Interaction of cylindrical polymer brushes in dilute and semi-dilute solution

We present a systematic study of flexible cylindrical brush-shaped macromolecules in a good solvent by small-angle neutron scattering (SANS), static light scattering (SLS), and by dynamic light scattering (DLS) in dilute and semi-dilute solution. The SLS and SANS data extrapolated to infinite dilution lead to the shape of the polymer that can be modeled in terms of a worm-like chain with a contour length of 380 nm and a persistence length of 17.5 nm. SANS data taken at higher polymer concentration were evaluated by using the polymer reference interaction site model (PRISM). We find that the persistence length reduce from 17.5 nm at infinite dilution to 5.3 nm at the highest concentration (volume fraction 0.038). This is comparable with the decrease of the persistence length in semi-dilute concentration predicted theoretically for polyelectrolytes. This finding reveals a softening of stiffness of the polymer brushes caused by their mutual interaction.     

Microwave assisted one pot synthesis of biocompatible gold nanoparticles in Triton X-100 aqueous micellar medium using tryptophan as reducing agent

The present work reports an environmentally benign process for the synthesis of gold nanoparticles via microwave-assisted heating method, using a basic amino acid l-Tryptophan as reducing agent. The synthesis was carried out in the presence of a nonionic surfactant Triton X-100 (TX-100) aqueous micellar system. Influence of various reaction parameters such as microwave irradiation time and concentrations of precursor ion were analyzed. The effect of pH on the plasmonic properties and stability of synthesized AuNPs were studied in detail. The various size distributions of gold nanostructures obtained were characterized and analyzed by ultraviolet visible spectroscopy (UV-Vis), TEM and DLS analysis. Fourier transform infrared (FT-IR) measurements were carried out to identify the interaction sites responsible for capping and efficient stabilization by the amino acid as well as the surfactant. The synthesized gold nanoparticles were stable for more than 6 months at ambient conditions.     

Potential use of capillary zone electrophoresis in size characterization of quantum dots for environmental studies

Quantum dot (QD) nanoparticles (NPs) are of great interest to various researchers due to their wide range of applications, from photovoltaic sensitizers to in vivo fluorescent probes. There is a need to characterize environmental fate, degradation, and ecotoxicity of QDs because these NPs may be introduced into the environment upon disposal of waste products containing QDs following the anticipated increase in their production and use. Because the properties of QDs are defined primarily by their composition and size, it is imperative that QD size be measured accurately and quickly. Current methods for measuring the size of QDs tend to be relatively slow, require large amounts of sample and may not be suitable for environmental or biological samples. Capillary zone electrophoresis (CZE), with its inherently high separation efficiency based on the size-to-charge ratio of analytes, holds promise for efficient size determination of NPs in aqueous samples.This review examines the potential use of CZE in characterizing and separating QDs compared to the conventional methods employed in determining size distribution of NPs. We briefly discuss the advantages and the limitations of commonly used techniques for size characterization.In addition to published literature, we present results from our laboratory using CZE with laser-induced fluorescence (LIF) to examine the effect of natural organic matter and buffer composition on the electrophoretic mobility of QDs. The use of CZE in environmental studies can provide insights into the degradation and the potential impacts of QDs upon exposure to environmental and biological matrices.     

Nonelectrolyte-Induced Micellar Shape Changes in Aqueous Solutions of Silicone Surfactants

Dynamic light scattering, cloud point (CP), and surface tension studies have been carried out to examine the influence of six (including two acetates, two alkoxyethanols, and two sugars) nonelectrolyte additives on two silicone surfactants based on poly (dimethyl siloxane)—graft—polyethers in aqueous solutions. The results indicate that the presence of alkoxyethanols induced the oblate ellipsoidal to spherical micellar transition, while sugars increase the size of the ellipsoidal micelles. The effect of cosolvent or additives on critical micelle concentration (CMC) and CP is discussed on the basis of water structure making and breaking effect. The thermodynamic and surface active parameters were calculated from the surface tension isotherm curves.     

Surfactant-free coating of thiols on gold nanoparticles using sonochemistry: A study of competing processes

A method for the surfactant-free coating of gold nanoparticles with thiols using sonochemistry is presented. The gold nanoparticles were prepared by a modified Zsigmondy method, affording good control over the particle-size distribution, and the thiol coating was performed by the sonication of a biphasic system consisting of a nanoparticle suspension in water and thiols in toluene. The effects of two important reaction parameters on the particle morphology, viz. sonication time and thiol concentration, were investigated in detail using transmission electron microscopy. The effect of the thiol chain length was also studied. We show that the morphology of the coated particles is determined through a competition between two opposing effects: particle fusion, due to the sonication conditions, and digestive ripening, due to the action of the thiols. Additionally, we illustrate the utility of our technique for various applications, including surface-enhanced Raman scattering from bound molecules, and further functionalization using a thiol-exchange reaction. Our technique paves the way for an efficient synthesis of thiol-coated AuNPs of different shapes and sizes, suitable for a range of diverse applications.     

Preparation of a variety of fluoroalkyl end‐capped N‐(1,1‐dimethyl‐3‐oxobutyl)acrylamide oligomer/silica nanocomposites possessing no weight loss characteristic at 800°C

A variety of fluoroalkyl end‐capped N‐(1,1‐dimethyl‐3‐oxobutyl)acrylamide oligomer [R_F‐(DOBAA)_n‐ R_F]/silica nanocomposites, in which the oligomer contents are 18–96%, were prepared by reactions of the corresponding fluorinated oligomer with tetraethoxysilane and silica nanoparticles under alkaline conditions. Each fluorinated oligomer/silica composite thus obtained is nanometer size‐controlled very fine particles (22–68 nm) possessing a good dispersibility and stability in a variety of solvents including water. Interestingly, the weight loss of R_F‐(DOBAA)_n‐R_F/silica nanocomposites, in which the oligomer contents are 18–72%, were not observed at all even at 800°C, as well as the original silica nanoparticles, although the corresponding sub‐micrometer size‐controlled R_F‐ (DOBAA)_n‐R_F/silica composites (particle size: 359 nm) decomposed completely at 800°C to afford the weight loss in proportion to the content of R_F‐(DOBAA)_n‐R_F oligomer in composites. On the other hand, a slight weight loss of R_F‐(DOBAA)_n‐R_F/silica nanocomposites, in which the oligomer contents are 75–94%, was observed at 800°C compared to that of the original silica nanoparticles. Copyright © 2008 John Wiley & Sons, Ltd.