Syntheses and Crystal Structures of Fused Thiophenes: [7]Helicene and Double Helicene, a D-2-Symmetric Dimer of 3,3 '-Bis(dithieno[2,3-b:3 ',2 '-d]thiophene)

The efficient synthesis of (TMS)(2)-[7]helicene (rac-3) and double helicene, a D-2-symmetric dimer of 3,3'-bis(dithieno-[2,3-b:3',2'-d]thiophene) (rac-4) was developed. The crystal structures of 3 and 4 show both strong intermolecular pi-pi interactions and S center dot center dot center dot S interactions. UV/vis spectra reveal that both 3 and 4 show significant pi-electron delocalization.

Efficient Electrophosphorescence from a Platinum Metallopolyyne Featuring a 2,7-Carbazole Chromophore

The synthesis, thermal and emission properties of an electrophosphorescent platinum(II) metallopolyyne polymer consisting of 9-butylcarbazole-2,7-diyl spacer P1 are described. The optical and electronic properties of P1 are compared to their molecular diplatinum(II) and digold(I) model complexes. The photophysical properties of P1 are somehow analogous to its 2,7-fluorene-linked congener but differs significantly from that for the 3,6-carbazole derivative. Its optical band gap is notably reduced as compared to that for the 3,6-carbazole analog. Multi-layer polymer light-emitting diodes (PLEDs) were fabricated with P1 as the emitting layer which gave a strong green-yellow electrophosphorescence. The best PLED can reach the maximum current efficiency of 4.7 cd . A(-1) at 5 wt.-% doping level, corresponding to an external quantum efficiency of 1.5%. This represents the first literature example of efficient PLEDs exhibiting pure triplet emission under electrical excitation for metallopolyynes without the concomitant singlet emission.

7-Amino actinomycin D bound to single-stranded hairpin DNA enhanced by loop sequence-dependent luminescent Eu3+ and Tb3+ binding

Lanthanide Eu3+ and Tb3+ ions have been widely used in luminescent resonance energy transfer (LRET) for bioassays to study metal binding microenvironments. We report here that Eu3+ or Tb3+ can increase the binding affinity of antitumor antibiotic drug agent, 7-amino actinomycin D (7AACTD), binding to 5'-GT/TG-5' or 5'-GA/AG-5' mismatched stem region of the single-stranded hairpin DNA. Further studies indicate that the effect of Eu3+ or Tb3+ on 7AACTD binding is related to DNA loop sequence. Our results will provide new insights into how metal ions can enhance antitumor agents binding to their targets.

Synthesis and chain-length dependent properties of monodisperse oligo(9,9-di-n-octylfluorene-2,7-vinylene)s

A series of monodisperse oligo(9,9-di-n-octylfluorene-2,7-vinylene)s (OFVs) with fluorene units up to 11 has been synthesized following a divergent approach. Chain length was found to affect not only photophysical properties but also thermal properties. Absorption and photoluminescence spectra are red-shifted with increasing chain length. The effective conjugated length has been extrapolated to be as long as 19 fluorene vinylene units, indicative of a well-conjugated system. With the number of fluorene units > 5, the oligomers exhibit nematic mesomorphism. Glass transition temperature (T-g) and clearing point temperature (T-c) increase with increasing molecular length and with those of OFV11 up to 71 and 230 degrees C, respectively. The oligomers can form uniform films by solution casting for fabrication of light-emitting diodes. With a device structure of ITO/ PEDOT:PSS/OFV11/Ca/Al, a current efficiency of 0.8 cd.A(-1) at a brightness of 1300 cd.m(-2) along with a maximum brightness of 2690 cd.m(-2) have been realized. This performance is notably superior to that of the corresponding polymer.

Structure and electrochemical characteristics of TiV1.1Mn0.9Nix (x=0.1-0.7) alloys

The structure and electrochemical properties of TiV1.1Mn0.9Nix (x = 0.1-0.7) solid solution electrode alloys have been investigated. It is found that these alloys mainly consist of a solid solution phase with body centered cubic (bcc) structure and a C14 Laves secondary phase. The solid solution alloys show easy activation behavior, high temperature dischargeability, high discharge capacity and favorable high-rate dischargeability as a negative electrode material in Ni-MH battery. The maximum discharge capacity is 502 mAh g(-1) at 303 K when x = 0.4. Electrochemical impedance spectroscopy (EIS) test shows that the charge-transfer resistance at the surface of the alloy electrodes decreases obviously with increasing Ni content.

Synthesis and characterization of novel sulfonated polyimides from 1,4-bis(4-aminophenoxy)-naphthyl-2,7-disulfonic acid

A novel sulfonated diamine monomer, 1,4-bis(4-aminophenoxy)-naphthyl-2,7-disulfonic acid (BAPNDS), was synthesized. A series of sulfonated polyimide copolymers were prepared from BAPNDS, 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) and nonsulfonated diamine 4,4'-diaminodiphenyl ether (ODA). Flexible, transparent, and mechanically strong membranes were obtained. The membranes displayed slightly anisotropic membrane swelling. The dimensional change in thickness direction was larger than that in planar. The novel SPI membranes showed higher conductivity, which was comparable or even higher than Nafion 117. Membranes exhibited methanol permeability from 0.24 x 10(-6) to 0.80 X 10(-6) cm(2)/s at room temperature, which was much lower than that of Nafion (2 x 10-6 CM2/s). The copolymers were thermally stable up to 340 degrees C. These preliminary results have proved its potential availability as proton-exchange membrane for PEMFCs or DMFCs.

Green light-emitting polyfluorenes with improved color purity incorporated with 4,7-diphenyl-2,1,3-benzothiadiazole moieties

By incorporating 4,7-diphenyl- 2,1,3 benzothiadiazole instead of 2,1,3-benzothiadiazole into the backbone of polyfluorene, we developed a novel series of green light- emitting polymers with much improved color purity. Compared with the state-of-the-art green light-emitting polymer, poly(fluorene-co-benzothiadiazole) (lambda max = 537 nm), the resulting polymers (lambda(max) = 521 nm) showed 10-20 nm blueshifted electroluminescence (EL) spectra and greatly improved color purity because the insertion of two phenylene units between the 2,1,3-benzothiadiazole unit and the fluorene unit reduced the effective conjugation length in the vicinity of the 2,1,3-benzothiadiazole unit. As a result, the resulting polymers emitted pure green light with CIE coordinates of (0.29, 0.63), which are very close to (0.26, 0.65) of standard green emission demanded by the National Television System Committee (NTSC). Moreover, the insertion of the phenylene unit did not affect the photoluminescence (PL) and EL efficiencies of the resulting polymers. PL quantum efficiency in solid films up to 0.82 was demonstrated. Single-layer devices (ITO/PEDOT/ polymer/Ca/Al) of these polymers exhibited a turn-on voltage of 4.2 V, luminous efficiency of 5.96 cd A(-1) and power efficiency of 2.21 lm W-1. High EL efficiencies and good color purities made these polymers very promising for display applications.

2-十八烷基-7,7,8,8-四氰基对苯二醌二甲烷和3,3',5,5'-四甲基连苯胺电荷转移配合物Langmuir-Blodgett膜的制备及光谱研究

本文利用Langmuir-Blodgett技术制备2-十八烷基-7,7,8,8-四氰基对苯二醌二甲烷和3,3',5,5'-四甲基连苯胺电荷转移配合物超薄膜.并利用红外光谱和紫外-可见-近红外光谱研究其分子取向及结构.

Phase behavior of BaLn(2)Mn(2)O(7) (Ln = rare earth) with a layered perovskite structure

Many phases appear in BaLn(2)Mn(2)O(7) family (Ln = rare earth) belonging to one of the Ruddlesden-Popper type compounds, depending upon the experimental conditions such as heating conditions when prepared and composition. Some of these phases were characterized by powder X-ray diffraction method using Rietveld analysis. These phases have only a little difference in crystal structure which has fundamentally K2NiF4 type structure, although the X-ray diffraction patterns are clearly different: a little deformation or tilting of the oxygen octahedron surrounding a central manganese ion composing the main frame of this structure induce these different diffraction patterns. Phase behavior of these compounds, mainly the detailed relation between various phases in BaTb2Mn2O7, was refined including the data of high temperature X-ray diffractometry.

Electrolummescence from (5)Do -> F-7(J) and D-5(1) -> F-7(J) (J=0-4) transitions with a europium complex as emitter

Electroluminescence (EL) devices with Eu(HTH)(3)phen [HTH: 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)-1,3-hexanedione, phen: I 10-phenanthroline] as an emissive centre were fabricated using vacuum evaporation. In addition to the Eu3+ 5D0 --> F-7(J) (J = 0-4) lines that were visible in the photoluminescence signal, the device also showed strong emission from the D-5(1) --> F-7(J) (J = 0-4) transitions. The enhanced emission from the D-5(1) F-7(J) (J = 0-4) transitions was attributed to the increased excitation intensity in the EL device. The luminescence lifetimes of the 5 D, and 5 Do levels were measured to be 0.6 mus and 866 mus, respectively.

Enthalpy/entropy compensation: Influence of DNA flanking sequence on the binding of 7-amino actinomycin D to its primary binding site in short DNA duplexes

The effect of the context of the flanking sequence on ligand binding to DNA oligonucleotides that contain consensus binding sites was investigated for the binding of the intercalator 7-amino actinomycin D. Seven self-complementary DNA oligomers each containing a centrally located primary binding site, 5'-A-G-C-T-3', flanked on either side by the sequences (AT)(n) or (AA)(n) (with n = 2, 3, 4) and AA(AT)(2), were studied. For different flanking sequences, (AA)(n)-series or (AT)(n)-series, differential fluorescence enhancements of the ligand due to binding were observed. Thermodynamic studies indicated that the flanking sequences not only affected DNA stability and secondary structure but also modulated ligand binding to the primary binding site. The magnitude of the ligand binding affinity to the primary site was inversely related to the sequence dependent stability. The enthalpy of ligand binding was directly measured by isothermal titration calorimetry, and this made it possible to parse the binding free energy into its energetic and entropic terms.

Effect of La/Ce ratio on the structure and electrochemical characteristics of La0.7-xCexMg0.3Ni2.8Co0.5 (x=0. 1-0.5) hydrogen storage alloys

The effect of La/Ce ratio on the structure and electrochemical characteristics of the La0.7-xCexMg0.3Ni2.8Co0.5 (x = 0.1, 0.2, 0.3, 0.4, 0.5) alloys has been studied systematically. The result of the Rietveld analyses shows that, except for small amount of impurity phases including LaNi and LaNi2, all these alloys mainly consist of two phases: the La(La, Mg)(2)Ni-9 phase with the rhombohedral PuNi3-type structure and the LaNi5 phase with the hexagonal CaCU5-type structure. The abundance of the La(La, Mg)(2)Ni-9 phase decreases with increasing cerium content whereas the LaNi5 phase increases with increasing Ce content, moreover, both the a and cell volumes of the two phases decrease with the increase of Ce content. The maximum discharge capacity decreases from 367.5 mAh g(-1) (x = 0.1) to 68.3 mAh g(-1) (x = 0.5) but the cycling life gradually improve. As the discharge current density is 1200 mA g(-1), the HRD increases from 55.4% (x = 0.1) to 67.5% (x = 0.3) and then decreases to 52.1% (x = 0.5). The cell volume reduction with increasing x is detrimental to hydrogen diffusion D and accordingly decreases the low temperature dischargeability of the La0.7-xCexMg0.3Ni2.8Co0.5 (x = 0.1-0.5) alloy electrodes.

2-十八烷基-7,7,8,8-四氰基对醌二甲烷和3,3′,5,5′-四甲基联苯胺电荷转移配合物LB膜的制备和表征

利用LB技术制备了2-十八烷基-7,7,8,8-四氰基对醌二甲烷(C18TCNQ)和3,3,′5,5′-四甲基联苯胺(TMB)的电荷转移配合物(CT comp lex)薄膜,即TMB.C18TCNQ LB膜.利用红外(IR)光谱、紫外-可见-近红外(UV-V is-NIR)光谱以及原子力显微镜(AFM)研究了TMB.C18TCNQ在LB膜中的分子取向、结构及表面形貌.结果表明,配合物为混合堆积类型,LB膜中电子给体TMB和电子受体C18TCNQ的环面分别垂直于固体基板表面,而且给体和受体以面对面的方式堆积.5层TMB.C18TCNQ LB膜的AFM照片显示,其表面形貌是由许多堆积在一起的六边形片状微晶组成的,微晶的宽度约为180 nm.与通过LB技术和掺杂技术制备的TMB.C18TCNQ掺杂膜比较,TMB.C18TCNQ LB膜具有明显不同的结构,其长的脂肪烃链有向垂直于基板表面方向变化的趋势,LB膜与掺杂膜的表面形貌也有明显不同.这表明不同的制备方法可以影响薄膜的结构和形貌.