Synthesis and characterization of polyimides derived from (3‐amino‐2,4,6‐trimethylphenyl)‐(3′‐aminophenyl)methanone and aromatic dianhydrides

A series of new polyimides were prepared via the polycondensation of (3‐amino‐2,4,6‐trimethylphenyl)‐(3′‐aminophenyl)methanone and aromatic dianhydrides, that is, 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), 4,4′‐oxydiphthalic anhydride, 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride, and 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride. The structures of the polyimides were characterized by Fourier transform infrared and NMR measurements. The properties were evaluated by solubility tests, ultraviolet–visible analysis, differential scanning calorimetry, and thermogravimetric analysis. The two different meta‐position‐located amino groups with respect to the carbonyl bridge in the diamine monomer provided it with an unsymmetrical structure. This led to a restriction on the close packing of the resulting polymer chains and reduced interchain interactions, which contributed to the solubility increase. All the polyimides except that derived from BPDA had good solubility in strong aprotic solvents, such as N‐methyl‐2‐pyrrolidinone, N,N′‐dimethylacetamide, N,N‐dimethylformamide, and dimethyl sulfone, and in common organic solvents, such as cyclohexanone and chloroform. In addition, these polyimides exhibited high glass‐transition values and excellent thermal properties, with an initial thermal decomposition temperature above 470 °C and glass‐transition temperatures in the range of 280–320 °C. The polyimide films also exhibited good transparency in the visible‐light region, with transmittance higher than 80% at 450 nm and a cutoff wavelength lower than 370 nm. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1291–1298, 2006     

Synthesis and polymerization of a new nitrogen‐containing bis‐ortho‐diynylarene monomer

This study focuses on the preparation, characterization, and optical properties of new bis(3,4‐diphenylethynylphenyl)phenylamine. This is the first nitrogen‐containing bis‐ortho‐diynylarene (BODA) monomer having a nitrogen atom as the spacer group. BODA monomers are usually prepared from common bisphenols, thereby providing great synthetic versatility and the opportunity to develop a wide array of novel polyarylene thermosets by varying the aromatic spacer group. The new bis(3,4‐bisphenylethynylphenyl)phenylamine was synthesized in five steps. This compound emits an intense blue color (λ = 438 nm) upon irradiation by UV light and may be suitable for use as an emitting layer in electroluminescent devices. Bis‐(3,4‐bisphenylethynylphenyl)phenylamine and its polymer have photoluminescence quantum yields 34 and 38%, respectively, and long excited‐state lifetimes of 3.2 and 3.6 ns, respectively. The structure of the monomer and its polymer were characterized using spectroscopic techniques including Ultraviolet–visible Spectrophotometer, Photoluminescence Spectrophotometer, Fourier Transform infrared spectroscopy, and Gel Permeation Chromatography. The polymerizations were studied by Differential Scanning Calorimeter. The amount of weight loss and the thermostability of the nitrogen‐containing polymer were determined from thermogravimetric analysis. The electrical conductivity of neat HCl‐doped BODA‐derived polymer film was measured according to the standard four‐point probe technique. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6988–6996, 2006     

Polymer electrolyte membranes for the direct methanol fuel cell: A review

The direct methanol fuel cell (DMFC) has the potential to replace lithium‐ion rechargeable batteries in portable electronic devices, but currently experiences significant power density and efficiency losses due to high methanol crossover through polymer electrolyte membranes (PEMs). Numerous publications document the synthesis and characterization of new PEMs for the DMFC. This article reviews this research, transport phenomena in PEMs, and experimental techniques used to evaluate new PEMs for the DMFC. Although many PEMs do not show significant improvements over Nafion®, the benchmark PEM in DMFCs, experimental results show that several new PEMs exhibit lower methanol crossover at similar proton conductivities and/or higher DMFC power densities. These results and recommendations for future research are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Parts B: Polym Phys 44: 2201–2225, 2006     

Chiral separation of synthetic vicinal diol compounds by capillary zone electrophoresis with borate buffer and beta-cyclodextrin as buffer additive.

The investigation on capillary electrophoretic enantioseparation of six synthetic compounds containing vicinal diol groups has been undertaken to acquire the optimum conditions using native beta-cyclodextrin (beta-CD) as chiral selector and borate as a background electrolyte. The separation was carried out in an uncoated capillary (58.5 cm x 75 microm i.d., effective length 48.5 cm) and the effects of several important factors were investigated in detail. The results showed that beta-CD as a chiral selector exhibited good enantioselectivity and that the enantioseparation was greatly influenced by the structure of the diols, the borate concentration and the buffer pH. The optimum performance was obtained for the chiral vicinal diols under the conditions of 200 mM borate buffer of pH 9.8 containing 1.7% beta-CD at an applied voltage of 15 kV and a capillary temperature of 20 degrees C. Under the conditions, four diols were baseline separated with fast analysis time and the good theoretical plate numbers (above 10 x 10(4)) and favorable migration-time reproducibilities (RSDs below 3.0%) were obtained. The separation results were satisfactory.     

Innately transitive subgroups of wreath products in product action

A permutation group is innately transitive if it has a transitive minimal normal subgroup, which is referred to as a plinth. We study the class of finite, innately transitive permutation groups that can be embedded into wreath products in product action. This investigation is carried out by observing that such a wreath product preserves a natural Cartesian decomposition of the underlying set. Previously we classified the possible embeddings in the case where the plinth is simple. Here we extend that classification and identify several different types of Cartesian decompositions that can be preserved by an innately transitive group with a non-abelian plinth. These different types of decompositions lead to different types of embeddings of the acting group into wreath products in product action. We also obtain a full characterisation of embeddings of innately transitive groups with diagonal type into such wreath products.

     

Direct single-layered fabrication of 3D concavo–convex patterns in nano-stereolithography

A nano-surfacing process (NSP) is proposed to directly fabricate three-dimensional (3D) concavo–convex-shaped microstructures such as micro-lens arrays using two-photon polymerization (TPP), a promising technique for fabricating arbitrary 3D highly functional micro-devices. In TPP, commonly utilized methods for fabricating complex 3D microstructures to date are based on a layer-by-layer accumulating technique employing two-dimensional sliced data derived from 3D computer-aided design data. As such, this approach requires much time and effort for precise fabrication. In this work, a novel single-layer exposure method is proposed in order to improve the fabricating efficiency for 3D concavo–convex-shaped microstructures. In the NSP, 3D microstructures are divided into 13 sub-regions horizontally with consideration of the heights. Those sub-regions are then expressed as 13 characteristic colors, after which a multi-voxel matrix (MVM) is composed with the characteristic colors. Voxels with various heights and diameters are generated to construct 3D structures using a MVM scanning method. Some 3D concavo–convex-shaped microstructures were fabricated to estimate the usefulness of the NSP, and the results show that it readily enables the fabrication of single-layered 3D microstructures. PACS 85.40.Hp; 81.16.Nd; 42.82.Cr     

Local chemical distribution and electronic structure of Ge1−xTx DMS single crystals (T=Cr,Mn, Fe)

The spatial concentration distribution and local electronic structure of ferromagnetic Ge_1−xT_x (T=Cr, Mn, Fe) DMS single crystals have been investigated by using scanning photoelectron microscopy (SPEM), X-ray absorption spectroscopy (XAS), and photoemission spectroscopy (PES). It is found that doped T ions in Ge_1−xT_x crystals are chemically phase-separated, suggesting that the observed ferromagnetism arises from the phase-separated T-rich phases in Ge_1−xT_x.