Facile synthesis and photoluminescent properties of redispersible CeF3, CeF3 : Tb3+, and CeF3 : Tb3+/LaF3 (core/shell) nanoparticles

CeF3, CeF3:Tb3+, and CeF3:Tb3+/LaF3 (core/shell) nanoparticles were prepared by the polyol method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), UV-vis absorption spectra, photoluminescence (PL) spectra, and lifetimes. The results of XRD indicate that the obtained CeF3, CeF3:Tb3+, and CeF3:Tb3+/LaF3 (core/shell) nanoparticles crystallized well at 200 degrees C in diethylene glycol (DEG) with a hexagonal structure. The TEM images illustrate that the CeF3 and CeF3:Tb3+ nanoparticles are spherical with a mean diameter of 7 nm. The growth of the LaF3 shell around the CeF3:Tb3+ core nanoparticles resulted in an increase of the average size (11 nm) of the nanopaticles as well as in a broadening of their size distribution. These nanocrystals can be well-dispersed in ethanol to form clear colloidal solutions. The colloidal solutions of CeF3 and CeF3:Tb3+ show the characteristic emission of Ce3+ 5d-4f (320 nm) and Tb3+ D-5(4)-F-7(J) (J = 6-3, with D-5(4)-F-7(5) green emission at 542 nm as the strongest one) transitions, respectively. The emission intensity and lifetime of the CeF3:Tb3+/LaF3 (core/shell) nanoparticles increased with respect to those of CeF3:Tb3+ core particles.

Polyhedral oligomeric silsesquioxane nanocomposite thin films via layer-by-layer electrostatic self-assembly

Fabrication of ultrathin polymer composite films with low dielectric constants has been demonstrated. Octa( aminophenyl) silsesquioxane (OAPS) was synthesized and assembled with poly( acrylic acid) (PAA) and poly( styrene sulfonate) (PSS) via a layer-by-layer electrostatic self-assembly technique to yield nanoporous ultrathin films. The OAPS was soluble in water at pH 3 or lower, and suitable pH conditions for the OAPS/PAA and OAPS/PSS assemblies were determined. The multilayer formation process was studied by contact angle analysis, X-ray photoelectron spectroscopy, atomic force microscopy, quartz crystal microgravimetry, UV-vis spectroscopy, and ellipsometry. The multilayer growth was found to be steady and uniform, and the analysis of the film surface revealed a rough topography due to OAPS aggregates. The incorporation of porous OAPS molecules into the thin films significantly lowered their dielectric constants. The OAPS/PAA multilayer thin film thus prepared exhibited a dielectric constant of 2.06 compared to 2.58 for pure PAA film. The OAPS/PAA multilayer film was heated to effect cross-linking between the OAPS and the PAA layers, and the transformation was verified by reflection-absorption Fourier transform infrared spectroscopy.

Synthesis of PtNPs/AQ/Ru(bpy)(3)(2+) colloid and its application as a sensitive solid-state electrochemiluminescence sensor material

The facile synthesis of the novel platinum nanoparticles/Eastman AQ55D/ruthenium(II) tris( bipyridine) (PtNPs/ AQ/Ru(bpy)(3)(2+)) colloidal material for ultrasensitive ECL solid-state sensors was reported for the first time. The cation ion-exchanger AQ was used not only to immobilize ECL active species Ru(bpy)(3)(2+) but also as the dispersant of PtNPs. Colloidal characterization was accomplished by transmission electron microscopy (TEM), X-ray photoelectron spectrum (XPS), and UV-vis spectroscopy. Directly coating the as-prepared colloid on the surface of a glassy carbon electrode produces an electrochemiluminescence (ECL) sensor. The electronic conductivity and electroactivity of PtNPs in composite film made the sensor exhibit faster electron transfer, higher ECL intensity of Ru(bpy)(3)(2+), and a shorter equilibration time than Ru(bpy)(3)(2+) immobilized in pure AQ film. Furthermore, it was demonstrated that the combination of PtNPs and permselective cation exchanger made the sensor exhibite excellent ECL behavior and stability and a very low limit of detection (1 x 10(-15) M) of tripropylamine with application prospects in bioanalysis. This method was very simple, effective, and low cost.

Surface-enhanced Raman scattering studies on aggregated silver nanoplates in aqueous solution

Four different sizes of citrate-protected silver nanoplates with the corresponding in-plane dipole resonance band at 530, 619, 778, and 858 nm, respectively, are synthesized for surface-enhanced Raman scattering (SERS) study. Their aggregation behaviors are monitored by use of UV-vis spectroscopy. During the aggregation process, a marked red shift of the in-plane dipole resonance of silver nanoplates is observed, whereas other resonance modes of them only have small alterations in the site or intensity. Aggregated silver nanoplates can serve as active SERS substrates with an enhancement factor of about 4.5 x 10(5) using 2-aminothiophenol as a probing molecule. The SERS performance of silver nanoplates is even superior to the commonly used Lee-Meisel silver colloid, making them very attractive for SERS applications.

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.

Sequential deprotonation of meso-(p-hydroxyphenyl)porphyrins in DMF: From hyperporphyrins to sodium porphyrin complexes

Sequential deprotonations of meso-(p-hydroxyphenyl)porphyrins (p-OHTPPH2) in DMF + H2O (V/V = 1:1) mixture have been verified to result in the appearance of hyperporphyrin spectra. However, when the deprotonations of these p-OHTPPH2 are carried out in DMF, the spectral changes differ considerably from those in the mixture mentioned above. At low [OH-], the optical spectra in the visible region are still considered to have characteristics of hyperporphyrin spectra. Further deprotonation at much higher basicity makes the optical spectra form three-banded spectra similar to those in the acidic solution. To clarify the molecular origins of these changes, UV-vis, resonance Raman (RR), proton nuclear magnetic resonance (H-1 NMR) experiments are carried out. Our data give evidence that p-OHTPPH2 in DMF can be further deprotonated of pyrrolic-H by higher concentrated NaOH, due to an aprotic medium like DMF effectively weakening the basicity of the porphyrin relative to that of the NaOH, and coordinates with two sodium ions (except the sodium ions that interact with the peripherial phenoxide anions) to form the sodium complexes of p-OHTPPH2 (Na2P, to lay a strong emphasis on the sodium ions that coordinate with the central nitrogen atom), which can be regarded as the porphyrin anions being perturbed by the sodium cations due to their highly ionic character.

Morphology-controllable synthesis and characterization of single-crystal molybdenum trioxide

Molybdenum trioxide nanobelts and prism-like particles with good crystallinity and high surface areas have been prepared by a facile hydrothermal method, and the morphology could be controlled by using different inorganic salts, such as KNO3, Ca(NO3)(2), La(NO3)(3), etc. The possible growth mechanism of molybdenum trioxide prism-like particles is discussed on the basis of the presence of HI and the modification of metal cations. The as-prepared nanomaterials are characterized by means of powder X-ray diffraction (PXRD), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), Fourier transformation infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and ultraviolet and visible spectroscopy (UV-vis). TEM and HRTEM micrographs show that the molybdenum trioxide nanobelts and prism-like particles have a relatively high degree of crystallinity and uniformity. BET specific surface areas of the as-prepared molybdenum trioxide nanocrystals are 67-79 m(2)g(-1). XPS analysis indicates that the hexavalent molybdenum is predominant in the nanocrystals. UV-vis spectra reveal that the direct band gap energy of the annealed molybdenum trioxide prism-like particles shows a pronounced blue shift compared to that of bulk MoO3 powder.

Effect of DNA flanking sequence on charge transport in short DNA duplexes

Several factors can influence charge transport (CT)-mediated DNA, such as sequence, distance, base stacking, base pair mismatch, conformation, tether length, etc. However, the DNA context effect or how flanking sequences influence redox active drugs in the DNA CT reaction and later in DNA enzymatic repair and synthesis is still not well understood. The set of seven DNA molecules in this study have been characterized well for the study of flanking sequence effects. These DNA duplexes are formed from self-complementary strands and contain the common central four-base sequence 5'-A-G-C-T-3', flanked on both sides by either (AT)(n) or (AA)(n) (n = 2, 3, or 4) or AA(AT)(2). UV-vis, fluorescence, UV melting, circular dichroism, and cyclic voltammetry experiments were used to study the flanking sequence effect on CT-mediated DNA by using daunomycin or adriamycin cross-linked with these seven DNA molecules. Our results showed that charge transport was related to the flanking sequence, DNA melting free energy, and ionic strength. For (AA)(n) or (AT)(n) species of the same length, (AA)(n) series were more stable and more efficient CT was observed through the (AA)(n) series. The same trend was observed for (AA)(n) and (AT)(n) series at different ionic strengths, further supporting the idea that flanking sequence can result in different base stacking and modulate charge transport through these seven DNA molecules.

Didodecyldimethylammonium bromide lipid bilayer-protected gold nanoparticles: Synthesis, characterization, and self-assembly

Didodecyldimethylammonium bromide (DDAB) lipid bilayer-protected gold nanoparticles (AuNPs), which were stable and hydrophilic, were synthesized by in situ reduction of HAuCl4 with NaBH4 in an aqueous medium in the presence of DDAB. As-prepared nanoparticles were characterized by UV-vis spectra, transmission electron microscopy, dynamic light scattering analysis, and X-ray photoelectron spectroscopy. All these data supported the formation of AuNPs. Fourier transform infrared spectroscopy (FTIR) and differential thermal analysis/thermogravimetric analysis data revealed that DDAB existed in a bilayer structure formed on the particle surface, resulting in a positively charged particle surface. The FTIR spectra also indicated that the DDAB bilayer coated on the surface of AuNPs was probably in the ordered gel phase with some end-gauche defects. On the basis of electrostatic interactions between such AuNPs and anionic polyelectrolyte poly(sodium 4-styrenesulfonate) (PSS), we successfully fabricated (PSS/AuNP)(n) multilayers on a cationic polyelectrolyte poly(ethylenimine) coated indium tin oxide substrate via the layer-by-layer self-assembly technique and characterized as-formed multilayers with UV-vis spectra and atomic force microscopy.

Rapid self-assembly of oligo(o-phenylenediamine) into one-dimensional structures through a facile reprecipitation route

The self-assembly of oligo(o-phenylenediamine) (OPD) into 1-D nanostructures on a macroscopic length scale was found when they were transferred from N-methyl pyrrolidone to deionized water. Field emission scanning electron microscopy and confocal fluorescence microscopy were used to investigate the morphology of the precipitates. Results showed that large amounts of OPD 1-D supertructures could be obtained through the simple reprecipitation route, and the length of the fibers could be tuned from microscale to macroscale by adjusting the ratio of two solvents. X-ray diffraction patterns and UV-vis spectra revealed that pi-pi interactions between OPD molecules that facilitated the formation of 1-D structures became predominant when they were transferred from a good solvent to a bad one. Accordingly, a possible formation mechanism was proposed.

Syntheses of fully sulfonated polyaniline nano-networks and its application to the direct electrochemistry of cytochrome c

Fully sulfonated polyaniline nano-particles, nano-fibrils and nano-networks have been achieved for the first time by electrochemical homopolymerization of orthanilic acid using a three-step electrochemical deposition procedure in a mixed solvent of acetonitrile (ACN) and water. The diameter of the uniform nano-particles is about 60nm, and the nano-fibrils can be organized in two-dimensional (21)) or three-dimensional (313) non-periodic networks with good electrical contact. Average distance between contacts is about 850 and 600 nm for a 2D and 3D system, respectively. The details of the poly(orthanilic acid) (POA) nano-structure were examined with a field emission scanning electron microscope (SEM). The structure and properties of POA were characterized with FTIR, UV-vis and electrochemical methods. The 3D POA nano-networks coated platinum electrode gave a direct electrochemical behavior of horse heart cytochrome c (Cyt c) immobilized on this electrode surface, a pair of well-defined redox waves with formal potential (E-ol) of -0.032 V (versus Ag/AgCl) was achieved. The interaction between Cyt c and POA makes the formal potential shift negatively compared to that of Cyt c in solution. Spectrophotometric and electrochemical methods were used to investigate the interaction of Cyt c with POA.

Modification of electrode surface through electrospinning followed by self-assembly multilayer film of polyoxometalate and its photochromic

Electrospun poly (vinyl alcohol) (PVA) nanofibers mat was collected on indium tin oxide (ITO) substrate. Heat crosslinked nanofibers mat became water-insoluble and firmly fixed on ITO substrate even in water. Oppositely charged poly (allylamine hydrochloride) (PAH) and Dawson-type polyoxometalate (POM), Na6P2Mo18O62 (P2Mo18), were alternately assembled on PVA nanofibers-coated ITO substrate to construct multilayer film through an electrostatic layer-by-layer (LBL) technique. The scanning electron microscope (SEM) images showed that P2Mo18 multilayer film was selectively deposited on PVA nanofibers while the unoccupied space by nanofibers on bare ITO was acted as substrate at the same time because the electrospun nanofibers have larger surface area and surface energy than the flat substrate. The cyclic voltammograms current responses of the P2Mo18 multilayer film on PVA/ITO electrode showed three well-defined redox couples of P2Mo18, but very small because P2Mo18 multilayer film was selectively deposited on PVA nanofibers with poor conductivity. In addition, the photochromic behavior of P2Mo18 multilayer film on PVA/ITO was investigated through UV-vis spectra and electron spin resonance (ESR). Fourier-transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) proved that the charge-transfer complex was formed between PAH and P2Mo18 after UV irradiation.

Self-assembly of cinnamic acid-capped gold nanoparticles

In this work, a new capping agent, cinnamic acid ( CA) was used to synthesize Au nanoparticles (NPs) under ambient conditions. The size of the NPs can be controlled by adjusting the concentration of reductant ( in our experiment sodium borohydride was used) or CA. The CA-stabilized Au NPs can self-assemble into 'nanowire-like' or 'pearl-necklace-like' nanostructures by adjusting the molar ratio of CA to HAuCl4 or by tuning the pH value of the Au colloidal solution. The process of Au NPs self-assembly was investigated by UV - vis spectroscopy and transmission electron microscopy. The results reveal that the induced dipole - dipole interaction is the driving force of Au NP linear assemblies.

One-step preparation and characterization of PDDA-protected gold nanoparticles

Poly(diallyl dimethylammonium) chloride (PDDA), an ordinary and watersoluble, cationic polyelectrolyte, was investigated for its ability to generate and stabilize gold colloids from a chloroauric acid precursor. In this reaction, PDDA acted as both reducing and stabilizing agents for gold nanoparticles (AuNPs). More importantly, PDDA is a quaternary ammonium polyelectrolyte, which shows that the scope of the reducing and stabilizing agents for metal nanoparticles can be extended from the amine-containing molecules to quaternary ammonium polyelectrolytes or salts. UV-vis spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS) and Fourier transform infrared (FTIR) were used to characterize the synthetic AuNPs. The PDDA-protected AuNPs obtained are very stable and have relative narrow size distribution.

The first synthesis of a water-soluble alpha-cyclodextrin/C-60 supramolecular complex using anionic C-60 as a building block

A novel supramolecular inclusion complex of alpha-CD/C-60 was synthesized using anionic C-60. The reaction progress was monitored in situ by visible and near-IR spectroscopy. The obtained complex was characterized by UV-vis, C-13 NMR, MALDI-TOF, and cyclic voltammetry. The induction and dispersion forces are considered to be the major driving forces for the formation of a resulting alpha-CD/C-60(.-) inclusion complex.