A Novel In Situ Sol-Gel Synthesis Method for PDMS Composites Reinforced with Silica Nanoparticles.

The addition of nanostructures to polymeric materials allows for a direct interaction between polymeric chains and nanometric structures, resulting in a synergistic process through the physical (electrostatic forces) and chemical properties (bond formation) of constituents for the modification of their properties and potential cutting-edge materials. This study explores a novel in situ synthesis method for PDMS-%SiO2 nanoparticle composites with varying crosslinking degrees (PDMS:TEOS of 15:1, 10:1, and 5:1); particle concentrations (5%, 10%, and 15%); and sol-gel catalysts (acidic and alkaline). This investigation delves into the distinct physical and chemical properties of silicon nanoparticles synthesized under acidic (SiO2-a) and alkaline (SiO2-b) conditions. A characterization through Raman, FT-IR, and XPS analyses confirms particle size and agglomeration differences between both the SiO2-a and SiO2-b particles. Similar chemical environments, with TEOS and ethanol by-products, were detected for both systems. The results on polymer composites elucidate the successful incorporation of SiO2 nanoparticles into the PDMS matrix without altering the PDMS's chemical structure. However, the presence of nanoparticles did affect the relative intensities of specific vibrational modes over composites from -35% to 24% (Raman) and from -14% to 59% (FT-IR). The XPS results validate the presence of Si, O, and C in all composites, with significant variations in atomic proportions (C/Si and O/Si) and Si and C component analyses through deconvolution techniques. This study demonstrates the successful in situ synthesis of PDMS-SiO2 composites with tunable properties by controlling the sol-gel and crosslinking synthesis parameters. The findings provide valuable insights into the in situ synthesis methods of polymeric composite materials and their potential integration with polymer nanocomposite processing techniques.

Biocompatibility Evaluation of TiO2, Fe3O4, and TiO2/Fe3O4 Nanomaterials: Insights into Potential Toxic Effects in Erythrocytes and HepG2 Cells.

Nanomaterials such as titanium dioxide and magnetite are increasingly used in several fields, such as water remediation and agriculture. However, this has raised environmental concerns due to potential exposure to organisms like humans. Nanomaterials can cause adverse interactions depending on physicochemical characteristics, like size, morphology, and composition, when interacting with living beings. To ensure safe use and prevent the risk of exposure to nanomaterials, their biocompatibility must be assessed. In vitro cell cultures are beneficial for assessing nanomaterial-cell interactions due to their easy handling. The present study evaluated the biocompatibility of TiO2, Fe3O4, and TiO2/Fe3O4 nanomaterials thermally treated at 350 °C and 450 °C in erythrocytes and HepG2 cells. According to the hemolysis experiments, non-thermally treated NMs are toxic (>5% hemolysis), but their thermally treated counterparts do not present toxicity (<2%). This behavior indicates that the toxicity derives from some precursor (solvent or surfactant) used in the synthesis of the nanomaterials. All the thermally treated nanomaterials did not show hemolytic activity under different conditions, such as low-light exposure or the absence of blood plasma proteins. In contrast, non-thermally treated nanomaterials showed a high hemolytic behavior, which was reduced after the purification (washing and thermal treatment) of nanomaterials, indicating the presence of surfactant residue used during synthesis. An MTS cell viability assay shows that calcined nanomaterials do not reduce cell viability (>11%) during 24 h of exposure. On the other hand, a lactate dehydrogenase leakage assay resulted in a higher variability, indicating that several nanomaterials did not cause an increase in cell death as compared to the control. However, a holotomographic microscopy analysis reveals a high accumulation of nanomaterials in the cell structure at a low concentration (10 µg mL-1), altering cell morphology, which could lead to cell membrane damage and cell viability reduction.

Synthesis of TiO2-Cu2+/CuI Nanocomposites and Evaluation of Antifungal and Cytotoxic Activity.

Fungal infections have become a significant public health concern due to their increasing recurrence and harmful effects on plants, animals, and humans. Opportunistic pathogens (among others from the genera Candida and Aspergillus) can be present in indoor air, becoming a risk for people with suppressed immune systems. Engineered nanomaterials are novel alternatives to traditional antifungal therapy. In this work, copper(I) iodide (CuI) and a copper-doped titanium dioxide-copper(I) iodide (TiO2-Cu2+/CuI) composite nanomaterials (NMs)-were synthesized and tested as antifungal agents. The materials were synthesized using sol-gel (TiO2-Cu2+) and co-precipitation (CuI) techniques. The resulting colloids were evaluated as antifungal agents against Candida parapsilosis and Aspergillus niger strains. The NMs were characterized by XRD, HRTEM, AFM, and DLS to evaluate their physicochemical properties. The NMs present a high size dispersion and different geometrical shapes of agglomerates. The antifungal capacity of the NMs by the minimum inhibitory concentration (MIC) and minimum fungicidal concentration (MFC) was below 15 µg/mL against Candida parapsilosis and below 600 µg/mL against Aspergillus niger for both NMs. Holotomography microscopy showed that the NMs could penetrate cell membranes causing cell death through its rupture and reactive oxygen species (ROS) production. Cytotoxicity tests showed that NMs could be safe to use at low concentrations. The synthesized nanomaterials could be potential antifungal agents for biomedical or environmental applications.

PDMS/TiO2 and PDMS/SiO2 Nanocomposites: Mechanical Properties' Evaluation for Improved Insulating Coatings.

The use of nanoparticles (NPs) as reinforcements in polymeric coatings allows for direct interaction with the polymeric chains of the matrix, resulting in a synergistic process through physical (electrostatic forces) and chemical interactions (bond formation) for the improvement of the mechanical properties with relatively low weight concentrations of the NPs. In this investigation, different nanocomposite polymers were synthesized from the crosslinking reaction of the hydroxy-terminated polydimethylsiloxane elastomer. Different concentrations (0, 2, 4, 8, and 10 wt%) of TiO2 and SiO2 nanoparticles synthesized by the sol-gel method were added as reinforcing structures. The crystalline and morphological properties of the nanoparticles were determined through X-ray diffraction (XRD), Raman spectroscopy, and transmission electron microscopy (TEM). The molecular structure of coatings was through infrared spectroscopy (IR). The crosslinking, efficiency, hydrophobicity, and adhesion degree of the study groups were evaluated with gravimetric crosslinking tests, contact angle, and adhesion tests. It was observed that the crosslinking efficiency and surface adhesion properties of the different nanocomposites obtained were maintained. A slight increase in the contact angle was observed for the nanocomposites with 8 wt% compared to the polymer without reinforcements. The mechanical tests of indentation hardness and tensile strength following the ASTM E-384 and ISO 527 standards, respectively, were performed. As the nanoparticle concentration increased, a maximum increase of 157% in Vickers hardness, 71.4% in elastic modulus, and 80% in tensile strength was observed. However, the maximum elongation remained between 60 and 75%, ensuring that the composites did not become brittle.

Medicago sativa L. Plant Response against Possible Eustressors (Fe, Ag, Cu)-TiO2: Evaluation of Physiological Parameters, Total Phenol Content, and Flavonoid Quantification.

The present study analyzed Medicago sativa L. crops irrigated by TiO2 in the anatase phase and TiO2 doped with Ag, Fe, and Cu ions at 0.1%w synthesized using the sol-gel method (SG) and the sol-gel method coupled with microwave (Mw-SG). The materials were added to the irrigation water at different concentrations (50, 100, and 500 ppm). Stress induction by nanomaterials was observed by measuring stem morphology, chlorophyll index, total phenols and flavonoids, and antioxidant activity through the DPPH (2,2-diphenyl-1-picrylhydrazy) radical inhibition assay. The nanomaterial treatments caused statistically significant reductions in parameters such as stem length, leaf size, and chlorophyll index and increases in total phenol content and DPPH inhibition percentage. However, the observed effects did not show clear evidence regarding the type of nanomaterial used, its synthesis methodology, or a concentration-dependent response. By generally grouping the results obtained to the type of dopant used and the synthesis method, the relationship between them was determined employing a two-way ANOVA. It was observed that the dopant factors, synthesis, and interaction were relevant for most treatments. Additionally, the addition of microwaves in the synthesis method resulted in the largest number of treatments with a significant increase in the total content of phenols and the % inhibition compared to the traditional sol-gel synthesis. In contrast, parameters such as stem size and chlorophyll index were affected under different treatments from both synthesis methods.

Elicitation of Bacillus cereus-Amazcala (B.c-A) with SiO2 Nanoparticles Improves Its Role as a Plant Growth-Promoting Bacteria (PGPB) in Chili Pepper Plants.

Agriculture needs to decrease the use of agrochemicals due to their high toxicity and adopt new strategies to achieve sustainable food production. Therefore, nanoparticles (NPs) and plant growth-promoting bacteria (PGPB) have been proposed as viable strategies to obtain better crop yields with less environmental impact. Here, we describe the effect of silica nanoparticles (SiO2-NPs) on survival, antioxidant enzymatic activity, phosphate solubilization capacity, and gibberellin production of Bacillus cereus-Amazcala (B.c-A). Moreover, the effect of the co-application of SiO2-NPs and B.c-A on seed germination, physiological characteristics, and antioxidant enzymatic activity of chili pepper plants was investigated under greenhouse conditions. The results indicated that SiO2-NPs at 100 ppm enhanced the role of B.c-A as PGPB by increasing its phosphate solubilization capacity and the production of GA7. Moreover, B.c-A catalase (CAT) and superoxide dismutase (SOD) activities were increased with SiO2-NPs 100 ppm treatment, indicating that SiO2-NPs act as a eustressor, inducing defense-related responses. The co-application of SiO2-NPs 100 ppm and B.c-A improved chili pepper growth. There was an increase in seed germination percentage, plant height, number of leaves, and number and yield of fruits. There was also an increase in CAT and PAL activities in chili pepper plants, indicating that bacteria-NP treatment induces plant immunity.

Nanomaterials as an alternative to increase plant resistance to abiotic stresses.

The efficient use of natural resources without negative repercussions to the environment has encouraged the incursion of nanotechnology to provide viable alternatives in diverse areas, including crop management. Agriculture faces challenges due to the combination of different abiotic stresses where nanotechnology can contribute with promising applications. In this context, several studies report that the application of nanoparticles and nanomaterials positively affects crop productivity through different strategies such as green synthesis of nanoparticles, plant targeted protection through the application of nanoherbicides and nanofungicides, precise and constant supply of nutrients through nanofertilizers, and tolerance to abiotic stress (e.g., low or high temperatures, drought, salinity, low or high light intensities, UV-B, metals in soil) by several mechanisms such as activation of the antioxidant enzyme system that alleviates oxidative stress. Thus, the present review focuses on the benefits of NPs against these type of stress and their possible action mechanisms derived from the interaction between nanoparticles and plants, and their potential application for improving agricultural practices.

Green Synthesis via Eucalyptus globulus L. Extract of Ag-TiO2 Catalyst: Antimicrobial Activity Evaluation toward Water Disinfection Process.

The problem of water pollution by persistent substances and microorganisms requires solutions that materials such as silver-modified titanium dioxide can provide due to their excellent photocatalytic and antimicrobial properties. However, the synthesis methods conventionally used to obtain these materials involve toxic chemical reagents such as sodium borohydride (NaBH4). The search for alternative synthesis methods that use environmentally friendly substances, such as the biosynthesis method, was evaluated. Silver-titanium dioxide (Ag-TiO2) was synthesized by a Eucalyptus globulus L. extract as a reductive agent through sol-gel and microwave-assisted sol-gel processes. Four different solvents were tested to extract secondary metabolites to determine their roles in reducing silver nanoparticles. Titanium dioxide nanoparticles with sizes from 11 to 14 nm were obtained in the anatase phase, and no narrowing of the bandgap was observed (3.1-3.2 eV) for the Ag-TiO2 materials compared with the pure TiO2. Interestingly, the bacterial inhibition values were close to 100%, suggesting an effective antimicrobial mechanism related to the properties of silver. Finally, by the physicochemical characterization of the materials and their antimicrobial properties, it was possible to obtain a suitable biosynthesized Ag-TiO2 material as a green option for water disinfection that may be compared to the conventional methods.

Effect on plant growth parameters and secondary metabolite content of lettuce (Lactuca sativa L.), coriander (Coriandrum sativum), and chili pepper (Capsicum annuum L.) watered with disinfected water by Ag-TiO2 nanoparticles.

Nowadays, the use of different nanoscale structures has been introduced to a large number of research areas. One of these is the treatment and remediation of water through photocatalytic processes, seeking to reuse wastewater for agriculture. In this paper, Lactuca sativa, Coriandrum sativum, and Capsicum annuum were used as crop models to observe the effects in plant growth and the secondary metabolism of different water qualities and types used in the watering process. Initial results show that the photocatalytic process's water maintains a pH and ion concentration within the allowed limits, significantly reducing the number of bacteria. Along the growth process, an influence on germination times, appearance of true leaves, maturation, and fruit production depending on the type of water used is observed, obtaining the best results in both growth times and quantity of fruits, for the 50% and 70% disinfected water/tap water (DW/TAW) study groups. Secondary metabolites, such as phenols, flavonoids, and antioxidant activity, were studied to evaluate changes in the vegetables' composition, showing increased concentration for the disinfected water groups in most specimens. Additionally, no traces of metals and microorganisms were detected, concluding that the crops are viable to be consumed by human beings.

Nanoparticles in Agroindustry: Applications, Toxicity, Challenges, and Trends.

Nanotechnology is a tool that in the last decade has demonstrated multiple applications in several sectors, including agroindustry. There has been an advance in the development of nanoparticulated systems to be used as fertilizers, pesticides, herbicides, sensors, and quality stimulants, among other applications. The nanoencapsulation process not only protects the active ingredient but also can affect the diffusion, interaction, and activity. It is important to evaluate the negative aspects of the use of nanoparticles (NPs) in agriculture. Given the high impact of the nanoparticulated systems in the agro-industrial field, this review aims to address the effects of various nanomaterials on the morphology, metabolomics, and genetic modification of several crops.

Flowering phenology, growth forms, and pollination syndromes in tropical dry forest species: Influence of phylogeny and abiotic factors.

PREMISE OF THE STUDY: Analyses of the influence of temporal variation in abiotic factors on flowering phenology of tropical dry forest species have not considered the possible response of species with different growth forms and pollination syndromes, while controlling for phylogenetic relationships among species. Here, we investigated the relationship between flowering phenology, abiotic factors, and plant functional attributes, while controlling for phylogenetic relationship among species, in a dry forest community in Mexico. METHODS: We characterized flowering phenology (time and duration) and pollination syndromes of 55 tree species, 49 herbs, 24 shrubs, 15 lianas, and 11 vines. We tested the influence of pollination syndrome, growth form, and abiotic factors on flowering phenology using phylogenetic generalized least squares. KEY RESULTS: We found a relationship between flowering duration and time. Growth form was related to flowering time, and the pollination syndrome had a more significant relationship with flowering duration. Flowering time variation in the community was explained mainly by abiotic variables, without an important phylogenetic effect. Flowering time in lianas and trees was negatively and positively correlated with daylength, respectively. CONCLUSIONS: Functional attributes, environmental cues, and phylogeny interact with each other to shape the diversity of flowering patterns. Phenological differentiation among species groups revealed multiples strategies associated with growth form and pollination syndromes that can be important for understanding species coexistence in this highly diverse plant community.