Nanotubes of mixed-valence, transition metal compounds synthesized by solution phase approach

A solution-phase approach to synthesize four kinds of mixed-valence, transition metal compounds nanotube is described. The approach is based on the self-assembly of siloxane sol. The resulted production of mixed-valence, transition metal compounds share a common structural characteristic of tubular geometrical morphology, at least for the ones we studied. The results demonstrate that the synthesis strategy can be a general route for preparation of compound nanotubes. In addition, the size control of nanotubular materials can be easily achieved through varying the ionic strength of solution. Based on the strategy, the diameters of ultrathin Ru-Fe nanotubes can be easily tuned between 100 nm and 800 nm.

Design of polymeric stabilizers for size-controlled synthesis of monodisperse gold nanoparticles in water

A new methodology is described for the one-step aqueous preparation of highly monodisperse gold nanoparticles with diameters below 5 nm using thioether- and thiol-functionalized polymer ligands. The particle size and size distribution was controlled by subtle variation of the polymer structure. It was shown that poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA) were the most effective stabilizing polymers in the group studied and that relatively low molar mass ligands (similar to 2500 g/mol) gave rise to the narrowest particle size distributions. Particle uniformity and colloidal stability to changes in ionic strength and pH were strongly affected by the hydrophobicity of the ligand end group. "Multidentate" thiol-terminated ligands were produced by employing dithiols and tetrathiols as chain-transfer agents, and these ligands gave rise to particles with unprecedented control over particle size and enhanced colloidal stability. It was found throughout that dynamic light scattering (DLS) is a very useful corroboratory technique for characterization of these gold nanoparticles in addition to optical spectroscopy and TEM.

Solvent extraction of lanthanides and yttrium from nitrate medium with CYANEX 925 in heptane

The extraction behavior of lanthanides and yttrium usinsg CYANEX 925 (mixture of branched chain alkylated phosphine oxides) in n-heptane from nitrate medium has been studied. The effects of aqueous phase ionic strength, CYANEX 925 concentration in the organic phase, and temperature on Sm3+, Nd3+ and Y3+ extraction have been investigated. The extractability of the lanthanides and yttrium increases with increasing nitrate concentration, as well as with increasing CYANEX 925 concentration. An extraction mechanism is proposed based on slope analysis. Furthermore, the infra-red spectra of CYANEX 925 saturated with lanthanides are employed to provide evidence of the composition of the complex. The relationship between the logarithm of the distribution ratio and lanthanide atomic number is also discussed which indicates that yttrium can be separated from fight lanthanides. In addition separation of the light and heavy lanthanide groups is also possible using CYANEX 925. From the temperature dependence data, the thermodynamic parameters values (Delta H, Delta S and Delta G) are calculated.

Polyelectrolyte complexes based on chitosan and poly(L-glutamic acid)

Polyelectrolyte complexes (PECs) were prepared by mixing aqueous solutions of chitosan (CS) and poly(L-glutamic acid) (PLGA) at various pH. It was found that the stoichiometry of the PECs depends on pH.An investigation of the PECs using Fourier transform infrared spectroscopy proved that the formation of the complexes is due to electrostatic interaction between –NH3 + groups of CS and –COO− groups of PLGA. The solid PECs were characterized using wide-angle X-ray diffraction, which suggested that a strong interaction occurs between the two polymers at pH = 4 or 5 and relatively weak interaction at pH = 3. These results were further confirmed by thermogravimetric analysis data. Transmission electron microscopy showed that the complexes have a spherical shape. The effect of ionic strength on the size of the PECs was also studied using dynamic light scattering. It was found that the size of the PECs is dependent on pH.

Determination of reserpine in urine by capillary electrophoresis with electrochemiluminescence detection

A fast and sensitive approach to detect reserpine in urine using micellar electrokinetic capillary chromatography with electrochemiluminescence (ECL) of Ru(bpy)(3)(2+) detection is described. Using a 25 mum i.d. capillary as separation column, the ECL detector was coupled to the capillary in the absence of an electric field decoupler. Field-amplified injection was used to minimize the effect of ionic strength in the sample and to achieve high sensitivity. In this way, the sample was analyzed directly without any pretreatment. The method was validated for reserpine in the urine over the range of 1 x 10(-6) - 1 x 10(-4) mol/L with a correlation coefficient of 0.996. The RSD for reserpine at a level of 5 mumol/L was 4.3%. The LOD (S/N = 3) was estimated to be 7.0 x 10(-8) mol/L. The average recoveries for 10 mumol/L reserpine spiked in human urine were 94%.

Reversibly strain-tunable elastomeric photonic crystals

Reversibly strain-tunable polymeric photonic crystals made of thermoplastic polyester elastomer (TPEE) were fabricated by using the self-assembled silica opals as templates. The stop band of the polymeric photonic crystal locates at the near infrared (IR) regime in its transmission spectrum, and exhibits a blue shift with the increase of the incident angle. Because of the elasticity of the TPEE, the stop band of the TPEE photonic crystal can also be reversibly tuned at ambient temperature through to and fro uniaxially or biaxially stretching and recovering by changing the lattice spacing and the symmetry of the crystal along (1 1 1) plane.

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.

CE coupling with end-column electrochemiluminescence detection for chiral separation of disopyramide

CE with electrochemiluminescence, (ECL) detection technique was successfully applied for the chiral separation of a kind of class IA antiarrhythmic racemic drug. To the best of our knowledge, this is the first report of ECL detection used in chiral CE. To get better detection sensitivity and good enantioresolution at the same time, the conditions of capillary inlet and outlet buffer were systematically optimized. Unlike the traditional chiral separation method, the buffers we used in the capillary inlet and outlet differed from each other in terms of buffer pH, ionic strength, type of BGE as well as buffer composition. Under the optimum conditions, baseline enantioseparation and highly sensitive detection of the enantiomers were achieved. Wide linear relationship of each enantiomer was achieved in the range of 5 x 10(-7) to 2 x 10(-5) mol/L with relative coefficients of 0.996 and 0.997, respectively. The detection limits were estimated to be 8 x 10(-8) and 1.0 X 10(-7) mol/L (S/N = 3) for the enantiomers, respectively. In addition, a successful application of this new method to the chiral separation of the racemic drug in spiked plasma samples confirmed the validity and applicability of the chiral CE-ECL method.

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.

In vitro study on the binding of neutral red to bovine serum albumin by molecular spectroscopy

In this paper, the binding of neutral red (NR) to bovine serum albumin (BSA) under physiological conditions has been studied by spectroscopy method including fluorescence, circular dichroism (CD) and Fourier transform infrared (FT-IR) spectroscopy. The Stern-Volmer fluorescence quenching constant (K-SV), binding constant (K-b) and the number of binding sites (It) were measured by fluorescence quenching method. Fluorescence experiments were also performed at different ionic strengths. It was found K-SV was ionic strength dependent, which indicated the electrostatic interactions were part of the binding forces. The distance r between donor (BSA) and acceptor (NR) was obtained according to Foster's non-radiative energy transfer theory. CD spectroscopy and FT-IR spectroscopy were used to investigate the structural information of BSA molecules on the binding of NR, and the results showed no change of BSA conformation in our experimental conditions.

Interfacial behavior of DEHEHP and the kinetics of cerium(IV) extraction in nitrate media

The effects of diluents, temperature, acidity, and ionic strength of the aqueous phase on the interfacial properties of DEHEHP have been extensively investigated using the Du Nouy ring method. In addition, the effect of cerium(IV) concentration loaded in the organic phase on the interfacial tension has also been studied. With the increase of DEHEHP concentration, the value of interfacial tension (gamma) decreases in the studied system, which shows that DEHEHP has interfacial activity as a kind of surfactant. The surface excess at the saturated interface (Gamma(max)) and the minimum bulk concentration of the extractant necessary to saturate the interface (C-min) under the different conditions are calculated according to two adsorption equations such as the Gibbs and Szyszkowski functions to be presented in comprehensive tables and figures. The relationship between the interfacial activity of DEHEHP and cerium(IV) extraction kinetics by DEHEHP has been discussed by considering different factors such as the effects of diluents and temperature. However, the interfacial activity parameter of extractant only is a qualitative parameter, but cannot provide strong enough evidence to quantitatively explain the relationship between extraction kinetics and interfacial properties of an extractant.

Simultaneous determination of tramadol and lidocaine in urine by end-column capillary electrophoresis with electrochemiluminescence detection

Tramadol and lidocaine, used as analgesic and local anesthetic in surgery, are partly excreted by kidney. For the first time, we developed a simple and sensitive method, based on capillary electrophoresis with electrochemiluminescence (ECL) detection by end column mode without joint to monitor tramadol and lidocaine in urine. To eliminate the influence of ionic strength of urine sample, analytes were extracted by ether. Tripropylamine (TPA) was used as internal standard. ne recoveries of tramadol and lidocaine were between 94% and 97% at different levels. The method exhibited the linear range for the tramadol and lidocaine from 1.0 X 10(-7) to 1.0 X 10(-4) mol/L with correlation efficient of 0.998. The relative standard deviation (RSD) was 2.9% and 2.7% (n = 8) for tramadol and lidocaine, respectively. The limit of detection (LOD) was 6.0 x 10(-8) mol/L and 4.5 x 10(-8), mol/L (S/N = 3) for tramadol and lidocaine, respectively. The application for detecting tramadol and lidocaine in urine of patients showed that the method was valuable in clinical and biochemical laboratories for detecting tramadol, lidocaine and other tertiary amine pharmaceuticals for various purpose, such as metabolism investigation.

Interfacial activity of sec-nonylphenoxy acetic acid and kinetics of yttrium extraction

The interfacial behavior of sec-nonylphenoxy acetic acid (CA-100) at various diluents/(H, Na)Cl interfaces was examined using the Du Nouy ring method. Different adsorption isotherms such as the Gibbs and Szyszkowski were in good agreement with the experimental data. The values of interfacial excess at saturated interface increase in the following order: n-heptane > kerosene > cyclohexane > CCl4 > toluene > benzene > chloroform. The effects of temperature, acidity, and ionic strength of the aqueous phase on the interfacial activity of CA- 100 were also examined. The interfacial-activity data were used to discuss the mechanism and kinetics of yttrium (Y) extraction.

Real-time immunoassay of antibody activity in serum by surface plasmon resonance biosensor

A surface plasmon resonance biosensor has been used to determine antibody activity in serum. As a model system, the interaction of mouse IgG and sheep anti-mouse IgG polyclonal antibody was investigated in real time. The factors, including pH value, ionic strength, protein concentration, influencing electrostatic adsorption of mouse IgG protein onto carboxylated dextran-coated sensor chip surface, were studied. The procedures of mouse IgG protein immobilization and immune reaction were monitored in real time. The regeneration effect using the different elution reagents was also investigated. The same mouse IgG immobilized surface can be used for 100 cycles of binding and elution with only 0.38% loss per regeneration in reactivity. The results show that the surface plasmon resonance biosensor is a rapid, simple, sensitive, accurate and reliable detection technique for real-time immunoassay of antibody activity. The assay allows antibodies to be detected and studied in their native form without any purification. (C) 2000 Elsevier Science B.V. All rights reserved.

Mass transfer of Er(III) between HBTMPTP dissolved in n-heptane and HAc-NaAc

The rate of extraction of Er(III) from aqueous acetate solutions at 0. 2 mol/L ionic strength by HBTMPTP in n-heptane was studied by using a constant interfacial area cell with laminar flow at (30+/- 0. 5)degrees C. The interfacial activity of HBTMPTP was investigated at n-heptane/0. 2 mol/L (H, Na)Ac (pH=5. 00) interface, The rate of Er(III) extraction was measured at different chemical compositions by varying hydrogen ion, HBTMPTP, Cyanex 302 and chlorine ion concentrations, The effect of stirring speed, temperature and special interfacial area on the rate of extraction was also studied. The results showed that, under the conditions of the experiments, the overall rate is diffusion controlled, that the impurities of Cyanex 302 have the effect of synergistic extraction.