Synthesis of novel thermosetting imide compounds having phenylethynyl carbonyl groups at both terminal ends and production of new network polymers based on the imide compounds

A novel thermosetting imide compound having a respective phenylethynyl carbonyl group at both terminal ends was newly synthesized from an acid anhydride having a phenylethynyl carbonyl group and various diamine compounds. The thermosetting behavior of the obtained novel thermosetting imide compound having phenylethynyl carbonyl groups was analyzed through differential scanning calorimetry measurements and infrared spectroscopic analysis. As a result, it became clear that a curing reaction of phenylethynyl carbonyl groups proceeds at approximately 200°C and that the curing reaction thereof proceeds at a temperature that is lower by 150°C or more compared with that of phenylethynyl groups. Examination of the polymerization reaction of the imide compounds having phenylethynyl carbonyl groups using model compounds revealed that a reaction that imparted an alkene C=C and polycyclic aromatic structure progressed. Moreover, a network polymer obtained from a thermosetting imide compound having respective phenylethynyl carbonyl groups at both terminal ends exhibited extremely superior heat resistance and thermal decomposition resistance. These superior thermal properties are thought to be due to the strong molecular interaction (molecular packing) that results from the polycyclic aromatic structures and alkenes produced through polymerization of the phenylethynyl carbonyl groups and to the suppression of the movement of the molecular chains.     

Electron transfer of quinone self-assembled monolayers on a gold electrode

Dialkyl disulfide-linked naphthoquinone, (NQ-C_n-S)₂, and anthraquinone, (AQ-C_n-S)₂, derivatives with different spacer alkyl chains (C_n: n = 2, 6, 12) were synthesized and these quinone derivatives were self-assembled on a gold electrode. The formation of self-assembled monolayers (SAMs) of these derivatives on a gold electrode was confirmed by infrared reflection-absorption spectroscopy (IR-RAS). Electron transfer between the derivatives and the gold electrode was studied by cyclic voltammetry. On the cyclic voltammogram a reversible redox reaction between quinone (Q) and hydroquinone (QH₂) was clearly observed under an aqueous condition. The formal potentials for NQ and AQ derivatives were −0.48 and −0.58 V, respectively, that did not depend on the spacer length. The oxidation and reduction peak currents were strongly dependent on the spacer alkyl chain length. The redox behavior of quinone derivatives depended on the pH condition of the buffer solution. The pH dependence was in agreement with a theoretical value of E_1/2 (mV) = E′ − 59pH for 2H⁺/2e⁻ process in the pH range 3–11. In the range higher than pH 11, the value was estimated with E_1/2 (mV) = E′ − 30pH , which may correspond to H⁺/2e⁻ process. The tunneling barrier coefficients (β) for NQ and AQ SAMs were determined to be 0.12 and 0.73 per methylene group (CH₂), respectively. Comparison of the structures and the alkyl chain length of quinones derivatives on these electron transfers on the electrode is made.     

Cowaniin, a C-glucosidic ellagitannin dimer linked through catechin from Cowania mexicana

A new complex tannin, cowaniin (1) was isolated from the leaves and stems of Cowania mexicana (Rosaceae), and its structure was characterized as novel C-glucosidic tannin dimer linked through (+)-catechin on the basis of spectral and chemical evidence. The inhibitory effect on activation of the Epstein-Barr virus early antigen was assessed for cowaniin. Six known polyphenols and related compounds, including a nitrile glucoside, purshianin, were also characterized.     

Application of fluorescence resonance energy transfer (FRET) to investigation of light-induced conformational changes of the phoborhodopsin/transducer complex

The photoreceptor phoborhodopsin (ppR; also called sensory rhodopsin II) forms a complex with its cognate the Halobacterial transducer II (pHtrII) in the membrane, through which changes in the environmental light conditions are transmitted to the cytoplasm in Natronomonas pharaonis to evoke negative phototaxis. We have applied a fluorescence resonance energy transfer (FRET)-based method for investigation of the light-induced conformational changes of the ppR/pHtrII complex. Several far-red dyes were examined as possible fluorescence donors or acceptors because of the absence of the spectral overlap of these dyes with all the photointermediates of ppR. The flash-induced changes of distances between the donor and an acceptor linked to cysteine residues which were genetically introduced at given positions in pHtrII(1-159) and ppR were determined from FRET efficiency changes. The dye-labeled complex was studied as solubilized in 0.1% n-dodecyl-beta-D-maltoside (DDM). The FRET-derived changes in distances from V78 and A79 in pHtrII to V185 in ppR were consistent with the crystal structure data (Moukhametzianov, R. et al. [2006] Nature, 440, 115-119). The distance from D102 in pHtrII linker region to V185 in ppR increased by 0.33 angstroms upon the flash excitation. These changes arose within 70 ms (the dead time of instrument) and decayed with a rate of 1.1 +/- 0.2 s. Thus, sub-angstrom-scale distance changes in the ppR/pHtrII complex were detected with this FRET-based method using far-red fluorescent dyes; this method should be a valuable tool to investigate conformation changes in the transducer, in particular its dynamics.     

Synthesis of styrene–acrylonitrile random copolymers (SAN) and polyarylate block copolymers and the control of their mechanical properties by morphology generation

The idea of repulsion in random copolymers was applied to the miscibility modification between polystyrene (PS) and polyarylate (PAr) segments of PS–PAr block copolymer (PAr–PS–PAr). Acrylonitrile (AN), which has a large positive interaction parameter against styrene, was used as a miscibility modifier toward PAr segments. AN was introduced into the carboxyl terminated telechelic‐PS at AN wt % ranging from 12 to 37 wt %. Based on these telechelic acrylonitrile–styrene random copolymers (SAN_x's where x represents AN wt %), SAN_x and PAr block copolymers (PAr–SAN_x–PAr's) were synthesized. The miscibility of SAN_x and PAr segments was estimated from the results of DSC with Fox's equation and spin–spin relaxation time measured by pulsed NMR. These results evidenced that the miscibility between PS and PAr segments can be modified by introducing AN into PS segments. The estimated volume fraction of the interfacial layer between SAN_x and PAr segments was increased as x was increased toward 24 wt %, around which the predicted miscibility reaches a maximum. Above that AN wt %, it began to decrease. The flexural strength increased as the miscibility between SAN_x and PAr segments increased. In particular, when x was between 20 and 30 wt %, PAr–SAN_x–PAr exhibited three times larger flexural strength than PAr–PS–PAr. The fracture behavior changed from brittle to ductile, even though the telechelic SAN_x by themselves exhibited almost the same fracture strength as the telechelic PS. The results of dynamic mechanical measurements and the percolation model suggested that around these AN wt % the continuum matrices in PAr–SAN_x–PAr changed from SAN_x phase to a cocontinuous phase of SAN_x and PAr. From these results, PAr–SAN_x–PAr was explained to perform such a high flexural strength by this phase change in the continuum matrices. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 127–137, 2000