Journal: Nanomaterials (Basel, Switzerland)
For the last decades, nanocomposites materials have been widely studied in the scientific literature as they provide substantial properties enhancements, even at low nanoparticles content. Their performance depends on a number of parameters but the nanoparticles dispersion and distribution state remains the key challenge in order to obtain the full nanocomposites' potential in terms of, e.g., flame retardance, mechanical, barrier and thermal properties, etc., that would allow extending their use in the industry. While the amount of existing research and indeed review papers regarding the formulation of nanocomposites is already significant, after listing the most common applications, this review focuses more in-depth on the properties and materials of relevance in three target sectors: packaging, solar energy and automotive. In terms of advances in the processing of nanocomposites, this review discusses various enhancement technologies such as the use of ultrasounds for in-process nanoparticles dispersion. In the case of nanocoatings, it describes the different conventionally used processes as well as nanoparticles deposition by electro-hydrodynamic processing. All in all, this review gives the basics both in terms of composition and of processing aspects to reach optimal properties for using nanocomposites in the selected applications. As an outlook, up-to-date nanosafety issues are discussed.
The main goal of the present work is to study the coherent phonon in strongly confined CdSe quantum dots (QDs) under varied pump fluences. The main characteristics of coherent phonons (amplitude, frequency, phase, spectrogram) of CdSe QDs under the red-edge pump of the excitonic band [1S(e)-1S3/2(h)] are reported. We demonstrate for the first time that the amplitude of the coherent optical longitudinal-optical (LO) phonon at 6.16 THz excited in CdSe nanoparticles by a femtosecond unchirped pulse shows a non-monotone dependence on the pump fluence. This dependence exhibits the maximum at pump fluence ~0.8 mJ/cm². At the same time, the amplitudes of the longitudinal acoustic (LA) phonon mode at 0.55 THz and of the coherent wave packet of toluene at 15.6, 23.6 THz show a monotonic rise with the increase of pump fluence. The time frequency representation of an oscillating signal corresponding to LO phonons revealed by continuous wavelet transform (CWT) shows a profound destructive quantum interference close to the origin of distinct (optical phonon) and continuum-like (exciton) quasiparticles. The CWT spectrogram demonstrates a nonlinear chirp at short time delays, where the chirp sign depends on the pump pulse fluence. The CWT spectrogram reveals an anharmonic coupling between optical and acoustic phonons.
Heavily boron-doped silicon layers and boron etch-stop techniques have been widely used in the fabrication of microelectromechanical systems (MEMS). This paper provides an introduction to the fabrication process of nanoscale silicon thermoelectric devices. Low-dimensional structures such as silicon nanowire (SiNW) have been considered as a promising alternative for thermoelectric applications in order to achieve a higher thermoelectric figure of merit (ZT) than bulk silicon. Here, heavily boron-doped silicon layers and boron etch-stop processes for the fabrication of suspended SiNWs will be discussed in detail, including boron diffusion, electron beam lithography, inductively coupled plasma (ICP) etching and tetramethylammonium hydroxide (TMAH) etch-stop processes. A 7 μm long nanowire structure with a height of 280 nm and a width of 55 nm was achieved, indicating that the proposed technique is useful for nanoscale fabrication. Furthermore, a SiNW thermoelectric device has also been demonstrated, and its performance shows an obvious reduction in thermal conductivity.
Magnesium silicate as a high-performance adsorption material has attracted increasing attention for the removal of organic dye pollution. Here, we prepared a series of magnesium silicate hydrates (MSH) in a hydrothermal route, and carefully investigated the corresponding adsorption behavior towards methylene blue (MB) as well as the effect of surface charge on adsorption capacity. The results show that surface charge plays a key role in the adsorption performance of MSH for MB, a negative surface charge density follows the increase of Si/Mg feeding ratio from 1.00 to 1.75, and furthermore the higher negative charge favors the improvement of the adsorption capacity. Among four investigated samples (MSH = 1.00, 1.25, 1.50, and 1.75), MSH-1.75 has the highest negative surface charge and shows the largest adsorption capacity for MB. For example, the equilibrium adsorption quantity is 307 mg·g−1 for MSH-1.75, which is 35% higher than that of 227 mg·g−1 for MSH-1.00. Besides, for MSH-1.75, the as-prepared sample with negative charge exhibits ca. 36% higher adsorption quantity compared to the sample at the zero point of charge (pHZPC). Furthermore, magnesium silicate hydrate material with Si/Mg feeding ratio = 1.75 demonstrates the promising removal efficiency of beyond 98% for methylene blue in 10 min, and the maximum adsorption capacity of 374 mg·g−1 calculated from the Langmuir isotherm model.
Here we report a low-cost synthetic approach for the direct fabrication of large-area Au nanourchin arrays on indium tin oxide (ITO) via a facile galvanic-cell-reaction-driven deposition in an aqueous solution of chloroauric acid and poly(vinyl pyrrolidone) (PVP). The homogeneous Au nanourchins are composed of abundant sharp nanotips, which can served as nanoantennas and increase the local electromagnetic field enhancement dramatically. Finite element theoretical calculations confirm the strong electromagnetic field can be created around the sharp nanotips and located in the nanogaps between adjacent tips of the Au nanourchins. In addition, the interparticle nanogaps between the neighboring Au nanourchins may create additional hotspots, which can induce the higher electromagnetic field intensity. By using rhodamine 6G as a test molecule, the large-area Au nanourchin arrays on ITO exhibit active, uniform, and reproducible surface-enhanced Raman scattering (SERS) effect. To trial their practical application, the Au nanourchin arrays are utilized as SERS substrates to detect 3,3’,4,4’-tetrachlorobiphenyl (PCB-77) one congener of polychlorinated biphenyls (PCBs) as a notorious class of persistent organic pollutants. The characteristic Raman peaks can be still identified when the concentration of PCB-77 is down to 5 × 10−6 M.
Nanodiamonds (NDs) and graphene oxide (GO) are modern carbon-based nanomaterials with promising features for the inhibition of microorganism growth ability. Here we compare the effects of nanodiamond and graphene oxide in both annealed (oxidized) and reduced (hydrogenated) forms in two types of cultivation media-Luria-Bertani (LB) and Mueller-Hinton (MH) broths. The comparison shows that the number of colony forming unit (CFU) ofEscherichia coliis significantly lowered (45%) by all the nanomaterials in LB medium for at least 24 h against control. On the contrary, a significant long-term inhibition ofE. coligrowth (by 45%) in the MH medium is provided only by hydrogenated NDs terminated with C-H X groups. The use of salty agars did not enhance the inhibition effects of nanomaterials used, i.e. disruption of bacterial membrane or differences in ionic concentrations do not play any role in bactericidal effects of nanomaterials used. The specific role of the ND and GO on the enhancement of the oxidative stress of bacteria or possible wrapping bacteria by GO nanosheets, therefore isolating them from both the environment and nutrition was suggested. Analyses by infrared spectroscopy, photoelectron spectroscopy, scanning electron microscopy and dynamic light scattering corroborate these conclusions.
Small fluoride nanoparticles (NPs) with strong down-conversion (DC) luminescence at 1.5 μm are quite desirable for optical fiber communication systems. Nevertheless, a problem exists regarding how to synthesize small fluoride NPs with strong DC emission at 1.5 μm. Herein, we propose an approach to improve 1.5 μm emission of BaLuF₅:Yb3+,Er3+ NPs by way of combining doping Ce3+ ions and coating multiple BaLuF₅: Yb3+ active-shells. We prepared the BaLuF₅:18%Yb3+,2%Er3+,2%Ce3+ NPs through a high-boiling solvent method. The effect of Ce3+ concentration on the DC luminescence was systematically investigated in the BaLuF₅:Yb3+,Er3+ NPs. Under a 980 nm laser excitation, the intensities of 1.53 μm emission of BaLuF₅:18%Yb3+,2%Er3+,2%Ce3+ NPs was enhanced by 2.6 times comparing to that of BaLuF₅:18%Yb3+,2%Er3+ NPs since the energy transfer between Er3+ and Ce3+ ions: Er3+:⁴I11/2 (Er3+) + ²F5/2 (Ce3+) → ⁴I13/2 (Er3+) + ²F7/2 (Ce3+). Then, we synthesized BaLuF₅:18%Yb3+,2%Er3+,2%Ce3+@BaLuF₅:5%Yb3+@BaLuF₅:5%Yb3+ core-active-shell-active-shell NPs via a layer-by-layer strategy. After coating two BaLuF₅:Yb3+ active-shell around BaLuF₅:Yb3+,Er3+,Ce3+ NPs, the intensities of the 1.53 μm emission was enhanced by 44 times compared to that of BaLuF₅:Yb3+,Er3+ core NPs, since the active-shells could be used to not only suppress surface quenching but also to transfer the pump light to the core region efficiently through Yb3+ ions inside the active-shells.
Light-activated therapies are ideal for treating cancer because they are non-invasive and highly specific to the area of light application. Photothermal therapy (PTT) and photodynamic therapy (PDT) are two types of light-activated therapies that show great promise for treating solid tumors. In PTT, nanoparticles embedded within tumors emit heat in response to laser light that induces cancer cell death. In PDT, photosensitizers introduced to the diseased tissue transfer the absorbed light energy to nearby ground state molecular oxygen to produce singlet oxygen, which is a potent reactive oxygen species (ROS) that is toxic to cancer cells. Although PTT and PDT have been extensively evaluated as independent therapeutic strategies, they each face limitations that hinder their overall success. To overcome these limitations, we evaluated a dual PTT/PDT strategy for treatment of triple negative breast cancer (TNBC) cells mediated by a powerful combination of silica core/gold shell nanoshells (NSs) and palladium 10,10-dimethyl-5,15-bis(pentafluorophenyl)biladiene-based (Pd[DMBil1]-PEG750) photosensitizers (PSs), which enable PTT and PDT, respectively. We found that dual therapy works synergistically to induce more cell death than either therapy alone. Further, we determined that low doses of light can be applied in this approach to primarily induce apoptotic cell death, which is vastly preferred over necrotic cell death. Together, our results show that dual PTT/PDT using silica core/gold shell NSs and Pd[DMBil1]-PEG750 PSs is a comprehensive therapeutic strategy to non-invasively induce apoptotic cancer cell death.
The inhibitory effect of gallium (Ga) ions on bone resorption and their superior microbial activity are attractive and sought-after features for the vast majority of implantable devices, in particular for implants used for hard tissue. In our work, for the first time, Ga ions were successfully incorporated into the surface of titanium metal (Ti) by simple and cost-effective chemical and heat treatments. Ti samples were initially treated in NaOH solution to produce a nanostructured sodium hydrogen titanate layer approximately 1 μm thick. When the metal was subsequently soaked in a mixed solution of CaCl₂ and GaCl₃, its Na ions were replaced with Ca and Ga ions in a Ga/Ca ratio range of 0.09 to 2.33. 8.0% of the Ga ions were incorporated into the metal surface when the metal was soaked in a single solution of GaCl₃ after the NaOH treatment. The metal was then heat-treated at 600 °C to form Ga-containing calcium titanate (Ga-CT) or gallium titanate (GT), anatase and rutile on its surface. The metal with Ga-CT formed bone-like apatite in a simulated body fluid (SBF) within 3 days, but released only 0.23 ppm of the Ga ions in a phosphate-buffered saline (PBS) over a period of 14 days. In contrast, Ti with GT did not form apatite in SBF, but released 2.96 ppm of Ga ions in PBS. Subsequent soaking in hot water at 80 °C dramatically enhanced apatite formation of the metal by increasing the release of Ga ions up to 3.75 ppm. The treated metal exhibited very high antibacterial activity against multidrug resistant Acinetobacter baumannii (MRAB12). Unlike other antimicrobial coating on titanium implants, Ga-CT and GT interfaces were shown to have a unique combination of antimicrobial and bioactive properties. Such dual activity is essential for the next generation of orthopaedic and dental implants. The goal of combining both functions without inducing cytotoxicity is a major advance and has far reaching translational perspectives. This unique dual-function biointerfaces will inhibit bone resorption and show antimicrobial activity through the release of Ga ions, while tight bonding to the bone will be achieved through the apatite formed on the surface.
The present pilot study tested the efficiency of nanoTiO2 sunscreen to prevent the oxidative stress/inflammation caused by ultraviolet (UV) radiation using biomarkers in subjects' blood, urine, and exhaled breath condensate (EBC). In addition, the skin absorption of nanoTiO2 was studied. Six identical subjects participated in three tests: (A) nanoTiO2 sunscreen, (B) UV radiation, and © sunscreen + UV. The first samples were collected before the test and the second after sunscreen application and/or UV exposure. On day 4, the third samples were collected, and the sunscreen was washed off, and the fourth samples were collected on day 11. The following biomarkers were measured: malondialdehyde, 4-hydroxy-trans-hexenal, 4-hydroxy-trans-nonenal, aldehydes C6-C12, 8-iso-Prostaglandin F2α, o-tyrosine, 3-chlorotyrosine, 3-nitrotyrosine, 8-hydroxy-2-deoxyguanosine, 8-hydroxyguanosine, 5-hydroxymethyl uracil, and leukotrienes, using liquid chromatography-electrospray ionisation-tandem mass spectrometry. Titania was measured using inductively coupled plasma mass spectrometry and TiO2 nanoparticles by transmission and scanning electron microscopy. Sunscreen alone did not elevate the markers, but UV increased the biomarkers in the plasma, urine, and EBC. The sunscreen prevented skin redness, however it did not inhibit the elevation of oxidative stress/inflammatory markers. Titania and nanoTiO2 particles were found in the plasma and urine (but not in the EBC) in all sunscreen users, suggesting their skin absorption.