Recent Advances in Light-Driven Semiconductor-Based Micro/Nanomotors: Optimization Strategies and Emerging Applications.

Micro/nanomotors represent a burgeoning field of research featuring small devices capable of autonomous movement in liquid environments through catalytic reactions and/or external stimuli. This review delves into recent advancements in light-driven semiconductor-based micro/nanomotors (LDSM), focusing on optimized syntheses, enhanced motion mechanisms, and emerging applications in the environmental and biomedical domains. The survey commences with a theoretical introduction to micromotors and their propulsion mechanisms, followed by an exploration of commonly studied LDSM, emphasizing their advantages. Critical properties affecting propulsion, such as surface features, morphology, and size, are presented alongside discussions on external conditions related to light sources and intensity, which are crucial for optimizing the propulsion speed. Each property is accompanied by a theoretical background and conclusions drawn up to 2018. The review further investigates recent adaptations of LDSM, uncovering underlying mechanisms and associated benefits. A brief discussion is included on potential synergistic effects between different external conditions, aiming to enhance efficiency-a relatively underexplored topic. In conclusion, the review outlines emerging applications in biomedicine and environmental monitoring/remediation resulting from recent LDSM research, highlighting the growing significance of this field. The comprehensive exploration of LDSM advancements provides valuable insights for researchers and practitioners seeking to leverage these innovative micro/nanomotors in diverse applications.

Multivariate analysis applied to X-ray fluorescence to assess soil contamination pathways: case studies of mass magnetic susceptibility in soils near abandoned coal and W/Sn mines.

Determining the origin and pathways of contaminants in the natural environment is key to informing any mitigation process. The mass magnetic susceptibility of soils allows a rapid method to measure the concentration of magnetic minerals, derived from anthropogenic activities such as mining or industrial processes, i.e., smelting metals (technogenic origin), or from the local bedrock (of geogenic origin). This is especially effective when combined with rapid geochemical analyses of soils. The use of multivariate analysis (MVA) elucidates complex multiple-component relationships between soil geochemistry and magnetic susceptibility. In the case of soil mining sites, X-ray fluorescence (XRF) spectroscopic data of soils contaminated by mine waste shows statistically significant relationships between magnetic susceptibility and some base metal species (e.g., Fe, Pb, Zn, etc.). Here, we show how qualitative and quantitative MVA methodologies can be used to assess soil contamination pathways using mass magnetic susceptibility and XRF spectra of soils near abandoned coal and W/Sn mines (NW Portugal). Principal component analysis (PCA) showed how the first two primary components (PC-1 + PC-2) explained 94% of the sample variability, grouped them according to their geochemistry and magnetic susceptibility in to geogenic and technogenic groups. Regression analyses showed a strong positive correlation (R2 > 0.95) between soil geochemistry and magnetic properties at the local scale. These parameters provided an insight into the multi-element variables that control magnetic susceptibility and indicated the possibility of efficient assessment of potentially contaminated sites through mass-specific soil magnetism.

Molecularly Imprinted Methyl-Modified Hollow TiO2 Microspheres.

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

Exploration of the reactive modelling of sol-gel polycondensation in the presence of templates.

The polycondensation of silicic acid, methylsilicic acid, or their mixture was studied by reactive force field simulation. These were found to be feasible systems for the simulation of two-step acid hydrolysis-alkaline condensation of their alkoxysilane counterparts, usually taken experimentally as sol-gel precursors. The approach avoided the alkoxysilane hydrolysis step and allowed high degrees of polycondensation at relatively low temperature (700-1000 K), from the computational efficiency perspective. Being the ultimate interest of the present study the sol-gel polycondensation of templated gels whose microstructural pattern is affected by the presence of a template, the role of the intermolecular forces was decisive, and promoted high polycondensation at the lowest possible temperature. Polycondensation with added damascenone did not result in any perceived templating effect, i.e., damascenone was not able to interact significantly with the growing clusters, in a way that would allow its occlusion or a surface molding effect on the clusters. A possible reason for this is the intermolecular interaction strength being too weak at the temperatures set for the simulations. However, when using luteolin as the template, a molecule with several hydrogen bond interaction points, it was possible to observe different microscopic events involving the template molecules, some of them corresponding to actual templating effects, such as partial enveloping by the network around the template. These restricted events did not allow the inference of any macroscopic property of the final gel. However, it was shown that polycondensates shaped by the template or a template dimer may be obtained. The sites thus obtained will be essential for future in silico studies of the selectivity of such sites.

Cationic imprinting of Pb(II) within composite networks based on bovine or fish chondroitin sulfate.

Imprinting chondroitin sulfate (CS)/silica composites with Pb(II) and Cu(II) cations was explored with CS of bovine and different fish species origin. The process was based on the assumption that particular arrangements of the linear CS chains in aqueous solution, induced so as to accommodate cross complexation with the cations, would be embodied into a tridimensional matrix created through an organoalkoxysilane sol-gel scheme. The presence of Cu(II) 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. Inversely, for Pb(II), the materials obtained exhibited a "memory" effect for the Pb(II) ions, expressed in the observation of stronger (13%-44%) binding as compared to the nonimprinted counterparts, and increased selectivity (1.5-2 folds) against Cd(II). The imprinting features observed were dependent on the CS source. However, it was not possible to identify, among a set of their properties (carboxylate and sulfate abundance, percent of disulfated units, 4S/6S ratio, and molecular weight), any that correlated directly with the observed imprinting features. The augmented selectivity provided by the cation-imprinting process may be advantageous in areas such as analytical separation, remediation, purification, sensing, and others, particularly in those cases where a certain cation is of special interest within a mixture of them.

Molecular dynamics simulations of complex mixtures aimed at the preparation of naproxen-imprinted xerogels.

The main objective of this study was to simulate for the first time a complex sol-gel system aimed at preparing the (S)-naproxen-imprinted xerogel with an explicit representation of all the ionic species at pH 9. For this purpose, a series of molecular dynamics (MD) simulations of different mixtures, including species never studied before using the OPLS-AA force field, were prepared. A new parametrization for these species was developed and found to be acceptable. Three different systems were simulated, representing two types of pregelification models: the first one represented the initial mixture after complete hydrolysis and condensation to cyclic trimers (model A); the second one corresponded to the same mixture after the evaporation process (model B); and the last one was a simpler initial mixture without an explicit representation of all of the imprinting-mixture constituents (model C). The comparison of systems A and C mainly served the purpose of evaluating whether an explicit representation of all of the components (model A) was needed or if a less computationally demanding system in which the alkaline forms of the silicate species were ignored (model C) would be sufficient. The results confirmed our hypothesis that an explicit representation of all of the imprinting-mixture constituents is essential to study the molecular imprinting process because a poor representation of the ionic species present in the mixture may lead to erroneous conclusions or lost information. In general, the radial distribution function (RDF) analysis and interaction energies demonstrated a high affinity of the template molecule, 2-(6-methoxynaphthalen-2-yl)propanoate (NAP(-), the conjugate base of (S)-naproxen), for the gel backbone, especially targeting the units containing the dihydroimidazolium moiety used as a functional group. Model B, representing a nearly gelled sol where the density of silicates and solvent polarity were much higher relative to the other models, allowed for much faster simulations. That gave us the chance to observe the templating effect through a comparative analysis and observation of the trajectories from simulations with the template- versus non-template-containing mixtures. Overall, a strong coherence between the imprinting-relevant interactions, aggregation, or the silicate network texturing effects taken out of the simulations and the experimentally high imprinting performance and porosity features of the corresponding gels was achieved.

Unravelling the combined impacts of drought and Cu in barley plants - double trouble?

The occurrence of drought in soils, particularly in those contaminated by metals, poses a current threat to crops, as these factors can interact and induce unique stress responses. Therefore, this study mainly focused on understanding the crosstalk between drought and copper (Cu) stress in the physiology of the barley (Hordeum vulgare L.) plant. Using a bifactorial experimental design, seedlings were grown in a natural soil under the following treatments: plants continuously irrigated in uncontaminated soil for 14 days (control); plants continuously irrigated in Cu-contaminated soil (115 mg Cu kg-1) for 14 days (Cu); plants only irrigated during the initials 7 days of growth in uncontaminated soil (drought); plants co-exposed to Cu and drought (combined). After 14 days of growth, the results revealed that drought prevented Cu bioaccumulation in barley roots, which were still severely affected by the metal, both individually and in combination with the water deficit. Furthermore, individual and combined exposure to these stressors resulted in impaired photosynthetic performance in barley plants. Despite the increased activation of enzymatic and non-enzymatic antioxidant defence mechanisms, particularly in the green organs, the plants co-exposed to both stress factors still showed higher oxidative damage, severely impacting biomass production.

Computational and experimental study of the effect of PEG in the preparation of damascenone-imprinted xerogels.

Macromolecules, such as polyethylene glycol (PEG), have been frequently used in the preparation of xerogels, mainly with the purpose of tuning the meso- or macroporosity. However, PEG has never been applied in the context of the preparation of molecularly imprinted xerogels for small molecules. Thus, we decided to conduct a computational and experimental study of the incorporation of PEG into formerly studied sol-gel mixtures for the preparation of damascenone-imprinted xerogels. Computationally, two types of pregelification models were studied, one representing the initial mixture (SI3/SIPA:5:3 models) and the other representing the same mixtures after considerable solvent loss (SI3/SIPA:40:1 models). The latter ones were particularly prolific in providing clear effects of the PEG. In the SI3:40:1 model (containing SI3 units of Si(3)O(3)(OH)(6) mimicking the final xerogels backbone), a prohibitive instead of a promoting effect of PEG on the template-SI3 association was observed. PEG was found to interpose the SI3 aggregates, turning them smaller and more disperse. In agreement with that, a much higher porosity and surface area were found for the corresponding xerogel prepared with PEG, while no appreciable improvement of the imprinting efficiency could be observed. In the SIPA:40:1 model (containing both SI3 and SIPA units; SIPA, Si(3)O(3)(OH)(5)C(3)H(6)NHC(6)H(5), representing the introduction of the organic functional group into the xerogel network), the interactions related to the network structuring were not significantly affected. This was due to the fact that the SIPA units themselves had a dispersive effect on the silica network; the PEG molecules were "pushed" into the aqueous/methanolic continuum, and their presence was somewhat redundant. Accordingly, both prepared SIPA-xerogels (with PEG or not) exhibited higher porosity compared to SI3-xerogels. Although the simulation results were not conclusive about the effect of PEG on the template-functional group association, experimentally it was clear that the imprinting effect was not improved with PEG.

Imprinted Hydrogel Nanoparticles for Protein Biosensing: A Review.

Over the past decade, molecular imprinting (MI) technology has made tremendous progress, and the advancements in nanotechnology have been the major driving force behind the improvement of MI technology. The preparation of nanoscale imprinted materials, i.e., molecularly imprinted polymer nanoparticles (MIP NPs, also commonly called nanoMIPs), opened new horizons in terms of practical applications, including in the field of sensors. Currently, hydrogels are very promising for applications in bioanalytical assays and sensors due to their high biocompatibility and possibility to tune chemical composition, size (microgels, nanogels, etc.), and format (nanostructures, MIP film, fibers, etc.) to prepare optimized analyte-responsive imprinted materials. This review aims to highlight the recent progress on the use of hydrogel MIP NPs for biosensing purposes over the past decade, mainly focusing on their incorporation on sensing devices for detection of a fundamental class of biomolecules, the peptides and proteins. The review begins by directing its focus on the ability of MIPs to replace biological antibodies in (bio)analytical assays and highlight their great potential to face the current demands of chemical sensing in several fields, such as disease diagnosis, food safety, environmental monitoring, among others. After that, we address the general advantages of nanosized MIPs over macro/micro-MIP materials, such as higher affinity toward target analytes and improved binding kinetics. Then, we provide a general overview on hydrogel properties and their great advantages for applications in the field of Sensors, followed by a brief description on current popular routes for synthesis of imprinted hydrogel nanospheres targeting large biomolecules, namely precipitation polymerization and solid-phase synthesis, along with fruitful combination with epitope imprinting as reliable approaches for developing optimized protein-imprinted materials. In the second part of the review, we have provided the state of the art on the application of MIP nanogels for screening macromolecules with sensors having different transduction modes (optical, electrochemical, thermal, etc.) and design formats for single use, reusable, continuous monitoring, and even multiple analyte detection in specialized laboratories or in situ using mobile technology. Finally, we explore aspects about the development of this technology and its applications and discuss areas of future growth.

Impact of Combined Heat and Salt Stresses on Tomato Plants-Insights into Nutrient Uptake and Redox Homeostasis.

Currently, salinity and heat are two critical threats to crop production and food security which are being aggravated by the global climatic instability. In this scenario, it is imperative to understand plant responses to simultaneous exposure to different stressors and the cross-talk between underlying functional mechanisms. Thus, in this study, the physiological and biochemical responses of tomato plants (Solanum lycopersicum L.) to the combination of salinity (100 mM NaCl) and heat (42 °C; 4 h/day) stress were evaluated. After 21 days of co-exposure, the accumulation of Na+ in plant tissues was superior when salt-treated plants were also exposed to high temperatures compared to the individual saline treatment, leading to the depletion of other nutrients and a harsher negative effect on plant growth. Despite that, neither oxidative damage nor a major accumulation of reactive oxygen species took place under stress conditions, mostly due to the accumulation of antioxidant (AOX) metabolites alongside the activation of several AOX enzymes. Nonetheless, the plausible allocation of resources towards the defense pathways related to oxidative and osmotic stress, along with severe Na toxicity, heavily compromised the ability of plants to grow properly when the combination of salinity and heat was imposed.

Subcellular compartmentalization of aluminum reduced its hazardous impact on rye photosynthesis.

Aluminum (Al) toxicity limits crops growth and production in acidic soils. Compared to roots, less is known about the toxic effects of Al in leaves. Al subcellular compartmentalization is also largely unknown. Using rye (Secale cereale L.) Beira (more tolerant) and RioDeva (more sensitive to Al) genotypes, we evaluated the patterns of Al accumulation in leaf cell organelles and the photosynthetic and metabolic changes to cope with Al toxicity. The tolerant genotype accumulated less Al in all organelles, except the vacuoles. This suggests that Al compartmentalization plays a role in Al tolerance of Beira genotype. PSII efficiency, stomatal conductance, pigment biosynthesis, and photosynthesis metabolism were less affected in the tolerant genotype. In the Calvin cycle, carboxylation was compromised by Al exposure in the tolerant genotype. Other Calvin cycle-related enzymes, phoshoglycerate kinase (PGK), glyceraldehyde 3-phosphate dehydrogenase (GAPDH), triose-phosphate isomerase (TPI), and fructose 1,6-bisphosphatase (FBPase) activities decreased in the sensitive line after 48 h of Al exposure. Consequentially, carbohydrate and organic acid metabolism were affected in a genotype-specific manner, where sugar levels increased only in the tolerant genotype. In conclusion, Al transport to the leaf and compartmentalization in the vacuoles tolerant genotype's leaf cells provide complementary mechanisms of Al tolerance, protecting the photosynthetic apparatus and thereby sustaining growth.

Molecular dynamics simulations of pregelification mixtures for the production of imprinted xerogels.

A series of molecular dynamics (MD) simulations of different pregelification mixtures representing intermediate stages of the sol-gel process were set up to gain insight into the molecular imprinting process in xerogels, namely, to assess the template-gel affinity and template self-aggregation. The physical plausibility of the parametrization was checked, confirming the reliability of the simulations. The simulated mixtures differed in the water/methanol ratio (1:3, 5:3, and 5:1) and in the absence/presence of an organic functional group (phenylaminopropyl-) in the silicate species. The simulation results, expressed mainly by the radial distribution functions and respective coordination numbers, showed that the affinity of the template molecule, damascenone (a hydrophobic species), for the gel backbone would not be attained without the tested functional group, phenylaminopropyl-. The affinity, related to the capability to trap the template within the gel network, was derived mostly from the hydrophobic interaction. It was also inferred from MD simulations that lower water contents (methanol-richer mixtures) would facilitate a better dispersion of both the functional group and the template within the final gel, therefore favoring the imprinting process. From the experimental counterparts of the simulated mixtures, a series of imprinted and nonimprinted xerogels were obtained. There was only one xerogel exhibiting the imprinting effect, namely, the one containing the organic group obtained at the lower water/methanol ratio (1:3), in agreement with predictions from the MD simulations. Such congruence demonstrates the ability of MD simulations to provide information regarding the fine aspects of molecular interactions in pregelification mixtures for imprinting.

Specific glutathione-S-transferases ensure an efficient detoxification of diclofenac in Solanum lycopersicum L. plants.

Diclofenac (DCF) is a very common pharmaceutical that, due to its high use and low removal rate, is considered a prominent contaminant in surface and groundwater worldwide. In this study, Solanum lycopersicum L. cv. Micro-Tom (tomato) was used to disclose the role of glutathione (GSH)-related enzymes, as GSH conjugation with DCF is a well reported detoxification mechanism in mammals and some plant species. To achieve this, S. lycopersicum plants were exposed to 0.5 and 5 mg L-1 of DCF for 5 weeks under a semi-hydroponic experiment. The results here obtained point towards an efficient DCF detoxification mechanism that prevents DCF bioaccumulation in fruits, minimizing any concerns for human health. Although a systemic response seems to be present in response to DCF, the current data also shows that its detoxification is mostly a root-specific process. Furthermore, it appears that GSH-mediated DCF detoxification is the main mechanism activated, as glutathione-S-transferase (GST) activity was greatly enhanced in roots of tomato plants treated with 5 mg L-1 DCF, accompanied by increased glutathione reductase activity, responsible for GSH regeneration. By applying a targeted gene expression analysis, we provide evidence, for the first time, that SlGSTF4 and SlGSTF5 genes, coding for GSTs from phi class, were the main players driving the conjugation of this contaminant. In this sense, and even though tomato plants appear to be somewhat tolerant to DCF exposure, research on GST activity can prove to be instrumental in remediating DCF-contaminated environments and improving plant growth under such conditions.

Foliar application of 24-epibrassinolide improves Solanum nigrum L. tolerance to high levels of Zn without affecting its remediation potential.

Although Solanum nigrum L. is a phytoremediator for different metals, its growth and physiology are still compromised by toxic levels of zinc (Zn). Thus, the development of eco-friendly strategies to enhance its tolerance, maintaining remediation potential is of special interest. This study evaluated the potential of 24-epibrassinolide (24-EBL) to boost S. nigrum defence against Zn towards a better growth rate and remediation potential. After 24 days of exposure, the results revealed that Zn-mediated inhibitory effects on biomass and biometry were efficiently mitigated upon application of 24-EBL, without affecting Zn accumulation. The evaluation of oxidative stress markers reported that Zn excess stimulated the accumulation of superoxide anion (O2.-), but reduced hydrogen peroxide (H2O2) levels, while not altering lipid peroxidation (LP). This was accompanied by an up-regulation of the antioxidant system, especially proline, superoxide dismutase (SOD) and ascorbate peroxidase (APX) in both organs, and ascorbate in roots of Zn-exposed plants. Foliar application of 24-EBL, however, induced distinctive effects, lowering proline levels in both organs, as well as APX activity in shoots and SOD in roots, whilst stimulating GSH and total thiols in both organs, as well as SOD and APX activity, in shoots and in roots, respectively. Probably due to a better antioxidant efficiency, levels of O2.- and H2O2 in pre-treated plants remained identical to the control, while LP further decreased in shoots. Overall, our results indicate a protective effect of 24-EBL on S. nigrum response to excess Zn, contributing for a better tolerance and growth rate, without disturbing its phytoremediation potential.

The requisite level of theory for the computational design of molecularly imprinted silica xerogels.

The present manuscript reports the first application of molecular modelling to the design of molecularly imprinted polymers (MIPs) prepared by alkoxysilane sol-gel polymerization. The major goal was to determine the requisite level of theory for the selection of suitable alkoxysilane functional monomers. A comparative study, applied to the design of a MIP for beta-damascenone, involving different levels of theory, basis set superposition error (BSSE) correction and basis set augmentation and also semi-empirical methods, was performed. The computations results suggest that the use of the 3-21G basis set concomitantly with a method for BSSE correction represents a good compromise between theory level and computation time for the successful screening of functional monomers. Additionally, a few selected MIPs and their corresponding non-imprinted congeners (NIPs) were prepared and tested in the role of solid-phase extraction (SPE) sorbents. The confrontation of the computational results with the observed performance and morphological characteristics of the prepared MIPs suggest that besides the strength and type of interactions existing between template and functional monomers other concomitant features, related with the sol-gel process, must also be accounted for so that effective molecular imprinting is achieved in an alkoxysilane xerogel. Nevertheless, since an optimal template-functional monomer interaction is a necessary condition for successful imprinting, the choice of the best monomers is still of the greatest importance and the proposed computational method may constitute an expeditious and reliable screening tool.

Differential effects of acetophenone on shoots' and roots' metabolism of Solanum nigrum L. plants and implications in its phytoremediation.

The wide ranges of uses for acetophenone make it more available and expected to accumulate in the biosphere, where consequently it can threat ecosystems. To remediate this problem, the use of Solanum nigrum L. plants for the clean-up of acetophenone-contaminated sites was explored. Also, plant root and shoot biometry and metabolism where assayed to better understand the effects of this organic compound and to pinpoint possible metabolic pathways to be targeted for future manipulations for increasing this plant species' remediation efficiency. Although undergoing through some stress, detected by increases in ROS and lipid peroxidation in both organs, plants were able to rapidly eliminate all acetophenone from the nutrient solution after 7 days of exposure, being this compound mainly detoxified at the root level. Additionally, acetophenone lead to a differential metabolic response in roots and shoots, where antioxidant mechanisms where differentially activated, while nitrogen assimilation was repressed in shoots and activated in roots. These results confirm that S. nigrum is a good phytoremediation tool for acetophenone and suggest that enhancing shoot GS activity may provide more nitrogen precursors for the synthesis of thiolated proteins and glutathione to increase tolerance to acetophenone in roots and shoots, respectively.

SiO2 nanomaterial as a tool to improve Hordeum vulgare L. tolerance to nano-NiO stress.

This work was designed to assess the potential role of silicon dioxide nanomaterial (nano-SiO2) in enhancing barley's tolerance to nickel oxide nanomaterial (nano-NiO). For this purpose, plants were grown for 14days under nano-NiO (120mgkg-1) single and co-exposure with nano-SiO2 (3mgkg-1). The exposure of barley to nano-NiO caused a significant decrease in growth-related parameters and induced a negative response on the photosynthetic apparatus. However, upon nano-SiO2 co-exposure, the inhibitory effects of nano-NiO were partially reduced, with lower reductions in fresh and dry biomass, and with the recovery of the photosynthesis-related parameters. Plants growing under nano-NiO stress showed an overproduction of superoxide anion (O2.-), which favored the occurrence of oxidative stress and the enhancement of lipid peroxidation (LP), but the co-treatment with nano-SiO2 reverted this tendency, generally lowering or maintaining the levels of LP and stimulating the redox pathway of thiols. The evaluation of the antioxidant (AOX) system revealed that nano-NiO induced the accumulation of proline, along with a decrease in ascorbate in leaves. Furthermore, superoxide dismutase (SOD) activity was significantly enhanced and catalase (CAT) and ascorbate peroxidase (APX) seemed to have a pivotal role in H2O2 detoxification in leaves and roots, respectively. The response of the AOX system was even more prominent upon nano-SiO2 co-exposure, reinforcing the ameliorating functions of this nanomaterial. Overall, the present study highlighted the protective role of nano-SiO2 in barley plants under nano-NiO stress, possibly due to the Si-mediated protection against oxidative stress, by a more proactive performance of the plant AOX system.

Metalaxyl Effects on Antioxidant Defenses in Leaves and Roots of Solanum nigrum L.

Overuse of pesticides has resulted in environmental problems, threating public health through accumulation in food chains. Phytoremediation is a powerful technique to clean up contaminated environments. However, it is necessary to unravel the metabolic mechanisms underlying phytoremediation in order to increase the efficiency of this process. Therefore, growth, physiological and biochemical responses in leaves and roots of Solanum nigrum L. exposed to the commonly used fungicide metalaxyl were investigated. This species shows characteristics that make it valuable as a potential tool for the remediation of organic pollutants. We found that once inside the plant, metalaxyl altered carbon metabolism, which resulted in a reduction of growth and lower biomass accumulation due to impairment of carbohydrate production (total soluble sugar, starch, rubisco) and increased photorespiration (glycolate oxidase, Gly/Ser ratio). A significant increase of antioxidant defenses (polyphenols, flavonoids, tocopherols, ascorbate, glutathione, superoxide dismutase, catalase, peroxidases, monodehydroascorbate- and dehydroascorbate reductase, gluthatione reductase) kept reactive oxygen species (ROS) levels under control (superoxide anion) leaving cell membranes undamaged. The results suggest that enhancing carbon assimilation and antioxidant capacity may be target parameters to improve this species' phytoremediation capacities. Highlights • Metalaxyl inhibits growth by reducing photosynthesis and inducing photorespiration • Elevated antioxidant defenses protect metalaxyl-treated plants from oxidative damage • Ascorbate and glutathione are key antioxidants in metalaxyl tolerance.

Measurement artifacts identified in the UV-vis spectroscopic study of adduct formation within the context of molecular imprinting of naproxen.

The ultraviolet-visible spectroscopy has been assessed as a technique for the evaluation of the strength of template-precursor adduct in the development of molecular imprints of the non-steroidal anti-inflammatory drug naproxen (NAP). The commonly employed approach relies on the collection of UV spectra of drug+precursor mixtures at different proportions, the spectra being recorded against blanks containing the same concentration of the precursor. The observation of either blue or red band-shifts and abatement of a major band are routinely attributed to template-precursor adduct formation. Following the described methodology, the precursors 1-(triethoxysilylpropyl)-3-(trimethoxysilylpropyl)-4,5-dihydroimidazolium iodide (AO-DHI(+)) and 4-(2-(trimethoxysilyl)ethyl)pyridine (PETMOS) provoked a blue-shift and band abatement effect on the NAP spectrum. Molecular dynamics simulations indicated a reasonable affinity between NAP and these precursors (coordination numbers 0.33 for AO-DHI(+) and 0.18 for PETMOS), hence showing that NAP-precursor complexation is in fact effective. However, time dependent density functional theory (TD-DFT) calculations of the spectra of both free and precursor-complexed NAP were identical, thus providing no theoretical basis for the complexation-induced effects observed. We realized that the intense spectral bands of AO-DHI(+) and PETMOS (at around 265 nm) superimpose partially with the NAP bands, and the apparent "blue-shifting" in the NAP spectra when mixed with AO-DHI+ and PETMOS was in this case a spurious effect of the intense background subtraction. Therefore, extreme care must be taken when interpreting other spectroscopic results obtained in a similar fashion.

Acylated-naproxen as the surface-active template in the preparation of micro- and nanospherical imprinted xerogels by emulsion techniques.

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.