Actinyl peroxide clusters, a unique class of uranyl‐containing nanoclusters discovered in recent years, are crucial intermediates between the (UO2)2+ aqua‐ion monomer and bulk uranyl minerals. Herein, two actinyl polyoxometalate nanoclusters of Cs15[(Ta(O2)4)Cs4K12(UO2(O2)1.5)28] ? 20 H2O (CsK U28 ) and Na6K9[(Ta(O2)4)Rb4Na12(UO2(O2)1.5)28] ? 20 H2O (RbNa U28 ) were synthesized by incorporating a central Ta(O2)43? anion that templates a hollow shell of 28 uranyl peroxide polyhedra. When dissolved in aqueous solutions with additional electrolytes, those 1.8 nm‐size macroanions self‐assembled into spherical, hollow, blackberry‐type supramolecular structures, as was characterized by laser‐light scattering (LLS) and TEM techniques. These clusters are the smallest macroions reported to date that form blackberry structures in solution, therefore, can be treated as valuable models for investigating the transition from simple ions to macroions. Kinetic studies showed an unusually long lag phase in the initial self‐assembly process, which is followed by a rapid formation of the blackberry structures in solution. The small cluster size and high surface‐charge density are essential in regulating the supramolecular structure formation, as was shown from the high activation energy barrier of 51.2±2 kJ mol?1. Different countercations were introduced into the system to investigate the effect of ion binding to the length of the lag phase. The current research provides yet another scale of self‐assembly of uranyl peroxide complexes in aqueous media. 相似文献
In dynamic laser light scattering (LLS), for a given polydisperse sample, a line-width distribution G(Γ) or the translational diffusion coefficient distribution G(D) can be obtained from the measured time correlation function. For rigid colloid particles, G(Γ) can be directly related to the hydrodynamic size distribution. However, for flexible polymer chains, G(Γ) depends not only on the chain length distribution, but also on the relaxation of the chain conformation; that is, even for a monodisperse polymer sample there still exists a chain conformation distribution. If the time scale of the chain conformation relaxation is comparable to that of the translational diffusion, such as in the case of a very long polymer chain, the conformation relaxation might lead to an additional broadening in G (Γ). This "conformation broadening" has been directly observed for the first time by comparing two G(Γ) s obtained from a poly(N-isopropyl-acrylamide) solution at~25℃ and~32℃ at which the solution is ther 相似文献
Summary: N‐methacryloyl‐1‐aminopropane ( 1 ), N‐methacryloyl‐1‐aminobutane ( 2 ), N‐methacryloyl‐1‐aminopentane ( 3 ), and N‐methacryloyl‐1‐aminohexane ( 4 ) are synthesized and treated with an aqueous solution of randomly methylated β‐cyclodextrin (Me‐β‐CD) to form the water‐soluble host‐guest complexes 1a – 4a . In case of the aqueous polymerization of the free monomers 1 – 4 the initial polymerization rate increases with increasing water solubility. The opposite effect is observed in the case of the polymerizations of the Me‐β‐CD‐complexed methacrylamide monomers 1a – 4a . The polymerization rates are increased with increasing alkyl chain length of the complexed monomers 1a – 4a and decreasing water solubility of the free monomers 1 – 4 .
Initial polymerization rate v0 of CD‐complexed monomers 1a – 4a (○) vs. water solubilities of monomers 1 – 4 (▪). 相似文献
Cationic polyelectrolyte with primary amine pendant groups, poly (4-vinyl benzyl amine hydrochloride salt) (poly (4-VBAHS)), was characterized by static light scattering. Using light scattering measurement, the conformation transition of poly (4-VBAHS) chains in pure water, and THF/H2O (v/v: 1/3) binary solvent mixture was discussed. Concentration-dependent multiple morphologies including interpenetrating networks, tubular micelles, branched micelles, hexagonal phases, vesicles, and needle crystals were observed by TEM. In addition, effect of poly (4-VBAHS) on the morphology, stability, and critical vesicle/micelle concentration of anionic surfactant sodium bis (2-ethylhexyl) sulfosucciante vesicles were detected using dynamic light scattering, zeta potential, surface tension, and transmission measurements. 相似文献