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41.
Self‐Assembly of a Highly Organized,Hexameric Supramolecular Architecture: Formation,Structure and Properties
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Dr. Gaël Schaeffer Dr. Olaf Fuhr Prof. Dieter Fenske Prof. Jean‐Marie Lehn 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(1):179-186
Two derivatives, 3 L and 9 L , of a ditopic, multiply hydrogen‐bonding molecule, known for more than a decade, have been found, in the solid state as well as in solvents of low polarity at room temperature, to exist not as monomers, but to undergo a remarkable self‐assembly into a complex supramolecular species. The solid‐state molecular structure of 3 L , determined by single‐crystal X‐ray crystallography, revealed that it forms a highly organized hexameric entity 3 L 6 with a capsular shape, resulting from the interlocking of two sets of three monomolecular components, linked through hydrogen‐bonding interactions. The complicated 1H NMR spectra observed in o‐dichlorobenzene (o‐DCB) for 3 L and 9 L are consistent with the presence of a hexamer of D3 symmetry in both cases. DOSY measurements confirm the hexameric constitution in solution. In contrast, in a hydrogen‐bond‐disrupting solvent, such as DMSO, the 1H NMR spectra are very simple and consistent with the presence of isolated monomers only. Extensive temperature‐dependent 1H NMR studies in o‐DCB showed that the L 6 species dissociated progressively into the monomeric unit on increasing th temperature, up to complete dissociation at about 90 °C. The coexistence of the hexamer and the monomer indicated that exchange was slow on the NMR timescale. Remarkably, no species other than hexamer and monomer were detected in the equilibrating mixtures. The relative amounts of each entity showed a reversible sigmoidal variation with temperature, indicating that the assembly proceeded with positive cooperativity. A full thermodynamic analysis has been applied to the data. 相似文献
42.
Dr. Damien Hudry Dr. Christos Apostolidis Dr. Olaf Walter Dr. Arne Janßen Dr. Dario Manara Dr. Jean‐Christophe Griveau Dr. Eric Colineau Dr. Tonya Vitova Tim Prüßmann Dr. Di Wang Dr. Christian Kübel Dr. Daniel Meyer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(33):10431-10438
Apart from its technological importance, plutonium (Pu) is also one of the most intriguing elements because of its non‐conventional physical properties and fascinating chemistry. Those fundamental aspects are particularly interesting when dealing with the challenging study of plutonium‐based nanomaterials. Here we show that ultra‐small (3.2±0.9 nm) and highly crystalline plutonium oxide (PuO2) nanocrystals (NCs) can be synthesized by the thermal decomposition of plutonyl nitrate ([PuO2(NO3)2] ? 3 H2O) in a highly coordinating organic medium. This is the first example reporting on the preparation of significant quantities (several tens of milligrams) of PuO2 NCs, in a controllable and reproducible manner. The structure and magnetic properties of PuO2 NCs have been characterized by a wide variety of techniques (powder X‐ray diffraction (PXRD), X‐ray absorption fine structure (XAFS), X‐ray absorption near edge structure (XANES), TEM, IR, Raman, UV/Vis spectroscopies, and superconducting quantum interference device (SQUID) magnetometry). The current PuO2 NCs constitute an innovative material for the study of challenging problems as diverse as the transport behavior of plutonium in the environment or size and shape effects on the physics of transuranium elements. 相似文献
43.
Pyranoside‐into‐Furanoside Rearrangement: New Reaction in Carbohydrate Chemistry and Its Application in Oligosaccharide Synthesis
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Dr. Vadim B. Krylov Dmitry A. Argunov Dmitry Z. Vinnitskiy Stella A. Verkhnyatskaya Dr. Alexey G. Gerbst Dr. Nadezhda E. Ustyuzhanina Dr. Andrey S. Dmitrenok Prof. Dr. Johannes Huebner Prof. Dr. Otto Holst Prof. Dr. Hans‐Christian Siebert Prof. Dr. Nikolay E. Nifantiev 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(50):16516-16522
Great interest in natural furanoside‐containing compounds has challenged the development of preparative methods for their synthesis. Herein a novel reaction in carbohydrate chemistry, namely a pyranoside‐into‐furanoside (PIF) rearrangement permitting the transformation of selectively O‐substituted pyranosides into the corresponding furanosides is reported. The discovered process includes acid‐promoted sulfation accompanied by rearrangement of the pyranoside ring into a furanoside ring followed by solvolytic O‐desulfation. This process, which has no analogy in organic chemistry, was shown to be a very useful tool for the synthesis of furanoside‐containing complex oligosaccharides, which was demonstrated by synthesizing disaccharide derivatives α‐D ‐Galp‐(1→3)‐β‐D ‐ Galf ‐OPr, 3‐O‐s ‐lactyl‐β‐D ‐ Galf ‐(1→3)‐β‐D ‐Glcp‐OPr, and α‐L ‐ Fucf ‐(1→4)‐β‐D ‐GlcpA‐OPr related to polysaccharides from the bacteria Klebsiella pneumoniae and Enterococcus faecalis and the brown seaweed Chordaria flagelliformis. 相似文献
44.
On the Electronic Structure and Photochemistry of Coordinatively Unsaturated Complexes: The Case of Nickel Bis‐dinitrogen,Ni(N2)2
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Dr. Olaf Hübner Dr. Laurent Manceron Prof. Hans‐Jörg Himmel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(51):17025-17038
The electronic ground and excited states of the coordinatively unsaturated complex Ni(η1‐N2)2, isolated in an Ar matrix, are analyzed in detail by vibrational and electronic absorption and emission spectroscopies allied with quantum chemical calculations. The bond force constants are determined from a normal coordinate analysis and compared with those of the isoelectronic carbonyl complex. The consequences for the bond properties are discussed, and the trend in the force constants is compared with the standard formation enthalpies. The linear complex Ni(η1‐N2)2 with two terminal dinitrogen ligands can be photoisomerized to two isomeric, metastable forms Ni(η1‐N2)(η2‐N2) and Ni(η2‐N2)2, with one and two side‐on coordinated dinitrogen ligands, respectively. 相似文献
45.
Counting of Oxygen Defects versus Metal Surface Sites in Methanol Synthesis Catalysts by Different Probe Molecules
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Matthias B. Fichtl Julia Schumann Igor Kasatkin Nikolas Jacobsen Malte Behrens Robert Schlögl Martin Muhler Olaf Hinrichsen 《Angewandte Chemie (International ed. in English)》2014,53(27):7043-7047
Different surface sites of solid catalysts are usually quantified by dedicated chemisorption techniques from the adsorption capacity of probe molecules, assuming they specifically react with unique sites. In case of methanol synthesis catalysts, the Cu surface area is one of the crucial parameters in catalyst design and was for over 25 years commonly determined using diluted N2O. To disentangle the influence of the catalyst components, different model catalysts were prepared and characterized using N2O, temperature programmed desorption of H2, and kinetic experiments. The presence of ZnO dramatically influences the N2O measurements. This effect can be explained by the presence of oxygen defect sites that are generated at the Cu‐ZnO interface and can be used to easily quantify the intensity of Cu‐Zn interaction. N2O in fact probes the Cu surface plus the oxygen vacancies, whereas the exposed Cu surface area can be accurately determined by H2. 相似文献
46.
Olaf Kirchner 《Macromolecular Symposia》1995,100(1):143-147
The combination of using high performance flexible engineering polymers and their processing by blow moulding technology allows traditional rubber and rubber-metal composite parts to be replaced to obtain improved performance, lower cost and greater design freedom. Two examples of automobile applications are detailed to support this concept - constant velocity joint boots and engine air ducting. 相似文献
47.
48.
Olaf Kühl Stephan Millinghaus Gottfried J. Palm 《Central European Journal of Chemistry》2011,9(4):706-711
Starting from the paddlewheel complex copper(II)acetate, the green N-methylimidazole adduct of copper(II)acetate is formed
and transformed into the monomeric and dimeric N-methylimidazole adducts of copper(II)acetate [Cu(C4H6N2)2(CH3COO)2]n·xH2O (n = 1,2; x = 0, 6). The formation of the blue dimer or the purple monomer depends on the solvent and the presence or absence
of water. 相似文献
49.
Olaf Bröcker 《Journal of Geometry》2002,75(1-2):46-60
For M?bius planes Schaeffer [9] has proved that all seven
point degenerations of Miquel's Theorem characterize miquelian M?bius
planes. For Laguerre planes we have several degenerations of Miquel's
Theorem with eight and seven points. We prove that all except one of
these degenerations characterize miquelian Laguerre planes. The
remaining degeneration characterizes elation Laguerre planes.
Received 14 September 2001; revised 1 September 2002. 相似文献
50.