Showing papers in "Journal of Nanoparticle Research in 2017"

The role of tannic acid and sodium citrate in the synthesis of silver nanoparticles.

Abstract: We describe herein the significance of a sodium citrate and tannic acid mixture in the synthesis of spherical silver nanoparticles (AgNPs). Monodisperse AgNPs were synthesized via reduction of silver nitrate using a mixture of two chemical agents: sodium citrate and tannic acid. The shape, size and size distribution of silver particles were determined by UV-Vis spectroscopy, dynamic light scattering (DLS) and scanning transmission electron microscopy (STEM). Special attention is given to understanding and experimentally confirming the exact role of the reagents (sodium citrate and tannic acid present in the reaction mixture) in AgNP synthesis. The oxidation and reduction potentials of silver, tannic acid and sodium citrate in their mixtures were determined using cyclic voltammetry. Possible structures of tannic acid and its adducts with citric acid were investigated in aqueous solution by performing computer simulations in conjunction with the semi-empirical PM7 method. The lowest energy structures found from the preliminary conformational search are shown, and the strength of the interaction between the two molecules was calculated. The compounds present on the surface of the AgNPs were identified using FT-IR spectroscopy, and the results are compared with the IR spectrum of tannic acid theoretically calculated using PM6 and PM7 methods. The obtained results clearly indicate that the combined use of sodium citrate and tannic acid produces monodisperse spherical AgNPs, as it allows control of the nucleation, growth and stabilization of the synthesis process. Graphical abstractᅟ.

Reliable nanomaterial classification of powders using the volume-specific surface area method

Abstract: The volume-specific surface area (VSSA) of a particulate material is one of two apparently very different metrics recommended by the European Commission for a definition of "nanomaterial" for regulatory purposes: specifically, the VSSA metric may classify nanomaterials and non-nanomaterials differently than the median size in number metrics, depending on the chemical composition, size, polydispersity, shape, porosity, and aggregation of the particles in the powder. Here we evaluate the extent of agreement between classification by electron microscopy (EM) and classification by VSSA on a large set of diverse particulate substances that represent all the anticipated challenges except mixtures of different substances. EM and VSSA are determined in multiple labs to assess also the level of reproducibility. Based on the results obtained on highly characterized benchmark materials from the NanoDefine EU FP7 project, we derive a tiered screening strategy for the purpose of implementing the definition of nanomaterials. We finally apply the screening strategy to further industrial materials, which were classified correctly and left only borderline cases for EM. On platelet-shaped nanomaterials, VSSA is essential to prevent false-negative classification by EM. On porous materials, approaches involving extended adsorption isotherms prevent false positive classification by VSSA. We find no false negatives by VSSA, neither in Tier 1 nor in Tier 2, despite real-world industrial polydispersity and diverse composition, shape, and coatings. The VSSA screening strategy is recommended for inclusion in a technical guidance for the implementation of the definition. Graphical abstractWe evaluate the extent of agreement between classification by electron microscopy (EM) and classification by Volume-Specific Surface Area (VSSA) on a large set of diverse particulate substances. These represent the challenges anticipated for identification of nanomaterials by the European Commission recommendation for a definition of nanomaterials for regulatory purposes.

Agglomeration, colloidal stability, and magnetic separation of magnetic nanoparticles: collective influences on environmental engineering applications

Abstract: Magnetic nanoparticles (MNPs) which exhibit magnetic and catalytic bifunctionalities have been widely accepted as one of the most promising nanoagents used in water purification processes. However, due to the magnetic dipole-dipole interaction, MNPs can easily lose their colloidal stability and tend to agglomerate. Thus, it is necessary to enhance their colloidal stability in order to maintain the desired high specific surface area. Meanwhile, in order to successfully utilize MNPs for environmental engineering applications, an effective magnetic separation technology has to be developed. This step is to ensure the MNPs that have been used for pollutant removal can be fully reharvested back. Unfortunately, it was recently highlighted that there exists a conflicting role between colloidal stability and magnetic separability of the MNPs, whereby the more colloidally stable the particle is, the harder for it to be magnetically separated. In other words, attaining a win-win scenario in which the MNPs possess both good colloidal stability and fast magnetic separation rate becomes challenging. Such phenomenon has to be thoroughly understood as the colloidal stability and the magnetic separability of MNPs play a pivotal role on affecting their effective implementation in water purification processes. Accordingly, it is the aim of this paper to provide reviews on (i) the colloidal stability and (ii) the magnetic separation of MNPs, as well as to provide insights on (iii) their conflicting relationship based on recent research findings.

Synthesis and characterization of silver nanoparticles from (bis)alkylamine silver carboxylate precursors

Abstract: A comparative study of amine and silver carboxylate adducts [R1COOAg-2(R2NH2)] (R1 = 1, 7, 11; R2 = 8, 12) as a key intermediate in NPs synthesis is carried out via differential scanning calorimetry, solid-state FT-infrared spectroscopy, 13C CP MAS NMR, powder X-ray diffraction and X-ray photoelectron spectroscopy, and various solution NMR spectroscopies (1H and 13C NMR, pulsed field gradient spin-echo NMR, and ROESY). It is proposed that carboxyl moieties in the presence of amine ligands are bound to silver ions via chelating bidentate type of coordination as opposed to bridging bidentate coordination of pure silver carboxylates resulting from the formation of dimeric units. All complexes are packed as lamellar bilayer structures. Silver carboxylate/amine complexes show one first-order melting transition. The evidence presented in this study shows that phase behavior of monovalent metal carboxylates are controlled, mainly, by head group bonding. In solution, insoluble silver salt is stabilized by amine molecules which exist in dynamic equilibrium. Using (bis)amine-silver carboxylate complex as precursor, silver nanoparticles were fabricated. During high-temperature thermolysis, the (bis)amine-carboxylate adduct decomposes to produce silver nanoparticles of small size. NPs are stabilized by strongly interacting carboxylate and trace amounts of amine derived from the silver precursor interacting with carboxylic acid. A corresponding aliphatic amide obtained from silver precursor at high-temperature reaction conditions is not taking part in the stabilization. Combining NMR techniques with FTIR, it was possible to follow an original stabilization mechanism.

Effect of the size of silver nanoparticles on SERS signal enhancement

Abstract: The localized surface plasmon resonance arising from plasmonic materials is beneficial in solution-based and thin-film sensing applications, which increase the sensitivity of the analyte being tested. Silver nanoparticles from 35 to 65 nm in diameter were synthesized using a low-temperature method and deposited in a monolayer on a (3-aminopropyl)triethoxysilane (APTES)-functionalized glass slide. The effect of particle size on monolayer structure, optical behavior, and surface-enhanced Raman scattering (SERS) is studied. While increasing particle size decreases particle coverage, it also changes the localized surface plasmon resonance and thus the SERS activity of individual nanoparticles. Using a laser excitation wavelength of 633 nm, the stronger localized surface plasmon resonance coupling to this excitation wavelength at larger particle sizes trumps the loss in surface coverage, and greater SERS signals are observed. The SERS signal enhancement accounts for the higher SERS signal, which was verified using a finite element model of a silver nanoparticle dimer with various nanoparticle sizes and separation distances.

Green synthesis of fluorescent carbon dots for sensitive detection of Fe 2+ and hydrogen peroxide

Abstract: 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.

Validation of a particle tracking analysis method for the size determination of nano- and microparticles.

Abstract: Particle tracking analysis (PTA) is an emerging technique suitable for size analysis of particles with external dimensions in the nano- and sub-micrometre scale range. Only limited attempts have so far been made to investigate and quantify the performance of the PTA method for particle size analysis. This article presents the results of a validation study during which selected colloidal silica and polystyrene latex reference materials with particle sizes in the range of 20 nm to 200 nm were analysed with NS500 and LM10-HSBF NanoSight instruments and video analysis software NTA 2.3 and NTA 3.0. Key performance characteristics such as working range, linearity, limit of detection, limit of quantification, sensitivity, robustness, precision and trueness were examined according to recommendations proposed by EURACHEM. A model for measurement uncertainty estimation following the principles described in ISO/IEC Guide 98-3 was used for quantifying random and systematic variations. For nominal 50 nm and 100 nm polystyrene and a nominal 80 nm silica reference materials, the relative expanded measurement uncertainties for the three measurands of interest, being the mode, median and arithmetic mean of the number-weighted particle size distribution, varied from about 10% to 12%. For the nominal 50 nm polystyrene material, the relative expanded uncertainty of the arithmetic mean of the particle size distributions increased up to 18% which was due to the presence of agglomerates. Data analysis was performed with software NTA 2.3 and NTA 3.0. The latter showed to be superior in terms of sensitivity and resolution.

Adsorption and photocatalytic degradation of methylene blue using high surface area titanate nanotubes (TNT) synthesized via hydrothermal method

Abstract: Removal of methylene blue (MB) via adsorption and photocatalysis using titanate nanotubes (TNTs) with different surface areas were investigated and compared to commercial titanium dioxide (TiO2) P25 Degussa nanoparticles. The TNTs with surface area ranging from 20 m2/g to 200 m2/g were synthesized via hydrothermal method with different reaction times. TEM imaging confirmed the tubular structure of TNT while XRD spectra indicated all TNTs exhibited anatase crystallinity. Batch adsorption rate showed linearity with surface properties of TNTs, where materials with higher surface area showed higher adsorption rate. The highest MB adsorption (70%) was achieved by TNT24 in 60 min whereas commercial TiO2 exhibited the lowest adsorption of only 10% after 240 min. Adsorption isotherm studies indicated that adsorption using TNT is better fitted into Langmuir adsorption isotherm than Freundlich isotherm model. Furthermore, TNT24 was able to perform up to 90% removal of MB within 120 min, demonstrating performance that is 2-fold better compared to commercial TiO2. The high surface area and surface Bronsted acidity are the main reasons for the improvement in MB removal performance exhibited by TNT24. The improvement in surface acidity enhanced the adsorption properties of all the nanotubes prepared in this study.

A toxicity assessment of hydroxyapatite nanoparticles on development and behaviour of Drosophila melanogaster

Abstract: 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.

Facile hydrothermal synthesis and characterization of cesium-doped PbI 2 nanostructures for optoelectronic, radiation detection and photocatalytic applications

Abstract: Low-temperature hydrothermal-assisted synthesis of pure and cesium (Cs) (1, 3, 5, 7 and 10 wt%) doped lead iodide (PbI2) nanorods and nanosheets have been achieved successfully for the first time. The structural and vibrational studies confirm the formation of a 2H-polytypic PbI2 predominantly. Scanning electron microscope analysis confirms the formation of well-aligned nanorods of average size ~ 100 nm at low concentration and nanosheets of average thicknesses in the range of ~ 20–40 nm at higher concentrations of Cs doping. The presence of Cs doping was confirmed by energy dispersive X-ray study. Ultra-violet-visible absorbance spectra were recorded, and energy gap was calculated in the range of 3.33 to 3.45 eV for pure and Cs-doped PbI2 nanostructures which is higher than the bulk value (i.e., ~ 2.27 eV) due to quantum confinement effect. Dielectric constant, loss, and AC conductivity studies have been done. Enhancement in Gamma linear absorption coefficient due to Cs doping confirms the suitability of prepared nanostructures for radiation detection applications. Furthermore, the photocatalytic performance of the synthesized nanostructures was evaluated in the decolorization of methyl green (MG) and methyl orange (MO) under the illumination of visible light (λ > 420 nm). The observed photocatalytic activity for 5 and 7 wt% Cs-doped PbI2 was observed to be more than pure PbI2 and also > 10 times higher than the commercially available photocatalysts. The results suggest that the prepared nanostructures are highly applicable in optoelectronic, radiation detection and many other applications.

Amine functionalized magnetic nanoparticles for removal of oil droplets from produced water and accelerated magnetic separation

Abstract: Magnetic nanoparticles (MNPs) with surface coatings designed for water treatment, in particular for targeted removal of contaminants from produced water in oil fields, have drawn considerable attention due to their environmental merit. The goal of this study was to develop an efficient method of removing very stable, micron-scale oil droplets dispersed in oilfield produced water. We synthesized MNPs in the laboratory with a prescribed surface coating. The MNPs were superparamagnetic magnetite, and the hydrodynamic size of amine functionalized MNPs ranges from 21 to 255 nm with an average size of 66 nm. The initial oil content of 0.25 wt.% was reduced by as much as 99.9% in separated water. The electrostatic attraction between negatively charged oil-in-water emulsions and positively charged MNPs controls, the attachment of MNPs to the droplet surface, and the subsequent aggregation of the electrically neutral oil droplets with attached MNPs (MNPs-oils) play a critical role in accelerated and efficient magnetic separation. The total magnetic separation time was dramatically reduced to as short as 1 s after MNPs, and oil droplets were mixed, in contrast with the case of free, individual MNPs with which separation took about 36∼72 h, depending on the MNP concentrations. Model calculations of magnetic separation velocity, accounting for the MNP magnetization and viscous drag, show that the total magnetic separation time will be approximately 5 min or less, when the size of the MNPs-oils is greater than 360 nm, which can be used as an optimum operating condition.

Theranostic multimodal potential of magnetic nanoparticles actuated by non-heating low frequency magnetic field in the new-generation nanomedicine

Abstract: The scope of this review involves one of the most promising branches of new-generation biomedicine, namely magnetic nanotheranostics using remote control of functionalized magnetic nanoparticles (f-MNPs) by means of alternating magnetic fields (AMFs). The review is mainly focused on new approach which utilizes non-heating low frequency magnetic fields (LFMFs) for nanomechanical actuation of f-MNPs. This approach is compared to such traditional ones as magnetic resonance imaging (MRI) and radio-frequency (RF) magnetic hyperthermia (MH) which utilize high frequency heating AMF. The innovative principles and specific models of non-thermal magnetomechanical actuation of biostructures by MNP rotational oscillations in LFMF are described. The discussed strategy allows biodistribution monitoring in situ, delivering drugs to target tissues and releasing them with controlled rate, controlling biocatalytic reaction kinetics, inducing malignant cell apoptosis, and more. Optimization of both LFMF and f-MNP parameters may lead to dramatic improvement of treatment efficiency, locality, and selectivity on molecular or cellular levels and allow implementing both drug and drugless, i.e., pure nanomechanical therapy, in particular cancer therapy. The optimal parameters within this approach differ significantly from those used in MH or MRI because of the principal difference in the f-MNP actuation modes. It is shown that specifically designed high gradient, steady magnetic field enables diagnostic and therapeutic LFMF impact localization in the deep tissues within the area ranging from a millimeter to a few centimeters and 3D scanning of affected region, if necessary.

Mycorrhizal fungi influence on silver uptake and membrane protein gene expression following silver nanoparticle exposure

Abstract: The rapid growth of nanotechnology and the high demand for nanomaterial use have greatly increased the risk of particle release into the environment. Understanding nanomaterial interactions with crop species and their associated microorganisms is critical to food safety and security. In the current study, tomato was inoculated with mycorrhizal fungi and subsequently exposed to 12, 24, or 36 mg/kg of 2- or 15-nm silver nanoparticles (Ag-NPs). Mycorrhizal (M) and non-mycorrhizal (NM) tomatoes exposed to 36 mg/kg of 2-nm Ag-NPs accumulated 1300 and 1600 μg/g silver in their tissues, respectively. Mycorrhizal plants accumulated 14% less silver compared to non-mycorrhizal plants. To begin to understand the mechanisms by which plants accumulate NPs, the expression of two aquaporin channel genes, the plasma membrane intrinsic protein (PIP) and the tonoplast membrane intrinsic protein (TIP), and one potassium channel (KC) gene were studied. In non-mycorrhizal plants, the expression of KC, PIP, and TIP was eight, five, and nine times higher than the control, respectively. These expressions for mycorrhizal plants were 5.8, 3.5, and 2 times higher than controls, respectively. The expression of KC and PIP, which are located on the plasma membrane, was 3.5 and 2.5, respectively, times higher than TIP, which is located on the tonoplast. PIP expression was significantly higher in NM tomatoes exposed to 12 mg/kg of 2-nm Ag-NPs compared to M plants. These results show that mycorrhizal colonization decreases Ag accumulation in NP-exposed plants and also moderates changes in expression level of membrane transport proteins.

Hydrogen generation by reaction of Si nanopowder with neutral water.

Abstract: Si and its oxide are nonpoisonous materials, and thus, it can be taken for medical effects. We have developed a method of generation of hydrogen by use of reactions of Si nanopowder with water in the neutral pH region. Si nanopowder is fabricated by the simple bead milling method. Si nanopowder reacts with water to generate hydrogen even in cases where pH is set at the neutral region between 7.0 and 8.6. The hydrogen generation rate strongly depends on pH and in the case of pH 8.0, ∼55 ml/g hydrogen which corresponds to that contained in approximately 3 L saturated hydrogen-rich water is generated in 1 h. The reaction rate for hydrogen generation greatly increases with pH, indicating that the reacting species is hydroxide ions. The change of pH after the hydrogen generation reaction is negligibly low compared with that estimated assuming that hydroxide ions are consumed by the reaction. From these results, we conclude the following reaction mechanism: Si nanopowder reacts with hydroxide ions in the rate-determining reaction to form hydrogen molecules, SiO2, and electrons in the conduction band. Then, generated electrons are accepted by water molecules, resulting in production of hydrogen molecules and hydroxide ions. The hydrogen generation rate strongly depends on the crystallite size of Si nanopowder, but not on the size of aggregates of Si nanopowder. The present study shows a possibility to use Si nanopowder for hydrogen generation in the body in order to eliminate hydroxyl radicals which cause various diseases.

MRI based on iron oxide nanoparticles contrast agents: effect of oxidation state and architecture

Abstract: Iron oxide nanoparticles (IONPs) extensively employed beyond regenerative medicines to imaging disciplines because of their great constituents for magneto-responsive nano-systems. The unique superparamagnetic behavior makes IONPs very suitable for hyperthermia and imaging applications. From the last decade, versatile functionalization with surface capabilities, efficient contrast properties and biocompatibilities make IONPs an essential imaging contrast agent for magnetic resonance imaging (MRI). IONPs have shown signals for both longitudinal relaxation and transverse relaxation; therefore, negative contrast as well as dual contrast can be used for imaging in MRI. In the current review, we have focused on different oxidation state of iron oxides, i.e., magnetite, maghemite and hematite for their T1 and T2 contrast enhancement properties. We have also discussed different factors (synthesis protocols, biocompatibility, toxicity, architecture, etc.) that can affect the contrast properties of the IONPs.

Room-temperature synthesis of pure perovskite-related Cs 4 PbBr 6 nanocrystals and their ligand-mediated evolution into highly luminescent CsPbBr 3 nanosheets

Abstract: Currently, all-inorganic cesium lead-halide perovskite nanocrystals have attracted enormous attentions owing to their excellent optical performances. While great efforts have been devoted to CsPbBr3 nanocrystals, the perovskite-related Cs4PbBr6 nanocrystals, which were newly reported, still remained poorly understood. Here, we reported a novel room-temperature reaction strategy to synthesize pure perovskite-related Cs4PbBr6 nanocrystals. Size of the products could be adjusted through altering the amount of ligands, simply. A mixture of two good solvents with different polarity was innovatively used as precursor solvent, being one key to the high-yield Cs4PbBr6 nanocrystals synthesis. Other two keys were Cs+ precursor concentration and surface ligands. Ingenious experiments were designed to reveal the underlying reaction mechanism. No excitonic emission was observed from the prepared Cs4PbBr6 nanocrystals in our work. We considered the green emission which was observed in other reports originated from the avoidless transformation of Cs4PbBr6 into CsPbBr3 nanocrystals. Indeed, the new-prepared Cs4PbBr6 nanocrystals could transform into CsPbBr3 nanosheets with surface ligands mediated. The new-transformed two-dimensional CsPbBr3 nanosheets could evolve into large-size nanosheets. The influences of surface ligand density on the fluorescent intensity and stability of transformed CsPbBr3 nanosheets were also explained. Notably, the photoluminescence quantum yield of the as-transformed CsPbBr3 nanosheets could reach as high as 61.6% in the form of thin film. The fast large-scale synthesis of Cs4PbBr6 nanocrystals and their ligand-mediated transformation into high-fluorescent CsPbBr3 nanosheets will be beneficial to the future optoelectronic applications. Our work provides new approaches to understand the structural evolution and light-emitting principle of perovskite nanocrystals.

Colloidal behavior of goethite nanoparticles modified with humic acid and implications for aquifer reclamation

Abstract: Nanosized colloids of iron oxide adsorb heavy metals, enhance the biodegradation of contaminants, and represent a promising technology to clean up contaminated aquifers. Goethite particles for aquifer reclamation were recently synthesized with a coating of humic acids to reduce aggregation. This study investigates the stability and the mobility in porous media of this material as a function of aqueous chemistry, and it identifies the best practices to maximize the efficacy of the related remediation. Humic acid-coated nanogoethite (hydrodynamic diameter ∼90 nm) displays high stability in solutions of NaCl, consistent with effective electrosteric stabilization. However, particle aggregation is fast when calcium is present and, to a lesser extent, also in the presence of magnesium. This result is rationalized with complexation phenomena related to the interaction of divalent cations with humic acid, inducing rapid flocculation and sedimentation of the suspensions. The calcium dose, i.e., the amount of calcium ions with respect to solids in the dispersion, is the parameter governing stability. Therefore, more concentrated slurries may be more stable and mobile in the subsurface than dispersions of low particle concentration. Particle concentration during field injection should be thus chosen based on concentration and proportion of divalent cations in groundwater.

Fluorescent carbon dots: facile synthesis at room temperature and its application for Fe2+ sensing

Abstract: A new route for one-pot preparation of carbon dots (CDs) was developed at room temperature using PEG400 as both the carbon source and passitive agent. The new method possesses the advantages of facile, rapid, energy-saving, without any external stimulus and environment friendly. By changing the content of NaOH, the PEG400-CDs with blue-emitting, yellow-emitting, orange red-emitting and red-emitting were obtained, and the formation mechanism were carefully investigated. In addition, a sensitive fluorescence sensor were developed for Fe2+ detection based on PEG400-CDs since the fluorescence of PEG400-CDs could be enhanced by Fe2+. It was found that there is a good linear relationship between the enhanced fluorescence and Fe2+ concentration in the range of 0.5 to 2.0 μmol·L−1 with the detection limit of 6.0 × 10−8 mol·L−1, and Fe2+ in water samples was also determined with high accuracy and repeatability.

Safety assessment of nanomaterials using an advanced decision-making framework, the DF4nanoGrouping.

Abstract: As presented at the 2016 TechConnect World Innovation Conference on 22–25 May 2016 in Washington DC, USA, the European Centre for Ecotoxicology and Toxicology of Chemicals (ECETOC) ‘Nano Task Force’ proposes a Decision-making framework for the grouping and testing of nanomaterials (DF4nanoGrouping) consisting of three tiers to assign nanomaterials to four main groups with possible further subgrouping to refine specific information needs. The DF4nanoGrouping covers all relevant aspects of a nanomaterial’s life cycle and biological pathways: intrinsic material properties and system-dependent properties (that depend upon the nanomaterial’s respective surroundings), biopersistence, uptake and biodistribution, and cellular and apical toxic effects. Use, release, and exposure route may be applied as ‘qualifiers’ to determine if, e.g., nanomaterials cannot be released from products, which may justify waiving of testing. The four main groups encompass (1) soluble, (2) biopersistent high aspect ratio, (3) passive, and (4) active nanomaterials. The DF4nanoGrouping foresees a stepwise evaluation of nanomaterial properties and effects with increasing biological complexity. In case studies covering carbonaceous nanomaterials, metal oxide, and metal sulfate nanomaterials, amorphous silica and organic pigments (all nanomaterials having primary particle sizes below 100 nm), the usefulness of the DF4nanoGrouping for nanomaterial hazard assessment was confirmed. The DF4nanoGrouping facilitates grouping and targeted testing of nanomaterials. It ensures that sufficient data for the risk assessment of a nanomaterial are available, and it fosters the use of non-animal methods. No studies are performed that do not provide crucial data. Thereby, the DF4nanoGrouping serves to save both animals and resources.

Oral intake of zirconia nanoparticle alters neuronal development and behaviour of Drosophila melanogaster

Abstract: Zirconia nanoparticles (ZrO2 NPs) have been extensively used in teeth and bone implants and thus get a chance to interact with the physiological system. The current study investigated the oral administration of various concentrations of ZrO2 NPs synthesized by the hydrothermal method (0.25 to 5.0 mg L−1) on Drosophila physiology and behaviour. The size of the currently studied nanoparticle varies from 10 to 12 nm. ZrO2 NPs accumulated within the gut in a concentration-dependent manner and generate reactive oxygen species (ROS) only at 2.5 and 5.0 mg L−1 concentrations. ROS was detected by nitroblue tetrazolium (NBT) assay and 2′,7′-dichlorofluorescein (H2DCF) staining. The ROS toxicity alters the larval gut structure as revealed by DAPI staining. The NP stress of larvae affects the Drosophila development by distressing pupa count and varying the phenotypic changes in sensory organs (eye, thorax bristle, wings). Besides phenotypic changes, flawed climbing behaviour against gravity was seen in ZrO2 NP-treated flies. All together, for the first time, we have reported that a ROS-mediated ZrO2 NP toxicity alters neuronal development and functioning using Drosophila as a model organism.

Magnetic nanoparticles: reactive oxygen species generation and potential therapeutic applications

Abstract: Magnetic nanoparticles have been demonstrated to produce reactive oxygen species (ROS), which play a major role in various cellular pathways, via Fenton and Haber-Weiss reaction. ROS act as a double-edged sword inside the body. At normal conditions, the generation of ROS is in balance with their elimination by scavenger systems, and they can promote cell proliferation as well as differentiation. However, at an increased level, they can cause damages to protein, lead to cellular apoptosis, and contribute to many diseases including cancer. Many recent studies proposed a variety of strategies to either suppress toxicity of ROS generation or exploit the elevated ROS levels for cancer therapy.

Facile fabrication of a stable and recyclable lipase@amine-functionalized ZIF-8 nanoparticles for esters hydrolysis and transesterification

Abstract: Zeolitic imidazolate frameworks (ZIF) represent one of the metal organic frameworks (MOF) with high potential for enzyme immobilization due to their exceptional chemical and thermal stability, negligible cytotoxicity, and easy synthesis under mild biocompatible conditions. Amine-functionalized ZIF-8 (An-ZIF-8) are capable of forming multipoint attachment via hydrogen bonding with lipase which will immobilize and further enhance stabilization of lipase. In addition, increased hydrophilicity of An-ZIF-8 will increase partitioning of An-ZIF-8 immobilized lipase at the aqueous/organic interface which enable lipase to expose its active site and retain its catalytic activity at its highest. Present study reports the use of ZIF-8 and An-ZIF-8 nanoparticles as carrier for Burkholderia cepacia lipase (BCL), compares the ester hydrolysis and transesterification activities of immobilized lipase with those of free lipase, and evaluates the reusability and recovery rate of the immobilized lipase. An-ZIF-8 nanoparticles (average 130.42 ± 0.55 nm) were facilely synthesized via mixing ZIF-8 nanoparticles with ammonia hydroxide solution. Despite having similar characteristics of high crystallinity and forming cuboid-like particles, An-ZIF-8 demonstrated significantly (P < 0.05) lower Brunauer-Emmett-Teller (BET) surface area and higher thermal stability than ZIF-8. BCL were successfully immobilized on ZIF-8 (BCL@ZIF-8) and An-ZIF-8 (BCL@An-ZIF-8) nanoparticles with an average lipase loading rate of ~ 8 mg/g MOF. The immobilized BCL demonstrated no significant differences in terms of esters hydrolysis and transesterification activities with those of free BCL. BCL@An-ZIF-8 demonstrated superior catalytic stability in comparison to BCL@ZIF-8 with retainment of more than 80% of its initial hydrolysis and transesterification activity for at least 10 repeated runs. In addition, more than 80% of the BCL@An-ZIF-8 can be easily recovered during each cycle of the reusability test through simple centrifugation.

Investigating interfacial contact configuration and behavior of single-walled carbon nanotube-based nanodevice with atomistic simulations

Abstract: Carbon nanotubes (CNTs), including single-walled carbon nanotubes (SWNTs) and multi-walled carbon nanotubes (MWNTs), are considered to be the promising candidates for next-generation interconnects with excellent physical and chemical properties ranging from ultrahigh mechanical strength, to electrical properties, to thermal conductivity, to optical properties, etc. To further study the interfacial contact configurations of SWNT-based nanodevice with a 13.56-A diameter, the corresponding simulations are carried out with the molecular dynamic method. The nanotube collapses dramatically into the surface with the complete collapse on the Au/Ag/graphite electrode surface and slight distortion on the Si/SiO2 substrate surface, respectively. The related dominant mechanism is studied and explained. Meanwhile, the interfacial contact configuration and behavior, depended on other factors, are also analyzed in this article.

Application of carbon nanotubes to immobilize heavy metals in contaminated soils

Abstract: The contamination of soils with heavy metals is a growing concern in modern societies. To avoid the spread of contamination, soil stabilization techniques can be applied mixing materials with the soil in order to partially immobilize heavy metals. Carbon nanotubes (CNTs) are nanomaterials known for its exceptional properties, like high surface area and adsorption capacity. Due to these unique properties, the potential use of CNTs in heavy metal contaminated water has been studied, with very satisfactory results; however, their application in contaminated soils is practically unexplored. This experimental work is focused on studying the potential of using CNTs in soil remediation, especially to immobilize the heavy metals ions: lead (Pb2+), copper (Cu2+), nickel (Ni2+), and zinc (Zn2+), commonly present in contaminated soils. In order to avoid CNT agglomeration, which originates the loss of their beneficial properties, an aqueous suspension of CNTs was prepared using a non-ionic surfactant combined with ultrasonic energy to promote CNTs dispersion. Then, the soil, with and without the addition of CNTs, was subjected to adsorption tests to evaluate the CNT capacity to improve heavy metal immobilization. To validate the adsorption test results, permeability tests were executed, simulating the conditions of a real-case scenario. The results obtained led to the conclusion that the addition of a small amount of dispersed CNTs can successfully increase the adsorption capacity of the soil and consequently improve the immobilization of heavy metals in the soil matrix. The immobilization percentage varies with the different heavy metals under study.

Unusual attempt to direct the growth of bimetallic Ag@Pt nanorods on electrochemically reduced graphene oxide nanosheets by electroless exchange of Cu by Pt for an efficient alcohol oxidation

Abstract: A simple and an efficient tool for the direct growth of bimetallic Ag@Pt nanorods (NRDs) on electrochemically reduced graphene oxide (ERGO) nanosheets was developed at glassy carbon electrode (GCE). Initially, Cu shell was grown on Ag core as Ag@Cu NRD by the seed-mediated growth method. Accordingly, Cu shell has been successfully replaced by Pt using the electroless galvanic replacement method with ease by effective functionalization of L-tryptophan on ERGO surface (L-ERGO), which eventually plays an important role in the direct growth of one-dimensional bimetallic NRDs. As a result, the synthesized Ag@Pt NRD-supported L-ERGO nanosheets (Ag@Pt NRDs/L-ERGO/GCE) were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDAX) and Raman spectroscopy. Anodic stripping voltammetry was used to explore its electrochemical properties. Finally, the developed bimetallic Ag@Pt NRDs/L-ERGO/GCEs were studied as a better electrocatalyst compared to the commercial catalysts such as Pt40/C or Pt20/C-loaded electrode for the oxidation of ethanol or methanol with a high tolerance level and an enhanced current density. In addition, the long-term stability was studied using chronoamperometry for 1000 s at the bimetallic NRD electrode for alcohol oxidation which impedes the fouling properties. The unfavourable and favourable electrooxidation of ethanol at Ag@Cu NRDs/L-ERGO/GCE (a) and Ag@Pt NRDs/L-ERGO/GCE (b) is discussed. The synergistic effect of Ag core and catalytic properties of Pt shell at Ag@Pt NRDs/L-ERGO/GCE tend to strongly minimize the CO poisoning effect and enhanced ethanol electrooxidation.

Nitric oxide-releasing nanoparticles: synthesis, characterization, and cytotoxicity to tumorigenic cells

Abstract: Nitric oxide (NO) is involved in several biological processes, including toxicity against tumor cells. The aim of this study was to synthesize, characterize, and evaluate the cytotoxicity of NO-releasing chitosan nanoparticles. A thiol-containing molecule, mercaptosuccinic acid (MSA), was encapsulated (encapsulation efficiency of 99%) in chitosan/sodium tripolyphosphate nanoparticles (CS NPs). The obtained nanoparticles showed an average hydrodynamic size of 108.40 ± 0.96 nm and polydispersity index of 0.26 ± 0.01. MSA-CS NPs were nitrosated leading to S-nitroso-MSA-CS NPs, which act as NO donor. The cytotoxicity of CS NPs, MSA-CS NPs, and S-nitroso-MSA-CS NPs were evaluated in several tumor cells, including human hepatocellular carcinoma (HepG2), mouse melanoma (B16F10), and human chronic myeloid leukemia (K562) cell lines and Lucena-1, a vincristine-resistant K562 cell line. Both CS NPs and MSA-CS NPs did not cause toxic effects in these cells, whereas S-nitroso-MSA-CS NPs caused potent cytotoxic effects in all the tested tumor cell lines. The half-maximal inhibitory concentration values of S-nitroso-MSA-CS NPs were 19.7, 10.5, 22.8, and 27.8 μg·mL−1 for HepG2, B16F10, K562, and Lucena-1 cells, respectively. In contrast, S-nitroso-MSA-CS NPs exhibited lower cytotoxic to non-tumorigenic melanocytes (Melan-A) when compared with melanoma B16F10. Therefore, the results highlight the potential use of NO-releasing CS NPs in antitumor chemotherapy.

Synthesis and adsorption properties of hierarchical Fe3O4@MgAl-LDH magnetic microspheres

Abstract: In this study, Fe3O4 microspheres were prepared by a hydrothermal method, and then the synthesized Fe3O4 microspheres were used as template to prepare Fe3O4@MgAl-LDH composite microspheres by a coprecipitation process. Morphology, composition, and crystal structure of synthesized nanomaterials were characterized by X-ray powder diffractometry, scanning electron microscopy, and Fourier transform infrared spectroscopy technologies. The composite hierarchical microspheres are composed of inner Fe3O4 core and outer MgAl-LDH-nanoflake layer, and the average thickness of MgAl-LDH-nanoflake is about 70 nm. The adsorption property of the products toward congo red was also measured using UV–vis spectrometer. The result demonstrated that the Fe3O4@MgAl-LDH composite adsorbent could remove 99.8% congo red in 30 min, and the maximum adsorption capacity is about 404.6 mg/g, while congo red removal rate of pure MgAl-LDH and Fe3O4 are only 86.3 and 53.1% in 40 min, respectively, and their adsorption capacity are 345.72 and 220.56 mg/g, respectively. It indicates the composite Fe3O4@ MgAl-LDH nanomaterials have better adsorption performance than pure Fe3O4 and MgAl-LDH nanomaterials. In addition, the magnetic nanocomposites could be separated easily, and it demonstrated good cycle performance.

Atomistic simulations on the axial nanowelding configuration and contact behavior between Ag nanowire and single-walled carbon nanotubes

Abstract: As for the interesting new building blocks, the Ag nanowires (AgNWs) and single-walled carbon nanotubes (SWNTs) as the interesting new building blocks are viewed as the promising candidates for the next-generation interconnects due to their most remarkable electrical, thermal, optical, mechanical, and other properties. The axial nanowelding of head-to-head style and side-to-side style is relatively simulated with the molecular dynamics method. As for the head-to-head structural style, SWNTs will move toward the AgNWs and contact with the head of AgNWs. And, the part of the Ag nanowire may be subsequently encapsulated in SWNT with the core-filling Ag atom chain as the final atomic contact configuration during nanowelding, which is related to the nanowelding temperature. When the SWNTs and AgNWs are arranged by the side-to-side contact style, the SWNTs will move along the SWNT surface and may eventually catch up with the AgNW being neck and neck. Aiming at the final axial atomic configurations and the contact behavior during nanowelding process, the related dominant mechanism is revealed in this paper.

Transforming single domain magnetic CoFe 2 O 4 nanoparticles from hydrophobic to hydrophilic by novel mechanochemical ligand exchange

Abstract: Single-phase uniform-sized (~9 nm) cobalt ferrite (CFO) nanoparticles have been synthesized by hydrothermal synthesis using oleic acid as a surfactant. The as-synthesized oleic acid-coated CFO (OA-CFO) nanoparticles were well dispersible in nonpolar solvents but not dispersible in water. The OA-CFO nanoparticles have been successfully transformed to highly water-dispersible citric acid-coated CFO (CA-CFO) nanoparticles using a novel single-step ligand exchange process by mechanochemical milling, in which small chain citric acid molecules replace the original large chain oleic acid molecules available on CFO nanoparticles. The OA-CFO nanoparticle’s hexane solution and CA-CFO nanoparticle’s water solution remain stable even after 6 months and show no agglomeration and their dispersion stability was confirmed by zeta-potential measurements. The contact angle measurement shows that OA-CFO nanoparticles are hydrophobic whereas CA-CFO nanoparticles are superhydrophilic in nature. The potentiality of as-synthesized OA-CFO and mechanochemically transformed CA-CFO nanoparticles for the demulsification of highly stabilized water-in-oil and oil-in-water emulsions has been demonstrated.

A novel colorimetric method based on copper nanoclusters with intrinsic peroxidase-like for detecting xanthine in serum samples

Abstract: A facile strategy for detecting xanthine in serum samples by copper nanocluster (CuNCs) with high intrinsic peroxidase-like activity was reported. Firstly, a simple, mild and time-saving method for preparing CuNCs was developed, in which dithiothreitol (DTT) and bovine serum albumin (BSA) were used as reductant and stabilizer, respectively. The as-prepared CuNCs exhibited a fluorescence emission at 590 nm with a quantum yield (QY) of approximately 5.29%, the fluorescence intensity of the as-prepared CuNCs exhibited no considerable change when stored under ambient condition with the lifetime is 1.75 μs. Moreover, the as-prepared CuNCs exhibited high intrinsic peroxidase-like activity with lower K m (K m = 8.90 × 10−6 mol L−1) for H2O2, which indicated that CuNCs have a higher affinity for H2O2. Compared with natural enzyme, the as-synthesized CuNCs are more catalytic stable over a wide range of pH (4.0~13.0) and temperature (4~80 °C). Finally, an indirect method for sensing xanthine was established because xanthine oxidase can catalyse the oxidation of xanthine to produce H2O2. Xanthine could be detected as low as 3.8 × 10−7 mol L−1 with a linear range from 5.0 × 10−7 to 1.0 × 10−4 mol L−1. These results proved that the proposed method is sensitive and accurate and could be successfully applied to the determination of xanthine in the serum sample with satisfaction.