Angewandte Chemie International Edition

Cover image for Vol. 45 Issue 31

August 4, 2006

Volume 45, Issue 31

Pages 5027–5225

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Book Review
    7. Highlight
    8. Essay
    9. Minireview
    10. Review
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    1. Cover Picture: Antibacterial Natural Products in Medicinal Chemistry—Exodus or Revival? (Angew. Chem. Int. Ed. 31/2006) (page 5027)

      Franz von Nussbaum, Michael Brands, Berthold Hinzen, Stefan Weigand and Dieter Häbich

      Version of Record online: 31 JUL 2006 | DOI: 10.1002/anie.200690106

      The exceptional often hides within the ordinary. In 1503, Albrecht Dürer saw a complex microcosm concealed in an apparently unimportant piece of turf (“Great Piece of Turf” with courtesy of http://reisserbilder.at). In a similar fashion, chemical postevolution can elicit exceptional properties from known natural products. In their Review on page 5072 ff., Häbich and co-workers analyze the application of this principle on antibiotics.

  2. Editorial

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      The Heat Is On … (pages 5030–5032)

      Peter Gölitz

      Version of Record online: 31 JUL 2006 | DOI: 10.1002/anie.200602672

  3. Graphical Abstract

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    3. Editorial
    4. Graphical Abstract
    5. News
    6. Book Review
    7. Highlight
    8. Essay
    9. Minireview
    10. Review
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  4. News

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    3. Editorial
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  5. Book Review

    1. Top of page
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    3. Editorial
    4. Graphical Abstract
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    6. Book Review
    7. Highlight
    8. Essay
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  6. Highlight

    1. Top of page
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    6. Book Review
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    1. MicroRNAs—Future Drug Targets? (pages 5048–5050)

      Christoph Arenz

      Version of Record online: 21 JUL 2006 | DOI: 10.1002/anie.200601537

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      Big things come in small packages: MicroRNAs (miRNAs) are small regulatory RNA molecules in eukaryotes. Altered miRNA expression patterns can be used as a diagnostic tool, for example, in patients with chronic lymphatic leukemia. Also, the inhibition of miRNA function in vivo has been recently achieved by using “antagomirs”—antisense cholesterol conjugates (see scheme; miRNP=miRNA–protein complex, RISC=RNA-induced silencing complex).

  7. Essay

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    1. Shaping the Future with Chemistry: What's in Store for Chemistry Graduates in Research and Industry? (pages 5052–5056)

      Jürgen Hambrecht

      Version of Record online: 31 JUL 2006 | DOI: 10.1002/anie.200602160

      Innovation through communication: What is required of young graduates in chemistry today and how can these skills be developed? An open dialogue between universities and the chemical industry may push innovations and thus lead the way to a successful future.

  8. Minireview

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    1. Relationship between One-Electron Transition-Metal Reactivity and Radical Polymerization Processes (pages 5058–5070)

      Rinaldo Poli

      Version of Record online: 4 JUL 2006 | DOI: 10.1002/anie.200503785

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      Radical processes: An understanding of one-electron transition-metal reactivity is of fundamental importance for the correct interpretation of experimental results in metal-mediated radical polymerization processes. Thermodynamics and kinetics parameters, the effect of the coordination geometry and spin state of the metal complex, and the properties of the ligand are considered.

  9. Review

    1. Top of page
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    8. Essay
    9. Minireview
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    1. Antibacterial Natural Products in Medicinal Chemistry—Exodus or Revival? (pages 5072–5129)

      Franz von Nussbaum, Michael Brands, Berthold Hinzen, Stefan Weigand and Dieter Häbich

      Version of Record online: 31 JUL 2006 | DOI: 10.1002/anie.200600350

      Thumbnail image of graphical abstract

      Nature's universe of antibacterial compounds has evolved over millions of years and chemists have exploited this treasure of lead structures for half a century. The β-lactams and the macrolides are outstanding success stories of this era. Today, natural products and basic antibacterial research seem to be “endangered species”. Revisiting natural products with modern chemistry and reversed genomics is one option for their revival.

  10. Communications

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    4. Graphical Abstract
    5. News
    6. Book Review
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    8. Essay
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    1. An [{Fe(mecam)}2]6− Bridge in the Crystal Structure of a Ferric Enterobactin Binding Protein (pages 5132–5136)

      Axel Müller, Anthony J. Wilkinson, Keith S. Wilson and Anne-K. Duhme-Klair

      Version of Record online: 6 JUL 2006 | DOI: 10.1002/anie.200601198

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      Bridging the gap: The dinuclear ferric enterobactin mimic [{Fe(mecam)}2]6− (H6-mecam=1,3,5-N,N′,N′′-tris(2,3-dihydroxybenzoyl)triaminomethylbenzene) is recognized by two periplasmic binding protein molecules (yellow and blue; see structure). The assembly is stabilized through hydrophobic interactions between the ligand backbones of the dinuclear iron complex.

    2. Substrate Distortion by a Lichenase Highlights the Different Conformational Itineraries Harnessed by Related Glycoside Hydrolases (pages 5136–5140)

      Victoria A. Money, Nicola L. Smith, Adrian Scaffidi, Robert V. Stick, Harry J. Gilbert and Gideon J. Davies

      Version of Record online: 5 JUL 2006 | DOI: 10.1002/anie.200600802

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      Pick-a-path: A series of enzymatic snapshots along the reaction coordinate of a lichenase (specific for gluco-configured substrates) demonstrates that this enzyme uses a different reaction pathway, featuring a 1S3[RIGHTWARDS ARROW]4H3[RIGHTWARDS ARROW]4C1 migration, to that previously observed for the closely related mannanases.

    3. A Resonance Energy Transfer between Chemiluminescent Donors and Luminescent Quantum-Dots as Acceptors (CRET) (pages 5140–5143)

      Xiangyi Huang, Liang Li, Huifeng Qian, Chaoqing Dong and Jicun Ren

      Version of Record online: 7 JUL 2006 | DOI: 10.1002/anie.200601196

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      No need to FRET: An efficient chemiluminescence resonance energy transfer (CRET) between luminol and CdTe quantum dots (QDs) is demonstrated. The system is based on horseradish peroxidase (HRP)–QD conjugates and the luminol/hydrogen peroxide chemiluminescence reaction. Multiple QD acceptors with different emission wavelengths can also be used simultaneously. The CRET approach can offer an alternative to fluorescence energy transfer (FRET) investigations.

    4. A High-Conductivity Crystal Containing a Copper(I) Coordination Polymer Bridged by the Organic Acceptor TANC (pages 5144–5147)

      Makoto Tadokoro, Syuma Yasuzuka, Masaharu Nakamura, Takumi Shinoda, Toshinori Tatenuma, Minoru Mitsumi, Yoshiki Ozawa, Koshiro Toriumi, Harukazu Yoshino, Daisuke Shiomi, Kazunobu Sato, Takeji Takui, Takehiko Mori and Keizo Murata

      Version of Record online: 6 JUL 2006 | DOI: 10.1002/anie.200600553

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      Molecular conductors: A new, modifiable electron acceptor with a 5,6,11,12-tetraazanaphthacene (TANC) framework was introduced in CuI–TANC coordination polymers (see picture). The conduction mechanism of a high-conductivity crystal constructed from these polymers can be described as 1D variable-range hopping based on the disordered F ions.

    5. [Zn9Bi11]5−: A Ligand-Free Intermetalloid Cluster (pages 5147–5150)

      Jose M. Goicoechea and Slavi C. Sevov

      Version of Record online: 3 JUL 2006 | DOI: 10.1002/anie.200601805

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      A profitable merger: The reaction of K5Bi4 with ZnPh2 yields the 20-atom cluster [Zn@(Zn8Bi4)@Bi7]5− (see structure; zinc green, bismuth orange), which consists of a central zinc atom within a Zn8Bi4 icosahedron (red) capped by seven bismuth atoms. Extensive amalgamation of the two types of atoms, reminiscent of an alloy, occurs in this intermetalloid cluster.

    6. Hierarchical Structured Nanohelices of ZnS (pages 5150–5154)

      Daniel Moore, Yong Ding and Zhong Lin Wang

      Version of Record online: 6 JUL 2006 | DOI: 10.1002/anie.200600429

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      Twists and turns: ZnS nanohelices have been synthesized in high yield by using a simple vapor deposition process. These nanohelices also have Y-shaped branched secondary growths, which always point toward the inside of the helix. The formation of these hierarchical structures is discussed based on structural information.

    7. Ultrafast Electron Crystallography of Phospholipids (pages 5154–5158)

      Songye Chen, Marco T. Seidel and Ahmed H. Zewail

      Version of Record online: 31 JUL 2006 | DOI: 10.1002/anie.200601778

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      The structure and dynamics of monolayer and bilayer (see picture) phospholipids have been studied with spatiotemporal resolutions by ultrafast electron crystallography. The expansion and restructuring of the chains were observed after a femtosecond temperature jump in the substrate, and a transient structural ordering was revealed. The atomic forces were identified to be coherent in the non-equilibrium state of the assembly.

    8. A Stoichiometric Molecularly Imprinted Polymer for the Class-Selective Recognition of Antibiotics in Aqueous Media (pages 5158–5161)

      Javier L. Urraca, Andrew J. Hall, Maria C. Moreno-Bondi and Börje Sellergren

      Version of Record online: 6 JUL 2006 | DOI: 10.1002/anie.200601636

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      Making a good impression: A molecularly imprinted polymer is prepared against Penicillin G by using a stoichiometric quantity of a urea-based monomer. This polymer displays a high affinity for the template (see picture) and other β-lactam antibiotics, as determined by chromatographic retention factors in high quantities of buffer (90 %). Retention values on the nonimprinted polymer were dramatically lower under the same conditions.

    9. Catalytic Conversion of Cellulose into Sugar Alcohols (pages 5161–5163)

      Atsushi Fukuoka and Paresh L. Dhepe

      Version of Record online: 6 JUL 2006 | DOI: 10.1002/anie.200601921

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      Sweetly done: Pt or Ru catalysts supported on inorganic oxides show high activity for the conversion of cellulose into sugar alcohols (mainly sorbitol) in water under hydrogen pressure; furthermore, the catalysts can be recycled over repeated runs. Glucose is produced in low yields, thus suggesting that the Pt (or Ru)/oxide works as a bifunctional catalyst for the hydrolysis of cellulose and subsequent reduction to sugar alcohols.

    10. Highly Selective 1,6-Addition of Aryl Boronic Acids to α,β,γ,δ-Unsaturated Carbonyl Compounds Catalyzed by an Iridium Complex (pages 5164–5166)

      Takahiro Nishimura, Yuichi Yasuhara and Tamio Hayashi

      Version of Record online: 3 JUL 2006 | DOI: 10.1002/anie.200601719

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      Perfect control: The catalytic 1,6-addition of aryl boronic acids to electron-deficient dienes was realized by use of an iridium catalyst (see scheme). High yields of the corresponding δ-arylated carbonyl compounds were obtained with perfect 1,6-selectivity.

    11. Spectroscopy of Isolated Gramicidin Peptides (pages 5166–5169)

      Ali Abo-Riziq, Bridgit O. Crews, Michael P. Callahan, Louis Grace and Mattanjah S. de Vries

      Version of Record online: 7 JUL 2006 | DOI: 10.1002/anie.200601516

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      An eye for detail: Double-resonant IR–UV spectroscopy of isolated gramicidin peptides in the gas phase shows evidence for a helical structure, similar to that in the condensed phase. This approach probes local details in isolated molecules, free of interactions.

    12. Trigonal Pyramids: Alternative Ground-State Structures for Sixteen-Electron Complexes (pages 5169–5173)

      Detlev Ostendorf, Clark Landis and Hansjörg Grützmacher

      Version of Record online: 7 JUL 2006 | DOI: 10.1002/anie.200601352

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      A structural alternative for sixteen-electron ML4 complexes is the trigonal-pyramidal (TP) form. This has been demonstrated by the preparation of TP complexes of rhodium(I) with three equatorial olefin ligands and one axial silyl ligand (see picture: C black, Rh blue, Si orange).

    13. Highly Diastereoselective Aldol Reaction with α-CF3-Substituted Enolates (pages 5174–5176)

      Xavier Franck, Blandine Seon-Meniel and Bruno Figadère

      Version of Record online: 5 JUL 2006 | DOI: 10.1002/anie.200600927

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      A CF3group and a chiral auxiliary are the key features of the Ti enolate used in the aldol reaction shown above. The syn aldol is formed in good yields, and defluorination leading to the vinylic CF2 product is not observed. The aldol product may be used to prepare more elaborate CF3-containing compounds, for instance, through the corresponding 1,3-diol.

    14. Thermally Induced and Silver-Salt-Catalyzed [2+2] Cycloadditions of Imines to (Alkoxymethylene)cyclopropanes (pages 5176–5179)

      Itaru Nakamura, Tetsuya Nemoto, Yoshinori Yamamoto and Armin de Meijere

      Version of Record online: 6 JUL 2006 | DOI: 10.1002/anie.200600961

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      A silver lining: [2+2] Cycloadditions of imines 2 to (alkoxymethylene)cyclopropanes 1 proceed readily at 80 °C and ambient pressure to furnish spirocyclopropanated 2-alkoxyazetidines 3 in good to excellent yields. The same reaction can be brought about at 30 °C in the presence of a catalytic amount of [Ag(fod)] (fod=6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato).

    15. Preparation, Characterization, and Crystal Structures of the SO3NHF and SO3NF2 Ions (pages 5179–5184)

      Ralf Haiges, Ross Wagner, Jerry A. Boatz, Muhammed Yousufuddin, Markus Etzkorn, G. K. Surya Prakash, Karl O. Christe, Robert D. Chapman, Mark F. Welker and Charles B. Kreutzberger

      Version of Record online: 6 JUL 2006 | DOI: 10.1002/anie.200601020

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      Safe difluoroaminating reagents: Salts of the elusive SO3NF2 ion were prepared by aqueous fluorination of SO3NH2 with F2. These salts were characterized (see ORTEP of the anion) and shown to be excellent reagents for the preparation of gem-bis(difluoroamines). Salts of the intermediate SO3NHF ion were also isolated and characterized.

    16. Nanocrystal-Mediated Crystallization of Silicon and Germanium Nanowires in Organic Solvents: The Role of Catalysis and Solid-Phase Seeding (pages 5184–5187)

      Hsing-Yu Tuan, Doh C. Lee and Brian A. Korgel

      Version of Record online: 5 JUL 2006 | DOI: 10.1002/anie.200601078

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      The top seed: Various metal nanocrystals are studied as crystallization seeds for silicon and germanium nanowires. The wires are grown by decomposing silane or germane reactants in supercritical organic solvents. Co and Ni nanocrystals promote the seeding of high-quality nanowires and catalyze reactant decomposition under the reaction conditions.

    17. Encapsulation and IR Probing of Cube-Shaped Octasilasesquioxane H8Si8O12 in Carbon Nanotubes (pages 5188–5191)

      Jiawei Wang, Marina K. Kuimova, Martyn Poliakoff, G. Andrew D. Briggs and Andrei N. Khlobystov

      Version of Record online: 3 JUL 2006 | DOI: 10.1002/anie.200504273

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      A spectroscopic probe of nanotube diameter: The strength of the interaction of H8Si8O12 with the inner walls of carbon nanotubes (see picture) depends on the inner diameter. This, in turn, affects the Si[BOND]H stretching frequency, which can be probed by IR spectroscopy.

    18. Turn-On and Selective Luminescence Sensing of Copper Ions by a Water-Soluble Cd10S16 Molecular Cluster (pages 5191–5194)

      Katsuaki Konishi and Takayuki Hiratani

      Version of Record online: 5 JUL 2006 | DOI: 10.1002/anie.200601491

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      A large turn-on effect in the form of a notable photoluminescence (PL) enhancement was observed for an oligo(ethylene glycol)-appended CdS cluster molecule with a Cd10S16 core upon mixing with CuI in water (see graphic). Analysis by the Job method and size-exclusion chromatography suggested that the turn-on response, which was found to be specific for CuI, is associated with the formation of a CuI-containing multicluster network.

    19. Iridium Catalysts with Bicyclic Pyridine–Phosphinite Ligands: Asymmetric Hydrogenation of Olefins and Furan Derivatives (pages 5194–5197)

      Stefan Kaiser, Sebastian P. Smidt and Andreas Pfaltz

      Version of Record online: 5 JUL 2006 | DOI: 10.1002/anie.200601529

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      Superior bicyclics: Iridium catalysts as 1 derived from pyridine–phosphinite ligands considerably extend the scope of asymmetric hydrogenation. In addition to various unfunctionalized and functionalized olefins, furans, and benzofurans, for which no catalysts were known before, are also hydrogenated with high enantioselectivity (see scheme).

    20. Lipoyl Synthase Inserts Sulfur Atoms into an Octanoyl Substrate in a Stepwise Manner (pages 5197–5199)

      Paul Douglas, Marco Kriek, Penny Bryant and Peter L. Roach

      Version of Record online: 11 JUL 2006 | DOI: 10.1002/anie.200601910

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      One step at a time: The insertion of the two sulfur atoms found in lipoyl groups requires the enzyme lipoyl synthase (LipA). The order of insertion of the two sulfur groups has been elucidated by spectroscopic characterization of a monothiolated species.

    21. Biocatalytic Single-Step Alkene Cleavage from Aryl Alkenes: An Enzymatic Equivalent to Reductive Ozonization (pages 5201–5203)

      Harald Mang, Johannes Gross, Miguel Lara, Christian Goessler, Hans E. Schoemaker, Georg M. Guebitz and Wolfgang Kroutil

      Version of Record online: 20 JUL 2006 | DOI: 10.1002/anie.200601574

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      O2can do: Innocuous molecular oxygen O2 is the only reagent needed to perform highly chemoselective biocatalytic single-step alkene-cleavage reactions (see scheme). The products are analogous to those of (reductive) ozonization and related metal-based methods. In contrast neither special equipment nor an additional reducing agent is required. The biocatalytic reaction can be performed at ambient temperature. Depending on the substrate, aldehydes or ketones are obtained.

    22. meta-Directing Cobalt-Catalyzed Diels–Alder Reactions (pages 5204–5206)

      Gerhard Hilt, Judith Janikowski and Wilfried Hess

      Version of Record online: 7 JUL 2006 | DOI: 10.1002/anie.200601974

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      Overcoming theortho/pararule? The regioselectivity of Diels–Alder reactions with neutral electron demand between 1,3-dienes with alkynes can be controlled by simple cobalt diimine complexes so that the meta-substituted cycloadducts are generated in good yields and excellent regioselectivity (see scheme; DDQ=2,3-dichloro-5,6-dicyano-1,4-benzoquinone).

    23. “Naked” Ga+ and In+ as Pure Acceptor Ligands: Structure and Bonding of [GaPt(GaCp*)4][BArF] (pages 5207–5210)

      Beatrice Buchin, Christian Gemel, Thomas Cadenbach, Israel Fernández, Gernot Frenking and Roland A. Fischer

      Version of Record online: 6 JUL 2006 | DOI: 10.1002/anie.200601007

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      In the buff: The reaction of [Pt(GaCp*)4] with the Ga+ source [Ga2Cp*][BArF] (Cp*=C5Me5; BArF=B{C6H3(3,5-CF3)2}4) leads to the title complex, which exhibits a naked gallium atom coordinated to a platinum center. DFT calculations reveal that the Ga+ ligand serves as a σ acceptor, and the Pt[BOND]Ga bond is additionally supported by strong π interactions.

    24. Spherical Particles of Phenylene-Bridged Periodic Mesoporous Organosilica for High-Performance Liquid Chromatography (pages 5210–5214)

      Vivian Rebbin, Rainer Schmidt and Michael Fröba

      Version of Record online: 6 JUL 2006 | DOI: 10.1002/anie.200504568

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      Alternative adsorbents: Spherical particles of a phenylene-bridged periodic mesoporous organosilica material (see picture) are applied in HPLC for the first time. Three test mixtures of up to four components with different polarities can be separated with the new column material.

    25. Flying Capsules: Mass Spectrometric Detection of Pyrogallarene and Resorcinarene Hexamers (pages 5214–5218)

      Ngong K. Beyeh, Michael Kogej, Antti Åhman, Kari Rissanen and Christoph A. Schalley

      Version of Record online: 5 JUL 2006 | DOI: 10.1002/anie.200600687

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      Survival of the fittest: Only those hexameric pyrogallarene and resorcinarene capsules which contain a guest with the right size, shape, and symmetry (see picture) survive the electrospray ionization process that makes them detectable by mass spectrometry. Tandem MS experiments with mass-selected ions provide evidence that the hexamers retain their capsular structure even in the gas phase.

    26. Ligation of a Synthetic Peptide to the N Terminus of a Recombinant Protein Using Semisynthetic Protein trans-Splicing (pages 5218–5221)

      Christina Ludwig, Martina Pfeiff, Uwe Linne and Henning D. Mootz

      Version of Record online: 5 JUL 2006 | DOI: 10.1002/anie.200600570

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      Splice it! An active intein can be reconstituted from a recombinant C-terminal and a short synthetic N-terminal fragment. This allows ligation of a synthetic peptide to the N terminus of a recombinant protein of interest by protein trans-splicing and circumvents the requirement for a C-terminal thioester or other reactive groups common to chemical ligation approaches.

  11. Preview

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