Angewandte Chemie International Edition

Cover image for Vol. 46 Issue 4

January 15, 2007

Volume 46, Issue 4

Pages 475–639

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Book Reviews
    8. Highlight
    9. Minireview
    10. Review
    11. Communications
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    1. Cover Picture: Total Synthesis of Paliurine F (Angew. Chem. Int. Ed. 4/2007) (page 475)

      Mathieu Toumi, François Couty and Gwilherm Evano

      Version of Record online: 10 JAN 2007 | DOI: 10.1002/anie.200790000

      The sedative paliurine F, which was isolated from the roots of Paliurus ramossisimus, is part of a huge family of natural products that display interesting biological effects and possess an especially appealing and challenging macrocyclic structure. In their Communication on page 572 ff., G. Evano and co-workers describe the synthesis of one of these cyclopeptide alkaloids, paliurine F, using a route that showcases the recent advances in copper(I)-mediated coupling reactions.

  2. Inside Cover

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Book Reviews
    8. Highlight
    9. Minireview
    10. Review
    11. Communications
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    1. Inside Cover: Rapid In Vivo Fingerprinting of Nonvolatile Compounds in Breath by Extractive Electrospray Ionization Quadrupole Time-of-Flight Mass Spectrometry (Angew. Chem. Int. Ed. 4/2007) (page 476)

      Huanwen Chen, Arno Wortmann, Weihua Zhang and Renato Zenobi

      Version of Record online: 10 JAN 2007 | DOI: 10.1002/anie.200790001

      Metabolic dynamics can be followed in real time by mass spectral fingerprints of breath by extractive electrospray ionization (EESI) quadrupole TOF mass spectrometry on a commercial instrument. Neither sample pretreatment nor hardware modifications are necessary for this rapid, online, and in vivo method. Furthermore, selective ion/molecule reactions in the EESI interface can lead to the detection of interesting compounds. For more details see the Communication by R. Zenobi and co-workers on page 580ff.

  3. Graphical Abstract

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    5. Corrigendum
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    10. Review
    11. Communications
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  4. Corrigendum

    1. Top of page
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    4. Graphical Abstract
    5. Corrigendum
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      Solid-State Phase Transition of an Inclusion Complex of 5-Methyl-2-pyridone with 1,3,5-Benzenetricarboxylic Acid (page 486)

      Shinya Hirano, Shinji Toyota, Fumio Toda, Kotaro Fujii and Hidehiro Uekusa

      Version of Record online: 10 JAN 2007 | DOI: 10.1002/anie.200790003

      This article corrects:
  5. News

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Book Reviews
    8. Highlight
    9. Minireview
    10. Review
    11. Communications
    12. Preview
  6. Book Reviews

    1. Top of page
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    1. Surface and Nanomolecular Catalysis. Edited by Ryan Richards. (page 492)

      Bert Weckhuysen

      Version of Record online: 10 JAN 2007 | DOI: 10.1002/anie.200685450

  7. Highlight

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    1. The Crystallization Behavior of Proline and Its Role in Asymmetric Organocatalysis (pages 494–497)

      Richard M. Kellogg

      Version of Record online: 21 DEC 2006 | DOI: 10.1002/anie.200603028

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      What you have and what you get are not necessarily the same: for example, solid enantiomerically enriched proline provides solutions of constant ee, 99 % in CHCl3 and 50 % in DMSO. The Highlight discusses recent papers that give insight into the behavior of enantioenriched proline under heterogeneous conditions which may provide an explanation for the nonlinear effects sometimes observed.

  8. Minireview

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    1. Polishing a Diamond in the Rough: “Cu[BOND]H” Catalysis with Silanes (pages 498–504)

      Sebastian Rendler and Martin Oestreich

      Version of Record online: 30 OCT 2006 | DOI: 10.1002/anie.200602668

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      Copper hydride strikes back: The rediscovery of silanes as stoichiometric hydride sources for copper(I)-catalyzed reductions (see scheme) has triggered an avalanche of enantioselective procedures for 1,2- as well as 1,4-reductions and related tandem processes.

  9. Review

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    1. Photomechanics of Liquid-Crystalline Elastomers and Other Polymers (pages 506–528)

      Tomiki Ikeda, Jun-ichi Mamiya and Yanlei Yu

      Version of Record online: 10 JAN 2007 | DOI: 10.1002/anie.200602372

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      Muscling in on the action: Liquid-crystalline elastomers are promising materials for artificial muscles driven by external stimuli. This Review describes the recent progress in the area of soft materials (liquid-crystalline elastomers and other polymers) that can effectively convert light into mechanical energy (photomechanical effect, see picture).

  10. Communications

    1. Top of page
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    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Book Reviews
    8. Highlight
    9. Minireview
    10. Review
    11. Communications
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    1. Photoswitching of the Fluorescent Protein asFP595: Mechanism, Proton Pathways, and Absorption Spectra (pages 530–536)

      Lars V. Schäfer, Gerrit Groenhof, Astrid R. Klingen, G. Matthias Ullmann, Martial Boggio-Pasqua, Michael A. Robb and Helmut Grubmüller

      Version of Record online: 9 NOV 2006 | DOI: 10.1002/anie.200602315

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      Molecular light-switch: Off–on switching of the fluorescence of the protein asFP595 involves a transcis isomerization. Mixed quantum/classical simulations elucidate the spectroscopic properties of asFP595 and give detailed insights into the photoswitching mechanism. The conformational transcis switching triggers a proton-transfer cascade between the chromophore and adjacent amino acids.

    2. Enantioselective Synthesis of Oasomycin A, Part I: Synthesis of the C1–C12 and C13–C28 Subunits (pages 537–540)

      David A. Evans, Pavel Nagorny, Kenneth J. McRae, Dominic J. Reynolds, Louis-Sebastian Sonntag, Filisaty Vounatsos and Risheng Xu

      Version of Record online: 8 DEC 2006 | DOI: 10.1002/anie.200603653

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      Putting the pieces together: The total synthesis of the natural macrolide oasomycin A has been realized. Key fragment couplings include an anti-Felkin selective aldol addition (green), Kociensky–Julia olefinations (red), and competitive Weinreb amide acylation reaction (blue). The utility of the 4,5-diphenyloxazole as a carboxy surrogate and the late-stage macrolactonization affording the 42-membered macrocycle of oasomycin A are also described.

    3. Enantioselective Synthesis of Oasomycin A, Part II: Synthesis of the C29–C46 Subunit (pages 541–544)

      David A. Evans, Pavel Nagorny, Dominic J. Reynolds and Kenneth J. McRae

      Version of Record online: 8 DEC 2006 | DOI: 10.1002/anie.200603654

      Thumbnail image of graphical abstract

      Putting the pieces together: The total synthesis of the natural macrolide oasomycin A has been realized. Key fragment couplings include an anti-Felkin selective aldol addition (green), Kociensky–Julia olefinations (red), and competitive Weinreb amide acylation reaction (blue). The utility of the 4,5-diphenyloxazole as a carboxy surrogate and the late-stage macrolactonization affording the 42-membered macrocycle of oasomycin A are also described.

    4. Enantioselective Synthesis of Oasomycin A, Part III: Fragment Assembly and Confirmation of Structure (pages 545–548)

      David A. Evans, Pavel Nagorny, Kenneth J. McRae, Louis-Sebastian Sonntag, Dominic J. Reynolds and Filisaty Vounatsos

      Version of Record online: 8 DEC 2006 | DOI: 10.1002/anie.200603652

      Thumbnail image of graphical abstract

      Putting the pieces together: The total synthesis of the natural macrolide oasomycin A has been realized. Key fragment couplings include an anti-Felkin selective aldol addition (green), Kociensky–Julia olefinations (red), and competitive Weinreb amide acylation reaction (blue). The utility of the 4,5-diphenyloxazole as a carboxy surrogate and the late-stage macrolactonization affording the 42-membered macrocycle of oasomycin A are also described.

    5. Visualization of Complex-Anion Site Conversion on a Metal Oxide Surface (pages 549–552)

      A. J. Limb, O. Bikondoa, C. A. Muryn and Geoff Thornton

      Version of Record online: 5 DEC 2006 | DOI: 10.1002/anie.200602938

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      Oxygen vacancies are shown by STM to play a fundamental role in the stabilization of complex anions on an oxide surface at elevated temperatures. By increasing the temperature in the range 120–420 K, sulfite is transformed into sulfate on a TiO2(110) surface, and there is a change in the adsorption site which seems to be driven by stabilization of the adsorbate by an oxygen vacancy (see picture; Ti: red, O: blue, turquoise, and white, S: bronze).

    6. Is an Electronic Shield at the Molecular Origin of Lead Poisoning? A Computational Modeling Experiment (pages 553–556)

      Christophe Gourlaouen and Olivier Parisel

      Version of Record online: 7 DEC 2006 | DOI: 10.1002/anie.200603037

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      Chop and change: Upon substitution of native Zn2+ by exogenous Pb2+ ions in a model of δ-aminolevulinic acid dehydratase, a dramatic change occurs in the topology of the electron localization function at the active site of the protein. This effect is expected to disrupt the natural function of the metalated domain.

    7. RNA Ligands That Distinguish Metabolite-Induced Conformations in the TPP Riboswitch (pages 557–560)

      Günter Mayer, Marie-Sophie L. Raddatz, Julia D. Grunwald and Michael Famulok

      Version of Record online: 5 DEC 2006 | DOI: 10.1002/anie.200603166

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      Molecular diversity meets RNA conformation: In vitro selected RNA hairpins (red) bind to the thiM riboswitch of E. coli and are released upon addition of thiamine pyrophosphate (TPP; see scheme). These hairpins guide the identification of nucleotides that are important for riboswitch function.

    8. Use of Fluorescence Sensors To Determine that 2-Deoxyribonolactone Is the Major Alkali-Labile Deoxyribose Lesion Produced in Oxidatively Damaged DNA (pages 561–564)

      Liang Xue and Marc M. Greenberg

      Version of Record online: 8 DEC 2006 | DOI: 10.1002/anie.200603454

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      Throwing light on lesions: DNA oxidation is a ubiquitous but potentially dangerous process that produces a variety of structural modifications in the biopolymer. One modified unit, 2-deoxyribonolactone (L), produces cross-links with DNA repair proteins and is mutagenic. Selective fluorescence sensors (e.g. 1) show that L is the major alkali-labile deoxyribose lesion produced in DNA exposed to γ radiolysis.

    9. Stereoselective Intermolecular Formal [3+3] Cycloaddition Reaction of Cyclic Enamines and Enones (pages 565–568)

      Mohammad Movassaghi and Bin Chen

      Version of Record online: 5 DEC 2006 | DOI: 10.1002/anie.200603302

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      A convergent strategy for the synthesis of tricyclic imino alcohols was partly inspired by a postulated biosynthesis of galbulimima alkaloids. In this sequential α,α′ alkylation of unsymmetrical ketoimines, at least three stereocenters are created with a high level of diastereoselectivity. Organocatalytic and asymmetric variants of this methodology complement an organocuprate-based approach (see scheme).

    10. Absolute and Accurate Quantification of Protein Phosphorylation by Using an Elemental Phosphorus Standard and Element Mass Spectrometry (pages 569–571)

      A. Pereira Navaza, J. Ruiz Encinar and A. Sanz-Medel

      Version of Record online: 5 DEC 2006 | DOI: 10.1002/anie.200602517

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      The simpler the better: The combination of element mass spectrometry under optimized conditions and an elemental phosphorus standard provides a generic approach for absolute quantitative phosphoproteomics. This approach allows for simultaneous and reliable quantification of each individual phosphopeptide (corresponding to the different phosphorylation sites) present in a tryptic digest of a protein mixture.

    11. Total Synthesis of Paliurine F (pages 572–575)

      Mathieu Toumi, François Couty and Gwilherm Evano

      Version of Record online: 11 OCT 2006 | DOI: 10.1002/anie.200602865

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      A couple of coppers: An efficient, asymmetric synthesis of the sedative cyclopeptide alkaloid paliurine F has been achieved. The strategy employs two copper(I)-mediated coupling reactions as key steps to install the aryl ether linkage as well as to form the enamide with a concomitant unprecedented macrocyclization.

    12. Radical Cyclization of N-Acylcyanamides: Total Synthesis of Luotonin A (pages 576–579)

      Aurore Servais, Mériam Azzouz, David Lopes, Christine Courillon and Max Malacria

      Version of Record online: 8 DEC 2006 | DOI: 10.1002/anie.200602940

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      As radical chain cascade precursors, N-acylcyanamides give rise to amide–iminyl radicals which, when appropriately substituted, can finally yield pyrroloquinazolines. The versatility of these new radical acceptors is illustrated by the formation of N-heterocycles with wide structural variation and by the total synthesis of luotonin A.

    13. Rapid In Vivo Fingerprinting of Nonvolatile Compounds in Breath by Extractive Electrospray Ionization Quadrupole Time-of-Flight Mass Spectrometry (pages 580–583)

      Huanwen Chen, Arno Wortmann, Weihua Zhang and Renato Zenobi

      Version of Record online: 2 NOV 2006 | DOI: 10.1002/anie.200602942

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      A blow-by-blow account: Extractive electrospray ionization (EESI) quadrupole TOF (QTOF) mass spectrometry has been established with a commercial instrument without hardware modification for the rapid analysis of breath without sample pretreatment (see picture). Sulfur-containing compounds can be selectively detected by using silver cationization in the EESI source—a method of interest for in vivo metabolic studies and clinical diagnosis.

    14. Dioxygen Reduction at Dicobalt Complexes of a Schiff Base Calixpyrrole Ligand (pages 584–586)

      Gonzalo Givaja, Manuel Volpe, Michael A. Edwards, Alexander J. Blake, Claire Wilson, Martin Schröder and Jason B. Love

      Version of Record online: 7 DEC 2006 | DOI: 10.1002/anie.200603201

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      Fixed and reduced: Dicobalt complexes of a Schiff base calixpyrrole ligand adopt rigid, wedged “pacman” structures that can accommodate oxygen (see picture) and reduce it within the bimetallic molecular cleft.

    15. Mechanisms of the Elementary Processes of Electron Wavepacket Dynamics Coupled with Proton Transfer and Hydrogen-Atom Migration in H2O+H3O+ (pages 587–590)

      Hiroshi Ushiyama and Kazuo Takatsuka

      Version of Record online: 7 DEC 2006 | DOI: 10.1002/anie.200603553

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      The dynamics of the coupled transfer of electrons and protons were studied theoretically in the colliding system H2O+H3O+. In the ground-state dynamics, the proton, tightly covered with electrons, carries a net charge of as much as about +0.4, and therefore about 0.6 electrons are carried back in the reverse direction through a different path (see scheme).

    16. Total Synthesis of Rapamycin (pages 591–597)

      Matthew L. Maddess, Miles N. Tackett, Hidenori Watanabe, Paul E. Brennan, Christopher D. Spilling, James S. Scott, David P. Osborn and Steven V. Ley

      Version of Record online: 8 DEC 2006 | DOI: 10.1002/anie.200604053

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      Rapamycin synthesis all wrapped up: A new convergent synthesis of rapamycin (1) is reported that involves a macroetherification/catechol tethering strategy for construction of the macrocyclic core of this intriguing natural product. Other studies on this commercialized potent immunosuppressant delineate new cell signaling pathways of relevance to cancer chemotherapy.

    17. [Fe(CNXyl)4]2−: An Isolable and Structurally Characterized Homoleptic Isocyanidemetalate Dianion (pages 598–600)

      William W. Brennessel and John E. Ellis

      Version of Record online: 7 DEC 2006 | DOI: 10.1002/anie.200603746

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      World's record: The first isolation and structural characterization of a homoleptic isocyanidemetalate dianion has been achieved with [Fe(CNXyl)4]2− (Xyl=2,6-dimethylphenyl; see structure, Fe red, N blue, C gray). Spectral and structural data indicate that metal-to-isocyanide back-bonding in this electron-rich species is the largest ever observed in a homoleptic isocyanide complex containing only terminally bound ligands.

    18. Reaction of Molecular Oxygen with an NHC-Coordinated Pd0 Complex: Computational Insights and Experimental Implications (pages 601–604)

      Brian V. Popp, Johanna E. Wendlandt, Clark R. Landis and Shannon S. Stahl

      Version of Record online: 8 DEC 2006 | DOI: 10.1002/anie.200603667

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      O2activation: Computational studies of the reaction of O2 with an [(NHC)2Pd0] (NHC=N-heterocyclic carbene) complex reveal an unexpectedly small driving force for formation of a PdII2-O2) product. This result led to experimental demonstration of reversible O2 coordination to the (NHC)2Pd center. Computational analysis of the reaction coordinate reveals that O2 reacts with Pd0 through a stepwise mechanism involving an η1-O2 transition state.

    19. Incorporation of In Vitro Synthesized GPCR into a Tethered Artificial Lipid Membrane System (pages 605–608)

      Rudolf Robelek, Eva S. Lemker, Birgit Wiltschi, Vinzenz Kirste, Renate Naumann, Dieter Oesterhelt and Eva-Kathrin Sinner

      Version of Record online: 7 DEC 2006 | DOI: 10.1002/anie.200602231

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      Controlling the context: A novel strategy for the in vitro expression and immediate post-translational membrane insertion of complex membrane proteins into an artificial membrane system is described. In this way problems are circumvented that arise when complex membrane proteins are overexpressed, detergent-solubilized, and subsequently reconstituted into suitable artificial membrane systems for biophysical characterization. GPCR= G-protein coupled receptor.

    20. Proline-Catalyzed Mannich Reaction of Aldehydes with N-Boc-Imines (pages 609–611)

      Jung Woon Yang, Michael Stadler and Benjamin List

      Version of Record online: 13 DEC 2006 | DOI: 10.1002/anie.200603188

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      A curious cat.: The proline-catalyzed Mannich reaction between aldehydes and N-Boc-imines (Boc=tert-butoxycarbonyl) gives crystalline β-amino aldehydes with exceptionally high diastereoselectivities and enantioselectivities (see scheme). The products of this reaction typically precipitate from the reaction mixture and are useful intermediates in the synthesis of α- and β-substituted β-amino acids.

    21. Catalytic Asymmetric Acylcyanation of Imines (pages 612–614)

      Subhas Chandra Pan, Jian Zhou and Benjamin List

      Version of Record online: 12 DEC 2006 | DOI: 10.1002/anie.200603630

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      The less problematic acetyl cyanide can be used instead of toxic HCN for the highly enantioselective acyl-Strecker-type reaction. In the presence of an N-benzylimine and a catalytic amount of Jacobsen's catalyst 1, the desired α-amidonitrile is obtained in excellent enantioselectivity and yield.

    22. On the Polymorphism of Aspirin (pages 615–617)

      Andrew D. Bond, Roland Boese and Gautam R. Desiraju

      Version of Record online: 28 NOV 2006 | DOI: 10.1002/anie.200602378

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      More headaches with aspirin: No new polymorph? Reduction and re-indexing of X-ray data collected on a crystal of the well-known form I of aspirin in a unit cell recently reported for the new form II results in a data set from which this so-called new form can be obtained and even refined isotropically! Form II, if it exists, needs to be identified with more rigorous experimentation and modeling.

    23. On the Polymorphism of Aspirin: Crystalline Aspirin as Intergrowths of Two “Polymorphic” Domains (pages 618–622)

      Andrew D. Bond, Roland Boese and Gautam R. Desiraju

      Version of Record online: 1 DEC 2006 | DOI: 10.1002/anie.200603373

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      Aspirin: No end to the headaches? The two known crystalline arrangements of aspirin are so closely related that aspirin crystals form intergrowth structures containing domains of form I and domains of form II. The ratio and distribution of the domains is variable among aspirin samples, raising questions for the definition of the term polymorph in this case.

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      Structure and Stability of Molybdenum Sulfide Fullerenes (pages 623–627)

      Andrey N. Enyashin, Sibylle Gemming, Maya Bar-Sadan, Ronit Popovitz-Biro, Sung You Hong, Yehiam Prior, Reshef Tenne and Gotthard Seifert

      Version of Record online: 12 DEC 2006 | DOI: 10.1002/anie.200602136

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      Opening the window: Hollow multilayer nano-octahedra (see TEM image and structure) often appear in the laser-ablation products of layered transition-metal chalcogenides. Calculations on MoS2 nanoparticles demonstrate that nano-octahedra exist in a window of stability between nanoplatelets and spherical fullerene-like nanoparticles.

    25. Nanocomposites Prepared by Twin Polymerization of a Single-Source Monomer (pages 628–632)

      Silke Grund, Patrick Kempe, Gisela Baumann, Andreas Seifert and Stefan Spange

      Version of Record online: 7 DEC 2006 | DOI: 10.1002/anie.200504327

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      A common source: In a novel twin polymerization, a single monomer is transformed into an organic–inorganic nanocomposite. For example, tetrafurfuryloxysilane polymerizes to form a dense interpenetrating network of poly(furfuryl alcohol) and SiO2 (see picture). Nanoporous silicate, and potentially other metal oxides, can be obtained when the organic components are removed.

  11. Preview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Book Reviews
    8. Highlight
    9. Minireview
    10. Review
    11. Communications
    12. Preview
    1. You have free access to this content
      Preview: Angew. Chem. Int. Ed. 5/2007 (page 639)

      Version of Record online: 10 JAN 2007 | DOI: 10.1002/anie.200790004

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