Aggregation-driven growth of size-tunable organic nanoparticles using electronically altered conjugated polymers

A novel class of monodisperse conjugated polymer nanoparticles have been readily prepared by the facile reprecipitation of poly{1,3-bis[2-(3-alkylthienyl)]azulene} or poly{1,3-bis[2-(3-alkoxythienyl)]azulene}. The multicomponent poly(bithiophene-alt-azulene) macromolecules were efficiently self-assembled into a wide range of size-tunable nanoparticles from a few tens to five hundred nanometers via the hydrophobic and pi-stacking effects in the mixed chloroform/methanol solutions. Electronically altered polymer structures with different alkyl or alkoxy substitutes exhibited variable self-assembling behaviors to precisely tune the size and the optical/electronic properties of nanoparticles. A strong size dependence of continuous bathochromic absorption and significant enhanced emission were observed with the increase of particle size. A linear relationship between the absorption or fluorescence intensities and the particle size was demonstrated as well, and this is very useful to probe the intermolecular interactions and the size evolutions of conjugated polymer nanoparticles. After the size-dependent optical and electronic properties are created, they can be further optimized to improve the performance of materials prior to the use in novel organic nanodevices in a cost-effective way.     

Deformation-induced accelerated dynamics in polymer glasses

Molecular dynamics simulations are used to investigate the effects of deformation on the segmental dynamics in an aging polymer glass. Individual particle trajectories are decomposed into a series of discontinuous hops, from which we obtain the full distribution of relaxation times and displacements under three deformation protocols: step stress (creep), step strain, and constant strain rate deformation. As in experiments, the dynamics can be accelerated by several orders of magnitude during deformation, and the history dependence is entirely erased during yield (mechanical rejuvenation). Aging can be explained as a result of the long tails in the relaxation time distribution of the glass, and similarly, mechanical rejuvenation is understood through the observed narrowing of this distribution during yield. Although the relaxation time distributions under deformation are highly protocol specific, in each case they may be described by a universal acceleration factor that depends only on the strain.     

Aggregation induced polyelectrolyte multilayer film containing cubic silsesquioxane nanoparticles

Polyelectrolyte multilayer (PEM) films offer a method to functionalize substrates with specific properties that enable the films to be used for a variety of purposes. Desirable qualities of PEM films can include mechanical strengths, ease of preparations, flexibility, and their abilities to have their properties tailored to suit a particular process. We present a simple method to fabricate a class of PEM films that incorporate cubic silsesquioxane nanoparticles (CSSQ). Through a spin self-assembly (SSA) process, a hybrid multilayered film with two-components, namely, poly(styrene sulfonate) (PSS) and octaammonium cubic silsesquioxane (CSSQ) nanoparticle have been fabricated. The formation of this multilayer film is further verified by ellipsometry, contact angle studies, and atomic force microscopy (AFM). The water contact angle and ellipsometric measurements exhibit that the (PSS/OA-CSSQ) films are deposited onto the substrate. The surface topography of the deposited bilayers of PSS/OA-CSSQ film appears to be uniformly distributed with extremely small granules but the film uniformity of the granular surface is diminished and clusters of granules are observed at above 5 bilayers due to the aggregation of the OA-CSSQ nanoparticles.     

一种简便的溶胶-凝胶法制备的La0.67Ca0.33MnO3纳米晶粉末的结构与性能（英文）

采用一种比较简单的溶胶-凝胶法在相对较低的温度下制备了钙钛矿锰氧化物La0.67Ca0.33MnO3纳米粉末。XRD结果显示干凝胶直接在500℃下煅烧即可得到单一钙钛矿相,而无需任何其他中间步骤。当煅烧温度从500℃上升到900℃时,纳米晶的尺寸相应的从30纳米长大到80纳米左右。分别采用扫描电镜和传统的四探针法表征了多晶靶材的表面形貌和电输运性能,观察到了电阻率-温度(ρ-T)曲线上绝缘体-金属转变温度TIM附近(270 K左右)非常陡的电阻率变化。     

Electrical transport properties and laser-induced voltage effect in La0.8Ca0.2MnO3 epitaxial thin films

La_0.8Ca_0.2MnO₃ (LCMO) thin films about 200 nm thickness were grown on untilted and tilted (5°, 10° and 15°) LaAlO₃ (100) single crystal substrates by pulsed laser deposition technique. Electrical properties of the epitaxial thin films were studied by conventional four-probe technique and the anisotropic thermoelectric properties of the films grown on the tilted substrates have been investigated by laser-induced voltage (LIV) measurements. X-ray diffraction analysis and atomic force microscopy results show that the prepared LCMO thin films have a single phase and high crystalline quality. The remarkably large temperature coefficient of resistance (TCR) values (above 11 %/K) are observed in the all films. TCR value reaches 18 %/K on the film grown on 10° tilted substrate. The intensity of LIV signals monotonously increases with the tilting angles, and the largest signal is 148 mV with the fast time response 229 ns for the film grown on 15° tilted substrate.     

PEG-POSS assisted facile preparation of amphiphilic gold nanoparticles and interface formation of Janus nanoparticles

A general approach to transfer water-soluble nanoparticles with different shapes, sizes, and surface charges into organic solvents, retaining their surface charge properties was developed, and its application in fabrication of hybrid Janus particles with opposite charges in solution was also demonstrated.     

Self-assembly of brush-like poly[poly(ethylene glycol) methyl ether methacrylate] synthesized via aqueous atom transfer radical polymerization

Self-assembly of brush-like well-defined poly[poly(ethylene glycol) methyl ether methacrylate] homopolymers, abbreviated as P(PEGMA-475) and P(PEGMA-1100) is investigated in aqueous solution by employing dynamic/static light scattering (DLS/SLS) and transmission electron microscopy (TEM), whereas 475 and 1100 is molar mass of the respective PEGMA macromonomer. The mentioned brush-like homopolymers are synthesized by aqueous ATRP at room temperature. The critical association concentration (CAC) of the synthesized polymers in water depends on the length of the PEG side chains but not on the overall molar mass of the polymer. Thus, approximately the same CAC of approximately 0.35 mg/mL is estimated for various P(PEGMA-1100) samples, and approximately 0.7 mg/mL is estimated for P(PEGMA-475) series. All the investigated P(PEGMA-1100) samples form multimolecular micelles in aqueous solution, where the hydrodynamic size (Rh) and the aggregation number (Nagg) of micelles decreases as the molecular weight of P(PEGMA-1100) increases. This can be attributed to the increased steric hindrances between the PEG side chains in corona of micelles formed by higher molar mass P(PEGMA-1100). The tendency of micelle formation by samples of P(PEGMA-475) series is significantly lower than that of P(PEGMA-1100) series, as demonstrated by their significantly higher CAC and micelles of lower Nagg. The Rh of micelles does not depend strongly on polymer concentration, which suggests that these micelles are formed via the closed association model. Micelles formed by P(PEGMA-1100) series slightly shrink with increase in temperature from 25 to 60 degrees C, while those of P(PEGMA-475) series are found to be insensitive to the same temperature variation. Finally, TEM is carried out to visualize the formed micelles after transferring the aqueous solution to carbon film.