Extraction and separation of cadmium(II), iron(III), zinc(II), and europium(III) by Cyanex302 solutions using hollow fiber membrane modules

The mass transfer behaviors of Cd(II), Fe(III), Zn(II), and Eu(III) in sulfuric acid solution using microporous hollow fiber membrane (HFM) containing bis(2,4,4-trimethylpentyl)monothiophosphinic acid (commercial name Cyanex302) were investigated in this paper. The experimental results showed that the values of the mass transfer coefficients (K-w) decreased with an increase of H+ concentration and increased with an increase of extractant Cyanex302 concentration. The mass transfer resistance of Eu3+ was the largest because K-w value of Eu3+ was the smallest. The order of mass transfer rate of metal ions at low pH was Cd > Zn > Fe > Eu. Mixtures of Zn2+ and Eu3+ or of Zn2+ and Cd2+ were well separated in a counter-current circulation experiment using two modules connected in series at different initial acidity and concentration ratio. These results indicate that a hollow fiber membrane extractor is capable of separating the mixture compounds by controlling the acidity of the aqueous solution and by exploiting different mass transfer kinetics. The interfacial activity of Cyanex302 in sulfuric acid solution was measured and interfacial parameters were obtained according to Gibbs adsorption equation.

Synthesis of chitosan-stabilized gold nanoparticles in the absence/presence of tripolyphosphate

Gold nanoparticles were prepared by reducing gold salt with a polysaccharide, chitosan, in the absence/ presence of tripolyphosphate (TPP). Here, chitosan acted as a reducing/stabilizing agent. The obtained gold nanoparticles were characterized with UV-vis spectroscopy and transmission electron microscopy. The results indicated that the shape and size distribution of gold nanoparticles changed with the molecular weight and concentration of chitosan. More interestingly, the gelation of chitosan upon contacting with polyanion (TPP) can also affect the shape and size distribution of gold nanoparticles. By adding TPP to chitosan solution before the reduction of gold salt, gold nanoparticles have a bimodal size distribution, and at the same time, polygonal gold particles were obtained in addition to spherical gold nanoparticles.

Investigation of sandwiched gadolinium(III) complexes with tungstosilicates as potential MRI contrast agents

Two gadolinium-sandwiched complexes with tungstosilicates, K-13[Gd(SiW11O39)(2)] (Gd(SiW11)(2)) and K11H6[Gd2O3(SiW9O34)(2)] (Gd-3(SiW9)(2)), have been investigated by in vitro and in vivo experiments as potential contrast agents for magnetic resonance imaging (MRI). T-1-relaxivity of Gd(SiW11)(2)was 6.59 mM(-1) . s(-1) in aqueous solution and 6.85 mM(-1) . s(-1) in 0.725 mmol . L-1 bovine serum albumin solution at 25degreesC and 9.39 T, respectively. The corresponding T-1-relaxivity of Gd-3(SiW9)(2) was 12.6 and 19.3 mM(-1) . s(-1) per Gd, respectively. MRI for Sprague-Dawley rats showed longer and more remarkable enhancement in rat liver after i.v. injection of these two complexes: 39.4 +/- 3.9% and 57.4 +/- 11.6% within the first 30 min after injection, 31.2 +/- 2.6% and 39.9 +/- 7.6% in the next 60 min for Gd(SiW11)(2) and Gd-3(SiW9)(2) at doses of 0.081 and 0.084 mmol Gd/kg, respectively. Our preliminary in vitro and in vivo study indicates that Gd(SiW11)(2) and Gd-3(SiW9)(2) are favorable candidates for hepatic contrast agents for MRI. However, the two complexes exhibit higher acute toxicity and need to be modified and studied further before clinical use.

Gadolinium heteropoly complex K-17[Gd(P2W17O61)(2)] as a potential MRI contrast agent

Gadolinium heteropoly complex K-17[Gd(P2W17O61)(2)] has been evaluated by in vitro and in vivo experiments as a potential contrast agent for magnetic resonance imaging (MRI). The thermal analysis and conductivity study indicate that this complex has good thermal stability and wide pH stability range. The T-1 relaxivity is 7.59 mM(-1) s(-1) in aqueous solution and 7.97 mM(-1) s(-1) in 0.725 mmol l(-1) bovine serum albumin (BSA) solution at 25degreesC and 9.39 T, respectively. MR imaging of three male Sprague-Dawley rats showed remarkable enhancement in rat liver after intravenous injection, which persisted longer than with Gd-DTPA. The signal intensity increased by 57.1 +/- 16.9% during the whole imaging period at 0.082 mmol kg(-1) dose. Our preliminary in vitro and in vivo studies indicate that K-17[Gd(P2W17O61)(2)] is a potential liver-specific MRI contrast agent.

Electrochemical deposition of silver in room-temperature ionic liquids and its surface-enhanced Raman scattering effect

The use of room-temperature ionic liquids (RTILs) as media for electrochemical application is very attractive. In this work, the electrochemical deposition of silver was investigated at a glassy carbon electrode in hydrophobic 1-n-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6) and hydrophilic 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4) RTILs and in KNO3 aqueous solution by cyclic voltammetric and potentiostatic transient techniques. The voltammograms showed the presence of reduction and oxidation peaks associated with the deposition and dissolution of silver from AgBF4 in both BMIMPF6 and BMIMBF4, resembling the redox behavior of AgNO3 in KNO3 aqueous solution. A crossover loop was observed in all the cyclic voltammograms of these electrochemical systems, indicating a nucleation process. From the analysis of the experimental current transients, it was shown that the electrochemical deposition process of silver in these media was characteristic of 3D nucleation with diffusion-controlled hemispherical growth, and the silver nucleation closely followed the response predicted for progressive nucleation in BMIMPF6 and instantaneous nucleation in KNO3 aqueous solution, respectively.

Pt nanoparticles: Heat treatment-based preparation and Ru(bpy)(3)(2+)-mediated formation of aggregates that can form stable films on bare solid electrode surfaces for solid-state electrochemiluminescence detection

A simple thermal process for the preparation of small Pt nanoparticles is presented, carried out by heating a H-2-PtCl6/3- thiophenemalonic acid aqueous solution. The following treatment of such colloidal Pt solution with Ru( bpy)(3)(2+) causes the assembly of Pt nanoparticles into aggregates. Most importantly, directly placing such aggregates on bare solid electrode surfaces can produce very stable films exhibiting excellent electrochemiluminescence behaviors.

Electrogenerated chemiluminescence sensors using Ru(bpy)(3)(2+) doped in silica nanoparticles

A novel electrogenerated chemiluminescence (ECL) sensor based on Ru(bpy)(3)(2+)-doped silica (RuDS) nanoparticles conjugated with a biopolymer chitosan membrane was developed. These uniform RuDS nanoparticles ( similar to 40 nm) were prepared by a water-in-oil microemulsion method and were characterized by electrochemical and transmission electron microscopy technology. The Ru( bpy)(3)(2+)-doped interior maintained its high ECL efficiency, while the exterior nanosilica prevented the luminophor from leaching out into the aqueous solution due to the electrostatic interaction. This is the first attempt to branch out the application of RuDS nanoparticles into the field of ECL, and since a large amout of Ru(bpy)(3)(2+) was immobilized three-dimensionally on the electrode, the Ru( bpy)(3)(2+) ECL signal could be enhanced greatly, which finally resulted in the increased sensitivity. This sensor shows a detection limit of 2.8 nM for tripropylamine, which is 3 orders of magnitude lower than that observed at a Nafion-based ECL sensor. Furthermore, the present ECL sensor displays outstanding long-term stability.

Micellization and reversible pH-sensitive phase transfer of the hyperbranched multiarm PEI-PBLG copolymer

A novel, hyperbranched, amphiphilic multiarm biodegradable polyethylenimine-poly(gamma-benZyl-L-gluta- mate) (PEI-PBLG) copolymer was prepared by the ring-opening polymerization of gamma-benzyl-L-glutamate-N-car-boxyanhydride (BLG-NCA) with hyperbranched PEI as a macroinitiator. The copolymer could self-assemble into core-shell micelles in aqueous solution with highly hydrophobic micelle cores. As the PBLG content was increased, the size of the micelles increased and the critical micelle concentration (CMC) decreased. The surface of the micelles had a positive potential. The cationic micelles were capable of complexing with plasmid DNA (pDNA), which could be released subsequently by treatment with polyanions. The PEI-PBLG copolymer formed unimolecular micelles in chloroform solution. ne pH-sensitive phase-transfer behavior exhibited two critical pH points for triggering the encapsulation and release of guest molecules. Both the encapsulation and release processes were rapid and reversible. Under strong acidic or alkaline conditions, the release process became partially or completely irreversible.

Surfactantless synthesis of multiple shapes of gold nanostructures and their shape-dependent SERS spectroscopy

A useful method for the synthesis of various gold nanostructures is presented. The results demonstrated that flowerlike nanoparticle arrays, nanowire networks, nanosheets, and nanoflowers were obtained on the solid substrate under different experimental conditions. In addition, surface-enhanced Raman scattering (SERS) spectra of 4-aminothiophenol (4-ATP) on the as-prepared gold nanostructures of various shapes were measured, and their shape-dependent properties were evaluated. The intensity of the SERS signal was the smallest for the gold nanosheets, and the flowerlike nanoparticle arrays gave the strongest SERS signals.

Templated assembly of gold nanoparticles into microscale tubules and their application in surface-enhanced Raman scattering

We report a simple procedure to assemble gold nanoparticles into hollow tubular morphology with micrometer scale, wherein the citrate molecule is used not only as a reducing and capping agent, but also as an assembling template. The nanostructure and growth mechanism of microtubes are explored via SEM, TEM, FTIR spectra, and UV-vis spectra studies. The incorporation of larger gold nanoparticles by electroless plating results in an increase in the diameter of microtubes from 900 nm to about 1.2 mu m. The application of the microtubes before and after electroless plating in surface-enhanced Raman scattering (SERS) is investigated by using 4-aminothiophenol (4-ATP) as probe molecules. The results indicate that the microtubes both before and after electroless plating can be used as SERS substrates. The microtubes after electroless plating exhibit excellent enhancement ability.

Noncovalent functionalization of multiwalled carbon nanotubes: Application in hybrid nanostructures

We developed a reproducible, noncovalent strategy to functionalize multiwalled carbon nanotubes (MWNTs) via embedding nanotubes in polysiloxane shells. (3-Aminopropyl)triethoxysilane molecules adsorbed to the nanotube surfaces via hydrophobic interactions are polymerized simply by acid catalysis and form a thin polysiloxane layer. On the basis of the embedded MWNTs, negatively charged gold nanoparticles are anchored to the nanotube surfaces via electrostatic interactions between the protonated amino groups and the gold nanoparticles. Furthermore, these gold nanoparticles can further grow and magnify along the nanotubes through heating in HAuCl4 aqueous solution at 100 degrees C; as a result these nanoparticles are joined to form continuous gold nanowires with MWNTS acting as templates.

ZnO-based hollow microspheres: Biopolymer-assisted assemblies from ZnO nanorods

Many efforts have been made in fabricating three-dimensional (3D) ordered zinc oxide (ZnO) nanostructures due to their growing applications in separations, sensors, catalysis, bioscience, and photonics. Here, we developed a new synthetic route to 3D ZnO-based hollow microspheres by a facile solution-based method through a water-soluble biopolymer (sodium alginate) assisted assembly from ZnO nanorods. The products were characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, and X-ray photoelectron spectroscopy. Raman and photoluminescence spectra of the ZnO-based hollow microspheres were obtained at room temperature to investigate their optical properties. The hollow microspheres exhibit exciting emission features with a wide band covering nearly all the visible region. The calculated CIE (Commission Internationale d'Eclairage) coordinates are 0.24 and 0.31, which fall at the edge of the white region (the 1931 CIE diagram). A possible growth mechanism of the 3D ZnO superstructures based on typical biopolymer-crystal interactions in aqueous solution is tentatively proposed, which might be really interesting because of the participation of the biopolymer.

Large-scale synthesis of Berlin green Fe[Fe(CN)(6)] microcubic crystals

Berlin green FeFe(CN)(6) microcubic crystals have been successfully prepared by a simple hydrothermal process between K-3[Fe(CN)(6)] with Na2S2O3 aqueous solution, free of any surfactant or template. The experimental results clearly show that the molar ratio of K-3[Fe(CN)(6)] to Na2S2O3 and their concentrations are the dominant processing factors in controlling the size, morphology, and composition of the resulting products.

Seed-mediated synthesis of branched gold nanoparticles with the assistance of citrate and their surface-enhanced Raman scattering properties

We report an easy synthesis of highly branched gold particles through a seed-mediated growth approach in the presence of citrate. The addition of citrate in the growth solution is found to be crucial for the formation of these branched gold particles. Their size can be varied from 47 to 185 nm. The length of the thumb-like branch is estimated to be between about 5 and 20 nm, and changes slightly as the particle size increases. Owing to these obtuse and short branches, their surface plasmon resonance displays a marked red-shift with respect to the normal spherical particles. These branched gold particles exhibit stronger SERS activity than the non-branched ones, which is most likely related to these unique branching features.

Facile sonochemical synthesis of CePO4 : Tb/LaPO4 core/shell nanorods with highly improved photoluminescent properties

A simple, efficient and quick method has been established for the synthesis of CePO4:Tb nanorods and CePO4:Tb/LaPO4 core/shell nanorods via ultrasound irradiation of inorganic salt aqueous solution under ambient conditions for 2 h. The as-prepared products were characterized by means of powder x-ray diffraction (PXRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction ( SAED), x-ray photoelectron spectroscopy (XPS), photoluminescence (PL) spectra and lifetimes. TEM micrographs show that all of the as-prepared cerium phosphate products have rod-like shape, and have a relatively high degree of crystallinity and uniformity. HRTEM micrographs and SAED results prove that these nanorods are single crystalline in nature. The emission intensity and lifetime of the CePO4:Tb/LaPO4 core/shell nanorods increased significantly with respect to those of CePO4: Tb core nanorods under the same conditions. A substantial reduction in reaction time as well as reaction temperature is observed compared with the hydrothermal process.