Polymer segmental dynamics near the interface of silica particles in the particle/polymer composites.

We demonstrate an approach to examine the local segmental dynamics of a polymer near the interface of an inorganic filler by observing the rotational dynamics of the fluorescent probe at the chain ends of polymer brushes grafted onto the surface of the filler particles. Localization of the fluorescent probe was realized by designing and synthesizing fluorophore-tethered polystyrene (PS) brushes anchored on the surface of silica particles of controlled sizes. Fluorophore-functionalized telechelic PS with an azide functionality at the other chain end was achieved via a combination of atom transfer radical polymerization and post-polymerization modification. The azide-bearing PS chains were tethered to alkyne-functionalized particles via copper-catalyzed cycloaddition reaction. The molecular weight of the grafted polymer chains was controlled to be less than the critical entanglement molecular weight, and the chain density was controlled to be low enough so that the observed dynamics was not perturbed by the polymer brush conformation and brush-matrix polymer entanglement. The polymer dynamics near the surface of the particles at low concentrations was closely examined in the bulk film geometry by employing imaging rotational fluorescence correlation microscopy (irFCM). The observed polymer dynamics near the interface were not altered in the inorganic/polymer composite geometry when the surface did not have favorable interaction with the matrix polymer. The presented rational design of the chemical route and examination of local dynamics highlight a feasible approach to construct material systems with high complexities towards a deeper understanding of composite materials.

Eutectic friction transfer lithography: a facile solid-state route for highly crystalline semiconducting polymers.

Herein, we report a solid-state lithography technique utilizing eutectic friction transfer lithography (EFTL). The EFTL technique employs eutectic pellets made of semiconducting polymers and volatile organic solid matrices. Using frictional heating and eutectic melting, various semiconducting polymer crystals were formed by a simple rubbing process under mild conditions. The strong anisotropic optical properties suggest that J-type packing is dominant in EFTL microwires because of the highly extended and planarized crystal structures.

Perovskite Nanoparticle Composite Films by Size Exclusion Lithography.

Perovskite nanoparticle composite films with capability of high-resolution patterning (≥2 µm) and excellent resistance to various aqueous and organic solvents are prepared by in situ photosynthesis of acrylate polymers and formamidinium lead halide (FAPbX3 ) nanoparticles. Both positive- and negative-tone patterns of FAPbX3 nanoparticles are created by controlling the size exclusive flow of nanoparticles in polymer networks. The position of nanoparticles is spatially controlled in both lateral and vertical directions. The composite films show high photoluminescence quantum yield (up to 44%) and broad color tunability in visible region (λpeak = 465-630 nm).

Vivid colours in hyperuniform complex-index photonic structures by resonant interference of photonic band gaps and optical band gaps.

Hyperuniform photonic structures (HPSs) have been doped with complex index materials to increase their reflectivity and colour expression range. HPSs synthesized using dielectric SiO2 nanoparticles have been mixed with a small amount of dopant nanoparticles (c d ≤ 1%) having a complex refractive index. Various dyes including Sudan I, Sudan Blue II, Alizarin yellow GG, Bromocresol purple and polydopamine (PDA) are used as dopants. Large reflectivity enhancements of HPSs (∼100%) are observed by resonant interference of photonic band gaps (PBGs) and optical band gaps (OBGs). Reflectivity enhancements are observed only when PBGs of HPSs match with OBGs of dopants. The colour expression range of HPS increases by 600% by doping with melanine-like PDA nanoparticles, which have the imaginary part of the refractive index in whole visible range.

2-Hydroxypropyltrimethylammonium xylan adsorption onto rod-like cellulose nanocrystal.

Chemical incompatibility and relatively weak interaction between lignocellulosic fibers and synthetic polymers have made studies of wood fiber-thermoplastic composite more challenging. In this study, adsorption of 2-hydroxypropyltrimethylammonium xylans onto rod-like cellulose nanocrystals are investigated by zeta-potential measurements, and polarized and depolarized dynamic light scattering as a factor for better understanding of lignocellulosic fibers and cellulose nanocrystals. Zeta-potential measurements show xylan derivative adsorption onto cellulose nanocrystals. Decay time distributions of the ternary system and binary system from dynamic light scattering show that aggregates exist in the binary system and they disappear in the ternary system. At low 2-hydroxypropyltrimethylammonium xylan concentrations relative to that of cellulose nanocrystal, xylan derivatives adsorbed onto some of the cellulose nanocrystal. Hence, more xylan derivatives adsorbed onto cellulose nanocrystal increased with increasing xylan derivative concentration. Also, the concentration dependence of the ratio of the rotational diffusion coefficient to the translational diffusion coefficient revealed a strong adsorptive interaction between xylan derivatives and the cellulose nanocrystals.

Opening and blocking the inner-pores of halloysite.

Aggregation and dispersion behaviours of halloysite nanotubes (HNTs) were influenced by pH. The meso- and micro-porosity of halloysite were determined by N2 gas physisorption. The blocking and opening of halloysite nanotube pores with acid, neutral, and base treatment were detected in a micro- and mesoporous matrix of tunable porosity. The inner pores of HNTs were opened with base treatment, but were closed with acid or neutral treatment.

Facile preparation of a new gadofullerene-based magnetic resonance imaging contrast agent with high 1H relaxivity.

A new magnetic resonance imaging (MRI) contrast agent based on the trimetallic nitride templated (TNT) metallofullerene Gd(3)N@C(80) was synthesized by a facile method in high yield. The observed longitudinal and transverse relaxivities r(1) and r(2) for water hydrogens in the presence of the water-soluble gadofullerene 2 Gd(3)N@C(80)(OH)(approximately 26)(CH(2)CH(2)COOM)(approximately 16) (M = Na or H) are 207 and 282 mM(-1) s(-1) (per C(80) cage) at 2.4 T, respectively; these values are 50 times larger than those of Gd(3+) poly(aminocarboxylate) complexes, such as commercial Omniscan and Magnevist. This high (1)H relaxivity for this new hydroxylated and carboxylated gadofullerene derivative provides high signal enhancement at significantly lower Gd concentration as demonstrated by in vitro and in vivo MRI studies. Dynamic light scattering data reveal a unimodal size distribution with an average hydrodynamic radius of ca. 78 nm in pure water (pH = 7), which is significantly different from other hydroxylated or carboxylated fullerene and metallofullerene derivatives reported to date. Agarose gel infusion results indicate that the gadofullerene 2 displayed diffusion properties different from those of commercial Omniscan and those of PEG5000 modified Gd(3)N@C(80). The reactive carboxyl functionality present on this highly efficient contrast agent may also serve as a precursor for biomarker tissue-targeting purposes.

Conjugation of a water-soluble gadolinium endohedral fulleride with an antibody as a magnetic resonance imaging contrast agent.

Water-soluble gadofullerides exhibited high efficiency as magnetic resonance imaging (MRI) contrast agents. In this paper, we report the conjugation of the newly synthesized gadofulleride, Gd@C82O6(OH) 16(-)(NHCH2CH2COOH)8, with the antibody of green fluorescence protein (anti-GFP), as a model for "tumor targeted" imaging agents based on endohedral metallofullerenes. In this model system, the activity of the anti-GFP conjugate can be conveniently detected by green fluorescence protein (GFP), leading to in vitro experiments more direct and facile than those of tumor antibodies. Objective-type total internal reflection fluorescence microscopy revealed that each gadofulleride aggregate conjugated on average five anti-GFPs, and the activity of anti-GFPs was preserved after conjugation. In addition, the gadofulleride/antibody conjugate exhibited higher water proton relaxivity (12.0 mM (-1) s (-1)) than the parent gadofulleride aggregate (8.1 mM (-1) s (-1)) in phosphate buffered saline at 0.35 T, as also confirmed by T1-weighted images of phantoms. These observations clearly indicate that the synthesized gadofulleride/antibody conjugate not only has targeting potential, but also exhibits higher efficiency as an MRI contrast agent.