Publications

Abstract Charge (ion and electron)-transfer reactions at a liquid/ liquid interface are critical processes in many important biological and chemical systems. An ion-transfer (IT) process is usually very fast, making it difficult to accurately measure its kinetic parameters. Nano-liquid/liquid interfaces supported at nanopipettes are advantageous approaches to study the kinetics of such ultrafast IT processes due to their high mass transport rate. However, correct measurements of IT kinetic parameters at nanointerfaces supported at nanopipettes are inhibited by a lack of knowledge of the nanometer-sized interface geometry, influence of the electric double layer, wall charge polarity, etc. Herein, we propose a new electrochemical characterization equation for nanopipettes and make a suggestion on the shape of a nano-water/1,2-dichloroethane (nano-W/DCE) interface based on the characterization and calculation results. A theoretical model based on the Poisson-Nernst-Planck equation was applied to systematically study how the electric double layer influences the IT process of cations (TMA(+), TEA(+), TPrA(+), ACh(+)) and anions (ClO4-, SCN-, PF6 (-), BF4-) at the nano-W/DCE interface. The relationships between the wall charge conditions and distribution of concentration and potential inside the nanopipette revealed that the measured standard rate constant (k(0)) was enhanced when the polarity of the ionic species was opposite to the pipette wall charge and reduced when the same. This work lays the right foundation to obtain the kinetics at the nano-liquid/liquid interfaces.

Abstract Matricaria chamomilla L. is a famous medicinal plant distributed worldwide. It is widely used in traditional medicine to treat all kinds of diseases, including infections, neuropsychiatric, respiratory, gastrointestinal, and liver disorders. It is also used as a sedative, antispasmodic, antiseptic, and antiemetic. In this review, reports on M. chamomilla taxonomy, botanical and ecology description, ethnomedicinal uses, phytochemistry, biological and pharmacological properties, possible application in different industries, and encapsulation were critically gathered and summarized. Scientific search engines such as Web of Science, PubMed, Wiley Online, SpringerLink, ScienceDirect, Scopus, and Google Scholar were used to gather data on M. chamomilla. The phytochemistry composition of essential oils and extracts of M. chamomilla has been widely analyzed, showing that the plant contains over 120 constituents. Essential oils are generally composed of terpenoids, such as alpha-bisabolol and its oxides A and B, bisabolone oxide A, chamazulene, and beta-farnesene, among other compounds. On the other hand, M. chamomilla extracts were dominated by phenolic compounds, including phenolic acids, flavonoids, and coumarins. In addition, M. chamomilla demonstrated several biological properties such as antioxidant, antibacterial, antifungal, anti-parasitic, insecticidal, anti-diabetic, anti-cancer, and anti-inflammatory effects. These activities allow the application of M. chamomilla in the medicinal and veterinary field, food preservation, phytosanitary control, and as a surfactant and anti-corrosive agent. Finally, the encapsulation of M. chamomilla essential oils or extracts allows the enhancement of its biological activities and improvement of its applications. According to the findings, the pharmacological activities of M. chamomilla confirm its traditional uses. Indeed, M. chamomilla essential oils and extracts showed interesting antioxidant, antibacterial, antifungal, anticancer, antidiabetic, antiparasitic, anti-inflammatory, anti-depressant, anti-pyretic, anti-allergic, and analgesic activities. Moreover, the most important application of M. chamomilla was in the medicinal field on animals and humans.

Abstract Lipid nanoparticles (LN) composed of biodegradable lipids and produced by green methods are candidates for the encapsulation of pesticides, potentially contributing to decreasing their release in the environment. From a safety-by-design concept, this work proposes LN for the encapsulation of insecticide active ingredients (AI). However, given the complexity of nanoparticles, ecotoxicological studies are often controversial, and a detailed investigation of their effects on the environment is required. Accordingly, this work aimed to produce and characterize LN containing the insecticide lambda-cyhalothrin (LC) and evaluate their safety to crops (Solanum lycopersicum and Zea mays), soil invertebrates (Folsomia candida and Eisenia fetida), and soil microbial parameters. The average particle size for LN-loaded with LC (LN-LC) was 165.4 +/- 2.34 nm, with narrow size distribution and negative charge (-38.7 +/- 0.954 mV). LN were able to encapsulate LC with an entrapment efficacy of 98.44 +/- 0.04%, maintaining the stability for at least 4 months. The LN-LC showed no risk to the growth of crops and reproduction of the invertebrates. The effect on microbial parameters showed that the activity of certain soil microbial parameters can be inhibited or stimulated by the presence of LN at highest concentrations, probably by changing the pH of soil or by the intrinsic properties of LN.

Abstract Carbon dots (CDs) are carbon-based nanomaterials with remarkable properties that can be produced from a wide variety of synthesis routes. Given that standard bottom-up procedures are typically associated with low synthesis yields, different authors have been trying to devise alternative high-yield fabrication strategies. However, there is a doubt if sustainability-wise, the latter should be really preferred to the former. Herein, we employed a Life Cycle Assessment (LCA) approach to compare and understand the environmental impacts of high-yield and standard bottom-up strategies, by applying different life cycle impact assessment (LCIA) methods. These routes were: (1) production of hydrochar, via the hydrothermal treatment of carbon precursors, and its alkaline peroxide treatment into high-yield CDs; (2) microwave treatment of carbon precursors doped with ethylenediamine; (3) and (6) thermal treatment of carbon precursor and urea; (4) hydrothermal treatment of carbon precursor and urea; (5) microwave treatment of carbon precursor and urea. For this LCA, four LCIA methods were used: ReCiPe, Greenhouse Gas Protocol, AWARE, and USEtox. Results identified CD-5 as the most sustainable synthesis in ReCiPe, Greenhouse Gas Protocol, and USEtox. On the other hand, in AWARE, the most sustainable synthesis was CD-1. It was possible to conclude that, in general, high-yield synthesis (CD-1) was not more sustainable than standard bottom-up synthesis, such as CD-5 and CD-6 (also with relatively high-yield). More importantly, high-yield synthesis (CD-1) did not generate much lower environmental impacts than standard approaches with low yields, which indicates that higher yields come with relevant environmental costs.

Abstract Monoamine oxidases (MAOs) are attractive targets in drug design. The inhibition of one of the isoforms (A or B) is responsible for modulating the levels of different neurotransmitters in the central nervous system, as well as the production of reactive oxygen species. Molecules that act selectively on one of the MAO isoforms have been studied deeply, and coumarin has been described as a promising scaffold. In the current manuscript we describe a comparative study between 3-phenylcoumarin (endo coumarin-resveratrol-inspired hybrid) and trans-6-styrylcoumarin (exo coumarin-resveratrol-inspired hybrid). Crystallographic structures of both compounds were obtained and analyzed. 3D-QSAR models, in particular CoMFA and CoMSIA, docking simulations and molecular dynamics simulations have been performed to support and better understand the interaction of these molecules with both MAO isoforms. Both molecules proved to inhibit MAO-B, with trans-6-styrylcoumarin being 107 times more active than 3-phenylcoumarin, and 267 times more active than trans-resveratrol.

Abstract A new sensing platform based on long-period fiber gratings (LPFGs) for direct, fast, and selective detection of human immunoglobulin G (IgG; Mw = 150 KDa) was developed and characterized. The transducer's high selectivity is based on the specific interaction of a molecularly imprinted polymer (MIPs) design for IgG detection. The sensing scheme is based on differential refractometric measurements, including a correction system based on a non-imprinted polymer (NIP)-coated LPFG, allowing reliable and more sensitive measurements, improving the rejection of false positives in around 30%. The molecular imprinted binding sites were performed on the surface of a LPFG with a sensitivity of about 130 nm/RIU and a FOM of 16 RIU-1. The low-cost and easy to build device was tested in a working range from 1 to 100 nmol/L, revealing a limit of detection (LOD) and a sensitivity of 0.25 nmol/L (0.037 mu g/mL) and 0.057 nm.L/nmol, respectively. The sensor also successfully differentiates the target analyte from the other abundant elements that are present in the human blood plasma.

Abstract In this work, the stability of antioxidant compounds in malting barley seeds before and after the production of the final products is reported. In this reflection, the findings revealed that the process of fermentation had a significant impact on antioxidant activity. In vitro, antioxidant capacities were evaluated using DPPH free radical scavenging assay. The results obtained from the spectrophotometric analysis showed that the lowest inhibition value was observed in the samples that were obtained by the classical fermentation process (ABC) and the samples of non-alcoholic beer obtained by the thermal process (NABT), with free radical inhibition capacity values of 8.50% and 5.50%, respectively. The samples of hopped wort (HW) and malted barley seeds extract (BSE) showed very high antioxidant activity with free radical inhibition capacity of 14% and 12.60%, respectively. The obtained extracts were analyzed by gas chromatography and high-performance liquid chromatography, both combined with mass spectrometry detection (GC-MS, HPLC-MS). GC-MS analysis of the SPME extraction showed the presence of 29 compounds with isopentyl alcohol in major concentration (18.19%) in the alcoholic beer; on the other hand, the HPLC-DAD-ESI/MS analysis of the ethyl acetate extract showed the presence of 13 phenolic compounds. Interestingly, the degradation of 3-Hydroxyphloretin 2'-O-glucoside in the final products of the non-alcoholic beers was found. Finally, the FTIR analysis was also employed in order to detect the type of efficient groups present in the extracts.

Abstract Simple Summary Gametes are particularly susceptible to oxidative stress that impairs the reproductive function. This study was conducted to study the effect of a mitochondria-targeted dietary antioxidant (AntiOxBEN2) on bovine sperm function. Different doses of this antioxidant were tested during spermatozoa capacitation and/or fertilization processes. Spermatozoa mitochondrial function was improved when AntiOxBEN2 was supplemented to the capacitation medium. Supplementation of both capacitation and fertilization media with AntiOxBEN2 (lowest dose) improved the fertilization process and embryo production. Our results showed that AntiOxBEN2 can be used for the prevention of oxidative stress in bovine spermatozoa and may constitute a putative novel therapeutic strategy to improve the outcomes of assisted reproductive techniques. Sperm cells are particularly vulnerable to reactive oxygen species (ROS), impairing their fertilizing ability. Our objective was to study the effect of a novel mitochondrial-directed antioxidant, AntiOxBEN2, on bovine sperm function. This antioxidant was added to the semen capacitation medium (CAP), during the swim-up process, and to the fertilization medium (FERT) during the co-incubation of matured oocytes and capacitated spermatozoa, in concentrations of 0 (control), 1, and 10 mu M. After the swim-up, sperm motility (CASA and visual analysis), vitality (eosin-nigrosin), mitochondrial membrane potential (JC1), intracellular ROS, adenosine triphosphate (ATP) levels, and basal metabolism (Seahorse Xfe96) were evaluated. Embryo development and quality were also assessed. Higher cleavage rates were obtained when 1 mu M AntiOxBEN2 were added to CAP and FERT media (compared to control, p < 0.04). A positive effect of AntiOxBEN2 on intracellular ROS reduction (p = 0.01), on the increment of mitochondrial membrane potential (p <= 0.003) and, consequently, on the sperm quality was identified. However, the highest dose impaired progressive motility, ATP production, and the number of produced embryos. The results demonstrate a beneficial effect of AntiOxBEN2 (1 mu M) on sperm capacitation and fertilization processes, thus improving embryonic development. This may constitute a putative novel therapeutic strategy to improve the outcomes of assisted reproductive techniques (ART).

Abstract Thymus capitatus is a Mediterranean endemic plant commonly known as Zaitra in northern Morocco. As T. capitatus is widely used in traditional medicine and food, this present work aims to investigate the chemical compositions and biological activities of the T. capitatus leaves essential oil (TcLEO), acetonic (TcLAE), and methanolic extract (TcLME). The spectrophotometric determination demonstrated that T. capitatus is a natural source rich in phenolic contents (TPC) and flavonoid contents (TFC) and that TcLME revealed the highest TPC and TFC than TcLAE and TcLEO. The LC-MS analysis of phenolic compounds showed that paraben acid was predominant in both TcLME and TcLAE, followed by cinnamic acid and p-hydroxybenzoic acid. GC-MS analysis of the TcLEO revealed the presence of a total of 10 compounds, which were predominated by carvacrol. The antioxidant activity by ORAC was observed to be significantly higher in TcLEO and TcLAE than in TcLME. All samples used to assess DNA degradation effectively prevented DNA oxidation and, at the same time, had a prooxidant effect. The genotoxicity test showed that the T. capitatus were devoid of any mutagenic activity. Concerning antifungal activity, all samples were able to inhibit the growth of all microorganisms tested at low concentrations. TcLAE showed higher activity than TcLME, and in general, dermatophytes were more susceptible, being Microsporum canis the most sensitive one. Overall, the results obtained from this study confirm the wide uses of T. capitatus. Furthermore, the finding results suggest that the T. capitatus essential oil and extracts can be highly useful for pharmaceutical industries.

Abstract Parkinson's disease (PD) is an incurable neurodegenerative movement disorder. PD affects 2% of the population above 65 years old; however, with the growing number of senior citizens, PD prevalence is predicted to increase in the following years. Pathologically, PD is characterized by dopaminergic cell neurodegeneration in the substantia nigra, resulting in decreased dopamine levels in the nigrostriatal pathway, triggering motor symptoms. Although the pathological mechanisms leading to PD are still unclear, large evidence indicates that oxidative stress plays an important role, not only because it increases with age which is the most significant risk factor for PD development, but also as a result of alterations in several processes, particularly mitochondria dysfunction. The modulation of oxidative stress, especially using dietary mitochondriotropic antioxidants, represents a promising approach to prevent or treat PD. Although most mitochondria-targeted antioxidants with beneficial effects in PD-associated models have failed to show any therapeutic benefit in clinical trials, several questions remain to be clarified. Hereby, we review the role played by oxidative stress in PD pathogenesis, emphasizing mitochondria as reactive oxygen species (ROS) producers and as targets for oxidative stress-related dysfunctional mechanisms. In addition, we also describe the importance of using dietary-based mitochondria-targeted antioxidants as a valuable strategy to counteract the deleterious effects of ROS in pre-clinical and/or clinical trials of PD, pointing out their significance to slow, and possibly halt, the progression of PD.