Chemistry - A European Journal

Cover image for Vol. 15 Issue 7

February 2, 2009

Volume 15, Issue 7

Pages 1535–1787

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
    7. Communications
    8. Full Papers
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    1. Cover Picture: The Chemistry of Escapin: Identification and Quantification of the Components in the Complex Mixture Generated by an L-Amino Acid Oxidase in the Defensive Secretion of the Sea Snail Aplysia californica (Chem. Eur. J. 7/2009) (page 1535)

      Michiya Kamio, Ko-Chun Ko, Shilong Zheng, Binghe Wang, Stacy L. Collins, Giovanni Gadda, Phang C. Tai and Charles D. Derby

      Version of Record online: 26 JAN 2009 | DOI: 10.1002/chem.200990013

      Thumbnail image of graphical abstract

      Defensive chemicals such as the ink secretion of this marine gastropod mollusk—the sea hares Aplysia californica—are released following attacks from predators for protection. One might expect these secretions to be complex mixtures of products, given that they must work against a diversity of predators. In their Full Paper on page 1597 ff., C. D. Derby et al. describe some of the chemical complexity of the ink of sea hares attributable to the enzyme “escapin”. Escapin is an L-amino acid oxidase that oxidatively deaminates its major substrate, L-lysine, to produce an equilibrium mixture of the molecules shown in this image. Photograph from Genny Anderson (Santa Barbara City College).

  2. Graphical Abstract

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    4. Corrigendum
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  3. Corrigendum

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    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
    7. Communications
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  4. News

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    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
    7. Communications
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  5. Concept

    1. Top of page
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    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
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    1. Bioinorganic Chemistry

      Prospects of Metal Complexes Peripherally Substituted with Sugars in Biomedicinal Applications (pages 1548–1557)

      Michael Gottschaldt and Ulrich S. Schubert

      Version of Record online: 7 JAN 2009 | DOI: 10.1002/chem.200802013

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      Sugar is good for you! The latest developments in the field of sugar substitution of metal complexes and its influence on the action of these complexes in biological systems are discussed (see figure). In particular, the progress in applications as selective tracers and therapeutics in connection to the underlying chemical structure is highlighted.

  6. Communications

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    4. Corrigendum
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    1. Iron Carbodiimide

      FeNCN and Fe(NCNH)2: Synthesis, Structure, and Magnetic Properties of a Nitrogen-Based Pseudo-oxide and -hydroxide of Divalent Iron (pages 1558–1561)

      Xiaohui Liu, Ludwig Stork, Manfred Speldrich, Heiko Lueken and Richard Dronskowski

      Version of Record online: 29 DEC 2008 | DOI: 10.1002/chem.200802422

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      Iron man challenge: Iron carbodiimide, FeNCN, and its precursor iron (bis)monohydrocyanamide, Fe(NCNH)2, have been synthesized and physically characterized. Both FeNCN and Fe(NCNH)2 exhibit nitrogen-mediated antiferromagnetic superexchange interactions with reduced magnetic moments very similar, but not identical, to the correlated 3d oxides.

    2. Organocatalysis

      Highly Enantioselective Conjugate Additions of Aldehydes to Vinyl Sulfones (pages 1562–1565)

      Aitor Landa, Miguel Maestro, Carme Masdeu, Ángel Puente, Silvia Vera, Mikel Oiarbide and Claudio Palomo

      Version of Record online: 2 JAN 2009 | DOI: 10.1002/chem.200802441

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      Joined together, organocatalysts aldehydes and sulfones: A diaryl prolinol silyl ether was found to catalyse efficiently and enantioselectively the conjugate addition of aldehydes to vinyl sulfones (see scheme). The ample synthetic utility of the resulting adducts is illustrated.

    3. Asymmetric Catalysis

      Catalyzed Vinylogous Mukaiyama Aldol Reactions with Controlled Enantio- and Diastereoselectivities (pages 1566–1569)

      Marcus Frings, Iuliana Atodiresei, Jan Runsink, Gerhard Raabe and Carsten Bolm

      Version of Record online: 2 JAN 2009 | DOI: 10.1002/chem.200802359

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      In control: A new catalytic vinylogous Mukaiyama aldol reaction provides products with high diastereo- and enantioselectivities (up to 99 % de and ee; see scheme). The relative and absolute stereochemistry of a representative product was rigorously assigned by NMR and CD spectroscopies (measured and calculated), X-ray diffraction, and quantum-chemical calculations.

    4. Enantioselective Allylation

      Enantioselective and Catalytic Method for α-Crotylation of Aldehydes with a Kinetic Self-Refinement of Stereochemistry (pages 1570–1573)

      Andrei V. Malkov, Mikhail A. Kabeshov, Maciej Barłog and Pavel Kočovský

      Version of Record online: 2 JAN 2009 | DOI: 10.1002/chem.200802224

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      Kinetic refinery: A practical, highly stereoselective, two-step catalytic protocol for the α-allylation of aldehydes, starting from crotyltrichlorosilanes, has been developed (see scheme). In each reaction step, one of the stereoisomers reacted faster than the other, which resulted in a kinetic stereochemical (E/Z) self-refinement of the system and led to the formation of virtually enantiomerically and geometrically pure linear homoallylic alcohols in high yield.

    5. Organocatalysis

      Dual Organocatalysis: Asymmetric Allylic–Allylic Alkylation of α,α-Dicyanoalkenes and Morita–Baylis–Hillman Carbonates (pages 1574–1577)

      Hai-Lei Cui, Jing Peng, Xin Feng, Wei Du, Kun Jiang and Ying-Chun Chen

      Version of Record online: 8 JAN 2009 | DOI: 10.1002/chem.200802534

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      The first highly enantioselective allylic–allylic alkylation of α,α-dicyanoalkenes and Morita–Baylis–Hillman carbonates by dual catalysis of (DHQD)2AQN and (S)-BINOL has been investigated. Excellent stereoselectivities have been achieved for a broad spectrum of substrates (d.r. > 99:1, up to 99 % ee). The multifunctional allylic products could be efficiently converted to a range of complex chiral cyclic frameworks. EWG=electron-withdrawing group, (DHQD)2AQN=hydroquinidine (anthraquinone-1,4-diyl) diether, (S)-BINOL =(S)-(−)-1,1′-bi-2-naphthol.

    6. C[BOND]C Coupling

      N4-Tetradentate Dicarboxyamidate/Dipyridyl Palladium Complexes as Robust Catalysts for the Heck Reaction of Deactivated Aryl Chlorides (pages 1578–1581)

      Pottabathula Srinivas, Pravin R. Likhar, Hariharasarma Maheswaran, Balasubramanian Sridhar, Krishnan Ravikumar and Mannepalli Lakshmi Kantam

      Version of Record online: 2 JAN 2009 | DOI: 10.1002/chem.200802144

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      Structurally well defined and thermally stable PdII complexes, derived from N4-tetradentate dicarboxyamide/dipyridyl ligands, were evaluated as catalysts for the Heck reactions of deactivated aryl chlorides and olefins (see scheme). The concept of using an anionic carboxyamide as an ancillary ligand for palladium demonstrated here provides a new opportunity for the development of phosphine-free transition-metal catalysis.

    7. Nanocatalysts

      Nanoparticle-Supported and Magnetically Recoverable Ruthenium Hydroxide Catalyst: Efficient Hydration of Nitriles to Amides in Aqueous Medium (pages 1582–1586)

      Vivek Polshettiwar and Rajender S. Varma

      Version of Record online: 2 JAN 2009 | DOI: 10.1002/chem.200802264

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      Magnetic attraction not filtration: A magnetic nanoparticle-supported ruthenium hydroxide catalyst (see figure) was readily prepared from inexpensive starting materials and shown to catalyze the hydration of nitriles with excellent yield in a benign aqueous medium. Catalyst recovery using an external magnetic field, superior activity, and the inherent stability of the catalyst system are additional sustainable attributes of this protocol.

  7. Full Papers

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    9. Preview
    1. Bioinorganic Chemistry

      Photoinduced Reactions of cis,trans,cis-[PtIV(N3)2(OH)2(NH3)2] with 1-Methylimidazole (pages 1588–1596)

      Hazel I. A. Phillips, Luca Ronconi and Peter J. Sadler

      Version of Record online: 12 JAN 2009 | DOI: 10.1002/chem.200802206

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      Lighting up new platinum anticancer complexes: Photoactivation of a platinum(IV) diazido anticancer complex in the presence of a derivative of imidazole, an important constituent of biomolecules, gives surprising photoproducts, including a tetrakis imidazole platinum(II) adduct (see figure), together with free azide, dioxygen and ammonia.

    2. Natural Products

      The Chemistry of Escapin: Identification and Quantification of the Components in the Complex Mixture Generated by an L-Amino Acid Oxidase in the Defensive Secretion of the Sea Snail Aplysia californica (pages 1597–1603)

      Michiya Kamio, Ko-Chun Ko, Shilong Zheng, Binghe Wang, Stacy L. Collins, Giovanni Gadda, Phang C. Tai and Charles D. Derby

      Version of Record online: 7 JAN 2009 | DOI: 10.1002/chem.200801696

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      A complex mixture of products in an enzymatic reaction: Aplysia californica releases amino acid oxidase and its substrate lysine in defensive secretions to produce a mixture of multiple compounds (see figure).

    3. Mixed-Valent Compounds

      Electronic Structure and Absorption Spectra of Biferrocenyl and Bisfulvalenide Diiron Radical Cations: Detection and Assignment of New Low-Energy Transitions (pages 1604–1617)

      Ralf Warratz, Hanane Aboulfadl, Thomas Bally and Felix Tuczek

      Version of Record online: 7 JAN 2009 | DOI: 10.1002/chem.200801054

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      New transitions: Low-energy electronic transitions have been detected spectroscopically in the FeII–FeIII mixed-valent biferrocenyl radical cation, but are absent in the spectra of the neutral analogue. They have been assigned by time-dependent DFT calculations (squares in figure). Analogous investigations were performed for the bisfulvalenide FeII–FeIII radical cation.

    4. Conformation Analysis

      Conformational Change of Spermidine upon Interaction with Adenosine Triphosphate in Aqueous Solution (pages 1618–1626)

      Keisuke Maruyoshi, Kaori Nonaka, Takeshi Sagane, Tetsuo Demura, Toshiyuki Yamaguchi, Nobuaki Matsumori, Tohru Oishi and Michio Murata

      Version of Record online: 7 JAN 2009 | DOI: 10.1002/chem.200801961

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      A complex rotation: The solution conformation of spermidine (SPD) was elucidated by using diastereospecifically deuterated and 13C-labeled derivatives to diagnose the orientation of seven conformationally relevant bonds. NMR coupling constants were determined for a complex formed from spermidine and adenosine triphosphate (ATP; see figure).

    5. Natural Products

      Total Syntheses of Casuarine and Its 6-O-α-Glucoside: Complementary Inhibition towards Glycoside Hydrolases of the GH31 and GH37 Families (pages 1627–1636)

      Francesca Cardona, Camilla Parmeggiani, Enrico Faggi, Claudia Bonaccini, Paola Gratteri, Lyann Sim, Tracey M. Gloster, Shirley Roberts, Gideon J. Davies, David R. Rose and Andrea Goti

      Version of Record online: 2 JAN 2009 | DOI: 10.1002/chem.200801578

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      Selective glucosylation: Total synthesis of naturally occurring casuarine (1) and the first total synthesis of casuarine 6-O-α-glucoside (2) were achieved through complete stereoselective nitrone cycloaddition, Tamao–Fleming oxidation and selective α-glucosylation as key steps. Biological assays of the two compounds proved their strong and selective inhibitory properties towards glucoamylase NtMGAM and trehalase Tre37A, respectively, which place them among the most powerful inhibitors of these enzymes.

    6. Micelles

      Supramolecular Assembly of Self-Labeled Amphicalixarenes (pages 1637–1648)

      Miriam S. Becherer, Boris Schade, Christoph Böttcher and Andreas Hirsch

      Version of Record online: 2 JAN 2009 | DOI: 10.1002/chem.200802008

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      Shape-persistent micelles consisting of exactly 12 molecules (see picture), which coexist with rodlike micelles, are formed by the self-labeled amphicalixarene at pH 7. In contrast to other examples of structurally defined micelles, this new type of amphiphile serves as a fluorescence reporter and provides an extended cavity structure in the hydrophilic part, thereby facilitating the inclusion of guest molecules.

    7. Glyconanoparticles

      Chemoselective Capture of Glycans for Analysis on Gold Nanoparticles: Carbohydrate Oxime Tautomers Provide Functional Recognition by Proteins (pages 1649–1660)

      Mikkel B. Thygesen, Jørgen Sauer and Knud J. Jensen

      Version of Record online: 29 DEC 2008 | DOI: 10.1002/chem.200801521

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      Open or closed: N-Glycosyl oxyamine versus open-chain glycosyl oxime is the key to protein recognition on glyconanoparticles. Unprotected glycans are captured by oxime formation with a novel bifunctional reagent and the resulting glycan-linker conjugates are anchored to gold nanoparticles (AuNPs). These glyconanoparticles maintain the structural integrity of glycans in the study of protein–carbohydrate interactions (see figure).

    8. Single-Molecule Studies

      Tuning Single-Molecule Dynamics in Functionalized Mesoporous Silica (pages 1661–1672)

      Timo Lebold, Lea A. Mühlstein, Julia Blechinger, Melanie Riederer, Heinz Amenitsch, Ralf Köhn, Kalina Peneva, Klaus Müllen, Jens Michaelis, Christoph Bräuchle and Thomas Bein

      Version of Record online: 2 JAN 2009 | DOI: 10.1002/chem.200801380

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      Diffusion of single molecules of a substituted terrylene diimide dye in functionalized mesoporous silica films was monitored by single-molecule fluorescence microscopy. By varying the chemical nature and density of the functional groups, the diffusion dynamics of the dye molecules can be controlled precisely. The picture shows a sketch of a dye molecule in a pore, diffusion data for different phenyl functionalization densities, and the trajectory of one molecule in a cyanopropyl-functionalized film.

    9. Chemical Bonding

      Electronic Structure, Chemical Bonding, and Solid-State NMR Spectroscopy of the Digallides of Ca, Sr, and Ba (pages 1673–1684)

      Frank Haarmann, Katrin Koch, Daniel Grüner, Walter Schnelle, Oliver Pecher, Raul Cardoso-Gil, Horst Borrmann, Helge Rosner and Yuri Grin

      Version of Record online: 2 JAN 2009 | DOI: 10.1002/chem.200801131

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      Delving into digallides: The characteristics of the chemical bonding of the digallides of the alkaline-earth metals (see figure) have been studied by application of experimental methods, such as single-crystal X-ray diffraction and solid-state NMR spectroscopy, in combination with quantum mechanical calculations.

    10. Hydrogen Storage

      Effect of Doped Transition Metal on Reversible Hydrogen Release/Uptake from NaAlH4 (pages 1685–1695)

      Jianjun Liu, You Han and Qingfeng Ge

      Version of Record online: 29 DEC 2008 | DOI: 10.1002/chem.200801045

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      Storage facility: A dihydrogen complex formed in transition-metal-doped NaAlH4 was found to play important roles in hydrogen release/uptake (see figure). Electronic structure analysis revealed that the electron transfer between hydrogen and Al groups was mediated by the d orbitals of transition metals. Hydrogen release/uptake from the transition-metal-doped NaAlH4 was accompanied by an exchange of Al[BOND]H and H[BOND]H bond ligands through σ-bond metathesis.

    11. Kinetic Stability

      Equilibrium and Kinetic Properties of the Lanthanoids(III) and Various Divalent Metal Complexes of the Heptadentate Ligand AAZTA (pages 1696–1705)

      Zsolt Baranyai, Fulvio Uggeri, Giovanni B. Giovenzana, Attila Bényei, Ernő Brücher and Silvio Aime

      Version of Record online: 7 JAN 2009 | DOI: 10.1002/chem.200801803

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      Towards improved kinetic stability: A detailed account of the complexation properties of the ligand 1,4-bis(hydroxycarbonylmethyl)-6-[bis(hydroxycarbonylmethyl)]amino-6-methylperhydro-1,4-diazepine (AAZTA; see figure) is reported. Its Gd3+ complex shows a kinetic stability superior to that of complexes formed by higher denticity ligands and opens the way for a new reference structure for MRI contrast agents.

    12. Domino Ketone Allylations

      Stereoselective Allylation of Ketones: Explanation for the Unusual Inversion of the Induced Stereochemistry in the Auxiliary-Mediated Crotylation and Pentenylation of Butanone by DFT Calculations (pages 1706–1712)

      Lutz F. Tietze, Tom Kinzel and Stefan Schmatz

      Version of Record online: 2 JAN 2009 | DOI: 10.1002/chem.200801889

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      The solvent makes the difference: While attack at the Re face of the intermediate oxocarbenium ion becomes less energy demanding with increasing size of R′, it is the solvent effect that makes this attack the main trajectory, leading to inversed stereochemistry (see picture).

    13. Asymmetric Synthesis

      Metal-Dependent Reaction Tuning with Cyclopentylmetal Reagents: Application to the Asymmetric Synthesis of (+)-α-Conhydrine and (S)-2-Cyclopentyl-2-phenylglycolic Acid (pages 1713–1722)

      Siddharth Roy, Anubha Sharma, Soumyaditya Mula and Subrata Chattopadhyay

      Version of Record online: 7 JAN 2009 | DOI: 10.1002/chem.200801603

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      Tuning in: The reaction of halocyclopentane organometallic reagents can be tuned by the choice of metal (see scheme). Cyclopentylmagnesium bromide reduces aldehydes and ketones to the corresponding alcohols. However, in the presence of ZnCl2, normal Grignard addition to the ketones gives tertiary alcohols with complete diastereoselectivity. These protocols were used in the asymmetric synthesis of two medicinally important compounds.

    14. DNA cleavage

      Multinuclear Non-Heme Iron Complexes for Double-Strand DNA Cleavage (pages 1723–1733)

      Rik P. Megens, Tieme A. van den Berg, A. Dowine de Bruijn, Ben L. Feringa and Gerard Roelfes

      Version of Record online: 7 JAN 2009 | DOI: 10.1002/chem.200801409

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      Bleomycin mimics: Efficient oxidative double-strand DNA cleavage has been achieved with multinuclear non-heme iron complexes (see scheme). These complexes therefore represent model compounds that mimic the mode of action of the anti-tumor drug bleomycin.

    15. Asymmetric Catalysis

      Density Functional Study of Proline-Catalyzed Intramolecular Baylis–Hillman Reactions (pages 1734–1746)

      Filipe J. S. Duarte, Eurico J. Cabrita, Gernot Frenking and A. Gil Santos

      Version of Record online: 2 JAN 2009 | DOI: 10.1002/chem.200801624

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      A rationalization of stereoselectivity: The mechanisms of proline-catalyzed and imidazole-co-catalyzed intramolecular Baylis–Hillman reactions have been studied by using density functional theory methods. The computational data has allowed us to rationalize the experimental outcome, validating some of the mechanistic steps proposed in the literature, as well as to propose new ones that considerably change and improve our understanding of the full reaction path (see scheme).

    16. Organophosphorus Chemistry

      Studies on the Efficient Generation of Phosphorus[BOND]Carbon Bonds via a Rearrangement of PIII Esters Catalysed by Trimethylhalosilanes (pages 1747–1756)

      Wojciech Dabkowski, Alfred Ozarek, Sebastian Olejniczak, Marek Cypryk, Julian Chojnowski and Jan Michalski

      Version of Record online: 2 JAN 2009 | DOI: 10.1002/chem.200800435

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      Unprecedented C[BOND]P systems: Me3SiX (X=Br, I) catalyses rearrangements of PIII esters R′R′′P[BOND]OR into the corresponding phosphoryl systems, providing a simple, mild and efficient route to a variety of structures containing P[BOND]C bonds. The mechanism has been found to be fundamentally different from that of the Arbuzov–Michaelis reaction and includes three definite steps a, b and c (see scheme).

    17. Magnetic Materials

      [M(N3)2(H2O)2]⋅(bpeado): Unusual Antiferromagnetic Heisenberg Chain (M=Mn) and Ferromagnetic Ising Chain (M=Co) with Large Coercivity and Magnetic Relaxation (bpeado=1,2-Bis(4-pyridyl)ethane-N,N′-dioxide) (pages 1757–1764)

      Hao-Ling Sun, Zhe-Ming Wang and Song Gao

      Version of Record online: 2 JAN 2009 | DOI: 10.1002/chem.200801685

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      Contrasting magnetic properties: Two isostructural metal-azido magnetic chains embedded in 3D threefold interpenetrated H-bonded frameworks and separated by a long bpeado spacer have been assembled (see figure). Incorporation of Mn2+ displays a rarely observed antiferromagnetic Heisenberg chain, while incorporation of Co2+ displays a ferromagnetic Ising chain.

    18. Logic Gates

      Systems Chemistry: Logic Gates, Arithmetic Units, and Network Motifs in Small Networks (pages 1765–1775)

      Nathaniel Wagner and Gonen Ashkenasy

      Version of Record online: 23 DEC 2008 | DOI: 10.1002/chem.200801850

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      How much “systems chemistry” really exists within small networks? To answer this question, the authors study tertiary networks that facilitate molecular replication through all Boolean logic operations and show how such gates can be wired together to perform computational and feed-forward based network motifs (see graphic).

    19. Nanostructures

      Bi2O3 Hierarchical Nanostructures: Controllable Synthesis, Growth Mechanism, and their Application in Photocatalysis (pages 1776–1782)

      Lin Zhou, Wenzhong Wang, Haolan Xu, Songmei Sun and Meng Shang

      Version of Record online: 29 DEC 2008 | DOI: 10.1002/chem.200801234

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      Flower power: Unique 3D flower-like Bi2O3 hierarchical nanostructures were synthesized using a mild aqueous template-free method (see figure). By introducing VO3 into the reaction system, which mediated the nucleation and growth of Bi2O3, the in situ self-assembly of 3D hierarchitectures from 2D nanosheets has been realized.

  8. Preview

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    9. Preview
    1. You have free access to this content
      Preview: Chem. Eur. J. 8/2009 (page 1787)

      Version of Record online: 26 JAN 2009 | DOI: 10.1002/chem.200990017

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