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Carbon nanotubes (CNTs) are receiving special attention due to their remarkable thermal, electrical, and mechanical properties. The present work reports an innovative synthesis procedure to decorate MWCNTs with silver nanoparticles (Ag-NPs) via pulsed reverse deposition technique using a deep eutectic solvent (DES) based on choline chloride and glycerol as an electrolyte at room temperature, not requiring any previous surface modification of MWCNTs. MWCNTs decorated with Ag-NPs disclose a significant enhancement of their electrochemical performance as demonstrated by the increase of electrode stability and specific capacitance. Electrochemical characterization of the composite material was performed using cyclic voltammetry and charge/discharge curves, achieving a specific capacitance up to 28.50 F. g−1, against 4.70 F. g−1 for the commercial MWCNTs in a three-electrode system. Retention of the specific capacitance up to 99% for the Ag-MWCNTs composites compared with a value of 78% for electrodes modified with commercial MWCNTs. The Ag-MWCNTs composites were characterized through SEM/EDX analysis, ultrahigh-resolution STEM, in which the Z – Contrast image was collected, and Raman analysis to prove the successful attachment of the Ag-NPs to the MWCNTs surface. AFM was performed to evaluate the conductivity of the composites.

The design and synthesis of artificial receptors based on molecular imprinting (MI) technology for the development of a new MIP-based biosensor for detection of the stress biomarker α-amylase in human saliva in point-of-care (PoC) applications is described in this work. The portable electrochemical devices for monitoring α-amylase consists of cost-effective and disposable gold screen-printed electrodes (AuSPEs). To build the electrochemical device, the template biomolecule was firstly immobilized directly over the working area of the gold chip previously activated with a self-assembled monolayer (SAM) of cysteamine (CA). Then, pyrrole (Py) monomer was selected as building block of a polymeric network prepared by CV electropolymerization. After the electropolymerization process, the enzyme was removed from the polymer film in order to build the specific recognition sites for the target enzyme. The MIP biosensor showed a very wide linear concentration range (between 3.0 × 10−4 to 0.60 mg mL−1 in buffer solution and between 3.0 × 10−4 to 3.0 × 10−2 mg mL−1 in human saliva) and low detection levels were achieved (LOD &lt, 3.0 × 10−4 mg mL−1) using square wave voltammetry (SWV) as the electroanalytical technique.

The study of sensing materials to the detection of carbon dioxide (CO2) was achieved using p-nitrophenol (pNPh) as a colorimetric indicator. The sensing material was polymerized (NPLn), functionalized with 3-triethoxysilyl propyl isocyanate (IPTES) which sensitivity was tested in the form of a membrane as is and encapsulated in hollow silica nanoparticles. The sensing membranes were tested in a closed gas system comprising very precise flow controllers to deliver different concentrations of CO2 (vs. N2). The combination of the sensing membranes with multimode optical fibers and a dual-wavelength diode (LED) allows the measurement of the CO2 through the analysis of the induced absorbance changes with a self-referenced ratiometric scheme. The analysis of the sensing materials have shown significant changes in their chemical and physical properties and the results attest these materials with a strong potential for assessing CO2 dynamics in environmental, medical, and industrial applications.

This work reports the role of different dispersants, namely, polyethylene glycol (PEG 200 2%), ethylene glycol 5%, ethanol 2%, dimethyl sulfoxide (DMSO 5%), and polyvinyl alcohol (PVA 5%) in the toxicity profile of several commercial nanomaterials (NM), such as hydrophilic and hydrophobic TiO2, hydrophilic SiO2, SiO2 in aqueous suspension (aq), and ZnO towards the bioluminescent bacterium Aliivibrio fischeri. The majority of NM showed tendency to form agglomerates in the different dispersants. Although some particle agglomeration could be detected, DMSO at 5% was the best dispersant for hydrophobic TiO2 NM while PVA at 5% was the most effective dispersant for the other types of NM. Average size was not the most relevant aspect accounting for their toxicity. A remarkable reduction in average size was followed by a decrease in NM toxicity, as demonstrated for SiO2 aq. in PVA 5%. Contrarily, despite of high particle agglomeration, ZnO NM showed a higher toxicity to bacteria when compared with other tested NM. Independently of the average particle size or surface charge, the dispersant either enhanced the toxicity to bacteria or acted as physical barrier decreasing the NM harmful effect to A. fischeri.

The synthesis of noble metal nanoparticles (i.e., silver and gold) for electrochemical applications has been widely studied using mainly wet synthesis chemical methods or electrochemical deposition methods. In this work, we propose a single-step flash photochemical method for synthesizing noble metal nanoparticles (i.e., silver, gold, and Au:Ag) in solution for electrochemical applications. The method is based on the intense pulsed radiation emitted from a xenon flashlamp, which induce the reduction of metal cations in solution to form metallic nanoparticles. The present method is based on the selective light absorption of the metal precursor salts combined with the decomposition of polyvinylpyrrolidone added to the solution. This approach can be termed as flash light synthesis.

The aim of the present study was to investigate the eco-cytotoxicity of several forms of nanomaterials (NM), such as nano-CuO, nano-TiO2, nano-SiO2 and nano-ZnO, on different aquatic species (Raphidocelis subcapitata, Daphnia magna and Lemna minor) following standard protocols and on human cell lines (Caco-2, SV-80, HepG2 and HaCaT). Predicted no-effect concentrations (PNEC) or hazard concentrations for 5% of the species (HC5) were also estimated based on the compilation of data available in the literature. Most of the NM agglomerated strongly in the selected culture media. For the ecotoxicity assays, nano-CuO and nano-ZnO even in particle agglomeration state were the most toxic NM to the freshwater organisms compared to nano-TiO2 and nano-SiO2. Nano-ZnO was the most toxic NM to R. subcapitata and D. magna, while nano-CuO was found to be very toxic to L. minor. Nano-CuO was very toxic to Caco-2 and HepG2 cells, particularly at the highest tested concentrations, while the other NM showed no toxicity to the different cell lines. The HC5 and PNEC values are still highly protective, due to data limitations. However, the present study provides consistent evidence of the potential risks of both nano-CuO and nano-ZnO against aquatic organisms and also their effects on public health.

The urgent need to reduce the consumption of fossil fuels drives the demand for renewable energy and has been attracting the interest of the scientific community to develop materials with improved energy storage properties. We propose a sustainable route to produce nanoporous carbon materials with a high−surface area from commercial graphite using a dry ball−milling procedure through a systematic study of the effects of dry ball−milling conditions on the properties of the modified carbons. The microstructure and morphology of the dry ball−milled graphite/carbon composites are characterized by BET (Brunauer–Emmett–Teller) analysis, SEM (scanning electron microscopy), ATR−FTIR (attenuated total reflectance–Fourier transform infrared spectroscopy) and Raman spectroscopy. As both the electrode and electrolyte play a significant role in any electrochemical energy storage device, the gravimetric capacitance was measured for ball−milled material/glassy carbon (GC) composite electrodes in contact with a deep eutectic solvent (DES) containing choline chloride and ethylene glycol as hydrogen bond donor (HBD) in a 1:2 molar ratio. Electrochemical stability was tracked by measuring charge/discharge curves. Carbons with different specific surface areas were tested and the relationship between the calculated capacitance and the surface treatment method was established. A five−fold increase in gravimetric capacitance, 25.27 F·g−1 (G40) against 5.45 F·g−1, was found for commercial graphene in contact with DES. Optimal milling time to achieve a higher surface area was also established.

Molecular dynamics simulations of the electrical double layer at electrode–ionic liquid interfaces allow for molecular level interpretation of the interfacial phenomena and properties, such as differential capacitance (C). In this work, we have simulated an ionic liquid – 1-butyl-3-methylimidazolium hexafluorophosphate – at three gold surfaces, namely: Au(100), Au(110), and Au(111) surfaces. Atomic corrugation of the gold surface leads to higher C values due to the rapprochement of the surface and electrolyte charge planes. Likewise, by accounting for the shift of surface charge plane position towards the electrolyte also results in higher C values. The presented insight shows that a simple correction to the simulation data improves the agreement with the experimental data.

Here we report the rational development of a carbon dot (CDs)-based fluorescent pH nanosensor by employing an active surface preservation strategy. More specifically, citric acid, urea and fluorescein were subjected to a one-pot hydrothermal treatment, which preserved fluorescein-like structures on the surface of the CDs. The obtained CDs showed pH-sensitive green emission, which can be used to determine pH variations from 3.7 to 12.1 by fluorescence enhancement. Moreover, the obtained nanoparticles showed excellent selectivity toward pH, fluorescence reversibility in different pH values, photostability, while being compatible with human cell lines (even at high concentrations). Furthermore, their performance as pH sensors was comparable with reference pH determination procedures. Thus, an active surface preservation strategy was successfully employed to develop fluorescence pH nanosensors in a rational manner and without post-synthesis functionalization strategies, which show potential for future use in pH determination.

In this work, we describe an innovative methodology based on combined surface plasmon resonance (SPR) and electrochemical responses (eSPR) in the same immunoassay for screening CA 153 cancer biomarker with high sensitivity (and selectivity), in a very simple, label-free, accurate, and fully automated manner. Detection was achieved by performing two simple steps. In the first step, direct SPR was used to monitor CA 153 interaction with surface immobilized antibody. Two linear response ranges were obtained and the detection limit achieved is poor (LOD of 21 U mL1). However, in the second detection step, electrochemical measurements at the SPR gold surface were performed to measure the decrease of redox probe peak current upon antigenantibody interaction, providing a suitable amplification strategy to lower detection levels of CA 153 (LOD of 0.0998 U mL1), without the need of additional complex and/or expensive amplification steps to enhance the sensitivity. Moreover, selectivity studies were performed against other common cancer biomarkers and the results showed that the eSPR immunosensor is selective for the CA 153 protein. Finally, the clinical applicability of the developed eSPR biosensing methodology was successfully applied to detect CA 153 in human serum samples at clinically relevant levels due to the high sensitivity of electrochemical readout. The same concept may be further extended to other proteins of interest., This research had the financial support of FCT (Fundaca̧õ para a Ciencia e Tecnologia) and co ̂ financed by the European Union (FEDER funds) under the Partnership Agreement PT2020, Research Grants Pest-C/QUI/UIDB/00081/2020 (CIQUP) and NORTE-01-0247-FEDER-017834 (project RamSERS). J.A.R. (ref SFRH/BPD/105395/2014) and C.M.P. (ref SFRH/BSAB/150320/2019) acknowledge FCT under the QREN − POPH − Advanced Training, subsidized by European Union and national MEC funds. We thank BioMark/ISEP researchers Felismina Moreira and Joana Guerreiro for all the support to perform the ellipsometry measurements, info:eu-repo/semantics/publishedVersion

The aim of this work is to quantify the evolution of the various noncovalent interparticle interactions in the binary mixtures of imidazolium-based ionic liquids (ILs) with perfluorinated anions, hexafluorophosphate (C4mimPF6), bis(fluorosulfonyl)imide (C4mimNTf2), and tris(pentafluoroethyl)trifluorophosphate (C4mimFAP), and deep eutectic solvents (DESs), composed by choline chloride (ChCl), and ethylene- (EG) and propylene glycol (PG) molecules. For this purpose, by using combined molecular dynamics and density functional theory methodology, we analyze the most important intermolecular, interionic, and ion-molecular hydrogen bonding interactions in ILs and DESs. We found that the addition of FAP− to a mixture enhances the nonpolar domain segregations and weakens the hydrogen-bond network. It was confirmed that H2-site is the most prone to cation–anion interactions, whereas in the binary mixtures of ILs two anions compete for the most acidic hydrogen of imidazolium ring. Nonetheless, most of the hydrogen bonds in the studied IL mixtures are rather weak and can be referred to as “hydrogen-bond-like interactions.” The FAP-anion forms notably less hydrogen-bond-like interactions and only in neat IL or in FAP-rich regions of IL mixtures, stabilizing the ion pair mostly electrostatically. For the DES mixtures, it was established that ethaline-2 (molar ratio of ChCl and EG is 1:2) does not contain any real hydrogen bonds. Propeline (DES-based on ChCl and PG), however, presents weak hydrogen-bond formation between cation and anion and medium hydrogen-bond formation between anion and PG molecule.

Metal and alloys electrodeposition from aqueous electrolytes is restricted due to the narrow electrochemical window and hydrogen evolution. To overcome these disadvantages, over the past years, ionic liquids (ILs) and deep eutectic solvents (DES) based on choline chloride have been successfully applied for the electrodeposition of different metals.Tin (Sn) layers applied to automotive or decorative plating are thought of as ecological alternatives to exchange lead and nickel/chromium coatings. Over the past few years, the attention drawn by metallic alloys and composites, namely Sn alloys (nickel, indium, copper, zinc…) and Sn-carbon materials composites, has increased due to the possibility of applying these materials as anodes for lithium-ion batteries.This review will highlight the leading research regarding the electrodeposition of Sn and several alloys and carbon composites, emphasizing the morphological changes of the alloy combinations using DESs as electrolytes.

Mesoporous sorbent composites, evolving from previous work on microporous composites of polyanionic polysaccharides were developed with the purpose of increasing the sorptive features of the materials. Using the widely successful classical surfactant micelle approach, it was observed, in this particular case, that the composites remained essentially microporous. The alternative consisted on the application of deep eutectic solvents (DES). The most common DES (choline chloride + neutral hydrogen bond donor), were tested because of their advantages over other possibilities such as imidazolium-based ionic liquids: lower cost, easy in-house preparation, safe constituents and water stability and solubility. Possible mechanisms underlying the observed mesoporosity were discussed. The surface area ranged between 76 and 267 m2/g and the average pore size was in the range 3–5 nm. DES had not a negative effect on synthesis yields and, in the case of fucoidan, composites bearing a higher content of the biopolymer were produced. As a consequence and in line with the initial expectations these new composites revealed highly enhanced Pb (II) sorptive features comparatively to their microporous predecessors: chondroitin sulfate composites - up to a 5 fold capacity enhancement; fucoidan composites- up to a 3.5 fold capacity enhancement. The highest capacity was observed for the fucoidan composite prepared with choline chloride-ethyleneglycol DES, 79 mg Pb (II)/g, which is slightly above the highest value (77 mg Pb (II)/g) found in the literature for Pb (II) sorbents based on polysaccharides, sol-gels or their composites.

International audience; The air–ionic liquid interface for a series of ionic liquids involving imidazolium cations [Cnmim] with different alkyl chain lengths (n = 2, 4, 6, 8, 10, and 12) and the same [NTf2] imide anion has been studied by polarization-resolved second harmonic generation (SHG). An increase as a function of the alkyl chain length of the orientational parameter reveals the increasing ordering of the air–pure ionic liquid interfaces although it is not possible to disentangle the change in mean tilt angle from a change in the tilt angle probability distribution width. Besides, the study of the air–mixed ([C12mim])x([C2mim])1–x[NTf2] ionic liquid interface clearly demonstrates the interfacial nonideality of the mixed ionic liquids. The long alkyl chain cation perturbs the interface as seen from the orientational parameter and displaces the short alkyl chain one for bulk mixture contents as low as 10%. At higher long alkyl chain cation bulk mixture contents, the interface behaves close to a pure long alkyl chain ionic liquid.

The impact of fullerene side chain functionalization with thiophene and carbazole groups on the device properties of bulk-heterojunction polymer:fullerene solar cells is discussed through a systematic investigation of material blends consisting of the conjugated polymer poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3&rsquo, &rsquo, di(2-octyldodecyl)-2,2&rsquo, 5&rsquo, 2&rsquo, quaterthiophen-5,5&rsquo, diyl)] (PffBT4T-2OD) as donor and C60 or C70 fulleropyrrolidines as acceptors. The photovoltaic performance clearly depended on the molecular structure of the fulleropyrrolidine substituents although no direct correlation with the surface morphology of the photoactive layer, as determined by atomic force microscopy, could be established. Although some fulleropyrrolidines possess favorable lowest unoccupied molecular orbital levels, when compared to the standard PC71BM, they originated OPV cells with inferior efficiencies than PC71BM-based reference cells. Fulleropyrrolidines based on C60 produced, in general, better devices than those based on C70, and we attribute this observation to the detrimental effect of the structural and energetic disorder that is present in the regioisomer mixtures of C70-based fullerenes, but absent in the C60-based fullerenes. These results provide new additional knowledge on the effect of the fullerene functionalization on the efficiency of organic solar cells.

l -tyrosine controlled release systems, based on imprinted polymers radically polymerized in modified organic solvents (dimethyl sulfoxide and methanol) were developed. A set of copolymers synthesized with different functional monomers and the crosslinker ethylene glycol dimethylacrylate were evaluated regarding both the imprinting and controlled release features. Those prepared in modified-DMSO were mesoporous (surface area ranging 370–690 m2/g) but not the ones prepared in modified methanol with the exception of the imprinted polymer prepared with the monomer vinylbenzoic acid (209 m2/g). The swelling degree ranged 32 to 64% and appeared to be mostly dependent on the functional group employed in the synthesis of the polymers. When tested in dynamic mode a clear imprinting effect has been observed in some of the imprinted polymers. However, selectivity for l -Tyr against similar compounds could not be found in these conditions. Selectivity could be observed when carrying out the isothermal analysis, with selectivity factors up to 2.7. A few polymers exhibited also other remarkable features such as high l -Tyr load capacity (up to 253 mg l -Tyr/g) and large binding strength (up to 55 Lmmg(1-m))/g). Therefore, imprinted polymers capable of a selective sorption of l -Tyr upon equilibration, containing stronger binding sites for l -Tyr, appeared promising vehicles for its controlled release. In fact, the release assays with l -Tyr impregnation by adsorption, showed profiles corresponding to controlled release systems, with high yield (40–50%) and continuous release (up to at least 7 h). In addition, release mechanisms recommended for controlled release systems were deduced from kinetic data fitting to the Korsmeyer and Order 0 models.

Artificial receptors that mimic their natural biological counterparts have several advantages, such as lower production costs and increased shelf-life stability/versatility, while overcoming the ethical issues related to raising antibodies in animals. In this work, the proposed tailor-made molecularly imprinted polymer (MIP)-allergen receptors aimed at substituting or even transcending the performance of biological antibodies. For this purpose, a MIP was proposed as an artificial antibody for the recognition of hazelnut Cor a 14-allergen. The target protein was grafted onto the conducting polypyrrole receptor film using gold screen-printed electrodes (Au-SPE). The electrochemical assessment presented a linear response for the dynamic range of 100 fg mL−1-1 μg mL−1 and a LOD of 24.5 fg mL−1, as determined by square wave voltammetry from the calibration curves prepared with standards diluted in phosphate buffer. Surface plasmon resonance (SPR) was used as a secondary transducer to evaluate the performance of the Cor a 14-MIP sensor, enabling a linear dynamic range of 100 fg mL−1- 0.1 μg mL−1 and a LOD of 18.1 fg mL−1. The selectivity of the tailored-made Cor a 14-MIP was tested against potentially cross-reactive plant/animal species based on the rebinding affinity (Freundlich isotherm-KF) of homologues/similar proteins, being further compared with custom-made polyclonal anti-Cor a 14 IgG immunosensor. Results evidenced that the MIP mimics the biorecognition of biological antibodies, presenting higher selectivity (only minor cross-reactivity towards walnut and Brazil nut 2S albumins) than the Cor a 14/anti-Cor a 14 IgG immunosensor. The application of electrochemical Cor a 14-MIP sensor to model mixtures of hazelnut in pasta enabled quantifying hazelnut down to 1 mg kg−1 (corresponding to 0.16 mg kg−1 of hazelnut protein in the matrix). To the best of our knowledge, Cor a 14-MIP is the first sensor based on an artificial/synthetic biorecognition platform for the specific detection of hazelnut allergens, while presenting high-performance parameters with demonstrated application in food safety management.

Two immunosensors were advanced to target hazelnut Cor a 14 based on electrochemical and optical transduction. Both approaches were developed with two types of custom-made antibodies, namely anti-Cor a 14 IgG (rabbit) and anti-Cor a 14 IgY (hen’s egg) targeting the Cor a 14 allergen. Antibody immobilisation was performed via EDC/NHS onto disposable screen-printed electrodes. The detection limit (LOD) of the electrochemical immunoassay for Cor a 14 was 5-times lower than the optical, being down to 0.05 fg mL−1 with a dynamic range of 0.1 fg mL−1 to 0.01 ng mL−1. Antibody selectivity was verified against non-target 2S albumins (potential cross-reactive plant species). Anti-Cor a 14 IgY exhibited the best specificity, presenting minor cross-reactivity with peanut/walnut. Preliminary results of the application of anti-Cor a 14 IgY electrochemical immunosensor to incurred foods established a LOD of 1 mg kg−1 of hazelnut in wheat (0.16 mg kg−1 hazelnut protein).

Mixing of ionic liquids provides new opportunities for their tuning, enabling the applications of ionic liquid mixtures to expand. At the same time, the genesis of the fundamental properties of ionic liquid mixtures is still poorly understood. In this study we carried out a molecular dynamics simulation of binary mixtures of 1-buthyl-3-methylimidazolium hexafluorophosphate, 1-buthyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, and 1-buthyl-3-methylimidazolium tris(perfluoroethyl)trifluorophosphate ([C4mim][PF6] + [C4mim][NTf2], [C4mim][PF6] + [C4mim][FAP], [C4mim][FAP] + [C4mim][NTf2]) in a wide concentration range at 303.15 K and complemented it with quantum mechanical calculations. Three pure ionic liquids underwent the same kind of analysis for comparison purposes. We found that the addition of the [FAP]--anion to a mixture enhances the segregation of non-polar domains and weakens the hydrogen-bond network. The H-bonds in the studied mixtures are rather weak, as follows from QTAIM analysis, with the rarest occurrence for the [FAP]--anion. The competition of two anions in the mixtures for the most acidic hydrogen of the 1-butyl-3-methylimidazolium cation is reported. In most of the cases, the smaller anion ([PF6]- or [NTf2]-) with stronger charge concentration displaces the bigger one ([NTf2]- or [FAP]-) from the preferred coordination site. The existing nano-segregation in some mixtures notably slows down ion diffusion. Our results show that the differences in anion size, shape and nature are the main reasons for nano-segregation and the non-ideal behavior of ionic liquid mixtures.

An alternative route is proposed for direct electrodeposition of TiO2 films. The electrochemical behaviour of Ti(IV) species in the deep eutectic solvent formed between choline chloride (ChCl) and ethylene glycol (EG) was studied by chronoamperometry and cyclic voltammetry. It was discussed that during the cathodic scan soluble subvalent TiClχ species were formed using the eutectic system 1ChCl:2EG. Using ethylenediamine or LiF as additives it was possible to obtain a titanium dioxide thin film in the orthorhombic variant named brookite. Chronoamperometric investigations revealed a nucleation mechanism involving the simultaneous presence of 2D instantaneous nucleation process including lattice incorporation and a 3D diffusion-limited nucleation and growth process.

Evolution from fossil fuel energy to renewable energy sources and technologies is in the spotlight towards an accelerated energy transition process. One of the challenges of the intermittent renewable energy production is related to the existence of an appropriate energy storage technology in order to effectively use the renewable energy generated. Electrochemical energy storage devices rely on the key property of the electrical double layer integral capacitance. The use of mixed ionic liquids can be an effective strategy to increase the performance of electric double layer capacitors. Here, the studies on the interfacial behaviour of ionic liquids mixtures containing a common ion for a model mercury/ionic liquid interface are reported. Enhancement of the differential capacitance, nearly 3 times higher compared to ILs in the pure state, was achieved by an appropriate combination of ion size both in cation and the anion and asymmetry. The results are interpreted as a consequence of surface voids occupation and by the accumulation of more counter ions and displacement larger anion by the smaller anion in the mixture.

The electrochemical behaviour of the alkaloids berberine and palmatine at the polarized water/1,2-dichloroethane interface is studied by first time. The interface is supported on the micropores of a PET (polyethylene terephthalate) membrane by using an electrochemical cell employed in previous works. Chronoamperometry and square wave voltammetry are applied in order to determine the concentrations of the ions berberine and palmatine in water. Thus, calibration curves are built with both techniques and the resulting detection limits are discussed and compared. In addition, the chronoamperograms and square wave voltammograms recorded are used to estimate the standard transfer potentials and the aqueous diffusion coefficients for the two cations. The diffusion coefficient values are further compared with results of molecular dynamic simulations, finding a good correlation between experimental and simulated data.

In this work we developed a new force field model (FFM) for propylene glycol (PG) based on the OPLS all-atom potential. The OPLS potential was refined using quantum chemical calculations, taking into account the densities and self-diffusion coefficients. The validation of this new FFM was carried out based on a wide range of physicochemical properties, such as density, enthalpy of vaporization, self-diffusion coefficients, isothermal compressibility, surface tension, and shear viscosity. The molecular dynamics (MD) simulations were performed over a large range of temperatures (293.15-373.15 K). The comparison with other force field models, such as OPLS, CHARMM27, and GAFF, revealed a large improvement of the results, allowing a better agreement with experimental data. Specific structural properties (radial distribution functions, hydrogen bonding and spatial distribution functions) were then analyzed in order to support the adequacy of the proposed FFM. Pure propylene glycol forms a continuous phase, displaying no microstructures. It is shown that the developed FFM gives rise to suitable results not only for pure propylene glycol but also for mixtures by testing its behavior for a 50 mol % aqueous propylene glycol solution. Furthermore, it is demonstrated that the addition of water to the PG phase produces a homogeneous solution and that the hydration interactions prevail over the propylene glycol self-association interactions.

Co–Sn alloy films were electrodeposited from choline chloride (ChCl)–ethylene glycol (EG) and choline chloride (ChCl)–urea (U) eutectic mixtures. The deposition of Co–Sn alloy on a copper electrode was studied by cyclic voltammetry, which demonstrates that the coelectrodeposition was achieved. For comparison of properties, Co–Sn alloys were deposited from electrolytes with different Co/Sn ratios. The X-ray diffraction patterns (XRD) showed that the phase structure was affected by the Co/Sn ratio; nevertheless, Co3Sn2 was always the predominant phase. Traces of metallic cobalt were also detected. The nature of the electrolyte used and the metallic composition affected the morphologies of the deposits and their corrosion resistance. The best corrosion resistant coating, with a corrosion potential of −617 mV, was composed by 44.4 wt % of Co and 55.6% of Sn, and it was obtained from the ChCl–EG electrolyte. The magnetic properties of the analyzed samples did not present an evident relationship with the metall...

The paper presents experimental results regarding the electrodeposition and characterization of cobalt and cobalt composites with carbon nanotubes from a choline-chloride-based deep eutectic solvent. Dispersion stability of multi-walled carbon nanotubes (MWCNTs) was excellent in the eutectic solvent used. According to Raman and XRD analysis, the carbon nanotubes were successfully inserted into the metallic matrix. Furthermore, XRD results suggested that the incorporation of CNTs on the deposit promoted a preferred orientation of the Co crystallites on (220) plane. The Co and Co-composites coatings obtained onto a copper substrate are adherent and uniform. Pure Co deposit was formed by sharp edge grains, Co-composites appeared to be less compact and formed by relatively spherical particles connected by MWCNTS. Furthermore, it was found that the presence of MWCNTs contributed to decreasing the deposit's roughness. From corrosion tests, Co-composite films exhibit a comparable or slightly better corrosion performance as compared to pure Co films.

The effect of the addition of a group of organic additives on the electrodeposition behavior of zinc was investigated in choline chloride:ethylene glycol (ChCl:EG) eutectic mixture in the molar ratio of 1:2. Cyclic voltammograms recorded on steel electrode showed a cathodic peak is only observed after reversing of the scan. Chronoamperometric measurements indicated that the deposition of zinc occurs through 3D progressive nucleation mechanism. The morphology of the zinc deposits and was evident that additives influence the deposits morphologies. X-ray diffraction confirmed the presence of crystalline zinc and reveal the grain refinement effect obtained by using the additives selected where the smallest grain size of 31.7 nm was obtained in the presence of Dimethyl sulfoxide (DMSO). Moreover the XRD data showed that the addition of additives modified the preferential growth plane. The corrosion resistance properties of the electrodeposited Zn coatings were evaluated in 3% NaCl aqueous solution using potentiodynamic polarization. The results showed that the zinc film deposited with DMSO was the best corrosion resistant coating.

Targeting mitochondrial oxidative stress is an effective therapeutic strategy. In this context, a rational design of mitochondriotropic antioxidants (compounds 22-27) based on a dietary antioxidant (caffeic acid) was performed. Jointly named as AntiOxCINs, these molecules take advantage of the known ability of the triphenylphosphonium cation to target active molecules to mitochondria. The study was guided by structure-activity-toxicity-property relationships, and we demonstrate in this work that the novel AntiOxCINs act as mitochondriotropic antioxidants. In general, AntiOxCINs derivatives prevented lipid peroxidation and acted as inhibitors of the mitochondrial permeability transition pore. AntiOxCINs toxicity profile was found to be dependent on the structural modifications performed on the dietary antioxidant. On the basis of mitochondrial and cytotoxicity/antioxidant cellular data, compound 25 emerged as a potential candidate for the development of a drug candidate with therapeutic application in mitochondrial oxidative stress-related diseases. Compound 25 increased GSH intracellular levels and showed no toxicity on mitochondrial morphology and function.

Oxidative stress and mitochondrial dysfunction have been associated with metabolic and age-related diseases. Thus, the prevention of mitochondrial oxidative damage is nowadays a recognized pharmacological strategy to delay disease progression. Epidemiological studies suggested an association between the consumption of polyphenol-rich diet and the prevention of different pathologies, including diseases with a mitochondrial etiology. The development of mitochondrial-targeted antioxidants based on dietary antioxidants may decrease mitochondrial oxidative damage. Herein, we report the design and synthesis of two new mitochondriotropic antioxidants based on hydroxybenzoic acids (AntiOxBENs). The results obtained showed that the novel antioxidants are accumulated inside rat liver mitochondria driven by the organelle transmembrane electric potential and prevented lipid peroxidation, exhibiting low toxicity. Some of the observed effects on mitochondrial bioenergetics resulted from an increase of proton leakage through the mitochondrial inner membrane. The new derivatives present a higher lipophilicity than the parent compounds (protocatechuic and gallic acids) and similar antioxidant and iron chelating properties. AntiOxBENs are valid mitochondriotropic antioxidant prototypes, which can be optimized and used in a next future as drug candidates to prevent or slow mitochondrial oxidative stress associated to several pathologies.

Fucoidan, a sulfated polysaccharide extracted from brown seaweed, was, in the form of a silica composite, studied as a prospective cation imprinting matrix. The preparation of such composites in the presence of cations with a strong interaction with the biopolymer chains was expected to direct them towards arrangements, optimized for the sorption of those cations. As expected, the presence of Cu(II), a weakly fucoidan-binding cation, in the synthesis of the composites did not result in the production of significantly stronger Cu(II)-oriented binding arrangements, and therefore the imprinting was not successful. However, with Pb(II), with much stronger affinity for fucoidan, the materials obtained exhibited stronger (22%) binding as compared to the non-imprinted counterparts, and increased selectivity (1.4–1.6 fold) against Cd(II). Although these imprinting features were close to those observed previously with other sulfated polysaccharides, the fucoidan-based Pb(II) imprints developed here presented superior sorption properties, namely a higher capacity and higher binding strength for Pb(II). These features, demonstrated by the material developed here, may easily be put to work in different areas where Pb(II) sensing, determination, separation or remediation is of the utmost importance.

Novel C60 and C70 N-methyl-fulleropyrrolidine derivatives, containing both electron withdrawing and electron donating substituent groups, were synthesized by the well-known Prato reaction. The corresponding highest occupied molecular orbital (HOMO)/lowest unoccupied molecular orbital (LUMO) energy levels were determined by cyclic voltammetry, from the onset oxidation and reduction potentials, respectively. Some of the novel fullerenes have higher LUMO levels than the standards PC61BM and PC71BM. When tested in PffBT4T-2OD based polymer solar cells, with the standard architecture ITO/PEDOT:PSS/Active-Layer/Ca/Al, these fullerenes do not bring about any efficiency improvements compared to the standard PC71BM system, however they show how the electronic nature of the different substituents strongly affects the efficiency of the corresponding organic photovoltaic (OPV) devices. The functionalization of C70 yields a mixture of regioisomers and density functional theory (DFT) calculations show that these have systematically different electronic properties. This electronic inhomogeneity is likely responsible for the lower performance observed in devices containing C70 derivatives. These results help to understand how new fullerene acceptors can affect the performance of OPV devices., This work was partially funded by National Funds through FCT—Portuguese Foundation for Science and Technology, Reference UID/CTM/50025/2019 and FEDER funds through the COMPETE 2020 Programme under the project number POCI-01-0145-FEDER-007688 (i3N). Thanks are also due to FCT/MEC for the financial support to QOPNA (FCT UID/QUI/00062/2019), CICECO-Aveiro Institute of Materials (FCT UID/CTM/50011/2019), CQE (FCT UID/QUI/0100/2019) and CIQUP (FCT UID/QUI/UI0081/2019) research units, through national funds and where applicable co-financed by the FEDER, within the PT2020 Partnership Agreement. This work was also financially supported by project UID/EQU/00511/2019—Laboratory for Process Engineering, Environment, Biotechnology and Energy—LEPABE funded by national funds through FCT/MCTES (PIDDAC). H.G. thanks Fundação para a Ciência e a Tecnologia (FCT) for his PhD scholarship (SFRH/BD/103009/2014). The research contracts of F.F. (REF. -168-89-ARH/2018) is funded by national funds (OE), through FCT—Fundação para a Ciência e Tecnologia, I.P., in the scope of the framework contract foreseen in the numbers 4, 5 and 6 of the article 23, of the Decree-Law 57/2016, of August 29, changed by Law 57/2017, of July 19. M.M.-F. acknowledges also support from FCT under the project IF/00894/2015.

Considering the high incidence level and mortality rate of ovarian cancer, particularly among the European female population, the carbohydrate antigen 125 (CA-125) was selected as the protein target for this study for the development of a MIP-based biosensor. This work presents the development of molecular imprinting polymers (MIPs) on gold electrode surface for CA-125 biomarker recognition. The preparation of the CA-125 imprinting was obtained by electropolymerization of pyrrole (Py) monomer in a gold electrode using cyclic voltammetry (CV) in order to obtain highly selective materials with great molecular recognition capability. The quantification of CA-125 biomarker was made through the comparison of two methods: electrochemical (square wave voltammetry -SWV) and optical transduction (surface plasmon resonance -SPR). SWV has been widely used in biological molecules analysis since it is a fast and sensitive technique. In turn, SPR is a non-destructive optical technique that provides high-quality analytical data of CA-125 biomarker interactions with MIP. Several analytical parameters, such as sensitivity, linear response interval, and detection limit were determined to proceed to the performance evaluation of the electrochemical and optical transduction used in the development of the CA-125 biosensor. The biosensor based in the electrochemical transduction was the one that presented the best analytical parameters, yielding a good selectivity and a detection limit (LOD) of 0.01 U/mL, providing a linear concentration range between 0.01 and 500 U/mL. This electrochemical biosensor was selected for the study and it was successfully applied in the CA-125 analysis in artificial serum samples with recovery rates ranging from 91 to 105% with an average relative error of 5.8%.

An immobilization scheme, via glycidyloxypropyl-trimethoxysilane sol-gel crosslinking, of chondroitin sulfate (CS) or fucoidan (Fd), inspired by the biological silicate bridge found in CS, is presented here. It revealed to constitute a simple and effective way of producing biopolymer-silicate composites without compromising the carboxylate- and sulfate- groups of the biopolymers, those which play a determinant role in the binding to metal cations. In the case of the Fd composite, the immobilization process resulted in the ∼4-fold enhancement of the negatively charged sorption sites, probably due to unfolding effects induced by the synthesis conditions. Textural analysis of the composites showed a microporous, low surface area (6–12 m2/g), microstructure which did not prevent the observation of relevant sorption features for metal cations, especially for Pb(II) and Cd(II). Rate constants (1–14 g/mg min−1) and affinity constants (79–370 L/mg) in the same order of magnitude of chitosan-based sorbents were determined, whereas capacities (2–24 mg/g) were smaller than the generality of those same sorbents. Globally, the sorption of metal cations by the Fd composite was superior to that by the CS composite. Furthermore, high stability of the sorbents and acceptable reproducibility of the synthesis was observed. Overall, the developed scheme of immobilization of CS and Fd appears capable of providing an effective way for integrating these biopolymers into metal cation-related applications such as biosorption, sensing or separation.

Electrified double-layer (EDL) of ionic liquids electrode interfaces have been attracting considerable interest both from the fundamental and applied points of view. So far from the large set of ionic liquids synthetized only a very limited number has been electrochemically studied. As a consequence, the effect of complex shape and chemical properties of the ions and surface morphology on the structure and mechanism of formation of EDL is far from being understood. Binary mixtures of ionic liquids with a common cation (1-ethyl-3-methylimidazolium) paired with two different anions (bis(trifuoromethylsulfonyl)imide, [ T f 2 N ] − and tris(pentafluoroethyl)trifluorophosphate, [ FAP ] − ) were prepared and their molecular mixing behavior was followed through the changes in their vibrational structure by Fourier transform infrared (ATR-FT-IR) spectroscopy. The interface at Hg and each of the binary mixture was followed by electrochemical impedance spectroscopy and drop time measurements. Differential capacitance and charge-potential curves were obtained and compared with those corresponding to the pure liquids. The data is interpreted as suggesting the coexistence at the interface of a mixture of two limiting structures each of which containing essentially one of the anions and sharing the common cation in a co-network.

A strategy based on water-in-oil emulsion for the dispersion of a sol-gel mixture into small droplets was employed with the view of the production of naproxen-imprinted micro- and nanospheres. The procedure, aiming at a surface imprinting process, comprised the synthesis of a naproxen-derived surfactant. The imprinting process occurred at the interface of the emulsions or microemulsions, by the migration of the NAP-surfactant head into the sol-gel drops to leave surficial imprints due mainly to ion-pair interaction with a cationic group contained within the growing sol-gel network. The surface-imprinted microspheric particles exhibited a log-normal size distribution with geometric mean diameter of 3.1μm. A mesoporous texture was found from measurements of the specific surface area (206m(2)/g) and pore diameter (Dp 2nm). Evaluation of the microspheres as packed HPLC stationary phases resulted in the determination of the selectivity factor against ibuprofen (α=2.1), demonstrating the successful imprinting. Chromatographic efficiency, evaluated by the number of theoretical plates (222platescm(-3)), emerged as an outstanding feature among the set of all relatable formats produced before, an advantage intrinsic to the location of the imprinted sites on the surface. The material presented a capacity of 3.2μmolg(-1). Additionally, exploratory work conducted on their nanoscale counterparts resulted in the production of nanospheres in the size order of 10nm providing good indications of a successful imprinting process.

In the past few years a large effort is being made aiming at the development of fast and reliable tests for cancer biomarkers. Protein imprinted sensors can be a fast and reliable strategy to develop tailor made sensors for a large number of relevant molecules. This work aims to produce, optimize and use in biological samples a biosensor for microseminoprotein-beta (MSMB). Caffeic acid (CAF) electropolimerization was performed in the presence of microseminoprotein-beta (MSMB) creating target protein specific cavities on the surface of a screen-printed carbon. Dopamine was introduced as charged monomer labelling the binding site and was allowed to self-organize around the protein. The subsequent electropolimerization was made by applying a constant potential of +2.0 V, for 30 s, on a carbon screen-printed electrode, immersed in a solution of protein and CAF prepared in phosphate buffer. The sensor with charged monomers showed a more sensitive response, with an average slope of −7.59 μA/decade, linear concentration range of 0.5–100 ng/mL and a detection limit of 0.12 ng/mL. The corresponding non-imprinted sensor displayed an inconsistent response over the range of the calibration curve. The biosensor was successfully applied to the analysis of MSMB in serum and urine samples.

In this work, we combined electrochemical techniques with SPR (eSPR) for the label-free detection of cancer biomarker miRNA-145. Detection was performed in a simple two-step assay. In the first step, the gold sensor surface, previously functionalized with a self-assembled monolayer (SAM) of thiolated RNA probes is incubated with the sample containing the target RNA biomarker. In this step, hybridization of RNA fragments with complementary immobilized probes was monitored in real-time by SPR. In the second step, eSPR measurements were performed to improve the sensitivity of the hybridization assay. Potential-induced deposition of a redox probe at the sensor surface resulted in enhanced SPR response promoted by the electrochemical process, thereby allowing the detection of miRNA-145 at femtomolar level (LOD = 0.56 fM), without sample derivatization or post-hybridization treatment for signal amplification. Good linearity was achieved (R2 = 0.984) over the concentration range from 1.0 fM and 10 nM. Furthermore, the developed eSPR biosensor showed high selectivity towards single-base and two-base mismatch sequences and detection of target miRNA-145 in synthetic human serum was successful achieved., This research had the financial support of FCT (Fundação para a Ciência e Tecnologia) and co-financed by the European Union (FEDER funds) under the Partnership Agreement PT2020, Research Grants UIDB/00081/2020 (CIQUP), NORTE-2020 under the project RamSERS (grant NORTE-01-0247-FEDER-017834). J.A. Ribeiro (ref. SFRH/BPD/105395/2014) acknowledges FCT under the QREN – POPH – Advanced Training, subsidized by European Union and national MEC funds.

Nano carbons, such as graphene and carbon nanotubes, show very interesting electrochemical properties and are becoming a focus of interest in many areas, including electrodeposition of carbon&ndash, metal composites for battery application. The aim of this study was to incorporate carbon materials (namely oxidized multi-walled carbon nanotubes (ox-MWCNT), pristine multi-walled carbon nanotubes (P-MWCNT), and reduced graphene oxide (rGO)) into a metallic tin matrix. Formation of the carbon&ndash, tin composite materials was achieved by electrodeposition from a choline chloride-based ionic solvent. The different structures and treatments of the carbon materials will create metallic composites with different characteristics. The electrochemical characterization of Sn and Sn composites was performed using chronoamperometry, potentiometry, electrochemical impedance, and cyclic voltammetry. The initial growth stages of Sn and Sn composites were characterized by a glassy-carbon (GC) electrode surface. Nucleation studies were carried out, and the effect of the carbon materials was characterized using the Scharifker and Hills (SH) and Scharifker and Mostany (SM) models. Through a non-linear fitting method, it was shown that the nucleation of Sn and Sn composites on a GC surface occurred through a 3D instantaneous process with growth controlled by diffusion. According to Raman and XRD analysis, carbon materials were successfully incorporated at the Sn matrix. AFM and SEM images showed that the carbon incorporation influences the coverage of the surface as well as the size and shape of the agglomerate. From the analysis of the corrosion tests, it is possible to say that Sn-composite films exhibit a comparable or slightly better corrosion performance as compared to pure Sn films.

Ion transfer electrochemistry is a powerful tool for the study of ionic species in solution. In this paper, square wave voltammetry and chronoamperometry are applied for the quantification and characterization of denatonium ion (N-benzyl-2-(2,6-dimethylphenylamino)-N,N-diethyl-2-oxoethanaminium) in water, an important additive present in commercial products. The method presented is based on the monitoring of the transfer of the cation across a microporous membrane separating an aqueous solution and an organic solution of 1,2-dichloroethane. Calibration curves are built with both techniques and the resulting detection limits and linear ranges of response are discussed. Furthermore, the different performance characteristics of the two techniques are exploited to extract the values of the aqueous diffusion coefficient of the ion denatonium and its standard transfer potential from water to 1,2-dichloroethane. The last parameter is of great importance for the evaluation of the ion lipophilicity, that plays a role in its distribution in living organisms and its impact on biological media.

In this work, we report for the first time the accumulation activity by energized rat heart mitochondria and the ionic transfer process at a liquid–liquid interface of a novel mitochondria-targeted antioxidant, named as AntiOxCIN4, which is structurally based on a hydroxycinnamic acid. Lipophilicity studies conducted at the water/1,6-dichlorohexane (DCH) interface allowed the building up of an ionic partition diagram of AntiOxCIN4 in accordance with the electrochemical data obtained. The partition coefficients of both positively charged (−2.3) and zwitterionic (0.2) forms of the antioxidant were determined. This study contributed to gaining an insight about the ability of the synthesized antioxidants to cross biomembrane barriers by using an interface between two immiscible electrolyte solutions (ITIES) as a model system.

Naproxen-imprinted xerogels in the microspherical and nanospherical forms were prepared by W/O emulsion and microemulsion, respectively. The work evolved from a sol–gel mixture previously reported for bulk synthesis. It was relatively simple to convert the original sol–gel mixture to one amenable to emulsion technique. The microspheres thus produced presented mean diameter of 3.7 μm, surface area ranging 220–340 m2/g, selectivity factor 4.3 (against ibuprofen) and imprinting factor 61. A superior capacity (9.4 μmol/g) was found, when comparing with imprints obtained from similar pre-gelification mixtures. However, slow mass transfer kinetics was deduced from column efficiency results. Concerning the nanospherical format, which constituted the first example of the production of molecularly imprinted xerogels in that format by microemulsion technique, adapting the sol–gel mixture was troublesome. In the end, nanoparticles with diameter in the order of 10 nm were finally obtained, exhibiting good indications of an efficient molecular imprinting process. Future refinements are necessary to solve serious aggregation issues, before moving to more accurate characterization of the binding characteristics or to real applications of the nanospheres.

Development of new and better performing energy storage devices rely on the use of innovative materials. The combination of nanostructured materials with high specific area, such as graphene, and conventional electrode materials such as Glassy Carbon (GC) and the use of the composite electrode in ionic liquids (IL) are considered to be a promising strategy for improved energy storage devices. Following our previous studies of electrochemical interfaces involving 1-butyl-3-methylimidazolium (tris(pentafluoroethyl) trifluorophosphate) ([C 4 MIM][FAP]) ionic liquid and Hg, Au, Pt and GC we extended the search for better electrochemical performance by preparing GC electrode surfaces modified with different carbon materials (reduced graphene oxide, reduced graphite oxide and graphite). Cyclic voltammetry of these electrode surfaces in [C 4 MIM][FAP] ionic liquid shows a 100 fold increase in the capacitive current of the composite electrode when compared with plain GC electrode.