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Bridging the gap between Mind, Brain and Body: exosome role and monitoring
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Molecular imprinting on nanozymes for sensing applications
Publication . Cardoso, Ana R.; Frasco, Manuela F.; Serrano, Verónica; Fortunato, Elvira; Sales, Maria Goreti Ferreira; CENIMAT-i3N - Centro de Investigação de Materiais (Lab. Associado I3N); DCM - Departamento de Ciência dos Materiais; UNINOVA-Instituto de Desenvolvimento de Novas Tecnologias; MDPI - Multidisciplinary Digital Publishing Institute
As part of the biomimetic enzyme field, nanomaterial-based artificial enzymes, or nanozymes, have been recognized as highly stable and low-cost alternatives to their natural counterparts. The discovery of enzyme-like activities in nanomaterials triggered a broad range of designs with various composition, size, and shape. An overview of the properties of nanozymes is given, including some examples of enzyme mimics for multiple biosensing approaches. The limitations of nanozymes regarding lack of selectivity and low catalytic efficiency may be surpassed by their easy surface modification, and it is possible to tune specific properties. From this perspective, molecularly imprinted polymers have been successfully combined with nanozymes as biomimetic receptors conferring selectivity and improving catalytic performance. Compelling works on constructing imprinted polymer layers on nanozymes to achieve enhanced catalytic efficiency and selective recognition, requisites for broad implementation in biosensing devices, are reviewed. Multimodal biomimetic enzyme-like biosensing platforms can offer additional advantages concerning responsiveness to different microenvironments and external stimuli. Ultimately, progress in biomimetic imprinted nanozymes may open new horizons in a wide range of biosensing applications.
An ultrasensitive paper-based SERS sensor for detection of nucleolin using silver-nanostars, plastic antibodies and natural antibodies
Publication . Suleimenova, Akmaral; Frasco, Manuela F.; Sales, M. Goreti F.; CENIMAT-i3N - Centro de Investigação de Materiais (Lab. Associado I3N); Elsevier
A state-of-the-art, ultrasensitive, paper-based SERS sensor has been developed using silver nanostars (AgNSs) in combination with synthetic and natural antibodies. A key component of this innovative sensor is the plastic antibody, which was synthesized using molecularly imprinted polymer (MIP) technology. This ground-breaking combination of paper substrates/MIPs with AgNSs, which is similar to a sandwich immunoassay, is used for the first time with the aim of SERS detection and specifically targets nucleolin (NCL), a cancer biomarker. The sensor device was carefully fabricated by synthesizing a polyacrylamide-based MIP on cellulose paper (Whatman Grade 1 filter) by photopolymerization. The binding of NCL to the MIP was then confirmed by natural antibody binding using a sandwich assay for quantitative SERS analysis. To facilitate the detection of NCL, antibodies were pre-bound to AgNSs with a Raman tag so that the SERS signal could indicate the presence of NCL. The composition of the sensory layers/materials was meticulously optimized. The intensity of the Raman signal at ∼1078 cm−1 showed a linear trend that correlated with increasing concentrations of NCL, ranging from 0.1 to 1000 nmol L−1, with a limit of detection down to 0.068 nmol L−1 in human serum. The selectivity of the sensor was confirmed by testing its analytical response in the presence of cystatin C and lysozyme. The paper-based SERS detection system for NCL is characterized by its simplicity, sustainability, high sensitivity and stability and thus embodies essential properties for point-of-care applications. This approach is promising for expansion to other biomarkers in various fields, depending on the availability of synthetic and natural antibodies.
Amplified Sensitivity in SERS Detection of L1CAM With Silver Plasmonic Mesoporous Silica Capsules on an Imprinted Films
Publication . Castaño-Guerrero, Yuselis; Arjones-Fernández, Bélen; Moreira, Felismina T.C.; Alvarez-Puebla, Ramon A.; Correa-Duarte, Miguel A.; Águas, H.; Sales, M. Goreti F.; DCM - Departamento de Ciência dos Materiais; CENIMAT-i3N - Centro de Investigação de Materiais (Lab. Associado I3N); John Wiley and Sons Ltd
This study presents a novel approach for dual detection, leveraging a combination of a Raman reporter-bearing nanomaterial and molecular imprinting polymers (MIP). A core-shell Au-Ag nanoparticles (Au-Ag NPs) encapsulated in mesoporous silica nanocapsules (Au-Ag NCs) and a new MIP-based material targeting L1CAM are used. The MIP prepared via surface imprinting on a carbon screen-printed electrode (C-SPE) used thionine (TH) as a monomer. The plasmonic Au-AgNCs are further functionalized with the Raman reporter 4-mercaptobenzoic acid (MBA) and anti-L1CAM for selective detection by surface-enhanced Raman scattering (SERS) spectroscopy. The biosensor's analytical performance is evaluated using both SERS and electrochemical impedance spectroscopy (EIS). EIS analysis reveals a linear response within the concentration range of 0.1 to 100 ng mL−1 in buffer and serum samples. SERS demonstrates a sensitivity ten times higher than EIS. Selectivity study demonstrates the biosensor's excellent specificity toward L1CAM, with minimal interference from other compounds such as creatinine, glucose, and carbohydrate antigen 19-9 (CA 19-9). The Raman signal from the reporter molecule correlates with increasing L1CAM concentrations, reinforcing the analytical findings obtained through electrochemical analysis. Thus, the combination of dual detection and recognition capabilities presents promising potential for detecting diverse biomarkers, especially in critical scenarios where reducing false-positive or false-negative errors is crucial.
Paper-based (bio)sensor for label-free detection of 3-nitrotyrosine in human urine samples using molecular imprinted polymer
Publication . Martins, Gabriela V.; Marques, Ana C.; Fortunato, Elvira; Sales, M. Goreti F.; CENIMAT-i3N - Centro de Investigação de Materiais (Lab. Associado I3N); DCM - Departamento de Ciência dos Materiais; UNINOVA-Instituto de Desenvolvimento de Novas Tecnologias; Elsevier BV
Over the last years, paper technology has been widely spread as a more affordable, sustainable and reliable support material to be incorporated in the design of point-of-care (POC) diagnostic devices. However, the single work employing a paper-based device for 3-nitrotyrosine (3-NT), a relevant biomarker for oxidative stress (OS) that is a major origin for many diseases, is incapable of reading successfully complex samples because every species that oxidizes before ~0.75 V will also contribute to the final response. Thus, the introduction of a selective element was made into this set-up by including a molecularly-imprinted polymer (MIP) tailored in-situ. Herein, a novel MIP for 3-NT was assembled directly on a paper platform, made conductive with carbon ink and suitable for an electrochemical transduction. The biomimetic material was produced by electropolymerization of phenol after optimizing several experimental parameters, such a scan-rate, number of cycles, range of potential applied, monomer and template concentrations. Under optimal conditions, the label-free sensor was able to respond to 3-NT from 500 nM to 1 mM, yielding a limit of detection of 22.3 nM. Finally, the applicability of the (bio)sensor was tested by performing calibration assays in human urine samples and a good performance was obtained in terms of sensitivity, selectivity and reproducibility. Overall, the attributes of the herein described sensing approach can be compared to a very limited number of other electrochemical devices, that are still using a conventional three electrode system, making this paper-sustained device the first electrochemical (bio)sensor with potential to become a portable and low-cost diagnostic tool for 3-NT. In general, the incorporation of molecular imprinting technology coupled to electrochemical transduction enabled the fabrication of suitable smart sensors for wide screening approaches.
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Entidade financiadora
European Commission
Programa de financiamento
H2020
Número da atribuição
829040