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Nanomaterials, Volume 7, Issue 10 (October 2017)

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Cover Story (view full-size image) The most efficient removal of organic pollutants is achieved with enzymatic reagents grafted on [...] Read more.
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Open AccessArticle Enhanced Efficiency in Dye-Sensitized Solar Cells by Electron Transport and Light Scattering on Freestanding TiO2 Nanotube Arrays
Nanomaterials 2017, 7(10), 345; https://doi.org/10.3390/nano7100345
Received: 14 September 2017 / Revised: 18 October 2017 / Accepted: 19 October 2017 / Published: 24 October 2017
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Abstract
Dye-sensitized solar cells (DSSCs) were fabricated with closed- or open-ended freestanding TiO2 nanotube arrays as photoelectrodes that were decorated with carbon materials and large TiO2 nanoparticles (NPs) to enhance energy conversion efficiency. The energy conversion efficiency of DSSCs based on open-ended
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Dye-sensitized solar cells (DSSCs) were fabricated with closed- or open-ended freestanding TiO2 nanotube arrays as photoelectrodes that were decorated with carbon materials and large TiO2 nanoparticles (NPs) to enhance energy conversion efficiency. The energy conversion efficiency of DSSCs based on open-ended freestanding TiO2 nanotube arrays increased from 4.47% to 5.39%, compared to the DSSCs based on closed-ended freestanding TiO2 nanotube arrays. In DSSCs based on the open-ended freestanding TiO2 nanotube arrays, the energy conversion efficiency with carbon materials increased from 5.39% to 6.19% due to better electron transport, and that with a scattering layer from 5.39% to 6.24% due to more light harvesting compared to the DSSCs without carbon materials or scattering layer. Moreover, the energy conversion efficiency of DSSCs based on the open-ended freestanding TiO2 nanotube arrays with both carbon materials and scattering layer increased from 5.39% to 6.98%, which is an enhancement of 29.50%. In DSSCs based on the TiO2 nanotube arrays, the carbon materials can improve electron transport by π-π conjugation, and the large TiO2 NPs can enhance the capacity to light-harvest by scattering. Full article
(This article belongs to the Special Issue New Developments in Nanomaterials for Energy Storage and Conversions)
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Open AccessArticle Evaluation of the Effects of Nanoparticle Mixtures on Brassica Seed Germination and Bacterial Bioluminescence Activity Based on the Theory of Probability
Nanomaterials 2017, 7(10), 344; https://doi.org/10.3390/nano7100344
Received: 2 September 2017 / Revised: 11 October 2017 / Accepted: 17 October 2017 / Published: 23 October 2017
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Abstract
Effects of binary mixtures of six metal oxide nanoparticles (NPs; 54 combinations) on the activities of seed germination and bacterial bioluminescence were investigated using the theory of probability. The observed toxicities of various NPs combinations were compared with the theoretically expected toxicities, calculated
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Effects of binary mixtures of six metal oxide nanoparticles (NPs; 54 combinations) on the activities of seed germination and bacterial bioluminescence were investigated using the theory of probability. The observed toxicities of various NPs combinations were compared with the theoretically expected toxicities, calculated based on individual NPs toxicities. Different sensitivities were observed depending on the concentrations and the types of NPs. The synergistic mode (67%; observed toxicity greater than expected toxicity) was predominantly observed in the bioluminescence test, whereas both synergistic (47%) and additive (50%) modes were prevalent in the activity of seed germination. With regard to overall analysis, a slightly high percentage (56%) of the synergistic mode of action was (30 out of 54 binary mixture combinations; p < 0.0392) observed. These results suggest that the exposure of an NPs mixture in the environment may lead to a similar or higher toxicity level than the sum of its constituent NPs would suggest. In addition, one organism for assessment did not always show same results as those from a different assessment. Therefore, combining results of different organisms exposed to a wide range of concentrations of binary mixture will more properly predict and evaluate the expected ecotoxicity of pollutants on environments. Full article
(This article belongs to the Special Issue Oxide Nanomaterials for Chemical Sensors)
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Open AccessArticle Ti-Based Biomedical Material Modified with TiOx/TiNx Duplex Bioactivity Film via Micro-Arc Oxidation and Nitrogen Ion Implantation
Nanomaterials 2017, 7(10), 343; https://doi.org/10.3390/nano7100343
Received: 29 September 2017 / Revised: 16 October 2017 / Accepted: 18 October 2017 / Published: 23 October 2017
Cited by 2 | PDF Full-text (7125 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Titanium (Ti) and Ti-based alloy are widely used in the biomedical field owing to their excellent mechanical compatibility and biocompatibility. However, the bioinert bioactivity and biotribological properties of titanium limit its clinical application in implants. In order to improve the biocompatibility of titanium,
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Titanium (Ti) and Ti-based alloy are widely used in the biomedical field owing to their excellent mechanical compatibility and biocompatibility. However, the bioinert bioactivity and biotribological properties of titanium limit its clinical application in implants. In order to improve the biocompatibility of titanium, we modified its surface with TiOx/TiNx duplex composite films using a new method via micro-arc oxidation (MAO) and nitrogen ion implantation (NII) treatment. The structural characterization results revealed that the modified film was constructed by nanoarrays composed of TiOx/TiNx composite nanostitches with a size of 20~40 nm. Meanwhile, comparing this with pure Ti, the friction property, wear resistance, and bioactivity were significantly improved based on biotribological results and in vitro bioactivity tests. Full article
(This article belongs to the Special Issue ZnO and TiO2 Based Nanostructures)
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Open AccessFeature PaperArticle Flotation Assembly of Large-Area Ultrathin MWCNT Nanofilms for Construction of Bioelectrodes
Nanomaterials 2017, 7(10), 342; https://doi.org/10.3390/nano7100342
Received: 1 October 2017 / Revised: 18 October 2017 / Accepted: 19 October 2017 / Published: 21 October 2017
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Abstract
We report a simple, versatile, and rapid method for the fabrication of optically-transparent large-area carbon nanotube (CNT) films via flotation assembly. After solvent-induced assembly, floating films were transferred to a flat supporting substrate to form conductive and transparent CNT film electrodes. The resulting
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We report a simple, versatile, and rapid method for the fabrication of optically-transparent large-area carbon nanotube (CNT) films via flotation assembly. After solvent-induced assembly, floating films were transferred to a flat supporting substrate to form conductive and transparent CNT film electrodes. The resulting electrodes, with uniform 40 ± 20 nm multi-walled CNT (MWCNT) layers, were characterized by electrochemical and microscopy methods. The flotation method does not require specialized thin-film instrumentation and avoids the need for surfactants and pre-oxidized CNTs which can hamper electrochemical performance. A proof-of-concept nanostructured bioelectrode demonstrating high sensitivity for glucose was developed with an electropolymerized poly(pyrene-adamantane) layer for host–guest immobilization of active β-cyclodextrin tagged GOx enzymes. The polymer provides pyrene groups for cross-linking to CNTs and pendant adamantane groups for binding the β-cyclodextrin groups of the tagged enzyme. This demonstration offers a new approach for the preparation of stable and transparent CNT film electrodes with attractive electrochemical properties towards future photobio- and bio-electrochemical fuel cells, electrochemical sensors, and electroanalysis. Full article
(This article belongs to the Special Issue Nanostructured Biofuel Cells)
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Open AccessFeature PaperReview Advances in Single-Chain Nanoparticles for Catalysis Applications
Nanomaterials 2017, 7(10), 341; https://doi.org/10.3390/nano7100341
Received: 28 September 2017 / Revised: 18 October 2017 / Accepted: 19 October 2017 / Published: 21 October 2017
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Abstract
Enzymes are the most efficient catalysts known for working in an aqueous environment near room temperature. The folding of individual polymer chains to functional single-chain nanoparticles (SCNPs) offers many opportunities for the development of artificial enzyme-mimic catalysts showing both high catalytic activity and
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Enzymes are the most efficient catalysts known for working in an aqueous environment near room temperature. The folding of individual polymer chains to functional single-chain nanoparticles (SCNPs) offers many opportunities for the development of artificial enzyme-mimic catalysts showing both high catalytic activity and specificity. In this review, we highlight recent results obtained in the use of SCNPs as bioinspired, highly-efficient nanoreactors (3–30 nm) for the synthesis of a variety of nanomaterials (inorganic nanoparticles, quantum dots, carbon nanodots), polymers, and chemical compounds, as well as nanocontainers for CO2 capture and release. Full article
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Open AccessArticle Enhancing Photovoltaic Performance Using Broadband Luminescent Down-Shifting by Combining Multiple Species of Eu-Doped Silicate Phosphors
Nanomaterials 2017, 7(10), 340; https://doi.org/10.3390/nano7100340
Received: 23 September 2017 / Revised: 16 October 2017 / Accepted: 18 October 2017 / Published: 21 October 2017
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Abstract
This paper demonstrates the application of a broadband luminescent downshifting (LDS) layer with multiple species of europium (Eu)-doped silicate phosphors using spin-on film technique to enhance the photovoltaic efficiency of crystalline silicon solar cells. The surface morphology of the deposited layer was examined
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This paper demonstrates the application of a broadband luminescent downshifting (LDS) layer with multiple species of europium (Eu)-doped silicate phosphors using spin-on film technique to enhance the photovoltaic efficiency of crystalline silicon solar cells. The surface morphology of the deposited layer was examined using a scanning electron microscope (SEM). The chemical composition of the Eu-doped silicate phosphors was analyzed using energy-dispersive X-ray spectroscopy (EDS). The fluorescence emission of the Eu-doped silicate phosphors was characterized using photoluminescence (PL) measurements at room temperature. We also compared the optical reflectance and external quantum efficiency (EQE) response of cells with combinations of various Eu-doped phosphors species. The cell coated with two species of Eu-doped phosphors achieved a conversion efficiency enhancement (∆η) of 19.39%, far exceeding the ∆η = 15.08% of the cell with one species of Eu-doped phosphors and the ∆η = 8.51% of the reference cell with the same silicate layer without Eu-doped phosphors. Full article
(This article belongs to the Special Issue Nanomaterials for Renewable and Sustainable Energy)
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Open AccessArticle Few-Flakes Reduced Graphene Oxide Sensors for Organic Vapors with a High Signal-to-Noise Ratio
Nanomaterials 2017, 7(10), 339; https://doi.org/10.3390/nano7100339
Received: 23 September 2017 / Revised: 14 October 2017 / Accepted: 18 October 2017 / Published: 21 October 2017
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Abstract
This paper reports our findings on how to prepare a graphene oxide-based gas sensor for sensing fast pulses of volatile organic compounds with a better signal-to-noise ratio. We use rapid acetone pulses of varying concentrations to test the sensors. First, we compare the
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This paper reports our findings on how to prepare a graphene oxide-based gas sensor for sensing fast pulses of volatile organic compounds with a better signal-to-noise ratio. We use rapid acetone pulses of varying concentrations to test the sensors. First, we compare the effect of graphene oxide deposition method (dielectrophoresis versus solvent evaporation) on the sensor’s response. We find that dielectrophoresis yields films with uniform coverage and better sensor response. Second, we examine the effect of chemical reduction. Contrary to prior reports, we find that graphene oxide reduction leads to a reduction in sensor response and current noise, thus keeping the signal-to-noise ratio the same. We found that if we sonicated the sensor in acetone, we created a sensor with a few flakes of reduced graphene oxide. Such sensors provided a higher signal-to-noise ratio that could be correlated to the vapor concentration of acetone with better repeatability. Modeling shows that the sensor’s response is due to one-site Langmuir adsorption or an overall single exponent process. Further, the desorption of acetone as deduced from the sensor recovery signal follows a single exponent process. Thus, we show a simple way to improve the signal-to-noise ratio in reduced graphene oxide sensors. Full article
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Open AccessArticle Study of the Photodynamic Activity of N-Doped TiO2 Nanoparticles Conjugated with Aluminum Phthalocyanine
Nanomaterials 2017, 7(10), 338; https://doi.org/10.3390/nano7100338
Received: 29 September 2017 / Revised: 14 October 2017 / Accepted: 17 October 2017 / Published: 20 October 2017
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Abstract
TiO2 nanoparticles modified with phthalocyanines (Pc) have been proven to be a potential photosensitizer in the application of photodynamic therapy (PDT). However, the generation of reactive oxygen species (ROS) by TiO2 nanoparticles modified with Pc has not been demonstrated clearly. In
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TiO2 nanoparticles modified with phthalocyanines (Pc) have been proven to be a potential photosensitizer in the application of photodynamic therapy (PDT). However, the generation of reactive oxygen species (ROS) by TiO2 nanoparticles modified with Pc has not been demonstrated clearly. In this study, nitrogen-doped TiO2 conjugated with Pc (N-TiO2-Pc) were studied by means of monitoring the generation of ROS. The absorbance and photokilling effect on HeLa cells upon visible light of different regions were also studied and compared with non-doped TiO2-Pc and Pc. Both N-TiO2-Pc and TiO2-Pc can be activated by visible light and exhibited much higher photokilling effect on HeLa cells than Pc. In addition, nitrogen-doping can greatly enhance the formation of 1O2 and •O2, while it suppresses the generation of OH•. This resulted in significant photodynamic activity. Therefore, N-TiO2-Pc can be an excellent candidate for a photosensitizer in PDT with wide-spectrum visible irradiation. Full article
(This article belongs to the Special Issue ZnO and TiO2 Based Nanostructures)
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Open AccessArticle Raman Enhancement and Photo-Bleaching of Organic Dyes in the Presence of Chemical Vapor Deposition-Grown Graphene
Nanomaterials 2017, 7(10), 337; https://doi.org/10.3390/nano7100337
Received: 18 September 2017 / Revised: 10 October 2017 / Accepted: 16 October 2017 / Published: 19 October 2017
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Abstract
Fluorescent organic dyes photobleach under intense light. Graphene has been shown to improve the photo-stability of organic dyes. In this paper, we investigated the Raman spectroscopy and photo-bleaching kinetics of dyes in the absence/presence of chemical vapor deposition (CVD)-grown graphene. We show that
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Fluorescent organic dyes photobleach under intense light. Graphene has been shown to improve the photo-stability of organic dyes. In this paper, we investigated the Raman spectroscopy and photo-bleaching kinetics of dyes in the absence/presence of chemical vapor deposition (CVD)-grown graphene. We show that graphene enhances the Raman signal of a wide range of dyes. The photo-bleaching of the dyes was reduced when the dyes were in contact with graphene. In contrast, monolayer hexagonal boron nitride (h-BN) was much less effective in reducing the photo-bleaching rate of the dyes. We attribute the suppression of photo-bleaching to the energy or electron transfer from dye to graphene. The results highlight the potential of CVD graphene as a substrate for protecting and enhancing Raman response of organic dyes. Full article
(This article belongs to the Special Issue Synthesis, Structure and Applications of 2D Nanomaterials)
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Open AccessArticle Enhanced UV-Visible Light Photocatalytic Activity by Constructing Appropriate Heterostructures between Mesopore TiO2 Nanospheres and Sn3O4 Nanoparticles
Nanomaterials 2017, 7(10), 336; https://doi.org/10.3390/nano7100336
Received: 25 September 2017 / Revised: 12 October 2017 / Accepted: 13 October 2017 / Published: 19 October 2017
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Abstract
Novel TiO2/Sn3O4 heterostructure photocatalysts were ingeniously synthesized via a scalable two-step method. The impressive photocatalytic abilities of the TiO2/Sn3O4 sphere nanocomposites were validated by the degradation test of methyl orange and •OH trapping
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Novel TiO2/Sn3O4 heterostructure photocatalysts were ingeniously synthesized via a scalable two-step method. The impressive photocatalytic abilities of the TiO2/Sn3O4 sphere nanocomposites were validated by the degradation test of methyl orange and •OH trapping photoluminescence experiments under ultraviolet (UV) and visible light irradiation, respectively. Especially under the visible light, the TiO2/Sn3O4 nanocomposites demonstrated a superb photocatalytic activity, with 81.2% of methyl orange (MO) decomposed at 30 min after irradiation, which greatly exceeded that of the P25 (13.4%), TiO2 (0.5%) and pure Sn3O4 (59.1%) nanostructures. This enhanced photocatalytic performance could be attributed to the mesopore induced by the monodispersed TiO2 cores that supply sufficient surface areas and accessibility to reactant molecules. This exquisite hetero-architecture facilitates extended UV-visible absorption and efficient photoexcited charge carrier separation. Full article
(This article belongs to the Special Issue ZnO and TiO2 Based Nanostructures)
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Open AccessArticle Precise Placement of Metallic Nanowires on a Substrate by Localized Electric Fields and Inter-Nanowire Electrostatic Interaction
Nanomaterials 2017, 7(10), 335; https://doi.org/10.3390/nano7100335
Received: 25 September 2017 / Revised: 11 October 2017 / Accepted: 16 October 2017 / Published: 19 October 2017
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Abstract
Placing nanowires at the predetermined locations on a substrate represents one of the significant hurdles to be tackled for realization of heterogeneous nanowire systems. Here, we demonstrate spatially-controlled assembly of a single nanowire at the photolithographically recessed region at the electrode gap with
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Placing nanowires at the predetermined locations on a substrate represents one of the significant hurdles to be tackled for realization of heterogeneous nanowire systems. Here, we demonstrate spatially-controlled assembly of a single nanowire at the photolithographically recessed region at the electrode gap with high integration yield (~90%). Two popular routes, such as protruding electrode tips and recessed wells, for spatially-controlled nanowire alignment, are compared to investigate long-range dielectrophoretic nanowire attraction and short-range nanowire-nanowire electrostatic interaction for determining the final alignment of attracted nanowires. Furthermore, the post-assembly process has been developed and tested to make a robust electrical contact to the assembled nanowires, which removes any misaligned ones and connects the nanowires to the underlying electrodes of circuit. Full article
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Open AccessArticle Microstructuring of Mesoporous Titania Films Loaded with Silver Salts to Enhance the Photocatalytic Degradation of Methyl Blue under Visible Light
Nanomaterials 2017, 7(10), 334; https://doi.org/10.3390/nano7100334
Received: 22 September 2017 / Revised: 29 September 2017 / Accepted: 5 October 2017 / Published: 17 October 2017
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Abstract
The microstructuring of the distribution of silver nanoparticles (NPs) in mesoporous titania films loaded with silver salts, using two-beam interference lithography leading to 1 Dimension (1D) grating, induces variations in the photocatalytic efficiency. The influence of the structuration was tested on the degradation
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The microstructuring of the distribution of silver nanoparticles (NPs) in mesoporous titania films loaded with silver salts, using two-beam interference lithography leading to 1 Dimension (1D) grating, induces variations in the photocatalytic efficiency. The influence of the structuration was tested on the degradation of methyl blue (MB) under ultraviolet (UV) and visible illumination, giving rise to a significant improvement of the photocatalytic efficiency. The periodic distribution of the NPs was characterized by transmission electron microscopy (TEM), high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and scanning electron microscopy (SEM). Full article
(This article belongs to the Special Issue ZnO and TiO2 Based Nanostructures)
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Open AccessArticle AuPd Bimetallic Nanocrystals Embedded in Magnetic Halloysite Nanotubes: Facile Synthesis and Catalytic Reduction of Nitroaromatic Compounds
Nanomaterials 2017, 7(10), 333; https://doi.org/10.3390/nano7100333
Received: 28 September 2017 / Revised: 13 October 2017 / Accepted: 13 October 2017 / Published: 17 October 2017
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Abstract
In this research, a facile and effective approach was developed for the preparation of well-designed AuPd alloyed catalysts supported on magnetic halloysite nanotubes (HNTs@Fe3O4@AuPd). The microstructure and the magnetic properties of HNTs@Fe3O4@AuPd were confirmed by
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In this research, a facile and effective approach was developed for the preparation of well-designed AuPd alloyed catalysts supported on magnetic halloysite nanotubes (HNTs@Fe3O4@AuPd). The microstructure and the magnetic properties of HNTs@Fe3O4@AuPd were confirmed by transmission electron microscopy (TEM), high resolution TEM (HRTEM), energy-dispersive X-ray spectroscopy (EDS), and vibrating sample magnetometry (VSM) analyses. The catalysts, fabricated by a cheap, environmentally friendly, and simple surfactant-free formation process, exhibited high activities during the reduction of 4-nitrophenol and various other nitroaromatic compounds. Moreover, the catalytic activities of the HNTs@Fe3O4@AuPd nanocatalysts were tunable via adjusting the atomic ratio of AuPd during the synthesis. As compared with the monometallic nanocatalysts (HNTs@Fe3O4@Au and HNTs@Fe3O4@Pd), the bimetallic alloyed HNTs@Fe3O4@AuPd nanocatalysts exhibited excellent catalytic activities toward the reduction of 4-nitrophenol (4-NP) to 4-aminophenol. Furthermore, the as-obtained HNTs@Fe3O4@AuPd can be recycled several times, while retaining its functionality due to the stability and magnetic separation property. Full article
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Open AccessFeature PaperArticle PMA-Induced THP-1 Macrophage Differentiation is Not Impaired by Citrate-Coated Platinum Nanoparticles
Nanomaterials 2017, 7(10), 332; https://doi.org/10.3390/nano7100332
Received: 25 September 2017 / Revised: 12 October 2017 / Accepted: 13 October 2017 / Published: 17 October 2017
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Abstract
The innate immune system consists of several complex cellular and molecular mechanisms. During inflammatory responses, blood-circulating monocytes are driven to the sites of inflammation, where they differentiate into tissue macrophages. The research of novel nanomaterials applied to biomedical sciences is often limited by
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The innate immune system consists of several complex cellular and molecular mechanisms. During inflammatory responses, blood-circulating monocytes are driven to the sites of inflammation, where they differentiate into tissue macrophages. The research of novel nanomaterials applied to biomedical sciences is often limited by their toxicity or dangerous interactions with the immune cell functions. Platinum nanoparticles (PtNPs) have shown efficient antioxidant properties within several cells, but information on their potential harmful role in the monocyte-to-macrophage differentiation process is still unknown. Here, we studied the morphology and the release of cytokines in PMA-differentiated THP-1 pre-treated with 5 nm PtNPs. Although NP endocytosis was evident, we did not find differences in the cellular structure or in the release of inflammatory cytokines and chemokines compared to cells differentiated in PtNP-free medium. However, the administration of PtNPs to previously differentiated THP-1 induced massive phagocytosis of the PtNPs and a slight metabolism decrease at higher doses. Further investigation using undifferentiated and differentiated neutrophil-like HL60 confirmed the harmlessness of PtNPs with non-adherent innate immune cells. Our results demonstrate that citrate-coated PtNPs are not toxic with these immune cell lines, and do not affect the PMA-stimulated THP-1 macrophage differentiation process in vitro. Full article
(This article belongs to the Special Issue Nanoparticles in Immunology)
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Open AccessArticle A Sub-Microanalysis Approach in Chemical Characterisation of Gold Nanorods Formed by a Novel Polymer-Immobilised Gold Seeds Base
Nanomaterials 2017, 7(10), 331; https://doi.org/10.3390/nano7100331
Received: 29 August 2017 / Revised: 19 September 2017 / Accepted: 10 October 2017 / Published: 16 October 2017
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Abstract
Gold nanorods (GNRs) have been fabricated by a novel polymer-immobilised seed mediated method using ultraviolet (UV) photoreduced gold-polymethylmethacrylate (Au–PMMA) nanocomposites as a seed platform and characterised at sub-micron scale regime with synchrotron-based techniques; near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and X-ray fluorescence
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Gold nanorods (GNRs) have been fabricated by a novel polymer-immobilised seed mediated method using ultraviolet (UV) photoreduced gold-polymethylmethacrylate (Au–PMMA) nanocomposites as a seed platform and characterised at sub-micron scale regime with synchrotron-based techniques; near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and X-ray fluorescence (XRF) mapping. In this report, it is shown that investigating polymer nanocomposites using combination of XRF mapping and NEXAFS spectromicroscopy can help to see the growth phenomenon from different perspective than conventional characterisation techniques. XRF maps are used to explore distribution of the constituent elements and showing how polymer matrix making stripe patterns along with regions where GNRs are formed. NEXAFS carbon (C) K-edge spectra have been taken at three different stages of synthesis: (1) on Au–PMMA nanocomposites before UV irradiation, (2) after gold nanoparticles formation, and (3) after GNRs formation. It reveals how polymer matrix has been degraded during GNRs formation and avoiding chemically or physically damage to polymer matrix is crucial to control the formation of GNRs. Full article
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