Facile syntheses of surface-functionalized micelles and shell cross-linked nanoparticles

Block copolymer micelles and shell cross-linked nanoparticles (SCKs) presenting Click-reactive functional groups on their surfaces were prepared using two separate synthetic strategies, each employing functionalized initiators for the controlled radical polymerization of acrylate and styrenic monomers to afford amphiphilic block copolymers bearing an alkynyl or azido group at the α-terminus. The first route for the synthesis of the azide-functionalized nanostructures was achieved via sequential nitroxide-mediated radical polymerization (NMP) of tert-butyl acrylate and styrene, originating from a benzylic chloride-functionalized initiator, followed by deprotection of the acrylic acids, supramolecular assembly of the block copolymer in water and conversion of the benzylic chloride to a benzylic azide. In contrast, the second strategy utilized an alkynyl-functionalized reversible addition fragmentation transfer (RAFT) agent directly for the RAFT-based sequential polymerization of tetrahydropyran acrylate and styrene, followed by selective cleavage of the tetrahydropyran esters to give the α-alkynyl-functionalized block copolymers. These Click-functionalized polymers, with the functionality located at the hydrophilic polymer termini, were then self-assembled using a mixed-micelle methodology to afford surface-functionalized “Clickable” micelles in aqueous solutions. The optimum degree of incorporation of the Click-functionalized polymers was investigated and determined to be ca. 25%, which allowed for the synthesis of well-defined surface-functionalized nanoparticles after cross-linking selectively throughout the shell layer using established amidation chemistry. Functionalization of the chain ends was shown to be an efficient process under standard Click conditions and the resulting functional groups revealed a more “solution-like” environment when compared to the functional group randomly inserted into the hydrophilic shell layer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5203–5217, 2006     

Synthesis of silicon nitride based ceramic nanoparticles by the pyrolysis of silazane block copolymer micelles

Diblock copolymer poly(1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane)‐block‐polystyrene (polyVSA‐b‐polySt) and triblock copolymer poly(1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane)‐block‐polystyrene‐block‐poly(1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane) (polyVSA‐b‐polySt‐b‐polyVSA), consisting of silazane and nonsilazane segments, were prepared by the living anionic polymerization of 1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane and styrene. PolyVSA‐b‐polySt formed micelles having a poly(1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane) (polyVSA) core in N,N‐dimethylformamide, whereas polyVSA‐b‐polySt and polyVSA‐b‐polySt‐b‐polyVSA formed micelles having a polyVSA shell in n‐heptane. The micelles with a polyVSA core were core‐crosslinked by UV irradiation in the presence of diethoxyacetophenone as a photosensitizer, and the micelles with a polyVSA shell were shell‐crosslinked by UV irradiation in the presence of diethoxyacetophenone and 1,6‐hexanedithiol. These crosslinked micelles were pyrolyzed at 600 °C in N₂ to give spherical ceramic particles. The pyrolysis process was examined by thermogravimetry and thermogravimetry/mass spectrometry. The morphologies of the particles were analyzed by atomic force microscopy and transmission electron microscopy. The chemical composition of the pyrolysis products was analyzed by X‐ray fluorescence spectroscopy and Raman scattering spectroscopy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4696–4707, 2006     

Comprehensive study on the formation of polyelectrolyte complexes from (quaternized) poly[2‐(dimethylamino)ethyl methacrylate] and poly(2‐acrylamido‐2‐methylpropane sodium sulfonate)

Polyelectrolyte complexes (PECs) have been prepared from well‐defined (quaternized) poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA) and high molecular weight poly(2‐acrylamido‐2‐methylpropane sodium sulfonate) (PAMPSNa) after a thorough study of their viscometric properties. The effect of pH and quaternization degree of PDMAEMA on PECs stoichiometry has been examined. PEC‐based materials have been characterized in terms of thermal stability, equilibrium swelling degree, and free/bound water composition. The stoichiometry and swellability of the physically crosslinked hydrogels obtained from fully quaternized PDMAEMA/PAMPSNa complexes do not depend on pH. In contrast, PECs made of non quaternized PDMAEMA and PAMPSNa are highly affected by pH, and could reversibly disintegrate at pH ≥ 9. Partially quaternized PDMAEMA/PAMPSNa PECs exhibit intermediate properties and form stable loose structures in the whole investigated pH range. Finally, stable dispersions of PECs nanoparticles have been successfully produced from dilute solutions of the complementary polyelectrolytes. The nanoparticle average diameter as determined by dynamic light scattering proved to depend on the molar fraction of DMAEMA‐based subunits and on the initial polyelectrolyte concentration. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5468–5479, 2006     

Probing the use of small‐angle light scattering for characterizing structure of titanium dioxide/low‐density polyethylene nanocomposites

Small‐angle light scattering (SALS) measurements were used to study the structure of titanium dioxide (TiO₂)/low‐density polyethylene (LDPE) nanocomposites. The results showed that the scattering from LDPE crystalline structures and the scattering from TiO₂ nanoparticles can be resolved and separated. It is shown that the independent effects of crystallization conditions and the presence of nanoparticle aggregates on the spherulitic structure of the LDPE matrix can be determined by analyzing the scattering patterns using the methods proposed. From the SALS results, we conclude that the nanoparticle surface chemistry affects both nucleation of spherulites and their structure particularly under rapid cooling conditions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1084–1095, 2006     

Activity evaluation of carbon paste electrodes loaded with pt nanoparticles prepared in different radiolytic conditions

Three Pt-based catalysts prepared in different radiolytic conditions and supported on graphite powder were packed into a carbon paste electrode configuration. They were compared to each other, to the commercial (Pt) deposited on activated carbon powder (Johnson Matthey) and to pure Vulcan XC-72 for their respective abilities toward the hydrogen evolution reaction (HER). The Tafel parameters were determined for all these electrodes. From the I–V curves and their quantitative treatment, the following order of activity emerged unambiguously and reads: (PtCO)₂ (fcc structure) > (PtCO)₁ (Chini cluster) > (Pt)_neat > (Pt)_JM (Johnson Matthey) ≫ (Vulcan XC-72). As expected, all the Pt-loaded electrodes were more efficient than Vulcan XC-72. The classification appears to be linked with the mean nanoparticle size, and for comparable sizes, with the surface morphology of the materials. The results and the stability of the electrodes suggest that the small particle sizes and the good dispersity on the carbon support were maintained during the HER.     

On degeneracy and collapsing in the construction of the set of objective values in a multiple objective linear program

In this paper an algorithm is developed to generate all nondominated extreme points and edges of the set of objective values of a multiple objective linear program. The approach uses simplex tableaux but avoids generating unnecessary extreme points or bases of extreme points. The procedure is based on, and improves, an algorithm Dauer and Liu developed for this problem. Essential to this approach is the work of Gal and Kruse on the neighborhood problem of determining all extreme points of a convex polytope that are adjacent to a given (degenerate) extreme point of the set. The algorithm will incorporate Gal's degeneracy graph approach to the neighborhood problem with Dauer's objective space analysis of multiple objective linear programs.     

Nuclear spin-lattice relaxation mechanisms in kaolinite confirmed by magic-angle spinning

Spin-lattice relaxation mechanisms in kaolinite have been reinvestigated by magic-angle spinning (MAS) of the sample. MAS is useful to distinguish between relaxation mechanisms: the direct relaxation rate caused by the dipole-dipole interaction with electron spins is not affected by spinning while the spin diffusion-assisted relaxation rate is. Spin diffusion plays a dominant role in ¹H relaxation. MAS causes only a slight change in the relaxation behavior, because the dipolar coupling between ¹H spins is strong. ²⁹Si relaxes directly through the dipole-dipole interaction with electron spins under spinning conditions higher than 2 kHz. A spin diffusion effect has been clearly observed in the ²⁹Si relaxation of relatively pure samples under static and slow-spinning conditions. ²⁷Al relaxes through three mechanisms: phonon-coupled quadrupole interaction, spin diffusion and dipole-dipole interaction with electron spins. The first mechanism is dominant, while the last is negligibly small. Spin diffusion between ²⁷Al spins is suppressed completely at a spinning rate of 2.5 kHz. We have analyzed the relaxation behavior theoretically and discussed quantitatively. Concentrations of paramagnetic impurities, electron spin-lattice relaxation times and spin diffusion rates have been estimated.     

A Novel Method to Synthesize Polyorganozircosilazane

A new kind of polyorganozircosilazane as Si/Zr/C/N-based ceramic precursor was synthesized from the condensation reaction of hexamethyleyclotrisilazane lithium salts(D3^NLi）and zirconium tetrachloride(ZrCl4).In the presence of N,N,N’,N’-tetramethyl ethylene diamine(TMEDA),polyorganozircosilazane was obtained in high yield.     

纳米氧化铜的制备及常温脱硫效能研究

采用硝酸铜为原料、氢氧化钠溶液为沉淀剂、使用体积比为1∶1的乙醇-水溶液为分散剂的直接沉淀法制备，通过改变工艺条件得到了三种纳米氧化铜产品，平均粒径分别为25.63，10.74和7.57 nm。采用TG-DTA、FIR、XRD和TEM等对纳米氧化铜进行表征。对产品的常温脱硫活性进行了穿透试验，并与已开发的其他常温精脱硫产品进行了比较，结果表明纳米氧化铜应用于H₂S脱硫，可在常温条件下具有优异的脱硫活性，对H₂S的脱除精度可以达到0.05 mg·m^-3以下。经过优选，产品在3 000 h^-1空速下穿透硫容达到25.3%，高于同类型的其他脱硫剂产品。     

聚合物-金属纳米复合材料的制备与应用

综述了聚合物-金属纳米复合材料的制备方法，包括原位形成法、沉积法、离子注入法、辐射化学法、光照化学法、直接分散法、球磨法；介绍了聚合物．金属纳米复合材料的应用领域，最后展望了这种材料的发展前景。