Publications

Abstract The objective of this work was the exploration of low calcination temperature ranges (< 350 degrees C) to obtain molecularly imprinted microspheres (MIM) with a high crystallinity as anatase, in cooperation of an acidic pretreatment aiming at the preservation of the hollow shape and also of the selective binding sites. It was confirmed the possibility of obtaining bilirubin-imprinted crystalline TiO2 microspheres (highly crystalline anatase, as confirmed by XRD) exhibiting higher photocatalytic efficiency associated especially with the hollow shape and calcination at lower temperatures (200 degrees C or 250 degrees C). It was with the calcination temperature of 250 degrees C that the highest photocatalytic efficiency was obtained, under UV irradiation, associated with the highest adsorption selectivity (alpha(K) = 19) and degradation selectivity (alpha(k) = 2.7) observed for the degradation of the template against a closely related analogue compound.

Abstract The possibility of generating organically modified hollow TiO2 microspheres via a simple sol-gel synthesis was demonstrated for the first time in this work. A mixture of titania precursors, including an organically modified precursor, was used to obtain methyl-modified hollow TiO2 microspheres selective for bilirubin by the molecular imprinting technique (Methyl-HTM-MIM). Methyl-HTM-MIM were prepared by a sol-gel method using titanium (IV) isopropoxide (TTIP), and methyltitanium triisopropoxide (MTTIP) as precursors. Two ratios of titania precursors were tested (1/6 and 1/30 mol(MTTIP)/mol(TTIP)). With the characterization results obtained by the SEM and ATR-FTIR techniques, it was possible to establish that only the 1/30 mol(MTTIP)/mol(TTIP) ratio allowed for the preparation of hollow spheres with a reasonably homogeneous methylated-TiO2 shell. It was possible to obtain a certain degree of organization of the hybrid network, which increased with calcination temperatures. By adjusting isothermal adsorption models, imprinting parameters were determined, indicating that the new methylated microspheres presented greater selectivity for bilirubin than the totally inorganic hollow TiO2 microspheres. The effectiveness of the molecular imprinting technique was proven for the first time in an organically modified titania material, with imprinting factor values greater than 1.4, corresponding to a significant increase in the maximum adsorption capacity of the template represented by the molecularly imprinted microspheres. In summary, the results obtained with the new methyl-HTM-MIM open the possibility of exploring the application of these microspheres for selective sorption (separation or sensing, for example) or perhaps even for selective photocatalysis, particularly for the degradation of organic compounds.

Abstract A suitable dispersion of carbon materials (e.g., carbon nanotubes (CNTs)) in an appropriate dispersant media, is a prerequisite for many technological applications (e.g., additive purposes, functionalization, mechanical reinforced materials for electrolytes and electrodes for energy storage applications, etc.). Deep eutectic solvents (DES) have been considered as a promising "green" alternative, providing a versatile replacement to volatile organic solvents due to their unique physical-chemical properties, being recognized as low-volatility fluids with great dispersant ability. The present work aims to contribute to appraise the effect of the presence of MWCNTs and Ag-functionalized MWCNTs on the physicochemical properties (viscosity, density, conductivity, surface tension and refractive index) of glyceline (choline chloride and glycerol, 1:2), a Type III DES. To benefit from possible synergetic effects, AgMWCNTs were prepared through pulse reverse electrodeposition of Ag nanoparticles into MWCNTs. Pristine MWCNTs were used as reference material and water as reference dispersant media for comparison purposes. The effect of temperature (20 to 60 degrees C) and concentration on the physicochemical properties of the carbon dispersions (0.2-1.0 mg cm(-3)) were assessed. In all assessed physicochemical properties, AgMWCNTs outperformed pristine MWCNTs dispersions. A paradoxical effect was found in the viscosity trend in glyceline media, in which a marked decrease in the viscosity was found for the MWCNTs and AgMWCNTs materials at lower temperatures. All physicochemical parameters were statistically analyzed using a two-way analysis of variance (ANOVA), at a 5% level of significance.

Abstract Biogenic amines (BAs) are compounds found in a vast range of food products. In recent years, there has been a crescent awareness toward food safety, followed by an increase in food regulations. Long-period fiber gratings (LPFGs) coated with titanium dioxide (TiO2) were used to monitor the optical properties of a layer of poly(ethylene-co-vinyl acetate) (PEVA) doped with maleic anhydride (MA), which was polymerized on top of TiO2. This hydrophobic polymeric structure is permeable to BA, which causes a steady increase in its effective refractive index (RI) causing a wavelength shift in the coated LPFG attenuation band. LPFG wavelength shift was observed and measured for the monoamine tyramine (TYR), to the diamines, putrescine (PUT), cadaverine (CAD), histamine (HIS), and tryptamine (TRYP), and to the polyamines, spermidine (SPED), and spermine (SPEM). It was determined that, while PEVA-coated devices present a residual sensitivity to BA, the MA greatly increases it. In fact, for PEVA only coated LPFGs, the sensitivities of 1.45 +/- 0.11, 0.97 +/- 0.05, 0.46 +/- 0.08, and 0.94 +/- 0.09 nmM-1 for PUT, CAD, HIS, and TYR, respectively, were measured. However, for PEVA-doped MA-coated LPFGs, the sensitivities are 3.34 +/- 0.13, 3.06 +/- 0.11, 2.62 +/- 0.14, and 3.65 +/- 0.23 nmM-1 for PUT, CAD, HIS, and TYR, respectively. Thus, the RI of PEVA increases with BAs in- diffusion, and MA doping further enhances the PEVA sensitivity to BA. The proposed sensor is expected to play a part in the further development of a biosensor for the quantification of BA in real foodstuff, providing a methodology for quality control.

Abstract Relative humidity (RH) monitorization is of extreme importance on scientific and industrial applications, and optical fiber sensors (OFS) may provide adequate solutions. Typically, these kinds of sensors depend on the usage of humidity responsive polymers, thus creating the need for the characterization of the optical and expansion properties of these materials. Four different polymers, namely poly(vinyl alcohol), poly(ethylene glycol), Hydromed (TM) D4 and microbiology agar were characterized and tested using two types of optical sensors. First, optical fiber Fabry-Perot (FP) tips were made, which allow the dynamical measurement of the polymers' response to RH variations, in particular of refractive index, film thickness, and critical deliquescence RH. Using both FP tips and Long-Period fiber gratings, the polymers were then tested as RH sensors, allowing a comparison between the different polymers and the different OFS. For the case of the FP sensors, the PEG tips displayed excellent sensitivity above 80%RH, outperforming the other polymers. In the case of LPFGs, the 10% (wt/wt) PVA one displayed excellent sensitivity in a larger working range (60 to 100%RH), showing a valid alternative to lower RH environment sensing.

Abstract Plasmonic bio/chemical sensing based on optical fibers combined with molecularly imprinted nanoparticles (nanoMIPs), which are polymeric receptors prepared by a template-assisted synthesis, has been demonstrated as a powerful method to attain ultra-low detection limits, particularly when exploiting soft nanoMIPs, which are known to deform upon analyte binding. This work presents the development of a surface plasmon resonance (SPR) sensor in silica light-diffusing fibers (LDFs) functionalized with a specific nanoMIP receptor, entailed for the recognition of the protein human serum transferrin (HTR). Despite their great versatility, to date only SPR-LFDs functionalized with antibodies have been reported. Here, the innovative combination of an SPR-LFD platform and nanoMIPs led to the development of a sensor with an ultra-low limit of detection (LOD), equal to about 4 fM, and selective for its target analyte HTR. It is worth noting that the SPR-LDF-nanoMIP sensor was mounted within a specially designed 3D-printed holder yielding a measurement cell suitable for a rapid and reliable setup, and easy for the scaling up of the measurements. Moreover, the fabrication process to realize the SPR platform is minimal, requiring only a metal deposition step.

Abstract Long period fiber gratings coated with TiO2 and poly(ethylene-co-vinyl acetate) (PEVA), a polymeric structure permeable biogenic amines found in foodstuff, were used to detect these compounds through the wavelength shift of its attenuation band. © 2022 The Author(s).

Abstract The use of concrete has been widespread in our society in housing and infrastructure, despite the environmental cost associated with its production. Its decay poses a social, economic, and environmental problem. Currently, the carbonation of cement paste is monitored through the measurement of its pH, with several optical fiber sensors (OFS) have been produced for this purpose. In the current work the focus is, also, on the carbonation monitoring of cement paste through an OFS, but not through pH measurements. Single fiber reflectance spectroscopy, previously employed to measure cement paste durability, is used to monitor the discoloration of cement paste caused by carbonation. As the carbonation front reaches the fiber tip embedded in the cement paste, the signal reflected onto the fiber increases. The accelerated carbonation of two limestone cement paste samples in an atmosphere of 100% CO2 was successfully monitored. The applicability of the sensor for operational use with ambient CO2 was confirmed through the measurement of carbonation at 3% CO2. The cross interference from water ingress and egress was also evaluated, and it didn't hinder the measurements of carbonation. Therefore, a novel OFS capable of measuring cement paste carbonation and durability, was achieved. © Published under licence by IOP Publishing Ltd.

Abstract Fiber optic-based refractometers is a thoroughly researched field, with many different configurations being used. However, most designs require external calibration using substances of known refractive index (RI) and their fabrication process might be impractical and time consuming, creating the need for a quick and accurate method of measuring RI of different substances. A simple method for simultaneous measurement in real-time of RI and thickness of polymer thin films is presented, allowing dynamic measurements in the presence of changing environmental parameters, such as temperature or humidity. This method, which does not require previous calibration, is based on an inline Fabry-Perot (FP) cavity, created by dipping the tip of a cleaved optical fiber (OF) in a polymer solution. The procedure consists of using the equations of the low finesse FP interferometers to directly extract information from the structure created, such as RI and cavity length, by working in the spectral window from 1500 to 1600nm. The method was validated by creating FP cavities with liquids of known RI, for which a typical precision of 3 x 10(-3) was achieved, along with errors lower than 0.6% and 1% for RI and cavity length determination, respectively, The procedure was then used to monitor three different curing processes, namely the temperature curing of Sylgard (TM) 184, the UV curing of Norland Optical Adhesives (TM) 65 and the mixing and curing of Ceys (TM) Araldite epoxy glue. Both RI and cavity length were compared to reference values, showing excellent agreement with the experimental results for a method that does not require external calibration.

Abstract A strategy for the detection of H2O2 as a milk adulterant using a single shot membrane sensor, is presented. Direct quantitative evaluation of H2O2 in raw, skimmed, semi-skimmed and whole milk was carried out based on a chemiluminescence reaction with luminol. For H2O2 water solutions a linear response was attained from 0.0001% to 0.007 %w/w, with a limit of detection of 3x10(-5) %w/w. A coefficient of determination, R-2, greater than 0.97 was achieved, with a relative standard deviation (RSD) not exceeding 10%. In the analyzed milk samples, the lowest H2O2 concentration detected was 0.001% w/w for raw and for skim milk and 0.002%w/w for, semi-skimmed and whole milk. The presented method is original, sensitive, rapid, and cost-effective. Due to the achieved sensitivity the method has great potential to be used for H2O2 detection in diverse areas, such as environmental monitoring and food quality.