Chemistry - A European Journal

Cover image for Chemistry - A European Journal

July 18, 2008

Volume 14, Issue 21

Pages 6279–6559

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
    7. Review
    8. Communications
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    1. Cover Picture: Distinct Columnar and Lamellar Liquid Crystalline Phases Formed by New Bolaamphiphiles with Linear and Branched Lateral Hydrocarbon Chains (Chem. Eur. J. 21/2008) (page 6279)

      Marko Prehm, Claudia Enders, Maryam Yahyaee Anzahaee, Benjamin Glettner, Ute Baumeister and Carsten Tschierske

      Version of Record online: 11 JUL 2008 | DOI: 10.1002/chem.200890080

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      Polyphilic T-shaped molecules self-assemble into new liquid-crystalline phases in which rodlike aromatic units form arrays of polygonal cylinders that are fused by hydrogen-bonding networks running along the edges to give honeycomb-like networks in which the cells are filled by fluid alkyl chains. A range of different molecular structures are reported in the Full Paper by C. Tschierske et al. on page 6352 ff.

  2. Graphical Abstract

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  3. Corrigendum

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      Optically Active Mixed Phthalocyaninato–porphyrinato Rare-Earth Double-Decker Complexes: Synthesis, Spectroscopy, and Solvent-Dependent Molecular Conformation (page 6288)

      Xiaomei Zhang, Atsuya Muranaka, Wei Lv, Yuexing Zhang, Yongzhong Bian, Jianzhuang Jiang and Nagao Kobayashi

      Version of Record online: 11 JUL 2008 | DOI: 10.1002/chem.200890082

  4. News

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  5. Concept

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    1. Organic–Inorganic Nanohybrids through the Direct Tailoring of Semiconductor Nanocrystals with Conjugated Polymers (pages 6294–6301)

      Zhiqun Lin

      Version of Record online: 9 APR 2008 | DOI: 10.1002/chem.200800078

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      Electroactive polymer-tailored nanocrystals: Two main synthetic strategies are introduced to place conjugated oligomers (COs) or polymers (CPs) in intimate contact with semiconductor nanocrystals (NCs). The resulting CO–NC or CP–NC nanohybrids (illustrated here) possess a well-defined interface, thereby promoting an efficient electronic interaction between them.

  6. Review

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    1. One-Pot Oxidative Esterification and Amidation of Aldehydes (pages 6302–6315)

      Kekeli Ekoue-Kovi and Christian Wolf

      Version of Record online: 3 JUN 2008 | DOI: 10.1002/chem.200800353

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      Save a step! One-pot oxidative esterification and amidation of aldehydes provide efficient and fast access to esters and amides, while isolation of carboxylic acid intermediates becomes unnecessary (see scheme). An overview of methods exhibiting complementary applications is presented.

  7. Communications

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    1. Organocatalytic Asymmetric Synthesis of Functionalized 3,4-Dihydropyran Derivatives (pages 6317–6321)

      Patrick T. Franke, Bo Richter and Karl Anker Jørgensen

      Version of Record online: 5 JUN 2008 | DOI: 10.1002/chem.200800850

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      Organocatalysis can control both the chemo-, diastereo- and enantioselectivity in the domino addition of 1,3-cycloalkanediones to α,β-unsaturated aldehydes providing optically active 3,4-dihydropyrans (see scheme) with excellent enantioselectivies and good diastereoselectivities for a broad range of aryl- and aliphatic-substituted α,β-unsaturated aldehydes. The 3,4-dihydropyrans were transformed to various important derivatives.

    2. Entry to Coronene Chemistry—Making Large Electron Donors and Acceptors (pages 6322–6325)

      Ralph Rieger, Marcel Kastler, Volker Enkelmann and Klaus Müllen

      Version of Record online: 3 JUN 2008 | DOI: 10.1002/chem.200800832

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      Make it flat: Coronene is made by dehydrogenation of cyclophanes, a method that offers great opportunities to introduce substituents and to control the symmetry of the molecule. Several methoxy-substituted coronenes have been prepared and studied by crystal structure analysis and optical spectroscopy. They can be converted into strongly electron-accepting coronene ketones, which offer many possibilities for further reactions in the future.

    3. Total Synthesis of (+)-trans-Dihydronarciclasine by a Catalytic Enantioselective Regiodivergent Nitroso Diels–Alder Reaction (pages 6326–6328)

      Chandan Kumar Jana and Armido Studer

      Version of Record online: 18 JUN 2008 | DOI: 10.1002/chem.200800903

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      A novel approach to enantiomerically pure (+)-trans-dihydronarciclasine (1), a biologically active natural product of the Amaryllidaceae group, uses a catalytic enantioselective regiodivergent nitroso Diels–Alder reaction as the key step. Compound 1 is prepared in a 17-step synthesis in 5.6 % overall yield.

    4. Asymmetric Organocatalysis: An Efficient Enantioselective Access to Benzopyranes and Chromenes (pages 6329–6332)

      Magnus Rueping, Erli Sugiono and Estíbaliz Merino

      Version of Record online: 24 JUN 2008 | DOI: 10.1002/chem.200800836

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      Valuable, biologically active chromenones such as those depicted were synthesized based on a diaryl prolinol ether catalyzed, enantioselective reaction of diketones with α,β-unsaturated aldehydes. In these efficient addition–acetalization cascade reactions, diverse aliphatic and aromatic α,β-unsaturated aldehydes, as well as various diketones, can be successfully applied and the 2-hydroxychromenones can be isolated in good yields and with excellent enantioselectivities.

    5. Chiral Amine-Catalyzed Enantioselective Cascade Aza–Ene-Type Cyclization Reactions (pages 6333–6335)

      Liansuo Zu, Hexin Xie, Hao Li, Jian Wang, Xinhong Yu and Wei Wang

      Version of Record online: 11 JUN 2008 | DOI: 10.1002/chem.200800829

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      A new asymmetric cascade aza–ene-type cyclization process has been developed. The cascade reaction of α,β-unsaturated aldehydes with enamides is efficiently catalyzed by simple chiral diphenylprolinol–TMS ether with high enantioselectivity to afford synthetically useful enantioenriched six-membered ring enamide hemiaminals (see scheme, DNBA=2,4-dinitrobenzoic acid). A multistep imminium/enamine transformation involved in the cascade sequence is described for the first time.

    6. Highly Stereoselective Synthesis of β-Lactams Utilizing α-Chloroimines as New and Powerful Chiral Inductors (pages 6336–6340)

      Matthias D'hooghe, Willem Van Brabandt, Stijn Dekeukeleire, Yves Dejaegher and Norbert De Kimpe

      Version of Record online: 11 JUN 2008 | DOI: 10.1002/chem.200800845

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      A new and efficient one-pot approach towards chiral azetidin-2-ones has been developed starting from (2S)-chloro-1-propanol, affording novel β-lactams in high diastereomeric (80–89 %) and enantiomeric excess (90 %).

  8. Full Papers

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    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
    7. Review
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    1. A Fluorescent-Switch-Based Computing Platform in Defending Information Risk (pages 6342–6351)

      Wei Sun, Can Zhou, Chun-Hu Xu, Chen-Jie Fang, Chao Zhang, Zhan-Xian Li and Chun-Hua Yan

      Version of Record online: 13 JUN 2008 | DOI: 10.1002/chem.200800576

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      Molecular defense: A secured molecular computing platform to defend against illegal information theft and invasion is obtained by the rational control of chemical reaction sequences in a newly prepared multi-switchable fluorophore. The binding between the fluorescent switch and the guest signal is activated after sequence sensitive in situ conversion, therefore, the user's password entry enables not only the user's identity to be checked (see figure).

    2. Distinct Columnar and Lamellar Liquid Crystalline Phases Formed by New Bolaamphiphiles with Linear and Branched Lateral Hydrocarbon Chains (pages 6352–6368)

      Marko Prehm, Claudia Enders, Maryam Yahyaee Anzahaee, Benjamin Glettner, Ute Baumeister and Carsten Tschierske

      Version of Record online: 2 JUN 2008 | DOI: 10.1002/chem.200800141

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      Ordered fluids: Complex fluid superstructures were obtained through self-assembly of polyphilic molecules. A variety of different polygonal cylinder structures was observed, which were replaced by lamellar phases and a noncylinder hexagonal columnar phase as either molecular structure or temperature was changed (see graphic).

    3. Novel Biodegradable Adaptive Hydrogels: Controlled Synthesis and Full Characterization of the Amphiphilic Co-Networks (pages 6369–6378)

      Laetitia Mespouille, Olivier Coulembier, Dilyana Paneva, Philippe Degée, Iliya Rashkov and Philippe Dubois

      Version of Record online: 9 JUN 2008 | DOI: 10.1002/chem.200800088

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      Adaptive gels: The copolymerization of N,N-dimethylamino-2-ethyl methacrylate (DMAEMA) and α,ω-methacrylate poly(ε-caprolactone) (PCLDMA) by atom-transfer radical polymerization (ATRP) yields homogeneous amphiphilic poly(N,N-dimethylamino-2-ethyl methacrylate-graft-poly[ε-caprolactone]) co-networks (netP(DMAEMA-g-PCL), see inset). SEM analysis confirms the organized surface of the gel obtained (see graphic).

    4. p-Phenyleneethynylene Molecular Wires: Influence of Structure on Photoinduced Electron-Transfer Properties (pages 6379–6390)

      Mateusz Wielopolski, Carmen Atienza, Timothy Clark, Dirk M. Guldi and Nazario Martín

      Version of Record online: 13 JUN 2008 | DOI: 10.1002/chem.200800159

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      Building bridges: A systematic study on the length and planarity of oligo(p-phenyleneethynylene) (oPPE) chains in π-extended tetrathiafulvalene–oPPE–C60 systems (see figure) reveals their strong impact on molecular-wire behaviour.

    5. Effects of Geometric Isomerism and Anions on the Kinetics and Mechanism of the Stepwise Formation of Long-Range DNA Interstrand Cross-Links by Dinuclear Platinum Antitumor Complexes (pages 6391–6405)

      Junyong Zhang, Donald S. Thomas, Susan J. Berners-Price and Nicholas Farrell

      Version of Record online: 9 JUN 2008 | DOI: 10.1002/chem.200800408

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      Geometry affects the reaction pathway: [1H,15N] HSQC NMR studies on the cis (1,1/c,c) and trans (1,1/t,t) isomers of dinuclear platinum anticancer complexes reveal subtle differences in the individual steps that lead to the formation of DNA interstrand cross-links (see figure). The presence of phosphate causes a dramatic slowing of cross-link formation only for the cis isomer due to the formation of phosphate-bound intermediates.

    6. Observation of Contraction and Expansion in a Bis(peptide)-Based Mechanical Molecular Actuator (pages 6406–6412)

      Christian E. Schafmeister, Laura G. Belasco and Patrick H. Brown

      Version of Record online: 2 JUN 2008 | DOI: 10.1002/chem.200701942

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      Contract and expand: The contraction and expansion of a hinged, mechanical molecular actuator is controlled by the addition and removal of Cu2+ (see figure), and is demonstrated by the direct observation of a change in hydrodynamic properties by using sedimentation analysis and size exclusion chromatography. The molecule undergoes a large change in its sedimentation coefficient, axial ratio, and size exclusion chromatography elution time when it binds copper.

    7. Mesoporous Silicas by Self-Assembly of Lipid Molecules: Ribbon, Hollow Sphere, and Chiral Materials (pages 6413–6420)

      Haiying Jin, Huibin Qiu, Yasuhiro Sakamoto, Peng Shu, Osamu Terasaki and Shunai Che

      Version of Record online: 9 JUN 2008 | DOI: 10.1002/chem.200701988

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      A cool twist and a hotter rod: By using lipids (N-acyl amino acids) and 3-aminopropyltriethoxysilane as structure- and co-structure-directing agents, mesoporous silicas with four different morphologies, that is, helical ribbon, hollow sphere, circular disk, and helical hexagonal rod (see images), were synthesized by just changing the synthesis temperature from 0 °C to 10, 15, or 20 °C, respectively.

    8. Morphology-Controlled Assembly of ZnO Nanostructures: A Bioinspired Method and Visible Luminescence (pages 6421–6427)

      Gousia Begum, Sunkara V. Manorama, Shashi Singh and Rohit Kumar Rana

      Version of Record online: 5 JUN 2008 | DOI: 10.1002/chem.200800129

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      ZnO gets the green light: Positively charged polypeptides and related polyamines catalyze ZnO mineralization under “green” conditions of room temperature and neutral pH (see picture). The polyamines not only act as mineralizing agents for ZnO nanoparticles, but also self-assemble the particles to form spindle- and rodlike morphologies that exhibit green photoluminescence with controllable intensity.

    9. Label-Free Fluorescent Probing of G-Quadruplex Formation and Real-Time Monitoring of DNA Folding by a Quaternized Tetraphenylethene Salt with Aggregation-Induced Emission Characteristics (pages 6428–6437)

      Yuning Hong, Matthias Häußler, Jacky W. Y. Lam, Zhen Li, King Keung Sin, Yongqiang Dong, Hui Tong, Jianzhao Liu, Anjun Qin, Reinhard Renneberg and Ben Zhong Tang

      Version of Record online: 2 JUN 2008 | DOI: 10.1002/chem.200701723

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      Lighting up: Nonemissive TTAPE dye becomes emissive when bound to a guanine-rich single-stranded (ss) DNA molecule. The emission red-shifts when the ssDNA folds into a G-quadruplex structure. This folding process can be monitored by time-dependent fluorescence measurement owing to the aggregation-induced emission characteristics of the probe (see picture; PL=photoluminescence).

    10. On the Mechano-Chiral Effect of Vortical Flows on the Dichroic Spectra of 5-Phenyl-10,15,20-tris(4-sulfonatophenyl)porphyrin J-Aggregates (pages 6438–6443)

      Zoubir El-Hachemi, Oriol Arteaga, Adolf Canillas, Joaquim Crusats, Carlos Escudero, Reiko Kuroda, Takunori Harada, Mònica Rosa and Josep M. Ribó

      Version of Record online: 2 JUN 2008 | DOI: 10.1002/chem.200800307

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      Chiral sculpting: Phase-modulated ellipsometry of the J-aggregates of the title porphyrin shows that the material gives a true CD signal, which confirms that there is a real chiral transfer by mechanical forces, mediated by shear gradient flows, from the macroscopic to the electronic transition level (see picture). Dislocations in the structure of the aggregate could justify the formation of chirality at the level of the electronic transitions once the mesophases can be sculptured by hydrodynamic gradient flows.

    11. Endohexosaminidase-Catalysed Glycosylation with Oxazoline Donors: Fine Tuning of Catalytic Efficiency and Reversibility (pages 6444–6464)

      Thomas W. D. F. Rising, Christoph D. Heidecke, James W. B. Moir, Zhenlian Ling and Antony J. Fairbanks

      Version of Record online: 9 JUN 2008 | DOI: 10.1002/chem.200800365

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      Synthesise, don't hydrolyse! The use of structurally modified oxazolines as activated glycosyl donors enables both endohexosaminidases M and A to ligate synthetic oligosaccharides to glycosyl amino acids, to form products that these enzymes are not capable of hydrolysing (see scheme).

    12. Theoretical Exploration of the Oxidative Properties of a [(trenMe1)CuO2]+ Adduct Relevant to Copper Monooxygenase Enzymes: Insights into Competitive Dehydrogenation versus Hydroxylation Reaction Pathways (pages 6465–6473)

      Aurélien de la Lande, Olivier Parisel, Hélène Gérard, Vicente Moliner and Olivia Reinaud

      Version of Record online: 2 JUN 2008 | DOI: 10.1002/chem.200701595

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      Intramolecular redox behavior of the [(trenMe1)CuO2]+ core as a model of the active site of noncoupled dicopper monooxygenases was explored by DFT calculations, and revealed a cationic intermediate that spontaneously evolves toward hydroxylation of an alkyl group on reduction by one electron (see scheme). On the basis of the computational results, a new mechanistic description of the reactivity of copper monooxygenases is proposed.

    13. Synthesis and Immunochemical characterization of S-linked Glycoconjugate Vaccines against Candida albicans (pages 6474–6482)

      Xiangyang Wu, Tomasz Lipinski, Eugenia Paszkiewicz and David R. Bundle

      Version of Record online: 9 JUN 2008 | DOI: 10.1002/chem.200800352

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      Replacement of the glycosidic oxygen atom by a sulphur atom is a promising technique for creating glycoconjugates with increased resistance to hydrolysis by endogenous glycosidases. The synthesis and antigenic properties of two distinct (1[RIGHTWARDS ARROW]2)-β-mannan trisaccharides, such as depicted, with inter residue-S-linked mannopyranose residues are described.

    14. Insights into the Post-Translational Methylation of Arginine from Studies of Guanidinium–Water Nanodroplets (pages 6483–6489)

      Keri McQuinn, J. Scott McIndoe and Fraser Hof

      Version of Record online: 11 JUN 2008 | DOI: 10.1002/chem.200800101

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      Lost in translation? Highly solvated guanidinium ions ([MenGuan(H2O)21]+, n=0–6) were generated in an unmodified commercial electrospray ionization (ESI) mass spectrometer and their decomposition was monitored by energy-dependent ESI-MS (see graphic). The data suggest a mechanism by which post-translational arginine methylation controls the hydration of protein side chains.

    15. Intramolecular Sensitization of Photocleavage of the Photolabile 2-(2-Nitrophenyl)propoxycarbonyl (NPPOC) Protecting Group: Photoproducts and Photokinetics of the Release of Nucleosides (pages 6490–6497)

      Dominik Wöll, Julia Smirnova, Marina Galetskaya, Tamara Prykota, Jochen Bühler, Klaus-Peter Stengele, Wolfgang Pfleiderer and Ulrich E. Steiner

      Version of Record online: 9 JUN 2008 | DOI: 10.1002/chem.200800613

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      Higher efficiency at longer wavelength: Photostationary kinetic experiments in solution and tests on oligonucleotide chips demonstrate large increases in the light efficiency of the photolabile 2-(2-nitrophenyl)propoxycarbonyl (NPPOC) protecting group due to intramolecular sensitization at wavelengths longer than 350 nm (see figure).

    16. Definition of Magneto-Structural Correlations for the MnII Ion (pages 6498–6509)

      Carole Duboc, Marie-Noëlle Collomb, Jacques Pécaut, Alain Deronzier and Frank Neese

      Version of Record online: 9 JUN 2008 | DOI: 10.1002/chem.200800426

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      Magneto manganese: A combination of experimental and theoretical approaches allows us to define magneto-structural correlations for mononuclear MnII complexes characterized by a coordination sphere typically found in metalloenzymes, that is, with only oxygen- or nitrogen-based ligands and five or six coordinate.

    17. Anionic Cross-Coupling Reaction of α-Metallated Alkenyl Sulfoximines and Alkenyl Sulfoximines with Cuprates Featuring a 1,2-Metal-Ate Rearrangement of Sulfoximine-Substituted Higher Order Alkenyl Cuprates and an α-Metallation of Alkenyl Sulfoximines by Cuprates (pages 6510–6528)

      Hans-Joachim Gais, C. Venkateshwar Rao and Ralf Loo

      Version of Record online: 9 JUN 2008 | DOI: 10.1002/chem.200800455

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      Anion crossing: α-Lithioalkenyl sulfoximines undergo a stereoselective anionic cross-coupling reaction with organocuprates with formation of substituted alkenyl cuprates. It is proposed that sulfoximine-substituted higher order alkenyl cuprates are formed as intermediates, which suffer a stereoselective 1,2-metal-ate rearrangement.

    18. Reductive Degradation of nido-1-CB8H12 into Smaller-Cage Carborane Systems via New Monocarbaboranes [arachno-5-CB8H13] and closo-2-CB6H8 (pages 6529–6533)

      Mario Bakardjiev, Josef Holub, Drahomír Hnyk and Bohumil Štíbr

      Version of Record online: 30 MAY 2008 | DOI: 10.1002/chem.200800233

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      Arachno-philes: Reduction of the nido-1-CB8H12 carborane by using NaBH4 led to the isolation a new, stable carborane [arachno-5-CB8H13]. This can be conveniently converted by specific boron-removal reactions into various monocarbaboranes, such as arachno-4-CB7H13, [closo-2-CB6H7], closo-2-CB6H8, and nido-2-CB5H9 (see figure).

    19. Two-Component Hydrogels Comprising Fatty Acids and Amines: Structure, Properties, and Application as a Template for the Synthesis of Metal Nanoparticles (pages 6534–6545)

      Hajra Basit, Asish Pal, Saikat Sen and Santanu Bhattacharya

      Version of Record online: 9 JUN 2008 | DOI: 10.1002/chem.200800374

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      Two-component hydrogels from a mixture of fatty acids and di-/oligomeric amines were prepared and their structure and properties were studied. The gel network was used as a template for the synthesis of silver nanoparticles, which formed ordered assemblies on the gel fibers (see graphic).

    20. Direct Observation of Mixed-Valence and Radical Cation Dimer States of Tetrathiafulvalene in Solution at Room Temperature: Association and Dissociation of Molecular Clip Dimers Under Oxidative Control (pages 6546–6552)

      Pinn-Tsong Chiang, Nai-Chia Chen, Chien-Chen Lai and Sheng-Hsien Chiu

      Version of Record online: 2 JUN 2008 | DOI: 10.1002/chem.200800213

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      Radical dimers dude! Sequential oxidation of the tetrathiafulvalene sidewalls of a glycoluril-based molecular clip generates its mixed-valence and radical cationic dimers at low concentration (1 mM) and room temperature (see figure). Spectroelectrochemistry and nanoelectrospray ionization mass spectrometry confirmed the existence of these variously charged dimers during the oxidation process.

  9. Preview

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
    7. Review
    8. Communications
    9. Full Papers
    10. Preview
    1. You have free access to this content
      Preview: Chem. Eur. J. 22/2008 (page 6559)

      Version of Record online: 10 JUL 2008 | DOI: 10.1002/chem.200890084

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