Publications

Abstract <jats:p>The integration of bacteriophages, a particular class of viruses that specifically infect bacteria and archaea, in biosensors for the monitoring of pathogens in foods and beverages is highly desirable. To this end, an increasing focus has been set on the exploration of covalent and physical methods for the immobilization of phages on solid surfaces. This work investigates the electrostatic assembly of tailed phages, specifically anti-Listeria monocytogenes P100 phages, on an ultrathin self-assembled monolayer (SAM) of 11-amino-1-undecanethiol (AUT). The cationic properties of AUT may allow for the electrostatic capture of P100 in a capsid-down fashion, thus, exposing the specific receptor-binding proteins on their tails to the corresponding pathogens in analytical samples. The physical properties of immobilized phages have been studied using AFM, SEM, and electrochemical techniques, providing insight into the orientation of the phages and revealing that the pH plays a remarkable role in the morphology and charge transfer behavior of the adsorbed films. Overall, this research portrays SAMs of amino-akylthiols as a valid platform for the oriented immobilization of bacteriophages on surfaces for electroanalytical purposes.</jats:p>

Abstract Microdroplets and thin films of imidazolium-based ionic liquids (ILs) of different sizes and shapes were used as confining agents for the formation of high-quality perylene crystals by vapor deposition. The role of ILs to control the nucleation and subsequent crystal growth of perylene was investigated by sequential and simultaneous depositions of both materials using indium tin oxide (ITO) as the underlying substrate. The deposition of ILs onto the perylene film surface led to the formation of a complete 2D wetting layer, followed by island growth. Higher adhesion and affinity were found for longer-chain ILs. Inverting the deposition order, the perylene microcrystals were found to grow via the ILs droplets. Additionally, the nucleation and growth of perylene monocrystals enhanced the coalescence mechanisms of the ILs droplets. This wetting process was especially evident for longer-chain ILs. The deposition of perylene onto ITO surfaces fully covered with coalesced ionic liquid films led to the formation of a perylene film with the highest homogeneity as the result of a decrease in surface mobility. The co-deposition of perylene and ILs emphasized the potential application of ILs as crystallization solvents for the formation of thin organic films with improved crystalline quality without compromising the optoelectronic properties.

Abstract Currently, copper is approved as an active substance among plant protection products and is considered effective against more than 50 different diseases in different crops, conventional and organic. Tomato has been cultivated for centuries, but many fungal diseases still affect it, making it necessary to control them through antifungal agents, such as copper, making it the primary form of fungal control in organic farming systems (OFS). The objective of this work was to determine whether exogenous copper applications can affect AOX mechanisms and nitrogen use efficiency in tomato plant grown in OFS. For this purpose, plants were sprayed with 'Bordeaux' mixture (SP). In addition, two sets of plants were each treated with 8 mg/L copper in the root substrate (S). Subsequently, one of these groups was also sprayed with a solution of 'Bordeaux' mixture (SSP). Leaves and roots were used to determine NR, GS and GDH activities, as well as proline, H2O2 and AsA levels. The data gathered show that even small amounts of copper in the rhizosphere and copper spraying can lead to stress responses in tomato, with increases in total ascorbate of up to 70% and a decrease in GS activity down to 49%, suggesting that excess copper application could be potentially harmful in horticultural production by OFS.

Abstract In the last 60 years, auxinic herbicides like 2,4-dichlorophenoxyacetic acid (2,4-D) have been among the widest and successful herbicides used in agriculture because it is a selective herbicide that kills dicots and mimics the natural plant phytohormone indol-3-acetic acid (IAA) at the molecular level. In spite of industry attempts to reformulate 2,4-D-based herbicides and reduce their off-target movement, damage has been reported on sensitive plants, like tomato, at low ratesdi. Therefore, it is important to study the responses of such species to such conditions so that yield losses can be avoided or, at least, reduced. It is known that ethylene, abscisic acid (ABA) and reactive oxygen species (ROS) play a central role in 2,4-D toxicity, leading to numerous unbeneficial changes in plant tissues. Yet, how glutathione-related defense-and/or stress-related genes' expressions are affected needs to be more studied. In this study, tomato plants (Solanum lycopersicum L.) were used to determine the expression and participation of the different GST phi class gene family members, plus the plans' antioxidant system, in response to 2,4-D. When tomato plants were root-treated with 2.26 mM 2,4-D for 48 h, H2O2 and O2 & BULL;&#xe213; levels increased in shoots. Contrarily, in roots, 2,4-D did not provoke clear symptoms of oxidative stress, as lipid peroxidation, H2O2 and O2 & BULL;&#xe213; levels decreased. Despite the difference in ROS levels observed in both organs, the exposure of tomato plants to 2,4-D lead to the activation of key antioxidant enzymes in both organs, apart from superoxide dismutase (SOD), whose activity increased only in roots, while ascorbate peroxidase (APX) and catalase (CAT) activities increased in both. Also, tomato plants responded to 2.26 mM 2,4-D by increasing Ascorbate (AsA) levels in both organs while an increase in Glutathione (GSH) was only observed in shoots. The herbicide increased both the synthesis and the regeneration of GSH, as well as its usage to conjugate 2,4-D, as shoot & gamma;-glutamyl-cysteinyl synthetase (& gamma;-ECS), glutathione reductase (GR) and glutathione S-transferase (GST) activities increased. Shoot GST increased activity was due to an increased expression of SlGSTF4 and SlGSTF5, while no SlGSTFs increased their expression in roots. Shoots and roots of tomato plants were differentially affected by 2.26 mM 2,4-D, with 2,4-D detoxification occurring predominantly in leaves, with the specific participation of the GST phi class members SlGSTF4 and SlGSTF5. Also, this study reinforces the notion that the cultivation of tomato in 2,4-D-contaminated soils may result in yield reduction.

Abstract The integration of bacteriophages, a particular class of viruses that specifically infect bacteria and archaea, in biosensors for the monitoring of pathogens in foods and beverages is highly desirable. To this end, an increasing focus has been set on the exploration of covalent and physical methods for the immobilization of phages on solid surfaces. This work investigates the electrostatic assembly of tailed phages, specifically anti-Listeria monocytogenes P100 phages, on an ultrathin self-assembled monolayer (SAM) of 11-amino-1-undecanethiol (AUT). The cationic properties of AUT may allow for the electrostatic capture of P100 in a capsid-down fashion, thereby exposing the specific receptor-binding proteins on their tails to the corresponding pathogens in the analytical samples. The morphology and charge transfer behavior of the assembled films were studied with atomic force microscopy, scanning electron microscopy and electrochemical techniques. These methods provided valuable insights into the orientation of the phages and the relevant role of the pH. Biological plaque assays revealed that the immobilized phages remain active towards the target bacterium. Overall, this research portrays SAMs of amino-akylthiols as a valid platform for the oriented immobilization of bacteriophages on surfaces for electroanalytical purposes.

Abstract Isothermal titration calorimetry (ITC) has become the gold standard for studying molecular interactions in solution. Although it is increasingly being used in the soft matter and synthetic chemistry fields, ITC is most widely used for characterizing molecular interactions between ligands and macromolecules. This Primer starts by presenting the technique's foundations and instrumentation, including a brief description of the standard assay, followed by a review of common applications. Further extensions and modifications of the technique are explored. These adaptations enable key features to be studied, such as cooperative effects associated with complex biological interactions and their regulation, alongside applications to other fields, including partition to membranes, kinetics and soft matter. Advantages and caveats in ITC are discussed, with a focus on best practices, instrument calibration, experimental design, data analysis and data reporting, as well as recent and future developments.

Abstract Regardless of the many common properties shared by ionic liquids (ILs) and deep eutectic solvents (DES), these are two completely different classes of solvents. Unlike ILs, DES are not composed solely of ions, which adds an extra complexity to the systems. Indeed, DES possess a distinct nanostructure organization which is mainly due to the strong hydrogen network present in these solvents. For this reason ILs and DES cannot be treated as similar mixtures, having their own particularities and different promising applications. Nevertheless, both solvents are highly tunable owing to the infinite number of possible combinations of their components and so it is important to tailor their specific properties according to a specific task, by choosing the right components at the right molar ratios. The growing number of applications involving an IL/surface or DES/surface interface is increasing rapidly, but the upscaling of such technologies needs a profound knowledge of chemical compositions, structure and orientational arrangements at these interfaces, also known as the electrical double layer (EDL). In this work, we provide a summary of the progress made in the interfacial area involving ILs and DES, paying special attention to the EDL arrangements and dynamics. It is clear that classical EDL theories do not apply to neither of these solvents, being the one proposed by Kornyshev the most accepted for ILs. Yet, a multilayer organization of the mixtures components at the solvent|electrode interface is recognized by experimental and computational simulation communities for both electrolytes. Each system has its own characteristic differential capacitance curves, which vary greatly due to the different nature of adsorption/desorption species and their reorientation.

Abstract The enthalpies of formation in the gaseous phase of methyl 3-methylanthranilate and methyl 5-methylanthranilate were determined from experimental measurements of the corresponding standard energies of combustion, obtained from combustion calorimetry, and the standard enthalpies of vaporization and sublimation, obtained from Calvet microcalorimetry and Knudsen mass-loss effusion. A computational study, using the G3(MP2)//B3LYP composite method, has also been performed for the calculation of the gas-phase standard enthalpies of formation of those two molecules at T = 298.15 K, as well as for the remaining isomers, methyl 4-methylanthranilate and methyl 6-methylanthranilate. The results have been used to evaluate and analyze the energetic effect of the methyl substituent in different positions of the ring.

Abstract Chemiluminescence is a remarkable process in which light is emitted due to a chemical reaction, without the need for photoexcitation. Among some of the most well-known chemiluminescent systems is that of marine Coelenterazine. Herein, we report the synthesis of a novel halogenated Coelenterazine analog, as well as the characterization of its potential anticancer activity and chemiluminescence. We have found that this analog is capable of significantly enhanced emission in aqueous solution when triggered by superoxide anion while being compatible with human cell lines. So, this compound presents great potential for the sensitive and dynamic sensing of a molecule of interest in biological media. Furthermore, the analysis of its cytotoxicity provided structural insight into the properties of brominated Coelenterazines, which were previously found to possess selective anticancer activity. Namely, the introduction of bromine heteroatoms is not enough to provide cyto-toxicity, while the introduction of electro-withdrawing groups eliminates all previously reported anticancer activity. Finally, while this compound is not active, its use in a combination approach allowed to improve the profile of a known chemotherapeutic agent. These results should be useful to guide future optimizations of halogenated Coelenterazine analogs.

Abstract Carbon dots (CDs) have attracted considerable interest from the scientific community due to their exceptional properties, such as high photoluminescence, broadband absorption, low toxicity, water solubility and (photo)chemical stability. As a result, they have been applied in several fields, such as sensing, bioimaging, artificial lighting and catalysis. In particular, CDs may act as sole photocatalysts or as part of photocatalytic nanocomposites. This study aims to provide a comprehensive review on the use of CDs as sole photocatalysts in the areas of hydrogen production via water splitting, photodegradation of organic pollutants and photoreduction and metal removal from wastewaters. Furthermore, key limitations preventing a wider use of CDs as photocatalysts are pointed out. It is our hope that this review will serve as a basis on which researchers may find useful information to develop sustainable methodologies for the synthesis and use of photocatalytic CDs.