In the synthesis of nanostructures by pulsed laser deposition (PLD), a crucial role is played by the environmental deposition pressure and the substrate temperature. Due to the high temperature of nanoparticles (NPs) at landing, other factors may determine the structure of the resulting aggregates. Here, Au and TiO2 nanostructures are obtained by non-thermal fs-PLD in ambient conditions. On Si(100), only TiO2 NPs form fractals with areas up to ~ 1 × 106 nm2, while on quartz Au NPs also form fractals with areas up to ~ 5 × 103 nm2, a much smaller size with respect to the TiO2 case. The aggregation is described by a simple diffusive model, taking into account isotropic diffusion of the NPs, allowing quantitative simulations of the NPs and fractal area. The results highlight the key role of substrate thermal conductivity in determining the formation of fractals.
For safety and environmental risk assessments of nanomaterials (NMs) and to provide essential toxicity data, nano-specific toxicities, or excess toxicities, of ZnO, CuO, and Ag nanoparticles (NPs) (20, 20, and 30 nm, respectively) to Escherichia coli and Saccharomyces cerevisiae in short-term (6 h) and long-term (48 h) bioassays were quantified based on a toxic ratio. ZnO NPs exhibited no nano-specific toxicities, reflecting similar toxicities as ZnO bulk particles (BPs) (as well as zinc salt). However, CuO and Ag NPs yielded distinctly nano-specific toxicities when compared with their BPs. According to their nano-specific toxicities, the capability of these NPs in eliciting hazardous effects on humans and the environment was as follows: CuO > Ag > ZnO NPs. Moreover, long-term bioassays were more sensitive to nano-specific toxicity than short-term bioassays. Overall, nano-specific toxicity is a meaningful measurement to evaluate the environmental risk of NPs. The log Teparticle value is a useful parameter for quantifying NP nano-specific toxicity and enabling comparisons of international toxicological data. Furthermore, this value could be used to determine the environmental risk of NPs.
The mesoporous biosilica with unique 3D hierarchy in/organic functional groups is attractive material in terms of interfacial phenomena, and its high biocompatibility accelerates development in biomedical devices. In addition, their benefits also play a fundamental role in antimicrobial assessment. We hypothesize that the Diadesmis gallica biosilica surface acts as a biotemplate for AgCl and Au nanoparticle (NP) biosynthesis. Moreover, it exhibits antibacterial action human pathogenic bacteria. Nanoparticle biosynthesis was performed via a pure environmental-friendly, static, bottom-up in vitro regime. Minimal inhibitory concentrations evaluated systems with bionanocomposites for antibacterial efficiency in temporal time-dose-dependency. TEM and XRD depicts a biosilica “local sphere” which affects formation, stabilization and encapsulation of crystalline Au (9–27 nm) and AgCl (3–51 nm) NPs in one simple step. FTIR analysis reveals various functional in/organic groups, including Si–OH and polyamides. While both metal-bionanoparticles have analogical spherical shape with determined aggregation, ICP-AES analysis determined more effective 5.29 wt% Au NP formation than 1 wt% AgCl NPs. MIC analysis confirms that bionanocomposite with AgCl by concentration 0.014 mg/mL has the most effective antibacterial system for gram-positive and gram-negative bacteria strains. Although dual effect of Au/AgCl NP bionanocomposite has almost analogical influence on gram-positive bacteria, the synergic-antagonistic effect is irrelevant in this instance.
Nano-octahedra of cobalt ferrite CoxFe3???xO4 (1?≤?x?<?2), with a broad size distribution around 15–20 nm, were synthesized by a hydrothermal method using nitrates as precursors. For the first time, single-phased nano-octahedra of cobalt-rich ferrite CoxFe3???xO4 (x?=?1.5) were synthesized. The nano-octahedra are crystallized in a normal spinel structure, with tetrahedral sites occupied by Co2+. This specific octahedral shape was obtained with anionic, cationic, and nonionic surfactants. The nature of the surfactant influenced the chemical composition of the powder and the size of the nano-octahedra. The {100} truncation of the octahedra is more pronounced for the small particles. For the first time, single-phased nanoparticles with as much as x?=?1.8 cobalt were synthesized with ethylene glycol as solvent. These nanoparticles, around 8 nm in size, have no specific shape and possess a lacunar spinel structure similar to maghemite. The samples were characterized by X-ray diffraction, transmission electron microscopy, and energy-dispersive spectroscopy.
In this study Pt, Re, and SnO2 nanoparticles (NPs) were combined in a controlled manner into binary and ternary combinations for a possible application for ethanol oxidation. For this purpose, zeta potentials as a function of the pH of the individual NPs solutions were measured. In order to successfully combine the NPs into Pt/SnO2 and Re/SnO2 NPs, the solutions were mixed together at a pH guaranteeing opposite zeta potentials of the metal and oxide NPs. The individually synthesized NPs and their binary/ternary combinations were characterized by Fourier transform infrared spectroscopy (FTIR) and scanning transmission electron microscopy (STEM) combined with energy dispersive X-ray spectroscopy (EDS) analysis. FTIR and XPS spectroscopy showed that the individually synthesized Pt and Re NPs are metallic and the Sn component was oxidized to SnO2. STEM showed that all NPs are well crystallized and the sizes of the Pt, Re, and SnO2 NPs were 2.2, 1.0, and 3.4 nm, respectively. Moreover, EDS analysis confirmed the successful formation of binary Pt/SnO2 and Re/SnO2 NP, as well as ternary Pt/Re/SnO2 NP combinations. This study shows that by controlling the zeta potential of individual metal and oxide NPs, it is possible to assemble them into binary and ternary combinations.
The rise in environmental issues due to the catalytic degradation of pollutants in water has received much attention. In this report, a facile method was developed for the generation of a novel thermosensitive Ag-decorated catalyst, SiO2@PNIPAM@Ag (the average particle size is around 540 nm), through atom transfer radical polymerization (ATRP) and mild reducing reactions. First, poly(N-isopropylacrylamide) (PNIPAM) was used to create a shell around mercapto-silica spheres that allowed for enhanced catalyst support dispersion into water. Second, through a mild reducing reaction, these Ag nanoparticles (NPs) were then anchored to the surface of SiO2@PNIPAM spheres. The resulting catalyst revealed catalytic activity to degrade various nitrobenzenes and organic dyes in an aqueous solution with sodium borohydride (NaBH4) at ambient temperature. The catalytic activity can be adjusted in different temperatures through the aggregation or dispersion of Ag catalyst on the polymer supporters, which is due to the thermosensitive PNIPAM shell. The ease of preparation and efficient catalytic activity of the catalyst can make it a promising candidate for the use in degrading organic pollutants for environmental remediation.
Water dispersible boron nanoparticles have great potential as materials for boron neutron capture therapy of cancer and magnetic resonance imaging, if they are prepared on a large scale with uniform size and shape and hydrophilic modifiable surface. We report the first method to prepare spherical, monodisperse, water dispersible boron core silica shell nanoparticles (B@SiO2 NPs) suitable for aforementioned biomedical applications. In this method, 40 nm elemental boron nanoparticles, easily prepared by mechanical milling and carrying 10-undecenoic acid surface ligands, are hydrosilylated using triethoxysilane, followed by base-catalyzed hydrolysis of tetraethoxysilane, which forms a 10-nm silica shell around the boron core. This simple two-step process converts irregularly shaped hydrophobic boron particles into the spherically shaped uniform nanoparticles. The B@SiO2 NPs are dispersible in water and the silica shell surface can be modified with primary amines that allow for the attachment of a fluorophore and, potentially, of targeting moieties.
The effects of oral intake of hydroxyapatite nanoparticles (HApNPs) were investigated on growth, development and behaviour of Drosophila. The Drosophila responses to various concentrations of HApNPs were compared. At lower concentrations, i.e. 5 mg L?1 more amount of oxidative stress was produced than that of highest concentration, i.e. 80 mg L?1. The increased amounts of oxidative stress reflect a higher amount of ROS production and increased cell damage within the larval gut. HApNPs was further shown to interfere with the calcium and phosphorus absorption pathway. Besides all these damage, HApNPs causes developmental delay in the late third instar larvae. The most significant anomaly was observed in pupae count, fly hatching after the feeding of HApNPs. Flies hatched from treated vials have decreased body weight with defective walking behaviour. Hatched flies have a phenotypic defect in the wing, eye and thorax of the bristles. Along with these changes, the adult fly becomes more prone towards stress. The findings hint that HApNPs persuade noxious effects and alter the development, structure, function and behaviour of the fly in a concentration-dependent manner.
Graphical abstract Effect of Hydroxyapatite on the complete life cycle of Drosophila. Flies lay eggs in Hydroxyapatite containing food. As soon as the eggs hatch to larvae they start eating the NP contained food. The effect of Hydroxyapatite on various developmental stage is summerised by biochemical, immunohistochemical, behavioral, developmental and phenotypic defects.
Despite advancements in treatment of infectious diseases, opportunistic pathogens continue to pose a worldwide threat. Identifying a source of infection/inflammation is often challenging which highlights the need of improved diagnostic agents. Using a model of local S. aureus infection, here we evaluated the potential of betamethasone or dexamethasone loaded in poly (lactic acid) nanoparticles and radiolabeled with 99mTc to detect an infection/inflammation site in vivo. A betamethasone and dexamethasone nanoparticles (NPs) with 200 and 220 nm in size, respectively, were created with a 98% 99mTc radiolabeling efficiency. When injected in infected mice, betamethasone NPs presented a higher accumulation in the infected hind paw in comparison with dexamethasone NPs. Our results suggest that this nanosystem may be a valid nanoradiopharmaceutical for the detection of inflammation/infection foci in vivo.
Protein complexes that mediate secretion and adhesion are located on the plasma membrane of pancreatic β cells. Neuroligins and their binding partners, the neurexins, are among these complexes. β cell maturation and physiologically regulated insulin secretion, as a response to high levels of blood glucose, are dependent on their three-dimensional (3D) arrangement. Both insulin secretion and the proliferation rates of β cells dramatically increase when β cells are co-cultured with clusters of a member of the neuroligin family: NL-2. A membranal protein, such as NL-2, has very limited drugability owing to its low biostability and bioavailability. Thus, based on in silico modeling, a short NL-2 peptide (HSA-28), which was able to mimic NL-2-positive effects on β cells, was designed, as we described in previous publication. However, the peptide was active only as a cluster, created by the covering the maghemite (γ-Fe2O3)-based nanoparticles (NPs) with limited biocompatibility. In this brief communication, we will show that conjugation of HSA-28 to biocompatible hydrogel NPs exhibits an impressive protective effect on INS-1E β cells under oxidative stress and induces their proliferation rate via augmentation of PDX1 nuclear translocation. The diameter of coated by the peptide NPs was 206?±?63 nm (DLS) and 114?±?27 nm (cryo-TEM). This significant change in size can be explained by the very hydrophilic character of the proteinoid NPs, inducing adsorption of many water molecules on their surface, which are accounted only by the DLS. The ability of biocompatible hydrogel NPs to prevent apoptosis and increase β cell mass might be used for developing novel β cell protective therapies.
Metal nanoparticles have been combined with magnet metal–organic frameworks (MOFs) to afford new materials that demonstrate an efficient catalytic degradation, high stability, and excellent reusability in areas of catalysis because of their exceptionally high surface areas and structural diversity. Magnetic MxOy@N-C (M = Fe, Co, Mn) nanocrystals were formed on nitrogen-doped carbon surface by using 8-hydroxyquinoline as a C/N precursor. The Co@N-C, MnO@N-C, and Fe/Fe2O3@N-C catalysts were characterized by X-ray diffraction (XRD), Raman, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), N2 adsorption/desorption, and X-ray photoelectron spectroscopy (XPS). The catalytic performances of catalysts were thoroughly investigated in the oxidation of aniline solution based on sulfate radicals (SO4?.) toward Fenton-like reaction. Magnetic MxOy@N-C exhibits an unexpectedly high catalytic activity in the degradation of aniline in water. A high magnetic MxOy@N-C catalytic activity was observed after the evaluation by aniline degradation in water. Aniline degradation was found to follow the first-order kinetics, and as a result, various metals significantly affected the structures and performances of the catalysts, and their catalytic activity followed the order of Co > Mn > Fe. The nanoparticles displayed good magnetic separation under the magnetic field.
Carbon-based nanoparticles (NPs) such as fullerenes and nanotubes have been extensively studied for drug delivery in recent years. The permeation process of fullerene and its derivative molecules through membrane is essential to the utilization of fullerene-based drug delivery system, but the mechanism and the dynamics of permeation through cell membrane are still unclear. In this study, coarse-grained molecular dynamics simulations were performed to investigate the permeation process of functionalized fullerene molecules (ca. 0.72 nm) through the membrane. Our results show that single functionalized fullerene molecule in such nanoscale could permeate the lipid membrane in micro-second time scale. Pristine C60 molecules prefer to aggregate into several small clusters while C60OH15 molecules could aggregate into one big cluster to permeate through the lipid membrane. After permeation of C60 or its derivatives into membrane, all C60 and C60OH15 molecules disaggregated and monodispersed in the lipid membrane.
Addition reaction between C60 and ethylenediamine occurred at room temperature in an ambient condition. C60-ethylenediamine adduct particles were prepared by mixing toluene solutions of C60 and ethyelenediamine. Average diameter of the C60-ethylenediamine adduct particles was changed non-linearly according to the reaction time, which were observed using transmission electron microscopy. Early stage of the reaction, the diameter of the adduct particles was changed from about 250 to about 430 nm. Then, the size of the adduct particles was converged to about 300 nm. During this addition reaction, the crystalline sizes of adduct particles were constant about 2–3 nm, regardless of the sizes of the adduct particles, which were determined by X-ray diffraction measurement.
Ligand-free palladium nanoparticles supported on multi-walled carbon nanotubes (Pd/MWCNT) were prepared by the supercritical carbon dioxide (scCO2) deposition method using a novel scCO2-soluble Pd organometallic complex as a precursor. The precursor with the perfluoroalkyl chain group was synthesized and identified by microanalytic methods. The deposition was carried out at the temperature of 363.15 K and pressure of 27.6 MPa CO2. The prepared metallic nanoparticles were obtained with an average size of 2 nm. Pd/MWCNT was utilized as a heterogeneous catalyst in Suzuki cross-coupling reaction. The nanocatalyst was found very effective in Suzuki reaction and it could also be recovered easily from the reaction media and reused over several cycles without significant loss of catalytic activity under mild conditions.
Graphical Abstract Pd/MWCNT was prepared by the scCO2 deposition method using a new synthesized perfluroalkylated vic-dioxime Pd complex as the precursor. The prepared nanoparticle was very effective as catalyst and reusable for Suzuki cross coupling reaction under mild conditions.
A facile and efficient one-pot method for the synthesis of well-dispersed hollow CuFe2O4 nanoparticles (H-CuFe2O4 NPs) in the presence of cellulose nanocrystals (CNC) as the support was described. Based on the one-pot solvothermal condition control, magnetic H-CuFe2O4 NPs were in-situ grown on the CNC surface uniformly. TEM images indicated good dispersity of H-CuFe2O4 NPs with uniform size of 300 nm. The catalytic activity of H-CuFe2O4/CNC was tested in the catalytic reduction of 4-nitrophenol (4-NP) in aqueous solution. Compared with most CNC-based ferrite catalysts, H-CuFe2O4/CNC catalyst exhibited an excellent catalytic activity toward the reduction of 4-NP. The catalytic performance of H-CuFe2O4/CNC catalyst was remarkably enhanced with the rate constant of 3.24 s?1 g?1, which was higher than H-CuFe2O4 NPs (0.50 s?1 g?1). The high catalytic activity was attributed to the introduction of CNC and the special hollow mesostructure of H-CuFe2O4 NPs. In addition, the H-CuFe2O4/CNC catalyst promised good conversion efficiency without significant decrease even after 10 cycles, confirming relatively high stability. Because of its environmental sustainability and magnetic separability, H-CuFe2O4/CNC catalyst was shown to indicate that the ferrite nanoparticles supported on CNC were acted as a promising catalyst and exhibited potential applications in numerous ferrite based catalytic reactions.
Carbon materials have attracted great attention in CO2 capture and energy storage due to their excellent characteristics such as tunable pore structure, modulated surface properties and superior bulk conductivities, etc. Biomass, provided by nature with non-toxic, widespread, abundant, and sustainable advantages, is considered to be a very promising precursor of carbons for the view of economic, environmental, and societal issues. However, the preparation of high-performance biomass-derived carbons is still a big challenge because of the multistep process for their synthesis and subsequent activation. Herein, hierarchically porous structured carbon materials have been prepared by directly carbonizing dried cauliflowers without any addition of agents and activation process, featuring with large specific surface area, hierarchically porous structure and improved pore volume, as well as suitable nitrogen content. Being used as a solid-state CO2 adsorbent, the obtained product exhibited a high CO2 adsorption capacity of 3.1 mmol g?1 under 1 bar and 25 °C and a remarkable reusability of 96.7% retention after 20 adsorption/regeneration cycles. Our study reveals that choosing a good biomass source was significant as the unique structure of precursor endows the carbonized product with abundant pores without the need of any post-treatment. Used as an electrode material in electrochemical capacitor, the non-activated porous carbon displayed a fairly high specific capacitance of 228.9 F g?1 at 0.5 A g?1 and an outstanding stability of 99.2% retention after 5000 cycles at 5 A g?1.
Graphical abstract Hierarchically porous structured carbon materials are prepared by directly carbonizing dried cauliflower without any agents and process of activation for high performance of CO2 capture and capacitor.
In this paper, the green synthesis of fluorescent carbon dots (CDs) via one-step hydrothermal treatment of cornstalk was investigated. This approach is facile, economical, and effective. The obtained CDs with an average diameter of 5.2 nm possess many excellent properties such as emitting blue fluorescence under UV light (365 nm), high monodispersity, good stability, excellent water dispersibility, and absolute quantum yield of 7.6%. Then, these CDs were used as sensing probes for the detection of Fe2+ and H2O2 with detection limits as low as 0.18 and 0.21 μM, respectively. This sensing platform shows advantages such as high selectivity, good precision, rapid operation, and avoiding the precipitation of iron oxyhydroxides.
Carbon-coated ZnFe2O4 spheres with sizes of ~110–180 nm anchored on graphene nanosheets (ZF@C/G) are successfully prepared and applied as anode materials for lithium ion batteries (LIBs). The obtained ZF@C/G presents an initial discharge capacity of 1235 mAh g?1 and maintains a reversible capacity of 775 mAh g?1 after 150 cycles at a current density of 500 mA g?1. After being tested at 2 A g?1 for 700 cycles, the capacity still retains 617 mAh g?1. The enhanced electrochemical performances can be attributed to the synergetic role of graphene and uniform carbon coating (~3–6 nm), which can inhibit the volume expansion, prevent the pulverization/aggregation upon prolonged cycling, and facilitate the electron transfer between carbon-coated ZnFe2O4 spheres. The electrochemical results suggest that the synthesized ZF@C/G nanostructures are promising electrode materials for high-performance lithium ion batteries.
In this study, comparative evaluation of fluorescent carbon nanodots (C-Dots) prepared using carob molasses was reported by screening various biocompatible macromolecules as passivating agent (PA). Incorporation of PAs with different molecular weight, polarity, and chemical structure was examined, and compared with the polyethylene glycol (PEG, Mn = 10 kN) passivated and pristine C-Dots. Not only the fluorescence properties but also many other features including size, crystal structure, colloidal conductivity, resistance to photobleaching, quantum yield, and UV-modulated surface interaction of them with the reactive oxygen species (ROS) as well as ROS production were investigated. Photoluminescence (PL) capacity of C-Dots was found to be associated with the number of surface alkyl groups and polymeric hydrogen bounding present on the C-Dot surface (increased number is associated with decreased PL) while surface conductivity of C-Dots in water was proportional to the PL intensity. More importantly, C-Dots with relatively poorer fluorescent were investigated in various organic solvents (hexane, methanol, acetone, ethanol, dimethylformamide (DMF), and DMSO). As happens with the fluorescent dyes, their PL intensities were significantly enhanced (even for pristine C-Dots) depending on the solvent characteristics. All of the C-Dots synthesized were further evaluated by means of UV-induced generation of ROS and inhibition of ROS by using H2O2 as model. In contrary to other carbonaceous nanomaterials, they did not show any ROS generation, on the contrary, they showed ROS scavenging activity that can be modulated by UV-irradiation (λexc = 365 nm). PEG and alginate passivated C-Dots inhibited H2O2 activity at LC50 values below 10 mg/mL.
This study describes the synthesis method of water-soluble, low-toxicity, photostable highly luminescent probes based on I–III–VI2 type semiconductor quantum dots (QDs) and the possibility of tumor targeting in living animals. Cd-free high-quality CuInS2/ZnS core/shell QDs were synthesized, and their surfaces were reacted with mercaptoundecanoic acid for aqueous phase transfer followed by reaction with glycol-chitosan; lastly, Arg-Gly-Asp (RGD) integrin-binding peptide was covalently attached for in vivo tumor targeting. Dowtherm A, a highly viscous heat-transfer organic fluid, was used to control semiconductor crystal growth at high temperature (>230 °C) during organic synthesis. The structural and optical properties of the resulting CuInS2/ZnS QDs were investigated. The average diameters of CuInS2 and CuInS2/ZnS QDs were 3.0 and 3.7 nm, respectively. Cell toxicity and in vivo tumor targetability in RR1022 cancer cell-xenografted mice were further evaluated using cRGDyk-tagged glycol-chitosan-coated CuInS2/ZnS QDs. Glycol-chitosan-coated MUA-QDs displayed a Z-average diameter of 203.8 ± 7.67 nm in water by dynamic light scattering.
