Angewandte Chemie International Edition

Cover image for Vol. 52 Issue 1

January 2, 2013

Volume 52, Issue 1

Pages 1–466

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Editorials
    4. Graphical Abstract
    5. Flashback
    6. News
    7. Miscellaneous
    8. Interview
    9. Essays
    10. Minireviews
    11. Reviews
    12. Communications
    1. You have free access to this content
      Cover Picture: Champagne and Fireworks: Angewandte Chemie Celebrates Its Birthday (Angew. Chem. Int. Ed. 1/2013) (page 1)

      Dr. Peter Gölitz

      Article first published online: 13 DEC 2012 | DOI: 10.1002/anie.201209858

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      This fireworks will start the first issue of 2013. Read more about it in the Editorial of Peter Gölitz (DOI: 10.1002/anie.201209370).

    2. You have free access to this content
      Back Cover: Champagne and Fireworks: Angewandte Chemie Celebrates Its Birthday (Angew. Chem. Int. Ed. 1/2013) (page 468)

      Dr. Peter Gölitz

      Article first published online: 13 DEC 2012 | DOI: 10.1002/anie.201209857

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      There will glasses of champagne be raised in 2013 to Angewandte Chemie. Read more about it in the Editorial of Peter Gölitz (DOI: 10.1002/anie.201209370).

  2. Editorials

    1. Top of page
    2. Cover Pictures
    3. Editorials
    4. Graphical Abstract
    5. Flashback
    6. News
    7. Miscellaneous
    8. Interview
    9. Essays
    10. Minireviews
    11. Reviews
    12. Communications
    1. You have free access to this content
      Chemistry at Its Best (page 5)

      Prof. Dr. Barbara Albert

      Article first published online: 20 DEC 2012 | DOI: 10.1002/anie.201208702

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      … Contemplating the ideas published in Angewandte Chemie as well as the concepts and visions that can be derived from them allows us to experience cutting-edge chemistry. …” Read more in the Editorial by Barbara Albert

    2. You have free access to this content
      125 Years Angewandte Chemie (pages 6–7)

      Prof. François Diederich

      Article first published online: 3 DEC 2012 | DOI: 10.1002/anie.201205551

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      “… Angewandte Chemie looks back with pride on 125 years of successful publishing. The Journal stands for quality and innovation. Attractive, often artistically designed cover pages, informative tables of contents, and exciting author profiles are all aspects of the journal to which we have become accustomed …” Read more in the Editorial by François Diederich.

    3. You have free access to this content
      Champagne and Fireworks: Angewandte Chemie Celebrates Its Birthday (pages 8–10)

      Dr. Peter Gölitz

      Article first published online: 20 DEC 2012 | DOI: 10.1002/anie.201209370

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      A rousing force emanates from the important findings, which, in turn, inspires receptive natures to strive for achievements of their own. We produce our journal for such people. And we seek out these avant-garde. This constitutes our entire program. This program for Angewandte Chemie was formulated by Wilhelm Foerst 50 years ago, and still holds today. It is at the heart of this Editorial on the occasion of the journal’s 125th anniversary, in which a monument for the unknown referee is proposed.

  3. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Editorials
    4. Graphical Abstract
    5. Flashback
    6. News
    7. Miscellaneous
    8. Interview
    9. Essays
    10. Minireviews
    11. Reviews
    12. Communications
    1. Graphical Abstract: Angew. Chem. Int. Ed. 1/2013 (pages 12–34)

      Article first published online: 20 DEC 2012 | DOI: 10.1002/anie.201290083

  4. Flashback

    1. Top of page
    2. Cover Pictures
    3. Editorials
    4. Graphical Abstract
    5. Flashback
    6. News
    7. Miscellaneous
    8. Interview
    9. Essays
    10. Minireviews
    11. Reviews
    12. Communications
    1. 50 Years Ago ... (page 32)

      Article first published online: 20 DEC 2012 | DOI: 10.1002/anie.201209120

      Angewandte Chemie International Edition was first published in 1962, the mother journal first in 1888. In this monthly flashback, we feature some of the articles that appeared 50 years ago. This look back can open our eyes, stimulate discussion, or even raise a smile.

  5. News

    1. Top of page
    2. Cover Pictures
    3. Editorials
    4. Graphical Abstract
    5. Flashback
    6. News
    7. Miscellaneous
    8. Interview
    9. Essays
    10. Minireviews
    11. Reviews
    12. Communications
  6. Miscellaneous

    1. Top of page
    2. Cover Pictures
    3. Editorials
    4. Graphical Abstract
    5. Flashback
    6. News
    7. Miscellaneous
    8. Interview
    9. Essays
    10. Minireviews
    11. Reviews
    12. Communications
    1. Angewandte Chemie—many faces … one quality journal! (pages 44–45)

      Article first published online: 20 DEC 2012 | DOI: 10.1002/anie.201290084

  7. Interview

    1. Top of page
    2. Cover Pictures
    3. Editorials
    4. Graphical Abstract
    5. Flashback
    6. News
    7. Miscellaneous
    8. Interview
    9. Essays
    10. Minireviews
    11. Reviews
    12. Communications
    1. Meteorology

      Paul Crutzen on the Ozone Hole, Nitrogen Oxides, and the Nobel Prize (pages 48–50)

      Paul Crutzen, Gregor Lax and Carsten Reinhardt

      Article first published online: 3 DEC 2012 | DOI: 10.1002/anie.201208700

      An interview with the Nobel Laureate Professor Paul Crutzen was carried out by Gregor Lax and Carsten Reinhardt (both University of Bielefeld) as part of the centenary of the Max Planck Institute for Chemistry in Mainz. Paul Crutzen gives a fascinating insight into his scientific career and the development of his research area, meteorology.

  8. Essays

    1. Top of page
    2. Cover Pictures
    3. Editorials
    4. Graphical Abstract
    5. Flashback
    6. News
    7. Miscellaneous
    8. Interview
    9. Essays
    10. Minireviews
    11. Reviews
    12. Communications
    1. Surface Chemistry

      Molecules at Surfaces: 100 Years of Physical Chemistry in Berlin-Dahlem (pages 52–60)

      Prof. Dr. Gerhard Ertl

      Article first published online: 20 DEC 2012 | DOI: 10.1002/anie.201205401

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      Scratching the surface: For over 100 years the interactions of molecules at surfaces have been studied at the Fritz Haber Institute of the Max Planck Society, Berlin. Nobel Laureate Gerhard Ertl looks back at some of the key developments in this time, and the people who made them.

    2. Art Conservation

      A Chemist Remains a Chemist (pages 61–67)

      Prof. Richard R. Ernst

      Article first published online: 3 DEC 2012 | DOI: 10.1002/anie.201205461

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      Science, music, art, life: Nobel Laureate Richard Ernst discusses the influence of music and art on his life and how advanced Raman spectroscopy comes to his aid as a “hobby chemist” and art restorer.

    3. Protein Crystallography

      “How I Chose Research on Proteases or, More Correctly, How it Chose Me” (pages 68–73)

      Prof. Robert Huber

      Article first published online: 3 DEC 2012 | DOI: 10.1002/anie.201205629

      Crystal clear: “I was lucky to choose protein crystallography as the focus of my research activity at a time soon after its foundation by Perutz and Kendrew”. Nobel Laureate Robert Huber reflects on how protein crystallography has developed and now has a fundamental role in our understanding of biological processes.

    4. Nobel Prize

      Being Counted (page 74)

      Prof. Martin Chalfie

      Article first published online: 12 DEC 2012 | DOI: 10.1002/anie.201205223

      Collecting laureates: On receiving the Nobel Prize, Martin Chalfie found he was being added to lists. For example, he was the fourth Nobel Laureate his dentist knew. He discusses some of the other lists he has found himself on and explores the serious side of “collecting” Nobel Laureates.

    5. RNA Chemistry

      How a Chemist Looks at RNA (pages 75–78)

      Prof. Thomas R. Cech

      Article first published online: 3 DEC 2012 | DOI: 10.1002/anie.201205427

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      RNA, just another starting material? Nobel Laureate Tom Cech shows that with an education steeped in kinetics, thermodynamics, and molecular structure, and armed with the ability to synthesize molecules, the chemist is ideally suited to investigate RNA.

    6. Asymmetric Catalysis

      Facts are the Enemy of Truth—Reflections on Serendipitous Discovery and Unforeseen Developments in Asymmetric Catalysis (pages 79–92)

      Prof. Dr. Ryoji Noyori

      Article first published online: 3 DEC 2012 | DOI: 10.1002/anie.201205537

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      The art of science: The field of asymmetric catalysis has evolved over nearly 50 years from a seemingly insignificant investigation into a copper-catalyzed cyclopropanation reaction to applications that bring global benefits. In this Essay, Nobel Laureate Ryoji Noyori outlines the history of asymmetric catalysis using a chiral organometallic complex, and explains how scientific discovery requires not only talent but also serendipity.

    7. Nanomaterials

      Small but Strong Lessons from Chemistry for Nanoscience (pages 93–103)

      Prof. Roald Hoffmann

      Article first published online: 3 DEC 2012 | DOI: 10.1002/anie.201206678

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      In a different light: In a provocative look at nanoscience, Nobel Laureate Roald Hoffmann considers the structural and electronic perplexities of dimensionality, the consequences of bond severance in nano-object formation, the implications of simple acid-base chemistry for stabilization of nanostructures, and what lessons might be learned from surface science on structural relaxation and reconstruction.

    8. Methanol Economy

      Towards Oil Independence Through Renewable Methanol Chemistry (pages 104–107)

      Prof.Dr. George A. Olah

      Article first published online: 3 DEC 2012 | DOI: 10.1002/anie.201204995

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      Recycling of CO2 into methanol, dimethyl ether (DME), and derived fuels and materials is a feasible approach to address our carbon conundrum. It would free humankind from its dependence on fossil fuel while at the same time help mitigate the problems associated with excessive CO2 emission. The energy needed for this carbon cycle can come from renewable sources (hydro, solar, wind) as well as atomic energy.

    9. Future of Science and Society

      Science for the “Haves” (pages 108–111)

      Prof. Ahmed Zewail and Prof. Maha Zewail

      Article first published online: 3 DEC 2012 | DOI: 10.1002/anie.201206738

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      For centuries, the wisdom of the West of investing in basic science and technology led to its dominance in world politics and economics. Today, this wisdom is being put aside: fundamental research is losing its appeal to funding agencies and as a professional asset for job hunters. This state of affairs could exacerbate a dearth of innovations and lead to a transition of the “haves” into the “have-nots” of the world population. (Engraving: “Early Depiction of a Dutch Telescope” by Adriaen van de Venne, 1624).

    10. University Education

      American Universities at Risk (pages 112–113)

      Prof. Richard N. Zare

      Article first published online: 3 DEC 2012 | DOI: 10.1002/anie.201205709

      Learning to count the costs: What does a university education cost? Why does it cost this much? Who should pay? And what are the consequences if costs outstrip what students can afford? Richard Zare examines the US higher education system and finds a great past is no guarantee of a rosy future.

    11. Spotlight

      Chemistry in India: Unlocking the Potential (pages 114–117)

      Prof. Elangannan Arunan, Dr. Ramasamy Brakaspathy, Prof. Gautam R. Desiraju and Dr. Swaminathan Sivaram

      Article first published online: 3 DEC 2012 | DOI: 10.1002/anie.201206960

      Hidden talents: Chemistry in India is currently ranked as fifth in terms of worldwide research output. G. R. Desiraju et al. discuss the current state of chemistry in India and the historic, social, cultural, and economic factors that influence its growth. They also address the issue of how to unlock the true potential of chemistry in India.

    12. Scientific Best Practice

      The Seven Sins in Academic Behavior in the Natural Sciences (pages 118–122)

      Prof. Dr. Wilfred F. van Gunsteren

      Article first published online: 3 DEC 2012 | DOI: 10.1002/anie.201204076

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      “Seven deadly sins” in modern academic research and publishing can be condensed into a list ranging from poorly described experimental or computational setups to falsification of data. This Essay describes these sins and their ramifications, and serves as a code of best practice for researchers in their quest for scientific truth. Picture: Detail from “The Seven Deadly Sins” by Hieronymus Bosch.

    13. Natural Product Synthesis

      Natural Product Synthesis: Changes over Time (pages 123–130)

      Prof. Dr. Reinhard W. Hoffmann

      Article first published online: 3 DEC 2012 | DOI: 10.1002/anie.201203319

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      For almost 200 years, the synthesis of natural products has been practiced. In this time span, not only the target structures have become increasingly more complex (see two examples from the 1970s), the objectives of natural product synthesis have also changed. Likewise, the standards and criteria for the conduction of natural product synthesis have changed. It is these changes that form the subject of this Essay.

    14. Total Synthesis

      The Emergence of the Structure of the Molecule and the Art of Its Synthesis (pages 131–146)

      Prof. Dr. K. C. Nicolaou

      Article first published online: 3 DEC 2012 | DOI: 10.1002/anie.201207081

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      At the core of chemistry lie the structure of the molecule, the art of its synthesis, and the design of function within it. This Essay traces the understanding of the structure of the molecule, the emergence of organic synthesis, and the art of total synthesis from the 19th century to the present day.

    15. From Chemicals to Chemistry

      New Directions in Industrial Chemical Research as Reflected in Angewandte Chemie (pages 147–154)

      Dr. Andreas Kreimeyer

      Article first published online: 6 DEC 2012 | DOI: 10.1002/anie.201208912

      With its growing complexity and cross-linking of its disciplines, the profile of chemical sciences has changed radically over the last few decades: whereas individual molecules were originally the focus, emphasis has now shifted to intelligent chemistry in the form of holistic systems. How academia and industry find sustainable answers depends not least on the quality of the scientific dialogue, as documented and championed by Angewandte Chemie for 125 years.

    16. Origins of Life

      The Origins of Life: Old Problems, New Chemistries (pages 155–162)

      Prof. Dr. Stephen Mann

      Article first published online: 3 DEC 2012 | DOI: 10.1002/anie.201204968

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      Synthetic life: The origin of life on the early Earth, and the ex novo transition of non-living matter to artificial living systems are deep scientific challenges that provide a context for the development of new chemistries with unknown technological consequences. This Essay attempts to re-frame some of the epistemological difficulties associated with these questions into an integrative framework of proto-life science. Chemistry is at the heart of this endeavour.

    17. Glasses

      Towards a Molecular View of Glass Heterogeneity (pages 163–166)

      Prof. Michel Orrit

      Article first published online: 3 DEC 2012 | DOI: 10.1002/anie.201205231

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      Curds show the whey: The vexing problem of the glass transition has been frustrating experimentalists and theorists for more than a century. One difficulty is in quantifying the structure of an inhomogeneous system, even when “curds” and “whey” are made out of the same material. To explore the rich space of configurations of these complex systems, a new generation of experiments with a range of different local probes is needed.

    18. Metal Oxides

      Impact of Crystal Chemistry upon the Physics of Strongly Correlated Electrons in Oxides (pages 167–175)

      Prof. Bernard Raveau

      Article first published online: 3 DEC 2012 | DOI: 10.1002/anie.201204884

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      Transition-metal oxides have been widely studied for understanding the physics of strongly electron-correlated systems. The crucial role of crystal chemistry for the discovery of three families: the high Tc superconducting cuprates, the colossal magnetoresistance manganates, the thermoelectric, and multiferroic cobaltates, is explored.

    19. Carbon Complexes

      Coordination Chemistry at Carbon: The Patchwork Family Comprising (Ph3P)2C, (Ph3P)C(C2H4), and (C2H4)2C (pages 176–186)

      Prof. Hubert Schmidbaur and Dr. Annette Schier

      Article first published online: 3 DEC 2012 | DOI: 10.1002/anie.201205294

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      The revitalized concept of “coordination at carbon” allows relationships between seemingly unrelated families of carbon-centered compounds to be discovered generating fascinating patchwork families of compounds. It is shown how olefins and cyclopropanes can be regarded as donors for carbon acceptors C1, C2, and C3. Through this approach, hydrocarbons such as spiropentane and dicyclopropylidene are found to be counterparts of the bis-ylidic carbodiphosphoranes and the corresponding mixed mono-ylidic systems.

    20. Champagne

      The Fizzling Foam of Champagne (pages 187–190)

      Dr. Michèle Vignes-Adler

      Article first published online: 3 DEC 2012 | DOI: 10.1002/anie.201207299

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      Bubble, bubble: Why does champagne bubble? Why does it stop bubbling? Does the vintage affect its fizz? Chemistry can answer these and other questions about the wine that is so often associated with celebrations and anniversaries.

  9. Minireviews

    1. Top of page
    2. Cover Pictures
    3. Editorials
    4. Graphical Abstract
    5. Flashback
    6. News
    7. Miscellaneous
    8. Interview
    9. Essays
    10. Minireviews
    11. Reviews
    12. Communications
    1. Ubiquitination

      The Lysine48-Based Polyubiquitin Chain Proteasomal Signal: Not a Single Child Anymore (pages 192–198)

      Yelena Kravtsova-Ivantsiv, Thomas Sommer and Aaron Ciechanover

      Article first published online: 4 NOV 2012 | DOI: 10.1002/anie.201205656

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      Since its discovery more than three decades ago, the proteasomal targeting signal was accepted to be a polyubiquitin chain, in which the ubiquitin moieties are linked to one another through lysine 48 (K48, see picture), and which is anchored to one of the internal lysines of the target substrate. However, recent evidence suggests that the signal for proteasomal targeting is far more diverse and complex.

    2. Polymer Synthesis

      External Regulation of Controlled Polymerizations (pages 199–210)

      Frank A. Leibfarth, Kaila M. Mattson, Dr. Brett P. Fors, Dr. Hazel A. Collins and Prof. Dr. Craig J. Hawker

      Article first published online: 20 NOV 2012 | DOI: 10.1002/anie.201206476

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      So much control: Modern polymer chemists have the tools to create materials of almost infinite variety and architecture. The next frontier in controlled polymerization is external regulation, allowing the reactions to be turned “on” and turned “off” on demand. This temporal control may find significant utility in areas ranging from microelectronics to biomaterials.

    3. Hydrothiolation of Unsaturated Bonds

      The Emergence of Transition-Metal-Mediated Hydrothiolation of Unsaturated Carbon–Carbon Bonds: A Mechanistic Outlook (pages 211–222)

      Dr. Ricardo Castarlenas, Dr. Andrea Di Giuseppe, Prof. Jesús J. Pérez-Torrente and Prof. Luis A. Oro

      Article first published online: 4 DEC 2012 | DOI: 10.1002/anie.201205468

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      Juggling act: In recent years transition-metal-based catalysts for the control of the regio- and stereoselectivity in hydrothiolation of unsaturated carbon–carbon bonds have been developed. The complex mechanistic background of this transformation (see picture) is described to aid the design of better catalysts.

    4. Synthetic Methods

      You have free access to this content
      Asymmetric Catalysis with Bis(hydroxyphenyl)diamides/Rare-Earth Metal Complexes (pages 223–234)

      Dr. Naoya Kumagai and Prof. Dr. Masakatsu Shibasaki

      Article first published online: 23 NOV 2012 | DOI: 10.1002/anie.201206582

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      Cooperation: A series of asymmetric catalysts composed of conformationally flexible amide-based chiral ligands and rare-earth metals was developed for proton-transfer catalysis. The cooperative function of hydrogen bonding and metal coordination resulted in intriguing substrate specificity and stereocontrol, and the dynamic nature of the catalysts led to a switch of their function.

  10. Reviews

    1. Top of page
    2. Cover Pictures
    3. Editorials
    4. Graphical Abstract
    5. Flashback
    6. News
    7. Miscellaneous
    8. Interview
    9. Essays
    10. Minireviews
    11. Reviews
    12. Communications
    1. Since the Time of Robert Hooke

      Movies of Molecular Motions and Reactions: The Single-Molecule, Real-Time Transmission Electron Microscope Imaging Technique (pages 236–252)

      Prof. Eiichi Nakamura

      Article first published online: 17 DEC 2012 | DOI: 10.1002/anie.201205693

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      Robert Hooke was proud of watching a flea with his microscope, and now we can watch movies of the motions and reactions of single organic molecules through atomic-resolution transmission electron microscopy (see picture of a van der Waals molecular complex). Although the movie quality is still like that of the time of Edison, the new imaging method has great promise in research and the teaching of molecular science.

    2. Medicinal Chemistry

      N-Methylation of Peptides and Proteins: An Important Element for Modulating Biological Functions (pages 254–269)

      Dr. Jayanta Chatterjee, Florian Rechenmacher and Prof. Horst Kessler

      Article first published online: 19 NOV 2012 | DOI: 10.1002/anie.201205674

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      The peptide bond and Me: A large number of N-methylated peptides and proteins are found in nature; however, it is surprising that N-methylation of the peptide bonds is not used as a regulative element in proteins. On the other hand, many N-methylated peptides in natural bioactive peptides exhibit drug-like properties. Hence, N-methylation is a powerful tool in medicinal chemistry to modulate activity, selectivity, and bioavailability of peptidic drugs.

    3. Organometallic Chemistry

      Synthesis and Application of Water-Soluble NHC Transition-Metal Complexes (pages 270–289)

      Lars-Arne Schaper, Sebastian J. Hock, Wolfgang A. Herrmann and Fritz E. Kühn

      Article first published online: 9 NOV 2012 | DOI: 10.1002/anie.201205119

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      Water lot of catalysts: Transition-metals bound to water-soluble N-heterocyclic carbene (NHC) ligands often have excellent catalytic properties and can be used in water. The synthetic paths towards such complexes are examined and their catalytic applications discussed. Areas with great potential for future research are also presented.

    4. Pyrotechnics

      Strobes: Pyrotechnic Compositions That Show a Curious Oscillatory Combustion (pages 290–303)

      Justine M. L. Corbel, Dr. Joost N. J. van Lingen, Dr. John F. Zevenbergen, Dr. Onno L. J. Gijzeman and Prof. Dr. Andries Meijerink

      Article first published online: 19 DEC 2012 | DOI: 10.1002/anie.201207398

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      Flash dance: Strobes are pyrotechnic compositions which burn in an oscillatory manner: a dark and a flash phase alternate periodically (see scheme). They have various applications in the fireworks industry and also as flares. However, their mechanism is not well understood. A few better understood oscillatory systems (Belousov–Zhabotinsky reactions, cool flames, self-propagating high-temperature synthesis) are compared to observations made on strobe mixtures.

  11. Communications

    1. Top of page
    2. Cover Pictures
    3. Editorials
    4. Graphical Abstract
    5. Flashback
    6. News
    7. Miscellaneous
    8. Interview
    9. Essays
    10. Minireviews
    11. Reviews
    12. Communications
    1. Self-Assembly

      Photocontrol over Cooperative Porphyrin Self-Assembly with Phenylazopyridine Ligands (pages 304–309)

      Dr. Takashi Hirose, Dr. Floris Helmich and Prof. Dr. E. W. Meijer

      Article first published online: 23 SEP 2012 | DOI: 10.1002/anie.201205085

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      The cooperative self-assembly of chiral zinc porphyrins is regulated by a photoresponsive phenylazopyridine ligand (1; see picture). Porphyrin stacks depolymerize into dimers upon axial ligation and the strength of the coordination is regulated by its photoinduced isomerization, which shows more than 95 % conversion ratio for both photostationary states.

    2. Olefin Metathesis

      Concise Syntheses of Insect Pheromones Using Z-Selective Cross Metathesis (pages 310–314)

      Myles B. Herbert, Dr. Vanessa M. Marx, Dr. Richard L. Pederson and Dr. Robert H. Grubbs

      Article first published online: 10 OCT 2012 | DOI: 10.1002/anie.201206079

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      Very short synthetic routes to nine cis-olefin-containing pheromones containing a variety of functionality, including an unconjugated (E,Z) diene, are reported (see scheme). These lepidopteran pheromones are used extensively for pest control, and were easily prepared using ruthenium-based Z-selective cross metathesis, highlighting the advantages of this method over less efficient ways to form Z olefins.

    3. Heterofullerenes

      Formation of Heterofullerenes by Direct Exposure of C60 to Boron Vapor (pages 315–319)

      Paul W. Dunk, Dr. Antonio Rodríguez-Fortea, Dr. Nathan K. Kaiser, Prof. Hisanori Shinohara, Prof. Josep M. Poblet and Prof. Harold W. Kroto

      Article first published online: 6 DEC 2012 | DOI: 10.1002/anie.201208244

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      Introducing boron: Heterofullerenes that incorporate boron have been scarcely studied because a formation route from C60 is not known. It is now reported that C59B, an electronically closed-shell species, is formed directly from pristine C60 in the gas-phase by facile atom exchange reactions.

    4. Surface Science

      Charge Delocalization Induces Reaction in Molecular Chains at a Surface (pages 320–324)

      Dr. Zhanyu Ning and Prof. John C. Polanyi

      Article first published online: 23 NOV 2012 | DOI: 10.1002/anie.201207819

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      The molecular dynamics of an electron-induced reaction in a self-assembled molecular chain of four dimethyldisulfide molecules on Au(111) are studied (see figure, S[BOND]S bonds highlighted). Charge delocalization weakens all the S[BOND]S bonds causing a concurrent reaction along the entire chain (middle). All the original S[BOND]S bonds are broken and new S[BOND]S bonds form giving three altered S[BOND]S bonds and two chemisorbed thiyl radicals (bottom).

    5. Live Imaging of Thrombin

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      Ratiometric Activatable Cell-Penetrating Peptides Provide Rapid In Vivo Readout of Thrombin Activation (pages 325–330)

      Dr. Michael Whitney, Dr. Elamprakash N. Savariar, Dr. Beth Friedman, Rachel A. Levin, Dr. Jessica L. Crisp, Heather L. Glasgow, Dr. Roy Lefkowitz, Dr. Stephen R. Adams, Paul Steinbach, Nadia Nashi, Dr. Quyen T. Nguyen and Dr. Roger Y. Tsien

      Article first published online: 18 OCT 2012 | DOI: 10.1002/anie.201205721

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      In real time: Thrombin activation in vivo can be imaged in real time with ratiometric activatable cell penetrating peptides (RACPPs). RACPPs are designed to combine 1) dual-emission ratioing, 2) far red to infrared wavelengths for in vivo mammalian imaging, and 3) cleavage-dependent spatial localization. The most advanced RACPP uses norleucine (Nle)-TPRSFL as a linker that increases sensitivity to thrombin by about 90-fold (see figure).

    6. Structure Elucidation

      β2-Adrenergic Receptor Solutions for Structural Biology Analyzed with Microscale NMR Diffusion Measurements (pages 331–335)

      Dr. Reto Horst, Dr. Pawel Stanczak, Prof. Dr. Raymond C. Stevens and Prof. Dr. Kurt Wüthrich

      Article first published online: 24 OCT 2012 | DOI: 10.1002/anie.201205474

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      Microcoil NMR measurements were performed to determine the final composition of solutions of the β2-adrenergic receptor (β2AR) reconstituted with a detergent and to study the hydrodynamic properties of the detergent micelles containing β2AR (see picture). Standards are established for the reproducible preparation of G-protein-coupled receptor solutions for crystallization trials and solution NMR studies.

    7. Protein Engineering

      Engineering Cell Surfaces for Orthogonal Selectability (pages 336–340)

      Yingjie Peng, Dae Hee Kim, Teresa M. Jones, Diana I. Ruiz and Richard A. Lerner

      Article first published online: 12 DEC 2012 | DOI: 10.1002/anie.201201844

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      Vectors have been constructed that express the chitin-binding domain (ChBD) on eukaryotic cell surfaces. The ChBD is linked to enhanced green fluorescent protein (EGFP) through a protein that spans the plasma membrane (see picture). This binding functionality does not have a counterpart in eukaryotes, thereby endowing the modified cell surface with a property that is orthogonal to animal cells.

    8. Metal–Organic Frameworks

      Binary Janus Porous Coordination Polymer Coatings for Sensor Devices with Tunable Analyte Affinity (pages 341–345)

      Dr. Mikhail Meilikhov, Dr. Shuhei Furukawa, Kenji Hirai, Prof. Roland A. Fischer and Prof. Susumu Kitagawa

      Article first published online: 4 NOV 2012 | DOI: 10.1002/anie.201207320

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      Janus MOF: Thin films consisting of non-centrosymmetric heterostructured metal–organic frameworks (MOFs) were fabricated directly on quartz-crystal microbalance (QCM) sensor devices. Depending on the spatial configuration of two frameworks, the thin MOF films could tune the affinity for analytes, thus giving high selectivity to the QCM sensors.

    9. IR Spectroscopy

      Tunneling and Tunneling Switching Dynamics in Phenol and Its Isotopomers from High-Resolution FTIR Spectroscopy with Synchrotron Radiation (pages 346–349)

      Dr. Sieghard Albert, Dr. Philippe Lerch, Robert Prentner and Prof. Martin Quack

      Article first published online: 6 DEC 2012 | DOI: 10.1002/anie.201205990

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      Tunneling and chemical reactions by tunneling switching are reported for phenol and ortho-deuterophenol on the basis of high-resolution FTIR spectroscopy. Tunneling splittings are measured for the torsional motion in the ground and several vibrationally excited states of phenol. Tunneling times range from 10 ns to 1 ps, depending on excitation. For more-highly excited torsional levels in ortho-deuterophenol, delocalization and chemical reaction by tunneling switching is found.

    10. Magnetic Anisotropy

      Magnetic Anisotropy and Spin-Parity Effect Along the Series of Lanthanide Complexes with DOTA (pages 350–354)

      Dr. Marie-Emmanuelle Boulon, Giuseppe Cucinotta, Dr. Javier Luzon, Chiara Degl'Innocenti, Mauro Perfetti, Dr. Kevin Bernot, Dr. Guillaume Calvez, Prof. Dr. Andrea Caneschi and Prof. Dr. Roberta Sessoli

      Article first published online: 3 DEC 2012 | DOI: 10.1002/anie.201205938

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      Spotting trends: Upon going from TbIII to YbIII centers in the complexes of the DOTA4− ligand, a reorientation of the easy axis of magnetization from perpendicular to parallel to the Ln[BOND]O bond of the apical water molecule is experimentally observed and theoretically predicted (see picture; SMM=single-molecule magnet). Only ions with an odd number of electrons show slow relaxation of the magnetization.

    11. Hydrogenation

      A Functional-Group-Tolerant Catalytic trans Hydrogenation of Alkynes (pages 355–360)

      Karin Radkowski, Dr. Basker Sundararaju and Prof. Alois Fürstner

      Article first published online: 10 SEP 2012 | DOI: 10.1002/anie.201205946

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      Against the rules: During the hundred years following Sabatier's groundbreaking work on catalytic hydrogenation, syn delivery of the H atoms to the π system of a substrate remained the governing stereochemical rule. An exception has now be found with the use of cationic [Cp*Ru] templates, which accounts for the first practical, functional-group-tolerant, broadly applicable and highly E-selective semihydrogenation method for alkynes (see scheme).

    12. Protein Structures

      Intrinsically Disordered p53 and Its Complexes Populate Compact Conformations in the Gas Phase (pages 361–365)

      Dr. Kevin Pagel, Dr. Eviatar Natan, Zoe Hall, Prof. Dr. Alan R. Fersht and Prof. Dr. Carol V. Robinson

      Article first published online: 9 JUL 2012 | DOI: 10.1002/anie.201203047

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      Spontaneous shrinking: The intrinsically disordered tumor suppressor protein p53 was analyzed by using a combination of ion mobility mass spectrometry and molecular dynamics simulations. Structured p53 subdomains retain their overall topology upon transfer into the gas phase. When intrinsically disordered segments are introduced into the protein sequence, however, the complex spontaneously collapses in the gas phase to a compact conformation.

    13. Virus Detection

      Chemical Probes for Drug-Resistance Assessment by Binding Competition (RABC): Oseltamivir Susceptibility Evaluation (pages 366–370)

      Dr. Ting-Jen R. Cheng, Shi-Yun Wang, Dr. Wen-Hsien Wen, Dr. Ching-Yao Su, Mengi Lin, Wen-I Huang, Dr. Ming-Tsan Liu, Dr. Ho-Sheng Wu, Nung-Sen Wang, Chung-Kai Cheng, Chun-Lin Chen, Dr. Chien-Tai Ren, Dr. Chung-Yi Wu, Prof. Jim-Min Fang, Dr. Yih-Shyun E. Cheng and Prof. Chi-Huey Wong

      Article first published online: 13 NOV 2012 | DOI: 10.1002/anie.201204062

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      The wizard of OS (resistance): The binding difference of neuraminidase inhibitors (zanamivir versus oseltamivir (OS)) was used to establish an assay to identify the influenza subtypes that are resistant to OS but still sensitive to zanamivir (see scheme). This assay used a zanamivir-biotin conjugate to determine the OS susceptibility of a wide range of influenza viruses and over 200 clinical isolates.

    14. Non-Precious-Metal Catalyst

      Iron Encapsulated within Pod-like Carbon Nanotubes for Oxygen Reduction Reaction (pages 371–375)

      Dr. Dehui Deng, Dr. Liang Yu, Xiaoqi Chen, Dr. Guoxiong Wang, Li Jin, Prof. Xiulian Pan, Jiao Deng, Prof. Gongquan Sun and Prof. Xinhe Bao

      Article first published online: 6 DEC 2012 | DOI: 10.1002/anie.201204958

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      Chainmail for catalysts: A catalyst with iron nanoparticles confined inside pea-pod-like carbon nanotubes (see picture) exhibits a high activity and remarkable stability as a cathode catalyst in polymer electrolyte membrane fuel cells (PEMFC), even in presence of SO2. The approach offers a new route to electro- and heterogeneous catalysts for harsh conditions.

    15. Solar Cells

      The Molecular Engineering of Organic Sensitizers for Solar-Cell Applications (pages 376–380)

      Dr. Jared H. Delcamp, Dr. Aswani Yella, Dr. Thomas W. Holcombe, Dr. Mohammad K. Nazeeruddin and Prof. Michael Grätzel

      Article first published online: 24 AUG 2012 | DOI: 10.1002/anie.201205007

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      Positive to the core: Ullazine has both strong electron-donating and weak accepting properties. This heterocycle was incorporated into sensitizers for dye-sensitized solar cells (DSCs). One of these sensitizers demonstrated strong light absorption across the UV/Vis region. The corresponding DSC device has a maximum IPCE of 95 % at 520 nm, with a power conversion efficiency of 8.4 %.

    16. Kinetic Covalent Chemistry

      Quantitative Emergence of Hetero[4]rotaxanes by Template-Directed Click Chemistry (pages 381–387)

      Dr. Chenfeng Ke, Dr. Ronald A. Smaldone, Dr. Takashi Kikuchi, Hao Li, Prof. Anthony P. Davis and Prof. J. Fraser Stoddart

      Article first published online: 13 SEP 2012 | DOI: 10.1002/anie.201205087

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      In one fell swoop, polyrotaxanes comprising up to 64 rings can be synthesized as a result of cucurbit[6]uril-templated 1,3-dipolar azide-alkyne cycloadditions accelerated in the presence of cyclodextrins as a consequence of self-sorting and positive cooperativity, brought about by hydrogen bonding. Mixing six components (see picture) in one pot affords a hetero[4]rotaxane in one minute in quantitative yield.

    17. Biomineralization

      Guanine-Based Photonic Crystals in Fish Scales Form from an Amorphous Precursor (pages 388–391)

      Dvir Gur, Dr. Yael Politi, Prof. Berta Sivan, Prof. Peter Fratzl, Prof. Steve Weiner and Prof. Lia Addadi

      Article first published online: 5 SEP 2012 | DOI: 10.1002/anie.201205336

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      Starting from disorder: Anhydrous guanine crystals compose the photonic arrays responsible for the skin and scale iridescence found in Japanese Koi fish. These guanine crystals were found to form in intracellular vesicles (see picture) through an amorphous precursor phase. A combined cryo-SEM and synchrotron radiation X-ray diffraction study showed the evolution of the crystals in great detail.

    18. Electrocatalysis

      The Role of Catalysts and Peroxide Oxidation in Lithium–Oxygen Batteries (pages 392–396)

      Robert Black, Jin-Hyon Lee, Brian Adams, Prof. Charles A. Mims and Prof. Linda F. Nazar

      Article first published online: 19 NOV 2012 | DOI: 10.1002/anie.201205354

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      A promotor for lithium batteries: Nanocrystalline cobalt(II,III) oxide supported on graphene enhances the transport kinetics for both oxygen reduction and oxygen evolution in the lithium–oxygen cell. On cycling the lithium–oxygen cell, the effect of the promoter is, however, eventually overwhelmed by side reactions in the cell, such as, the deposition of carbonates (see picture).

    19. Supramolecular Device

      Stimuli-Responsive Folding and Unfolding of a Polymer Bearing Multiple Cerium(IV) Bis(porphyrinate) Joints: Mechano-imitation of the Action of a Folding Ruler (pages 397–400)

      Masayuki Shibata, Satoshi Tanaka, Dr. Tomohiro Ikeda, Prof. Seiji Shinkai, Prof. Kenji Kaneko, Dr. Soichiro Ogi and Prof. Dr. Masayuki Takeuchi

      Article first published online: 14 NOV 2012 | DOI: 10.1002/anie.201205584

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      A pivotal guest role: A new porphyrin polymer, poly(PorZn⋅DD) (see picture, pink/purple), composed of a porphyrinatozinc and a porphyrin double-decker complex as a repeating unit was synthesized. In poly(PorZn⋅DD), porphyrinatozinc complexes recognize a divalent amine (tan/red) to induce an intramolecular pivoting motion through the rotation of porphyrin double-decker complexes and the polymer undergoes shortening and compaction.

    20. Defects in Metal–Organic Frameworks

      Three-Dimensional Visualization of Defects Formed during the Synthesis of Metal–Organic Frameworks: A Fluorescence Microscopy Study (pages 401–405)

      Dr. Rob Ameloot, Frederik Vermoortele, Prof. Johan Hofkens, Prof. Frans C. De Schryver, Prof. Dirk E. De Vos and Prof. Maarten B. J. Roeffaers

      Article first published online: 9 NOV 2012 | DOI: 10.1002/anie.201205627

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      Imperfections in the spotlight: Fluorescence microscopy was used to detect defects in metal–organic frameworks formed during synthesis. In contrast to currently available techniques, confocal fluorescence microscopy offers the advantage of three-dimensional imaging at the single-crystal level combined with the sensitivity required to study the start of defect formation.

    21. pH Nanosensor

      Fluorescent pH-Sensitive Nanoparticles in an Agarose Matrix for Imaging of Bacterial Growth and Metabolism (pages 406–409)

      Dr. Xu-dong Wang, Dr. Robert J. Meier and Prof. Otto S. Wolfbeis

      Article first published online: 9 OCT 2012 | DOI: 10.1002/anie.201205715

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      Living color: Fluorescent pH-sensitive nanoparticles 12 nm in diameter were prepared and incorporated into agarose gel in a Petri dish to image pH changes during bacterial growth and metabolism (see picture).

    22. Biology-Oriented Synthesis

      A Natural Product Inspired Tetrahydropyran Collection Yields Mitosis Modulators that Synergistically Target CSE1L and Tubulin (pages 410–414)

      Dr. Tobias Voigt, Dr. Claas Gerding-Reimers, M. Sc. Tuyen Thi Ngoc Tran, M. Sc. Sabrina Bergmann, Dr. Hugo Lachance, Beate Schölermann, Dipl.-Ing. Andreas Brockmeyer, Dr. Petra Janning, Dr. Slava Ziegler and Prof. Dr. Herbert Waldmann

      Article first published online: 18 OCT 2012 | DOI: 10.1002/anie.201205728

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      A Prins cyclization between a polymer-bound aldehyde and a homoallylic alcohol served as the key step in the synthesis of tetrahydropyran derivatives. A phenotypic screen led to the identification of compounds that inhibit mitosis (as seen by the accumulation of round cells with condensed DNA and membrane blebs; see picture). These compounds were termed tubulexins as they target the CSE1L protein and the vinca alkaloid binding site of tubulin.

    23. Molecular Recognition

      Pyrrole-Imidazole Polyamides Distinguish Between Double-Helical DNA and RNA (pages 415–418)

      David M. Chenoweth, Jordan L. Meier and Prof. Peter B. Dervan

      Article first published online: 14 SEP 2012 | DOI: 10.1002/anie.201205775

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      Groove specificity: Pyrrole-imidazole polyamides are well-known for their specific interactions with the minor groove of DNA (see scheme). However, polyamides do not show similar binding to duplex RNA, and a structural rationale for the molecular-level discrimination of nucleic acid duplexes by minor-groove-binding ligands is presented.

    24. Hydrogen Generation

      Photocatalytic Water Reduction with Copper-Based Photosensitizers: A Noble-Metal-Free System (pages 419–423)

      Dr. Shu-Ping Luo, Dr. Esteban Mejía, Aleksej Friedrich, Alexandra Pazidis, Dr. Henrik Junge, Dr. Annette-Enrica Surkus, Dr. Ralf Jackstell, Stefania Denurra, Prof. Dr. Serafino Gladiali, Prof. Dr. Stefan Lochbrunner and Prof. Dr. Matthias Beller

      Article first published online: 9 OCT 2012 | DOI: 10.1002/anie.201205915

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      Of noble descent: A fully noble-metal-free system for the photocatalytic reduction of water at room temperature has been developed. This system consists of CuI complexes as photosensitizers and [Fe3(CO)12] as the water-reduction catalyst. The novel Cu-based photosensitizers are relatively inexpensive, readily available from commercial sources, and stable to ambient conditions, thus making them an attractive alternative to the widely used noble-metal based systems.

    25. Cell-Membrane Imaging

      A Switchable Two-Photon Membrane Tracer Capable of Imaging Membrane-Associated Protein Tyrosine Phosphatase Activities (pages 424–428)

      Dr. Lin Li, Xiaoqin Shen, Prof. Dr. Qing-Hua Xu and Prof. Dr. Shao Q. Yao

      Article first published online: 4 OCT 2012 | DOI: 10.1002/anie.201205940

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      When I look into your cells: A two-photon dye (Flu7) was developed (see scheme), which strongly fluoresces only upon selective binding to the plasma membrane of mammalian cells. Upon addition of a UV- and phosphatase-controlled quencher (Q12), the system exhibits ON/OFF/ON fluorescence switching and can be used to image membrane-associated receptor-like protein tyrosine phosphatase (RPTP) activity.

    26. Tissue Engineering

      Generation of Controllable Gradients in Cell Density (pages 429–432)

      Wenying Liu, Yu Zhang, Prof. Stavros Thomopoulos and Prof. Younan Xia

      Article first published online: 5 SEP 2012 | DOI: 10.1002/anie.201206060

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      Making the grad(ient): A gradient in cell density was generated on a substrate that was inserted into a homogeneous suspension of cells at a specific tilt angle by taking advantage of the gradual change in the number of cells available for sedimentation (see scheme). Reverse gradients were also fabricated on the same substrate using multiple sedimentation procedures.

    27. Computational Photochemistry

      Photoinduced Ultrafast Wolff Rearrangement: A Non-Adiabatic Dynamics Perspective (pages 433–436)

      Dr. Ganglong Cui and Prof. Dr. Walter Thiel

      Article first published online: 4 DEC 2012 | DOI: 10.1002/anie.201207628

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      One reaction, two routes: Full-dimensional non-adiabatic dynamics simulations shed light on the ultrafast photoinduced Wolff rearrangement in an α-diazocarbonyl compound. The trajectories show both concerted asynchronous and stepwise processes leading to the corresponding ketene (see scheme).

    28. Dehydrocoupling

      Paramagnetic Titanium(III) and Zirconium(III) Metallocene Complexes as Precatalysts for the Dehydrocoupling/Dehydrogenation of Amine–Boranes (pages 437–440)

      Dr. Holger Helten, Dr. Barnali Dutta, James R. Vance, Dr. Matthew E. Sloan, Dr. Mairi F. Haddow, Dr. Stephen Sproules, Prof. David Collison, Dr. George R. Whittell, Prof. Guy C. Lloyd-Jones and Prof. Ian Manners

      Article first published online: 29 NOV 2012 | DOI: 10.1002/anie.201207903

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      Complexes of Group 4 metallocenes in the +3 oxidation state and amidoborane or phosphidoborane function as efficient precatalysts for the dehydrocoupling/dehydrogenation of amine–boranes, such as Me2NH⋅BH3 (see scheme). Such TiIII–amidoborane complexes are generated in [Cp2Ti]-catalyzed amine–borane dehydrocoupling reactions, for which diamagnetic MII and MIV species have been previously postulated as precatalysts and intermediates.

    29. Synthetic Methods

      Enantioselective Decarboxylative Amination: Synthesis of Axially Chiral Allenyl Amines (pages 441–445)

      Baoqiang Wan and Prof. Dr. Shengming Ma

      Article first published online: 7 SEP 2012 | DOI: 10.1002/anie.201204796

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      Getting axed: Synthesis of the title amines, bearing functionality (R1 and R2), involves the enantioselective palladium-catalyzed decarboxylation of allenyl N-tosylcarbamates. The reaction proceeds smoothly using both the chiral ligands (S)- and (R)-DTBM-Segphos (1) to afford the allenyl amines in good yields and with high enantioseletivities.

    30. Dendrimers

      Dendritic Luminescent Gold(III) Complexes for Highly Efficient Solution-Processable Organic Light-Emitting Devices (pages 446–449)

      Man-Chung Tang, Daniel Ping-Kuen Tsang, Dr. Maggie Mei-Yee Chan, Dr. Keith Man-Chung Wong and Prof. Dr. Vivian Wing-Wah Yam

      Article first published online: 7 NOV 2012 | DOI: 10.1002/anie.201206457

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      Emission control: Carbazole-based dendritic alkynylgold(III) complexes have been evaluated as phosphorescent emitters in organic light-emitting devices. The energy as well as the bathochromic shift of the emissions can be tuned effectively through a control of the dendrimer generation (see spectra). The optimized devices show high current and external quantum efficiencies of up to 24.0 cd A−1 and 7.8 %, respectively.

    31. Metalloid Clusters

      Low-Valent Ge2 and Ge4 Species Trapped by N-Heterocyclic Gallylene (pages 450–454)

      Adinarayana Doddi, Dr. Christian Gemel, Manuela Winter, Dr. Roland A Fischer, Catharina Goedecke, Dr. Henry S. Rzepa and Dr. Gernot Frenking

      Article first published online: 21 NOV 2012 | DOI: 10.1002/anie.201204440

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      Much π and no σ: Quantum chemical calculations showed that the Ge atoms of the Ga2Ge2 core in Ge2[Ga(DPP)]2 are not bonded by σ interactions, but rather by a transannular π interaction (see picture). The compound is formed by reduction of (PCy3)⋅GeCl2 with Ga(DDP)/KC8 which also yielded a further product Ge4[Ga(DPP)]2 with a Ge4 tetrahedron (DDP=HC(CMeNC6H3-2,6-iPr2)2).

    32. Compartmentalized Ionic Systems

      Hyperbranched Polymeric Ionic Liquids with Onion-like Topology as Transporters and Compartmentalized Systems (pages 455–458)

      Dr. Fabian Schüler, Benjamin Kerscher, Fabian Beckert, Dr. Ralf Thomann and Prof. Dr. Rolf Mülhaupt

      Article first published online: 4 NOV 2012 | DOI: 10.1002/anie.201205130

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      A new family of hyperbranched polymeric ionic liquids (“hyperILs”) with onion-like topology and facile polarity design were tailored as transporters and compartmentalized systems. Applications include transport and dispersion of water-soluble dyes and functionalized graphene nanosheets from aqueous phase into nonpolar fluids, including polymer melts.

    33. Synthetic Biology

      Reconstitution of Pole-to-Pole Oscillations of Min Proteins in Microengineered Polydimethylsiloxane Compartments (pages 459–462)

      Katja Zieske and Prof. Dr. Petra Schwille

      Article first published online: 26 NOV 2012 | DOI: 10.1002/anie.201207078

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      Cell division in bacteria is highly regulated in time and space. The use of micrometer-sized sample volumes and model membranes allows the pole-to-pole oscillations of spatial regulators for bacterial cell division to be reconstituted in a synthetic minimal system (see schematic picture left as well as the confocal images of Min proteins on lipid membranes in a polydimethylsiloxane microcompartment right).

    34. Alkanes

      The Last Globally Stable Extended Alkane (pages 463–466)

      Dipl.-Chem. Nils O. B. Lüttschwager, Dr. Tobias N. Wassermann, Prof. Dr. Ricardo A. Mata and Prof. Dr. Martin A. Suhm

      Article first published online: 21 AUG 2012 | DOI: 10.1002/anie.201202894

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      Mother of all folding: Cold isolated linear alkanes CnH2n+2 prefer an extended all-trans conformation before cohesive forces between the chain ends induce a folded hairpin structure for longer chains. It is shown by Raman spectroscopy at 100–150 K that the folded structure becomes more stable beyond nC=17 or 18 carbon atoms. High-level quantum-chemical calculations yield nC=17±1 as the critical chain length.

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