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121.
122.
Probing the Coordinative Unsaturation and Local Environment of Ti3+ Sites in an Activated High‐Yield Ziegler–Natta Catalyst
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Elena Morra Prof. Elio Giamello Prof. Sabine Van Doorslaer Giuseppe Antinucci Dr. Maddalena D'Amore Prof. Vincenzo Busico Prof. Mario Chiesa 《Angewandte Chemie (International ed. in English)》2015,54(16):4857-4860
The typical activation of a fourth generation Ziegler–Natta catalyst TiCl4/MgCl2/phthalate with triethyl aluminum generates Ti3+ centers that are investigated by multi‐frequency continuous wave and pulse EPR methods. Two families of isolated, molecule‐like Ti3+ species have been identified. A comparison of the experimentally derived g tensors and 35,37Cl hyperfine and nuclear‐quadrupole tensors with DFT‐computed values suggests that the dominant EPR‐active Ti3+ species is located on MgCl2(110) surfaces (or equivalent MgCl2 terminations with tetra‐coordinated Mg). O2 reactivity tests show that a fraction of these Ti sites is chemically accessible, an important result in view of the search for the true catalyst active site in olefin polymerization. 相似文献
123.
Production of the Bengamide Class of Marine Natural Products in Myxobacteria: Biosynthesis and Structure–Activity Relationships
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Dr. Silke C. Wenzel Dr. Holger Hoffmann Dr. Jidong Zhang Dr. Laurent Debussche Dr. Sabine Haag‐Richter Dr. Michael Kurz Dr. Frederico Nardi Dr. Peer Lukat Irene Kochems Dr. Heiko Tietgen Prof. Dr. Dietmar Schummer Jean‐Paul Nicolas Dr. Loreley Calvet Dr. Valerie Czepczor Dr. Patricia Vrignaud Dr. Agnes Mühlenweg Priv.‐Doz. Dr. Stefan Pelzer Prof. Dr. Rolf Müller Prof. Dr. Mark Brönstrup 《Angewandte Chemie (International ed. in English)》2015,54(51):15560-15564
The bengamides, sponge‐derived natural products that have been characterized as inhibitors of methionine aminopeptidases (MetAPs), have been intensively investigated as anticancer compounds. We embarked on a multidisciplinary project to supply bengamides by fermentation of the terrestrial myxobacterium M. virescens, decipher their biosynthesis, and optimize their properties as drug leads. The characterization of the biosynthetic pathway revealed that bacterial resistance to bengamides is conferred by Leu 154 of the myxobacterial MetAP protein, and enabled transfer of the entire gene cluster into the more suitable production host M. xanthus DK1622. A combination of semisynthesis of microbially derived bengamides and total synthesis resulted in an optimized derivative that combined high cellular potency in the nanomolar range with high metabolic stability, which translated to an improved half‐life in mice and antitumor efficacy in a melanoma mouse model. 相似文献
124.
Dr. Sabine Lennarz MSc Therese Christine Alich Dr. Tony Kelly Dr. Michael Blind Prof. Dr. Heinz Beck Prof. Dr. Günter Mayer 《Angewandte Chemie (International ed. in English)》2015,54(18):5369-5373
Cellular behavior is orchestrated by the complex interactions of a myriad of intracellular signal transduction pathways. To understand and investigate the role of individual components in such signaling networks, the availability of specific inhibitors is of paramount importance. We report the generation and validation of a novel variant of an RNA aptamer that selectively inhibits the mitogen‐activated kinase pathway in neurons. We demonstrate that the aptamer retains function under intracellular conditions and that application of the aptamer through the patch‐clamp pipette efficiently inhibits mitogen‐activated kinase‐dependent synaptic plasticity. This approach introduces synthetic aptamers as generic tools, readily applicable to inhibit different components of intraneuronal signaling networks with utmost specificity. 相似文献
125.
Encapsulation of Functional Organic Compounds in Nanoglass for Optically Anisotropic Coatings
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Matthias Stöter Dr. Bernhard Biersack Dr. Sabine Rosenfeldt Markus J. Leitl Dr. Hussein Kalo Prof. Dr. Rainer Schobert Prof. Dr. Hartmut Yersin Prof. Geoffrey A. Ozin Prof. Dr. Stephan Förster Prof. Dr. Josef Breu 《Angewandte Chemie (International ed. in English)》2015,54(16):4963-4967
A novel approach is presented for the encapsulation of organic functional molecules between two sheets of 1 nm thin silicate layers, which like glass are transparent and chemically stable. An ordered heterostructure with organic interlayers strictly alternating with osmotically swelling sodium interlayers can be spontaneously delaminated into double stacks with the organic interlayers sandwiched between two silicate layers. The double stacks show high aspect ratios of >1000 (typical lateral extension 5000 nm, thickness 4.5 nm). This newly developed technique can be used to mask hydrophobic functional molecules and render them completely dispersible in water. The combination of the structural anisotropy of the silicate layers and a preferred orientation of molecules confined in the interlayer space allows polymer nanocomposite films to be cast with a well‐defined orientation of the encapsulated molecules, thus rendering the optical properties of the nanocoatings anisotropic. 相似文献
126.
127.
Anke Schwarzer Sabine Fels Uwe Bhme 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(6):511-516
Dimethyl[N‐(4‐oxidopent‐3‐en‐2‐ylidene)valinato‐κ3O,N,O′]silicon(IV), C12H21NO3Si, (II), crystallizes in the orthorhombic space group P212121. The chiral compound undergoes two sharp enantiotropic phase transitions upon cooling. The first transformation occurs at 163 K to yield a unit cell with one axis having double length. This intermediate‐temperature form has the monoclinic space group P21. The second transition takes place at 142 K and converts the single crystal into the low‐temperature form in the orthorhombic space group P212121. This transition proceeds under tripling of the a axis of the high‐temperature form. Both phase transitions are fully reversible and correspond to order–disorder transitions of the isopropyl group of the valine unit in the ligand backbone. The phase transitions presented here raise questions, since they do not fit into the rules of group–subgroup relationships. 相似文献
128.
Dominik Grtner Andr Luiz Stein Sabine Grupe Johannes Arp Axel JacobivonWangelin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(36):10691-10695
Stable C O linkages are generally unreactive in cross‐coupling reactions which mostly employ more electrophilic halides or activated esters (triflates, tosylates). Acetates are cheap and easily accessible electrophiles but have not been used in cross‐couplings because the strong C O bond and high propensity to engage in unwanted acetylation and deprotonation. Reported herein is a selective iron‐catalyzed cross‐coupling of diverse alkenyl acetates, and it operates under mild reaction conditions (0 °C, 2 h) with a ligand‐free catalyst (1–2 mol %). 相似文献
129.
Silke C. Wenzel Holger Hoffmann Jidong Zhang Laurent Debussche Sabine Haag‐Richter Michael Kurz Frederico Nardi Peer Lukat Irene Kochems Heiko Tietgen Dietmar Schummer Jean‐Paul Nicolas Loreley Calvet Valerie Czepczor Patricia Vrignaud Agnes Mühlenweg Stefan Pelzer Rolf Müller Mark Brnstrup 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(51):15781-15785
130.
Synthesis of Cembranoid Analogues through Ring‐Closing Metathesis of Terpenoid Precursors: A Challenge Regarding Ring‐Size Selectivity
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Tanja Heidt Dr. Angelika Baro Prof. Andreas Köhn Prof. Sabine Laschat 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(35):12396-12404
A systematic study on ring‐closing metathesis with Grubbs II catalyst to cembranoid macrocycles is described. Acyclic terpenoids with a functional group X in the homoallylic position relative to an RCM active terminus and substituents R, R1 directly attached to the other terminal double bond were prepared from geraniol derived trienes and fragments that are based on bromoalkenes and dimethyl malonate. Such terpenoids were suitable precursors, despite the presence of competing double bonds in their framework. The size of R and R1 is crucial for successful macrocyclization. Whereas small alkyl substituents at the double bond directed the RCM towards six‐membered ring formation, cross metathesis leading to dimers dominated for bulkier alkyl groups. A similar result was obtained for precursors without functional group X. In the case of unsymmetrically substituted terpenoid precursor (R=Et, R1=Me) with homoallylic OTBS or OMe group, the RCM could be controlled towards formation of macrocyclic cembranoids, which were isolated with excellent E‐selectivity. The role of the substituents was further studied by quantum chemical calculations of simplified model substrates. Based on these results a mechanistic rationale is proposed. 相似文献