Biochemical and physiological alterations caused by Diuron and Triclosan in mussels (Mytilus galloprovincialis).

The rise in the utilization of pesticides within industrial and agricultural practices has been linked to the occurrence of these substances in aquatic environments. The objective of this work was to evaluate the uptake and adverse impacts of Diuron (Di) and Triclosan (TCS) on the mussel species Mytilus galloprovincialis. To accomplish this, the accumulation and toxicity of these pesticides were gauged following a brief period of exposure spanning 14 days, during which the mussels were subjected to two concentrations (50 and 100 µg/L) of each substance that are ecologically relevant. Chemical analysis of Di and TCS within gills and digestive gland showed that these pesticides could be accumulated in mussel's tissues. In addition, Di and TCS are preferably accumulated in digestive gland. Measured biomarkers included physiological parameters (filtration FC and respiration RC capacity), antioxidant enzyme activities (superoxide dismutase and catalase), oxidative damage indicator (Malondialdheyde concentration) and neurotoxicity level (acetylcholinesterase activity) were evaluated in gills and digestive glands. Both pesticides were capable of altering the physiology of this species by reducing the FC and RC in concentration and chemical dependent manner. Both pesticides induced also an oxidative imbalance causing oxidative stress. The high considered concentration exceeded the antioxidant defense capacity of the mussel and lead to membrane lipid peroxidation that resulted in cell damage. Finally, the two pesticides tested were capable of interacting with the neuromuscular barrier leading to neurotoxicity in mussel's tissues by inhibiting acetylcholinesterase. The ecotoxicological effect depended on the concentration and the chemical nature of the contaminant. Obtained results revealed also that the Di may exert toxic effects on M. galloprovincialis even at relatively low concentrations compared to TCS. In conclusion, this study presents innovative insights into the possible risks posed by Diuron (Di) and Triclosan (TCS) to the marine ecosystem. Moreover, it contributes essential data to the toxicological database necessary for developing proactive environmental protection measures.

Shape influence on the ultrafast plasmonic properties of gold nanoparticles.

The aim of shape-controlled colloidal synthesis of gold (Au) is to produce Au nanoparticles (NPs) with fine control of shapes, sizes, and dispersities. We show how transient absorption spectroscopy (TAS) can be used to rapidly and accurately quantify the vast ensemble of shapes of Au NPs in solution within minutes, including the synthesized nanorods, decahedra, and nanospheres. Colloidal solutions containing Au NPs were measured in TAS and their localized surface plasmon resonance (LSPR) modes were classified according to the shape, wavelength and number of peaks. Then their excited-state relaxation dynamics were used to ascertain their electron-phonon (e-ph) coupling time constant and frequency of optomechanical modes. TAS can quickly show that an Au nanosphere sample contains a tiny fraction of Au nanorods, whereas steady-state absorbance is totally blind to the presence of nanorods. Additionally, the TAS experiments indicate that the characteristic e-ph coupling time constants in Au nanorods depend on the NPs dimensions at high excitation intensity (> 6 µJ/cm2) which can help identify if there are any elongated Au NPs in Au spheres samples. Finally, optomechanical oscillations formed by NPs breathing modes were observed, providing information related to the average size and monodispersity of Au nanospheres and nanorods.

Synthesis of 3D Dendritic Gold Nanostructures Assisted by a Templated Growth Process: Application to the Detection of Traces of Molecules.

Complex architectures like 3D gold dendritic nanostructures were synthesized by an in situ templated growth method using a thin film of a block copolymer [polystyrene-b-poly(4-vinylpyridine)] deposited onto silicon substrates. The overall study has demonstrated the strong link between the morphology, size, and distribution of the structures and the synthetic physicochemical parameters, such as pH, reaction temperature, concentration, and nature of reactants. A nonequilibirum state of the medium has been required to create a fractal growth of the gold structures onto a prepatterned gold-seeded surface and has led to a better control of the structures' surface coverage rate. Those as-prepared nanodendrites have also exhibited high electrocatalytic activity toward a significant enhancement factor, as well as important sensitivity, thanks to tip effects. The electrochemical experiment results have demonstrated efficient adsorption and quantification of very low traces of specific molecules like glutathione or hexadecanethiol.

Channeling motion of gold nanospheres on a rippled glassed surface.

Gold nanospheres have been manipulated by atomic force microscopy on a rippled glass surface produced by ion beam sputtering and coated with an ultrathin (10 nm thick) graphitic layer. This substrate is characterized by irregular wavy grooves running parallel to a preferential direction. Measurements in ambient conditions show that the motion of the nanoparticles is confined to single grooves ('channels'), along which the particles move till they are trapped by local bottlenecks. At this point, the particles cross the ripple pattern in a series of consecutive jumps and continue their longitudinal motion along a different channel. Moreover, due to the asymmetric shape of the ripple profiles, the jumps occur in the direction of minimum slope, resembling a ratchet mechanism. Our results are discussed, extending a collisional model, which was recently developed for the manipulation of nanospheres on flat surfaces, to the specific geometry of this problem.

The pharmaceutical triclosan induced oxidative stress and physiological disorder in marine organism and nanoparticles as a potential mitigating tool.

Environmental research plays a crucial role in formulating novel approaches to pollution management and preservation of biodiversity. This study aims to assess the potential harm of pharmaceutical triclosan (TCS) to non-target aquatic organism, the mussel Mytilus galloprovincialis. Furthermore, our study investigates the potential effectiveness of TiO2 and ZnO nanomaterials (TiO2 NPs and ZnO NPs) in degrading TCS. To ascertain the morphology, structure, and stability of the nanomaterials, several chemical techniques were employed. To evaluate the impact of TCS, TiO2 NPs, and ZnO NPs, both physiological (filtration rate (FR) and respiration rate (RR)), antioxidant enzymes (superoxide dismutase (SOD), catalase (CAT), glutathione-S-transferase (GST)) activities and malondialdehyde (MDA) contents were measured in M. galloprovincialis gills and digestive gland. The mussel's responses varied depending on the contaminant, concentration, and organ, underscoring the significance of compiling these factors in ecotoxicity tests. The main toxic mechanisms of TCS and ZnO NPs at a concentration of 100 µg/L were likely to be a decrease in FR and RR, an increase in oxidative stress, and increased lipid peroxidation. Our findings indicate that a mixture of TCS and NPs has an antagonist effect on the gills and digestive gland. This effect is particularly notable in the case of TCS2 = 100 µg/L combined with TiO2 NP2 = 100 µg/L, which warrants further investigation to determine the underlying mechanism. Additionally, our results suggest that TiO2 NPs are more effective than ZnO NPs at degrading TCS, which may have practical implications for pharmaceutical control in marine ecosystems and in water purification plants. In summary, our study provides valuable information on the impact of pharmaceuticals on non-target organisms and sheds light on potential solutions for their removal from aqueous environments.

Doping zinc oxide and titanium dioxide nanoparticles with gold induces additional oxidative stress, membrane damage, and neurotoxicity in Mytilus galloprovincialis: Results from a laboratory bioassay.

BACKGROUND: While previous studies have provided insights into the effects of zinc oxide (ZnO) and titanium dioxide (TiO2) nanoparticles (NPs) on aquatic organisms, there is still a substantial amount of information lacking about the possible effects of their doped counterparts. The goal of the current work was to address this gap by examining Mytilus galloprovincialis reaction to exposure to doped and undoped nanoparticles. METHODS: Two concentrations (50 or 100 µg/L) of undoped ZnO and TiO2 NPs, as well as their gold (Au) doped counterparts, were applied on mussels for 14 days, and the effects on biomarkers activities in digestive glands and gills were assessed by spectrophotometry. RESULTS: The NPs were quasi-spherical in shape (below 100 nm), stable in seawater, and with no aggregation for both doped and undoped forms. Analytical results using inductively coupled plasma atomic emission spectroscopy indicated the uptake of NPs in mussels. Furthermore, it was found that biometal dyshomeostasis could occur following NP treatment and that doping the NPs aggravated this response. At the biochemical level, exposure to undoped NPs caused membrane damage, neurotoxic effect, and changes in the activities in the gills and digestive glands of superoxide dismutase, catalase, and glutathione-S-transferase, in a concentration and organ-dependent manner. CONCLUSION: Doping ZnO NPs and TiO2NPs with Au induced additional oxidative stress, membrane damage, and neurotoxicity in mussels.

Heat-induced morphological changes in silver nanowires deposited on a patterned silicon substrate.

Metallic nanowires (NWs) are sensitive to heat treatment and can split into shorter fragments within minutes at temperatures far below the melting point. This process can hinder the functioning of NW-based devices that are subject to relatively mild temperatures. Commonly, heat-induced fragmentation of NWs is attributed to the interplay between heat-enhanced diffusion and Rayleigh instability. In this work, we demonstrated that contact with the substrate plays an important role in the fragmentation process and can strongly affect the outcome of the heat treatment. We deposited silver NWs onto specially patterned silicon wafers so that some NWs were partially suspended over the holes in the substrate. Then, we performed a series of heat-treatment experiments and found that adhered and suspended parts of NWs behave differently under the heat treatment. Moreover, depending on the heat-treatment process, fragmentation in either adhered or suspended parts can dominate. Experiments were supported by finite element method and molecular dynamics simulations.

Smart Nematic Liquid Crystal Polymers for Micromachining Advances.

The miniaturization of tools is an important step in human evolution to create faster devices as well as precise micromachines. Studies around this topic have allowed the creation of small-scale objects capable of a wide range of deformation to achieve complex tasks. Molecular arrangements have been investigated through liquid crystal polymer (LCP) to program such a movement. Smart polymers and hereby liquid crystal matrices are materials of interest for their easy structuration properties and their response to external stimuli. However, up until very recently, their employment at the microscale was mainly limited to 2D structuration. Among the numerous issues, one concerns the ability to 3D structure the material while controlling the molecular orientation during the polymerization process. This review aims to report recent efforts focused on the microstructuration of LCP, in particular those dealing with 3D microfabrication via two-photon polymerization (TPP). Indeed, the latter has revolutionized the production of 3D complex micro-objects and is nowadays recognized as the gold standard for 3D micro-printing. After a short introduction highlighting the interest in micromachines, some basic principles of liquid crystals are recalled from the molecular aspect to their implementation. Finally, the possibilities offered by TPP as well as the way to monitor the motion into the fabricated microrobots are highlighted.

Comparative Study of Flax and Pineapple Leaf Fiber Reinforced Poly(butylene succinate): Effect of Fiber Content on Mechanical Properties.

In this study, we compare the reinforcing efficiency of pineapple leaf fiber (PALF) and cultivated flax fiber in unidirectional poly(butylene succinate) composites. Flax, known for robust mechanical properties, is contrasted with PALF, a less studied but potentially sustainable alternative. Short fibers (6 mm) were incorporated at 10 and 20% wt. levels. After two-roll mill mixing, uniaxially aligned prepreg sheets were compression molded into composites. At 10 wt.%, PALF and flax exhibited virtually the same stress-strain curve. Interestingly, PALF excelled at 20 wt.%, defying its inherently lower tensile properties compared to flax. PALF/PBS reached 70.7 MPa flexural strength, 2.0 GPa flexural modulus, and 107.3 °C heat distortion temperature. Comparable values for flax/PBS were 57.8 MPa, 1.7 GPa, and 103.7 °C. X-ray pole figures indicated similar matrix orientations in both composites. An analysis of extracted fibers revealed differences in breakage behavior. This study highlights the potential of PALF as a sustainable reinforcement option. Encouraging the use of PALF in high-performance bio-composites aligns with environmental goals.

Very High-Aspect-Ratio Polymeric Micropillars Made by Two-Photon Polymerization.

Polymeric micropillars with a high-aspect-ratio (HAR) are of interest for a wide range of applications, including drug delivery and the micro-electro-mechanical field. While molding is the most common method for fabricating HAR microstructures, it is affected by challenges related to demolding the final structure. In this study, we present very HAR micropillars using two-photon polymerization (TPP), an established technique for creating complex 3D microstructures. Polymeric micropillars with HARs fabricated by TPP often shrink and collapse during the development process. This is due to the lack of mechanical stability of micropillars against capillary forces primarily acting during the fabrication process when the solvent evaporates. Here, we report different parameters that have been optimized to overcome the capillary force. These include surface modification of the substrate, fabrication parameters such as laser power, exposure time, the pitch distance between the pillars, and the length of the pillars. On account of adopting these techniques, we were able to fabricate micropillars with a very HAR up to 80.

Synergistic Toughening of Epoxy Composite with Cellulose Nanofiber and Continuous Pineapple Leaf Fiber as Sustainable Reinforcements.

In this work, the effect of cellulose nanofiber (CNF) on the mechanical properties of long pineapple leaf fiber (PALF)-reinforced epoxy composites was investigated. The content of PALF was fixed at 20 wt.% and the CNF content was varied at 1, 3, and 5 wt.% of the epoxy matrix. The composites were prepared by hand lay-up method. Comparison was conducted between CNF-, PALF- and CNF-PALF-reinforced composites. It was found that the introduction of these small amounts of CNF into epoxy resin caused very small effects on flexural modulus and strength of neat epoxy. However, impact strength of epoxy with 1 wt.% CNF increased to about 115% that of neat epoxy, and, as the content of CNF increased to 3 and 5 wt.%, the impact strength decreased to that of neat epoxy. Observation of the fractured surface under electron microscope revealed the change in failure mechanism from a smooth surface to a much rougher surface. For epoxy containing 20 wt.% PALF, both flexural modulus and strength increased significantly to about 300% and 240% that of neat epoxy. The composite impact strength increased to about 700% that of the neat epoxy. For hybrid systems containing both CNF and PALF, there were few changes observed in both flexural modulus and strength compared to the PALF epoxy system. However, much improvement in impact strength was obtained. By using epoxy containing 1 wt.% CNF as the matrix, the impact strength increased to about 220% that of 20 wt.% PALF epoxy or 1520% that of neat epoxy. It thus could be deduced that the spectacular improvement in impact strength was due to the synergistic effect of CNF and PALF. The failure mechanism leading to the improvement in impact strength will be discussed.

Physiological Impairment and Biochemical Modifications Induced by Triclosan in Mediterranean Mussels.

The effects of pharmaceutical under aquatic biota are still not well established. In this investigation, we assessed the results of a common pharmaceutical's, triclosan (TCS), treatment on physiological and biochemical status of the Mediterranean mussels. Filtration and respiration rates were statistically reduced after treatment with highest considered concentration TCS2 = 100 µg·L-1. However, no modification (p > 0.05) was detected after treatment with TCS1 = 50 µg·L-1. For biochemical responses, oxidative stress parameters including H2O2 level and antioxidant enzymes were enhanced following concentration in considered organs. In parallel, Malondialdheyde content was measured in mussels after TCS treatment and lipid peroxidation occurred at high TCS concentration. Neurotoxicity evaluated by acetylcholinesterase (AChE) activity was induced in gills and digestive glands after exposure to TCS2. Overall, physiological impairment, oxidative stress, lipid peroxidation and neurotoxicity could be induced by triclosan in mussels. The association of physiological and biochemical biomarkers constitute a useful tool to measure the impact of pharmaceuticals in marine organism.

Metallic nanoparticles affect uptake of polycyclic aromatic hydrocarbons and impacts in the Mediterranean mussels Mytilus galloprovincialis.

The impact of metallic nanoparticles (NPs) on the uptake and toxicity of persistent organic pollutants by marine bivalves was assessed through a comparative laboratory study by exposing mussels to polycyclic aromatic hydrocarbon (PAHs), in the presence and absence of ZnO and TiO2 NPs. PAHs and NPs concentration was analyzed after 14 days of exposure in mussels by GC/MS and ICP/AES. Furthermore, impact on the physiology and neurotoxicity of PAHs and NPs acting alone or in mixtures were also determined. Our results confirmed the bio-uptake of PAHs and NPs by mussels. In addition, the exposure NPs-PAHs resulted in different bio-uptake profile to that of PAHs alone. The NPs and accumulation of PAHs led to disturbance of essential metals concentration and to different impact profiles in the filtration and respiration capacities as well as in the acetylcholinesterase activity. Antagonist interactions between NPs and PAHs could occur after exposure.

Sensitive Detection of SARS-CoV-2 Using a Novel Plasmonic Fiber Optic Biosensor Design.

The coronavirus (COVID-19) pandemic has put the entire world at risk and caused an economic downturn in most countries. This work provided theoretical insight into a novel fiber optic-based plasmonic biosensor that can be used for sensitive detection of SARS-CoV-2. The aim was always to achieve reliable, sensitive, and reproducible detection. The proposed configuration is based on Ag-Au alloy nanoparticle films covered with a layer of graphene which promotes the molecular adsorption and a thiol-tethered DNA layer as a ligand. Here, the combination of two recent approaches in a single configuration is very promising and can only lead to considerable improvement. We have theoretically analyzed the sensor performance in terms of sensitivity and resolution. To highlight the importance of the new configuration, a comparison was made with two other sensors. One is based on gold nanoparticles incorporated into a host medium; the other is composed of a bimetallic Ag-Au layer in the massive state. The numerical results obtained have been validated and show that the proposed configuration offers better sensitivity (7100 nm\RIU) and good resolution (figure of merit; FOM = 38.88 RIU - 1 and signal-to-noise ratio; SNR = 0.388). In addition, a parametric study was performed such as the graphene layers' number and the size of the nanoparticles.

Development of novel and ecological keratin/cellulose-based composites for absorption of oils and organic solvents.

Keratin/cellulose cryogels were successfully fabricated using chicken feathers (CF) and cardboard (C) from environmental waste for the first time, to be exploited in oil/solvent absorption. The keratin/cellulose-based composites were obtained by combining the dissolution of CF and C waste in 1-butyl-3-methylimidazolium chloride (Bmim-Cl+) ionic liquid green solvent via regeneration, simply by the freeze-drying method. The characterization analysis of the synthesized keratin/cellulose-based composites was performed using Fourier transform infrared spectrometry, X-ray diffractometry, scanning electron microscopy, and thermogravimetry. The as-prepared cryogel can absorb various oils and organic solvents. Moreover, its sorption capacity can reach up to 6.9-17.7 times the weight of the initial cryogel. This kind of CF/C cryogel revealed good and fast absorption efficiency. It could also be reused by simple absorption/distillation and absorption/desorption methods. Through the kinetic analysis, it was found that the pseudo-second-order model was more appropriate for the keratin/cellulose cryogel oil absorption process. Besides, owing to its low cost, good absorption capacity, and excellent reusability, this cryogel has potential for spill cleanup of oils and organic solvents.

Does the photocatalytic activity of nanoparticles protect the marine mussel Mytilus galloprovincialis from polycyclic aromatic hydrocarbon toxicity?

In the present study, five NPs (containing ZnO, Au-ZnO, Cu-ZnO, TiO2, and Au-TiO2) were characterized using dynamic light scattering and transmission electron microscopy, in order to observe their behavior under environmental change. The applicability of NPs for degradation of three polycyclic aromatic hydrocarbons (PAHs), including benzo(a)pyrene, fluoranthene, and benzanthracene, using UV irradiation showed the high photocatalytic efficiency of doped NPs for the removal of the study pollutants. To predict the environmental impact and interaction between NPs and PAHs on marine organisms, Mytilus galloprovincialis mussels were exposed to concentrations of each chemical (50 and 100 µg/L) for 14 days. The mussel's response was determined using the oxidative stress biomarker approach. Measured biomarkers in the mussel's digestive gland showed possible oxidative mechanisms in a concentration-dependent manner occurring after exposure to PAHs and NPs separately. Overall, this finding provides an interesting combination to remove PAHs in water, and the incorporation of chemical element into the crystallographic structure of NPs and the combination of two different NPs to form a binary hybrid NPs are promising materials.

Complex aggregation patterns in drying nanocolloidal suspensions: size matters when it comes to the thermomechanical stability of nanoparticle-based structures.

We report the results of a model study on the interrelation among the occurrence of complex aggregation patterns in drying nanofluids, the size of the constitutive nanoparticles (NPs), and the drying temperature, which is a critical issue in the genesis of complex drying patterns that was never systematically reported before. We show that one can achieve fine control over the occurrence and topological features of these drying-mediated complex structures through the combination of the particle size, the drying temperature, and the substrate surface energy. Most importantly, we show that a transition in the occurrence of the patterns appears with the temperature and the particle size, which accounts for the size dependence of the thermomechanical stability of the aggregates in the nanoscale range. Using simple phenomenological and scaling considerations, we showed that the thermomechanical stability of the aggregates was underpinned by physical quantities that scale with the size of the NPs (R) either as R(-2) or R(-3). These insights into the size-dependent dissipation mechanisms in nanoclusters should help in designing NPs-based structures with tailored thermomechanical and environmental stability and hence with an optimized morphological stability that guarantees their long-term functional properties.

Controlled manipulation of rigid nanorods by atomic force microscopy.

The motion of rigid nanorods caused by the normal vibrations of a nanotip rastering a flat surface is described within an original collisional model. Provided that the friction between the nanorods and the surface is sufficiently high, the direction of motion and the orientation of the nanorods are determined by two pairs of differential equations. In the limiting case of thin nanowires, the direction of motion is precisely related to the length of the nanowire, the tip radius and the density of the scan lines. At the same time the wire oscillates perpendicularly to this direction in a characteristic wobbling motion. Similar conclusions approximately hold also when the rod thickness is not negligible (compared to its length), as shown by a comparison between numerical solutions of our model and measurements on gold nanorods manipulated on a silicon oxide surface. Our results open the path to understanding and controlling the manipulation of arbitrarily shaped nanoparticles.

Synthesis of novel biocomposite powder for simultaneous removal of hazardous ciprofloxacin and methylene blue: Central composite design, kinetic and isotherm studies using Brouers-Sotolongo family models.

Over the past decades, extensive efforts have been made to use biomass-based-materials for wastewater-treatment. The first purpose of this study was to develop and characterize regenerated-reed/reed-charcoal (RR-ChR), an enhanced biosorbent from Tunisian-reed (Phragmites-australis). The second aim was to assess and optimize the RR-ChR use for the removal of binary ciprofloxacin antibiotic (CIP) and methylene blue dye (MB), using Central Composite Design under Response Surface methodology. The third purpose was to explain the mechanisms involved in the biosorption-process. The study revealed that the highest removal-percentages (76.66 % for the CIP and 100 % for the MB) were obtained under optimum conditions: 1.55 g/L of adsorbent, 35 mg/L of CIP, 75 mg/L of MB, a pH of 10.42 and 115.28 min contact time. It showed that the CIP biosorption mechanism was described by Brouers-Sotolongo-fractal model, with regression-coefficient (R2) of 0.9994 and a Person's Chi-square (X2) of 0.01. The Hill kinetic model better described the MB biosorption (R2 = 1 and X2 = 1.0E-4). The isotherm studies showed that the adsorbent surface was heterogeneous and the best nonlinear-fit was obtained with the Jovanovich (R2 = 0.9711), and Brouers-Sotolongo (R2 = 0.9723) models, for the CIP and MB adsorption, respectively. Finally, the RR-ChR lignocellulosic-biocomposite-powder could be adopted as efficient and cost-effective adsorbent.

The effect of heat treatment on the morphology and mobility of Au nanoparticles.

In the present paper, we investigate the effect of heat treatment on the geometry and mobility of Au nanoparticles (NPs) on a Si substrate. Chemically synthesized Au NPs of diameter ranging from 5 to 27 nm were annealed at 200, 400, 600 and 800 °C for 1 h. A change in the geometry from faceted to more rounded shapes were observed with increasing annealing temperature. Kinetic Monte Carlo simulations indicate that the NPs become rounded due to the minimization of the surface area and the transition to lower energy surface types {111} and {100}. The NPs were manipulated on a silica substrate with an atomic force microscope (AFM) in tapping mode. Initially, the NPs were immovable by AFM energy dissipation. However, annealed NPs became movable, and less energy was required to displace the NPs annealed at higher temperature. However, after annealing at 800 °C, the particles became immovable again. This effect was attributed to the diffusion of Au into the Si substrate and to the growth of the SiO2 layer.