Fabrication of Fe3O4 core-TiO2/mesoSiO2 and Fe3O4 core-mesoSiO2/TiO2 Double Shell Nanoparticles for Methylene Blue Adsorption: Kinetic, Isotherms and Thermodynamic Characterization.

Herein, Fe3O4 core-TiO2/mesoSiO2 and Fe3O4 core-mesoSiO2/TiO2 double shell nanoparticles were prepared by first (R1) and second (R2) routes and applied for the removal of methylene blue. The reported adsorption capacities for R1-0.2, R1-0.4 and R2 samples were 128, 118 and 133 mg.g-1, respectively, which were obtained after 80 min as equilibrium contact time, and pH of 6 using a methylene blue concentration of 200 ppm. The adsorption of methylene blue using the prepared Fe3O4 core-meso SiO2/TiO2 double shell was analyzed by kinetic and isotherms models. In addition, thermodynamic investigations were applied to assess the spontaneous nature of the process. The obtained results confirmed that the pseudo-second order model is well fitted with the adsorption data and the Freundlich-isotherm assumption suggested a multilayer adsorption mechanism. In addition, results of the thermodynamic investigation indicated that ΔG° was in the range of -2.3 to -6.8 kJ/mol for R1-0.2, -2.8 to -6.3 kJ/mol for R1-0.4 and -2.0 to -5.2 kJ/mol for R2. In addition, the ΔH° and ΔS° values were found in the range of 26.4 to 36.19 kJ.mol-1 and 94.9 to 126.3 Jmol-1 K-1, respectively. These results confirm that the surfaces of Fe3O4 core-mesoSiO2/TiO2 and Fe3O4 core-TiO2/mesoSiO2 double shell exhibit a spontaneous tendency to adsorb methylene blue from the aqueous solutions. The achieved performance of Fe3O4 core-meso SiO2/TiO2 and Fe3O4 core-TiO2/meso SiO2 double shell as adsorbent for methylene blue removal will encourage future research investigations on the removal of a broad range of contaminants from wastewater.

Effects of Zinc Oxide and Silicon Dioxide Nanoparticles on Physiological, Yield, and Water Use Efficiency Traits of Potato Grown under Water Deficit.

Water deficit is a major challenge for sustainable global food security, especially, in arid and semi-arid regions. Nanotechnology is regarded as an effective tool for managing a wide range of environmental stresses by providing novel and practical solutions. A field experiment was conducted to assess the effects of zinc oxide nanoparticles 'ZnO NPs' (0, 50, 100 ppm) and silicon dioxide nanoparticles 'SiO2 NPs' (0, 25, 50 ppm) as an exogenous application on the physiological indices, total yield and water use efficiency (WUE) of potato under water deficit conditions (50%, 75%, and 100% of crop evapotranspiration (ETc) water requirements). Water deficit significantly decreased most physiological indices and yield traits of potato, but increased proline content and WUE. In contrast, exogenous application of ZnO NPs and SiO2 NPs to plants grown under different water deficit treatments resulted in an increase in leaf gas exchange, leaves relative water contents (LRWC), photosynthetic pigments, and leaf green index. Under different water deficit treatments, the highest total yield and harvest index traits were obtained from plants treated with ZnO-NPs-100 ppm followed by 50 ppm of ZnO and SiO2 NPs, respectively. The highest WUE was recorded when the potato plants were irrigated with 50% ETc and exogenous treated with 100 ppm of ZnO NPs compared with fully irrigated plants. In conclusion, the exogenous application of ZnO NPs (100 ppm) can significantly mitigate the water deficit stress and improve the physiological, yield, and WUE of potato grown in arid regions under water deficit conditions.

Facile synthesized NaGdF4 :Yb,Er peanut-shaped, highly biocompatible, colloidal upconversion nanospheres.

A facile method was used for the synthesis of peanut-shaped very emissive NaGdF4 :Yb, Er upconversion nanospheres (UCNSs) at lower temperatures with uniform size distribution. Crystallographic structure, phase purity, morphology, thermal robustness, biocompatibility, colloidal stability, surface chemistry, optical properties, and luminesce properties were explored by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), zeta potential, thermogravimetric/differential thermal analysis (TGA/DTA), Fourier-transform infrared (FTIR), ultraviolet (UV)-visible and photoluminescence spectroscopic tools. XRD pattern verified the construction of a single-phase, highly-crystalline NaGdF4 phase with a hexagonal structure. Peanut-shaped morphology of the sample was obtained from SEM micrographs which were validated from high-resolution TEM images, to have an equatorial diameter of 170 to 200 nm and a length of 220 to 230 nm, with irregular size, monodispersed, porous structure, and rough surface of the particles. The positive zeta potential value exhibited good biocompatibility along with high colloidal stability as observed from the absorption spectrum. The prepared UCNSs revealed high dispersibility, irregular size peanut-shaped morphology, rough surface, good colloidal stability, and excellent biocompatibility in aqueous media. A hexagonal phase NaGdF4 doped with ytterbium (Yb) and erbium (Er) UCNSs revealed the characteristics of highly dominant emissions located at 520-525, 538-550, and 659-668 nm corresponding to the 2 H11/2 → 4 I15/2 , 4 S3/2 → 4 I15/2 , and 4 F9/2 → 4 I15/2 transition of Er3+ ions, respectively, as a result of energy transfer from sensitizer Yb3+ ion to emitter Er3+ ion.

Physiochemical characterization of highly biocompatible, and colloidal LaF3:Yb/Er upconversion nanoparticles.

Highly colloidal upconversion nanoparticles (UCNPs) were synthesized at low temperatures by the thermal decomposition process. The structure, morphology, crystallinity, surface chemistry, and optical properties were systematically optimized and studied through various spectroscopic techniques. X-ray diffraction (XRD) patterns have shown the formation of single-phase, highly purified, well-crystalline, hexagonal LaF3 NPs, while the TEM micrographs show small, irregular sizes, spherically shaped, and aggregated polycrystalline UCNPs with an average crystalline size of about 8-15 nm. The Negative Zeta Potential value exhibits good biocompatibility of the UCNPs, which supports the idea that surface-anchored hydroxyl groups facilitate the stabilization of the NPs in aqueous media, as well as enhance biomolecules' tagging efficiency. The absorption spectrum, Zeta Potential, and hydrodynamic size that were measured in aqueous media illustrate excellent dispersibility, colloidal stability, biocompatibility, and cytotoxicity character of the UCNPs. Zeta potential and MTT assay studies illustrated high biocompatibility, it could be due to the surface-anchored hydroxyl groups. The nanoproduct demonstrates an excellent UC luminescence spectrum (i.e., prominent green emission 4S3/2 → 4I/15/2) upon irradiation by the 980-nm laser diode. TEM micrographs, further, revealed that this optically active material with aqueous sensitivities, porous crystal structure, and excellent UCNPs, could be a favorable candidate for potential photonics-based bio-related applications.

Catalytic performance of the Ce-doped LaCoO3 perovskite nanoparticles.

A series of La1-xCexCoO3 perovskite nanoparticles with rhombohedral phases was synthesized via sol-gel chemical process. X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), Electron Diffraction Spectroscopy (EDS), Thermogravimetric Analysis (TGA), UV-Vis spectroscopy, Fourier Transform Infrared spectra (FTIR), Nitrogen Adsorption/desorption Isotherm, Temperature Program Reduction/Oxidation (TPR/TPO), X-ray Photoelectron Spectroscopy (XPS) techniques were utilized to examine the phase purity and chemical composition of the materials. An appropriate doping quantity of Ce ion in the LaCoO3 matrix have reduced the bond angle, thus distorting the geometrical structure and creating oxygen vacancies, which thus provides fast electron transportation. The reducibility character and surface adsorbed oxygen vacancies of the perovskites were further improved, as revealed by H2-TPR, O2-TPD and XPS studies. Furthermore, the oxidation of benzyl alcohol was investigated using the prepared perovskites to examine the effect of ceria doping on the catalytic performance of the material. The reaction was carried out with ultra-pure molecular oxygen as oxidant at atmospheric pressure in liquid medium and the kinetics of the reaction was investigated, with a focus on the conversion and selectivity towards benzaldehyde. Under optimum reaction conditions, the 5% Ce doped LaCoO3 catalyst exhibited enhanced catalytic activity (i.e., > 35%) and selectivity of > 99%, as compared to the other prepared catalysts. Remarkably, the activity of catalyst has been found to be stable after four recycles.

Facile synthesis of Pd@graphene nanocomposites with enhanced catalytic activity towards Suzuki coupling reaction.

A facile and chemical specific method to synthesize highly reduced graphene oxide (HRG) and Pd (HRG@Pd) nanocomposite is presented. The HRG surfaces are tailored with amine groups using 1-aminopyrene (1-AP) as functionalizing molecules. The aromatic rings of 1-AP sit on the basal planes of HRG through π-π interactions, leaving amino groups outwards (similar like self-assembled monolayer on 2D substrates). The amino groups provide the chemically specific binding sites to the Pd nucleation which subsequently grow into nanoparticles. HRG@Pd nanocomposite demonstrated both uniform distribution of Pd nanoparticles on HRG surface as well as excellent physical stability and dispersibility. The surface functionalization was confirmed using, ultraviolet-visible (UV-Vis), Fourier transform infra-red and Raman spectroscopy. The size and distribution of Pd nanoparticles on the HRG and crystallinity were confirmed using high-resolution transmission electron microscopy and powder X-ray diffraction and X-ray photoelectron spectroscopy. The catalytic efficiency of highly reduced graphene oxide-pyrene-palladium nanocomposite (HRG-Py-Pd) is tested towards the Suzuki coupling reactions of various aryl halides. The kinetics of the catalytic reaction (Suzuki coupling) using HRG-Py-Pd nanocomposite was monitored using gas chromatography (GC).

Solvothermal Preparation and Electrochemical Characterization of Cubic ZrO2 Nanoparticles/Highly Reduced Graphene (HRG) based Nanocomposites.

A single-step solvothermal approach to prepare stabilized cubic zirconia (ZrO2) nanoparticles (NPs) and highly reduced graphene oxide (HRG) and ZrO2 nanocomposite (HRG@ZrO2) using benzyl alcohol as a solvent and stabilizing ligand is presented. The as-prepared ZrO2 NPs and the HRG@ZrO2 nanocomposite were characterized using transmission electron microscopy (TEM) and X-ray diffraction (XRD), which confirmed the formation of ultra-small, cubic phase ZrO2 NPs with particle sizes of ~2 nm in both reactions. Slight variation of reaction conditions, including temperature and amount of benzyl alcohol, significantly affected the size of resulting NPs. The presence of benzyl alcohol as a stabilizing agent on the surface of ZrO2 NPs was confirmed using various techniques such as ultraviolet-visible (UV-vis), Fourier-transform infrared (FT-IR), Raman and XPS spectroscopies and thermogravimetric analysis (TGA). Furthermore, a comparative electrochemical study of both as-prepared ZrO2 NPs and the HRG@ZrO2 nanocomposites is reported. The HRG@ZrO2 nanocomposite confirms electronic interactions between ZrO2 and HRG when compared their electrochemical studies with pure ZrO2 and HRG using cyclic voltammetry (CV).

Mesoporous multi-silica layer-coated Y2O3:Eu core-shell nanoparticles: Synthesis, luminescent properties and cytotoxicity evaluation.

Mesoporous multi-layered silica-coated luminescent Y2O3:Eu nanoparticles (NPs) were prepared by a urea-based decomposition process, and their surfaces were gradually modified with nanoporous and mesoporous silica layers using modified sol-gel methods. The synthesized luminescent core-shell NPs were characterized thoroughly to investigate their structural, morphological, thermal, optical, photo luminescent properties and their surface chemistry. The morphology of the core NPs were nearly spherical in shape and were nano-sized grains. The observed luminescent efficiency of the mesoporous multi-layered silica-coated luminescent core NPs was gradually reduced because of bond formation between the Y2O3:Eu core and the amorphous silica shell via YOSiOH bridges on the surface of the NPs; the bonds suppressed the non-radiative transition pathways. Biocompatibility tests on Human breast cancer cells using the 3­(4,5­Dimethylthiazol­2­yl)­2,5­diphenyltetrazolium bromide and lactate dehydrogenase assays indicated that the core-shell NPs were non-toxic even at high concentrations. The mesoporous SiO2 layer played a key role in perfecting the solubility, biocompatibility, and non-toxicity of the NPs. The zeta potential, surface chemistry (Fourier transform infrared spectroscopy), and optical absorption spectral analyses revealed the high hydrophilicity of the as-prepared core-shell NPs because of the active surface-functionalized silanol (SiOH) groups, which could potentially offer many exciting opportunities in photonic-based biomedical applications.

Aqueous dispersible green luminescent yttrium oxide:terbium microspheres with nanosilica shell coating.

Tb-doped Y2O3 microspheres (MSs) were prepared via a homogeneous thermal degradation process at a low temperature and then coated with a nanosilica shell (Y2O3:Tb@SiO2) using a sol-gel process. The core MSs were highly crystalline and spherical with a porous surface, single cubic phase, and particle size of 100-250 nm. Transmission electron microscopy (TEM) images clearly showed the spherical shape of the as-prepared core MSs, which were fully covered with a thick and mesoporous nanosilica shell. Fourier transform infrared (FTIR) spectra displayed the well-resolved infrared absorption peaks of silica (SiO, SiOSi, etc.), confirming the presence of the silica surface coating. The core MSs retained their spherical shape even after heat treatment and subsequent silica surface coating. It was observed that the core/shell MSs are easily dispersible in aqueous media and form a semi-transparent colloidal solution. Ultraviolet/visible and zeta potential studies were tested to prove the changes in the surface chemistry of the as-designed core/shell MSs and compare with their core counterpart. The growth of the amorphous silica shell not only increased the particle size but also enhanced remarkably the solubility and colloidal stability of the MSs in aqueous media. The strongest emission lines originating from the characteristic intra-shell 4f-4f electronic transitions of Tb ions were quenched after silica layer deposition, but the MSs still showed strong green (5D4 → 7F5 at 530-560 nm as most dominant) emission efficiency, which indicates great potential in fluorescent bio-probes. The emission intensity is discussed in relation to the quenching mechanism induced by surface silanol (Si-OH) groups, particle size, and surface charge.

Highly biocompatible, monodispersed and mesoporous La(OH)3:Eu@mSiO2 core-shell nanospheres: Synthesis and luminescent properties.

Monodispersed La(OH)3:Eu nanospheres(core-NSs) were synthesized by urea-based homogeneous co-precipitation process, where mesoporous silica layer was coated over the surface of luminescent La(OH)3:Eu core-NSs. The XRD data exhibit the high crystalline, single hexagonal-shaped La(OH)3:Eu core and silica modified La(OH)3:Eu@mSiO2 (core-shell) NSs. Monodispersibility, spherical shaped, high surface area and mesoporosity were identified by TEM analysis and were further confirmed by BET analysis. The as-synthesized samples are highly soluble in aqueous media at ambient conditions. Spectroscopic analyses were also carried out to examine the impact of surface modification on structural, surface chemistry, optical and luminescence behavior of the as-designed silica coated core-shell NSs. The emission spectral study revealed that the luminescence intensity of magnetic-dipole transition (590 nm, 5D0 → 7F1) is dominant with respect to electric-dipole (614 nm, 5D0 → 7F2) transition. The high crystallinity of the hydroxide products supports the existence of good photoluminescence intensity, a good indication for their future use in detection of biomacromolecules through hypersensitive emission (614 nm, 5D0 → 7F2) transition. Excellent biocompatibility, cell viability and good luminescence properties suggested that the as-prepared core-shell NSs are an ideal candidate for luminescence biolabeling/bioimaging and as an optical bio-probe.

Pulicaria glutinosa extract: a toolbox to synthesize highly reduced graphene oxide-silver nanocomposites.

A green, one-step approach for the preparation of graphene/Ag nanocomposites (PE-HRG-Ag) via simultaneous reduction of both graphene oxide (GRO) and silver ions using Pulicaria glutinosa plant extract (PE) as reducing agent is reported. The plant extract functionalizes the surfaces of highly reduced graphene oxide (HRG) which helps in conjugating the Ag NPs to HRG. Increasing amounts of Ag precursor enhanced the density of Ag nanoparticles (NPs) on HRG. The preparation of PE-HRG-Ag nanocomposite is monitored by using ultraviolet-visible (UV-Vis) spectroscopy, powder X-ray diffraction (XRD), and energy dispersive X-ray (EDX). The as-prepared PE-HRG-Ag nanocomposities display excellent surface-enhanced Raman scattering (SERS) activity, and significantly increased the intensities of the Raman signal of graphene.

In-vitro cyto-toxicity, geno-toxicity, and bio-imaging evaluation of one-pot synthesized luminescent functionalized mesoporous SiO2@Eu(OH)3 core-shell microspheres.

Luminescent functionalized mesoporous SiO2@Eu(OH)3 core-shell microspheres (LFMCSMs) were prepared by coating of europium hydroxide (Eu(OH)3) shell on mesoporous silica (SiO2) nanospheres via a facile one-pot process at low temperature. The FETEM images revealed that a well-defined luminescent europium hydroxide shell was successfully grafted on the surface of mesoporous silica nanospheres. These experimental results showed that the LFMCSM has a typical diameter of ca. 392 nm consisting of the silica core with about 230 nm in diameter and europium hydroxide shell with an average thickness of about 162 nm. LFMCSMs exhibited strong red emission peak upon irradiation with ultraviolet light, which originated from the electric-dipole transition (5)D0 → (7)F2 (614 nm) of Eu(3+) ion. The biocompatibility of the synthesized LFMCSMs was evaluated in vitro by assessing their cytotoxic and genotoxic effect on human hepatoblastoma (HepG2) cells using MTT, TUNEL, fluorescent staining, DNA ladder and Gene expression assays respectively. FROM THE CLINICAL EDITOR: This paper describes the development of a one-pot synthesis of luminescent mesoporous SiO2@Eu(OH)3 core-shell microspheres and evaluates their favorable in vitro cyto-toxicity and geno-toxicity, and their applications in bio-imaging of these particles that emit bright red signal under UV exposure.