Cellulose-precursor synthesis of nanocrystalline Ce<Subscript>0.8</Subscript>Gd<Subscript>0.2</Subscript>O<Subscript>2−δ</Subscript> for SOFC anodes

Developments of intermediate-temperature solid oxide fuel cells (IT SOFCs) require novel anode materials with a high electrochemical activity at 800–1070 K. The polarization of cermet anodes, made of nickel, ceria and yttria-stabilized zirconia (YSZ) and applied onto a YSZ solid electrolyte, can be significantly reduced by catalytically active ceria additions, the relative role of which increases with decreasing temperature. Further improvement is observed when using Ce_0.8Gd_0.2O_2– (CGO) having a high oxygen ionic conductivity instead of undoped ceria, owing to enlargement of the electrochemical reaction zone. Nanocrystalline CGO powders with grain sizes of 8–35 nm were thus synthesized via the cellulose-precursor technique and introduced into Ni–CGO–YSZ cermets, and tested in contact with a (La_0.9Sr_0.1)_0.98Ga_0.8Mg_0.2O_3– (LSGM) electrolyte at 873–1073 K. The results showed that the anode performance can be enhanced by additional surface activation, in particular by impregnation with a Ce-containing solution, and also by incorporation of YSZ, which probably acts as a cermet-stabilizing component. The overpotential of the surface-modified Ni–CGO (25 wt%–75 wt%) anode in a 10% H₂/90% N₂ atmosphere was approximately 110 mV at 1073 K with a current density of 200 mA/cm².Presented at the OSSEP Workshop Ionic and Mixed Conductors: Methods and Processes, Aveiro, Portugal, 10–12 April 2003     

DIPOLE POLARIZATION RELAXATION AND MOLECULAR STRUCTURE OF MAIN-AND SIDE-CHAIN LIQUID-CRYSTALLINE POLYMERS

Molecular mobility in thermotropic polyesters and side-chain polymers with different struc-ture of mesogens and spacers has been studied by dielectrical method in dilutesolutions. The results made it possible to establish the multiplicity of dielectric relaxationtransitions which reflects the small- and large-scale types of molecular motion. It was shownthat dielectric relaxation processes occurring in accordance with local mechanism (relaxationtimes 10~(-9)--10~(-7)s. and the activation energy 10--50kJ/mol) are due to the mobility of kineticchain elements of different length within a monomer units. It was found that the dielectricrelaxation process connected with a large-scale form of molecular motion (relaxation times10~(-5)--10~(-6)s. and the activation energy 100kJ/mol) did not depend on the molecular massbut was infiuenced by factors changing the conformational state of the macromolecule. It isestablished tha the cooperative reorientation mobility of associated mesogenic fragments isthe source of the large-scale process.     

对固体圆二色光谱测试方法的再认识——兼谈“浓度效应”

对近期发展的固体圆二色(CD)光谱测试方法进行了概述、评价和比较, 着重探讨了“浓度效应”的存在使固体CD光谱失真的原因. 通过对本课题组和其他作者已报道的四种化合物的固体CD谱再测试的反思, 强调了依手性化合物的手性光谱学性质不同, 根据浓度梯度实验选择其合适测试浓度的必要性. 对固有手性的阻转异构化合物(S)-1,1'-联二萘酚(S-BINOL)进行了成膜法固体CD谱浓度梯度测试, 发现所得固体薄膜CD谱中也存在着“浓度效应”     

Chiroptical detection during liquid chromatography,part 5: On-line measurement of circular dichroism spectra Δε(λ) during stops of chromatographic flow

Summary A procedure is described which serves to measure circular dichrograms () on line during stops of flow in liquid chromatography. Since the concentration of substrate in the spectrometer cell during the stop is not known, the differential absorption coefficients are calculated from the experimental differential absorbances A by means of UV absorption (i. e. photomultiplier voltage) data. Verifications of the procedure are obtained by its application to three substrates (Table 1), the () spectra of which were known. The present on-line technique is compared with a corresponding off-line method.The N,N-dimethylthiobenzamides1 and2 as well as the 9,10-phenanthrenequinone7 consist of interconvertible enantiomers because their planar states are destabilized by steric overcrowding of groups. The unknown dichrograms () of1, 2 and7 are obtained (Figs. 2 and 4) and discussed with reference to the helicities of these molecules.In memory of the late Professor Dr. Dr. h. c. Günther Snatzke.     

Two-state irreversible thermal denaturation of anionic peanut (Arachis hypogaea L.) peroxidase

Detailed differential scanning calorimetry (DSC), steady-state tryptophan fluorescence and far-UV circular dichroism (CD) studies, together with enzymatic assays, were carried out to monitor the thermal stability of anionic peanut peroxidase (aPrx) at pH 3.0. The spectral parameters were seen to be good complements to the highly sensitive but integral method of DSC. Thus, changes in far-UV CD corresponded to changes in the overall secondary structure of the enzyme, while changes in intrinsic tryptophan fluorescence emission corresponded to changes in the tertiary structure of the enzyme. The results, supported with data concerning changes in enzymatic activity with temperature, show that thermally induced transitions for aPrx are irreversible and strongly dependent upon the scan rate, suggesting that denaturation is under kinetic control. It is shown that the process of aPrx denaturation can be interpreted with sufficient accuracy in terms of the simple kinetic scheme, , where k is a first-order kinetic constant that changes with temperature, as given by the Arrhenius equation; N is the native state, and D is the denatured state. On the basis of this model, the parameters of the Arrhenius equation were calculated.     

The absolute configuration of peroxisomicines A1 and A2

Peroxisomicine A1 is a potentially antineoplastic compound isolated from the seeds of Karwinskia parvifolia. It is considered as a useful chemotype for the preparation of topoisomerase II targeted anticancer cells. Stereochemically, it is characterized by the presence of two stereocenters and a rotationally hindered and thus likewise stereogenic biaryl axis. In this contribution, the absolute configuration of peroxisomicine A1 and its epimer, peroxisomicine A2, was established by means of a five-step degradative procedure giving the respective R- and S-configured methyl 2-(2′-methyl-5′-oxotetrahydrofuryl)acetates. The configuration of the degradation product was obtained by means of optical rotation, ¹H NMR analysis using a chiral displacement reagent, and by experimental and quantum chemical circular dichroism (CD) investigations. Based on the results obtained here and considering our previous work on the relative configuration at centers versus axis of these compounds, peroxisomicine A1 resulted to be the P,3S,3′S-isomer and peroxisomicine A2 the P,3R,3′S-isomer.     

A perylenedicarboxamide linker for DNA hairpins

The synthesis and properties of a perylenediamide diol linker and several DNA hairpins possessing this linker are described. The diol linker absorbs and fluoresces strongly in the visible. Hairpins having poly(dA)-poly(dT) stems have fluorescence quantum yields and decay times similar to those of the linker, indicating that hole injection does not occur from the singlet excited linker into the base pair domain. Fluorescence quenching by dG or dZ bases is observed when these bases are located near the linker. The strong distance dependence of fluorescence quenching is consistent with a superexchange mechanism for electron transfer. Failure to observe formation of the linker anion radical by means of femtosecond time resolved absorption spectroscopy is attributed to fast charge recombination. The properties and behavior of the perylene linker and its hairpins are compared to those of other arenedicarboxamide linkers.     

Polarization Dependent Photoinduced Supramolecular Chirality in High-Performance Azo Materials

Here, we will show photo-induced supramolecular chirality in thin films of achiral amorphous polymers with azo groups in their side-chain. A matter of particular interest is the effect of various film thicknesses on azimuthal rotation and ellipticity of incident/transmitted polarized light. Furthermore, we investigated the temporal stability of inscribed chirality. By polarimetric measurements, we found out that the azimuthal rotation gets higher with layer thickness. In this scope, we were able to measure a very high azimuthal rotation of Δψ/d=112.5∘/μm. The inscribed chirality was stable for several days. Furthermore, we investigated the time-resolved behavior of incident and transmitted polarization ellipticities for various thicknesses. The time dependency may be explained by a two-step process: (1) fast trans-cis-isomerization resulting in photo-orientation and (2) slow photo-induced mass flow.     

Lanthanide induced shifts of aromatic 1,2,3-trimethoxy compounds: Conformational analysis of tetrahydrofurofuran-lignans in solution

Summary The solution conformations of 1,4-diaryl-tetrahydro-1H,3H-furo[3,4-c]furans were determined by means of the LIS technique using a modified LIS-simulation program specially designed for the requirements of the aromatic 1,2,3-trimethoxy arrangement as a bidentate coordination site for the NMR shift reagent. The resulting geometries were confirmed by force field calculations (MM2-87) and compared with X-ray derived structures. Reliable data for the conformations in solution allowed a quantitative estimation of the circular dichroism based on the coupled oscillator model.

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Lanthanideninduzierte Verschiebungen von aromatischen 1,2,3-Trimethoxy-Verbindungen: Konformationsanalyse von Tetrahydrofurofuran-Lignanen in Lösung

Zusammenfassung Es wurden mittels der LIS-Technik die Konformationen von 1,4-Diaryl-tetrahydro-1H,3H-furo[3,4-c]furanen in Lösung bestimmt. Dazu mußte ein modifiziertes LIS-Simulationsprogramm entworfen werden, das auf die besonderen Verhältnisse der aromatischen 1,2,3-Trimethoxy-Gruppierung eingeht, welche in den untersuchten Verbindungen als zweizähnige Koordinationsstelle für das NMR-Verschiebungsreagens fungiert. Die resultierenden Geometrien wurden mittels Kraftfeldrechnungen (MM2-87) überprüft und soweit vorhanden auch mit Röntgenstrukturdaten verglichen. Für die Lösungskonformationen wurde eine quantitative Abschätzung des Circulardichroismus auf der Basis des Modells für gekoppelte Oszillatoren durchgeführt.

     

Contracted polarization functions for B to Ar

Using optimal exponents for B through Ne given by Dunning and those for Al through Ar by Woon and Dunning, d-type contracted polarization functions (2d/1d), (3d/1d), and (3d/2d) are generated from natural orbitals of atomic single and double excitation configuration interaction (SDCI) calculations, where the numbers before and after the slash are those of the primitive and contracted Gaussian type functions. The resulting contracted functions are tested on N₂ and P₂ molecules by self-consistent field and SDCI calculations, which clarify characteristics of the present polarization functions. Received: 5 June 1997 / Accepted: 20 August 1997