyl; DLS, Dynamic light scattering; EDS, Energy-dispersive X-ray spectroscopy; EOs, Essential oils; FeCl3, Iron chloride; FMOC-Cl, 9-fluorenylmethyl chloroformate; FRAP, Ferric reducing antioxidant power assay; FTIR, Fourier-transform infrared spectroscopy; GAE, Gallic acid equivalents; GEMAM, Greenness evaluation metric for analytical methods; Glyph, Glyphosate; H2O, Water; HCl, Hydrochloric acid; HPLC, High-performance liquid chromatography; HPLC-FLD, High-performance liquid chromatography with fluorescence detection; LC-MS, Liquid chromatography-mass spectrometry; MeOH, Methanol; MES, Green Certificate Modified Eco-scale; MoGAPI, Modified Green Analytical Procedure Index; MRLs, Maximum residue levels; MTT, (3-(4,5-dimethylthiazol-2-yl)-2,5- diphenyltetrazolium bromide); NaBH4, Sodium borohydrate; nZVI, Nano zero-valent iron; NaOH, Sodium hydroxide; NNP, No nanoparticles; NPs, Nanoparticles; NS, No soil; PCs, Phenolic compounds; PDI, Polydispersity index; SEM, Scanning electron microscopy; SQUID, Superconducting quantum interference device; TG, Thermogravimetric analysis; TPC, Total phenolic content; XPS, X-ray photoelectron spectroscopy; XRD, X-ray diffraction; ZP, Zeta potential; Fe3O4, Magnetite; γ-Fe2O3, Maghemite; γ-FeO, Lepidocrocite.
- Impact of the addition of botanical ingredients on the physicochemical properties, polyphenolic content, and antioxidant activity of craft beersPublication . Pereira, Maria João; Santos, Diana; Pinho, Cláudia; Oliveira, Ana Isabel; Oliveira, Ana IsabelThe incorporation of botanical ingredients into craft beer has emerged as a promising strategy to enhance nutritional value and expand its sensory diversity. Thus, this review aims to discuss the impact of adding botanical extracts on the physicochemical properties, phenolic content, and antioxidant potential of craft beers. A narrative review was conducted using PubMed, Science Direct, Web of Science, and b-on databases, with the keywords ‘craft beer’, ‘physicochemical properties’, ‘polyphenolic content’, and ‘antioxidant activity’. The incorporation of botanical ingredients into beers modified the physicochemical parameters, total phenolic content (TPC), and antioxidant activity. These effects varied according to the type of matrix, concentration, timing of addition, beer style, and brewing conditions. Overall, an increase in beer TPC and antioxidant activity was observed. However, higher TPC can present technological challenges, as phenolic–protein interaction may lead to turbidity. Conversely, enhanced antioxidant potential contributes to oxidative stability and extends the shelf-life of beer. Future studies should validate the current results, explore new bioactive matrices, and evaluate variables that ensure the functional quality of beer. Practical applications under real production conditions should also be prioritized to guarantee effective functional benefits without compromising the stability and sensory acceptance of craft beer.
- Advanced botanical authentication of honey: Using an ultrasensitive electrochemical genosensor and RT-qPCR for the detection of Castanea sativaPublication . Morais, Stephanie; Pereira, Eduarda; Ferreira, Mariana; Santos, Marlene; Soares, Sónia; Texeira, Ana L.; Domingues, Valentina; Delerue-Matos, Cristina; Barroso, M. Fátima; Santos, MarleneFood fraud is a reoccurring issue for the food industry, with significant public health and economic implications. Honey, a natural ingredient prized for its sweetness and inherent nutritional profile and health benefits, is one of the most frequently adulterated foods found in the international market. This fraudulent act not only damages the reputation of the honey industry but also presents a hazard to the consumers’ health. So, in this study, a disposable electrochemical genosensor was developed to detect Castanea sativa (chestnut tree) DNA in commercial honey samples. For this, a 103 bp C. sativa specific DNA-target oligonucleotide and its complementary probe were selected and designed. The genosensor methodology implied a sandwich hybridization format, for which the complementary sequence was cut into a 22 bp thiolated DNAcapture probe and an 81 bp fluorescein isothiocyanate-labelled DNA-signaling probe. Using chronoamperometric measurements, the enzymatic amplification of the electrochemical signal was obtained in a 0.03 to 1.00 nM concentration range, with a LOD and LOQ of 3.01 and 10.04 pM, respectively. The developed genosensor was able to detect the presence of the chestnut DNA in real chestnut plants and commercial honey samples. These results were then validated real-time quantitative PCR (RT-qPCR). In fact, conventional PCR coupled with gel electrophorese was not able to detect the presence of heather in honey. Therefore, electrochemical genosensors are a promising and cost-effective analytical tool to authenticate the botanical origin of honey, guaranteeing its safety, quality and authenticity.
- “Can a chatbot be used in the full-text screening in a systematic review?”Publication . Martins, André Miguel; Juan, Luis Félix Valero; Oliveira, Adriana; Martins, João Paulo; Santos, Marlene; Santos, Marlene; Oliveira Martins, João PauloLarge language model–based artificial intelligence tools are increasingly explored to support systematic reviews, yet evidence regarding their reliability in full-text screening remains limited. This study evaluated the performance of two versions of ChatGPT (4.0 and 5.0) compared with human reviewers during article selection for a systematic review on influenza vaccine effectiveness. A total of 170 full-text articles were independently assessed for eligibility using predefined inclusion and exclusion criteria. Human reviewers served as the gold standard. ChatGPT 4.0 and 5.0 were prompted using standardized instructions mirroring the review protocol. Agreement with human decisions was evaluated using accuracy, sensitivity, specificity, precision, F1-score, and Cohen’s κ. Intra-model reproducibility was assessed for ChatGPT 5.0. Results: ChatGPT 4.0 achieved an accuracy of 0.71 (95% CI: 0.64–0.78) and a Cohen’s κ of 0.43, indicating moderate agreement with human reviewers. ChatGPT 5.0 demonstrated improved performance, with accuracy increasing 0.06 to 0.77 (95% CI: 0.70–0.83), sensitivity of 0.87, specificity of 0.70, and κ of 0.55, corresponding to moderate-to-substantial agreement. Intra-model reproducibility for ChatGPT 5.0 showed 80% agreement (κ = 0.60), indicating partial but imperfect consistency. ChatGPT 5.0 outperformed ChatGPT 4.0 in full-text screening accuracy and reproducibility, approaching but not matching human performance. These findings support the use of current LLMs as decision- support tools rather than autonomous reviewers in systematic reviews. Transparent reporting of model versions, prompts, and input quality is essential to ensure credible AI-assisted evidence synthesis.
- Flow-through 3D-printed device for automatic microsampling and handling of dried urine spotsPublication . Fernandes, Sara R.; Cunha, Diana R.; Guidetti, Federica; Barreiros, Luísa; Miró, Manuel; Segundo, Marcela A.; Barreiros, Luisa; Fernandes, Sara3D printing has revolutionized analytical chemistry by allowing the development of miniaturized and high- precision devices. In bioanalysis, sample collection and pre-treatment can be facilitated using 3D printing combined with flow analysis and mass spectrometry. Hence, a customized 3D-printed device was designed for sampling, clean-up, and target retrieval using filter paper as a sample collection material and sorbent. This device was integrated into a flow network for fully automatic extraction and applied to detect three anticoagulants in human urine. Different printing materials, designs and other factors related to fused deposition modeling 3D printing such as the infill percentage were evaluated to achieve the configuration that allowed the implementation of sampling and separation procedures in the same device. After establishing the final design of the device, several parameters such as the eluent composition and the hydrodynamic conditions were studied to enhance the recovery of the target analytes, namely apixaban, rivaroxaban, and warfarin. The processed samples were analyzed by UHPLC-MS/MS in positive ionization mode using a BEH C18 column. The method demonstrated good linearity (r2 >0.998) for quantification of the target analytes at concentrations ranging from 0.20 to 20 μg L 1 for apixaban and warfarin, and from 0.50 to 20 μg L 1 for rivaroxaban. LOD and LOQ values of 0.06–0.2 μg L 1 and 0.1–0.5 μg L 1, respectively, for undiluted urine were obtained. The method was found to be accurate (97.0–102 %) and precise (CV ≤6.0 %). This new approach, according to the scores obtained by applying the AGREEprep (0.70), AGREE (0.65) and BAGI (70) metrics, can be described as environmentally friendly, practical and suitable for bioanalytical purposes.
- Understanding the influence of transfusion and blood loss on tranexamic acid concentration in scoliosis surgery with blood lossPublication . Sá, Paula Alexandra; Barreiros, Luísa; Segundo, Marcela A.; Cruz, Eugénia; Langenecker, Sibylle; Barreiros, LuisaTranexamic acid (TXA) stabilizes clot formation by inhibiting fibrin degradation and improves postoperative outcomes. However, rare adverse events (e.g., thrombosis, seizures) warrant dose–risk evaluation. This study examines how perioperative blood loss and transfusion practices affect TXA concentrations during paediatric scoliosis surgery. Forty-three patients undergoing scoliosis surgery with TXA were retrospectively analysed. The study assessed the impact of packed red blood cell (PRBC) transfusion on plasma TXA levels and whether maintaining concentrations ≥10 μg/ mL correlated with intraoperative blood loss. TXA levels were measured using UHPLC–MS/MS. Results: Median TXA concentration 30 min after the loading dose was 37.8 μg/mL (IQR: 31.4–39.6 μg/mL), decreasing to 10.6 μg/mL (IQR: 9.7–13.5 μg/mL) after transfusion. At surgery end, the mean concentration was 12.9 ± 2.5 μg/mL. Thirty-one patients maintained TXA levels ≥10 μg/mL, associated with 80% inhibition of tissue plasminogen activator. Of six patients below this threshold, five had received transfusions. A significant correlation was found between higher intraoperative blood loss and lower TXA levels, consistent with a dilutional effect. In contrast, among patients with TXA ≥ 10 μg/mL, correlation with blood loss was weak (Spearman's ρ = 0.11, p = 0.54). Findings suggest homologous PRBC transfusion reduces plasma TXA through volume expansion. Sustaining TXA concentrations >10 μg/mL is essential for antifibrinolytic efficacy and haemostatic outcomes. The dilutional impact of PRBC transfusion underscores the need for intraoperative dose adjustment. Optimizing TXA dosing requires understanding pharmacokinetics and patient variability.
- Targeted mass spectrometry method for the determination of multiple gut-microbiota metabolites in human plasmaPublication . Fernandes, Sara R.; Barreiros, Luísa; Azorín, Cristian; Silva, Eduarda M.P.; Segundo, Marcela A.; Barreiros, LuisaThe gut microbiota profoundly impacts human health by producing metabolites that can act as biomarkers for disease diagnosis and therapy. However, accurately measuring these metabolites in biomatrices is challenging due to their low concentrations, high molecular diversity, and interference from matrix components, demanding advanced and precise analytical methodologies. Hence, an ultra-high-performance liquid chromatography method coupled to triple quadrupole-tandem mass spectrometry detection, combined with a chemical derivatization procedure, was developed and validated to quantify seven gut metabolites, namely acetic acid, propionic acid, butyric acid, p-cresol sulfate, 3-indoxyl sulfate, indole-3-acetic acid, and L-tryptophan, in human plasma. Samples were prepared by protein precipitation with acetonitrile and subsequently derivatized using 3-nitrophenylhydrazine. Chromatographic separation was achieved using a BEH C18 column, with elution performed at a f low rate of 0.2mLmin 1 and in gradient mode using formic acid-water (1:1000, v/v) and formic acid- acetonitrile (1:1000, v/v) as mobile phase components. The mass spectrometer was operated in negative ionization mode and data was acquired in selected reaction monitoring. Good linearity was achieved (r 2 >0.997) for all the target gut metabolites in the evaluated concentration ranges, with low LLOQ values (0.4–8 M). The method proved to be accurate (87.0–114 %) and precise (CV ≤ 13.5 %), achieving a score of 65 in the Blue Applicability Grade Index (BAGI) metric, which confirmed its practicality. The developed method was ultimately employed to the analysis of plasma samples from children and adults involved in clinical studies, demonstrating its usefulness in medical research.
- Untargeted metabolomics HRMS data processing using regions of interest and multivariate curve resolution approaches to unveil health-to-disease transitionPublication . Barreiros, Luísa; Maia, Benedita Sampaio; Alencastre, Inês Soares; Tauler, Româ; Segundo, Marcela A.; Barreiros, LuisaEarly diagnosis has the potential to prevent or minimize the progression of diseases. The discovery of biomarkers that permit to pinpoint the health-to-disease transition is thus of crucial importance to improve diagnostic eff iciency and treatment. Over the last years, untargeted metabolomic analysis of biomatrices has become a valuable tool to identify biomarkers of health status. However, it is still a recent research field with many challenges to address, namely the implementation of data treatment strategies that allow to deal efficiently with the highly complex data sets generated, without losing accuracy or relevant information. This work pursued the application of the chemometrics method Regions of Interest-Multivariate Curve Resolution (ROIMCR) to the MS- based metabolomic profiling of plasma samples aiming at the identification of chronic kidney disease (CKD) biomarkers. ROIMCR successfully resolved the plasma profiles of three groups of individuals: healthy controls, intermediate stage (pre-dialysis) and end-stage (in dialysis) CKD patients. Positive (MS1+) and negative (MS1 ) data were processed simultaneously without requiring previous time alignment, resulting in time-effective analysis with increased metabolite coverage and identification. Multivariate analysis (PCA, PLS-DA, ASCA) revealed that samples were clustered according to health status and permitted to determine the most influential metabolites in differentiating groups. Metabolites identification evidenced recognized biomarkers of CKD, validating the proposed approach, and potential new indicators of disease onset and progression. A new analytical workflow involving instrumental analysis by UHPLC-HRMS and data treatment by chemometrics method ROIMCR, followed by multivariate analysis, is available for plasma metabolomic profiling. This platform can be easily adapted to other biomatrices and diseases, and applied to profile the same individual along time, fostering the development of personalized medicine.
- Enantiomeric biodistribution, metabolic profile, and toxicity of 3-chloromethcathinone in Wistar rats following acute exposurePublication . Langa, Ivan; Rocha-Pereira, Carolina; Silva, Paula; Milhazes, Nuno; Silva, Diana Dias da; Domingues, Susana; Resende, Albina Dolores; Barbosa, Joana; Faria, Juliana; Tiritan, Maria Elizabeth; Ribeiro, Cláudiaynthetic cathinones are a class of new psychoactive substances (NPS) with 3-chloromethcathinone (3-CMC) accounting for over 46% of NPS-related seizures in 2023. Sold as a racemate, 3-CMC exhibits enantioselective metabolism and pharmacological effects, making enantioselectivity a critical factor in evaluating its toxicokinetics and toxicodynamics. This study aimed to evaluate the enantiomeric biodistribution, metabolic profile, and toxicity of 3-CMC racemate in Wistar rats following acute exposure. For this purpose, a gas chromatography–mass spectrometry (GC–MS) method was validated for quantifying 3-CMC in biological matrices and for characterizing its biodistribution in vivo. Rats were intraperitoneally administered with saline (control) or 3-CMC (10 or 20 mg kg−1, b.w.). Animals were sacrificed 24 h after administration, and plasma, urine, and tissues were collected for biodistribution, biochemical, and histopathological analyses. 3-CMC was exclusively detected in the urine, along with three additional pairs of enantiomeric metabolites. Both 3-CMC and its metabolites exhibit enantiomeric fractions (EF) different from 0.5, indicating enantiomeric enrichment. Administration of 3-CMC significantly decreased plasma levels of creatine kinase-MB, alkaline phosphatase, and aspartate aminotransferase, along with increased levels of glucose and urea. In the urine, decreased levels of albumin were observed. Oxidative stress and energy biomarkers were altered in the brain, lungs, and kidneys. Histopathological analysis revealed morphological alterations in the brain, liver, and lungs at both doses, and in the kidneys at the highest dose. However, no significant alterations were observed in the other tissues. Taken together, our findings suggest enantioselective metabolism and indicate that, although rapidly eliminated by the kidneys, 3-CMC still causes significant toxicity in target organs, such as the brain, liver, lungs, and kidneys. This highlights the high toxicity of the drug or its metabolites, even over short-term exposure.
- Cost analysis of Multidose Drug Dispensing (MDD) system implementation in a community pharmacy in PortugalPublication . Reis, Ana; Jesus, Ângelo; Martín, Maria Luisa; Jesus, ÂngeloCommunity pharmacies are increasingly delivering structured services to support chronic disease management, such as Multidose Drug Dispensing (MDD). This strategy can improve adherence and safety, but evidence of its economic feasibility in Portuguese pharmacies remains limited. To estimate the cost of implementing and operating an MDD system in a community pharmacy, informing reimbursement models and policy. A micro-costing approach assessed fixed and variable expenses for serving polymedicated elderly patients. Costs were calculated in euros (2024/2025) and expressed per working day based on 253 annual preparation days. First-year costs totaled €70,985.68, including €8184.00 for setup, €21,579.00 for supplies, and €41,222.68 for staff salaries. The daily operating cost was €280.58, with labour representing the major expense. A break-even analysis indicated sustainability with around 700 users at €10/month. Although requiring significant initial investment, MDD can become financially viable through scaling, workflow efficiency, and supportive reimbursement strategies.