Facile synthesis and optical properties of polymer-laced ZnO-Au hybrid nanoparticles

Bi-phase dispersible ZnO-Au hybrid nanoparticles were synthesized via one-pot non-aqueous nanoemulsion using the triblock copolymer poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) as the surfactant. The characterization shows that the polymer-laced ZnO-Au nanoparticles are monosized and of high crystallinity and demonstrate excellent dispersibility and optical performance in both organic and aqueous medium, revealing the effects of quantum confinement and medium. The findings show two well-behaved absorption bands locating at approximately 360 nm from ZnO and between 520 and 550 nm from the surface plasmon resonance of the nanosized Au and multiple visible fingerprint photoluminescent emissions. Consequently, the wide optical absorbance and fluorescent activity in different solvents could be promising for biosensing, photocatalysis, photodegradation, and optoelectronic devices.     

Highly bright and photostable cyanine dye-doped silica nanoparticles for optical imaging: Photophysical characterization and cell tests

Spherical silica nanoparticles containing fluorescent trimethine indocyanine dyes (λ_abs = 547 nm, λ_em = 570 nm) were prepared using a water-in-oil microemulsion method. The nanoparticles were of 50 nm diameter and were almost monodispersed in aqueous solution at pH 5.5. Entrapment of dye molecules in the silica matrix stabilised photoemission over several hours of continuous irradiation. The photoemission intensity of the indocyanine was increased 13-fold over that recorded in solution. As each nanoparticle contained 110 dye molecules, the photoemission brightness of each particle was enhanced by three orders of magnitude. The fluorescent nanoparticles have been tested as imaging tools in in vitro tests. As an example of non-macrophagic cells, a highly differentiated neuronal cell line (GT1-7) was used and the results showed that the prepared nanoparticles can be incorporated into these cells with no apparent toxicity for up to three days.     

A novel copolymer of N-[(tert-butylperoxy)methyl]acrylamide and maleic anhydride for use as a reactive surfactant in emulsion polymerization

A new copolymer of N-[(tert-butylperoxy)methyl]acrylamide (tBPMAAm), containing a primary–tertiary peroxide group and maleic anhydride (MA), was synthesized and employed as a reactive surfactant (inisurf) for the emulsion polymerization of styrene to yield surface-functionalized (peroxidized) reactive latex particles. The copolymerization characteristics were analyzed to determine the monomer reactivity ratios and to provide a way to control the copolymer composition. The ability of tBPMAAm–MA to act as a reactive surfactant during emulsion polymerization was confirmed by the synthesis of monodisperse polystyrene latexes of varying particle size. In addition, peroxide groups were localized on the surface of the particles in a controllable amount (depending on the copolymer concentration), thus, providing the opportunity for further modification of the surface of the particles. This novel copolymer is expected to be a promising and efficient material in the synthesis of functional polymer nanoparticles with well-defined core–shell morphologies.     

Effect of Gd doping on structural,optical properties,photoluminescence and electrical characteristics of CdS nanoparticles for optoelectronics

Synthesis of pure and 0.1 to 5?wt.% Gd-doped CdS nanoparticles (NPs) was achieved through a modified domestic microwave-assisted route in a short timespan at 700?W power. The formation of hexagonal CdS NPs was verified via X-ray diffraction analysis, and no structural variation was observed except for lattice variation. The size of the crystallites (D), dislocation concentration, and lattice strain were calculated, and the D was in the range of 3–6?nm. Fourier transform-Raman analysis confirmed the presence of 1LO, 2LO, and 3LO modes at 294.76, 590, and 890?cm^?1, respectively, in all the synthesized nanostructures, with minute variations in their positions due to doping; however, no new mode was observed. The position of the vibration modes was red shifted compared to that of the bulk material, indicating a confinement effect. Scanning electron microscopy (SEM) mapping/energy-dispersive X-ray spectroscopy revealed homogeneous doping of Gd and the presence of all the constituents in the final products. The morphology of the synthesized materials was tested via field-emission SEM, which revealed spherical NPs with small dimensions. Additionally, high-resolution transmission electron microscopy was performed to visualize the shape and size of the prepared 0.1% Gd:CdS NPs. The energy gap was calculated using the Kubelka–Munk theory and found to be in the range of 2.31–2.41?eV. The photoluminescence emission spectra exhibited two green emission peaks at 516?±?2?nm and 555?±?2?nm and showed the reduction of defects with Gd doping in terms of intensity quenching. The dielectric constant (${\epsilon }^{\text{'}}$), loss, and alternating-current electrical properties were studied in the high-frequency range. The values of ${\epsilon }^{\text{'}}$ were in the range of 17–27. An enhancement of these values was observed for CdS when it was doped with Gd. The electrical conductivity exhibited frequency power law behavior.     

Reduced erbium-doped ceria nanoparticles: one nano-host applicable for simultaneous optical down- and up-conversions

This paper introduces a new synthesis procedure to form erbium-doped ceria nanoparticles (EDC NPs) that can act as an optical medium for both up-conversion and down-conversion in the same time. This synthesis process results qualitatively in a high concentration of Ce³⁺ ions required to obtain high fluorescence efficiency in the down-conversion process. Simultaneously, the synthesized nanoparticles contain the molecular energy levels of erbium that are required for up-conversion. Therefore, the synthesized EDC NPs can emit visible light when excited with either UV or IR photons. This opens new opportunities for applications where emission of light via both up- and down-conversions from a single nanomaterial is desired such as solar cells and bio-imaging.     

Microwave combustion synthesis,magneto-optical and electrochemical properties of NiMoO4 nanoparticles for supercapacitor application

Nickel molybdate (NiMoO₄) nanoparticles (NPs) were synthesized by a simplistic one-pot microwave combustion method using urea as the fuel. The produced NPs have been examined by powder X-ray diffraction (XRD), Fourier transform infrared (FT-IR) analysis, scanning electron microscope (SEM), energy dispersive X-ray (EDX), high-resolution transmission electron microscopy (HR-TEM) analysis. Further, optical and electronic properties were determined by UV-Visible and Photoluminescence (PL) analysis, respectively. The magnetic performance of the NiMoO₄ NPs was investigated by vibrating sample magnetometer (VSM) and the surface chemical composition was identified by X-ray photoelectron spectroscopy (XPS). The electrochemical activities of the NiMoO₄ NPs were studied by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatic charge/discharge (GCD) analysis. From the results, the CV curves indicated the occurrence of redox couples and besides with the EIS data (Nyquist plot), confirmed the supercapacitor nature of the synthesized NiMoO₄. The prepared NiMoO₄ exhibits a high specific capacitance and rateability. This electrode grants a high specific capacitance of 450?F?g^?1 at 2?mA?cm^?2 and the well permanency with a cycling proficiency of 94% after 1000 cycles. These results clearly showed that the synthesized NiMoO₄ NPs have potential application for the forthcoming flexible and lightweight energy storage.     

Methacrylate/acrylate ABA triblock copolymers by atom transfer radical polymerization; their properties and application as a mediator for organically dispersible gold nanoparticles

This investigation reports the preparation of a series of well-defined Poly(methyl methacrylate)-b-poly(hexyl acrylate)-b-poly (methyl methacrylate) (PMMA-b-PHA-b-PMMA) triblock copolymers by Atom Transfer Radical Polymerization (ATRP). Their morphology, dynamic mechanical and tensile properties are thoroughly investigated. Phase separation is observed for all the above-mentioned triblock copolymers, which contain PMMA outer blocks in the molecular weight (M_n) range of 10,000-80,000 and PHA inner blocks with M_n in the range 20,000-40,000. The dynamic mechanical measurements essentially reveal two glass transitions and an intermediate flat rubbery plateau in between. Tensile studies indicate that as the PMMA content increases, there is an increase in tensile strength and decrease in elongation at break, which is the case for most of the thermoplastic elastomers (TPE). Eventually, the as prepared block copolymers (with PMMA content 50-80%) offer to be an effective stabilizer for preparing gold nanoparticle aggregates, the shape and size of which can be modulated by tuning the block copolymer composition. The formation of nanoparticle aggregates and their possible non-covalent interaction with the base polymer has been substantiated by UV-vis analysis, transmission electron microscopy, energy-dispersive X-ray spectroscopy, dynamic light scattering and Fourier transform infrared spectroscopy.     

Olive leaves extract mediated zero-valent iron nanoparticles: synthesis,characterization, and assessment as adsorbent for nickel (II) ions in aqueous medium

Abstract

Zero-valent iron nanoparticles (NZVI-NPs) possess significantly high surface area and volume ratio, and this unique surface characteristic has enhanced reactivity to their adsorption potential. In this work, a bio-matter (Olive leaves extract) is deployed as a nature-inspired reducing agent for the synthesis of NZVI-NPs. The particle size of NZVI-NPs has been determined using particle sizer. The NZVI-NPs are characterized using analytical and morphological techniques such as ultraviolet???visible spectroscopy (UV???vis), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction spectroscopy (XRD), scanning electron microscope (SEM), Brunauer–Emmett–Teller (BET), and Fourier transform infrared (FTIR) spectroscopy. The average crystalline size of NZVI-NPs are around 30–60?nm while maximum adsorption is at 225?nm. XRD spectrum shows two distinctive diffraction peaks at 25.40° and 42.50° corresponding to lattice plane value indexed at (200) and (222) planes of faced centered cubic (FCC). At optimized experimental conditions, NZVI-NPs show 97% removal efficiency of Ni⁺² ions from aqueous solution. The equilibrium time has been found to be 55?min and the monolayer maximum adsorption capacity is 139.5?mg/g. Kinetically, Ni⁺² ions adsorption has been modelled using various physical isotherms and the data best fitted Freundlich isotherm model and pseudo-first-order kinetic; revealing a maximum adsorption capacity of 139.5?mg/g at 25?±?3?°C and pH of 6.5. Desorption tests affirm the possibility of recovering reasonable amount of NZVI-NPs after used. The specific surface area of the NZVI-NPs sample measured by BET analysis is 21.9967 m²/g indicating a high adsorption capacity.     

CFD modelling for a TiO2-coated glass-bead photoreactor irradiated by optical fibres: Photocatalytic degradation of oxalic acid

Computational fluid dynamics coupled with the radiant transport equation was used to simulate oxalic acid photodegradation in a TiO₂-coated glass-bead photoreactor irradiated by end-emitting optical fibre (EEOF) or side-emitting optical fibre (SEOF) bundles. Light irradiance distributions in the photoreactor were modelled for specular, partially specular and diffusive reactor wall reflectivities with specularly reflective reactor walls best representing the experimental data. The light irradiance distribution for the SEOF bundle was found to be more uniform along the fibre length than for the EEOF bundle. Under the experimental radiant power input (108 mW) the EEOF and SEOF bundles exhibited similar oxalic acid photodegradation rates. However, the developed model demonstrated that at incident radiant power more than ten times greater than the experimental power used, a uniform light distribution gave faster oxalic acid photodegradation with the relative improvement of the SEOF bundle over the EEOF bundle increasing with increasing radiant power. This was attributed to increased electron-hole recombination in photocatalytic surfaces close to the EEOF tip, induced by the increased light irradiance in this region. The model also demonstrated a constant light irradiance profile along the length of a SEOF bundle giving an improved photocatalytic performance when compared to linear or exponentially decaying light profiles.     

Bio-fabrication of gold nanoparticles using aqueous extract of red tomato and its use as a colorimetric sensor

In this work, we report a green method for the synthesis of gold nanoparticles (GNP) using the aqueous extract of red tomato (Lycopersicon esculentum). We believe that citric acid and ascorbic acid present in tomato juice are responsible for the reduction of gold ions. This biosynthesized GNP in the presence of sodium dodecyl sulfate has been used as a colorimetric sensor to detect and estimate the pesticide, methyl parathion. The GNP in the presence of methyl parathion shows a new peak at 400 nm due to the formation of 4-nitrophenolate ion by catalytic hydrolysis of methyl parathion in alkaline medium. A calibration curve between the absorption coefficients of the 400-nm peak versus the concentration of the pesticide allows the quantitative estimation of the 4-nitrophenolate ion, thereby enabling indirect estimation of methyl parathion present in the system.     

Beyond platinum: synthesis,characterization, and in vitro toxicity of Cu(II)-releasing polymer nanoparticles for potential use as a drug delivery vector

The field of drug delivery focuses primarily on delivering small organic molecules or DNA/RNA as therapeutics and has largely ignored the potential for delivering catalytically active transition metal ions and complexes. The delivery of a variety of transition metals has potential for inducing apoptosis in targeted cells. The chief aims of this work were the development of a suitable delivery vector for a prototypical transition metal, Cu²⁺, and demonstration of the ability to impact cancer cell viability via exposure to such a Cu-loaded vector. Carboxylate-functionalized nanoparticles were synthesized by free radical polymerization and were subsequently loaded with Cu²⁺ via binding to particle-bound carboxylate functional groups. Cu loading and release were characterized via ICP MS, EDX, XPS, and elemental analysis. Results demonstrated that Cu could be loaded in high weight percent (up to 16 wt.%) and that Cu was released from the particles in a pH-dependent manner. Metal release was a function of both pH and the presence of competing ligands. The toxicity of the particles was measured in HeLa cells where reductions in cell viability greater than 95% were observed at high Cu loading. The combined pH sensitivity and significant toxicity make this copper delivery vector an excellent candidate for the targeted killing of disease cells when combined with an effective cellular targeting strategy.     

Fabrication of CeO2 nanoparticles modified glassy carbon electrode and its application for electrochemical determination of UA and AA simultaneously

A glassy carbon electrode modified with CeO₂ nanoparticles was constructed and was characterized by electrochemical impedance spectrum (EIS) and cyclic voltammetry (CV). The resulting CeO₂ nanoparticles modified glassy carbon electrode (CeO₂ NP/GC electrode) was used to detect uric acid (UA) and ascorbic acid (AA) simultaneously in mixture. This modified electrode exhibits potent and persistent electron-mediating behavior followed by well-separated oxidation peaks towards UA and AA with activation overpotential. For UA and AA in mixture, one can well separate from the other with a potential difference of 273 mV, which was large enough to allow the determination of one in presence of the other. The DPV peak currents obtained in mixture increased linearly on the UA and AA in the range of 5.0 × 10⁻⁶ to 1.0 × 10⁻³ mol/L and 1.0 × 10⁻⁶ to 5.0 × 10⁻⁴ mol/L, with the detection limit (signal-to-noise ratio was 3) for UA and AA were 2.0 × 10⁻⁷ and 5.0 × 10⁻⁶ mol/L, respectively. The proposed method showed excellent selectivity and stability, and the determination of UA and AA simultaneously in serum was satisfactory.     

Effects of annealing temperature on some structural and optical properties of ZnO nanoparticles prepared by a modified sol-gel combustion method

Plate-shaped zinc oxide nanoparticles (ZnO-NPs) were successfully synthesized by a modified sol-gel combustion method. Zinc acetate, pure water and isopropanol were used as the starting materials. Acetic acid, diethanolamine and nitric acid were used as the polymerization agent, complexing agent and fuel, respectively. The precursors were formed by mixing aqueous solutions of zinc acetate, acetic acid and diethanolamine. Nitric acid was used to dry the produced gel. The resulting xerogel was annealed at 600 °C, 650 °C and 750 °C for 1 h. The synthesized ZnO-NPs were characterized by X-ray diffraction analysis (XRD), thermogravimetric analysis (TGA) and high-magnification transmission electron microscopy (TEM). The XRD results revealed that the samples produced were crystalline with a hexagonal wurtzite phase. The TEM results showed single-crystal ZnO-NPs with nearly hexagonal plate shapes. The optical properties of the ZnO-NPs were studied by UV-visible and Fourier-transform infrared spectroscopy (FTIR). The UV-vis absorption spectra of the ZnO-NPs indicated absorption peaks in the UV region, which were attributed to the band gap of the ZnO-NPs. The results of the FTIR and UV-vis studies showed that the optical properties of the ZnO-NPs depended on the annealing temperature.     

The synthesis and characterization of monodispersed chitosan-coated Fe3O4 nanoparticles via a facile one-step solvothermal process for adsorption of bovine serum albumin

Preparation of magnetic nanoparticles coated with chitosan (CS-coated Fe₃O₄ NPs) in one step by the solvothermal method in the presence of different amounts of added chitosan is reported here. The magnetic property of the obtained magnetic composite nanoparticles was confirmed by X-ray diffraction (XRD) and magnetic measurements (VSM). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) allowed the identification of spherical nanoparticles with about 150 nm in average diameter. Characterization of the products by Fourier transform infrared spectroscopy (FTIR) demonstrated that CS-coated Fe₃O₄ NPs were obtained. Chitosan content in the obtained nanocomposites was estimated by thermogravimetric analysis (TGA). The adsorption properties of the CS-coated Fe₃O₄ NPs for bovine serum albumin (BSA) were investigated under different concentrations of BSA. Compared with naked Fe₃O₄ nanoparticles, the CS-coated Fe₃O₄ NPs showed a higher BSA adsorption capacity (96.5 mg/g) and a fast adsorption rate (45 min) in aqueous solutions. This work demonstrates that the prepared magnetic nanoparticles have promising applications in enzyme and protein immobilization.     

A carboxyalkanethiol monolayer modified electrode for blocking of ascorbic acid oxidation and its application to a biosensor

Upon the application of amperometric biosensor to the biological fluid, ascorbic acid interferes the amperometric determination of analytes, because the oxidative potential of ascorbic acid is lower than that of electro active substances such as H₂O₂ produced by the enzymatic reaction. In this study we propose a method to block ascorbic acid based on the electrostatic interaction with self-assembled monolayer (SAM) and its application of the surface modified electrode to biosensor. In order to form SAM on the gold electrode with carboxyl group, 7-carboxy-heptanethiol (7-CHT) was used. The 7-CHT modified electrode did not show anodic response to ascorbic acid, but oxidized phenanthroline cobalt complex [Co(phen)₃²⁺], which can be used as a mediator of biosensor. Thus, the 7CHT-modified electrode was applied to biosensor mediated with Co(phen)₃²⁺. Fructose dehydrogenase (FDH) was immobilized to the 7-CHT modified electrode. Fructose was determined selectively with the FDH/7-CHT modified electrode at the range of 0.2-2 mM.     

Novel Pt-Ru nanoparticles formed by vapour deposition as efficient electrocatalyst for methanol oxidation: Part II. Electrocatalytic activity

The methods developed and described in paper—part I are employed to prepare nanometer size Pt-Ru particles on a Vulcan^® XC72R substrate with controlled metal loading. Transmission Electron Microscopy (TEM) confirmed uniform particles size (average diameter 2 nm) and homogeneous dispersion of the particles over the substrate. Energy Dispersive X-ray absorption (EDX) analysis confirmed the compositional homogeneity. The catalytic activity of these supported nanoparticles with regard to methanol electrooxidation is investigated using cyclic voltammetry (CV), chronoamperometry (CA) and CO-stripping voltammetry techniques at temperatures between 25 and 60 °C. Such investigation concerns supported catalysts prepared with ca. 10 and 18 wt.% overall metal loading (Pt + Ru) onto the Vulcan^® XC72R substrate. Comparative testing of our catalysts and a commercial Pt-Ru/Vulcan reveals markedly superior activity for our catalysts. In fact, we observe for the latter a five-fold increase of the oxidation current as compared to a commercial Pt-Ru/Vulcan with equal metal loading. One of the reasons for the greater activity is found to be the very high dispersion of the metals over the substrate, i.e. the large surface area of the active phase. Other reasons are plausibly ascribable to the varied Pt/Ru composition and/or reduced presence of contaminants at the catalyst surface.     

Synthesis and application of ethylenediamine tetrapropionic salt as a novel draw solute for forward osmosis application

The development of suitable draw solutes for forward osmosis (FO) process is a big obstacle on the way of its real industrialization. In this work, a novel draw solute, ethylenediamine tetrapropionic (EDTP) acid (salt) is developed for FO application. The successful synthesis is confirmed by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, and high resolution mass spectrum. By optimizing the pH of EDTP solution, its composition is varied, and therefore, its water solubility and osmotic pressure are effectively improved. The effects of EDTP concentration on the osmotic pressure and FO performance are also investigated. Its outstanding osmotic pressure and big molecular size result in a high water flux of 22.69 LMH and a low salt flux of 0.32 gMH with 0.8 M EDTP draw solution (water as the feed solution, pressure retarded osmosis mode). The good stability and easy recovery by nanofiltration of EDTP solution also demonstrate its great potential as the draw solute for future FO applications. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1309–1321, 2015     

Thiourea assisted one-pot easy synthesis of CdS/rGO composite by the wet chemical method: Structural,optical, and photocatalytic properties

We report on the synthesis of CdS/reduced graphene oxide (rGO) composite by a wet chemical method. Thiourea was used both as a sulfur source and as a reducing agent to convert graphene oxide to rGO. The structural and morphological confirmation for the reduction of graphene oxide and the formation of the CdS/rGO composite was demonstrated by X-ray diffractometry, Raman spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy analyses. Photoluminescence spectra of the composite exhibited a more efficient luminescence quenching in comparison with pure CdS nanoparticles. The composite demonstrated 99% photodegradation of methyl orange under UV irradiation, which is much superior than the photodegradation of methyl orange under similar conditions exhibited by CdS nanoparticles (72%).     

Well-defined second-order nonlinear optical polymers by controlled radical polymerization,via multifunctional macromolecular chain transfer agent: Design,synthesis, and characterizations

To address the issue of the aggregation in second-order nonlinear optical (NLO) polymers we developed an approach based on the synthesis of a multifunctional macromolecular chain transfer agent. The controlled monomer insertion polymerization into the main chain by a ‘reversible addition-fragmentation chain transfer’ (RAFT) mechanism allows the spatial arrangement of the NLO chromophores along the polymeric chain in order to obtain sequence-ordered polymers. In a first step, a novel trithiocarbonate based macroinitiator containing the disperse red 19 (DR19) units in the main chain was synthesized by polycondensation; in a second step, this polymeric precursor was applied to the synthesis of a sequentially ordered polymer by controlled insertion radical polymerization of styrene. Size exclusion chromatography (SEC), nuclear magnetic resonance (NMR) data revealed that, (i) for the first time, polystyrenes (PS) bearing DR19 dyes covalently bounded were obtained, and (ii) both the insertion reaction and the length of the polystyrene segments were accurately controlled. Whatever the incorporated dye amount, all the copolymers were soluble in common solvents. Second-order optical nonlinearity in corona-poled thin films was evaluated, and second harmonic coefficients up to 80 pm/V were determined for loading ratio lower than 10 wt-% (DR19/PS). This approach opens up opportunities for the incorporation of more efficient chromophores even in apolar matrices.     

Bridging the gap between homogeneous and heterogeneous gold catalysis: supported gold nanoparticles as heterogeneous catalysts for the benzannulation reaction

Gold nanoparticles supported on metal oxides and activated carbon are able to catalyze the benzannulation reaction of o-(phenylethynyl)benzaldehyde and phenylacetylene to 1-benzoyl-2-phenylnaphtalene with high selectivity at 99% conversion. Benzannulation of ortho-alkynyl benzaldehydes is a reaction typically catalyzed by soluble AuCl₃ and, now, we have found that it can also be catalyzed by heterogeneous gold supported catalysts. The heterogeneous catalytic system can be reused several times without loss of activity or selectivities.