Publications

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.

Abstract New paths to increase the sensing performance of plasmonic sensors have been reported in recent years. There are several methodologies to achieve such purpose, namely by optimizing the nanostructure, nanomaterial and even the sensing platform. Recently the use nanoparticles over plasmonic thin films have been reported and shown sensitivity enhancement, when compared to a bare thin film. Nevertheless, a nanomaterial combination between NP and thin film has not been studied. In this work it was studied such plasmonic materials in order to optimize not only refractometric sensitivity but also decrease the resultant plasmonic band width. It was found that for Au, Ag and Cu thin films, the deposition of plasmonic nanoparticles resulted in an overall refractometric sensitivity and figure of merit (FOM) increase. The larger FOM increase was obtained for the Ag thin film, from 42 to 162 when coupled to Si nanoparticles. The greater sensitivity increase was achieved for a Cu thin film coupled to a Si nanoparticle, with an increase from 1745 to 3230 nm/RIU. © Published under licence by IOP Publishing Ltd.

Abstract Plant cells face many changes through their life cycle and develop several mechanisms to cope with adversity. Stress caused by environmental factors is turning out to be more and more relevant as the human population grows and plant cultures start to fail. As eukaryotes, plant cells must coordinate several processes occurring between compartments and combine different pathways for protein transport to several cellular locations. Conventionally, these pathways begin at the ER, or endoplasmic reticulum, move through the Golgi and deliver cargo to the vacuole or to the plasma membrane. However, when under stress, protein trafficking in plants is compromised, usually leading to changes in the endomembrane system that may include protein transport through unconventional routes and alteration of morphology, activity and content of key organelles, as the ER and the vacuole. Such events provide the tools for cells to adapt and overcome the challenges brought on by stress. With this review, we gathered fragmented information on the subject, highlighting how such changes are processed within the endomembrane system and how it responds to an ever-changing environment. Even though the available data on this subject are still sparse, novel information is starting to untangle the complexity and dynamics of protein transport routes and their role in maintaining cell homeostasis under harsh conditions.

Abstract The present work reports an experimental thermodynamic study of two nitrogen heterocyclic organic compounds, fenclorim and clopyralid, that have been used as herbicides. The sublimation vapor pressures of fenclorim (4,6-dichloro-2-phenylpyrimidine) and of clopyralid (3,6-dichloro-2-pyridinecarboxylic acid) were measured, at different temperatures, using a Knudsen mass-loss effusion technique. The vapor pressures of both crystalline and liquid (including supercooled liquid) phases of fenclorim were also determined using a static method based on capacitance diaphragm manometers. The experimental results enabled accurate determination of the standard molar enthalpies, entropies and Gibbs energies of sublimation for both compounds and of vaporization for fenclorim, allowing a phase diagram representation of the (p,T) results, in the neighborhood of the triple point of this compound. The temperatures and molar enthalpies of fusion of the two compounds studied were determined using differential scanning calorimetry. The standard isobaric molar heat capacities of the two crystalline compounds were determined at 298.15 K, using drop calorimetry. The gas phase thermodynamic properties of the two compounds were estimated through ab initio calculations, at the G3(MP2)//B3LYP level, and their thermodynamic stability was evaluated in the gaseous and crystalline phases, considering the calculated values of the standard Gibbs energies of formation, at 298.15 K. All these data, together with other physical and chemical properties, will be useful to predict the mobility and environmental distribution of these two compounds.

Abstract This work reports the thermodynamic and morphological study and characterization of four salts consisting of a divalent/trivalent cobalt complex with pyrazole-pyridine ligands (FK 102 and FK 209 samples) and bis(trifluoromethylsulfonyl)imide (TFSI) moieties as counter anions. The oxidation state of the central metal (Co(II) or Co(III)) and the presence of tert-butyl (t-Bu) groups in the ligand structure were found to have a strong impact on the thermal behavior, phase stability, heat capacities, and thin-film morphology of each salt. The Co(II) complexes exhibited good thermal stability up to 600 K. Lower thermal stability was observed for the Co(III) congeners. The FK 209 Co(III) displayed a higher melting temperature but a partial decomposition during or above melting was detected. The higher melting temperatures observed for the Co(III) complexes were found to be entropically driven. However, the addition of t-Bu in the ligand (FK 209) leads to an increase in the melting temperature, which is driven by the enthalpy of fusion. The four compounds studied evidenced a large glass-forming ability. Moreover, the thermal stability of the glassy state was clearly increased when the ligands comprised t-Bu groups. The contribution of the t-Bu group for the molar heat capacity in the solid phase, at T = 298.15 K, was found to be (110 ± 3) J·K−1·mol−1 and (98 ± 4) J·K−1·mol−1 for the Co(II) and Co(III) complexes, respectively. These results are in good agreement with the contribution of the t-Bu group observed for both solid and liquid phases in other materials, indicating that the t-Bu groups are relatively unhindered in the crystalline phase of the salts. The morphological behavior of the thin films of FK 102 samples was found to be quite similar to the observed for typical ionic liquids, with the formation of micro- and nanodroplets onto different substrates. The introduction of t-Bu substituents in the ligand structure was found to have a strong impact on the formation of homogeneous and compact nanofilms for the FK 209 salts. © 2022 Elsevier Ltd