AC/DC Magnetic Field Sensing Based on a Piezoelectric Polymer and a Fully Printed Planar Spiral Coil.

Additive manufacturing (AM) is emerging as an eco-friendly method for minimizing waste, as the demand for responsive materials in IoT and Industry 4.0 is on the rise. Magnetoactive composites, which are manufactured through AM, facilitate nonintrusive remote sensing and actuation. Printed magnetoelectric composites are an innovative method that utilizes the synergies between magnetic and electric properties. The study of magnetoelectric effects, including the recently validated piezoinductive effect, demonstrates the generation of electric voltage through external AC and DC magnetic fields. This shift in magnetic sensors, utilizing piezoinductive effect of the piezoelectric polymer poly(vinylidene fluoride), PVDF, eliminates the need for magnetic fillers in printed devices, aligning with sustainability principles, essential for the deployment of IoT and Industry 4.0. The achieved sensitivity surpasses other studies by 100 times, showcasing linear outputs for both applied AC and DC magnetic fields. Additionally, the sensor capitalizes on the linear phase shift of the generated signal with an applied DC magnetic field, an unprecedented effect. Thus, this work introduces a remarkable magnetoactive device with a sensitivity of ST = 95.1 ± 0.9 µV Oe-1 mT-1, a significantly improved performance compared to magnetoelectric devices using polymer composites. As a functional proof of concept of the developed system, a magnetic position sensor has been demonstrated.

Self-sensing magnetic actuator based on sustainable collagen hybrid nanocomposites.

Taking into account that natural polymers are renewable and biodegradable, hybrid materials based on natural polymers are required for advanced technological applications with reduced environmental footprint. In this work, sustainable composites have been developed based on collagen as a polymeric matrix and different magnetic fillers, in order to tailor magnetic response. The composites were prepared by solution casting with 30 wt% of magnetite nanoparticles (Fe3O4 NPs), magnetite nanorods (Fe3O4 NRs) or cobalt ferrite nanoparticles (CoFe2O4 NPs). It is shown that the magnetic filler type has no bearing on the morphology, physical-chemical, or thermal characteristics of the composites, whereas the mechanical properties are determined by the magnetic filler, leading to a reduction in tensile strength, with values of 4.95 MPa for Fe3O4 NPs, 9.20 MPa for Fe3O4 NRs and 5.21 MPa for CoFe2O4 NPs containing samples. However, the highest magnetization saturation is obtained for Fe3O4 NPs (44 emu.g-1) and the higher coercive field for CoFe2O4 NPs (2062 Oe). In order to prove functionality of the developed composites, a self-sensing magnetic actuator device has been developed with the composite film with CoFe2O4 NPs, showing high stability over cycling.

Improving Definition of Screen-Printed Functional Materials for Sensing Application.

Screen printing is one of the most used techniques for developing printed electronics. It stands out for its simplicity, scalability, and effectivity. Specifically, the manufacturing of hybrid integrated circuits has promoted the development of the technique, and the photovoltaic industry has enhanced the printing process by developing high-performance metallization pastes and high-end screens. In recent years, fine lines of 50 µm or smaller are about to be adopted in mass production, and screen printing has to compete with digital printing techniques such as inkjet printing, which can reach narrower lines. In this sense, this work is focused on testing the printing resolution of a high-performance stainless-steel screen with commercial conductive inks and functional lab-made inks based on reduced graphene oxide using an interdigitated structure. We achieved electrically conductive functional patterns with a minimum printing resolution of 40 µm for all inks.

Ionic Thermoelectric Generators in Vertical and Planar Topologies Based on Fluorinated Polymer Hybrid Materials with Ionic Liquids.

Ionic thermoelectrics (TEs), in which voltage generation is based on ion migration, are suitable for applications based on their low cost, high flexibility, high ionic conductivity, and wide range of Seebeck coefficients. This work reports on the development of ionic TE materials based on the poly(vinylidene fluoride-trifluoroethylene), Poly(VDF-co-TrFE), as host polymer blended with different contents of the ionic liquid, IL, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [EMIM][TFSI]. The morphology, physico-chemical, thermal, mechanical, and electrical properties of the samples are evaluated together with the TE response. It is demonstrated that the IL acts as a nucleating agent for polymer crystallization. The mechanical properties and ionic conductivity values are dependent on the IL content. A high room temperature ionic conductivity of 0.008 S cm-1 is obtained for the sample with 60 wt% of [EMIM][TFSI] IL. The TE properties depend on both IL content and device topology-vertical or planar-the largest generated voltage range being obtained for the planar topology and the sample with 10 wt% of IL content, characterized by a Seebeck coefficient of 1.2 mV K-1. Based on the obtained maximum power density of 4.9 µW m-2, these materials are suitable for a new generation of TE devices.

Biodegradable and biocompatible collagen-based hybrid materials for force sensing applications.

With the aim of replacing synthetic macromolecules by biological macromolecules for advanced applications, collagen films were produced with two different ionic liquids (ILs), choline dihydrogen phosphate ([Ch][DHP]) and choline serinate ([Ch][Seri]), added in order to modulate the electrical responses. The films were prepared by casting, varying IL content between 0 and 6 wt%. The morphology and thermal properties of the resulting films were found to be independent of both IL type and content. However, the highest direct curret (d.c.) electrical conductivity (1.4 × 10-8 S·cm-1) was achieved for collagen films containing 3 wt% [Ch][DHP]. Furthermore, it was demonstrated that IL/collagen films were non-cytotoxic, with cell activity values exceeding 70 %. These collagen films were proven to be suitable for force sensing applications, displaying excellent sensitivity and stability upon repeated testing.

Sustainable Collagen Composites with Graphene Oxide for Bending Resistive Sensing.

This work reports on the development of collagen films with graphene oxide nanoparticles (GO NPs), aiming toward the development of a new generation of functional sustainable sensors. For this purpose, different GO NP contents up to 3 wt % were incorporated into a collagen matrix, and morphological, thermal, mechanical and electrical properties were evaluated. Independently of the GO NP content, all films display an increase in thermal stability as a result of the increase in the structural order of collagen, as revealed by XRD analysis. Further, the inclusion of GO NPs into collagen promotes an increase in the intensity of oxygen characteristic absorption bands in FTIR spectra, due to the abundant oxygen-containing functional groups, which lead to an increase in the hydrophilic character of the surface. GO NPs also influence the mechanical properties of the composites, increasing the tensile strength from 33.2 ± 2.4 MPa (collagen) to 44.1 ± 1.0 MPa (collagen with 3 wt % GO NPs). Finally, the electrical conductivity also increases slightly with GO NP content, allowing the development of resistive bending sensors.

Novel Foscan®-derived ring-fused chlorins for photodynamic therapy of cancer.

Photodynamic therapy (PDT) is an established anticancer treatment that combines the use of a photosensitiser (PS) and a light source of a specific wavelength for the generation of reactive oxygen species (ROS) that are toxic to the tumour cells. Foscan® (mTHPC) is a clinically-approved chlorin used for the PDT treatment of advanced head and neck, prostate and pancreatic cancers but is characterized by being photochemically unstable and associated with prolonged skin photosensitivity. Herein, we report the synthesis of new 4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-fused chlorins, having the meso-tetra(3-hydroxyphenyl)macrocycle core of mTHPC, by exploring the [8π + 2π] cycloaddition of a meso-tetra(3-hydroxyphenyl)porphyrin derivative with diazafulvenium methides. These chlorins have photochemical properties similar to Foscan® but are much more photostable. Among the novel compounds, two chlorins with a hydroxymethyl group and its azide derivative present in the 4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-fused system, are promising photodynamic agents with activity in the 100 nM range against triple-negative breast cancer cells and, in the case of azidomethyl chlorin, a safer phototherapeutic index compared to Foscan®.

Magnetic Polymer Actuators with Self-Sensing Resistive Bending Response Based on Ternary Polymer Composites.

A multifunctional polymer-based composite has been designed based on poly(vinylidene fluoride) (PVDF) as polymer matrix and cobalt ferrite (CoFe2O4, CFO) and multiwalled carbon nanotubes (MWCNTs) as fillers, allowing to combine magnetic and electrical responses. The composites were prepared by solvent casting with a fixed 20 wt % concentration of CFO and varying the MWCNTs content between 0 and 3 wt %, allowing to tailor the electrical behavior. The morphology, polymer phase, and thermal and magnetic properties are nearly independent of the MWCNT filler content within the polymer matrix. On the other hand, the mechanical and electrical properties strongly depend on the MWCNT content and a maximum d.c. electrical conductivity value of 4 × 10-4 S·cm-1 has been obtained for the 20 wt %CFO-3 wt %MWCNT/PVDF sample, which is accompanied by an 11.1 emu·g-1 magnetization. The suitability of this composite for magnetic actuators with self-sensing strain characteristics is demonstrated with excellent response and reproducibility.

Sustainable Collagen Blends with Different Ionic Liquids for Resistive Touch Sensing Applications.

Considering the sustainable development goals to reduce environmental impact, sustainable sensors based on natural polymers are a priority as the large im plementation of these materials is required considering the Internet of Things (IoT) paradigm. In this context, the present work reports on sustainable blends based on collagen and different ionic liquids (ILs), including ([Ch][DHP], [Ch][TSI], [Ch][Seri]) and ([Emim][TFSI]), processed with varying contents and types of ILs in order to tailor the electrical response. Varying IL types and contents leads to different interactions with the collagen polymer matrix and, therefore, to varying mechanical, thermal, and electrical properties. Collagen/[Ch][Seri] samples display the most pronounced decrease of the tensile strength (3.2 ± 0.4 MPa) and an increase of the elongation at break (50.6 ± 1.5%). The best ionic conductivity value of 0.023 mS cm-1 has been obtained for the sample with 40 wt % of the IL [Ch][Seri]. The functional response of the collagen-IL films has been demonstrated on a resistive touch sensor whose response depends on the ionic conductivity, being suitable for the next generation of sustainable touch sensing devices.

Valorisation of Wasted Immature Tomato to Innovative Fermented Functional Foods.

In this study, the lactic fermentation of immature tomatoes as a tool for food ingredient production was evaluated as a circular economy-oriented alternative for valorising industrial tomatoes that are unsuitable for processing and which have wasted away in large quantities in the field. Two lactic acid bacteria (LAB) were assessed as starter cultures in an immature tomato pulp fermentation to produce functional food ingredients with probiotic potential. The first trial evaluated the probiotic character of Lactiplantibacillus plantarum (LAB97, isolated from immature tomato microbiota) and Weissella paramesenteroides (C1090, from the INIAV collection) through in vitro gastrointestinal digestion simulation. The results showed that LAB97 and C1090 met the probiotic potential viability criterion by maintaining 6 log10 CFU/mL counts after in vitro simulation. The second trial assessed the LAB starters' fermentative ability. Partially decontaminated (110 °C/2 min) immature tomato pulp was used to prepare the individually inoculated samples (Id: LAB97 and C1090). Non-inoculated samples, both with and without thermal treatment (Id: CTR-TT and CTR-NTT, respectively), were prepared as the controls. Fermentation was undertaken (25 °C, 100 rpm) for 14 days. Throughout storage (0, 24, 48, 72 h, 7, and 14 days), all the samples were tested for LAB and Y&M counts, titratable acidity (TA), solid soluble content (SSC), total phenolic content (TPC), antioxidant capacity (AOx), as well as for organic acids and phenolic profiles, and CIELab colour and sensory evaluation (14th day). The LAB growth reached ca. 9 log10 CFU/mL for all samples after 72 h. The LAB97 samples had an earlier and higher acidification rate than the remaining ones, and they were highly correlated to lactic acid increments. The inoculated samples showed a faster and higher decrease rate in their SSC levels when compared to the controls. A nearly two-fold increase (p < 0.05) during the fermentation, over time, was observed in all samples' AOx and TPC (p < 0.05, r = 0.93; similar pattern). The LAB97 samples obtained the best sensory acceptance for flavour and overall appreciation scores when compared to the others. In conclusion, the L. plantarum LAB97 starter culture was selected as a novel probiotic candidate to obtain a potential probiotic ingredient from immature tomato fruits.

Influence of Air-Drying Conditions on Quality, Bioactive Composition and Sensorial Attributes of Sweet Potato Chips.

The drying process is an essential thermal process for preserving vegetables and can be used in developing dried products as healthy alternative snacks. The effects of air-drying conditions using a convection dryer with hot air at different temperatures (60°, 65°, 70°, 75°, and 80 °C, in the range 5-200 min, at a fixed air speed of 2.3 m/s) were tested on the quality of slices (2.0 ± 0.1 mm) of dried sweet potato (Bellevue PBR). For each time and temperature, drying condition, physicochemical parameters (moisture content, CIELab color, texture parameters, total phenolic and carotenoid contents) and a sensory evaluation by a panel at the last drying period (200 min) were assessed. Drying time was shown to have a more significant effect than temperature on the quality of dried sweet potato as a snack, except for carotenoid content. Given the raw tuber content, thermal degradation (p < 0.05) of total phenolic compounds (about 70%), regardless of tested conditions, contrasted with the higher stability of total carotenoids (<30%). The dried product, under optimal conditions (≥75 °C for 200 min), achieved a moisture content (≤10%) suitable for preservation, providing a crispy texture with favourable sensory acceptance and providing a carotenoid content similar to the raw product.

Development of an Innovative Lightweight Composite Material with Thermal Insulation Properties Based on Cardoon and Polyurethane.

The search for innovative and sustainable solutions to improve the energy efficiency of the construction industry has been a hot topic for researchers due to the tremendous impact of insulator materials in the thermal comfort of buildings. In the present work, an innovative lightweight composite material with thermal insulation properties was developed, for the first time, by using cardoon particles and polyurethane. The formulation of the composite material was optimized in terms of cardoon fraction and the polyol/isocyanate ratio, to achieve the best compromise between internal bond (IB) strength and thickness swelling (TS). The best performing composite was PU75-CP45, with 45 wt% of cardoon particles and 75% of isocyanate, achieving an IB of 0.41 MPa and a TS of 5.3%. Regarding insulation properties, the PU75-CP45 composite material exhibits a promising performance when compared to conventional construction industry materials by tuning its thickness. Additionally, the composite material presented very low emissions of volatile organic compounds and formaldehyde (bellow to legislation levels) and high resistance to biological degradation.

Differential Tunneling-Driven and Vibrationally-Induced Reactivity in Isomeric Benzazirines.

Quantum mechanical tunneling of heavy-atoms and vibrational excitation chemistry are unconventional and scarcely explored types of reactivity. Once fully understood, they might bring new avenues to conduct chemical transformations, providing access to a new world of molecules or ways of exquisite reaction control. In this context, we present here the discovery of two isomeric benzazirines exhibiting differential tunneling-driven and vibrationally-induced reactivity, which constitute exceptional results for probing into the nature of these phenomena. The isomeric 6-fluoro- and 2-fluoro-4-hydroxy-2H-benzazirines (3-a and 3'-s) were generated in cryogenic krypton matrices by visible-light irradiation of the corresponding triplet nitrene 3 2-a, which was produced by UV-light irradiation of its azide precursor. The 3'-s was found to be stable under matrix dark conditions, whereas 3-a spontaneously rearranges (τ1/2 ∼64 h at 10 and 20 K) by heavy-atom tunneling to 3 2-a. Near-IR-light irradiation at the first OH stretching overtone frequencies (remote vibrational antenna) of the benzazirines induces the 3'-s ring-expansion reaction to a seven-member cyclic ketenimine, but the 3-a undergoes 2H-azirine ring-opening reaction to triplet nitrene 3 2-a. Computations demonstrate that 3-a and 3'-s have distinct reaction energy profiles, which explain the different experimental results. The spectroscopic direct measurement of the tunneling of 3-a to 3 2-a constitutes a unique example of an observation of a species reacting only by nitrogen tunneling. Moreover, the vibrationally-induced sole activation of the most favorable bond-breaking/bond-forming pathway available for 3-a and 3'-s provides pioneer results regarding the selective nature of such processes.

Ring-Fused meso-Tetraarylchlorins as Auspicious PDT Sensitizers: Synthesis, Structural Characterization, Photophysics, and Biological Evaluation.

Novel 4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-fused meso-tetraarylchlorins, with different degrees of hydrophilicity (with methyl ester, hydroxymethyl, and carboxylic acid moieties), have been synthesized and their photophysical characterization as well as in vitro photocytotoxicity assessment against human melanoma and esophageal and bladder carcinomas was carried out. An integrated analysis of the photosensitizers' performance, considering the singlet oxygen generation data, cell internalization, and intracellular localization, allowed to establish relevant structure-photoactivity relationships and the rationalization of the observed photocytotoxicity. In the diacid and monoalcohol series, chlorins derived from meso-tetraphenylporphyrin proved to be the most efficient photodynamic therapy agents, showing IC50 values of 68 and 344 nM against A375 cells, respectively. These compounds were less active against OE19 and HT1376 cells, the diacid chlorin with IC50 values still in the nano-molar range, whereas the monohydroxymethyl-chlorin showed significantly higher IC50 values. The lead di(hydroxymethyl)-substituted meso-tetraphenylchlorin confirmed its remarkable photoactivity with IC50 values below 75 nM against the studied cancer cell lines. Subcellular accumulation of this chlorin in the mitochondria, endoplasmic reticulum, and plasma membrane was demonstrated.

Photochromism of a Spiropyran in Low-Temperature Matrices: Unprecedented Bidirectional Switching between a Merocyanine and an Allene Intermediate.

Photochromism of spiropyrans has attracted much attention due to its potential in many light-controlled system applications. However, several fundamental aspects regarding the structure, energetics, and mechanistic details of the transformations of spiropyrans are still not well understood. Here, we report the study of the photochromism of a 6-hydroxy-spiropyran (HBPS) under conditions of matrix isolation, where monomers of the compound are frozen in a solidified noble gas (krypton, at 15 K). The structure of the matrix-isolated HBPS was first elucidated by infrared (IR) spectroscopy supported by density functional theory computations. Then, the photochromism of HBPS, from the colorless spiropyran to the colored merocyanine, was induced by ultraviolet (UV) irradiation at 310 nm. The analysis of the IR spectrum of the photoproduced species revealed the exclusive formation of the most stable merocyanine MC-TTC stereoisomer. Subsequent visible-light (550 nm) irradiation of MC-TTC generated a new colorless allenic isomeric species ALN, where the UV irradiation (310 nm) of ALN was found to convert this species back to MC-TTC. This constitutes an unprecedented bidirectional transformation between a colored merocyanine and a colorless allene species. The newly observed photoswitching reaction (or photochromism) occurs along an intramolecular hydrogen bond existing in both merocyanine and allenic species, thus suggesting that it might be generally feasible in the chemistry of spiropyrans. On the other hand, the usual assumption that, as a general rule, merocyanines photochemically revert to spiropyrans is not supported in this work.

Isolation and Identification of Cytotoxic Compounds Present in Biomaterial Life®.

Direct pulp capping consists of a procedure in which a material is directly placed over the exposed pulp to maintain dental vitality. Although still widely used in clinical practice, previous in vitro studies found that the biomaterial Life® presented high cytotoxicity, leading to cell death. This study aimed to identify the Life® constituents responsible for its cytotoxic effects on odontoblast-like cells (MDPC-23). Aqueous medium conditioned with Life® was subjected to liquid-liquid extraction with ethyl acetate. After solvent removal, cells were treated with residues isolated from the organic and aqueous fractions. MTT and Trypan blue assays were carried out to evaluate the metabolic activity and cell death. The organic phase residue promoted a significant decrease in metabolic activity and increased cell death. On the contrary, no cytotoxic effects were observed with the mixture from the aqueous fraction. Spectroscopic and spectrometric methods allowed the identification of the toxic compounds. A mixture of the regioisomers ortho, para, and meta of N-ethyl-toluenesulfonamide was identified as the agent responsible for the toxicity of biomaterial Life® in MDPC-23 cells. These findings contribute to improving biomaterial research and development.

Selection of Autochthonous LAB Strains of Unripe Green Tomato towards the Production of Highly Nutritious Lacto-Fermented Ingredients.

Lactic fermentation of unripe green tomatoes as a tool to produce food ingredients is a viable alternative for adding value to industrial tomatoes unsuitable for processing and left in large quantities in the fields. Fermentation using starter cultures isolated from the fruit (plant-matrix adapted) can have advantages over allochthonous strains in obtaining fermented products with sensory acceptability and potentially probiotic characteristics. This paper details the characterisation of the unripe green tomato lactic microbiota to screen LAB strains for use as starter cultures in fermentation processes, along with LAB strains available from INIAV's collection. Morphological, biochemical (API system), and genomic (16S rDNA gene sequencing) identification showed that the dominant LAB genera in unripe green tomato are Lactiplantibacillus, Leuconostoc, and Weissella. Among nine tested strains, autochthonous Lactiplantibacillus plantarum and allochthonous Weissella paramesenteroides showed tolerance to added solanine (200 ppm) and the best in vitro probiotic potential. The results indicate that the two LAB strains are promising candidates for manufacturing probiotic fermented foods from unripe green tomatoes.

Inducing molecular reactions by selective vibrational excitation of a remote antenna with near-infrared light.

We demonstrate here that selective vibrational excitation of a moiety, remotely attached in relation to the molecular reaction site, might offer a generalized strategy for inducing bond-breaking/bond-forming reactions with exquisite precision. As a proof-of-principle, the electrocyclic ring-expansion of a benzazirine to a ketenimine was induced, in a cryogenic matrix, by near-IR light tuned at the overtone stretching frequency of its OH remote antenna. This accomplishment paves the way for harnessing IR vibrational excitation as a tool to guide a variety of molecular structure manipulations in an exceptional highly-selective manner.

Evidence of IR-Induced Chemistry in a Neat Solid: Tautomerization of Thiotropolone by Thermal, Electronic, and Vibrational Excitations.

Thiotropolone isolated in argon and xenon matrices (as monomers) or in a neat solid (as the crystalline or amorphous state) at low temperature was found to exist only in the thione-enol form. Visible light irradiation (λ ≥ 400 nm) leads to thione-enol → thiol-keto tautomerization in matrices and under neat solid conditions at 15 K. The assignment of the IR spectra of the two thiotropolone tautomers (thione-enol and thiol-keto) was carried out with the support of B3LYP/6-311+G(2d,p) computations. The thiol-keto form generated in situ in a neat solid was found to tautomerize back to the thione-enol upon annealing up to 100 K. Gaussian-4 (G4) computations estimate that such a tautomerization process has an energy barrier of ∼25 kJ mol-1, which is consistent with the observations. Moreover, it was found that narrowband IR irradiation of the thiol-keto form in a neat solid, at the frequency of its CH stretching overtones/combination modes, also induces tautomerization to the thione-enol form. Such a result constitutes an important demonstration of vibrationally induced chemistry under neat solid conditions.

Novel fluorinated ring-fused chlorins as promising PDT agents against melanoma and esophagus cancer.

Investigation of novel 4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-fused chlorins, derived from 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin, as PDT agents against melanoma and esophagus cancer is disclosed. Diol and diester fluorinated ring-fused chlorins, including derivatives with 2-(2-hydroxyethoxy)ethanamino groups at the phenyl rings, were obtained via a two-step methodology, combining SNAr and [8π + 2π] cycloaddition reactions. The short-chain PEG groups at the para-position of the phenyl rings together with the diol moiety at the fused pyrazole ring promote a red-shift of the Soret band, a decrease of the fluorescence quantum yield and an increase of the singlet oxygen formation quantum yield, improving the photophysical characteristics required to act as a photosensitizer. Introduction of these hydrophilic groups also improves the incorporation of the sensitizers by the cells reaching cellular uptake values of nearly 50% of the initial dose. The rational design led to a photosensitizer with impressive IC50 values, 13 and 27 nM against human melanoma and esophageal carcinoma cell lines, respectively.