Chemistry - A European Journal

Cover image for Vol. 12 Issue 2

December 23, 2005

Volume 12, Issue 2

Pages 339–639

    1. Cover Picture: Preparation and Functionalization of Multilayer Fullerenes (Carbon Nano-Onions) (Chem. Eur. J. 2/2006) (page 339)

      Arno S. Rettenbacher, Bevan Elliott, Joan S. Hudson, Armen Amirkhanian and Luis Echegoyen

      Version of Record online: 19 DEC 2005 | DOI: 10.1002/chem.200690003

      Round about The preparation, funtionalization, and characterization of carbon nano-onions (CNOs) is described by L. Echegoyen et al. on page 376 ff. CNOs represent the most recently discovered and least studied allotropic form of carbon.

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      Synthesis of the C(1)–C(11) Polyene Fragment of Apoptolidin with a New Sulfur Dioxide-Based Organic Chemistry (page 349)

      Laure C. Bouchez and Pierre Vogel

      Version of Record online: 19 DEC 2005 | DOI: 10.1002/chem.200690005

      This article corrects:
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      On the Regio- and Stereoselective Synthesis of Aminocyclitols from Cyclitol Epoxides: The Effect of Li as a Chelating Agent (page 349)

      Pedro Serrano, Amadeu Llebaria, Jordi Vázquez, Joan de Pablo, Josep M. Anglada and Antonio Delgado

      Version of Record online: 19 DEC 2005 | DOI: 10.1002/chem.200690007

      This article corrects:
    4. Stabilisation of Methylene Radicals by Cob(II)alamin in Coenzyme B12 Dependent Mutases (pages 352–362)

      Wolfgang Buckel, Christoph Kratky and Bernard T. Golding

      Version of Record online: 22 NOV 2005 | DOI: 10.1002/chem.200501074

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      Cob(II)alamin may not only be a spectator in coenzyme B12 dependent reactions. Evidence is presented that for carbon skeleton rearrangements and amino group 1,2-migrations cob(II)alamin may stabilise transition states and intermediate methylene radicals in the manner as indicated in the figure.

    5. X-ray Diffraction and Solid-State NMR Studies of a Germanium Binuclear Complex (pages 363–375)

      Luís Mafra, Filipe A. Almeida Paz, Fa-Nian Shi, João Rocha, Tito Trindade, Christian Fernandez, Anna Makal, Krzysztof Wozniak and Jacek Klinowski

      Version of Record online: 28 SEP 2005 | DOI: 10.1002/chem.200500281

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      High-resolution solid-state NMR studies have been performed on a novel organic–inorganic crystalline hybrid compound containing an anionic germanium complex with N-(phosphonomethyl)iminodiacetic acid residues (see picture).

    6. Preparation and Functionalization of Multilayer Fullerenes (Carbon Nano-Onions) (pages 376–387)

      Arno S. Rettenbacher, Bevan Elliott, Joan S. Hudson, Armen Amirkhanian and Luis Echegoyen

      Version of Record online: 28 SEP 2005 | DOI: 10.1002/chem.200500517

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      The first water-soluble carbon nano-onions (CNOs) have been synthesized in preparative quantities by using the graphite underwater arc discharge method. All functionalized CNO products were soluble in various organic solvents, and one synthesis produced water-soluble CNOs. The present work describes CNO synthesis, purification, functionalization, and characterization.

    7. Carbohydrate Chain of Ganglioside GM1 as a Ligand: Identification of the Binding Strategies of Three 15 mer Peptides and Their Divergence from the Binding Modes of Growth-Regulatory Galectin-1 and Cholera Toxin (pages 388–402)

      Hans-Christian Siebert, Karin Born, Sabine André, Martin Frank, Herbert Kaltner, Claus-Wilhelm von der Lieth, Albert J. R. Heck, Jesús Jiménez-Barbero, Jürgen Kopitz and Hans-Joachim Gabius

      Version of Record online: 3 NOV 2005 | DOI: 10.1002/chem.200500505

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      A prominent cell surface ligand, that is, the pentasaccharide chain of ganglioside GM1, is essential for the binding of endogenous growth regulators (galectins) and bacterial toxins. Based on the synthesis of mini-lectins (15 mer peptides), structural analysis of the interaction at the size limit of the protein part was made possible. We used a combined strategy of mass spectrometry, NMR spectroscopy and molecular modelling. Major contributions to affinity arise from the contact between the sialic acid (Neu5Ac) moiety and Arg/Lys residues or the positive N-terminal charge (see figure).

    8. A New Tool in Peptide Engineering: A Photoswitchable Stilbene-type β-Hairpin Mimetic (pages 403–412)

      Máté Erdélyi, Anders Karlén and Adolf Gogoll

      Version of Record online: 27 SEP 2005 | DOI: 10.1002/chem.200500648

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      Molecular switches: The design, synthesis, photochemical investigation, and conformational analysis of a stilbene-type β-hairpin mimetic capable of light-triggered conformational changes (see scheme) have been achieved. Standard spectroscopic techniques and self-diffusion measurements have been used in conformational studies of the oligopeptides.

    9. Expanding the Number of Stable Isomeric Structures of the C80 Cage: A New Fullerene Dy3N@C80 (pages 413–419)

      Shangfeng Yang and Lothar Dunsch

      Version of Record online: 13 OCT 2005 | DOI: 10.1002/chem.200500383

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      Novel fullerene cages: A completely new isomer of a novel fullerene Dy3N@C80 was identified, expanding the number of stable isomeric structures of the C80 cage. The three isomers (13) of Dy3N@C80 were produced at a high selectivity compared with the empty fullerenes. Although 13 are all classified as large-band-gap materials, they show quite different UV-Vis-NIR absorption properties, and hence very distinct colors in toluene, as shown here. This suggests remarkable differences in their electronic structures, dependent on the cage symmetries.

    10. Self-Assembly of Dialkyltin Moieties and Mercaptobenzoic Acid into Macrocyclic Complexes with Hydrophobic “Pseudo-Cage” or Double-Cavity Structures: Supramolecular Infrastructures Involving Intermolecular C[BOND]H⋅⋅⋅S Weak Hydrogen Bonds and π–π Interactions (pages 420–428)

      Chunlin Ma, Qingfu Zhang, Rufen Zhang and Daqi Wang

      Version of Record online: 27 SEP 2005 | DOI: 10.1002/chem.200500590

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      Novel supramolecular structures displaying weak intermolecular interactions: Four novel organotin complexes of two types—[R2Sn(o-SC6H4CO2)]6 (R=Me, 1⋅H2O; nBu, 2) and {[R2Sn(m-CO2C6H4S)R2Sn(m-SC6H4CO2)SnR2]O}2 (R=Me, 3; nBu, 4)—have been prepared by treatment of o- or m-mercaptobenzoic acid and the corresponding R2SnCl2 (R=Me, nBu) with sodium ethoxide in ethanol (95 %). Structure analyses reveal that both 1 (left) and 2 are hexanuclear macrocycles with hydrophobic “pseudo-cage” structures, while 3 (right) and 4 are hexanuclear macrocycles with double-cavity structures.

    11. Extremely Base-Resistant Organic Phosphazenium Cations (pages 429–437)

      Reinhard Schwesinger, Reinhard Link, Peter Wenzl, Sebastian Kossek and Manfred Keller

      Version of Record online: 28 SEP 2005 | DOI: 10.1002/chem.200500837

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      Putting up resistance: A series of polyaminophosphazenium cations, for example, 1+, has been efficiently generated from PCl5. Compared with known phase-transfer cations, the novel cations show unprecedented resistance towards alkali hydroxides and are thus recommended for base-catalyzed reactions under highly forcing conditions.

    12. Anhydrous Phosphazenium Fluorides as Sources for Extremely Reactive Fluoride Ions in Solution (pages 438–445)

      Reinhard Schwesinger, Reinhard Link, Peter Wenzl and Sebastian Kossek

      Version of Record online: 30 SEP 2005 | DOI: 10.1002/chem.200500838

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      “Naked” fluoride! Anhydrous phosphazenium fluoride salts, such as 1⋅F, have been made available and fully characterized. Comparison of the novel fluorides with known fluoride sources reveals unique reactivity and selectivity in E2 elimination reactions. The novel fluorides also allow generation of extremely reactive naked anions by element[BOND]silicon bond cleavage of silane precursors.

    13. Liquid-Crystalline Supramolecular Polymers Formed through Complementary Nucleobase-Pair Interactions (pages 446–456)

      Sona Sivakova, Jian Wu, Cheryl J. Campo, Patrick T. Mather and Stuart J. Rowan

      Version of Record online: 20 OCT 2005 | DOI: 10.1002/chem.200500827

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      Fluorescent liquid-crystalline polymeric systems can be obtained through the use of complementary single-nucleobase interactions. By mixing monomers that have complementary nucleobase derivatives attached to a mesogenic core, stable liquid-crystalline phases can be formed, from which oriented fluorescent fibers can be obtained (see graphic).

    14. Mechanism Studies of the Conversion of 13C-Labeled n-Butane on Zeolite H-ZSM-5 by Using 13C Magic Angle Spinning NMR Spectroscopy and GC–MS Analysis (pages 457–465)

      Mikhail V. Luzgin, Alexander G. Stepanov, Sergei S. Arzumanov, Vladimir A. Rogov, Valentin N. Parmon, Wei Wang, Michael Hunger and Dieter Freude

      Version of Record online: 15 SEP 2005 | DOI: 10.1002/chem.200500382

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      Cracking and scrambling, but no eggs? The conversion of 13C-labeled n-butane on zeolite HZSM-5 results in 13C-label scrambling in n-butane through a monomolecular mechanism (intramolecular process 1, red in scheme), whereas isobutane and propane form by intermolecular oligomerization-cracking and conjunct-polymerization processes (2, shown in blue). Similar activation energies for processes 1 and 2 were obtained.

    15. Bifunctional-Thiourea-Catalyzed Diastereo- and Enantioselective Aza-Henry Reaction (pages 466–476)

      Xuenong Xu, Tomihiro Furukawa, Tomotaka Okino, Hideto Miyabe and Yoshiji Takemoto

      Version of Record online: 27 SEP 2005 | DOI: 10.1002/chem.200500735

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      Synthesis ofsyn-β-nitroamines with moderate to high diastereo- and enantioselectivity was achieved by aza-Henry reaction of nitroalkanes with N-Boc-imines in the presence of bifunctional thiourea 1a as catalyst. Various types of nitroalkanes bearing aryl, alcohol, ether, and ester substituents can be used as nucleophiles. Synthetic versatility of the adducts is demonstrated by their transformation into optically active piperidine derivatives.

    16. Simulation of 59Co NMR Chemical Shifts in Aqueous Solution (pages 477–488)

      Michael Bühl, Sonja Grigoleit, Hendrik Kabrede and Frank T. Mauschick

      Version of Record online: 30 SEP 2005 | DOI: 10.1002/chem.200500285

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      NMR properties of small molecules are not always easy to calculate, especially if these species are highly charged, observed in a protic solvent, and involve an extremely sensitive NMR nucleus. Among the protocols from the computational chemist's toolkit that are able to describe 59Co chemical shifts of tervalent aqueous CoIII complexes, that based on Car–Parrinello molecular dynamics (CPMD) simulations performs very well, as shown by plotting calculated versus experimental shifts (see picture; solid line: ideal slope of 1; dotted line: linear fit).

    17. Controlling Metal–Ligand–Metal Oxidation State Combinations by Ancillary Ligand (L) Variation in the Redox Systems [L2Ru(μ-boptz)RuL2]n, boptz=3,6-bis(2-oxidophenyl)-1,2,4,5-tetrazine, and L=acetylacetonate, 2,2′-bipyridine, or 2-phenylazopyridine (pages 489–498)

      Srikanta Patra, Biprajit Sarkar, Somnath Maji, Jan Fiedler, Francisco A. Urbanos, Reyes Jimenez-Aparicio, Wolfgang Kaim and Goutam Kumar Lahiri

      Version of Record online: 31 AUG 2005 | DOI: 10.1002/chem.200500295

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      The excellent tolerance of the bpy co-ligand for both RuIII and RuII is demonstrated by the adoption of the mixed-valent form in [L2Ru(μ-boptz)RuL2]3+, (see graphic) L=bpy, whereas the corresponding system with L=pap stabilizes the RuII states to yield a phenoxyl radical ligand and the compound with L=acac contains two RuIII centers connected by a tetrazine radical-anion bridge.

    18. Nitrosation of Sugar Oximes: Preparation of 2-Glycosyl-1-hydroxydiazene-2-oxides (pages 499–509)

      Jörg Brand, Thomas Huhn, Ulrich Groth and Johannes C. Jochims

      Version of Record online: 13 OCT 2005 | DOI: 10.1002/chem.200500325

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      Nitric oxide transportation: Glycosylated 1-hydroxydiazene-2-oxides (e.g., 1 and 2) are expected to be transported into cells, where nitric oxide—known to exhibit various bioregulatory activities—would be released. A number of these oxides have been prepared by nitrosation of different open-chain sugar oximes, and X-ray structural analyses have been carried out.

    19. Synthesis of the Indene, THF, and Pyrrolidine Skeletons by Lewis Acid Mediated Cycloaddition of Methylenecyclopropanes with Aldehydes, N-Tosyl Aldimines, and Acetals (pages 510–517)

      Li-Xiong Shao, Bo Xu, Jin-Wen Huang and Min Shi

      Version of Record online: 15 SEP 2005 | DOI: 10.1002/chem.200500447

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      Prins-type reactions: Methylenecyclopropanes (MCPs) react with aldehydes, N-tosyl aldimines, and acetals to give the corresponding indene, THF, and pyrrolidine cycloaddition products in the presence of BF3⋅OEt2 under mild reaction conditions (see scheme).

    20. Structural, Electronic, and Bonding Properties of Zeolite Sn-Beta: A Periodic Density Functional Theory Study (pages 518–523)

      Sharan Shetty, Sourav Pal, Dilip G. Kanhere and Annick Goursot

      Version of Record online: 27 SEP 2005 | DOI: 10.1002/chem.200500487

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      Sn makes all the difference: A theoretical investigation of cohesive energy, bonding, and electronic properties of all the nine active T-sites in Sn-incorporated zeolite beta (illustrated here; Sn blue, O red, and Si green) suggest that the incorporation of Sn at the T1 or T2 site would be the most favorable.

    21. Heteroatom-Guided Torquoselective Olefination of α-Oxy and α-Amino Ketones via Ynolates (pages 524–536)

      Mitsuru Shindo, Takashi Yoshikawa, Yasuaki Itou, Seiji Mori, Takeshi Nishii and Kozo Shishido

      Version of Record online: 28 SEP 2005 | DOI: 10.1002/chem.200500574

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      Tetrasubstituted olefins were obtained with high Z selectivity by reaction of ynolates with α-oxy- and α-aminoketones at room temperature. According to experimental and theoretical studies, the high Z selectivity is induced by orbital interactions in the ring opening of the β-lactone enolate intermediate (see scheme), rather than the initially presumed chelation of the lithium atom.

    22. Environmental Effects on a Prion's Helix II Domain: Copper(II) and Membrane Interactions with PrP180–193 and Its Analogues (pages 537–547)

      Domenico Grasso, Giulia Grasso, Valeria Guantieri, Giuseppe Impellizzeri, Carmelo La Rosa, Danilo Milardi, Giovanni Micera, Katalin Õsz, Giuseppe Pappalardo, Enrico Rizzarelli, Daniele Sanna and Imre Sóvágó

      Version of Record online: 15 SEP 2005 | DOI: 10.1002/chem.200500534

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      The PrP180–193 (VNITIKQHTVTTTT) segment corresponding to the helix II region of the prion protein (PrP) and its shorter PrPAc184–188NH2 (IKQHT) analogue are reliable models for studying the interaction of a metal with the helix II domain (see picture). Copper(II) affinity for the PrPAc184–188NH2 fragment is higher than that of the octarepeats and PrP106–126 peptides, thus stressing the role of His187 as an anchoring binding site for this structured region of PrP.

    23. Synthesis and Characterization of Core-Shell Selenium/Carbon Colloids and Hollow Carbon Capsules (pages 548–552)

      Jimmy C. Yu, Xianluo Hu, Quan Li, Zhi Zheng and Yeming Xu

      Version of Record online: 15 SEP 2005 | DOI: 10.1002/chem.200500523

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      A novelt-Se/a-C nanocomposite with core-shell structures was prepared by a facile one-pot microwave-induced hydrothermal route. The Se/C composite can be converted to hollow carbon capsules by thermal treatment (see figure). The core-shell-structured Se/C colloids as well as hollow C capsules inherit functional groups and possess hydrophilic surfaces.

    24. Intramolecular Interactions in the Triplet Excited States of Benzophenone–Thymine Dyads (pages 553–561)

      Noureddine Belmadoui, Susana Encinas, Maria J. Climent, Salvador Gil and Miguel A. Miranda

      Version of Record online: 20 SEP 2005 | DOI: 10.1002/chem.200500345

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      Intramolecular photosensitization of thymidine by ketoprofen: Paterno–Büchi cycloaddition giving oxetanes and a formal hydrogen abstraction from the methyl group of thymidine by benzophenone are competing triplet processes (see scheme).

    25. Electrochemical Survey: The Effect of the Cage Size and Structure on the Electronic Structures of a Series of Ytterbium Metallofullerenes (pages 562–567)

      Jianxun Xu, Meixian Li, Zujin Shi and Zhennan Gu

      Version of Record online: 15 SEP 2005 | DOI: 10.1002/chem.200500210

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      The cyclic and differential plus voltammograms for a series of ytterbium metallofullerenes (see figure for examples) with different sized cages have been recorded for the first time. This article discusses the effect of the cage size and structure on the electronic structures of these metallofullerenes.

    26. Asymmetric Sulfonium Ylide Mediated Cyclopropanation: Stereocontrolled Synthesis of (+)-LY354740 (pages 568–575)

      Varinder K. Aggarwal and Emma Grange

      Version of Record online: 27 SEP 2005 | DOI: 10.1002/chem.200500693

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      There are pluses and minuses to everything! Sulfonium ylides 1 can be used to prepare cyclopropanes 3 and 4, which are useful precursors to the glutamic acid analogue LY354740 (see scheme, de and ee=diastereromeric and enantiomeric excess, respectively).

    27. Poly(styrene)-Supported Co–Salen Complexes as Efficient Recyclable Catalysts for the Hydrolytic Kinetic Resolution of Epichlorohydrin (pages 576–583)

      Xiaolai Zheng, Christopher W. Jones and Marcus Weck

      Version of Record online: 29 SEP 2005 | DOI: 10.1002/chem.200500786

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      Unsymmetric is fast: Poly(styrene)-immobilized chiral Co–salen complexes (shown here), prepared by the free-radical polymerization of a styryl-substituted unsymmetrical salen monomer and the subsequent metallation with Co(OAc)2, exhibited desirable catalytic properties in the hydrolytic kinetic resolution of racemic epichlorohydrin.

    28. Synthesis, Liquid-Crystalline Properties, and Supramolecular Nanostructures of Dendronized Poly(isocyanide)s and Their Precursors (pages 584–591)

      Yanqing Tian, Kaori Kamata, Hirohisa Yoshida and Tomokazu Iyoda

      Version of Record online: 27 SEP 2005 | DOI: 10.1002/chem.200500868

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      Cylinders of polymers: Novel dendronized π-conjugated poly(isocyanide)s (shown here) with various degrees of polymerization were synthesized through a living polymerization technique. The rigid poly(isocyanide)s formed have columnar supramolecular liquid-crystalline properties. Further, the cylindrical nanostructure was visualized clearly by transmission electron microscopy.

    29. Zinc Hydrazides and Alkoxyhydrazides: Organometallic Compounds with Novel Zn4N8, Zn4N6O and Zn4N4O2 Cage Structures (pages 592–599)

      Surajit Jana, Roland Fröhlich and Norbert W. Mitzel

      Version of Record online: 3 NOV 2005 | DOI: 10.1002/chem.200500626

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      A rare case of an M4N8cage structure, and the first reported for zinc, is among the nitrogen-rich zinc clusters [{RZn(NHNMe2)}4] (R = Me, Et; see picture) that can be obtained from zinc alkyls and N,N-dimethylhydrazine. Partial replacement of hydrazine units of these compounds by reactions with water and alcohols gives access to new Zn/N/O clusters, with controlled ratios of the elements.

    30. Synthesis and Structure of Novel Organocycloborates (pages 600–606)

      Holger Braunschweig, Giovanni D'Andola, Tom Welton and Andrew J. P. White

      Version of Record online: 7 NOV 2005 | DOI: 10.1002/chem.200500760

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      Cyclic and spirocyclic tetraalkyl borates were obtained in very high yield from α,ω-boryl(bromo)alkanes of the general formula R2B[BOND](CH2)n[BOND]Br (n=4, 5, 6; see picture) upon reaction with Mg turnings by an unprecedented, boron-centred cyclisation reaction. Four compounds were structurally characterised, thus providing the first X-ray data for tetraalkyl boratacyclopentanes, -hexanes, and -heptanes, respectively.

    31. Molecular Junctions Composed of Oligothiophene Dithiol-Bridged Gold Nanoparticles Exhibiting Photoresponsive Properties (pages 607–619)

      Wei Huang, Gou Masuda, Seisuke Maeda, Hirofumi Tanaka and Takuji Ogawa

      Version of Record online: 29 SEP 2005 | DOI: 10.1002/chem.200500822

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      Self-assembled thin films composed of oligothiophene dithiol-bridged gold nanoparticles between 1 μm gap Au-electrodes (schematically illustrated here), which have been characterized by SEM, TM-AFM, and CM-AFM, exhibit distance- and temperature-dependent I-V behaviors as well as photoresponsive properties.

    32. TiO2 Nanoparticles in Mesoporous TUD-1: Synthesis, Characterization and Photocatalytic Performance in Propane Oxidation (pages 620–628)

      Mohamed S. Hamdy, Otto Berg, Jacobus C. Jansen, Thomas Maschmeyer, Jacob A. Moulijn and Guido Mul

      Version of Record online: 21 SEP 2005 | DOI: 10.1002/chem.200500649

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      TiO2nanoparticles (anatase phase) inside TUD-1 mesoporous silica (see figure) were synthesized in a one-pot procedure. The TiO2 nanoparticles in TUD-1 showed higher selectivity towards acetone than commerical TiO2 in the photooxidation of propane at 365 nm.

    33. The Heat of Formation of the Uranyl Dication: Theoretical Evaluation Based on Relativistic Density Functional Calculations (pages 629–634)

      Lyudmila V. Moskaleva, Alexei V. Matveev, Sven Krüger and Notker Rösch

      Version of Record online: 6 DEC 2005 | DOI: 10.1002/chem.200500628

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      The heat of formation of uranyl (UO22+) in the gas phase was determined from quantum-chemical reaction enthalpies and experimental data for a set of model actinide compounds. The theoretical estimates, 365±10 and 370±12 kcal mol−1, are in quantitative agreement with a recent experimental result, 364±15 kcal mol−1.

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      Preview: Chem. Eur. J. 2/2006 (page 639)

      Version of Record online: 19 DEC 2005 | DOI: 10.1002/chem.200690006