Angewandte Chemie International Edition

Cover image for Vol. 51 Issue 47

November 19, 2012

Volume 51, Issue 47

Pages 11641–11903

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Retraction
    6. Corrigenda
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Essay
    13. Minireview
    14. Review
    15. Communications
    1. You have free access to this content
      Cover Picture: Solar-Driven Incorporation of Carbon Dioxide into α-Amino Ketones (Angew. Chem. Int. Ed. 47/2012) (page 11641)

      Dr. Naoki Ishida, Yasuhiro Shimamoto and Prof. Dr. Masahiro Murakami

      Article first published online: 6 NOV 2012 | DOI: 10.1002/anie.201208496

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      Carbon dioxide was incorporated into α-amino ketones through a consecutive process consisting of a solar-energy-harvesting photocyclization reaction and a CO2 incorporation reaction driven by the harvested energy. The single-flask operation described by M. Murakami and co-workers in their Communication on page 11750 ff. produced amino-substituted cyclic carbonates, thereby presenting a simple model of the chemical utilization of solar energy for CO2 incorporation.

    2. You have free access to this content
      Inside Cover: Design of an Active Site towards Optimal Electrocatalysis: Overlayers, Surface Alloys and Near-Surface Alloys of Cu/Pt(111) (Angew. Chem. Int. Ed. 47/2012) (page 11642)

      Dr. Aliaksandr S. Bandarenka, Ana Sofia Varela, Mohammedreza Karamad, Dr. Federico Calle-Vallejo, Dr. Lone Bech, Dr. Francisco J. Perez-Alonso, Dr. Jan Rossmeisl, Dr. Ifan E. L. Stephens and Prof. Ib Chorkendorff

      Article first published online: 9 NOV 2012 | DOI: 10.1002/anie.201208589

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      Positioning of copper atoms in the first two layers of a Pt single crystal changes the reactivity of the surface for CO electro-oxidation. In their Communication on page 11845 ff., I. Chorkendorff et al. visualize this effect using a 3D “volcano plot”. It shows the overpotential, or catalytic activity, for CO electro-oxidation as a function of the binding to CO and OH and that the most active catalyst should not bind too weak or too strong to CO and OH.

    3. You have free access to this content
      Inside Back Cover: Accelerated Carbon[BOND]Carbon Bond-Forming Reactions in Preparative Electrospray (Angew. Chem. Int. Ed. 47/2012) (page 11905)

      Dr. Thomas Müller, Dr. Abraham Badu-Tawiah and Prof. R. Graham Cooks

      Article first published online: 12 OCT 2012 | DOI: 10.1002/anie.201207836

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      Mass spectrometry is a new tool for microscale synthesis. In their Communication on page 11832 ff., T. Müller, A. Badu-Tawiah, and R. G. Cooks show that the carbon–carbon bond-forming Claisen–Schmidt condensation occurs at dramatically increased rates and gives high yields when the reactants are electrosprayed online into a mass spectrometer or offline onto a high-surface-area substrate.

    4. You have free access to this content
      Back Cover: Simple and Scalable Preparation of Highly Active Lewis Acidic Sn-β (Angew. Chem. Int. Ed. 47/2012) (page 11906)

      Dr. Ceri Hammond, Sabrina Conrad and Prof. Dr. Ive Hermans

      Article first published online: 17 OCT 2012 | DOI: 10.1002/anie.201208116

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      The heterogeneous catalyst Sn-β is currently prepared in a complicated hydrothermal synthesis, which has several hurdles that prevent its industrial implementation. In their Communication on page 11736 ff., I. Hermans and co-workers report a convenient preparation of Sn-β by solid-state ion exchange. It requires much less time and synthetic skill, and the product has more favorable catalytic properties, giving space–time yields over one order of magnitude higher than previously observed.

  2. Editorial

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Retraction
    6. Corrigenda
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Essay
    13. Minireview
    14. Review
    15. Communications
    1. You have free access to this content
      Defragmenting Catalysis (pages 11644–11645)

      Bruce C. Gates and Tobin J. Marks

      Article first published online: 14 NOV 2012 | DOI: 10.1002/anie.201207037

  3. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Retraction
    6. Corrigenda
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Essay
    13. Minireview
    14. Review
    15. Communications
  4. Retraction

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Retraction
    6. Corrigenda
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Essay
    13. Minireview
    14. Review
    15. Communications
    1. You have free access to this content
  5. Corrigenda

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Retraction
    6. Corrigenda
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Essay
    13. Minireview
    14. Review
    15. Communications
    1. You have free access to this content
      Corrigendum: Tumor-Homing Poly-siRNA/Glycol Chitosan Self-Cross-Linked Nanoparticles for Systemic siRNA Delivery in Cancer Treatment (page 11661)

      So Jin Lee, Dr. Myung Sook Huh, Seung Young Lee, Solki Min, Dr. Seulki Lee, Dr. Heebeom Koo, Dr. Jun-Uk Chu, Dr. Kyung Eun Lee, Dr. Hyesung Jeon, Dr. Yongseok Choi, Dr. Kuiwon Choi, Dr. Youngro Byun, Dr. Seo Young Jeong, Dr. Kinam Park, Dr. Kwangmeyung Kim and Dr. Ick Chan Kwon

      Article first published online: 14 NOV 2012 | DOI: 10.1002/anie.201207703

      This article corrects:
    2. You have free access to this content
      Corrigendum: The ortho and meta Magnesiation of Functionalized Anilines and Amino-Substituted Pyridines and Pyrazines at Room Temperature (page 11662)

      M. Sc. Gabriel Monzón, Dr. Ilaria Tirotta and Prof. Dr. Paul Knochel

      Article first published online: 14 NOV 2012 | DOI: 10.1002/anie.201208183

      This article corrects:
  6. News

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Retraction
    6. Corrigenda
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Essay
    13. Minireview
    14. Review
    15. Communications
  7. Author Profile

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Retraction
    6. Corrigenda
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Essay
    13. Minireview
    14. Review
    15. Communications
    1. Holger Braunschweig (pages 11670–11671)

      Article first published online: 27 JUN 2012 | DOI: 10.1002/anie.201203552

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      “I like refereeing because I hope that our publications will also be refereed with the same amount of interest. Without this mutual willingness, scientific publication would be impossible. The most significant scientific advance of the last 100 years has been quantum theory and the theory of relativity in terms of furthering knowledge, and computers and the internet in terms of changing our lives …” This and more about Holger Braunschweig can be found on page 11670.

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  8. News

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Retraction
    6. Corrigenda
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Essay
    13. Minireview
    14. Review
    15. Communications
  9. Book Review

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Retraction
    6. Corrigenda
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Essay
    13. Minireview
    14. Review
    15. Communications
    1. Cortison. Geschichte eines Hormons, 1900–1955. By Lea Haller. (page 11673)

      Hartmut Rehwinkel

      Article first published online: 29 OCT 2012 | DOI: 10.1002/anie.201207593

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      Chronos-Verlag, Zurich, 2012. 280 pp., softcover, € 59.00.—ISBN 978-3034011150

  10. Highlights

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Retraction
    6. Corrigenda
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Essay
    13. Minireview
    14. Review
    15. Communications
    1. Water Channels

      Artificial Water Channels (pages 11674–11676)

      Dr. Mihail Barboiu

      Article first published online: 8 OCT 2012 | DOI: 10.1002/anie.201205819

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      Going through the channels: Synthetic scaffolds mimicking natural protein functions have been developed that allow water/proton or only water translocation pathways in bilayer membranes (see picture). The ion-exclusion behaviors of the synthetic systems are based on hydrophobic or dimensional steric effects, while hydrodynamic effects appear to be less important.

    2. meta-Directing Groups

      Directed Functionalization of C[BOND]H Bonds: Now also meta Selective (pages 11677–11679)

      Thanh Truong and Prof. Dr. Olafs Daugulis

      Article first published online: 10 OCT 2012 | DOI: 10.1002/anie.201206568

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      Give a direction: A rationally designed, removable meta-directing group enables the selective, remote functionalization of aromatic substrates (see scheme). The generality of the concept was shown with alkenylation reactions of hydrocinnamic acid derivatives, the selectivities of which were similar to the ones described for benzyl derivatives.

  11. Essay

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Retraction
    6. Corrigenda
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Essay
    13. Minireview
    14. Review
    15. Communications
    1. Drug Discovery

      Challenges for Academic Drug Discovery (pages 11680–11684)

      Prof. William L. Jorgensen

      Article first published online: 24 OCT 2012 | DOI: 10.1002/anie.201204625

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      Modus operandi: There is increased interest and activity in drug discovery at universities and other non-profit organizations. The essay addresses challenges associated with progress in this area. Lead optimization and preclinical testing are identified as key bottlenecks.

  12. Minireview

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Retraction
    6. Corrigenda
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Essay
    13. Minireview
    14. Review
    15. Communications
    1. Natural Product Synthesis

      A Continuum of Progress: Applications of N-Hetereocyclic Carbene Catalysis in Total Synthesis (pages 11686–11698)

      Dr. Javier Izquierdo, Dr. Gerri E. Hutson, Daniel T. Cohen and Prof. Karl A. Scheidt

      Article first published online: 16 OCT 2012 | DOI: 10.1002/anie.201203704

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      A modern touch: The field of N-heterocyclic carbene catalysis has grown rapidly over the last decade. This expansion has generated a wide variety of new asymmetric transformations including benzoin and Stetter reactions as well as the more modern homoenolate equivalent and aroylation coupling reactions, which have been used successfully in total syntheses (see scheme).

  13. Review

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Retraction
    6. Corrigenda
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Essay
    13. Minireview
    14. Review
    15. Communications
    1. Self-Powered Nanosystems

      Nanotechnology-Enabled Energy Harvesting for Self-Powered Micro-/Nanosystems (pages 11700–11721)

      Prof. Zhong Lin Wang and Wenzhuo Wu

      Article first published online: 4 NOV 2012 | DOI: 10.1002/anie.201201656

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      A bumper harvest, albeit on a small scale, is required for micro-/nanosystems (MNSs) to function reliably without an external power source. MNSs that can harvest energy from the environment in which they are used have wide-ranging potential applications in health, environmental, and infrastructure monitoring, as well as networking and defense technologies. This Review explores possibilities for energy harvesting to meet the future demand for MNSs.

  14. Communications

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Retraction
    6. Corrigenda
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Essay
    13. Minireview
    14. Review
    15. Communications
    1. Fullerene Chemistry

      Pentaarylazafullerenes and their Triaryldihydro and Tetraarylmonohydro Precursors (pages 11722–11726)

      Regina Neubauer, Dr. Frank W. Heinemann, Dr. Frank Hampel, Prof. Dr. Yves Rubin and Prof. Dr. Andreas Hirsch

      Article first published online: 5 NOV 2012 | DOI: 10.1002/anie.201206878

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      Give me five! The title compounds were isolated from the acid-catalyzed reaction of a C59N precursor with electron-rich aromatic compounds. Single-crystal X-ray diffraction on two compounds reveals characteristic packing motifs; the triaryldihydro derivative has a pseudo-stacked arrangement (C violet/yellow, N blue, O red, H white).

    2. Carbon Nanotubes

      Statistical Raman Spectroscopy: A Method for the Characterization of Covalently Functionalized Single-Walled Carbon Nanotubes (pages 11727–11730)

      Ferdinand Hof, Sebastian Bosch, Jan M. Englert, Frank Hauke and Prof. Dr. Andreas Hirsch

      Article first published online: 25 OCT 2012 | DOI: 10.1002/anie.201204791

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      A powerful method based on statistical Raman analysis has been developed for the classification of the degree of functionalization, electronic selectivity, and sample homogeneity of functionalized carbon nanotubes (CNTs). The outcome of addition reactions to CNTs can easily be analyzed and quantitated by the determination of three characteristic Raman indices: the Raman defect (RDI), homogeneity (RHI), and selectivity index (RSI).

    3. Hydrogen Storage

      A Self-Contained Regeneration Scheme for Spent Ammonia Borane Based on the Catalytic Hydrodechlorination of BCl3 (pages 11731–11735)

      Christian Reller and Prof. Dr. Florian O. R. L. Mertens

      Article first published online: 24 OCT 2012 | DOI: 10.1002/anie.201201134

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      Recycling: A self-contained procedure for the recycling of BNH-waste, based on the three major steps: polymer break-up, amine supported catalytic hydrodehalogenation of boron halogens, and the base exchange in borane amine adducts, is developed (see picture). Beyond the original task of recycling spent ammonia borane, the process provides a new means to produce borohydride species efficiently, by the direct use of molecular hydrogen.

    4. Zeolites

      Simple and Scalable Preparation of Highly Active Lewis Acidic Sn-β (pages 11736–11739)

      Dr. Ceri Hammond, Sabrina Conrad and Prof. Dr. Ive Hermans

      Article first published online: 8 OCT 2012 | DOI: 10.1002/anie.201206193

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      Tin goes in: The solid Lewis acid Sn-zeolite β is obtained in a simple and scalable procedure (see scheme). A high metal content can be obtained, without undesirable side-effects. The space-time-yields of the resulting catalysis are over one order-of-magnitude larger than those of the state-of-the-art materials for the Baeyer–Villiger oxidation of cyclohexanone and the synthesis of ethyl lactate from the triose dihydroxyacetone.

    5. Functional Nanocomposites

      Biomimetic Oxygen Activation by MoS2/Ta3N5 Nanocomposites for Selective Aerobic Oxidation (pages 11740–11744)

      Dr. Qingsheng Gao, Dr. Cristina Giordano and Prof. Dr. Markus Antonietti

      Article first published online: 15 OCT 2012 | DOI: 10.1002/anie.201206542

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      Learning from nature: The development of an MoS2/Ta3N5 nanocomposite as a catalyst for selective aerobic oxidation by O2 activation was inspired by the nitrogenase enzymes in nature. The superior performance of this biomimetic catalyst, which shows potential for the selective oxidation of multifunctional substrates (see picture), results from the integration of Ta3N5 and MoS2 at the nanoscale and the synergistic enhancement of their activity.

    6. Magnetic Materials

      A Genuine Two-Dimensional Ising Ferromagnet with Magnetically Driven Re-entrant Transition (pages 11745–11749)

      Dr. Houria Kabbour, Rénald David, Dr. Alain Pautrat, Dr. Hyun-Joo Koo, Prof. Myung-Hwan Whangbo, Dr. Gilles André and Dr. Olivier Mentré

      Article first published online: 19 OCT 2012 | DOI: 10.1002/anie.201205843

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      BaFe2(PO4)2 consists of honeycomb layers containing high-spin d6 Fe2+ ions. It is the first genuine two-dimensional oxide Ising ferromagnet (FM) with uniaxial magnetism parallel to the crystallographic three-fold axis. BaFe2(PO4)2 undergoes a re-entrant structural transition between 170 K and its FM critical temperature (65.5 K) owing to competition between the uniaxial magnetism and Jahn–Teller instability.

    7. Solar Energy Utilization

      Solar-Driven Incorporation of Carbon Dioxide into α-Amino Ketones (pages 11750–11752)

      Dr. Naoki Ishida, Yasuhiro Shimamoto and Prof. Dr. Masahiro Murakami

      Article first published online: 6 NOV 2012 | DOI: 10.1002/anie.201206166

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      Power of the sun: Carbon dioxide was incorporated into α-amino ketones through a consecutive process consisting of a solar-energy-harvesting photocyclization reaction and a nucleophilic CO2 incorporation reaction. The single-flask operation produced amino-substituted cyclic carbonates, thereby presenting a simple model of the chemical utilization of solar energy for CO2 incorporation. R=sulfonyl group.

    8. Cluster Compounds

      Catalytic Hydrogen/Deuterium Exchange of Unactivated Carbon–Hydrogen Bonds by a Pentanuclear Electron-Deficient Nickel Hydride Cluster (pages 11753–11756)

      Dr. Robert Beck, Manar Shoshani and Prof. Dr. Samuel A. Johnson

      Article first published online: 19 OCT 2012 | DOI: 10.1002/anie.201205943

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      Exchangeable: The cluster [(iPr3P)Ni]5H6 (1; see picture) was prepared by the addition of hydrogen gas to the dinuclear dinitrogen complex [(iPr3P)2Ni]2(μ-N2). This unprecedented first-row transition-metal cluster is electron deficient and highly reactive. Complex 1 undergoes hydrogen/deuterium exchange in deuterated benzene at room-temperature with a half-life of 27 minutes.

    9. Metal Nanodendrites

      Manipulating Local Ligand Environments for the Controlled Nucleation of Metal Nanoparticles and their Assembly into Nanodendrites (pages 11757–11761)

      Nancy Ortiz and Dr. Sara E. Skrabalak

      Article first published online: 15 OCT 2012 | DOI: 10.1002/anie.201205956

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      Branching out: A simple two-component system comprised of a Pd precursor and oleylamine has shown that both the rate of nanoparticle nucleation and growth can be controlled by manipulating the local ligand environment, thus allowing the facile selection of either Pd nanodendrites or monodisperse Pd nanoparticles (see TEM images). This ligand-controlled approach connects fundamental principles of coordination chemistry to nanostructure design.

    10. Natural Product Synthesis

      Nature-Inspired Stereospecific Total Synthesis of P-(+)-Dispegatrine and Four Other Monomeric Sarpagine Indole Alkaloids (pages 11762–11765)

      Dr. Chitra R. Edwankar, Dr. Rahul V. Edwankar, Dr. Jeffrey R. Deschamps and Prof. Dr. James M. Cook

      Article first published online: 16 OCT 2012 | DOI: 10.1002/anie.201206015

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      All five: The first total synthesis of the C2-symmetric indole alkaloid 1 involved a late-stage thallium(III) acetate-mediated intermolecular oxidative coupling to construct the C9[BOND]C9′ bond with complete regio- and stereocontrol. The formation of a single atropodiastereomer in this critical step arises from internal asymmetric induction. The first total synthesis of four other monomeric sarpagine indole alkaloids is also described.

    11. NMR Spectroscopy

      Rapid Natural-Abundance 2D 13C–13C Correlation Spectroscopy Using Dynamic Nuclear Polarization Enhanced Solid-State NMR and Matrix-Free Sample Preparation (pages 11766–11769)

      Dr. Hiroki Takahashi, Dr. Daniel Lee, Dr. Lionel Dubois, Dr. Michel Bardet, Dr. Sabine Hediger and Dr. Gaël De Paëpe

      Article first published online: 18 OCT 2012 | DOI: 10.1002/anie.201206102

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      Ultra-fast: Substantial solid-state NMR sensitivity can be achieved using dynamic nuclear polarization and matrix-free sample preparation (that is, absence of solvent and cryoprotectant). This method avoids line-broadening, maximizes sample filling factor, and allows natural-abundance 2D 13C–13C dipolar correlation experiments to be carried out in tens of minutes. MW=microwaves.

    12. Heterogeneous Catalysis

      Co/CoO Nanoparticles Assembled on Graphene for Electrochemical Reduction of Oxygen (pages 11770–11773)

      Dr. Shaojun Guo, Sen Zhang, Liheng Wu and Prof. Shouheng Sun

      Article first published online: 16 OCT 2012 | DOI: 10.1002/anie.201206152

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      Good support: A solution-phase self-assembly approach leads to Co/CoO core/shell nanoparticles deposited on graphene (G–Co/CoO NPs). Their catalytic activity for the oxygen reduction reaction in O2-saturated KOH solution depends on the thickness of the CoO shell (green in picture). The optimized G–Co/CoO NPs have a comparative activity and better stability than the commercial Pt NP catalyst supported on carbon (C–Pt).

    13. Virulence Factors

      Total Synthesis of the Triglycosyl Phenolic Glycolipid PGL-tb1 from Mycobacterium tuberculosis (pages 11774–11777)

      Dr. Santiago Barroso, Dr. Riccardo Castelli, Marc P. Baggelaar, Danny Geerdink, Dr. Bjorn ter Horst, Dr. Eva Casas-Arce, Prof. Herman S. Overkleeft, Prof. Gijsbert A. van der Marel, Dr. Jeroen D. C. Codée and Prof. Adriaan J. Minnaard

      Article first published online: 19 OCT 2012 | DOI: 10.1002/anie.201206221

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      Complex: The synthesis of the glycolipid PGL-tb1 present in the outer membrane of hypervirulent strains of Mycobacterium tuberculosis has been accomplished for the first time by using a highly convergent strategy featuring a Sonogashira coupling to unite a phenolic trisaccharide with the phthiocerol. Efficient asymmetric Cu-catalyzed 1,4-additions to unsaturated thioesters and cyclic enones have been employed to introduce the methyl groups.

    14. Asymmetric Catalysis

      Enantioselective Construction of Pyrroloindolines Catalyzed by Chiral Phosphoric Acids: Total Synthesis of (−)-Debromoflustramine B (pages 11778–11782)

      Dr. Zuhui Zhang and Prof. Dr. Jon C. Antilla

      Article first published online: 17 SEP 2012 | DOI: 10.1002/anie.201203553

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      Acids in command: The asymmetric formation of pyrroloindolines with adjacent quaternary and tertiary carbon centers has been achieved through catalysis by a chiral phosphoric acid. Starting from readily available tryptamine, both Michael products and amination products were obtained in high yields and enantioselectivities. The significance of this study was further demonstrated by the total synthesis of (−)-debromoflustramine B.

    15. Catalytic Asymmetric Allenylation of Malonates with the Generation of Central Chirality (pages 11783–11786)

      Qiankun Li, Prof. Dr. Chunling Fu and Prof. Dr. Shengming Ma

      Article first published online: 10 OCT 2012 | DOI: 10.1002/anie.201204346

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      Water plays an important role in a palladium-catalyzed allenylation of diethyl malonate with 2,3-allenyl acetates to yield centrally chiral allenyl malonates bearing synthetically useful functional groups (see scheme). The products were formed with 92–96 % ee in the presence of a bulky, electron-rich biphenyl ligand at room temperature.

    16. Hyperpolarization

      Peptide Hydrogenation and Labeling with Parahydrogen (pages 11787–11790)

      Dr. Francesca Gruppi, Xiang Xu, Boyang Zhang, Dr. Joel A. Tang, Prof. Alexej Jerschow and Prof. James W. Canary

      Article first published online: 16 OCT 2012 | DOI: 10.1002/anie.201204403

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      Site-specific spin polarization labeling of a peptide was conducted by homogeneous hydrogenation with parahydrogen. Surprisingly, polarization transfer to a remote alanine residue was observed. The diastereoselectivity of the hydrogenation reaction was determined, and these results show that parahydrogen can be used to enhance signals and elucidate the hydrogenation processes of dehydropeptide units in complex molecules.

    17. Heterocycles

      Halogen Exchange (Halex) Reaction of 5-Iodo-1,2,3-triazoles: Synthesis and Applications of 5-Fluorotriazoles (pages 11791–11794)

      Brady T. Worrell, Dr. Jason E. Hein and Prof. Dr. Valery V. Fokin

      Article first published online: 12 OCT 2012 | DOI: 10.1002/anie.201204979

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      A good exchange: 5-Iodo-1,2,3-triazoles undergo facile substitution reactions with fluoride salts, thus providing ready access to 5-fluorotriazoles (see scheme). The latter can be further elaborated with various nucleophiles to furnish fully substituted 1,2,3-triazole compounds.

    18. Enantioselective Synthesis

      Enantioselective Synthesis and Cross-Coupling of Tertiary Propargylic Boronic Esters Using Lithiation–Borylation of Propargylic Carbamates (pages 11795–11799)

      Dr. Benjamin M. Partridge, Dr. Laëtitia Chausset-Boissarie, Matthew Burns, Alexander P. Pulis and Prof. Varinder K. Aggarwal

      Article first published online: 17 OCT 2012 | DOI: 10.1002/anie.201203198

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      Lithiation–borylation of propargylic carbamates leads to tertiary propargylic boronic esters in very high e.r., provided that ethylene glycol boronic esters are used. These versatile intermediates undergo a range of highly stereoselective transformations, including protodeboronation to give tertiary allenes and Suzuki–Miyaura cross-couplings of tertiary boron species leading to tetrasubstituted allenes with high enantiospecificity.

    19. Carbohydrate Detection

      Signal Amplification by Glyco-qPCR for Ultrasensitive Detection of Carbohydrates: Applications in Glycobiology (pages 11800–11804)

      Dr. Seok Joon Kwon, Prof. Kyung Bok Lee, Kemal Solakyildirim, Sayaka Masuko, Mellisa Ly, Dr. Fuming Zhang, Dr. Lingyun Li, Prof. Jonathan S. Dordick and Prof. Robert J. Linhardt

      Article first published online: 16 OCT 2012 | DOI: 10.1002/anie.201205112

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      Tiny amounts of carbohydrates (ca. 1 zmol) can be detected quantitatively by a real-time method based on the conjugation of carbohydrates with DNA markers (see picture). The proposed method (glyco-qPCR) provides uniform, ultrasensitive detection of carbohydrates, which can be applied to glycobiology, as well as carbohydrate-based drug discovery.

    20. Iron Catalysis

      Iron-Catalyzed Polymerization of Isoprene and Other 1,3-Dienes (pages 11805–11808)

      Dr. Jean Raynaud, Dr. Jessica Y. Wu and Prof. Tobias Ritter

      Article first published online: 18 OCT 2012 | DOI: 10.1002/anie.201205152

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      Ironing rubber: Iminopyridine-based FeCl2 catalysts catalyze the polymerization of 1,3-dienes and provide stereoselective access to elastomers such as polyisoprenes, polymyrcenes, and polyfarnesenes. The choice of ligand determines the double-bond geometry in the polymer repeating unit, which can be varied from trans/cis >99:1 to <1:99 (see scheme).

      Corrected by:

      Corrigendum: Corrigendum: Iron-Catalyzed Polymerization of Isoprene and Other 1,3-Dienes

      Vol. 51, Issue 52, 12920, Article first published online: 18 DEC 2012

    21. Synthetic Methods

      Development of a Povarov Reaction/Carbene Generation Sequence for Alkenyldiazocarbonyl Compounds (pages 11809–11813)

      Appaso Mahadev Jadhav, Vinayak Vishnu Pagar and Prof. Dr. Rai-Shung Liu

      Article first published online: 18 OCT 2012 | DOI: 10.1002/anie.201205692

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      Rings aplenty: A HOTf-catalyzed (Tf=trifluoromethanesulfonyl) Povarov reaction of alkenyldiazo species has been developed and delivers diazo-containing cycloadducts stereoselectively (see scheme). The resulting cycloadducts provide access to six- and seven-membered azacycles through the generation of metal carbenes as well as the functionalization of diazo group.

    22. Solution Processing

      Construction of Conjugated Carbon Nitride Nanoarchitectures in Solution at Low Temperatures for Photoredox Catalysis (pages 11814–11818)

      Yanjuan Cui, Prof. Zhengxin Ding, Prof. Xianzhi Fu and Prof. Xinchen Wang

      Article first published online: 18 OCT 2012 | DOI: 10.1002/anie.201206534

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      Hot: Conjugated carbon nitride polymers (LCNs) are synthesized by hot-fluid annealing in one pot. The LCNs possess a narrow band gap, have a complex nanostructure, and show enhanced photochemical performances. The described synthesis approach will allow the rational creation of a wide variety of polymeric carbon nitride semiconductors at low temperature in solutions, with control of structural complexity, electronic structure, and surface functionality.

    23. C[BOND]H Activation

      Rhodium(III)-Catalyzed Oxidative C[BOND]H Functionalization of Azomethine Ylides (pages 11819–11823)

      Wencui Zhen, Fen Wang, Miao Zhao, Prof. Dr. Zhengyin Du and Prof. Dr. Xingwei Li

      Article first published online: 19 OCT 2012 | DOI: 10.1002/anie.201207204

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      Put it on a ring: A rhodium(III) complex can catalyze the oxidative coupling of azomethine imines with olefins, leading to the synthesis of 1,2-dihydrophthalazines, olefinated aldehydes, or fused pyridines, depending on the conditions used.

    24. Natural Product Synthesis

      Total Synthesis of (−)-Lycoposerramine-S (pages 11824–11826)

      Naoaki Shimada, Dr. Yuzo Abe, Dr. Satoshi Yokoshima and Prof. Tohru Fukuyama

      Article first published online: 15 OCT 2012 | DOI: 10.1002/anie.201206863

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      To the core: The first total synthesis of (−)-lycoposerramine-S has been accomplished in 14 steps. The synthesis features the facile construction of the tetracyclic core through an intramolecular 1,3-dipolar cycloaddition of an azomethine ylide, with unexpected stereoselectivity, an 5-exo-trig radical cyclization, and an alkylation of p-nosyl (Ns) amide. TBS=tert-butyldimethylsilyl.

      Corrected by:

      Corrigendum: Corrigendum: Total Synthesis of (−)-Lycoposerramine-S

      Vol. 53, Issue 34, 8808, Article first published online: 13 AUG 2014

    25. Synthetic Methods

      Copper-Catalyzed Amination of Ketene Silyl Acetals with Hydroxylamines: Electrophilic Amination Approach to α-Amino Acids (pages 11827–11831)

      Naoki Matsuda, Dr. Koji Hirano, Prof. Dr. Tetsuya Satoh and Prof. Dr. Masahiro Miura

      Article first published online: 15 OCT 2012 | DOI: 10.1002/anie.201206755

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      Role reversal: The title reaction has been developed to deliver α-amino acids under very mild reaction conditions (see scheme; dpppen=1,5-bis(diphenylphosphino)pentane). The catalysis provides a new C[BOND]N bond-forming approach for the synthesis of α-amino acids by using an umpolung, electrophilic amination strategy.

    26. Synthesis using a Mass Spectrometer

      Accelerated Carbon[BOND]Carbon Bond-Forming Reactions in Preparative Electrospray (pages 11832–11835)

      Dr. Thomas Müller, Dr. Abraham Badu-Tawiah and Prof. R. Graham Cooks

      Article first published online: 8 OCT 2012 | DOI: 10.1002/anie.201206632

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      From analysis towards synthesis: Charged microdroplets act as microreaction vessels, extending the use of electrospray mass spectrometry from chemical analysis to synthesis. Application of this unique reaction conditions allows microscale carbon–carbon bond forming reactions to be performed rapidly and in high yields (see picture).

    27. Nanoparticles

      Bioorthogonal Copper-Free Click Chemistry In Vivo for Tumor-Targeted Delivery of Nanoparticles (pages 11836–11840)

      Dr. Heebeom Koo, Sangmin Lee, Jin Hee Na, Dr. Sun Hwa Kim, Dr. Sei Kwang Hahn, Dr. Kuiwon Choi, Dr. Ick Chan Kwon, Dr. Seo Young Jeong and Dr. Kwangmeyung Kim

      Article first published online: 18 OCT 2012 | DOI: 10.1002/anie.201206703

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      Right on target: An in vivo tumor-targeting strategy using nanoparticles has been developed. An unnatural sialic acid (green, see scheme) with azide groups is artificially generated on the target site by metabolic glycoengineering. These groups then effectively enhance the accumulation of nanoparticles in the target tumor site by an in vivo bioorthogonal copper-free click reaction.

    28. Photochemistry

      Low-Threshold Photon Upconversion Capsules Obtained by Photoinduced Interfacial Polymerization (pages 11841–11844)

      Ji-Hwan Kang and Prof. Elsa Reichmanis

      Article first published online: 17 OCT 2012 | DOI: 10.1002/anie.201205540

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      Nonlinear optics: Photoinduced interfacial polymerization within a microfluidic channel is shown to be an effective method to prepare microcapsules that provide for photon upconversion by triplet–triplet annihilation (see picture). In this approach, an elastomeric shell formed on the inner surface of the microcapsules served as an efficient protective shield, whereas a liquid core promoted the required energy transfer for the upconverted luminescence.

    29. Electrocatalysis

      Design of an Active Site towards Optimal Electrocatalysis: Overlayers, Surface Alloys and Near-Surface Alloys of Cu/Pt(111) (pages 11845–11848)

      Dr. Aliaksandr S. Bandarenka, Ana Sofia Varela, Mohammedreza Karamad, Dr. Federico Calle-Vallejo, Dr. Lone Bech, Dr. Francisco J. Perez-Alonso, Dr. Jan Rossmeisl, Dr. Ifan E. L. Stephens and Prof. Ib Chorkendorff

      Article first published online: 22 OCT 2012 | DOI: 10.1002/anie.201205314

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      I could never be without Cu: An active site has been designed for the catalysis of CO electroxidation. This was achieved by incorporating submonolayer amounts of Cu (orange spheres) into a single crystal of Pt (gray spheres). The electrochemical reactivity of this surface was highly sensitive to the exact position of Cu (see scheme).

    30. Amorphous/Crystalline Materials

      Amorphous-to-Crystalline Transformation with Fluorescence Enhancement and Switching of Molecular Nanoparticles Fixed in a Polymer Thin Film (pages 11849–11852)

      Ch. G. Chandaluri and Prof. T. P. Radhakrishnan

      Article first published online: 17 OCT 2012 | DOI: 10.1002/anie.201205081

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      Growth in a confined environment: A protocol for the amorphous-to-crystalline transformation (ACT) of nanoparticles has been developed, the critical step being the partial confinement of the particles by fixing in a polymer thin film and solvent vapor fuming. The ACT of a diaminodicyanoquinodimethane-based nanoparticle is accompanied by substantial fluorescence enhancement and switching of the emission color.

    31. Drug Delivery

      You have full text access to this OnlineOpen article
      DNA Self-Assembly of Targeted Near-Infrared-Responsive Gold Nanoparticles for Cancer Thermo-Chemotherapy (pages 11853–11857)

      Dr. Zeyu Xiao, Dr. Changwei Ji, Dr. Jinjun Shi, Eric M. Pridgen, Jillian Frieder, Dr. Jun Wu and Prof. Omid C. Farokhzad

      Article first published online: 18 OCT 2012 | DOI: 10.1002/anie.201204018

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      Targeted cancer therapy: Inspired by the ability of DNA hybridization, a targeted near-infrared (NIR) light-responsive delivery system has been developed through simple DNA self-assembly (see picture; PEG=polyethylene glycol). This DNA-based platform shows the ability of releasing therapeutics upon near-infrared irradiation, and remarkable targeted thermo- and chemotherapeutic efficacy in vitro and in vivo.

    32. Synthetic Biology

      Surface Topology Engineering of Membranes for the Mechanical Investigation of the Tubulin Homologue FtsZ (pages 11858–11862)

      Senthil Arumugam, Grzegorz Chwastek, Dr. Elisabeth Fischer-Friedrich, Carina Ehrig, Dr. Ingolf Mönch and Prof. Dr. Petra Schwille

      Article first published online: 31 AUG 2012 | DOI: 10.1002/anie.201204332

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      Bending over backward: Despite their small size, bacteria display highly organized cytoskeletal structures. Using microfabricated supports for model membranes, mechanical features of FtsZ (blue hexagons) filaments, a key component of bacterial cell division, can be addressed. Studying the curvature of an FtsZ filament into a groove or around a capillary (see picture) helps to understand its mechanics.

    33. RNA Thermodynamics

      2′-Fluoro RNA Shows Increased Watson–Crick H-Bonding Strength and Stacking Relative to RNA: Evidence from NMR and Thermodynamic Data (pages 11863–11866)

      Dr. Amritraj Patra, Michael Paolillo, Dr. Klaus Charisse, Dr. Muthiah Manoharan, Prof. Eriks Rozners and Prof. Martin Egli

      Article first published online: 10 OCT 2012 | DOI: 10.1002/anie.201204946

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      The way it is: Incorporation of 2′-deoxy-2′-fluororibonucleotides (2′-F RNA) into RNA oligomers leads to a marked increase in duplex stability. Using NMR spectroscopy (see picture) with native (red circles) and 2′-F modified (black squares) RNA duplexes, and UV melting and osmotic stress experiments the higher stability of 2′-F RNA relative to RNA is shown to be the result of both increased Watson–Crick H-bonding strength and favorable base stacking.

    34. Alkane Separation

      Computer-Assisted Screening of Ordered Crystalline Nanoporous Adsorbents for Separation of Alkane Isomers (pages 11867–11871)

      Dr. David Dubbeldam, Prof. Dr. Rajamani Krishna, Prof. Dr. Sofía Calero and Dr. Ahmet Özgür Yazaydın

      Article first published online: 19 OCT 2012 | DOI: 10.1002/anie.201205040

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      A matter of degree: Separation of di-branched alkanes from their linear and mono-branched isomers is important in producing high-octane gasoline. Using computational techniques to screen a large variety of adsorbent materials (see scheme), ZIF-77 emerges as the best adsorbent. It has the unique ability to fractionate isomer mixtures according to the degree of branching.

    35. Noncovalent Interactions

      The Chameleonic Nature of Diazaperopyrenium Recognition Processes (pages 11872–11877)

      Ashish N. Basuray, Dr. Henri-Pierre Jacquot de Rouville, Dr. Karel J. Hartlieb, Dr. Takashi Kikuchi, Nathan L. Strutt, Carson J. Bruns, Michael W. Ambrogio, Alyssa-Jennifer Avestro, Dr. Severin T. Schneebeli, Albert C. Fahrenbach and Prof. J. Fraser Stoddart

      Article first published online: 28 SEP 2012 | DOI: 10.1002/anie.201205089

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      Two for the price of one! The diazaperopyrenium dication behaves dichotomously in a homo- and heterophilic manner, allowing for complexation with itself and a variety of π-electron-rich donors. This chameleonic characteristic, in addition to its electronic properties, leads to self-assembled nanowires in the solid state, as well as to its acting as a template for aromatic crown ethers to form a [3]- and two [2]rotaxanes (see picture).

    36. Radical Cation Structures

      Synthesis, Characterization, and Structures of a Persistent Aniline Radical Cation (pages 11878–11881)

      Xiaoyu Chen, Dr. Xingyong Wang, Dr. Yunxia Sui, Prof. Yizhi Li, Prof. Jing Ma, Prof. Jinglin Zuo and Prof. Xinping Wang

      Article first published online: 18 OCT 2012 | DOI: 10.1002/anie.201205478

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      Feeling the heat: The aniline radical cation TBA.+ (TBA=2,4,6-tBu3C6H2NH2) has been successfully stabilized both in solution and in the solid state. It exists as two isomers in the crystal lattice that interchange with temperature, and features an exceptionally long C[BOND]N bond beyond theoretical prediction.

    37. Hierarchical Structures

      Tunable Supermicelle Architectures from the Hierarchical Self-Assembly of Amphiphilic Cylindrical B–A–B Triblock Co-Micelles (pages 11882–11885)

      Dr. Huibin Qiu, Giuseppe Russo, Dr. Paul A. Rupar, Dr. Laurent Chabanne, Prof. Mitchell A. Winnik and Prof. Ian Manners

      Article first published online: 15 OCT 2012 | DOI: 10.1002/anie.201205764

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      Crossing the block: Amphiphilic cylindrical B–A–B triblock co-micelles, micelle analogues of bolaamphiphiles, can be prepared by the crystallization-driven living self-assembly of diblock copolymers with core-forming polyferrocenylsilane blocks. These novel co-micelle building blocks form regular crossed or spherical supermicelles or elongated networks in polar media depending on the relative lengths of the A and B segments (see picture).

    38. Surface Organometallics

      [([TRIPLE BOND]SiO)TaVCl2Me2]: A Well-Defined Silica-Supported Tantalum(V) Surface Complex as Catalyst Precursor for the Selective Cocatalyst-Free Trimerization of Ethylene (pages 11886–11889)

      Yin Chen, Emmanuel Callens, Edy Abou-Hamad, Nicolas Merle, Andrew J. P. White, Mostafa Taoufik, Christophe Copéret, Erwan Le Roux and Jean-Marie Basset

      Article first published online: 22 OCT 2012 | DOI: 10.1002/anie.201206272

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      On the surface of it: In the absence of co-catalyst, a well-defined silica-supported surface organometallic complex [([TRIPLE BOND]SiO)TaVCl2Me2] selectively catalyzes the oligomerization of ethylene. The use of surface organometallic species allows three different pathways to be determined for the reduction of TaV to TaIII species under pressure of ethylene.

    39. Stereoselection

      Stereoselection in the Corey–Bakshi–Shibata Reduction: Insight from Kinetic Isotope Effects and Transition-Structure Modeling (pages 11890–11893)

      Dr. Hui Zhu, Prof. Daniel J. O'Leary and Prof. Matthew P. Meyer

      Article first published online: 16 OCT 2012 | DOI: 10.1002/anie.201206011

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      Flexible but demanding: Significant steric demand is isolated to the small (iPr) substituent in the oxazaborolidine-catalyzed borane (CBS) reduction of 2′,5′-dimethylisobutyrophenone. Computed transition-structure models (see picture) demonstrate that nearly equivalent steric demand can be achieved from conformationally distinct transition structures.

    40. DNA Sensing

      You have full text access to this OnlineOpen article
      Modular Assembly of a Pd Catalyst within a DNA Scaffold for the Amplified Colorimetric and Fluorimetric Detection of Nucleic Acids (pages 11894–11898)

      Deepak K. Prusty, Minseok Kwak, Jur Wildeman and Prof. Dr. Andreas Herrmann

      Article first published online: 17 OCT 2012 | DOI: 10.1002/anie.201206006

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      Phosphine ligands were covalently tethered to short oligonucleotide strands such that active palladium complexes formed in the presence of a specific nucleic acid target. This catalytic center on the double-stranded DNA then converted water-soluble iodo-BODIPY dyes, present in excess, into highly emissive deiodinated reporters (see picture). This approach is suitable for the rapid colorimetric or fluorimetric detection of nucleic acid targets with a lower detection limit of just 10 pM.

    41. Intracellular Delivery

      A Bioreducible Polymer for Efficient Delivery of Fas-Silencing siRNA into Stem Cell Spheroids and Enhanced Therapeutic Angiogenesis (pages 11899–11903)

      Dr. Min Suk Shim, Dr. Suk Ho Bhang, Dr. Kyunghwan Yoon, Prof. Kyunghee Choi and Prof. Younan Xia

      Article first published online: 16 OCT 2012 | DOI: 10.1002/anie.201206595

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      Larger is better: Fas-silencing siRNA can be delivered into the cytoplasm of human mesenchymal stem cells (hMSCs) by a bioreducible polymer (see picture). The enhanced anti-apoptotic activity of the Fas-silenced hMSCs means that they can be readily formulated as enlarged spheroids to significantly enhance angiogenic efficacy as compared to their smaller counterparts.

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