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Zika virus (ZIKV) is an arbovirus belonging to the genus Flavivirus (family Flaviviridae) and was first described in 1947 in Uganda following blood analyses of sentinel Rhesus monkeys. Until the twentieth century, the African and Asian lineages of the virus did not cause meaningful infections in humans. However, in 2007, vectored by Aedes aegypti mosquitoes, ZIKV caused the first noteworthy epidemic on the Yap Island in Micronesia. Patients experienced fever, skin rash, arthralgia and conjunctivitis. From 2013 to 2015, the Asian lineage of the virus caused further massive outbreaks in New Caledonia and French Polynesia. In 2013, ZIKV reached Brazil, later spreading to other countries in South and Central America. In Brazil, the virus has been linked to congenital malformations, including microcephaly and other severe neurological diseases, such as Guillain-Barré syndrome. Despite clinical evidence, direct experimental proof showing that the Brazilian ZIKV (ZIKV(BR)) strain causes birth defects remains absent. Here we demonstrate that ZIKV(BR) infects fetuses, causing intrauterine growth restriction, including signs of microcephaly, in mice. Moreover, the virus infects human cortical progenitor cells, leading to an increase in cell death. We also report that the infection of human brain organoids results in a reduction of proliferative zones and disrupted cortical layers. These results indicate that ZIKV(BR) crosses the placenta and causes microcephaly by targeting cortical progenitor cells, inducing cell death by apoptosis and autophagy, and impairing neurodevelopment. Our data reinforce the growing body of evidence linking the ZIKV(BR) outbreak to the alarming number of cases of congenital brain malformations. Our model can be used to determine the efficiency of therapeutic approaches to counteracting the harmful impact of ZIKV(BR) in human neurodevelopment.
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Modelos Animais de Doenças , Microcefalia/virologia , Zika virus/patogenicidade , Animais , Apoptose , Autofagia , Encéfalo/patologia , Encéfalo/virologia , Brasil/epidemiologia , Proliferação de Células , Feminino , Retardo do Crescimento Fetal/patologia , Retardo do Crescimento Fetal/virologia , Feto/virologia , Camundongos , Microcefalia/epidemiologia , Microcefalia/etiologia , Microcefalia/patologia , Células-Tronco Neurais/patologia , Células-Tronco Neurais/virologia , Organoides/patologia , Organoides/virologia , Placenta/virologia , Gravidez , Infecção por Zika virus/complicações , Infecção por Zika virus/epidemiologia , Infecção por Zika virus/patologia , Infecção por Zika virus/virologiaRESUMO
Molecularly imprinted polymers MIPs were successfully assembled around quantum dots (QDs), for the detection of the protein biomarker CA19-9 associated to pancreatic cancer (PC). These imprinted materials MIP@QDs were incorporated within the cellulose hydrogel with retention of its conformational structure inside the binding cavities. The concept is to use MIPs which function as the biorecognition elements, conjugated to cadmium telluride QDs as the sensing system. The excitation wavelength was set to 477 nm and the fluorescence signal was measured at its maximum intensity, with an emission range between 530 and 780 nm. The fluorescence quenching of the imprinted cellulose hydrogels occurred with increasing concentrations of CA19-9, showing linearity in the range 2.76 × 10 -2 - 5.23 × 10 2 U/ml, in a 1000-fold diluted human serum. Replicates of the imprinted hydrogel show a linear response below the cut-off values for pancreatic cancer diagnosis (< 23 U/ml), a limit of detection of 1.58 × 10 -3 U/ml and an imprinting factor (IF) of 1.76. In addition to the fact that the imprinted cellulose hydrogel displays good stability and selectivity towards CA19-9 when compared with the non-imprinted controls, the conjugation of MIPs to QDs increases the sensitivity of the system for an optical detection method towards ranges within clinical significance. This fact shows potential for the imprinted hydrogel to be applied as a sensitive, low-cost format for point-of-care tests (PoCTs).
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Impressão Molecular , Neoplasias , Pontos Quânticos , Biomarcadores Tumorais , Antígeno CA-19-9 , Celulose , Humanos , Hidrogéis , Impressão Molecular/métodos , Polímeros Molecularmente Impressos , Pontos Quânticos/químicaRESUMO
The present work focused on the development of a fluorescence resonance energy transfer (FRET)-based sensing platform for the monitoring of atenolol in pharmaceutical formulations. The implemented approach involved the assembly of d-penicillamine-capped AgInS2/ZnS quantum dots (QDs), as energy donors, and gold nanoparticles (AuNPs) as acceptors and the establishment of electrostatic interaction between both capping ligands at the nanoparticle surface, which induced the inhibition of the ternary QD photoluminescence (PL). The presence of a ZnS shell around the ternary QD core and the use of cysteamine (CA) as the AuNP capping ligand, instead of the typical citrate, allowed a more efficient FRET process to occur. The ability of Cd-free ternary QDs to be used as a sensing element in FRET-based assays was demonstrated, emphasizing the advantages relative to the common Cd-based QDs, when seeking the implementation of more environmentally friendly and less toxic analytical methodologies. The influence of several ß-blocker drugs on the FRET donor-acceptor assemblies was thoroughly assessed. Atenolol and nadolol caused the aggregation of CA-AuNPs via hydrogen bonding interactions which reduced the spectral overlap between the donor and acceptor, impairing the FRET process and consequently the emission of the QDs was restored. Under the optimized conditions, the obtained results exhibited a linear relationship between the QD PL recovery signal and atenolol concentration of up to 11.22 mg L-1 with a detection limit of 1.05 mg L-1. This FRET sensing platform was successfully applied in the determination of atenolol in pharmaceutical formulations with recovery values ranging from 97.4 to 104.3%.
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Nanopartículas Metálicas , Pontos Quânticos , Atenolol , Transferência Ressonante de Energia de Fluorescência , OuroRESUMO
The presence of endophytes promotes the biosynthesis of secondary plant metabolites. In this study, endophytic fungi were isolated from Schinus terebinthifolius to investigate their diversity and antimicrobial activity. A total of 272 endophytic fungi was obtained. These belonged to nine different genera: Alternaria, Colletotrichum, Diaporthe, Epicoccum, Fusarium, Pestalotiopsis, Phyllosticta, Xylaria, and Cryptococcus. Notably, Diaporthe foliorum was introduced as a new species, with accompanying morphological descriptions, illustrations, and a multigene phylogenetic analysis (using ITS, TEF1, TUB, HIS, and CAL). Among the 26 fungal morphotypes evaluated for antimicrobial activity, five strains had inhibitory effects against pathogenic microorganisms. Xylaria allantoidea CMRP1424 extracts showed antimicrobial activity against Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus. Diaporthe terebinthifolii CMRP1430 and CMRP1436 showed antimicrobial activity against E. coli, P. aeruginosa, S. aureus, and C. albicans. Meanwhile, D. foliorum CMRP1321 and D. malorum CMRP1438 extracts inhibited C. albicans alone. Three classes of chemical compounds were identified in D. foliorum CMRP1438 extracts: ferric chloride, potassium hydroxide, and vanillin-sulfuric acid. In conclusion, the endophytic isolates were able to produce bioactive agents with pharmaceutical potential as antibacterial and antifungal agents. As such, they may provide fresh leads in the search for new, biological sources of drug therapies.
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Anacardiaceae , Anti-Infecciosos , Anti-Infecciosos/farmacologia , Ascomicetos , Endófitos/genética , Escherichia coli , Fungos , Testes de Sensibilidade Microbiana , Filogenia , Staphylococcus aureusRESUMO
Immobilization of quantum dots (QDs) onto solid supports could improve their applicability in the development of sensing platforms and solid-phase reactors by allowing the implementation of reusable surfaces and the execution of repetitive procedures. As the reactivity of QDs relies mostly on their surface chemistry, immobilization could also limit the disruption of solution stability that could prevent stable measurements. Herein, distinct strategies to immobilize QDs onto porous aminated supports, such as physical adsorption and the establishment of chemical linking, were evaluated. This work explores the influence of QD capping and size, concentration, pH, and contact time between the support and the QDs. Maximum QD retention was obtained for physical adsorption assays. Freundlich and Langmuir isotherms were used to analyze the equilibrium data. Gibbs free energy, enthalpy, and entropy were calculated and the stability of immobilized QDs was confirmed.
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Macropores and water flow in soils and substrates are complex and are related to topics like preferential flow, nonequilibrium flow, and dual-continuum. Hence, the quantification of the number of macropores and the determination of their geometry are expected to provide a better understanding on the effects of pores on the soil's physical and hydraulic properties. This exploratory study aimed at evaluating the potential of using infrared thermography for mapping macroporosity at the soil surface and estimating the number and size of such macropores. The presented technique was applied to a small scale study (laboratory soil flume).
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Solo/química , Termografia/métodos , Laboratórios , Porosidade , Projetos de Pesquisa , Propriedades de Superfície , Água/metabolismoRESUMO
Chronic wounds (CW) present a significant healthcare challenge due to their prolonged healing time and associated complications. To effectively treat these wounds and prevent further deterioration, monitoring their healing progress is crucial. Traditional wound assessment methods relying on visual inspection and subjective evaluation are prone to inter-observer variability. Biomarkers play a critical role in objectively evaluating wound status and predicting healing outcomes, providing quantitative measures of wound healing progress, inflammation, infection, and tissue regeneration. Recent attention has been devoted to identifying and validating CW biomarkers. Various studies have investigated potential biomarkers, including growth factors, cytokines, proteases, and extracellular matrix components, shedding light on the complex molecular and cellular processes within CW. This knowledge enables a more targeted and personalized approach to wound management. Accurate and sensitive techniques are necessary for detecting CW biomarkers. Thus, this review compares and discusses the use of electrochemical and optical sensors for biomarker determination. The advantages and disadvantages of these sensors are highlighted. Differences in detection capabilities and characteristics such as non-invasiveness, portability, high sensitivity, specificity, simplicity, cost-effectiveness, compatibility with point-of-care applications, and real-time monitoring of wound biomarkers will be pointed out and compared. In summary, this work provides an overview of CW, explores the emerging field of CW biomarkers, and discusses methods for detecting these biomarkers, with a specific focus on optical and electrochemical sensors. The potential of further research and development in this field for advancing wound care and improving patient outcomes will also be noted.
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Técnicas Biossensoriais , Humanos , Biomarcadores/análise , Cicatrização , Atenção à SaúdeRESUMO
PURPOSE: Pan-retinal photocoagulation (PRP) is the mainstay of treatment for proliferative diabetic retinopathy (PDR), reducing the risk of severe vision loss. Pain poses a potential obstacle to effective laser delivery and patient compliance. Therefore, implementing pain relief strategies can enhance both treatment efficacy and patient comfort. DESIGN: A systematic review and meta-analysis. METHODS: We conducted a systematic review and meta-analysis according to PRISMA guidelines. The PubMed, Embase and Cochrane Central Register of Controlled Trials databases were searched for randomized controlled trials (RCTs) that enrolled patients undergoing PRP due to DR and compared analgesics or non-steroidal anti-inflammatory drugs (NSAID) to placebo. Pain was evaluated with the visual analogue scale. The version 2 of the Cochrane Collaboration's Risk of Bias in Randomized Controlled Trials tool and its version for crossover trials were used to assess the risk of bias. The Grading of Recommendations, Assessment, Development, and Evaluation tool was used to measure the certainty of evidence. RESULTS: A total of 13 studies were included, comprising 1404 eyes from RCTs, nine of which were crossover. Patients who were administered analgesia reported a significantly lower pain sensitivity compared to those who received placebo (Standardized mean difference [SMD] -0.38; 95% confidence interval [CI] -0.58, -0.17; P < .01; I2 = 69%). Subgroup analysis of systemic administration of analgesics/NSAIDs (metamizole, Entonox, acetaminophen, ibuprofen, caffeine, mefenamic acid, intramuscular ketorolac tromethamine, and potassium diclofenac) also showed a statistically significant reduction in pain when compared to placebo (SMD -0.28; 95% CI -0.50, -0.07; P < .01; I2 = 43%). Exclusive eye drops administration (ketorolac tromethamine 0.5% and sodium diclofenac 0.1%) also showed a significant difference in pain sensitivity (SMD -0.46; 95% CI -0.88, -0.05; I2 = 83%), however with a more significant heterogeneity. CONCLUSIONS: The results of this meta-analysis including over 1000 patients demonstrated that the use of analgesics significantly reduced pain sensitivity during PRP, and systemic analgesia is potentially better than topical administration when compared to placebo.
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Tuning the 8-anilino-1-naphthalenesulfonic acid (ANS) structure usually requires harsh conditions and long reaction times, which can result in low yields. Herein, ANS was modified to form an ANS group of uniform materials based on organic salts (GUMBOS), prepared with simple metathesis reactions and distinct cations, namely tetrabutylammonium (N4444), tetrahexylammonium (N6666), and tetrabutylphosphonium (P4444). These ANS-based GUMBOS were investigated as fluorescent probes for membrane binding studies with four proteins having distinct physicochemical properties. Liposomes of 1,2-dimyristoyl-sn-glycero-3-phosphocholine were employed as membrane models as a result of their ability to mimic the structure and chemical composition of cell membranes. Changes in fluorescence intensity were used to monitor protein binding to liposomes, and adsorption data were fitted to a Freundlich-like isotherm. It was determined that [N4444][ANS] and [P4444][ANS] GUMBOS have enhanced optical properties and lipophilicity as compared to parent ANS. As a result, these two GUMBOS were selected for subsequent protein-membrane binding studies. Both [N4444][ANS] and [P4444][ANS] GUMBOS and parent ANS independently reached membrane saturation within the same concentration range. Furthermore, distinct fluorescence responses were observed upon the addition of proteins to each probe, which demonstrates the impact of properties such as lipophilicity on the binding process. The relative maintenance of binding cooperativity and maximum fluorescence intensity suggests that proteins compete with ANS-based probes for the same membrane binding sites. Finally, this GUMBOS-based approach is simple, rapid, and involves relatively small amounts of reagents, making it attractive for high-throughput purposes. These results presented herein can also provide relevant information for designing GUMBOS with ameliorated properties.
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Naftalenossulfonato de Anilina , Lipossomos , Ligação Proteica , Naftalenossulfonato de Anilina/química , Lipossomos/química , Corantes Fluorescentes/química , Espectrometria de Fluorescência/métodos , Materiais Biomiméticos/química , Sais/química , Compostos de Amônio Quaternário/químicaRESUMO
DNA data storage based on synthetic oligonucleotides is a major attraction due to the possibility of storage over long periods. Nowadays, the quantity of data generated has been growing exponentially, and the storage capacity needs to keep pace with the growth caused by new technologies and globalization. Since DNA can hold a large amount of information with a high density and remains stable for hundreds of years, this technology offers a solution for current long-term data centers by reducing energy consumption and physical storage space. Currently, research institutes, technology companies, and universities are making significant efforts to meet the growing need for data storage. DNA data storage is a promising field, especially with the advancement of sequencing techniques and equipment, which now make it possible to read genomes (i.e., to retrieve the information) and process this data easily. To overcome the challenges associated with developing new technologies for DNA data storage, a message encoding and decoding exercise was conducted at a Brazilian research center. The exercise performed consisted of synthesizing oligonucleotides by the phosphoramidite route. An encoded message, using a coding scheme that adheres to DNA sequence constraints, was synthesized. After synthesis, the oligonucleotide was sequenced and decoded, and the information was fully recovered.
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A fast, simple, and reliable method for determination of metformin was developed by coupling surface-enhanced Raman spectroscopy (SERS) with chemometric methods. This relayed on the utilization of a portable Raman spectrometer and of citrate stabilized gold nanoparticles (AuNPs) as substrate, to carry out the measurement of SERS scattering signals, thus assuring improved sensitivity. The obtained datasets were analysed using principal component analysis (PCA) and partial least squares (PLS) regression. Upon optimization of the PLS model, in terms of latent variables, spectral region and pre-processing techniques, RMSECV and R2CV values of 0.42 mg/L and 0.94, respectively, were obtained. The optimized PLS regression model was further validated with the projection of commercial pharmaceutical samples, providing good results in terms of R2P (0.97), RE (4.54 %) and analytical sensitivity (2.13 mg/L).
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Nanopartículas Metálicas , Metformina , Análise Espectral Raman , Ouro , QuimiometriaRESUMO
The aim of the study is to evaluate whether the use of the new instrumentation Microplasty (MP) improves component positioning and the reliability of the surgical technique, reducing the implant outliers from the recommended range and providing a more accurate resection, while avoiding insufficient or excessive tibial resection and clinical scores. We prospectively analyzed clinical and radiographic outcomes of three consecutive cohorts for a total of 227 implants at a minimum follow-up of 36 months. The first cohort consisted of 67 Oxford unicompartmental knee arthroplasty (OUKA), using the phase III (Ph-III). The second cohort consisted of 136 OUKA, with the MP instrumentation. The third cohort consisted of 24 hypoallergenic OUKA, using the MP instrumentation (TiNbN). Postoperative alignment of the knee in the coronal and sagittal plane was measured using radiographs. No clinical differences were found among the three groups (p > 0.05). A significant difference was found on the slope between Ph-III and MP (p = 0.0005). Moreover, a significant difference was found in tibial angle and in tibial slope in arthroplasty with femoral size small (S), compared with size medium (M) or large (Ly) (tibia varus/valugs angle: p = 0.0484; tibial slope: p = 0.04). Similar results were found between small (AA, A, B) tibial size and large (C, D, E, F) tibial size for tibial varus/valgus (p = 0.03) angle and tibial slope (p = 0.003). A significant difference was found between Ph-III and MP in tibial slope in patients with body mass index (BMI) ≥25 kg/m2 (p = 0.0003). A positive correlation was noted between the femoral and tibial sizes and the tibial angle and the slope, and a negative correlation between weight and the tibial slope; furthermore, a positive correlation was found between Oxford knee score and radiographic angles. The MP instrumentation seems to be effective in determining the tibial cut and, particularly, improving the tibial slope, compared with Ph-III. The tibial slope is directly affected by the weight and measurements of the components, regardless of the instruments or the number of pegs, while clinical outcomes are correlated with implant position. This prospective comparative study reflects level of evidence II.
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Artroplastia do Joelho , Prótese do Joelho , Osteoartrite do Joelho , Humanos , Artroplastia do Joelho/métodos , Articulação do Joelho/cirurgia , Osteoartrite do Joelho/diagnóstico por imagem , Osteoartrite do Joelho/cirurgia , Estudos Prospectivos , Reprodutibilidade dos Testes , Estudos Retrospectivos , Tíbia/diagnóstico por imagem , Tíbia/cirurgiaRESUMO
The combination of multiple quantum dots (QDs) in a multi-emitter nanoprobe can be envisaged as a promising sensing scheme, as it enables obtaining a collective response of individual emitters towards a given analyte and allows for achieving specific analyte-response profiles. The processing of these profiles using adequate chemometric methods empowers a more sensitive, reliable and selective determination of the target analyte. In this work, we developed a kinetic fluorometric method consisting of a dual CdTe/AgInS2 quantum dots photoluminescence probe for the determination of acetylsalicylic acid (ASA). The fluorometric response was acquired as second-order time-based excitation/emission matrices that were subsequently processed using chemometric methods seeking to assure the second-order advantage. The data obtained in this work are considered second-order data as they have a three-dimensional size, I × J × K (where I represents the samples' number, J the fluorescence emission wavelength while K represents the time). In order to select the most adequate chemometric method regarding the obtained data structure, different chemometric models were tested, namely unfolded partial least squares (U-PLS), N-way partial least squares (N-PLS), multilayer feed-forward neural networks (MLF-NNs) and radial basis function neural networks (RBF-NNs).
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Compostos de Cádmio , Pontos Quânticos , Aspirina , Compostos de Cádmio/química , Quimiometria , Telúrio/químicaRESUMO
Diagnosing gastrointestinal parasites by microscopy slide examination often leads to human interpretation errors, which may occur due to fatigue, lack of training and infrastructure, presence of artifacts (e.g., various types of cells, algae, yeasts), and other reasons. We have investigated the stages in automating the process to cope with the interpretation errors. This work presents advances in two stages focused on gastrointestinal parasites of cats and dogs: a new parasitological processing technique, named TF-Test VetPet, and a microscopy image analysis pipeline based on deep learning methods. TF-Test VetPet improves image quality by reducing cluttering (i.e., eliminating artifacts), which favors automated image analysis. The proposed pipeline can identify three species of parasites in cats and five in dogs, distinguishing them from fecal impurities with an average accuracy of 98,6%. We also make available the two datasets with images of parasites of dogs and cats, which were obtained by processing fecal smears with temporary staining using TF-Test VetPet.
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Doenças do Gato , Doenças do Cão , Enteropatias Parasitárias , Parasitos , Gatos , Animais , Cães , Humanos , Doenças do Gato/diagnóstico por imagem , Doenças do Gato/parasitologia , Doenças do Cão/diagnóstico por imagem , Doenças do Cão/parasitologia , Enteropatias Parasitárias/diagnóstico por imagem , Enteropatias Parasitárias/veterinária , Fezes/parasitologiaRESUMO
The in-situ quantification of turbulent flux and evapotranspiration (ET) is necessary to monitor crop performance in stressful environments. Although cacti can withstand stressful conditions, plant responses and plant-environment interactions remain unclear. Hence, the objective of our study was to investigate the interannual and seasonal behaviour of components of the surface energy balance, environmental conditions, morphophysiological parameters, biomass yield and water relations in a crop of Nopalea cochenillifera in the semi-arid region of Brazil. The data were collected from a micrometeorological tower between 2015 and 2017. The results demonstrate that net radiation was significantly higher during the wet season. Latent heat flux was not significant between the wet season and dry season. During the dry-wet transition season in particular, sensible heat flux was higher than during the other seasons. We observed a large decline in soil heat flux during the wet season. There was no difference in ET during the wet or dry seasons; however, there was a 40% reduction during the dry-wet transition. The wet seasons and wet-dry transition showed the lowest Evaporative Stress Index. The plants showed high cladode water content and biomass during the evaluation period. In conclusion, these findings indicate high rates of growth, high biomass and a high cladode water content and explain the response of the cactus regarding energy partitioning and ET.
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Melatonin is a hormone, a derivative of tryptophan, that possesses a potent scavenging capacity for the most reactive and dangerous free radicals, being an important protection against oxidative stress. In this work, an automated flow-based procedure for assessment of melatonin, tryptophan, and 5-hydroxytryptophan scavenging capacity was developed. The presented methodology involved a multi-pumping flow system and exploited the ability of selected compounds to inhibit the chemiluminescence reaction of luminol with hydrogen peroxide, hydroxyl radical, and peroxynitrite anion. The system was based on the use of several solenoid actuated micro-pumps as the only active components of the flow manifold. This enabled the reproducible insertion and efficient mixing of very low volumes of sample and reagents as well as the transportation of the sample zone toward detection for monitoring the chemiluminometric response. Furthermore, the high versatility of the proposed multi-pumping flow system allowed the implementation of distinct reactions for the in-line generation of the different reactive species assayed without requiring physical reconfiguration. The results obtained demonstrated that 5-hydroxytryptophan is the most potent scavenger, followed by melatonin and tryptophan. The developed multi-pumping flow system exhibited good measurement precision (relative standard deviations typically <2%, n=10), low operational costs, and low reagent consumption.
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Técnicas de Química Analítica/métodos , Sequestradores de Radicais Livres/química , Sequestradores de Radicais Livres/farmacologia , Luminescência , Melatonina/química , Melatonina/farmacologia , Espécies Reativas de Oxigênio/química , 5-Hidroxitriptofano/análise , 5-Hidroxitriptofano/química , Automação Laboratorial , Técnicas de Química Analítica/instrumentação , Desenho de Equipamento , Peróxido de Hidrogênio/química , Radical Hidroxila/química , Luminol/química , Ácido Peroxinitroso/química , Triptofano/química , Triptofano/farmacologiaRESUMO
This tutorial demonstrates how to exploit the second-order advantage on excitation-emission fluorescence matrices (EEFMs) acquired from sensing platforms based on analyte-triggered semiconductor quantum dots (QDs) fluorescence modulation (quenching/enhancing). The advantage in processing such second-order EEFMs data from complex samples, seeking successful quantification, is comprehensively addressed. It is worth emphasizing that, aiming to exploit the second-order advantage, the selection of the most appropriate advanced chemometric model should rely on the matching between the data structure and the physicochemical chemometric model assumption. In this sense, the achievement of second-order advantage after EEFMs' processing is extensively addressed throughout this tutorial taking into consideration three different analytical situations, each involving a specific data structure: i) parallel factor analysis (PARAFAC), which is applied in a real dataset stacked in a three-way data array containing a trilinear data structure acquired from QDs-based detection with non-selective species; ii) multivariate curve resolution - alternating least-squares (MCR-ALS), which is also employed in a real dataset arranged in an augmented data matrix containing non-trilinear data structure acquired from QDs-based detection with a single breaking mode caused by background signals; iii) unfolded partial least-squares with residual bilinearization (U-PLS/RBL), which is applied in a dataset containing non-trilinear data acquired from a classical fluorescence system with two breaking modes caused by inner filter effect (IFE) in both instrumental modes (excitation and emission). The latter challenging data structure can be acquired via fluorescence quenching from IFE-based sensing platforms and chemometrically handled in two main steps. First, a set of calibration EEFMs data is converted into an unfolded data matrix during the unfolding process, followed by applying U-PLS model. Second, a post-calibration procedure using RBL analysis is applied to a test sample of EEFM maintained in its matrix form, in order to handle potential interferents. In the last section, the state-of-the-art of second-order EEFMs data acquired from semiconductor QDs-based sensing platforms and coupled to multi-way fluorescence data processing to accomplish a successful quantification, even with substantial interfering species, is critically reviewed.
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Pontos Quânticos , Algoritmos , Calibragem , Análise dos Mínimos Quadrados , Semicondutores , Espectrometria de Fluorescência/métodosRESUMO
A sensing platform combining carbon dots (CDs, with blue emission) and thiomalic acid (TMA)-capped AgInS2 quantum dots (QDs, with orange emission) was developed aiming the photoluminescence (PL) ratiometric determination of ibandronic acid (IBAN), a bisphosphonate pharmaceutical. The ternary AgInS2 QDs were used for IBAN probing, undergoing a concentration-related PL quenching in its presence, whilst the PL of CDs remained practically unaffected due to its chemical inertness towards the antiresorptive drug, provided an intrinsic self-reference fluorophore. In addition, a visual sensing approach was also proposed, employing for the first time ternary QDs. This relied on RGB images acquired by means of a digital camera and seek the development of a rapid IBAN screening test. The developed sensing platforms were employed for IBAN determination in samples with pharmaceutical interest providing good results, in accordance to the reported IBAN levels, and obtaining recovery values between 98 and 103%.
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Pontos Quânticos , Carbono , Corantes Fluorescentes , Ácido IbandrônicoRESUMO
GUMBOS (Group of Uniform Materials Based on Organic Salts) have recently emerged as interesting materials for protein analysis due to their unique features and high tunability. In this regard, four novel erythrosin B (EB)-based GUMBOS were synthesized and their potential to discriminate among proteins with distinct properties (e.g., size, charge, and hydrophobicity) was assessed. These solid-phase materials were prepared using a single-step metathesis reaction between EB and various phosphonium and ammonium cations, namely tetrabutylphosphonium (P4444+), tributylhexadecylphosphonium (P44416+), tetrabutylammonium (N4444+), and benzyldimethylhexadecylammonium (BDHA+). Subsequently, the effect of pH (3.0, 4.5, and 6.0) and reaction time (5, 10, and 15 min) on the discriminatory power of synthesized GUMBOS was evaluated. Absorption spectra resulting from the interaction between EB-based GUMBOS and proteins were analyzed using partial least squares discriminant analysis (PLSDA). Unlike time, the pH value was determined to have influence over GUMBOS discrimination potential. Correct protein assignments varied from 86.5% to 100.0%, and the best discriminatory results were observed for [P4444]2[EB] and [N4444]2[EB] at pH 6.0. Additionally, these two GUMBOS allowed discrimination of protein mixtures containing different ratios of albumin and myoglobin, which appeared as individualized clusters in the PLSDA scores plots. Overall, this study showcases EB-based GUMBOS as simple synthetic targets to provide a label-free, cost-effective, rapid, and successful approach for discrimination of single proteins and their mixtures.
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Quimiometria , Eritrosina , Proteínas , Sais , Análise EspectralRESUMO
In this work, the conjugation of molecularly imprinted polymers (MIPs) to quantum dots (QDs) was successfully applied in the assembly of an imprinted cellulose membrane [hydroxy ethyl cellulose (HEC)/MIP@QDs] for the specific recognition of the cardiac biomarker myoglobin (Myo) as a sensitive, user-friendly, and portable system with the potential for point-of-care (POC) applications. The concept is to use the MIPs as biorecognition elements, previously prepared on the surface of semiconductor cadmium telluride QDs as detection particles. The fluorescent quenching of the membrane occurred with increasing concentrations of Myo, showing linearity in the interval range of 7.39-291.3 pg/mL in a1000-fold diluted human serum. The best membrane showed a linear response below the cutoff values for myocardial infarction (23 ng/mL), a limit of detection of 3.08 pg/mL, and an imprinting factor of 1.65. The incorporation of the biorecognition element MIPs on the cellulose substrate brings an approach toward a portable and user-friendly device in a sustainable manner. Overall, the imprinted membranes display good stability and selectivity toward Myo when compared with the nonimprinted membranes (HEC/NIP@QDs) and have the potential to be applied as a sensitive system for Myo detection in the presence of other proteins. Moreover, the conjugation of MIPs to QDs increases the sensitivity of the system for an optical label-free detection method, reaching concentration levels with clinical significance.