End‐Capping as a Method for Improving Carrier Injection in Electrophosphorescent Light‐Emitting Diodes

The electronic properties, carrier injection, and transport into poly(9,9‐dioctylfluorene) (PFO), PFO end‐capped with hole‐transporting moieties (HTM), PFO–HTM, and PFO end‐capped with electron‐transporting moieties (ETM), PFO–ETM, were investigated. The data demonstrate that charge injection and transport can be tuned by end‐capping with HTM and ETM, without significantly altering the electronic properties of the conjugated backbone. End‐capping with ETM resulted in more closely balanced charge injection and transport. Single‐layer electrophosphorescent light‐emitting diodes (LEDs), fabricated from PFO, PFO–HTM and PFO–ETM as hosts and tris[2,5‐bis‐2′‐(9′,9′‐dihexylfluorene)pyridine‐κ²NC_3′]iridium(III ), Ir(HFP)₃ as the guest, emitted red light with brightnesses of 2040 cd m^–2, 1940 cd m^–2 and 2490 cd m^–2 at 290 mA cm^–2 (16 V) and with luminance efficiencies of 1.4 cd A^–1, 1.4 cd A^–1 and 1.8 cd A^–1 at 4.5 mA cm^–2 for PFO, PFO–HTM, and PFO–ETM, respectively.     

Synthesis of polyanilines with pendant fluorescent units

Functionalized polyanilines containing biphenyl, terphenyl, carbazole, anthracene, and 4-n-hexylphenyl moieties were synthesized though the reaction of polyaniline in emeraldine base form with sodium salt of corresponding vinylketoaromatics with quantitative yields. Polymers were characterized with Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, and thermogravimetry. The emission characteristics of these polymers in N-methyl-2-pyrrolidone solution were examined. The functionalized polyanilines exhibited an intense green emission.     

Synthesis of novel functional polyolefin containing carboxylic acid via Friedel-Crafts acylation reaction

The strong polar group, carboxylic acid, has triumphantly been introduced into ethylene and allylbenzene copolymers without obvious degradation or crosslinking via Friedel-Crafts (F-C) acylation reaction with glutaric anhydride (GA), succinic anhydride (SA) and phthalic anhydride (PA) in the presence of anhydrous aluminum chloride in carbon disulfide. Some important reaction parameters were examined in order to optimize the acylation process. In the optimum reaction conditions, almost all of the phenyls can be acylated with any anhydride. The microstructure of acylated copolymer was characterized by FT-IR, ¹H NMR and ¹H-¹H COSY. All the peaks of acylated copolymers can be accurately attributed, which indicates that all the acylation reactions occur only at the para-positions of the substituent of the aromatic rings. The thermal behavior was studied by differential scanning calorimetry (DSC), showing that the melting temperatures (T_ms) of acylated copolymers with GA firstly decrease slowly and then increase significantly with the increase of the amount of carboxyl acid groups.     

Synthesis, structure and properties of a novel hybrid bimodal network elastomer with inorganic cross-links: The case of silicone–nanocrystalline titania

We describe an innovative concept of synthesizing a novel hybrid bimodal network elastomer with high strength–high ductility combination involving utilization of functionalized nanocrystalline titania as short-chain cross-links between neighboring elastomer chains. This subject is germane both fundamentally and from an application viewpoint. Silicone rubber is selected as the model elastomer. The short-chain cross-links are acrylic acid functionalized nanocrystalline titania that are an integral component of bimodal network structure of the elastomer. To delineate and separate the effects of functionalization from nanoparticle effects, a relative comparison is made between silicone rubber–titania nanocomposite (i.e. containing dispersion of titania as a reinforcement filler) and silicone rubber–titania hybrid network elastomer (i.e. titania as short chain cross-links). An important finding is that the effect of functionalized titania present as short chain cross-links is far more significant than non-functionalized titania present as reinforcement filler, on mechanical behavior. This is presently ascribed to the double bonds introduced to nanocrystalline titania via functionalization with acrylic acid that provide active sites for the cross-linking reaction resulting in inorganic bridging chains. The basic physical mechanisms that govern elastic recovery in hybrid bimodal network elastomer with short chain cross-links of functionalized nanocrystalline inorganic particles are discussed. The hypothesis of the study described here is that the hybrid bimodal network elastomer with short chain cross-links of functionalized nanocrystalline inorganic particles modifies the unimodal long chain network elastomer with consequent increase in modulus and high strength–ductility combination.     

Optical properties of hybrid T3Pyr/SiO2/3C-SiC nanowires

A new class of nanostructured hybrid materials is developed by direct grafting of a model thiophene-based organic dye on the surface of 3C-SiC/SiO₂ core/shell nanowires. TEM-EDX analysis reveals that the carbon distribution is more spread than it would be, considering only the SiC core size, suggesting a main contribution from C of the oligothiophene framework. Further, the sulfur signal found along the treated wires is not detected in the as-grown samples. In addition, the fluorescent spectra are similar for the functionalized nanostructures and T3Pyr in solution, confirming homogeneous molecule grafting on the nanowire surface. Chemical and luminescence characterizations confirm a homogeneous functionalization of the nanowires. In particular, the fluorophore retains its optical properties after functionalization.     

Influence of support’s oxygen functionalization on the activity of Pt/carbon xerogels catalysts for methanol electro-oxidation

Highly mesoporous carbon xerogels (CXs) were synthesized using two different resorcinol to catalyst, R/C, molar ratios and functionalized with different oxidation treatments. The synthesized carbon materials were used as supports for Pt particles, deposited by impregnation and reduction in formic acid. Both carbon supports and the catalysts prepared were characterized by means of N₂ physisorption, scanning and transmission electron microscopy, temperature programmed desorption and X-ray diffraction. The electrochemical activity of the catalysts towards the oxidation of carbon monoxide and methanol was assayed by means of cyclic voltammetry and chronoamperometry. Textural characterization of the materials prepared evidenced more developed and mesopore-enriched porous structure for the carbon xerogel prepared using the highest R/C molar ratio. Enhanced textural properties of this material led to the preparation of highly active Pt-catalysts, which showed increased tolerance to CO and higher activity in methanol electro-oxidation, in comparison to Pt-E-TEK and the catalysts prepared in an analogous way using Vulcan XC-72R carbon black as support. Functionalization treatments resulted in enhanced dispersion, lower Pt crystal size and improved catalytic performance in the case of the catalysts prepared using the carbon xerogel possessing a less developed porous structure. Pt agglomeration was found to strongly determine the activity of the catalysts prepared. At high potentials, i.e. 1 V vs. RHE, the catalyst prepared using the carbon xerogel submitted to the most stringent oxidation treatment showed the highest specific peak activity towards methanol electro-oxidation, probably due to the positive influence of the presence of oxygen surface groups in Pt-carbon interaction, in spite of the higher agglomeration extent confirmed by TEM. On the other hand, at 0.60 V vs. RHE, highest activity towards methanol electro-oxidation was determined for the catalysts prepared using the non-functionalized carbon xerogel which can be explained in terms of enhanced reactant/product diffusion together with intrinsic higher catalytic activity due to lower Pt crystal size. In any case, the activity of this catalyst prepared using a carbon xerogel as support was found to be more than 2 times higher than the one determined for Pt/E-TEK, confirming the considerable improvement of the electrocatalytic system by means of optimization of the carbon support employed.     

Effect of silane structure on the properties of silanized multiwalled carbon nanotube-epoxy nanocomposites

Multiwalled carbon nanotubes (MWCNTs) were functionalized with aminosilanes via an aqueous deposition route. The size and morphology of siloxane oligomers grafted to the MWCNTs was tuned by varying the silane functionality and concentration and their effect on the properties of a filled epoxy system was investigated. The siloxane structure was found to profoundly affect the thermo-mechanical behavior of composites reinforced with the silanized MWCNTs. Well-defined siloxane brushes increased the epoxy T_g by up to 19 °C and significantly altered the network relaxation dynamics, while irregular, siloxane networks grafted to the MWCNTs had little effect. The addition of both types of silanized MWCNTs elicited improvements in the strength of the nanocomposites, but only the well-defined siloxane brushes engendered dramatic improvements in toughness. Because the silanization reaction is simple, rapid, and performed under aqueous conditions, it is also an industrially attractive functionalization route.     

树枝状大分子在药物领域的应用研究进展

树枝状大分子是一类高规整度、具有纳米尺度、三维结构的树枝状大分子,其结构和分子尺寸大小具有良好的可控性。树枝状大分子的大小呈线性增长,而外层功能化基团呈级数增长。因此树枝状大分子的功能化备受人们的关注。而其作为药物载体已成为当今研究热点之一。作者仅就树枝状大分子在药物领域中的应用研究进展作简要综述。     

The aza-Michael reaction as an alternative strategy to generate advanced silicon-based (macro)molecules and materials

Aza-Michael reaction is a simple and accessible addition reaction performed at moderate temperature, possibly without a catalyst and without releasing by-products. Its versatility allows designing specific structures thanks to the availability of a multitude of Michael acceptors and Michael donors. The reaction rate of the aza-Michael reaction can be improved by adding different co-reactants (polar protic solvents, catalysts) and/or adjusting the external energy sources (e.g. moderate to high temperatures or high pressures). Here, we show that this addition reaction is efficient for modifying or curing silicon-containing molecules, oligomers and polymers. The pros and cons of applying the aza-Michael reaction to silicon-containing molecules (including alkoxysilanes and PDMS) are highlighted. A large variety of intermediates such as coupling agents, reactive diluents, and sol-gel precursors prepared by the aza-Michael reaction are presented. Finally, applications of these, including products ranging from functional silicone intermediates to soft (unfilled) elastomers, are reported.     

Tubular shaped composites made from polythiophene covalently linked to Prato functionalized N-doped carbon nanotubes

A simple methodology to produce tubular nitrogen-doped carbon nanotube/polythiophene covalently linked composites is described. Nitrogen doped carbon nanotubes (N-CNTs) were made by the floating catalyst CVD method using toluene, ferrocene and tetramethylethylenediamine (TMEDA) as reagents. Functionalization of the N-CNTs was achieved using 3-thiophenecarboxaldehyde and N-methylglycine in 1,2-dichlorobenzene (Prato reaction). Elemental analysis showed nitrogen incorporation of N into the N-CNTs (1.8%) and also the N-methylglycine functionalized N-CNTs (f-N-CNTs; 6.2%). A series of f-N-CNT/thiophene monomer mixtures (weight ratios 1:3, 1:10 and 1:20) were used to make f-N-CNT/polythiophene tubular composites. As the amount of thiophene monomer was increased, the overall diameter of the polymer layer attached onto the N-CNTs increased. Polymer thickness also varied with reaction time (1 h, 12 h and 24 h). The combination of acid functionalization and N–doping gives the best coverage of the CNTs by polythiophene, in which the polythiophene preferentially binds to the f-N-CNTs to give tubular structures.