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Institute for Bioengineering and Biosciences

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Ultrasound and radiation-induced catalytic oxidation of 1-phenylethanol to acetophenone with iron-containing particulate catalysts
Publication . Soliman, Mohamed Mostafa Aboelhassan; Kopylovich, Maximilian N.; Alegria, Elisabete; Da Costa Ribeiro, Ana Paula; Ferraria, Ana Maria; Rego, Ana; Correia, Luís M. M.; Saraiva, Marta S.; Pombeiro, Armando
Iron-containingparticulatecatalystsof0.1–1 µmsizewerepreparedbywetandball-milling procedures from common salts and characterized by FTIR, TGA, UV-Vis, PXRD, FEG-SEM, and XPS analyses. It was found that when the wet method was used, semi-spherical magnetic nanoparticles were formed, whereas the mechanochemical method resulted in the formation of nonmagnetic microscale needles and rectangles. Catalytic activity of the prepared materials in the oxidation of 1-phenylethanol to acetophenone was assessed under conventional heating, microwave (MW) irradiation, ultrasound (US), and oscillating magnetic field of high frequency (induction heating). In general, the catalysts obtained by wet methods exhibit lower activities, whereas the materials prepared by ball milling afford better acetophenone yields (up to 83%). A significant increase in yield (up to 4 times) was observed under the induction heating if compared to conventional heating. The study demonstrated that MW, US irradiations, and induction heating may have great potential as alternative ways to activate the catalytic system for alcohol oxidation. The possibility of the synthesized material to be magnetically recoverable has been also verified.
Quality monitoring of biodiesel and diesel/biodiesel blends: a comparison between benchtop FT-NIR versus a portable miniaturized NIR spectroscopic analysis
Publication . Monteiro, Luísa; Zoio, Paulo; Carvalho, Bernardo B.; Fonseca, Luís P. P.; Calado, Cecília
A methodology such as near-infrared (NIR) spectroscopy, which enables in situ and in real-time analysis, is crucial to perform quality control of biodiesel, since it is blended into diesel fuel and the presence of contaminants can hinder its performance. This work aimed to compare the performance of a benchtop Fourier Transform (FT) NIR spectrometer with a prototype of a portable, miniaturized near-infrared spectrometer (miniNIR) to detect and quantify contaminants in biodiesel and biodiesel in diesel. In general, good models based on principal component analysis-linear discriminant analysis (PCA-LDA) of FT-NIR spectra were obtained, predicting with high accuracies biodiesel contaminants and biodiesel in diesel (between 75% to 95%), as well as good partial least square (PLS) regression models to predict contaminants concentration in biodiesel and biodiesel concentration in diesel/biodiesel blends, with high coefficients of determination (between 0.83 and 0.99) and low prediction errors. The miniNIR prototype’s PCA-LDA models enabled the prediction of target contaminants with good accuracies (between 66% and 86%), and a PLS model enabled the prediction of biodiesel concentration in diesel with a reasonable coefficient of determination (0.68), pointing to the device’s potential for preliminary analysis of biodiesel which, associated with its potential low cost and portability, could increase biodiesel quality control.
Luminescent carbon dots from wet olive pomace: structural insights, photophysical properties and cytotoxicity
Publication . Sousa, Diogo A.; Ferreira, L.F. Vieira; Fedorov, Alexander A.; Rego, Ana; Ferraria, Ana Maria; Cruz, Adriana; Berberan-Santos, Mario; Prata, José V.
Carbon nanomaterials endowed with significant luminescence have been synthesized for the first time from an abundant, highly localized waste, the wet pomace (WP), a semi-solid by-product of industrial olive oil production. Synthetic efforts were undertaken to outshine the photoluminescence (PL) of carbon nanoparticles through a systematic search of the best reaction conditions to convert the waste biomass, mainly consisting in holocellulose, lignin and proteins, into carbon dots (CDs) by hydrothermal carbonization processes. Blue-emitting CDs with high fluorescence quantum yields were obtained. Using a comprehensive set of spectroscopic tools (FTIR, Raman, XPS, and 1H/13C NMR) in combination with steady-state and time-resolved fluorescence spectroscopy, a rational depiction of WP-CDs structures and their PL properties was reached. WP-CDs show the up-conversion of PL capabilities and negligible cytotoxicity against two mammalian cell lines (L929 and HeLa). Both properties are excellent indicators for their prospective application in biological imaging, biosensing, and dynamic therapies driven by light.
Detection of azo dyes using carbon dots from olive mill wastes
Publication . Sousa, Diogo A.; Berberan-Santos, Mario; Prata, José Virgílio
Azo dyes are widely spread in our day life, being heavily used in cosmetics, healthcare products, textile industries, and as artificial food colorants. This intense industrial activity, which inherently includes their own production, inexorably leads to uncontrolled release of dyes into the environment. As emerging pollutants, their detection, particularly in water systems, is a priority. Herein, a fluorescence-based method was employed for the sensitive and selective detection of anionic and neutral azo dyes. Carbon dots (CDs) synthesized from wet pomace (WP), an abundant semi-solid waste of olive mills, were used as probes. An outstanding capability for detection of azo dyes methyl orange (MO) and methyl red (MR) in aqueous solutions was disclosed, which reached a limit of detection (LOD) of 151 ppb for MO. The selectivity of WP-CDs for the anionic azo dye (MO) was established through competitive experiments with other dyes, either anionic (indigo carmine) or cationic (fuchsin, methylene blue, and rhodamine 6G); perchlorate salts of transition metal cations (Cu(II), Co(II), Fe(II), Fe(III), Hg(II), and Pb(II)); and sodium salts of common anions (NO3-, CO32-, Cl-, and SO42-). Evidence has been collected that supports static quenching as the main transduction event underlying the observed quenching of the probe's fluorescence, combined with a dynamic resonance energy transfer (RET) mechanism at high MO concentrations.
Validation of a miniaturised near infrared spectrometer for contaminant assessment in biodiesel
Publication . Monteiro, Luísa; Zoio, Paulo; Carvalho, M. B. P.; Fonseca, Luís P. P.; Calado, Cecília
A new method to simultaneously predict cells viability, proliferation and metabolic status, in a rapid, simple but also specific and sensitive mode was developed. The method is based on mid-infrared (MIR) spectroscopic analysis of cells. As model system were used Human embryonic kidney (HEK) 293 cells and T lymphocytes. After submitting cells to different environments as the toxic dimethyl sulfoxide, or metabolic activation, cells viability was analyzed by optical microscopy after coloration with trypan blue, and the cell count was determined with a Neubauer hemocytometer. The principal component analysis (PCA) of the cells second derivative spectra enabled to discriminate the cells viability and the cells proliferation as assayed by conventional methods, while spectra PCA and Hierarchical Cluster Analysis (HCA) enabled to discriminate T cells metabolic activation. The new methods, based on MIR spectroscopy, present the advantages of being applicable in automatic, simple and high-throughput mode in relation to the conventional methods.

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Funding agency

Fundação para a Ciência e a Tecnologia

Funding programme

6817 - DCRRNI ID

Funding Award Number

UIDB/04565/2020

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