The oxidative potential (OP) of engineered nanomaterials (NM) is considered as promising metric for nanosafety research and risk assessment. Here, we present findings on the analysis of the oxidative potential of three different silver NM by means of a complementary electron paramagnetic resonance (EPR) spectroscopy-based approach, i.e., using the spin trap DMPO (5,5-dimethyl-1-pyrroline-N-oxide) and the spin probe CPH (l-hydroxy-3-carboxy-2,2,5,5-tetramethylpyrrolidine hydrochloride). The results revealed that both methods are principally applicable for OP analysis of nanosilver. However, one of the Ag NM (i.e., NM300) did not cause notable OH? generation in the presence of hydrogen peroxide, while a clear OP was detected using the CPH method for all three Ag NPs tested. For the NM300, also a strong OH? scavenging potency could be demonstrated, which was due to its surfactant-containing dispersant. This finding may explain for the reported differences in effects of this widely applied reference nanosilver versus other types of Ag NM in toxicological studies. Our findings also demonstrate the relevance of using more than one assay to determine the OP of NM in general.
Square sheet-like WO3·H2O have been efficiently synthesized via chemical precipitation route. The as-synthesized WO3·H2O nanosheets have fast adsorption rate and high-adsorption capacity for methylene blue (MB) removal from aqueous solution, which is attributed to plenty of O-H functional groups and {101} exposed facet effect. The as-synthesized material can be easily renewed via photodegradation under UV light irradiation after MB adsorption.
Graphical abstract WO3·H2O nanosheets, which can be easily renewed after MB adsorption via photodegradation, are synthesized by a facile ion-exchange route and exhibit excellent adsorption performance on MB.
A combined strategy of in situ oxidation and assembly is developed to prepare Ag/AgCl nanospheres and nanocubes from Ag nanoparticles under room temperature. It is a new facile way to fabricate Ag/AgCl with small sizes and defined morphologies. Ag/AgCl nanospheres with an average size of 80 nm were achieved without any surfactants, while Ag/AgCl nanocubes with a mean edge length of 150 nm were obtained by introduction of N-dodecyl-N,N-dimethyl-2-ammonio-acetate. The possible formation mechanism involves the self-assembly of AgCl nanoparticles, Ostwald ripening and photoreduction of Ag+ into Ag0 by the room light. The as-prepared Ag/AgCl nanospheres and nanocubes exhibit excellent photocatalytic activity and stability toward degradation of organic pollutants under visible-light irradiation. It is demonstrated that Ag/AgCl nanocubes display enhanced photocatalytic activity in comparison with Ag/AgCl nanospheres due to the more efficient charge transfer. This work may pave an avenue to construct various functional materials via the assembly strategy using nanoparticles as versatile building blocks.
Graphical abstract A combined strategy of in situ oxidation and assembly was developed to construct Ag/AgCl nanospheres and nanocubes from Ag nanoparticles, which exhibited highly photocatalytic activity and good stability for degrading methyl orange under visible light irradiation.
Plasmonic metal nanoparticles have shown great promise in enhancing the light absorption of organic dyes and thus improving the performance of dye-sensitized solar cells (DSSCs). However, as the plasmon resonance of spherical nanoparticles is limited to a single wavelength maximum (e.g., ~ 520 nm for Au nanoparticles), we have here utilized silica-coated gold nanorods (Au@SiO2 NRs) to improve the performance at higher wavelengths as well. By adjusting the aspect ratio of the Au@SiO2 NRs, we can shift their absorption maxima to better match the absorption spectrum of the utilized dye (here we targeted the 600–800 nm range). The main challenge in utilizing anisotropic nanoparticles in DSSCs is their deformation during the heating step required to sinter the mesoporous TiO2 photoanode and we show that the Au@SiO2 NRs start to deform already at temperatures as low as 200 °C. In order to circumvent this problem, we incorporated the Au@SiO2 NRs in a TiO2 nanoparticle suspension that does not need high sintering temperatures to produce a functional photoanode. With various characterization methods, we observed that adding the plasmonic particles also affected the structure of the produced films. Nonetheless, utilizing this low-temperature processing protocol, we were able to minimize the structural deformation of the gold nanorods and preserve their characteristic plasmon peaks. This allowed us to see a clear redshift of the maximum in the incident photon-to-current efficiency spectra of the plasmonic devices (Δλ ~ 14 nm), which further proves the great potential of utilizing Au@SiO2 NRs in DSSCs.
The effect of interaction of low-index atomic planes, (100), (110), and (111) terminating CdSe platelet nanocrystals is examined using molecular dynamics (MD) simulations. Asymmetry of the environment of atoms at the end surface layers leads to anisotropic deformation of the cubic lattice and to a relative shift of Cd and Se sub-lattices. Interference of distortions of the crystal lattice originating at the terminal surfaces leads to changes of symmetry of the CdSe lattice in the whole sample volume. In the models, 2–3 nm thick, for all types of surfaces under examination, the initial cubic lattice symmetry gets lost in the whole sample volume.
The most important limitation for boron neutron capture therapy of cancer is the selective accumulation of boron compounds in tumor tissues in significant quantities. In this paper, we describe the possibility to use magnetic Ni/Fe nanotubes as carriers for boron delivery. Carborane derivatives containing 10 and 21 boron atoms per molecule were immobilized on Ni/Fe nanotubes by covalent and ionic interactions. Magnetic properties of NTs were investigated by Mössbauer spectroscopy. Structure, element, chemical composition, and morphology of obtained magnetic nanotubes were studied by XRD, SEM-EDA, and FTIR spectroscopy. Results indicate success immobilization of carborane derivatives on Ni/Fe nanotubes and great potential to use them as carriers for boron neutron cancer therapy of cancer.
The results of molecular dynamics (MD) simulations of CdSe crystals terminated by low-index atomic planes, (100), (110) and (111), are presented. The effect of the crystal termination on the atomic arrangement (interatomic distances) at the surface and underneath the surface is examined. It is shown that the crystal lattice is distorted in lateral and normal directions to the depth of up to about 2 nm from the surface. The exact characteristic of the changes of interatomic distances is specific to the type of the atomic plane terminating the crystal lattice. At some surfaces, the very last monoatomic layer loses the long-range ordering and becomes quasi amorphous. The atoms group into randomly distributed pairs or short linear groups.
Gold nanoparticles 1.7 and 54 nm in diameters have been synthesized and functionalized successfully with their surfaces engineered using two atropisomeric capping ligands, 2,2′-bis(diphenylphosphino)-1,1′-binaphthalene (BINAP) and 1,1′-binaphthalene-2,2′-diamine (DABN), respectively. A systematic study to compare the two different gold nanoparticles is presented using multiple material characterization techniques. It was found that the two systems show different capping mechanism and hence differ in their intrinsic core and surface properties. The compound BINAP plays only surface capping agent and stabilizes the gold nanoparticles, resulting in small particle size and suppressed surface plasmon resonance absorption at 520 nm. The DABN capping ligand is different from BINAP and acts as both reducing and capping agent, causing the reduction of Au (III) to Au (0). The nucleation growth of the gold core occurs in accordance with the polymerization-passivation process by DABN, resulting in a big particle size of 20 nm. A strong surface plasmon resonance band shows a maximum peak at 564 nm, consistent with the Au core size. The simultaneous oxidative polymerization of DABN and the induced metal reduction process lead to the formation of gold nanoparticles encapsulated by a mixture of DABN oligomers or polymers.
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.
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.
Dendritic Pt–Cu nanoparticles were synthesized by a facile one-step method with the help of surfactant Brij58 at room temperature, and we also studied the effects of different Pt–Cu ratios on the morphology and size of nanoparticles. In addition, we further tuned the morphology of the Pt–Cu nanostructures by introducing bromide ions, eventually leading to the appearance of some tripod-like structures. Compared with dendritic Pt–Cu and commercial Pt black, these tripod-like Pt–Cu nanostructures exhibited higher electrocatalytic activity and CO tolerance for catalyzing methanol oxidation.
Monodisperse non-hybrid silica and hybrid colloidal silica of ≤?200 nm decorated with small Au nanoparticles (NPs) were synthesized in a simple single-step method. Non-hybrid silica NPs were synthesized in the absence and presence of different twin tail cationic surfactants, while tiny Au NPs were grown under in situ reaction conditions on non-hybrid silica synthesized previously by using cationic dextran. Bio-applicability and cytotoxicity of both hybrid as well as non-hybrid silica NPs were tested by using them for the extraction of protein fractions from complex aqueous protein solutions and treating them with blood cells, respectively. Both non-hybrid and hybrid silica NPs demonstrate excellent ability to extract proteins fractions predominantly of relatively low molecular masses, i.e., ~ 80 kDa. Extraction preferences between both kinds of silica became prominent when predominantly hydrophobic proteins such zein and rice proteins were used rather than mainly polar protein like BSA. Applicability for more complex biological fluid like serum indicated the competitive extractions among strongly versus weakly bound proteins. With significant bearing in in vivo conditions, hybrid silica was potentially toxic towards the blood cells in comparison to non-hybrid silica. It stems from the collective interactions of silica as well as nanometallic surfaces of Au NPs to interact with the blood cells causing hemolysis and hence may not be the suitable vehicles for drug release in systemic circulation.
Synthesis at the nanoscale has progressed at a very fast pace during the last decades. The main challenge today lies in precise localization to achieve efficient nanofabrication of devices. In the present work, we report on a novel method for the patterning of gold metallic nanoparticles into nanostructures on a silicon-on-insulator (SOI) wafer. The fabrication makes use of relatively accessible equipment, a scanning electron microscope (SEM), and wet chemical synthesis. The electron beam implants electrons into the insulating material, which further anchors the positively charged Au nanoparticles by electrostatic attraction. The novel fabrication method was applied to several substrates useful in microelectronics to add plasmonic particles. The resolution and surface density of the deposition were tuned, respectively, by the electron energy (acceleration voltage) and the dose of electronic irradiation. We easily achieved the smallest written feature of 68?±?18 nm on SOI, and the technique can be extended to any positively charged nanoparticles, while the resolution is in principle limited by the particle size distribution and the scattering of the electrons in the substrate.
It is well known that when nanoparticles (NPs) are exposed to biological fluid, it results into formation of nanoparticle protein corona, which has been the subject of extensive studies for the development of targeted drug delivery. In this work, we demonstrated the dynamic light scattering, fluorescence, and UV-visible spectroscopy as quantitative and qualitative tools to monitor adsorption of BSA protein onto silver nanoparticles (AgNPs). The adsorption resulted in significant gradual increase in average hydrodynamic radius of BSA-AgNP corona from 24 to 35 nm and its attainment of equilibrium point (saturation) that correlated with albumin concentration enables condition for bound and unbound protein adsorption to be interpreted. Using DLS, the dissociation constant (KD) was obtained for soft corona to be 2.09?±?0.30 μM. The UV-visible and fluorescence spectroscopy results were correlated with DLS. Loss of percent helicity in secondary structure of adsorbed BSA was monitored in both coronas as compared to native protein. Both coronas were found to be biocompatible with RBC membrane. Further, the results of adsorption isotherm model were used to validate the multilayer formation of albumin protein on silver nanoparticles. The obtained results would be relevant in the drug design development for tumor-targeted therapy.
Highly dispersed anisotropic Ag nanostructures were synthesized within the channels of 3-aminopropyltrimethoxysilane (APTMS)-modified mesoporous SBA-15 for catalyzing the reduction of p-dinitrobenzene, p-nitrophenol, and p-nitroacetophenone, respectively. A green templating process without involving any reducing agent, by varying the amount (1–10 wt.%) of Ag loading followed by calcination at 350 °C under H2 led to change in the morphology of Ag nanoparticles from nanospheres (~7–8 nm) to nanorods (aspect ratio ~12–30 nm) without any deformation in mesoporous sieves. In comparison to white bare SBA-15, gray-colored samples were formed with Ag impregnation exhibiting absorption bands at 484 and 840 nm indicating the formation of anisotropic Ag nanostructures within mesoporous matrix. TEM and FE-SEM micrographs confirmed the presence of evenly dispersed Ag nanostructures within as well as on the surface of mesoporous matrix. AFM studies indicated a small decrease in the average roughness of SBA-15 from 20.59 to 19.21 nm for 4 wt.% Ag/m-SBA-15, illustrating the encapsulation of majority of Ag nanoparticles in the siliceous matrix and presence of small amount of Ag nanoparticles on the mesoporous support. Moreover, due to plugging of mesopores with Ag, a significant decrease in surface area from 680 m2/g of SBA-15 to 385 m2/g was observed. The Ag-impregnated SBA-15 catalyst displayed superior catalytic activity than did bare SBA-15 with 4 wt.% Ag-loaded catalyst exhibiting optimum activity for selective reduction of p-nitrophenol to p-aminophenol (100 %), p-nitroacetophenone to p-aminoacetophenone (100 %), and p-dinitrobenzene to p-nitroaniline (87 %), with a small amount of p-phenylenediamine formation.
Graphical abstract This paper demonstrates the spontaneous formation of uniformly dispersed Ag nanospecies of various morphologies (nanospheres, size ~7–8 nm and nanorods, aspect ratio ~12–30 nm), both within as well as on the surface of the mesoporous SBA-15, as a function of increased Ag loading. Surface structural and other physiochemical properties of Ag/m-SBA-15 nanocomposites were considerably influenced w.r.t change in Ag loading. Ag/m-SBA-15 nanocomposites with 4 wt.% Ag loading exhibited the highest selectivity (87 %) for the selective reduction of p-dinitrobenzene to p-nitroaniline and 100 % selectivity for p-nitrophenol to p-aminophenol and p-nitroacetophenone to p-aminoacetophenone, respectively.
A general facile synthesis approach was used for fabrication of highly emissive aqueous dispersible hexagonal phase upconversion luminescent NaGdF4:Yb/Er nanorods (core NRs) through metal complex decomposition process. An inert NaGdF4 and porous silica layers were grafted surrounding the surface of each and every NRs to enhance their luminescence efficiency and colloidal dispersibility in aqueous environment. Optical properties in terms of band gap energy of core, core/shell, and silica-coated core/shell/SiO2 nanorods were observed to investigate the influence of surface coating, which was gradually decreased after surface coating because of increase crystalline size after growth of inert and silica shells. The inert shell formation before silica surface grafting, upconversion luminescence intensity was greatly improved by about 20 times, owing to the effective surface passivation of the seed core and, therefore, protection of Er3+ ion in the core from the nonradiative decay caused by surface defects. Moreover, after silica coating, core/shell nanorods shows strong upconversion luminescence property similar to the hexagonal upconversion core NRs. It is expected that these NaGdF4:Yb/Er@NaGdF4@SiO2 (core/shell/SiO2) NRs including highly upconversion emissive and aqueous dispersible properties make them an ideal materials for various photonic-based potential applications such as in upconversion luminescent bioimaging, magnetic resonance imaging, and photodynamic therapy.
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.
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.
The Neumann Schrödinger operator \(\mathcal{L}\) is considered on a thin 2D star-shaped junction, composed of a vertex domain Ωint and a few semi-infinite straight leads ωm, m = 1, 2, ..., M, of width δ, δ ? diam Ωint, attached to Ωint at Γ ? ?Ωint. The potential of the Schrödinger operator lω on the leads vanishes, hence there are only a finite number of eigenvalues of the Neumann Schrödinger operator Lint on Ωint embedded into the open spectral branches of lω with oscillating solutions χ±(x, p) = \(e^{ \pm iK_ + x} e_m \) of lωχ± = p2χ±. The exponent of the open channels in the wires is
, with constant em, on a relatively small essential spectral interval Δ ? [0, π2δ?2). The scattering matrix of the junction is represented on Δ in terms of the ND mapping
. We derive an approximate formula for \(\mathcal{N}\) in terms of the Neumann-to-Dirichlet mapping \(\mathcal{N}_{\operatorname{int} } \) of Lint and the exponent K? of the closed channels of lω. If there is only one simple eigenvalue λ0 ∈ Δ, Lintφ0 = λ0φ0 then, for a thin junction, \(\mathcal{N} \approx |\vec \phi _0 |^2 P_0 (\lambda _0 - \lambda )^{ - 1} \) with
. The related boundary condition for the components P+Ψ(0) and P+Ψ′(0) of the scattering Ansatz in the open channel \(P_ + \Psi (0) = (\bar \Psi _1 ,\bar \Psi _2 , \ldots ,\bar \Psi _M ), P_ + \Psi '(0) = (\bar \Psi '_1 , \bar \Psi '_2 , \ldots , \bar \Psi '_M )\) includes the weighted continuity (1) of the scattering Ansatz Ψ at the vertex and the weighted balance of the currents (2), where
. Conditions (1) and (2) constitute the generalized Kirchhoff boundary condition at the vertex for the Schrödinger operator on a thin junction and remain valid for the corresponding 1D model. We compare this with the previous result by Kuchment and Zeng obtained by the variational technique for the Neumann Laplacian on a shrinking quantum network.
