Coupling of plasmonic nanoparticles on a semiconductor substrate via a modified discrete dipole approximation method.

Understanding the plasmonic coupling between a set of metallic nanoparticles (NPs) in a 2D array, and how a substrate affects such coupling, is fundamental for the development of optimized optoelectronic structures. Here, a simple semi-analytical procedure based on discrete dipole approximation (DDA) is reported to simulate the far-field and near-field properties of arrays of NPs, considering the coupling between particles, and the effect of the presence of a semiconductor substrate based on the image dipole approach. The method is validated for Ag NP dimers and single Ag NPs on a gallium nitride (GaN) substrate, a semiconductor widely used in optical devices, by comparison with the results obtained by the finite element method (FEM), indicating a good agreement in the weak coupling regime. Next, the method is applied to square and random arrays of Ag NPs on a GaN substrate. The increase in the surface density of NPs on a GaN substrate mainly results in a redshift of the dipolar resonance frequency and an increase in the near-field enhancement. This model, based on a single dipole approach, grants very low computational times, representing an advantage to predict the optical properties of large NP arrays on a semiconductor substrate for different applications.

Flexural strength of 3Y-TZP bioceramics obtained by direct write assembly as function of residual connected-porosity.

OBJECTIVES: The present work reports the effect of the extrusion nozzles' size and consequent residual porosity on the flexural strength of 3Y-TZP bioceramics fabricated by direct write assembly technology. METHODS: A printable ink containing a volume fraction of 45% of 3Y-TZP (ZrO2 stabilized with 3 mol% Y2O3) submicron powder, carboxymethyl cellulose and polyethyleneimine as additives was fine-tuned by rheological measurements. Different nozzle diameters (0.41 mm, 0.33 mm, and 0.25 mm) were used to print 3D specimens with proper dimensions for structural and mechanical characterization after sintering, namely relative density, linear shrinkage, and three-point flexural strength. Bulk surface sample and exposed fractured surfaces after flexural strength tests were analyzed by X-ray diffraction, Rietveld refinement and scanning electronic microscopy. Strength reliability and failure probability of the three sample groups were analyzed by Weibull statistics. RESULTS: The sintered samples exhibited relative densities in the range of 78% (nozzle Ø 0.41 = mm) and 82% (nozzle Ø 0.25 = mm), i.e., a slight increase in the residual interfilamentous porosity is observed, as the extrusion tip diameter increases, while linear shrinkage is statistically similar (≈25%). Likewise, a progressive reduction of flexural strength and Weibull modulus as nozzle diameter increases was noticeable, being respectively σf = 337,5 ± 49 MPa and m = 6.6 for the smallest nozzle diameter (Ø = 0.25 mm) and σf = 261.4 ± 79 MPa and m = 3.2 for the biggest one (Ø = 0.41 mm). Unlike nozzle diameter, the material is constituted by 79-81 wt% tetragonal t-ZrO2 and 19-21 wt% cubic c-ZrO2 with equiaxed grain sizes between 0.3 and 0.6 µm. CONCLUSION: X-ray diffraction analyses on the fracture surface of flexural test samples suggests that the toughening mechanism by tetragonal→ monoclinic phase transformation is the main responsible for the mechanical strength of this structural ceramic. Additionally, the reduction of flexural strength for samples printed with extrusion nozzle of 0.41 mm could be explained by the surface roughness of the bending surfaces, as well as the lower effective resistance to crack-propagation arising from the higher size of residual pores on the fracture surface.

Photodegradation of Aquaculture Antibiotics Using Carbon Dots-TiO2 Nanocomposites.

In this work, carbon dots (CD) were synthesized and coupled to titanium dioxide (TiO2) to improve the photodegradation of antibiotics in aquaculture effluents under solar irradiation. Oxolinic acid (OXA) and sulfadiazine (SDZ), which are widely used in aquaculture, were used as target antibiotics. To prepare nanocomposites of CD containing TiO2, two modes were used: in-situ (CD@TiO2) and ex-situ (CD/TiO2). For CD synthesis, citric acid and glycerol were used, while for TiO2 synthesis, titanium butoxide was the precursor. In ultrapure water (UW), CD@TiO2 and CD/TiO2 showed the largest photocatalytic effect for SDZ and OXA, respectively. Compared with their absence, the presence of CD@TiO2 increased the photodegradation of SDZ from 23 to 97% (after 4 h irradiation), whereas CD/TiO2 increased the OXA photodegradation from 22 to 59% (after 1 h irradiation). Meanwhile, in synthetic sea salts (SSS, 30‱, simulating marine aquaculture effluents), CD@TiO2 allowed for the reduction of SDZ's half-life time (t1/2) from 14.5 ± 0.7 h (in absence of photocatalyst) to 0.38 ± 0.04 h. Concerning OXA in SSS, the t1/2 remained the same either in the absence of a photocatalyst or in the presence of CD/TiO2 (3.5 ± 0.3 h and 3.9 ± 0.4 h, respectively). Overall, this study provided novel perspectives on the use of eco-friendly CD-TiO2 nanocomposites for the removal of antibiotics from aquaculture effluents using solar radiation.

Biochar-TiO2 magnetic nanocomposites for photocatalytic solar-driven removal of antibiotics from aquaculture effluents.

Contamination of surrounding waters with antibiotics by aquaculture effluents can be problematic due to the possible increase of bacterial resistance, making it crucial the efficient treatment of those effluents before their release into the environment. In this work, the application of waste-based magnetic biochar/titanium dioxide (BC/TiO2) composite materials on the photodegradation of two antibiotics widely used in aquaculture (sulfadiazine (SDZ) and oxolinic acid (OXA)) was assessed. Four materials were synthesized: BCMag (magnetized BC), BCMag_TiO2 (BCMag functionalized with TiO2), BC_TiO2_MagIn and BC_TiO2_MagEx (BC functionalized with TiO2 and afterwards magnetized by in-situ and ex-situ approaches, respectively). SDZ half-life time (t1/2) noticeably decreased 3.9 and 3.4 times in presence of BCMag_TiO2 and BC_TiO2_MagEx, respectively. In the case of OXA, even though differences were not so substantial, the produced photocatalysts also allowed for a decrease in t1/2 (2.6 and 1.7 times, in presence of BCMag_TiO2 and BC_TiO2_MagEx, respectively). Overall, the here synthesized BC/TiO2 magnetic nanocomposites through a circular economy process are promising photocatalysts for a sustainable solar-driven removal of antibiotics from aquaculture effluents.

Highly Electroconductive Nanopapers Based on Nanocellulose and Copper Nanowires: A New Generation of Flexible and Sustainable Electrical Materials.

Nowadays, the development of sustainable high-performance functional nanomaterials is in the spotlight. In this work, we report the preparation of a new generation of flexible and high electroconductive nanopapers based on nanofibrillated cellulose (NFC) and copper nanowires (CuNWs). Homogeneous red brick color nanopapers (thickness 30.2-36.4 µm) were obtained by mixing different amounts of NFC aqueous suspensions and CuNWs (1, 5, 10, 20, and 50 wt %), followed by vacuum filtration and drying. scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) analysis confirmed the incorporation of the different amounts of CuNWs, and their uniform and random distribution. All of the nanomaterials displayed good mechanical properties, viz., Young's modulus = 2.62-4.72 GPa, tensile strength = 30.2-70.6 MPa, and elongation at break = 2.3-4.1% for the nanopapers with 50 and 1 wt % of CuNWs mass fraction, respectively. The electrical conductivity of these materials strongly depends on the CuNW content, attaining a value of 5.43 × 104 S·m-1 for the nanopaper with a higher mass fraction. This is one of the highest values reported so far for nanocellulose-based conductive materials. Therefore, these nanopapers can be seen as an excellent inexpensive and green alternative to the current electroconductive materials for applications in electronic devices, energy storage, or sensors.

Biocompatible chitosan-based composites with properties suitable for hyperthermia therapy.

Sustainably made, flexible and biocompatible composites, having environmentally friendly compositions and multifunctional capabilities, are promising materials for several emerging biomedical applications. Here, the development of flexible and multifunctional chitosan-based bionanocomposites with a mixed reduced graphene oxide-iron oxide (rGO-Fe3-xO4) filler is described. The filler is prepared by one-pot synthesis, ensuring good dispersibility of the Fe3-xO4 nanoparticles and rGO within the chitosan matrix during solvent casting. The resulting bionanocomposites present superparamagnetic response at room temperature. The antioxidant activity is 9 times higher than that of pristine chitosan. The mechanical properties of the films can be tuned from elastic (∼8 MPa) chitosan films to stiff (∼285 MPa) bionanocomposite films with 50% filler. The magnetic hyperthermia tests showed a temperature increase of 40 °C in 45 s for the 50% rGO-Fe3-xO4 film. Furthermore, the composites have no cytotoxicity to the nontumorigenic (HaCat) cell line, which confirms their biocompatibility and highlights the potential of these materials for biomedical applications, such as hyperthermia treatments.

Conductive polysaccharides-based proton-exchange membranes for fuel cell applications: The case of bacterial cellulose and fucoidan.

Conductive natural-based separators for application in polymer electrolyte fuel cells (PEFCs) were fabricated by combining a bacterial polysaccharide, i.e. bacterial cellulose (BC), and an algae sulphated polysaccharide, i.e. fucoidan (Fuc). The diffusion of fucoidan aqueous solution containing a natural-based cross-linker, viz. tannic acid, into the wet BC nanofibrous three-dimensional network, followed by thermal cross-linking, originated fully bio-based proton exchange membranes (PEMs). The PEMs present thermal-oxidative stability in the range of 180-200 °C and good dynamic mechanical performance (storage modulus ≥ 460 MPa). Additionally, the BC/Fuc membranes exhibit protonic conductivity that increases with increasing relative humidity (RH), which is a typical feature for numerous water-mediated proton conductors. The traditional Arrhenius-type plots demonstrate a linear behaviour with a maximum protonic conductivity of 1.6 mS cm-1 at 94 °C and 98 % RH. The results showed that these fully bio-based conductive membranes have potential as eco-friendly alternatives to other PEMs for application in PEFCs.

Establishment of a brain cell line (FuB-1) from mummichog (Fundulus heteroclitus) and its application to fish virology, immunity and nanoplastics toxicology.

The marine fish mummichog (Fundulus heteroclitus), extensively used as research model, including in ecotoxicology, for over a century has been surpassed by other fish species. This fact may be associated with the lack of cell lines from this species, excellent models for the comprehension of fish physiology, immunology, toxicology and virology, that contribute to the reduction in the number of animals used in research. We have generated, for the first time, a brain-derived cell line from mummichog, FuB-1, and evaluated its application to the fields of fish virology, immunity and toxicology. First, FuB-1 cells show epithelial morphology and neural stem/astroglial origin. Secondly, FuB-1 cells effectively supports the replication of both spring viremia carp (SVCV) and infectious pancreatic necrosis (IPNV) viruses, but not nodavirus (NNV), indicating its potential use for fish virology. Related to this, FuB-1 cells infected with NNV up-regulate the transcription of genes related to the antiviral immune response, leading to cell resistance; while they are unaltered when infected with IPNV and SVCV, facilitating viral replication. Finally, FuB-1 cells were used for toxicological purposes and we demonstrated that exposure to either polystyrene nanoplastics (PS-100) or several human-usage pharmaceuticals are cytotoxic. Additionally, PS-100 particles increase the antioxidant catalase and glutathione S-transferase activities and decrease the total non-protein thiols in FuB-1 cells. However, PS-100 particles are able to reduce the cytotoxic effects induced by the pharmaceuticals. In conclusion, we have generated a cell line from mummichog, which might represent a valuable model for fish studies in the fields of virology, immunology and toxicology.

The effects of nanoplastics on marine plankton: A case study with polymethylmethacrylate.

Marine biota is currently exposed to plastic pollution. The biological effects of plastics may vary according to polymer types (e.g. polystyrene, polyethylene, acrylate), size of particles (macro, micro or nanoparticles) and their shape. There is a considerable lack of knowledge in terms of effects of nanoplastics (NP) to marine biota particularly of polymers like polymethylmethacrylate (PMMA). Thus, this study aimed to assess its ecotoxicological effects using a battery of standard monospecific bioassays with four marine microalgae (Tetraselmis chuii, Nannochloropsis gaditana, Isochrysis galbana and Thalassiosira weissflogii) and a marine rotifer species (Brachionus plicatilis). The tested PMMA-NP concentrations allowed the estimation of median effect concentrations for all microalgae species. T. weissflogii and T. chuii were respectively the most sensitive (EC50,96h of 83.75 mg/L) and least sensitive species (EC50,96h of 132.52 mg/L). The PMMA-NP were also able to induce mortality in rotifers at concentrations higher than 4.69 mg/L with an estimated 48 h median lethal concentration of 13.27 mg/L. A species sensitivity distribution curve (SSD), constructed based on data available in the literature and the data obtained in this study, reveal that PMMA-NP appears as less harmful to marine biota than other polymers like polystyrene.

Polystyrene nanoplastics alter the cytotoxicity of human pharmaceuticals on marine fish cell lines.

There is an increasing concern on the consequences of the presence of micro(nano)plastics to marine organisms. The present study aimed to provide information on the effects of polystyrene nanoplastics (PSNPs) to fish cells alone and combined with human pharmaceuticals, other emerging contaminants, using as biological models marine fish cell lines SAF-1 and DLB-1. Cells were exposed for 24 h to 100 nm PSNPs, starting at 0.001 up to 10 mg/L, to assess effects on viability and activity of catalase (antioxidant defense) and glutathione S-transferases (phase II biotransformation and antioxidant defense). The viability of cells was also evaluated after exposure to human pharmaceuticals alone and combined with PSNPs. Overall, PSNPs failed to be cytotoxic but data proved their ability to alter the toxicity of human pharmaceuticals. DLB-1 was the most sensitive cell line to PSNPs. Data support the use of marine fish cell lines in the study of the effects of micro(nano)plastics.

Tuning lysozyme nanofibers dimensions using deep eutectic solvents for improved reinforcement ability.

Deep eutectic solvents (DESs), a novel generation of solvents, have recently been described as efficient and timesaving fibrillation agents for proteins. In this context, the present work aims at assessing the effect of the hydrogen bond donor (HBD) of cholinium chloride ([Ch]Cl):carboxylic acid based DESs on the dimensions (length and width) of lysozyme nanofibers (LNFs). Mono-, di- and tri-carboxylic acids (acetic, lactic, levulinic, malic and citric acids) were used to prepare different DES formulations, which were successfully used on the fibrillation of lysozyme. The results showed that the carboxylic acid (i.e. the HBD) plays an important role on the fibrillation efficiency and on the length of the ensuing LNFs with aspect-ratios always higher than those obtained by fibrillation with [Ch]Cl. The longest LNFs were obtained using lactic acid as the HBD with an average length of 1004 ±â€¯334 nm and width of 31.8 ±â€¯6.8 nm, and thus an aspect-ratio of ca. 32. The potential of these protein nanofibers as reinforcing additives was evaluated by preparing pullulan (PL)-based nanocomposite films containing 5% LNFs with different aspect-ratios, resulting in highly homogenous and transparent films with improved mechanical performance.

Applying differential dynamic logic to reconfigurable biological networks.

Qualitative and quantitative modeling frameworks are widely used for analysis of biological regulatory networks, the former giving a preliminary overview of the system's global dynamics and the latter providing more detailed solutions. Another approach is to model biological regulatory networks as hybrid systems, i.e., systems which can display both continuous and discrete dynamic behaviors. Actually, the development of synthetic biology has shown that this is a suitable way to think about biological systems, which can often be constructed as networks with discrete controllers, and present hybrid behaviors. In this paper we discuss this approach as a special case of the reconfigurability paradigm, well studied in Computer Science (CS). In CS there are well developed computational tools to reason about hybrid systems. We argue that it is worth applying such tools in a biological context. One interesting tool is differential dynamic logic (dL), which has recently been developed by Platzer and applied to many case-studies. In this paper we discuss some simple examples of biological regulatory networks to illustrate how dL can be used as an alternative, or also as a complement to methods already used.

Timesaving microwave assisted synthesis of insulin amyloid fibrils with enhanced nanofiber aspect ratio.

Insulin amyloid fibrils with enhanced aspect ratio, were prepared using a timesaving microwave assisted (MW) methodology, reducing the incubation time from 13 to 2h. The fibrillation process was followed indirectly by Thioflavin T Fluorescence and UV-vis analysis, by measuring the amount of ß-sheets formed and the insulin present in solution, respectively. TEM and AFM analysis revealed that the insulin fibrils obtained through the MW method, have very similar lengths but are much thinner than the ones obtained using the conventional method (CM). Additionally, it was verified that the nature of the peptides present in the final insulin fibrils was not affected by microwave irradiation. These morphological differences might reflect on noticeably enhanced mechanical and optical properties that can exploited on the development of advanced bionanomaterials.

Shaping gold nanocomposites with tunable optical properties.

We report the synthesis of morphological uniform composites using miniemulsions of poly(tert-butyl acrylate) or poly(styrene) containing organically capped gold nanocrystals (NCs). The optical features of such hybrid structures are dominated by plasmonic effects and depend critically on the morphology of the resulting nanocomposite. In particular, we demonstrate the ability to tune the overall optical response in the visible spectral region by varying the Au NCs arrangement within the polymer matrix, and therefore the interparticle plasmon coupling, using Au NCs resulting from the same batch of synthesis. This is a consequence of two well-known effects on the optical properties of Au particles: the variation of the surrounding dielectric refractive index and interparticle plasmonic coupling. The research reported here shows a general strategy to produce optical responsive nanocomposites via control of the morphology of submicrometric polymer particles containing metal nanocrystals and thus is an alternative to the more common strategy of size tuning metal nanoparticles used as nanofillers.

From single-molecule precursors to hybrid ZnS nanostructures.

A series of coordination compounds containing [Zn(amine)]2+ cationic complexes and alkyldithiocarbamates (RR'dtc-), as counter anions, are reported here: [Zn(amine)x][RR'dtc]2, where amine = ethylenediamine (en), diethylenetriamine (dien), 1,2-diaminopropane (dap) and, R,R' = ethyl (Et); butyl (Bu) and methyl (Me), hexyl (Hex). Hybrid nanoplates composed of hexagonal-ZnS nanoparticles and organic components were obtained after solution phase thermolysis of such precursors in oleylamine. These hybrid materials show quantum confinement effects in their optical spectra and convert into cubic-ZnS after further thermal treatment.

Photoluminescent, transparent and flexible di-ureasil hybrids containing CdSe/ZnS quantum dots.

We describe, in this paper, the sol-gel synthesis of di-ureasil based nanocomposites prepared in situ in the presence of organically capped CdSe quantum dots (QDs) or CdSe QDs which have been coated with a ZnS shell. For the latter a new chemical route to coat the CdSe QDs with ZnS shells was investigated and is now reported. The QDs became well dispersed in the final nanocomposites, whose microstructural homogeneity was evaluated by atomic force microscopy (AFM) and transmission electron microscopy (TEM) analyses. In order to understand the optical behaviour of di-ureasil containing QDs, a detailed photoluminescent study was undertaken for a selected particle size distribution of ZnS coated CdSe QDs (d∼4.5 nm). Emission quantum yields up to 0.11 were measured in the final nanocomposites that present a huge (between 3 and 6 orders of magnitude) increase in the lifetime of the QDs (relative to that of isolated ones), as a result of energy transfer occurring between the intimately mixed di-ureasil host and the QDs.

Hydroxyapatite micro- and nanoparticles: nucleation and growth mechanisms in the presence of citrate species.

Hydroxyapatite (HAP) particles with different morphologies were precipitated from homogeneous calcium/citrate/phosphate solutions at physiological temperature. Small variations of the starting solution pH in the range 7.4

Electrostatic assembly and growth of gold nanoparticles in cellulosic fibres.

Synthetic studies of nanocomposites containing gold nanoparticles attached onto wood or bacterial cellulosic fibres have been performed in situ in the presence of the fibres or by polyelectrolyte-assisted deposition. The optical properties of the final nanocomposites could be tailored not only by the starting Au nanoparticles characteristics but also by the preparative method associated to the type of cellulosic fibres used as the substrate. Thus, gold nanoparticles assembled or generated in situ within cellulosic fibres, are excellent components for long term optical and chemically stable nanocomposites, which appear particularly interesting for security paper applications.