Preparation and application of MS-M2+ nanoparticles as a novel resonance light-scattering probe

Metal-enriched metal sulfide nanoparticles (MS-M2+, M = Zn, Cu, Pb, Ni, Cd) have been prepared. We found ZnS-Zn2+ and CuS-Cu2+ nanoparticles are water-soluble and biocompatible. They could be used as new kind of resonance light-scattering (RLS) probes in the determination of gamma-globulin human, which was proved to be a simple, rapid and specific method. In comparison with organic dye probes, these nanoparticles probes are brighter, more stable against photobleaching, and do not suffer from blinking. Under the optimum conditions, the response is linearly proportional to the concentration of gamma-globulin human. ZnS-Zn2+ nanoparticles as a RLS probe: between 0.1 and 2.0 mg l(-1), and the limit of detection is 0.0403 mg l(-1); CuS-Cu2+ nanoparticles as a RLS probe: between 0.1 and 1.5 mg l(-1), and the limit of detection is 0.0646 mg l(-1). We find the effect of other protein on this assay is weak, this assay has good selectivity.     

Resonance Raman spectroscopy as a probe of the crystallite size of MoS2 nanoparticles

Irregularly shaped and inorganic fullerene-like MoS₂ compounds were characterized by Resonance Raman spectroscopy using an exciting line at 633 nm. It was shown that the relative intensity of the longitudinal acoustic mode at 226 cm⁻¹ and its overtone strongly depends on the MoS₂ crystallite size but not on the size of the particles made of agglomerated crystallites. This technique appeared as a promising probe to characterize in situ very small crystallites that are not observed by XRD.     

Incommensurate structures investigated by X-ray studies of electropolymerised methacrylic monomer with TiO2 nanoparticles

We explore the possibility of producing polymer nanocomposites with an ordered distribution of nanoparticles by using an electropolymerizable liquid crystal (LC) monomer. The nanoparticles are added to the monomer before polymerizing it. We study the polymer derived from the LC (E)-6-(3-hydroxy-4-(((4-octyloxy)phenyl)imino)methyl)phenoxy)hexyl methacrylate (M6R8) both pure and in the presence of 3.4 nm TiO₂ nanoparticles, at 30 wt%. This particular system is chosen since (1) the LC polymers we work with have the added advantage of having a specific orientation and structure which allows us to study its effect in the nanoparticles and (2) when considering the nanocomposite, it is polymerized with the nanoparticles included. The system is studied using grazing incidence small angle X-ray scattering and in-plane direction X-ray scattering. The polymer obtained alone appears to be tilted with respect to the surface of the substrate. The structure adopted by the nanoparticles in the nanocomposite is layered and apparently incommensurate with the polymer. It is formed through the association of the nanoparticles with the M6R8 aromatic cores during the process of electropolymerisation. This interpretation of the data is supported by the nanoparticle structures formed when the related, non-polymerizable LC, (E)-6-(3-hydroxy-4-(((4-octyloxy)phenyl)imino)methyl)phenoxy)hexyl isobutyrate (I6R8), is analysed. We find that for both, the pure polymer poly-((E)-6-(3-hydroxy-4-(((4-octyloxy)phenyl)imino)methyl)phenoxy)hexyl) methacrylate (EPM6R8) as well as the polymer with nanoparticles (EPM6R830TO), the electropolymerisation imposes a preferred growth direction of the polymer side chains, and therefore for the nanoparticle arrangement in the polymer.     

Effect of polyaniline as a surface modifier of TiO2 nanoparticles on the properties of polyvinyl chloride/TiO2 nanocomposites

Surface of TiO2 nanoparticles was modified with the in situ chemical oxidative polymerization of aniline. Polyaniline modified TiO2 nanoparticles (PANI-TiO2 ) were characterized with the FT-IR, XRD, SEM and TEM techniques. Results confirmed that PANI was grafted successfully on the surface of TiO2 nanoparticles, therefore agglomeration of nanoparticles decreased dramatically. Polyvinyl chloride nanocomposites filled with 1 wt% 5 wt% of PANI-TiO2 and TiO2 nanoparticles were prepared via the solution blending method. PVC nanocomposites were analyzed with FT-IR, XRD, SEM, TG/DTA, DSC and tensile test techniques. Effect of PANI as surface modifier of nanoparticles was discussed according to the final properties of PVC nanocomposites. Results demonstrated that deposition of PANI on the surface of TiO2 nanoparticles improved the interfacial adhesion between the constituents of nanocomposites, which resulted in better dispersion of nanoparticles in the PVC matrix. Also PVC/PANI-TiO2 nanocomposites showed higher thermal resistance, tensile strength and Young’s modulus compared to those of unfilled PVC and PVC/TiO2 nanocomposites.     

Determining the orientation and molecular packing of organic dyes on a TiO2 surface using X-ray reflectometry

The determination of the orientation and molecular density for several porphyrin dyes adsorbed on planar TiO(2) surfaces using X-ray reflectometry (XRR) is reported. Adsorption of nanoscale water layers occurred rapidly upon exposure of freshly prepared TiO(2) surfaces to ambient conditions; however, this was successfully eliminated, resulting in clearly discernible adsorbed dye layers for sensitized surfaces. Adsorbed dye orientations, determined from computations constrained by the measured dye layer thickness, were calculated to have a binding tilt angle of 35°-40°. Combining the XXR data with the orientation models indicates that the porphyrins form densely packed surfaces with an intermolecular spacing of 3-4 ?, consistent with π-π stacking interactions. Changes in the molecular size of probe dyes were reflected in corresponding changes in the measured dye layer thickness, confirming the ability of this technique to resolve small variations in dye layer thickness and consequently adsorption orientation. Application of these results to understanding the behavior of dye-sensitized devices is discussed.     

Interfacial surface properties of thiol-protected gold nanoparticles: a molecular probe EPR approach

We present a molecular probe technique for accessing interfacial surface electrostatics of ligand-protected gold nanoparticles. A series of ligands with variable length of the hydrocarbon bridge between the anchoring sulfur and the reporting pH-sensitive nitroxide is described. The protonation state of this probe is directly observed by EPR spectroscopy. For tiopronin-protected Au nanoparticles, we observed an increase in pKa of up to ca. 1.1 pH units that was affected by the position of the reporter moiety with respect to the monolayer interface.     

Synthesis of luminescent bioapatite nanoparticles for utilization as a biological probe

A europium-doped apatitic calcium phosphate was synthesized at low temperature (37°C) in water–ethanol medium. This apatite was calcium-deficient, rich in hydrogen phosphate ions, and poorly crystallized with nanometric sized crystallites. It is similar to the mineral part of calcified tissues of living beings and is thus a biomimetic material. The substitution limit of Eu³⁺ for Ca²⁺ ions in this type of bioapatite ranged about 2–3%. The substitution at this temperature was facilitated by vacancies in the calcium-deficient apatite structure. As the luminescence of europium is photostable, the doped apatite could be employed as a biological probe. Internalization of these nanoparticles by human pancreatic cells in culture was observed by luminescence confocal microscopy.     

Unmodified gold nanoparticles as a colorimetric probe for potassium DNA aptamers

Unmodified gold nanoparticles effectively differentiate unfolded and folded DNA, thus providing a novel approach to colorimetrically probe aptamer-based recognition processes.     

Anatase TiO2 nanoparticles on rutile TiO2 nanorods: a heterogeneous nanostructure via layer-by-layer assembly

We report here the use of a layer-by-layer assembly technique to prepare novel TiO2 heterogeneous nanostructures in which anatase nanoparticles are assembled on rutile nanorods. The preparation includes assembling anatase nanoparticle multilayers on rutile nanorods via electrostatic deposition using poly(sodium 4-styrene sulfonate) as a bridging or adhesion layer, followed by burning off the polymeric material via calcination. The composition of the heterogeneous nanostructures (i.e., the anatase-to-rutile ratio) can be tuned conveniently by controlling the experimental conditions of the layer-by-layer assembly. It was found that, with the optimum preparation conditions, the heterogeneous nanostructures showed better photocatalytic activity for decomposing gaseous acetaldehyde than either the original anatase nanoparticles or the rutile nanorods. This is discussed on the basis of the synergistic effect of the existence of both rutile and anatase in the heterogeneous nanostructure.     

ZnO nanowire arrays coating on TiO2 nanoparticles as a composite photoanode for a high efficiency DSSC

A novel composite photoanode with ZnO nanowire arrays coating on the top of TiO(2) nanoparticles is fabricated, and an efficiency of 4.52% is achieved for the composite cell, far higher than both 0.90% of the ZnO nanowire cell and 3.56% of the TiO(2) nanoparticle cell. The improved efficiency is resulted from the high surface area of nanoparticles, as well as fast electron transport and light scattering effect of nanowires.     

A gold-containing TiO complex: a crystalline molecular precursor as an alternative route to Au/TiO2 composites

The gold-containing titanium peroxo-complex AuCl4(NH4)7[Ti4(O2)4(Hcit)2(cit)2].12H2O 1 allows an easy reproducible access to pure Au/TiO2 composites.     

Frequency modulated spectroscopy as a probe of molecular collision dynamics

We describe the application of frequency modulated spectroscopy (FMS) with an external cavity tuneable diode laser to the study of the scalar and vector properties of inelastic collisions. CN X(2)Sigma(+) radicals are produced by polarized photodissociation of ICN at 266 nm, with a sharp velocity and rotational angular momentum distribution. The collisional evolution of the distribution is observed via sub-Doppler FMS on the A(2)Pi-X(2)Sigma(+) (2,0) band. He, Ar, N(2), O(2) and CO(2) were studied as collider gases. Doppler profiles were acquired in different experimental geometries of photolysis and probe laser propagation and polarization, and on different spectroscopic branches. These were combined to give composite Doppler profiles from which the speed distributions and specific speed-dependent vector correlations could be determined. The angular scattering dynamics with species other than He are found to be very similar, dominated by backward scattering which accompanies transfer of energy between rotation and translation. The kinematics of collisions with He are not conducive to the determination of differential scattering and angular momentum polarization correlations. Angular momentum correlations show interesting differences between reactive and non-reactive colliders. We propose that this reflects differences in the potential energy surfaces, in particular, the nature and depth of attractive potential wells.     

Cyclodextrin complexation as a probe of molecular photophys1cs

Three examples are described in which complexation of organic guests by a cyclodextrin (CD) alters the photophysical paths for excited state decay of the host-guest complex. The fluorescence properties ol the complexes between β- and γ-CD and the bichromophoric molecule 1.1'-bis-(α-naphthylmethyl) dithiane are presented to illustrate how complexation alters the dynamics of conformational interconversion. The complexation of β-naphthol by β-CD is shown by time-correlated emission spectroscopy to prevent the adiabatic deprotonation of the excited alcohol normally observed in aqueous solution. Lastly, solid complexes of CD's and aromatic donor-acceptor molecules such as p-nitroaniline (PNA) are shown to be active for generation of second harmonic radiation (SHG) when irradiated by 1.06 μ light from a Nd-YAG laser. Since PNA itself crystallizes in a centrosymmetric space group incapable of producing SHG, the complexation method effectively induces SHG activity in this polarizable, but nonpolar material.     

Heteroelemental diatomic secondary ions as a probe for molecular states

Summary The complete chemical characterization of environmental particles requires a depth resolved analysis of the chemical state of the elements. Using dynamic SIMS, a depth-resolved determination of the chemical state of chromium was derived from measurements of ten different chromium salts and oxides. The evaluation is based on the signals of Cr ₂ ⁺ , CrO⁺ and Cr₂O⁺ which are the most intense molecular ions. The valence state of chromium can be determined for concentrations far less than 1 atom %. The transferability of this kind of analysis is shown for manganese compounds. Additionally binary mixed metal clusters are shown to indicate binding partners of compounds in mixtures.     

Near monodisperse TiO2 nanoparticles and nanorods

Highly crystalline, near monodisperse TiO2 nanoparticles, nanorods and their metal-ion-doped (Sn4+, Fe3+, Co2+, and Ni2+, etc.) derivatives have been prepared by well-controlled solvothermal reactions. Through adjusting the reaction parameters, such as reaction temperature, duration, and concentration of the reactants, the size, shape, and dispersibility of the products can be controlled. A possible reaction mechanism can be proposed based on experimental evidence.     

Synthesis of ZnO and TiO2 nanoparticles

We report on the synthesis of ZnO and TiO₂ nanoparticles by solution-phase methods, with a particular focus on the influence of experimental parameters on the kinetics of nucleation and coarsening. The nucleation rate of ZnO from the reaction between ZnCl₂ and NaOH in ethanol was found to increase with increasing precursor concentration, while the coarsening rate is independent of precursor concentration up to a threshold concentration. The nucleation rate of ZnO from Zn(OOC-CH₃)₂ and NaOH in n-alkanols was found to decrease with decreasing chain length, which is explained by the increase of the dielectric constant of the solvent. Due to the larger solubility of ZnO, nucleation is significantly slower than that observed in the case of TiO₂. TiO₂ nanoparticles coarsen according to the Lifshitz-Slyozov-Wagner model for Ostwald ripening. We also show that using amorphous titania as a base material, pure anatase and brookite nanoparticles can be synthesized.     

Preparation and application of functionalized nanoparticles of CdS as a fluorescence probe

CdS nanoparticles have been prepared and modified with mercaptoacetic acid. The functionalized nanoparticles are water-soluble and biocompatible. They could be used as a fluorescence probe in the determination of bovine serum albumin (BSA), which was proved to be a simple, rapid and specific method. In comparison with single organic fluorophores, these nanoparticle probes are brighter, more stable against photobleaching, and do not suffer from blinking. Under the optimum conditions, the response is linearly proportional to the concentration of BSA between 0.1 and 3.2 μg ml⁻¹, and the limit of detection is 0.08 μg ml⁻¹.