Angewandte Chemie International Edition

Cover image for Vol. 47 Issue 18

April 21, 2008

Volume 47, Issue 18

Pages 3289–3467

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Reviews
    7. Highlights
    8. Essay
    9. Review
    10. Communications
    11. Preview
    1. Cover Picture: Influence of Amino Acid Side Chains on Long-Distance Electron Transfer in Peptides: Electron Hopping via “Stepping Stones” (Angew. Chem. Int. Ed. 18/2008) (page 3289)

      Meike Cordes, Angnieszka Köttgen, Christian Jasper, Olivier Jacques, Hassen Boudebous and Bernd Giese

      Version of Record online: 15 APR 2008 | DOI: 10.1002/anie.200890079

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      Relay amino acids forward electrons through peptides, as described by B. Giese and co-workers in their Communication on page 3461 ff. The cover picture shows a baton change in a relay race, which symbolizes electron transfer from one peptide sequence to the next via a relay amino acid. The olympic rings reflect the five participating sequences in the peptide molecule. Such an “electron relay” can explain long-distance electron transfer through enzymes.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Reviews
    7. Highlights
    8. Essay
    9. Review
    10. Communications
    11. Preview
    1. Inside Cover: Light-Powered Electrical Switch Based on Cargo-Lifting Azobenzene Monolayers (Angew. Chem. Int. Ed. 18/2008) (page 3290)

      Violetta Ferri, Mark Elbing, Giuseppina Pace, Michael D. Dickey, Michael Zharnikov, Paolo Samorì, Marcel Mayor and Maria Anita Rampi

      Version of Record online: 15 APR 2008 | DOI: 10.1002/anie.200890080

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      A molecular cargo lifter based on tightly packed monolayers (SAMs) of rigid azobenzene rods is described by M. A. Rampi et al. in their Communication on page 3407 ff. The monolayer, sandwiched between Hg and Au electrodes, is irradiated in situ through a transparent gold surface. The current flowing through the electrodes increases and decreases reversibly under alternating irradiation at 370 and 450 nm. The azobenzene SAM exerts a mechanical force and lifts the Hg drop electrode, and thus the system operates as a photoswitch.

  3. Graphical Abstract

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

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

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Reviews
    7. Highlights
    8. Essay
    9. Review
    10. Communications
    11. Preview
    1. Molecules that Changed the World. By K. C. Nicolaou and Tamsyn Montagnon. (pages 3309–3310)

      Rainer E. Metternich and Philippe G. Nantermet

      Version of Record online: 15 APR 2008 | DOI: 10.1002/anie.200885602

  6. Highlights

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Reviews
    7. Highlights
    8. Essay
    9. Review
    10. Communications
    11. Preview
    1. Betablockers at Work: The Crystal Structure of the β2-Adrenergic Receptor (pages 3314–3316)

      Felix Hausch

      Version of Record online: 17 MAR 2008 | DOI: 10.1002/anie.200705971

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      Rational drug design is still limited for many membrane proteins. For the β2-adrenergic receptor, a prototype of the class A GPCR family, structures with up to 2.4-Å resolution have now been solved. The structure (see figure) shows detailed contacts of the receptor (green) with its ligand carazolol (pink), and makes possible the formulation of hypotheses for the mode of action of G-protein-coupled receptors.

    2. Sustainable Metal Catalysis with Iron: From Rust to a Rising Star? (pages 3317–3321)

      Stephan Enthaler, Kathrin Junge and Matthias Beller

      Version of Record online: 15 APR 2008 | DOI: 10.1002/anie.200800012

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      Among the shades! With respect to its availability, low toxicity, and price, iron should be one of the most used metals in homogeneous catalysis. Surprisingly, so far the application of iron is underdeveloped in comparison with other transition metals. Some promising attempts obtained in redox reactions and coupling chemistry which nicely illustrate the potential of iron and hopefully initialize a ferric future for catalysis are highlighted.

  7. Essay

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Reviews
    7. Highlights
    8. Essay
    9. Review
    10. Communications
    11. Preview
    1. 100 Years of Bakelite, the Material of a 1000 Uses (pages 3322–3328)

      Daniel Crespy, Marianne Bozonnet and Martin Meier

      Version of Record online: 3 MAR 2008 | DOI: 10.1002/anie.200704281

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      The beginning of the plastics age: Just over one hundred years ago, on July 13 1907, Leo H. Baekeland applied for a patent for the processing of a product that had an enormous influence on the development of our technology, and which changed our habits forever. The patent described Bakelite, the first synthetic plastic, which heralded our entrance into the plastics age.

  8. Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Reviews
    7. Highlights
    8. Essay
    9. Review
    10. Communications
    11. Preview
    1. “Green” Pyrotechnics: A Chemists' Challenge (pages 3330–3347)

      Georg Steinhauser and Thomas M. Klapötke

      Version of Record online: 29 FEB 2008 | DOI: 10.1002/anie.200704510

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      The other “dirty bombs”: Fireworks and pyrotechnic applications cause multifaceted environmental pollution. This Review gives an overview about the recent “greening” of pyrotechnics: the use of nitrogen-rich energetic materials and other strategies to avoid the production of toxic combustion products.

  9. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Reviews
    7. Highlights
    8. Essay
    9. Review
    10. Communications
    11. Preview
    1. A Biomimetic Enantioselective Approach to the Decahydroquinoline Class of Dendrobatid Alkaloids (pages 3348–3351)

      Mercedes Amat, Rosa Griera, Robert Fabregat, Elies Molins and Joan Bosch

      Version of Record online: 28 MAR 2008 | DOI: 10.1002/anie.200705888

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      A princely synthesis: The hypothetical key step in the biosynthesis of the decahydroquinoline dendrobatid alkaloids, such as cis-195 A found in frogs, from 1,5-polycarbonyl derivatives is mimicked by using (R)-phenylglycinol as a chiral latent form of ammonia in a double cyclocondensation reaction.

    2. Cucurbit[6]uril: Organic Molecular Porous Material with Permanent Porosity, Exceptional Stability, and Acetylene Sorption Properties (pages 3352–3355)

      Soyoung Lim, Hyunuk Kim, Narayanan Selvapalam, Kyung-Jin Kim, Sung June Cho, Gon Seo and Kimoon Kim

      Version of Record online: 20 MAR 2008 | DOI: 10.1002/anie.200800772

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      Holely organic solid: Effective packing of the rigid macrocycle cucurbituril through C[BOND]H⋅⋅⋅O hydrogen-bonding and van der Waals interactions leads to a honeycomb-like structure with unprecedented stability and porosity. It shows extraordinary sorption properties toward gases, particularly acetylene, which are comparable or superior to those of metal–organic frameworks in terms of storage capacity.

    3. Experiment and Theory Reveal the Fundamental Difference between Two-State and Single-State Reactivity Patterns in Nonheme FeIV[DOUBLE BOND]O versus RuIV[DOUBLE BOND]O Oxidants (pages 3356–3359)

      Sunder N. Dhuri, Mi Sook Seo, Yong-Min Lee, Hajime Hirao, Yong Wang, Wonwoo Nam and Sason Shaik

      Version of Record online: 25 MAR 2008 | DOI: 10.1002/anie.200705880

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      Two-state reactivity involving close triplet ground and quintet excited states is responsible for the opposite reactivity trends of FeIV oxo complexes in O-transfer and H-abstraction reactions in dependence on the electron richness of the axial ligand X (see picture), as shown by comparison with RuIV analogues, in which both reactivities are solely governed by the electrophilicity of the complex because the quintet state is inaccessible.

    4. Mass Spectrometric Screening of Enantioselective Diels–Alder Reactions (pages 3360–3362)

      Antje Teichert and Andreas Pfaltz

      Version of Record online: 20 MAR 2008 | DOI: 10.1002/anie.200705082

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      A rapid cat. scan: Mass spectrometric monitoring of reaction intermediates of the retro-Diels–Alder reaction has allowed the rapid screening of catalysts for enantioselective Diels–Alder reactions (see scheme). Copper catalysts as well as metal-free organocatalysts were tested. A protocol for the simultaneous screening of catalyst mixtures has also been developed, which offers new possibilities for high-throughput catalyst development.

    5. Mass Spectrometric Screening of Chiral Catalysts by Monitoring the Back Reaction of Quasienantiomeric Products: Palladium-Catalyzed Allylic Substitution (pages 3363–3366)

      Constanze A. Müller and Andreas Pfaltz

      Version of Record online: 20 MAR 2008 | DOI: 10.1002/anie.200705081

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      Back to basics: The principle of microscopic reversibility is the basis of a new screening method for chiral catalysts. Monitoring the back reaction of quasienantiomeric allylation products by ESI-MS reveals the intrinsic enantioselectivity of palladium catalysts in allylic substitution reactions (see scheme).

    6. Transformation from H- to J-Aggregated Perylene Bisimide Dyes by Complexation with Cyanurates (pages 3367–3371)

      Shiki Yagai, Tomohiro Seki, Takashi Karatsu, Akihide Kitamura and Frank Würthner

      Version of Record online: 25 MAR 2008 | DOI: 10.1002/anie.200705385

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      Me, myself, and dye: Core-unsubstituted perylene bisimide dyes bearing a melamine hydrogen-bonding unit link with cyanurates giving H- (red, see picture) and J-aggregates (green). In solution the aggregates can interconvert on thermal treatment or by changing the stoichiometry. In solid films the green to red color change occurs upon scratching the surface.

    7. Water-Soluble Monofunctional Perylene and Terrylene Dyes: Powerful Labels for Single-Enzyme Tracking (pages 3372–3375)

      Kalina Peneva, Gueorgui Mihov, Fabian Nolde, Susana Rocha, Jun-ichi Hotta, Kevin Braeckmans, Johan Hofkens, Hiroshi Uji-i, Andreas Herrmann and Klaus Müllen

      Version of Record online: 26 MAR 2008 | DOI: 10.1002/anie.200705409

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      All in one: Exceptionally photostable, highly fluorescent, water-soluble, and monofunctional perylene and terrylene dyes bearing reactive groups for covalent attachment to biomolecules have been synthesized (see picture). Single-molecule enzyme tracking revealed that single enzymes could be visualized even on a substrate with fluorescent background.

    8. A Porous Coordination-Polymer Crystal Containing One-Dimensional Water Chains Exhibits Guest-Induced Lattice Distortion and a Dielectric Anomaly (pages 3376–3380)

      HengBo Cui, Biao Zhou, La-Sheng Long, Yoshinori Okano, Hayao Kobayashi and Akiko Kobayashi

      Version of Record online: 18 MAR 2008 | DOI: 10.1002/anie.200705846

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      Ice one: A porous molecular crystal with guest water molecules in the channels—[La2Cu3{NH(CH2COO)2}6](H2O)n (see picture)—exhibits a distinct peak for the dielectric constant at 180 K (εr≈150) with the electric field parallel to the channel direction. This crystalline compound also shows a large enhancement of εr above 250 K and a characteristic antiferroelectric hysteresis coupled with a liquid–solid transition of the guest water molecules at around 350 K.

    9. Active Template Synthesis of Rotaxanes and Molecular Shuttles with Switchable Dynamics by Four-Component PdII-Promoted Michael Additions (pages 3381–3384)

      Stephen M. Goldup, David A. Leigh, Paul J. Lusby, Roy T. McBurney and Alexandra M. Z. Slawin

      Version of Record online: 20 MAR 2008 | DOI: 10.1002/anie.200705859

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      Taking the Michael: Rotaxanes (see structure) and molecular shuttles are prepared in up to 99 % yield by successive PdII-promoted 1,4-conjugate additions in a one-pot four-component assembly process. This process represents the first active template reaction in which the template motif is retained in the interlocked product.

    10. Measurement of Amyloid Fibril Length Distributions by Inclusion of Rotational Motion in Solution NMR Diffusion Measurements (pages 3385–3387)

      Andrew J. Baldwin, Spencer J. Anthony-Cahill, Tuomas P. J. Knowles, Guy Lippens, John Christodoulou, Paul D. Barker and Christopher M. Dobson

      Version of Record online: 18 MAR 2008 | DOI: 10.1002/anie.200703915

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      Telling fibrils: Diffusion data obtained by solution NMR spectroscopy from flexible regions of amyloid fibrils for both rotational and translation diffusion combined is of similar magnitude to that measured using AFM and TEM (see picture). Fibrils in solution are calculated to be somewhat longer on average than those deposited on surfaces for microscopy experiments, which can be partially attributed to the sensitivity of fibrils to fracture.

    11. Protein Crystallography through Supramolecular Interactions between a Lanthanide Complex and Arginine (pages 3388–3391)

      Guillaume Pompidor, Anthony D'Aléo, Jean Vicat, Loïc Toupet, Nicolas Giraud, Richard Kahn and Olivier Maury

      Version of Record online: 18 MAR 2008 | DOI: 10.1002/anie.200704683

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      Crystal clear: Strong supramolecular interactions between tris(dipicolinate)lanthanide complexes and arginine-like moieties have been evidenced by NMR chemical shift titration and X-ray diffraction analyses. Since the lanthanide atom is a strong anomalous scatterer, and the complex itself is luminescent, this interaction could be used as a powerful tool in the preparation of crystals of protein derivatives with high phasing power.

    12. Desolvation of Ions in Subnanometer Pores and Its Effect on Capacitance and Double-Layer Theory (pages 3392–3395)

      John Chmiola, Celine Largeot, Pierre-Louis Taberna, Patrice Simon and Yury Gogotsi

      Version of Record online: 25 MAR 2008 | DOI: 10.1002/anie.200704894

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      Recasting the double layer: The implicit assumption that electrochemical double layers are governed only by ion/electrode charge separation may be short-sighted and lead to a fundamental misunderstanding of the phenomenological response. This is shown in a study performed on ions confined in nanoporous carbon with pores smaller than the size of an ion surrounded by a solvation shell (see picture; TEA+=tetraethylammonium, AN=acetonitrile).

    13. On-Chip Synthesis and Label-Free Assays of Oligosaccharide Arrays (pages 3396–3399)

      Lan Ban and Milan Mrksich

      Version of Record online: 26 MAR 2008 | DOI: 10.1002/anie.200704998

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      Sugar coated: A new strategy for solid-support oligosaccharide array synthesis and direct SAMDI-TOF (self-assembled monolayers for matrix-assisted laser desorption-ionization time-of-flight) mass spectrometry detection of the synthesis process is reported (see scheme). It incorporates an on-chip ligand array synthesis, a label-free detection method, and direct application to an enzymatic assay.

    14. Accommodation of a Single Protein Guest in Nanometer-Scale Wells Embedded in a “DNA Nanotape” (pages 3400–3402)

      Akinori Kuzuya, Kentaro Numajiri and Makoto Komiyama

      Version of Record online: 25 MAR 2008 | DOI: 10.1002/anie.200800028

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      All's well: A tapelike DNA scaffold with regularly arranged nanometer-scale wells is prepared by bundling nine DNA helices into U-shaped motifs (see picture). By attaching two biotin residues at two edges of each well, just one streptavidin tetramer is size-selectively captured to form a regularly oriented streptavidin nanoarray. The “anchored” tetramers nested in the wells are stable under repetitive AFM scanning.

    15. A Dynamic, Isocyanurate-Functionalized Porous Coordination Polymer (pages 3403–3406)

      Sujit K. Ghosh, Sareeya Bureekaew and Susumu Kitagawa

      Version of Record online: 26 MAR 2008 | DOI: 10.1002/anie.200705986

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      Like a sponge: Soft, three-dimensional, porous coordination frameworks {[Ln(tci)⋅H2O]⋅4 H2O}n (Ln=Ce, Gd; tciH3=tris(2-carboxyethyl)isocyanurate] were prepared from Ln(NO3)3x H2O and tciH3. The flexible arms and secondary functional groups of the ligand allow the framework to show spongelike dynamic behavior such as selective and stepwise adsorption, associated with single crystal to single crystal structural transformation (see scheme).

    16. Light-Powered Electrical Switch Based on Cargo-Lifting Azobenzene Monolayers (pages 3407–3409)

      Violetta Ferri, Mark Elbing, Giuseppina Pace, Michael D. Dickey, Michael Zharnikov, Paolo Samorì, Marcel Mayor and Maria Anita Rampi

      Version of Record online: 17 MAR 2008 | DOI: 10.1002/anie.200705339

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      We have liftoff! Tightly packed self-assembled monolayers (SAMs) of ultrarigid conjugated azobenzenes incorporated into a Hg-based junction undergo reversible photoisomerization (see picture). The current–voltage curves indicate that the junction operates as a current photoswitch as result of the forces expressed by the SAMs, which act as a light-powered cargo lifter.

    17. Enantioselective Synthesis of P-Stereogenic Alkynylphosphine Oxides by Rh-Catalyzed [2+2+2] Cycloaddition (pages 3410–3413)

      Goushi Nishida, Keiichi Noguchi, Masao Hirano and Ken Tanaka

      Version of Record online: 19 MAR 2008 | DOI: 10.1002/anie.200800144

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      Two plus two plus two: An enantioselective synthesis of P-stereogenic alkynylphosphine oxides through a cationic rhodium(I)/modified-binap complex catalyzed [2+2+2] cycloaddition of symmetrical dialkynylphosphine oxides with 1,6-diynes was developed (see scheme; binap=2,2′-bis(diphenylphosphanyl)-1,1′-binaphthyl, Z=CH2, O, or N-sulfonamide). Furthermore, this method permits the synthesis of a C2-symmetric P-stereogenic bis(alkynylphosphine oxide).

    18. Organocatalytic Asymmetric Formal [3+2] Cycloaddition Reaction of Isocyanoesters to Nitroolefins Leading to Highly Optically Active Dihydropyrroles (pages 3414–3417)

      Chang Guo, Meng-Xia Xue, Ming-Kui Zhu and Liu-Zhu Gong

      Version of Record online: 18 MAR 2008 | DOI: 10.1002/anie.200800003

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      Closing the circle: The asymmetric [3+2] formal cycloaddition reaction of α-substituted isocyanoesters with nitroolefins is catalyzed by cinchona alkaloid derivatives to yield 2,3-dihydropyrroles with high diastereo- and enantioselectivities (see scheme).

    19. One-Pot Synthesis of Potassium-Functionalized Mesoporous γ-Alumina: A Solid Superbase (pages 3418–3421)

      Lin Bing Sun, Jing Yang, Jia Hui Kou, Fang Na Gu, Yuan Chun, Ying Wang, Jian Hua Zhu and Zhi Gang Zou

      Version of Record online: 20 MAR 2008 | DOI: 10.1002/anie.200800034

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      Basically super: Potassium-functionalized mesoporous γ-alumina solid superbases that have a high base strength (H) of 27.0, a well-expressed mesoporous structure, and which are efficient in the isomerization of 1-hexene are synthesized by a one-pot method. The success of this method can be ascribed to the flexible application of K2CO3 as a pH adjustor and close control of the calcination process (see picture).

    20. Organic Reactions of Ionic Intermediates Promoted by Atmospheric-Pressure Thermal Activation (pages 3422–3425)

      Hao Chen, Livia S. Eberlin, Marcela Nefliu, Rodinei Augusti and R. Graham Cooks

      Version of Record online: 20 MAR 2008 | DOI: 10.1002/anie.200800072

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      A mild-mannered process: Novel methodology, in which electrosonic spray ionization (ESSI, see schematic diagram) is used as the proton source, has been used to generate ionic reaction intermediates whose conversion into products can be promoted by atmospheric-pressure thermal activation. Reactions performed under these mild conditions include Borsche–Drechsel cyclization, Fischer indole synthesis, and pinacol rearrangement.

    21. Total Synthesis of (−)-Pestalotiopsin A (pages 3426–3429)

      Ken-ichi Takao, Nobuhiko Hayakawa, Reo Yamada, Taro Yamaguchi, Urara Morita, Soujiro Kawasaki and Kin-ichi Tadano

      Version of Record online: 25 MAR 2008 | DOI: 10.1002/anie.200800253

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      A big “+”: The total synthesis of (−)-pestalotiopsin A has been achieved, thereby establishing the absolute stereochemistry of natural (+)-pestalotiopsin A (see scheme). The synthesis features a [2+2] cycloaddition, an aldol reaction, and an intramolecular Nozaki–Hiyama–Kishi reaction to construct the (E)-cyclononene ring.

    22. Do Special Noncovalent π–π Stacking Interactions Really Exist? (pages 3430–3434)

      Stefan Grimme

      Version of Record online: 18 MAR 2008 | DOI: 10.1002/anie.200705157

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      Van der Waals complexes are formed by almost all neutral molecules, which begs the question as to what is so special about the interaction between parallel stacks of arenes. The term π–π stacking interactions should primarily be used as a structural descriptor for unsaturated systems. Genuine π–π interactions are caused by specific electron correlations that are only at work for short intermolecular distances.

    23. Pseudopolyanions Based on Poly(NIPAAM-co-β-Cyclodextrin Methacrylate) and Ionic Liquids (pages 3435–3437)

      Sadik Amajjahe, Soowhan Choi, Maricica Munteanu and Helmut Ritter

      Version of Record online: 18 MAR 2008 | DOI: 10.1002/anie.200704995

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      A fine host: Copolymers from methacrylated β-cyclodextrin and N-isopropylacrylamide form inclusion complexes with anions of ionic liquids (IL; see picture). Complex formation alters the solubility properties of the copolymer, leading to pseudopolyelectrolytes. Turbidity and dynamic light scattering measurements show that, depending on the anion, expansion or contraction of the polymer chain takes place owing to electrostatic effects.

    24. Methylgallium as a Terminal Ligand in [(Cp*Ga)4Rh(GaCH3)]+ (pages 3438–3441)

      Thomas Cadenbach, Christian Gemel, Denise Zacher and Roland A. Fischer

      Version of Record online: 2 APR 2008 | DOI: 10.1002/anie.200705031

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      The smallest possible gallium alkyl species, the otherwise elusive GaCH3, has been generated by protolytic cleavage of Cp*H from a coordinated a {Ga(CH3)Cp*} moiety and trapped in the title complex (see structure; C white, Ga blue, Rh brown). The counterintuitive shortening of the Rh[BOND]GaCH3 bond upon adduct formation with pyridine illustrates that bond lengths alone are insufficient for the assignment of bond order.

    25. Click–Click–Click: Single to Triple Modification of DNA (pages 3442–3444)

      Philipp M. E. Gramlich, Simon Warncke, Johannes Gierlich and Thomas Carell

      Version of Record online: 28 MAR 2008 | DOI: 10.1002/anie.200705664

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      One, two, or three: An efficient, modular, and robust protocol has been developed for the multiple functionalization of DNA. It is based on the click reaction of azides with the alkyne substituents on an oligodeoxyribonucleotide (ODN), which was prepared by the standard phosphoramidite method (see scheme). ODNs can thus be labeled with two sensitive molecules, and even triple modification is possible.

    26. Total Synthesis of the Glycopeptide Recognition Domain of the P-Selectin Glycoprotein Ligand 1 (pages 3445–3449)

      Katharina Baumann, Danuta Kowalczyk and Horst Kunz

      Version of Record online: 20 MAR 2008 | DOI: 10.1002/anie.200705762

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      Block glycosylation of a T antigen–threonine conjugate with a sialyl Lewisx trichloroacetimidate was used to synthesize a sialyl Lewisx–T antigen–threonine building block. Selective protecting-group manipulations furnished a compound with exclusively acetyl-protected functions in the carbohydrate portion; this intermediate is sufficiently acid-stable that it is applicable to the solid-phase synthesis of binding site A of the P-selectin ligand PSGL-1.

    27. Porous, Covalent Triazine-Based Frameworks Prepared by Ionothermal Synthesis (pages 3450–3453)

      Pierre Kuhn, Markus Antonietti and Arne Thomas

      Version of Record online: 10 MAR 2008 | DOI: 10.1002/anie.200705710

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      Ordered and amorphous microporous polytriazine networks have been obtained from the trimerization of nitriles in a ZnCl2 melt at 400 °C (see structure of the polymer formed from 1,4-dicyanobenzene; C gray, N blue). The materials are high-performance polymers with very large surface areas and could find applications in gas storage, as sensors, or catalyst supports.

    28. Application of Ultrahigh-Field 59Co Solid-State NMR Spectroscopy in the Investigation of the 1,2-Polybutadiene Catalyst [Co(C8H13)(C4H6)] (pages 3454–3457)

      Patrick Crewdson, David L. Bryce, Frank Rominger and Peter Hofmann

      Version of Record online: 28 MAR 2008 | DOI: 10.1002/anie.200705204

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      Highly suitable: The 1,2-polybutadiene catalyst [Co(η32-C8H13)(η4-C4H6)] (1) was isolated and structurally characterized by ultrahigh-field 59Co solid-state NMR spectroscopy, demonstrating the utility of this technique. It can be applied to study the formation mechanism of syndiotactic 1,2-polybutadiene. The picture shows a QCPMG (a) and a quadrupole echo 59Co NMR spectrum (b) as well as a simulated spectrum of 1 (c).

    29. Variably Isotactic Poly(hydroxybutyrate) from Racemic β-Butyrolactone: Microstructure Control by Achiral Chromium(III) Salophen Complexes (pages 3458–3460)

      Manuela Zintl, Ferenc Molnar, Tobias Urban, Volker Bernhart, Peter Preishuber-Pflügl and Bernhard Rieger

      Version of Record online: 3 APR 2008 | DOI: 10.1002/anie.200703859

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      ROP artists: The ROP of racemic β-butyrolactone (BL) catalyzed by highly active chromium(III) salophen complexes 1 gives poly(hydroxybutyrate) (PHB) with high molecular weight and with isotacticities of 60–70 %. The product is a biodegradable polymer material with mechanical properties that can be varied from crystalline to thermoplastic. DFT calculations indicate that the induction of stereochemical information occurs through the formation of dimeric cagelike structures.

    30. Influence of Amino Acid Side Chains on Long-Distance Electron Transfer in Peptides: Electron Hopping via “Stepping Stones” (pages 3461–3463)

      Meike Cordes, Angnieszka Köttgen, Christian Jasper, Olivier Jacques, Hassen Boudebous and Bernd Giese

      Version of Record online: 9 APR 2008 | DOI: 10.1002/anie.200705588

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      It works both ways: The mechanism of electron transfer through peptides depends upon the side chain X located between the electron donor and the electron acceptor. Electron transfer occurs either by a slow single-step superexchange or by a two-step hopping process that is 20–30-times faster (see scheme). All intermediates in the hopping process could be observed simultaneously.

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    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Book Reviews
    7. Highlights
    8. Essay
    9. Review
    10. Communications
    11. Preview

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