Self‐assembly of two‐dimensional (2D) structures from functional molecules is of great scientific importance. Herein, using a typical linear conducting polymer, polyaniline as building blocks, 2D single crystalline microplates are successively produced. The structure of 2D microplates is clearly defined by selected area electron diffraction, X‐ray diffraction, and Raman spectroscopy. Owing to the anisotropic arrangement of linear conjugated PANI molecules, the microplate shows a typical anisotropic electrical transport property.
The mechanical behaviour of monodomain nematic side‐chain liquid‐crystalline elastomers containing azoderivatives as pendant groups or crosslinkers has been studied under UV irradiation and in the darkness at different temperatures. From the evaluation of the opto‐mechanical experiments, the mechanical efficiency, kinetic rates, activation energies and the isomerization mechanism of the azocompounds in the liquid‐crystalline matrix could be determined, as well as the effect of the chemical constitution of the azobenzene derivatives and their role in the elastomeric network.
Solid‐state complexation of syndiotactic polystyrene (sPS) with a crown ether compound, 1,4,7,10‐tetraoxa‐cyclododecane (12‐crown‐4), took place when a film of sPS/chloroform clathrate was subjected to a guest exchange procedure assisted with a plasticizing agent. The new guest 12‐crown‐4 molecules were incorporated into the crystalline region of the sPS film, without causing a large conformational change of host sPS helices. X‐ray diffraction and thermogravimetric investigations showed that sPS/12‐crown‐4 complex had a clathrate complex structure which contained four 12‐crown‐4 molecules per unit cell. IR and Raman data suggested that 12‐crown‐4 took a Ci‐type conformation in the sPS complex phase.
As a feasible way for controlling the density of ligands in polyrotaxanes, azidated polyrotaxanes comprising PEG (MW = 3 000 and 20 000 g · mol−1) and mono‐, di‐, or triazidated α‐cyclodextrins are prepared in a water/DMSO solution in a one‐pot synthesis. The azidated polyrotaxanes are then allowed to conjugate with propargyl‐modified mannose as a ligand via click chemistry. As proven by FTIR spectroscopy and 1H NMR‐spectroscopy, mannose molecules are efficiently introduced into all of the azide moieties of the polyrotaxanes. The results verify the achievement of ligand‐density‐controlled polyrotaxanes. The functionalized polyrotaxanes can be utilized for a variety of biological applications.
We report a new type of step‐growth radical addition‐coupling polymerization (RACP) involving consecutive addition of carbon‐centered radical derived from α,α′‐dibromo dibasic ester to NO double bond of C‐nitroso compound followed by cross‐coupling of carbon‐centered radical and in situ formed nitroxyl radical, which produces alternating copolymers with high molecular weight and unimodal molecular weight distribution from saturated and unsaturated monomers.
A novel chlorotitanium calix[4]arene complex was synthesized and tested, without activator, as catalyst for the polymerization of L ‐ and rac‐lactide under solvent‐free conditions. The catalyst displayed high activity, which depended on the monomer‐to‐catalyst molar ratio, and led to highly isotactic PLLA. Despite concomitant transesterification during the polymerization, polylactide formation was well‐controlled, the molar mass distribution indexes remaining in the restricted range of 1.2–1.4.
A series of selenophene oligomers incorporating conjugated fluorinated phenylene units have been synthesised as potential semiconductor materials for organic field‐effect transistors (OFETs). X‐ray crystallography shows that the molecules are held in close proximity by several short intermolecular contacts, making them ideal candidates for OFET applications.
Summary: It has been shown that stable aqueous dispersions of nanoparticles of the rigid‐rod ladder‐type polymer poly(benzo‐bisimidazobenzo‐phenanthroline) (BBL) can be prepared in order to facilitate BBL processing. The obtained dispersions have a controllable particle size in the range between 50 and 150 nm and, consequently, the deposition of layers by spin‐coating or drop‐casting is realized. The resultant films exhibit a particulate structure and their morphology has been characterized by means of SEM and AFM. Upon investigation of the BBL dispersions in organic field‐effect transistors an ambipolar charge carrier transport has been observed, which presumably is related to the presence of mobile ions.
SEM image of a drop‐cast film of the BBL nanoparticles. 相似文献
Synthesis of a water‐soluble polydiacetylene has been achieved by topochemical polymerization in the solid state of the bis(N‐methylimidazolium)diacetylene monomer. Structural characterization for the monomer by X‐ray diffraction and NMR spectroscopy supports a photopolymerization initiated at the surface. Characterization of the polymer (NMR, UV and Raman spectroscopy, and dynamic light scattering) is given along with a molecular modelling interpretation of the polymerization in the solid state.
This paper reports a new polyimide design with high internal free volume elements for fast mass transport simultaneously with high selectivity. Here, we show that the polymer design using a three‐dimensional rigid molecular structure having internal void space can lead to the formation of high fractional free volume with proper cavity size to separate small gas molecules with high selectivities as high permeabilities. These findings could strongly impact emerging gas separation applications using polymeric membranes such as natural gas purification and biogas purification to get clean energy resources.
We demonstrate the utility of soft X‐ray spectromicroscopy to simultaneously image the surface and bulk composition of polymer blend thin films. In addition to conventional scanning transmission X‐ray microscopy that employs a scintillator and photomultiplier tube to measure the transmitted X‐ray flux, channeltron detection of near‐surface photoelectrons is employed to provide information of the composition of the first few nanometers of the film. Laterally phase‐separated blends of two polyfluorene co‐polymers are studied, with the structure of both wetting and capping layers clearly imaged. This new information provides insight into the connectivity of bulk and surface structures that is of particular relevance to the operation of such blends in optoelectronic devices.
The preparation, characterization and properties of novel millable polyurethane/organoclay nanocomposites are reported. Clay treated with methyl tallow bis(2‐hydroxyethyl) quaternary ammonium chloride was used as an organoclay for nanocomposite preparation. X‐ray diffraction indicated the intercalation of polymer chains inside the interlayer spacings of the clay. Dynamic mechanical analysis showed a significant increase in storage modulus, and tensile strength increases with increased organoclay loading.
X‐ray diffraction patterns of millable polyurethane/organoclay nanocomposites. 相似文献
Polyimide/diamond nanocomposites have been synthesized from 4,4′‐diaminodiphenyl ether (ODA) and 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA). All the polyimides show non‐crystalline X‐ray diffraction. The frequent occurrence of particular interatomic distances (R) denoted by the non‐crystalline X‐ray diffraction maxima are determined. An ultramicro‐indentation technique is employed to evaluate the effects of nano‐diamond particles on the indentation behavior of polyimides. Indentation size effect is observed and discussed.
A Dissipative particle dynamics (DPD) simulations are performed to study the cooperative self‐assembly of coil–rod–coil triblock copolymers and nanoparticles in solution. The results show that, when the nanoparticle concentration exceeds a given value, the ternary systems can form a novel nanocage composed of two‐end coil‐caps and middle rod‐linkers. The novel nanocage is very similar to the real bird cage and the captured nanoparticles like the bird. It is the first nanocage from the self‐assembly of coil–rod–coil triblock copolymers. This may be used for the release of drugs and fertilizers, or as nanoreactors.
Low‐cost, responsive poly(N‐isopropylacrylamide)/polystyrene composite films were prepared by a facile electrospinning technique. The surface structures and wettabilities of the composite films are tunable by simply controlling the concentration of polymer. With a proper proportion of each polymer, the wettability of the surface can be switched between superhydrophilicity and superhydrophobicity when the temperature is changed from 20 °C to 50 °C. The combination of a stimuli‐responsive polymer with micro/nanostructures on the surface of the composite film contributes to this unique surface property.
A new versatile synthesis strategy for macromonomers has been developed that uses the living ring‐opening metathesis polymerization (ROMP) with commercial Grubbs first generation ruthenium initiators. Homopolymers as well as diblock copolymers were end‐functionalized with norbornene derivatives to serve as macromonomers. The graft copolymerization of the macromonomers was also carried out employing ROMP. Well‐defined and highly functional graft copolymers are accessible by this new synthetic route.
Summary: Polyaniline‐vanadium oxide nanocomposite nanosheets with thickness between 10 and 20 nm, and lateral dimensions in the range of hundreds of nanometers to several microns have been synthesized by in situ intercalation polymerization of aniline with layered V2O5 under hydrothermal conditions. The product was characterized by field‐emission scanning electron microscopy (FE‐SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT‐IR) spectroscopy, and X‐ray diffractometer (XRD). The effects of the concentration of aniline and reaction temperature on the morphologies of polyaniline‐vanadium oxide nanocomposites have also been investigated.
SEM image of tremella‐like polyaniline‐vanadium oxide nanocomposite nanosheets. 相似文献
Dendrimer‐protected gold nanoparticles have been facilely obtained by heating an aqueous solution containing third‐generation poly(propyleneimine) dendrimers and HAuCl4 without the additional step of introducing other reducing agents. Transmission electron microscopy (TEM) and UV‐vis data indicate the size, the nucleation, and growth kinetics of gold nanoparticles thus formed, which can be tuned by changing the initial molar ratio of dendrimer to gold.
The formation of dendrimer–gold nanoparticles by the heat treatment of an aqueous solution containing third‐generation poly(propyleneimine) dendrimers and HAuCl4. 相似文献
