Hydrolysis of p-nitrophenyl esters promoted by semifluorinated quaternary ammonium polymer latexes and films.

Semifluorinated polymer latexes were prepared by emulsion polymerization of 2.5-25% of a fluoroalkyl methacrylate, 25% chloromethylstyrene, 1% styrylmethyl(trimethyl)ammonium chloride, and the remainder 2-ethylhexyl methacrylate under surfactant-free conditions. The chloromethylstyrene units were converted to quaternary ammonium ions with trimethylamine. In aqueous dispersions at particle concentrations of less than 1 mg mL(-1) the quaternary ammonium ion latexes promoted hydrolyses of p-nitrophenyl hexanoate (PNPH) in pH 9.4 borate buffer and of diethyl p-nitrophenyl phosphate (Paraoxon) in 0.1 M NaOH at 30 °C with half-lives of less than 10 min. Thin 0.7-2 µm films of the latexes on glass promoted fast hydrolysis of Paraoxon but not of PNPH under the same conditions. Even after annealing the quaternary ammonium ion polymer films at temperatures well above their glass transition temperatures, AFM images of the film surfaces had textures of particles. Contact angle measurements of the annealed films against water and against hexadecane showed that the surfaces were not highly fluorinated.

Microscopic composition maps of poly(styrene-co-2-hydroxyethyl methacrylate) colloidal crystals and interconnected colloidal arrays.

Colloidal crystalline films were prepared from poly(styrene-co-2-hydroxyethyl methacrylate) (PS-HEMA) latex particles by evaporative deposition. The hexagonally ordered surfaces of the colloidal crystals (CCs) were transformed with styrene vapor at room temperature to interconnected colloidal arrays (ICAs) that have a honeycomb-like ridge of polymer surrounding hexagonally ordered dimples in the surface. When the styrene vapor temperatures were increased systematically to 45 degrees C, the regularity of ICA structure decreased and finally disappeared. Images from transmission electron microscopy (TEM) and from atomic force microscopy (AFM) show that the surfaces of the PS-HEMA particles and the ICAs have raspberry textures. Monolayer CCs and ICAs fabricated on TEM grids were analyzed by energy dispersive spectroscopy (EDS) to determine the elemental compositions of the different regions of the textured surfaces. Carbon, oxygen, and sulfur were distributed all over the surface of the CC. While carbon was distributed over the entire surface of the ICA, oxygen, sulfur, sodium, and potassium were concentrated mainly on the ridges of the honeycomb and not in the dimples of the ICA. The results are discussed in terms of a mechanism of transformation of the CC to the ICA in which styrene monomer swells the polystyrene-rich regions of the particles, and the swollen polystyrene rises to the surface. The polyHEMA-rich regions of the particles maintain the hexagonal periodicity, and liquid styrene evaporates to leave a more polystyrene-rich textured surface.

Attraction between weakly charged silica spheres at a water-air interface induced by surface-charge heterogeneity.

We report an optical and atomic force microscopic (AFM) study of interactions between weakly charged silica spheres at a water-air interface. Attractive interactions are observed at intermediate interparticle distances and the amplitude of the attraction increases with the amount of salt (NaCl) added into the water phase. AFM images obtained in the salty water show the formation of patchy charge domains of size approximately 100 nm on the silica surface. The experiment suggests that surface heterogeneity produced during ionization plays an important role in the generation of attractions between like-charged particles at the interface.

Hydrolysis of p-nitrophenyl esters in mixtures of water and a fluorous solvent.

Hydrolyses of p-nitrophenyl hexanoate (PNPH) and diethyl p-nitrophenyl phosphate (Paraoxon) were carried out in mixtures of basic aqueous solutions and HFE-7200 (an isomeric mixture of perfluorobutyl and perfluoroisobutyl ethyl ether). Hexadecyltrimethylammonium bromide (CTAB), a perfluoroalklpylpyridinium chloride surfactant, tetrabutylammonium salts, and colloidal particles of cross-linked copolymers of 2-ethylhexyl methacrylate and styrylmethyl(trimethyl)ammonium chloride dispersed in either the aqueous phase or the HFE phase were used to promote the reactions. In a pH 9.4 borate buffer, the surfactants and the aqueous colloidal particles were the most active for PNPH hydrolysis, the PNPH preferred the HFE phase, and the rates depended both on mass transfer of the PNPH from HFE to water and on the intrinsic rate of hydrolysis in the aqueous phase. In 0.10 M NaOH, CTAB and the aqueous colloidal particles were the most active for Paraoxon hydrolysis, Paraoxon preferred the aqueous phase, and the rates followed pseudo-first-order kinetics.

Improving photocurrent generation: supramolecularly and covalently functionalized single-wall carbon nanotubes-polymer/porphyrin donor-acceptor nanohybrids.

Novel nanohybrids based on covalently and noncovalently functionalized single-wall carbon nanotubes (SWNTs) have been prepared and assembled for the construction of photoactive electrodes. Polymer-grafted SWNTs were synthesized by free-radical polymerization of (vinylbenzyl)trimethylammonium chloride. Poly[(vinylbenzyl)trimethylammonium chloride] (PVBTAn+) was also noncovalently wrapped around SWNTs to form stable, positively charged SWNT/PVBTAn+ suspensions in water. Versatile donor-acceptor nanohybrids were prepared by using the electrostatic/van der Waals interactions between covalent SWNT-PVBTAn+ and/or noncovalent SWNT/PVBTAn+ and porphyrins (H2P8- and/or ZnP8-). Several spectroscopic, microscopic, transient, and photoelectrochemical measurements were taken to characterize the resulting supramolecular complexes. Photoexcitation of the nanohybrids afforded long-lived radical ion pairs with lifetimes as long as 2.2 micros. In the final part, photoactive electrodes were constructed by using a layer-by-layer technique on an indium tin oxide covered glass support. Photocurrent measurements gave remarkable internal photon-to-current efficiencies of 3.81 and 9.90 % for the covalent ZnP8-/SWNT-PVBTAn+ and noncovalent ZnP8-/SWNT/PVBTAn+ complex, respectively, when a potential of 0.5 V was applied.

Nature of cationic poly(propylenimine) dendrimers in aqueous solutions as studied using versatile indicator dyes.

Aqueous solutions of four cationic poly(propylenimine) low-generation dendrimers of different architecture and hydrophobicity have been examined as media for acid-base reactions of indicator dyes. The cationic dendrimers in solution can be considered as oligomers of cationic polyelectrolytes, or surfactant-like species, able to form micelles through self-association or sometimes even as unimolecular micelles. The dendrimers influence the ionization constants, tautomeric equilibria, and absorption/emission/excitation spectra of indicator dyes. The p K a values of the majority of the indicator dyes decrease in dendrimer solutions, often by 1-2 p K a units, similar to effects registered in micellar solutions of cationic surfactants. Analogously, the shifts of absorption band maxima indicate that the microenvironments of the dyes bound to the dendrimers are less polar than in water. However, some spectral effects denote the specificity of the dendrimers. The greatest difference between the dendrimers and spherical surfactant micelles is revealed by kinetic processes, especially of bromophenol blue alkaline fading in a dendrimer solution but not in a micellar surfactant solution. Within the dendrimer series, the most significant differences were observed for substances possessing n-dodecyl tails on the one hand and those without such hydrophobic portions on the other. For the last-named, the decrease in p K a's of indicators, band shifts of their anions, and in particular displacement of tautomeric equilibria compared with aqueous solutions are much smaller than for more hydrophobic dendrimers.

Measured long-ranged attractive interaction between charged polystyrene latex spheres at a water-air interface.

We report results of a systematic experimental study of interactions between charged polystyrene (PS) latex spheres at a water-air interface. Optical observations of stable bonded particle clusters and formation of circular chainlike structures at the interface demonstrate that the interaction potential is of dipole origin. Atomic force microscopy (AFM) is used to examine the distribution of charge groups on the colloidal surface. AFM phase images show patchy domains of size approximately 100 nm on the particle surface, indicating that the surface charge distribution of the PS spheres is not uniform, as is commonly believed. Such patchy charges can introduce fluctuating in-plane dipoles, leading to an attraction at short interparticle separations. A theoretical analysis is given to explain the mechanism for attractions between like-charged particles at the interface.

Versatile coordination chemistry towards multifunctional carbon nanotube nanohybrids.

Dispersible single-walled carbon nanotubes grafted with poly(4-vinylpyridine), SWNT-PVP, were tested in coordination assays with zinc tetraphenylporphyrin (ZnP). Kinetic and spectroscopic evidence corroborates the successful formation of a SWNT-PVPZnP nanohybrid. Within this SWNT-PVPZnP nanohybrid, static electron-transfer quenching (2.0+/-0.1) x 10(9) s(-1) converts the photoexcited-ZnP chromophore into a radical-ion-pair state with a microsecond lifetime, namely one-electron oxidized-ZnP and reduced-SWNT.

Long-ranged attraction between charged polystyrene spheres at aqueous interfaces.

We report an optical and atomic force microscopic study of interactions between charged polystyrene spheres at a water-air interface. Optical observations of bonded particle clusters and formation of circular chainlike structures at the interface demonstrate that the interaction potential is of dipole origin. Atomic force microscope phase images show patchy domains on the colloidal surface, indicating that the surface charge distribution is not uniform as is commonly believed. Such surface heterogeneity introduces in-plane dipoles, leading to an attraction at short interparticle distances.

Semiconductor nanoparticle/polystyrene latex composite materials.

Cadmium sulfide and cadmium selenide/cadmium sulfide core/shell nanoparticles stabilized with poly(cysteine acrylamide) have been bound to polystyrene (PS) latexes by three methods. First, anionic 5 nm diameter CdS particles were electrostatically attached to 130 nm surfactant-free cationic PS latexes to form stable dispersions when the amount of CdS particles was less than 10% of the amount required to form a monolayer on the surface of the PS particles or when the amount of CdS particles exceeded the amount required to form a monolayer on the PS particles. Transmission electron microscopy (TEM) showed nanoparticles on the surface of the latex particles. Fluorescence spectra showed unchanged emission from the nanoparticles. Second, anionic, surfactant-free PS latexes were synthesized in the presence of CdS and CdSe/CdS nanoparticles. TEM showed monodisperse latex particles with trapped nanoparticles. Third, surfactant-stabilized latexes were synthesized by copolymerization of styrene with vinylbenzyl(trimethyl)ammonium chloride electrostatically bound to the CdSe/CdS nanoparticle surface. Brownian motion of the submicroscopic composite particles in water was detected by fluorescence microscopy.

Surface heterogeneity of polystyrene latex particles determined by dynamic force microscopy.

Atomic force microscopy (AFM) was employed to characterize the surface chemistry distribution on individual polystyrene latex particles. The particles were obtained by surfactant-free emulsion polymerization and contained hydrophilic quaternary ammonium chloride, sodium sulfonate, or hydroxyethyl groups. The phase shift in dynamic force mode AFM is sensitive to charge/chemical interactions between an oscillating atomic force microscope tip and a sample surface. In this work, the phase imaging technique distinguished phase domains of 50-100 nm on the surfaces of dried latex particles in ambient air. The domains are attributed to the separation of ion-rich and ion-poor components of the polymer on the particle surface.

Donor-acceptor nanoensembles of soluble carbon nanotubes.

Donor-acceptor nanoensembles, prepared via electrostatic interactions of single wall carbon nanotubes and porphyrin salts, give rise to photoinduced intra-complex charge separation that lasts tens of microseconds.

Catalysis by hydrophobically modified poly(propylenimine) dendrimers having quaternary ammonium and tertiary amine functionality.

Four different quaternary ammonium chloride-modified poly(propylenimine) (PPI) dendrimers were synthesized by alkylation of a PPI dendrimer having eight dimethylamino end groups with 1-bromooctane or 1-bromododecane. By varying the mole ratio of alkyl bromide to dendrimer, averages of 4-10 quaternary ammonium groups were formed. The new amphiphilic dendrimers are surface active and are micellar catalysts in water. The dendrimers have critical aggregation concentrations between 8.5 x 10(-4) and 9.0 x 10(-5) M. Decarboxylation of 6-nitrobenzisoxazole-3-carboxylate at 25 degrees C was 650 times faster than in water alone in the presence of a dendrimer quaternized with eight dodecyl chains at a concentration of 2.45 mM in quaternary ammonium groups. The order of the catalytic efficiency of the new dendrimers decreased with the length and number of hydrophobic alkyl groups in the order (C(12))(8) > (C(12))(4) > (C(8))(10) > (C(8))(5). The pseudo-first-order rate constants for basic hydrolysis of p-nitrophenyl hexanoate in pH 9.4 buffer at 30 degrees C using the (C(12))(8) and (C(12))(4) dendrimers were 26 and 13 times higher than those for hydrolysis with no dendrimer. The kinetic data were fit to a single-site binding model to evaluate the contributions of binding constants of reactants to the dendrimers and catalytic rate constants of the bound species to the overall catalytic activity.

Nanoscale compression of polymer microspheres by atomic force microscopy.

Atomic force microscopy (AFM) was employed to probe the mechanical properties of surface-charged polystyrene microspheres with 1-12 mol% of vinylbenzyl(trimethyl)ammonium chloride (VBTA) units. On the basis of Hertz's theory of contact mechanics, compressive moduli between 1 and 2 GPa were measured by the analysis of force-displacement curves captured on the particles via the force-volume technique. The deformation of the top of the polystyrene particles by the AFM tip was used to calculate the surface modulus. The compressive moduli are slightly less than the moduli of polystyrene bulk materials. The modulus of the polystyrene microspheres increases with an increase of the VBTA content.

Polymer brushes on single-walled carbon nanotubes by atom transfer radical polymerization of n-butyl methacrylate.

Polymer brushes with single-walled carbon nanotubes (SWNT) as backbones were synthesized by grafting n-butyl methacrylate (nBMA) from the ends and sidewalls of SWNT via atom transfer radical polymerization (ATRP). Carboxylic acid groups on SWNT were formed by nitric acid oxidation. The ATRP initiators were covalently attached to the SWNT by esterification of 2-hydroxyethyl 2'-bromopropionate with carboxylic acid groups. Methyl 2-bromopropionate (MBP) was added as free initiator during the brush preparation to control growth of the brushes and to monitor the polymerization kinetics. Size-exclusion chromatography (SEC) results show that the molecular weight of free poly(n-butyl methacrylate) (PnBMA) increased linearly with nBMA monomer conversion. PnBMA cleaved from the SWNT after high conversion had the same molecular weight as PnBMA produced in solution. Thermogravimetric analyses (TGA) show that the amount of PnBMA grown from the SWNT increased linearly with the molecular weight of the free PnBMA. The most highly PnBMA-functionalized SWNT dissolve in 1,2-dichlorobenzene, chloroform, and tetrahydrofuran, and solubility increases with the amount of PnBMA bound to SWNT. Near-infrared and Raman spectra indicate that the side walls of the SWNT were lightly functionalized by the nitric acid treatment and that the degree of functionalization of the SWNT did not change significantly during the formation of initiator or during the polymerization. Atomic force microscopy (AFM) images show contour lengths of the SWNT brushes on a mica surface from 200 nm to 2.0 microm and an average height of the backbone of 2-3 nm, indicating that the bundles of original SWNT were broken into individual tubes by functionalization and polymerization.

Monitoring the transformation of colloidal crystals by styrene vapor using atomic force microscopy.

The stages of transformation of a colloidal crystalline film of latex spheres to a new periodic structure were imaged by atomic force microscopy. Colloidal crystalline films were prepared with 320 nm diameter poly(styrene-co-2-hydroxyethyl methacrylate) (PSt/HEMA) spheres. The hexagonally ordered surfaces of the colloidal crystalline films were transformed with styrene vapor at room temperature to a new morphology having holes in the surface and the same periodicity as the original films. The surfaces of colloidal crystals and the transformed films have a raspberry-like texture superposed on the 320 nm hexagonal periodicity. Both height images and phase images reveal that the latex spheres shrink and the transformation proceeds by an order-disorder-order sequence. The final structure is an interconnected colloidal array with smaller polystyrene particles dispersed in a continuous PSt/HEMA matrix.

Cadmium sulfide and cadmium selenide/cadmium sulfide nanoparticles stabilized in water with poly(cysteine acrylamide).

Cysteine acrylamide (N-acryloyl L-cysteine) stabilizes CdS nanoparticles as the particles form in aqueous dispersions. Cysteine acrylamide also exchanges for citrate on the surfaces of CdSe and core/shell CdSe/CdS nanoparticles to provide greater stability. Heating of the nanoparticle dispersions polymerizes the cysteine acrylamide on the surface to form a more efficient polydentate stabilizer. The polymer-coated nanoparticle dispersions are colloidally stable even after removal of low molecular weight solutes by dialysis. Emission quantum yields of the polymer-coated CdSe and CdSe/CdS samples were 0.9% and 2.6%, respectively, after aging of the samples in light. CdSe/CdS coated with poly(cysteine acrylamide) is colloidally stable for at least two years in the dark at 5 degrees C.