Mechanical relaxations in some ionene polymers. II. Influence of counterions and absorbed water

Six 6,10-ionenes with different counterions were prepared by ion exchange reactions in aqueous solutions. The counterions were Br, I, CIO₄, BF₄, SCN, and B(C₆H₅)₄. The dynamic mechanical properties of these polymers were investigated by use of a torsional braid analyser. Three relaxations α (25–140°C), β (?30–0°C), and γ (?140–120°C) were observed at the frequencies of 0.3–0.8 Hz. The temperature of the α and β relaxations were largely dependent on the size of counterions, but those of the γ relaxations had little variation. The effects of electrostatic forces in the polymers on each relaxation was discussed. The influence of absorbed water on the α, β, and γ relaxations was examined. The absorbed water in the polymers greatly depressed the temperature of the α relaxations and this phenomenon was interpreted to be the result of the specific hydration on ionic portions.     

W-algebras for generalized Toda theories

The generalized Toda theories obtained in a previous paper by the conformal reduction of WZNW theories possess a new class ofW-algebras, namely the algebras of gauge-invariant polynomials of the reduced theories. An algorithm for the construction of base-elements for theW-algebras of all such generalized Toda theories is found, and theW-algebras for the maximalSL(N,R) generalized Toda theories are constructed explicitly, the primary field basis being identified.     

Satellite phenomena in the X-ray photoelectron spectra of lanthanide trihydroxides

Using the direct CI method perturbation corrections to the Koopmans ionization energies have been obtained up to order 10 for the molecules CN^? and H₂O. The results are compared with those from the fully converged CI and B_k-type calculations. The convergence of the perturbation series is found to be quite slow although substantial improvement is possible using a variation-perturbation method.     

Ligand-free Pd/C-catalyzed Suzuki-Miyaura coupling reaction for the synthesis of heterobiaryl derivatives

We have developed a mild and efficient protocol for the ligand-free and heterogeneous Pd/C-catalyzed hetero Suzuki-Miyaura coupling reaction that allows for the synthesis of both heteroaryl-aryl and heteroaryl-heteroaryl derivatives in good to excellent yields.     

Enhancement of electroluminescence intensity in poly(3-alkylthiophene) with different alkyl side-chain length by doping of fluorescent dye

Electroluminescent diodes utilizing poly(3-alkylthiophene) (PAT) containing fluorescent dyes have been fabricated and their unique enhancement of emission characteristics have been studied. Remarkable enhancement of the electroluminescence efficiency has been observed for diodes with PAT doped with oxadiazole derivative (2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole; PBD) and perylene derivative (N,N′ - Bis(2,5 - di - tert - butylphenyl) - 3,4,9,10 - perylenedi- carboximide; BPPC). The mechanism of emission enhancement by doping of PBD into PAT has been discussed with different alkyl side-chain lengths. © 1997 John Wiley & Sons, Ltd.     

Nepalensinols D-G, new resveratrol oligomers from Kobresia nepalensis (Cyperaceae) as potent inhibitors of DNA topoisomerase II

Four new resveratrol oligomers, nepalensinols D-G, were isolated from the stem of Kobresia nepalensis (Cyperaceae). The structures were determined by detailed NMR spectral analysis. The compounds were assessed for their inhibitory activity against human topoisomerase II, a potential target of anti-tumor agents. These stilbenoids showed potent inhibitory activity against human topoisomerase II with IC50 values of 5-15 microM.     

Experimental evidence and bond characterization of a cyclopropenylgermylene

The reduction of p-anisyl(1,2,3-tri-tert-butylcycloprop-2-en-1-yl)dichlorogermane (1) with potassium in the presence of an excess of tert-butyldimethylsilane in benzene under reflux gave p-anisyl(tert-butyldimethylsilyl)(1,2,3-tri-tert-butylcycloprop-2-en-1-yl)germane (4) in 15% yield. The formation of 4 indicates that p-anisyl(1,2,3-tri-tert-butylcycloprop-2-en-1-yl)germylene (2), which is the first example of a (cycloprop-2-en-1-yl)germylene derivative, was generated and trapped by the hydrosilane. The DFT calculations revealed that the cis-2-p-anisyl-1,3,4-tri-tert-butyl-2-germabicyclo[1.1.0]butane-2,4-diyl structure cis-5 is 8.0 kJ/mol more stable than cis-2. The NBO analysis revealed that cis-5 has a 2-germabicyclo[1.1.0]butane diradical character.     

Precise determination of hyperfine interactions and second-order doppler shift in <Superscript>149</Superscript>Sm Mössbauer transition

We have succeeded in precisely determining the hyperfine interactions, particularly the isomer shifts, in the ¹⁴⁹Sm Mössbauer transition. The difference in the nuclear radii between the ground and excited states is critical for the determination of isomer shifts but is relatively small in ¹⁴⁹Sm. Therefore, the precise determination by ¹⁴⁹Sm Mössbauer spectroscopy is difficult. The recent development of synchrotron-radiation-based Mössbauer spectroscopy allows the isomer shifts to be determined more precisely than previously with the help of wellcollimated synchrotron radiation. In particular, the time-window effect assists the precise determination of hyperfine interactions in the ¹⁴⁹Sm Mössbauer transition because this effect enables us to measure spectra with higher energy resolution than natural linewidth determined by the lifetime of the excited states. Meanwhile, highenergy-resolution measurements to determine center shifts by SR-based Mössbauer spectroscopy enable us to observe the second-order Doppler shift, which has not been discussed, particularly for heavy Mössbauer nuclei. We have discussed the precise determination of isomer shifts and the observation of the second-order Doppler shift using ¹⁴⁹Sm synchrotron-radiation-based Mössbauer spectroscopy.     

Stabilization of atmospheric carbon dioxide via zero emissions-An alternative way to a stable global environment. Part 1: Examination of the traditional stabilization concept

The concept of "stabilization" of atmospheric CO2 concentration is re-examined in connection with climate-change mitigation strategies. A new "zero-emissions stabilization (Z-stabilization)" is proposed, where CO2 emissions are reduced to zero at some time and thereafter the concentration is decreased by natural removal processes, eventually reaching an equilibrated stable state. Simplified climate experiments show that, under Z-stabilization, considerably larger emissions are permissible in the near future compared with traditional stabilization, with the same constraint on temperature rise. Over longer time scales, the concentration and temperature decrease close to their equilibrium values, much lower than those under traditional stabilization. The smaller temperature rise at final state is essential to avoid longer-term risk of sea level rise, a significant concern under traditional stabilization. Because of these advantages a Z-stabilization pathway can be a candidate of practical mitigation strategies as treated in Part 2.(Contributed by Taroh MATSUNO, M.J.A.).