JOURNAL MENUFIND ISSUES
FIND ARTICLES
GET ACCESS
FOR CONTRIBUTORS
ABOUT THIS JOURNAL
SPECIAL FEATURES
Angewandte Chemie International EditionEarly View (Online Version of Record published before inclusion in an issue)Editor: Peter G&litz, Deputy Editors: Neville Compton, Haymo RossOnline ISSN: Associated Title(s): , , , , ,
Select AllVIEW1 - 100Phase Transitions | Hot PaperDr. Maxim Bykov, Dr. Elena Bykova, Dr. Michael Hanfland, Dr. Hanns-Peter Liermann, Dr. Reinhard K. Kremer, Prof. Dr. Robert Glaum, Prof. Dr. Leonid Dubrovinsky and Prof. Dr.
Sander van SmaalenVersion of Record online: 31 OCT 2016 | DOI: 10.1002/anie. Under pressure: The first example of a phosphorus atom coordinated by five oxygen atoms in an inorganic network structure was found in titanium(III) orthophosphate, TiPO4, at 48 GPa. This phase was characterized by synchrotron single-crystal X-ray diffraction in diamond anvil cells. Catalytic HydrogenationTobias Schwob and Prof. Dr. Rhett KempeVersion of Record online: 31 OCT 2016 | DOI: 10.1002/anie. Reduce, reuse, recycle: A reusable nanocomposite cobalt catalyst was developed that is easy to synthesize and can be handled in air. It efficiently mediates the selective hydrogenation of nitroarenes, as well as the direct synthesis of imines or benzimidazoles from nitroarenes and aldehydes. Functional groups that are highly sensitive to hydrogenation are well tolerated, and the hydrogenation activity can be regenerated through temperature-programmed reduction. Heme ProteinsDr. Rahul L. Khade, Yuwei Yang, Yelu Shi and Prof. Dr. Yong ZhangVersion of Record online: 31 OCT 2016 | DOI: 10.1002/anie. Nitroxyl coordination is an important step for its biological function. It is shown that 1) HNO preferably coordinates to iron(II) porphyrins as compared to iron(III) owing to better metal-to-ligand back-donation, 2) the axial ligand strongly influences HNO coordination through trans and charge donation effects, and 3) the heme protein environment has a significant effect on HNO hydrogen bonding. MOFs as SensorsDr. Omar Yassine, Dr. Osama Shekhah, Ayalew H. Assen, Dr. Youssef Belmabkhout, Prof. Khaled N. Salama and Prof. Mohamed EddaoudiVersion of Record online: 31 OCT 2016 | DOI: 10.1002/anie. Sense and sense ability: The detection of hydrogen sulfide at room temperature using the metal&organic framework (fum-fcu-MOF) as a sensitive layer deposited on capacitive interdigitated electrodes is demonstrated. H2S concentrations down to 100 ppb were detected with a limit of detection around 5 ppb. Zeolite EngineeringDr. Zhengxing Qin, Dr. Georgian Melinte, Prof. Jean-Pierre Gilson, Prof. Maguy Jaber, Prof. Krassimir Bozhilov, Dr. Philippe Boullay, Dr. Svetlana Mintova, Prof. Ovidiu Ersen and Dr. Valentin ValtchevVersion of Record online: 31 OCT 2016 | DOI: 10.1002/anie. Etch it out: A controlled fluoride medium treatment is used to expose the local structure of zeolite crystals. Unexpectedly high concentrations of nanometer-sized crystalline domains, separated by low-angle boundaries, were discovered. You have free access to this contentGiulia Morgese, Lucca Trachsel, Dr. Matteo Romio, Mohammad Divandari, Dr. Shivaprakash N. Ramakrishna and Dr. Edmondo M. BenettiVersion of Record online: 28 OCT 2016 | DOI: 10.1002/anie. Topological effects by cyclic polymers are enhanced in the confinement of a surface. In their Communication (DOI: ), E. M. Benetti et al. show that cyclic polyoxazoline brushes provide higher steric stabilization with respect to their linear analogues and display superlubricious behavior in water. Topological polymer chemistry enters surface science and reveals results that seem to confirm Wolfgang Pauli's famous statement: &G the surface was invented by the devil.& Version of Record online: 28 OCT 2016 | DOI: 10.1002/anie.
Methane DehydroaromatizationYou have full text access to this OnlineOpen articleDr. Nikolay Kosinov, Ferdy J. A. G. Coumans, Evgeny Uslamin, Prof. Freek Kapteijn and Prof. Emiel J. M. HensenVersion of Record online: 28 OCT 2016 | DOI: 10.1002/anie. Quicken the pulse: Supplying short oxygen pulses to a catalytic bed of molybdenum/ZSM-5 during methane dehydroaromatization leads to selective coke combustion. Catalyst deactivation is mitigated without degradation of molybdenum content and zeolite crystallinity, resulting in higher benzene productivity. Version of Record online: 28 OCT 2016 | DOI: 10.1002/anie.
Version of Record online: 28 OCT 2016 | DOI: 10.1002/anie.
My favorite place on earth is at home, especially after finishing a trip. I chose chemistry as a career because of an inspiring chemistry teacher in first-year chemistry at Queen's University. You have free access to this contentZhi-Long Yu, Guan-Cheng Li, Dr. Nina Fechler, Ning Yang, Zhi-Yuan Ma, Xin Wang, Prof. Dr. Markus Antonietti and Prof. Dr. Shu-Hong YuVersion of Record online: 28 OCT 2016 | DOI: 10.1002/anie. The polymerization of phenol&formaldehyde resin under hypersaline conditions, for example, in the presence of ZnCl2, generates a black monolith. In their Communication (DOI: ), N. Fechler, M. Antonietti, S. H. Yu, et al. further show that a foam-like carbon aerogel with good mechanical robustness can be directly obtained from the monolith without any special drying processes. ZnCl2 plays a key role in this process, serving as dehydration agent, foaming agent, and porogen. Molecular ElectronicsSonia Vela, Stefan Bauroth, Dr. Carmen Atienza, Dr. Agust&n Molina-Ontoria, Prof. Dr. Dirk M. Guldi and Prof. Dr. Nazario Mart&nVersion of Record online: 28 OCT 2016 | DOI: 10.1002/anie. Whizzing along the wire: A series of electron-donor&acceptor hybrids of a zinc porphyrin and C60 connected through molecular wires based on a combination of covalent and noncovalent interactions (see picture) exhibited efficient charge transport. Hydrogen-bonding interactions and p-phenylene oligomers of different lengths were responsible for electron transfer in these molecular wires. Cross-Coupling ReactionsRen-Qi Xu, Ping Yang, Hang-Fei Tu, Shou-Guo Wang and Prof. Dr. Shu-Li YouVersion of Record online: 28 OCT 2016 | DOI: 10.1002/anie. 2-Napthalenones made easy: Pd0-catalyzed intermolecular arylative dearomatization of &-naphthols with aryl halides is described. It was found that Q-Phos could facilitate the palladium-catalyzed cross-coupling dearomatization of &-naphthols while avoiding O-arylation, to construct 2-naphthalenones in excellent yields and with high chemoselectivity. PhotochromismAlex Juli&-L&pez, Dr. Jordi Hernando, Dr. Daniel Ruiz-Molina, Pablo Gonz&lez-Monje, Dr. Josep Sed& and Dr. Claudio RosciniVersion of Record online: 28 OCT 2016 | DOI: 10.1002/anie. Positive or negative: Solid composites with switchable positive/negative photochromism were obtained by embedding core&shell microcapsules containing photochromic solutions of spiropyran dyes in acidic phase-change media in polymeric matrices. The photochromism of these materials could be switched by inducing the melting/solidification of the encapsulated medium through a change in temperature. Molecular CapsulesDr. Kohei Yazaki, Shogo Noda, Dr. Yuya Tanaka, Dr. Yoshihisa Sei, Prof. Dr. Munetaka Akita and Dr. Michito YoshizawaVersion of Record online: 28 OCT 2016 | DOI: 10.1002/anie. Polyradical capsule: A new M2L4 molecular capsule is quantitatively formed by mixing metal ions and dihydrophenazine-based ligands. The capsule has a spherical nanocavity enclosed by eight redox-active, dihydrophenazine panels. Electrochemical and chemical oxidation of the capsule leads to the reversible generation of a stable tetra(radical cation) capsule. Metal&Organic Frameworks | Hot PaperDr. Qiang Gao, Dr. Jian Xu, Prof. Dapeng Cao, Dr. Ze Chang and Prof. Xian-He BuVersion of Record online: 28 OCT 2016 | DOI: 10.1002/anie. A thermal cork screw: Counterions act as removable corks blocking the pore openings of a rigid nested metal&organic framework (MOF). The thermoresponsive gating adsorption behavior of the MOF is dominated by the counterion corks, rather than the flexibility modes of other stimuli-responsive MOFs. On heating, the corks are removed from the openings, on cooling they return. Heterocycle SynthesisDr. Zhong-Liang Li, Dr. Xiao-Hua Li, Na Wang, Ning-Yuan Yang and Prof. Dr. Xin-Yuan LiuVersion of Record online: 28 OCT 2016 | DOI: 10.1002/anie. The old 1,2: A novel 1,2-formyl functionalization of unactivated alkenes involving formyl migration and addition of radicals to alkenes has been developed for access to synthetically important &-functionalized aldehydes. The analogous keto-carbonyl migration has been performed to synthesize challenging medium-sized diketones, which are additionally transformed into complex fused rings. PerovskiteMeiying Leng, Zhengwu Chen, Ying Yang, Dr. Zha Li, Kai Zeng, Kanghua Li, Dr. Guangda Niu, Yisu He, Qingchao Zhou and Prof. Jiang TangVersion of Record online: 28 OCT 2016 | DOI: 10.1002/anie. Better than Sn or Pb: The synthesis and optical characterization of bismuth-based MA3Bi2Br9 perovskite quantum dots with a photoluminescence quantum yield of up to 12&% is described. Further, the photoluminescence peaks of MA3Bi2X9 QDs (X=Cl, Br, I) could be easily tuned from 360 to 540 nm through anion exchange. Medical Chemistry | Hot PaperDr. Paul A. Bruno, Dr. Alex Morriss-Andrews, Andrew R. Henderson, Prof. Dr. Charles L. Brooks III and Prof. Dr. Anna K. MappVersion of Record online: 28 OCT 2016 | DOI: 10.1002/anie. A peptide-based inhibitor of canonical NF-&B signaling, in which a hydrogen bond in the NBD peptide is synthetically replaced by a non-labile bond, shows an about 10-fold increased potency relative to the original inhibitor. The success of the synthetic replacement of a peptide loop suggests that the general strategy could be broadly useful for discovering modulators of many protein&protein interactions mediated by such structures. Supramolecular Chemistry | Hot PaperDr. Se&n T. J. Ryan, Dr. Jes&s del Barrio, Dr. Reynier Suard&az, Dr. Daniel F. Ryan, Dr. Edina Rosta and Prof. Dr. Oren A. SchermanVersion of Record online: 28 OCT 2016 | DOI: 10.1002/anie. One ring to rule them all & and in the darkness bind them: A photoresponsive tetracationic macrocycle features a facile three-step synthesis and makes possible the noncovalent binding of a set of guest molecules, including N-oxide and carboxylate derivatives. The guest molecules can be actively released by UV light irradiation in a remote fashion. ElectrochemistryRainer Schwarz, Dr. Marijana Pejic, Philipp Fischer, Dr. Mario Marinaro, Dr. Ludwig J&rissen and Dr. Mario WachtlerVersion of Record online: 28 OCT 2016 | DOI: 10.1002/anie. Magnesium batteries: Reversible electrochemical magnesium plating and stripping is reported in a magnesocene-based electrolyte. The electrolyte shows minimal overpotentials, a high coulombic efficiency, and an excellent electrochemical cycling stability. The electrolyte is a first member of a new class of complex electrolytes. PerovskitesAlexander D. Jodlowski, Dr. Alfonso Y&pez, Prof. Rafael Luque, Prof. Luis Camacho and Prof. Gustavo de MiguelVersion of Record online: 28 OCT 2016 | DOI: 10.1002/anie. Mill it! A straightforward solventless mechanochemical method enabled the preparation of four types of hybrid perovskites in large amounts as polycrystalline powders with high purity and excellent optoelectronic properties. Two archetypal 3D perovskites (MAPbI3 and FAPbI3), a 2D perovskite (Gua2PbI4), and a &double-chain& 1D perovskite (GuaPbI3) were synthesized ( MA=methylammonium, FA=formamidinium, Gua=guanidinium). ArylationYingcheng Wang, Liang Jiang, Long Li, Jun Dai, Dan Xiong and Prof. Dr. Zhihui ShaoVersion of Record online: 27 OCT 2016 | DOI: 10.1002/anie. Enantioenriched propargylamines were synthesized in asymmetric Friedel&Crafts-type arylation reactions of in situ generated N-Boc-protected C-alkynyl imines with phenols, indoles, pyrrole, and 2-methoxyfuran. This process constitutes the first asymmetric Friedel&Crafts reaction with electron-deficient phenols. Alkene DifunctionalizationAndreas Lerchen, Tobias Knecht, Dr. Constantin G. Daniliuc and Prof. Dr. Frank GloriusVersion of Record online: 27 OCT 2016 | DOI: 10.1002/anie. It&s cobaltastic: An unprecedented regioselective and entirely atom-economic cobalt(III)-catalyzed method for the non-annulative, intermolecular carboamination of alkenes enables the direct synthesis of acyclic unnatural amino acid derivatives in a redox-neutral fashion. Moreover Cp*CoIII and Cp*RhIII catalysts gave different products under otherwise identical conditions. Quantum DotsYitao Cao, Dr. Wei Geng, Run Shi, Dr. Lu Shang, Prof. Geoffrey I. N. Waterhouse, Prof. Limin Liu, Prof. Li-Zhu Wu, Prof. Chen-Ho Tung, Prof. Yadong Yin and Prof. Tierui ZhangVersion of Record online: 27 OCT 2016 | DOI: 10.1002/anie. Not only metals: Low temperature photoinduced syntheses allow improved control over reaction kinetics and the synthesis of metal nanoparticles with unusual morphologies. Here, the photoinduced synthesis of ultrafine Ag2S quantum dots from Ag nanoparticles was demonstrated for the first time. Further, a fundamental bridge was established between the intrinsic structures of silver thiolate intermediates and the Ag2S. Surface ChemistryChen Shi, Bin Yan, Lei Xie, Ling Zhang, Jingyi Wang, Prof. Atsushi Takahara and Prof. Hongbo ZengVersion of Record online: 27 OCT 2016 | DOI: 10.1002/anie. Wetting phenomena: A long-range hydrophilic attraction in an oil medium was discovered between water and zwitterionic, cationic, and anionic polyelectrolyte molecules using an atomic force microscopy technique. The unexpected strong attraction could possibly be attributed to a strong dipolar interaction due to the large dipole moment of the polyelectrolyte molecules. Protein&Protein InteractionsYou have full text access to this OnlineOpen articleStijn M. Agten, Dr. Rory R. Koenen, Dr. Hans Ippel, Veit Eckardt, Dr. Philipp von Hundelshausen, Prof. Dr. Kevin H. Mayo, Prof. Dr. Christian Weber and Prof. Dr. Tilman M. HackengVersion of Record online: 27 OCT 2016 | DOI: 10.1002/anie. Kissing chemokines: Heteromeric chemokine interactions are implicated in various inflammatory diseases. Because it is unclear whether pathological effects are caused by heterodimerization or by additive effects of separate chemokines, a covalent oxime-linked chemokine heterodimer was synthesized. Oxime ligation was accelerated by interactions between the chemokines, and the heterodimer showed enhanced function compared to mixed chemokines. Borrowing HydrogenDr. Miguel Pe&a-L&pez, Patrick Piehl, Saravanakumar Elangovan, Dr. Helfried Neumann and Prof. Dr. Matthias BellerVersion of Record online: 27 OCT 2016 | DOI: 10.1002/anie. Something borrowed, something new: A hydrogen-autotransfer reaction catalyzed by manganese(I) PNP pincer complexes was developed for the &-alkylation of ketones with alcohols (see scheme). Structurally diverse primary alcohols were used to functionalize a wide range of ketones, including 2-oxindole, estrone 3-methyl ether, and testosterone, by this straightforward method. OrganocatalysisDr. Huilin Li, Prof. Rongbiao Tong and Prof. Jianwei SunVersion of Record online: 27 OCT 2016 | DOI: 10.1002/anie. Piancatelli rapido: An efficient organocatalytic enantioselective aza-Piancatelli rearrangement is disclosed. The powerful process provides rapid access to valuable chiral 4-amino-2-cyclopentenone building blocks from readily available 2-furfurylcarbinols with excellent chemo-, enantio-, and diastereoselectivities under mild reaction conditions. You have free access to this contentDr. Volodymyr Smetana and Prof. Dr. Anja-Verena MudringVersion of Record online: 26 OCT 2016 | DOI: 10.1002/anie. A rare family of compounds in which a metal forms a truly negatively charged ion, in this case Pt2& ions, is represented by the new cesium platinide hydride Cs9Pt4H. In their Communication (DOI: 10.1002/anie.), A.-V. Mudring and V. Smetana show that the existence of this compound and its properties which feature a band gap in the visible range of the electromagnetic spectrum together with optical transparency serve as an experimental evidence for the relativistic stabilization of the Pt 6s2 state. Inhibitors | Very Important PaperYou have full text access to this OnlineOpen articleChristopher Adamson, Robert J. Pengelly, Saeideh Shamsi Kazem Abadi, Dr. Saswati Chakladar, Jason Draper, Prof. Robert Britton, Dr. Tracey M. Gloster and Prof. Andrew J. BennetVersion of Record online: 26 OCT 2016 | DOI: 10.1002/anie. Cyclopropyl carbocycles inhibitors of a glycoside hydrolase act by covalently modifying the nucleophilic carboxylate while still retaining the strained cyclopropyl ring. A combined synthetic, kinetic, and structural study reveals the conformational itinerary for this family of carbocyclic inactivators through the incorporation of a fluorine atom into the inhibitor structure. Block CopolymersDr. Feng Zhou, Ke-Hua Gu, Zhen-Yu Zhang, Meng-Yao Zhang, Sheng Zhou, Prof. Dr. Zhihao Shen and Prof. Dr. Xing-He FanVersion of Record online: 26 OCT 2016 | DOI: 10.1002/anie. One or the other: By making use of host&guest interactions, the supramolecular rod&rod block copolymer P(EO@TPP)-b-PVBP was constructed. As the PVBP segments arrange themselves as nematic phases, the crystalline structure of the inclusion complex P(EO@TPP) is destroyed. The nanostructure is thus clearly affected by the interplay between the two blocks. AminationsZhihui Shao, Dr. Shaomin Fu, Mufeng Wei, Prof. Dr. Shaolin Zhou and Prof. Dr. Qiang LiuVersion of Record online: 26 OCT 2016 | DOI: 10.1002/anie. Selectivity is under control: A cobalt-catalyzed chemodivergent transfer hydrogenation of nitriles for the selective synthesis of primary, secondary, and even tertiary amines has been developed. This mild system achieved &2000 TONs and more than 70 amines were produced by this strategy, highlighting the efficiency and broad applicability of this cobalt catalysis system. C&H FunctionalizationZhunzhun Yu, Yongfeng Li, Jiameng Shi, Ben Ma, Prof. Dr. Lu Liu and Prof. Dr. Junliang ZhangVersion of Record online: 26 OCT 2016 | DOI: 10.1002/anie. Commercially available (C6F5)3B as the catalyst enables the highly chemo- and ortho-selective substitution of phenols with &-aryl &-diazoacetates. This reaction proceeds under simple and mild conditions with high efficiency, features a wide substrate scope, and can be easily scaled up. Drug Discovery | Very Important PaperDr. Franziska A. Mandl, Volker C. Kirsch, Dr. Ilke Ugur, Elena Kunold, Jan Vomacka, Christian Fetzer, Dr. Sabine Schneider, Dr. Klaus Richter, Prof. Dr. Thilo M. Fuchs, Prof. Dr. Iris Antes and Prof. Dr. Stephan A. SieberVersion of Record online: 26 OCT 2016 | DOI: 10.1002/anie. Aminoepoxycyclohexenones inhibit the growth of Gram-negative Salmonella in the low micromolar range. The bacterial targets of these antibiotics were analyzed by quantitative ABPP, which revealed a link to bacterial stress response that was validated by various assays. Aminoepoxybenzoquinones were thus validated as natural product scaffolds with suitable properties for the growth inhibition of Salmonella. Selective HomologationYou have full text access to this OnlineOpen articleAlexander Fawcett, Dr. Dominik Nitsch, Prof. Dr. Muhammad Ali, Joseph M. Bateman, Dr. Eddie L. Myers and Prof. Dr. Varinder K. AggarwalVersion of Record online: 26 OCT 2016 | DOI: 10.1002/anie. All under control: 1,2-Bis(boronic esters), derived from the enantioselective diboration of terminal alkenes, undergo selective homologation of the primary boronic ester by using enantioenriched lithiated primary/secondary carbamates/benzoates to give secondary-secondary and secondary-tertiary 1,3-diols with full stereocontrol. The methodology was applied to a concise total synthesis of the 14-membered macrolactone Sch&725674. Radical ActivationDr. Qingquan Lu and Prof. Dr. Frank GloriusVersion of Record online: 26 OCT 2016 | DOI: 10.1002/anie. Radical style: Several breakthroughs have recently been achieved in enantioselective C(sp3)&H functionalization through radical activation. These new strategies show how radical chemistry can be used to convert alkanes into functionalized chiral molecules ( HAT=hydrogen atom transfer). Version of Record online: 26 OCT 2016 | DOI: 10.1002/anie.
Looking back over my career, I am too busy looking ahead. When I was eighteen I wanted to be a nonrecrea higher education was plan B, and studying chemical engineering was improvisation. BiocatalysisCheau Yuaan Tan, Dr. Hidehiko Hirakawa, Risa Suzuki, Tomoaki Haga, Fumiya Iwata and Prof. Teruyuki NagamuneVersion of Record online: 26 OCT 2016 | DOI: 10.1002/anie. Multiple enzymes immobilized: Bacterial cytochrome P450 enzymes catalytically require electrons that are carried by electron-transfer proteins from NAD(P)H-dependent reductases. A heterotrimeric, protein-mediated assembly of a P450, electron-transfer protein, and reductase on solid supports enabled co-immobilization of the three proteins close to each other and allowed electron transfer between the P450 and reductase. Cascade Reactions | Hot PaperKe Li, Jinjie Ou and Prof. Dr. Shuanhu GaoVersion of Record online: 26 OCT 2016 | DOI: 10.1002/anie. Natural products containing indolizinone or quinolizinone moieties and analogues thereof were obtained by a cascade exo hydroamination followed by spontaneous lactamization. This method was applied to the total synthesis of camptothecin in nine steps and to efficiently prepare five biogenetically or structurally related natural alkaloids. PhotochemistryDr. Benoit Mignolet, Dr. Basile F. E. Curchod and Prof. Dr. Todd J. Mart&nezVersion of Record online: 26 OCT 2016 | DOI: 10.1002/anie. An outlaw molecule: Theoretical studies show that sulfine exhibits an incredibly rich chemistry upon light-irradiation, challenging the traditional view of photochemical and photodecomposition reactions due to highly nonstatistical behavior. Supramolecular ChemistryYou have full text access to this OnlineOpen articleDr. Fabian Dielmann, Dr. Eugenia V. Peresypkina, Barbara Kr&mer, Florian Hastreiter, Dr. Brian P. Johnson, Dr. Manfred Zabel, Dr. Claudia Heindl and Prof. Dr. Manfred ScheerVersion of Record online: 26 OCT 2016 | DOI: 10.1002/anie. The self-assembly of cyclo-P4 complexes [CpRTa(CO)2(&4-P4)] (CpR=Cp&&, Cp&&&) and CuX results in spherical supramolecules with non-classical fullerene-like topology (X=Cl, Br) and two supramolecules with unprecedented peanut- and pear-like scaffolds (X=I). The outer diameter of the macromolecules reached 2.5 nm. The solubility of the Cp&&& derivatives enabled their NMR spectroscopic characterization in solution. Gas-Phase ChemistryDr. Tao Yang, Dr. Tyler P. Troy, Dr. Bo Xu, Dr. Oleg Kostko, Dr. Musahid Ahmed, Prof. Dr. Alexander M. Mebel and Prof. Dr. Ralf I. KaiserVersion of Record online: 26 OCT 2016 | DOI: 10.1002/anie. Born of fire: The reaction routes leading to the formation of polycyclic aromatic hydrocarbons present in the interstellar medium remain ambiguous. By revealing the reactivity of the styrenyl and the ortho-vinylphenyl radicals with acetylene, the first solid experimental evidence on the formation of naphthalene in a simulated combustion environment is provided, validating the postulated hydrogen-abstraction/acetylene-addition mechanism. Graphene ChemistryRicarda A. Sch&fer, Konstantin Weber, Dr. Maria Koleśnik-Gray, Dr. Frank Hauke, Prof. Dr. Vojislav Krstić, Prof. Dr. Bernd Meyer and Prof. Dr. Andreas HirschVersion of Record online: 26 OCT 2016 | DOI: 10.1002/anie. The rear side of graphene: Mechanical exfoliated graphene was activated and functionalized via &-iodane chemistry. The resulting functionalized graphene was analyzed with scanning Raman microscopy. The experimental results were confirmed and explained by DFT calculations. The monolayer graphene was found to be more reactive than bilayer graphene. CyclophanesDr. Jos& L. Zafra, Lili Qiu, Naoyuki Yanai, Takamichi Mori, Dr. Masahiro Nakano, Dr. Miriam Pe&a Alvarez, Prof. Juan T. L&pez Navarrete, Prof. Carlos J. G&mez-Garc&a, Prof. Miklos Kertesz, Prof. Kazuo Takimiya and Prof. Juan CasadoVersion of Record online: 26 OCT 2016 | DOI: 10.1002/anie. Long and weak C&C bonds are formed from a quinonoidal diradical molecule and lead to either double &-bonded cyclophane dimers or &-bonded polymers. The highly strained character of the C&C bonds makes these reactions reversible and the quinonoidal&aromatic transformation results in a large change in the optical properties and thus large chromic effects. Activation of P4Ryan J. Schwamm, Dr. Matthias Lein, Dr. Martyn P. Coles and Dr. Christopher M. FitchettVersion of Record online: 26 OCT 2016 | DOI: 10.1002/anie. The stability of terminal Bi&P bonds in diamidobismuth(III) phosphanides towards single-electron decomposition depends on the phosphorus ligands. Diphenylphosphanides spontaneously decompose to BiII species, used to prepare a new diamidodibismuthane, whereas dicyclohexylphosphanides can be isolated. This is exploited in the reversible activation of P4 by an isolated BiII radical (see scheme). PolyynesMaximilian Krempe, Dr. Rainer Lippert, Dr. Frank Hampel, Prof. Dr. Ivana Ivanović-Burmazović, Prof. Dr. Norbert Jux and Prof. Dr. Rik R. TykwinskiVersion of Record online: 26 OCT 2016 | DOI: 10.1002/anie. Protective phenyl groups: A synthetic route to the longest known pyridyl-endcapped polyynes is developed. The wire-like molecules are stabilized based on steric shielding from pyridyl substituents, and the polyynes serve as molecular wires through endcapping with either Zn- or Ru-porphyrins via axial coordination. MetalloproteinsDr. Ladislav Benda, Dr. Jiř& Mareš, Dr. Enrico Ravera, Prof. Dr. Giacomo Parigi, Prof. Dr. Claudio Luchinat, Prof. Dr. Martin Kaupp and Prof. Dr. Juha VaaraVersion of Record online: 26 OCT 2016 | DOI: 10.1002/anie. Paramagnetic NMR spectroscopy: Long-range NMR pseudo-contact shifts (PCSs) of a paramagnetic metalloprotein were obtained by first-principles calculations. Based on EPR-parameter calculations by multi-reference methods and a point-dipole approximation, the PCSs of an entire metalloprotein domain could be computed. By comparison with experimental data, these were used to evaluate the quality of theoretical and experimental input structures. NanoclustersDr. Kiran Kumarvarma Chakrahari, Jian-Hong Liao, Dr. Samia Kahlal, Dr. Yu-Chiao Liu, Dr. Ming-Hsi Chiang, Prof. Jean-Yves Saillard and Prof. C. W. LiuVersion of Record online: 26 OCT 2016 | DOI: 10.1002/anie. Just like in the metal: Cu13 clusters with a centered cuboctahedral unit, a model of the bulk Cu metal fcc structure, have been synthesized. The [Cu13]11+ core can be described as a two- four of the eight triangular faces are capped by acetylide groups, and each of the six square faces is bridged by a dithiolate ligand to yield ideal tetrahedral symmetry. C&C CouplingDr. St&phanie Dupuy, Ke-Feng Zhang, Dr. Anne-Sophie Goutierre and Prof. Dr. Olivier BaudoinVersion of Record online: 26 OCT 2016 | DOI: 10.1002/anie. Remote control: Secondary alkyl bromides underwent regioconvergent Barbier&Negishi coupling with aryl triflates in the presence of a phosphine ligand favoring Pd migration to give linear products with good to high linear/branched selectivity (see scheme). This procedure was also applied to mixtures of secondary alkyl bromides, prepared from linear alkanes by standard bromination. Spectroscopic MethodsDr. Abhishek Banerjee, Arnab Dey and Prof. Dr. Narayanan ChandrakumarVersion of Record online: 26 OCT 2016 | DOI: 10.1002/anie. Two to tango, three to jive: A system of three spins (one electron and two nuclear spins), with strong electron&nuclear interactions which dominate nuclear spin relaxation, exhibits a monotonic exponential build-up of Overhauser dynamic nuclear polarization (ODNP) of both nuclear spins under microwave irradiation of the electron spin. When electron&nuclear interactions are weaker, and internuclear interactions are present, the build-up curve goes through an extremum, and reflects internuclear cross-relaxation. Lithium&Sulfur BatteriesYingying Mi, Dr. Wen Liu, Dr. Ke R. Yang, Dr. Jianbing Jiang, Dr. Qi Fan, Dr. Zhe Weng, Yiren Zhong, Zishan Wu, Prof. Gary W. Brudvig, Prof. Victor S. Batista, Prof. Henghui Zhou and Prof. Hailiang WangVersion of Record online: 25 OCT 2016 | DOI: 10.1002/anie. A lithium&sulfur battery cathode with excellent cycling stability was realized with polysulfide-confining ferrocene covalently anchored on graphene oxide. Polysulfide-binding originates from favorable cation&& interactions between Li+ of lithium polysulfides and the negatively charged cyclopentadienyl ligands of ferrocene. Main-Group ChemistryDr. Christian Marquardt, M. Sc. Tobias Kahoun, Dr. Andreas Stauber, Dr. G&bor Bal&zs, Dr. Michael Bodensteiner, Prof. Dr. Alexey Y. Timoshkin and Prof. Dr. Manfred ScheerVersion of Record online: 25 OCT 2016 | DOI: 10.1002/anie. Finally, thoroughly negative! Using alkali-metal salts of phosphanide and arsenide, the parent compounds of the phosphanyl- and arsanylboranes can be easily converted into linear anionic chain molecules. They are unique representatives of the anionic class of pnictogenylboranes and could be structurally characterized. Synthetic MethodsDr. Yajun Li and Prof. Fraser F. FlemingVersion of Record online: 25 OCT 2016 | DOI: 10.1002/anie. An orchestrated sequence: An efficient synthesis of alkeneisocyanides is achieved through the sequenced addition of RLi to nitriles, formylation, and dehydration. A key step in this one-pot sequence is a CuCN-catalyzed equilibration of a formyl imine to an N-formyl enamine. The utility of the reaction is illustrated in a new [4+2]-type cycloaddition/1,3-H shift/decyanation. MetalloproteinsPauline N. Serrano, Dr. Hongxin Wang, Dr. Jason C. Crack, Christopher Prior, Prof. Matthew I. Hutchings, Prof. Andrew J. Thomson, Dr. Saeed Kamali, Dr. Yoshitaka Yoda, Dr. Jiyong Zhao, Dr. Michael Y. Hu, Dr. Ercan E. Alp, Dr. Vasily S. Oganesyan, Prof. Nick E. Le Brun and Prof. Stephen P. CramerVersion of Record online: 25 OCT 2016 | DOI: 10.1002/anie. Nuclear resonance vibrational spectroscopy of NO-sensing proteins WhiD and NsrR reveal products of [4Fe-4S] cluster reaction with NO related to Roussin's Red Ester (RRE) and Roussin's Black Salt (RBS) species. RBS itself was not a product, but instead the results point to a new Roussin's Black Ester-type species featuring Cys thiolate coordination in place of sulfide. Transition Metal ComplexesDr. David J. Liptrot, Dr. Jing-Dong Guo, Prof. Shigeru Nagase and Prof. Philip P. PowerVersion of Record online: 25 OCT 2016 | DOI: 10.1002/anie. Gecko-fabulous: Dispersion-corrected density functional theory analysis on first row transition metal(IV) complexes of the norbornyl ligand, M(nor)4 (M=Co, Fe, Ni) and Ni(nor)3Br show that dispersion force attraction between these rigid substituents is fundamental to the stability of these unusually high oxidation state complexes. Fluorescent ProbesXiaofeng Wu, Dr. Lihong Li, Prof. Dr. Wen Shi, Dr. Qiuyu Gong and Prof. Dr. Huimin MaVersion of Record online: 24 OCT 2016 | DOI: 10.1002/anie. One fish, two fish, near-infrared fish: A highly specific NIR fluorescent probe (1) was developed for monitoring tyrosinase in vivo without interference from reactive oxygen species (ROS). Probe 1 contains a new tyrosinase-recognition moiety, 3-hydroxybenzyloxy, in a stable hemicyanine skeleton, and its high specificity permits the accurate detection of the tyrosinase activity in live cells and zebrafish. Drug DesignProf. Andreas Link and Prof. Christa E. M&llerVersion of Record online: 24 OCT 2016 | DOI: 10.1002/anie. Together forever? Functional selection was applied to finally achieve separation of the analgesic properties of opiods from serious side effects such as potentially lethal respiratory depression. A Gi-biased &-opioid-receptor agonist (PZM21) was identified that stabilizes previously unexplored receptor conformations. This compound relieves pain in mice without causing hypoventilation or addiction. Valentine P. AnanikovVersion of Record online: 24 OCT 2016 | DOI: 10.1002/anie. RSC Publishing, 4 pp., hardcover, &&#x.&ISBN&#x2620563 Multiple BondsDr. Lingbing Kong, Dr. Wei Lu, Dr. Yongxin Li, Dr. Rakesh Ganguly and Prof. Dr. Rei KinjoVersion of Record online: 24 OCT 2016 | DOI: 10.1002/anie. Metal-free regioselective carboboration of arylnitriles with L2PhB: 1 (L=oxazol-2-ylidene) afforded the acyclic 2-aza-4-borabutadienes 2&a&c. Thermal isomerization of 2&a&c gave C-borylimines while reactions of 2&a towards several substrates allowed construction of B,N-containing heterocycles with various ring sizes (three- to six-membered rings), thus demonstrating the synthetic utility of 2 as building blocks. Methane ActivationDr. Shaodong Zhou, Prof. Dr. Jilai Li, Dr. Maria Schlangen and Prof. Dr. Helmut SchwarzVersion of Record online: 24 OCT 2016 | DOI: 10.1002/anie. A mass of evidence: Thermal, gas-phase activation of methane by the closed-shell metal-oxide cluster [Al2TaO5]+ with C&H bond activation is investigated by FT-ICR mass spectrometry and quantum chemical calculations. The picture shows the thermal activation of methane by [Al2TaO5]+ (the signal labeled with &&& is due to reaction with background water). Hollow SpheresDr. Yawen Wang, Dr. Le Yu and Prof. Xiong Wen (David) LouVersion of Record online: 24 OCT 2016 | DOI: 10.1002/anie. Cheerful hollow: Triple-shelled Mo-polydopamine hollow spheres are synthesized from highly uniform Mo-glycerate solid spheres via a sequential self-templating mechanism. Upon annealing, they are transformed into triple-shelled MoO2/carbon composite hollow spheres, which show enhanced electrochemical properties as an anode material for lithium-ion batteries. Controlled ReleaseDr. Jiangping Xu, Dr. Jun Li, Yi Yang, Dr. Ke Wang, Nan Xu, Dr. Jingyi Li, Dr. Ruijing Liang, Prof. Lei Shen, Prof. Xiaolin Xie, Prof. Juan Tao and Prof. Jintao ZhuVersion of Record online: 24 OCT 2016 | DOI: 10.1002/anie. By employing a non-solvent as the template, block copolymer capsules with tunable shell structures were fabricated. The properties of the non-solvent dictate the phase separation sequence in the droplets and the capsule formation mechanism, which in turn determine the shell structures of the capsules and cargo release. Conformational AnalysisDr. Patrick S. Walsh, Karl N. Blodgett, Carl McBurney, Prof. Samuel H. Gellman and Prof. Timothy S. ZwierVersion of Record online: 24 OCT 2016 | DOI: 10.1002/anie. Gas-phase chemistry: Single-conformation laser spectroscopy studies of the glutamine-containing molecule Ac-Gln-Gln-NHBn reveal formation of a type-I &-turn in the gas phase. This structure demonstrates the ability of the glutamine sidechain to stabilize this backbone geometry through sidechain-to-backbone hydrogen bonds. This structural result is placed in the larger context of polyglutamine neurodegenerative diseases. Cesium Platinide HydrideDr. Volodymyr Smetana and Prof. Dr. Anja-Verena MudringVersion of Record online: 24 OCT 2016 | DOI: 10.1002/anie. Metal anions: The first cesium platinide hydride has been obtained and characterized. Cs9Pt4H contains Cs+ cations, Pt2&, and H& anions and demonstrates the ability of Cs2Pt to combine with salts into more complex formations. Transparency, band gap in the visible range of the electromagnetic spectrum, and ionic bonding confirm the relativistic stabilization of the Pt 6s2 state. Polymers | Very Important PaperGiulia Morgese, Lucca Trachsel, Dr. Matteo Romio, Mohammad Divandari, Dr. Shivaprakash N. Ramakrishna and Dr. Edmondo M. BenettiVersion of Record online: 24 OCT 2016 | DOI: 10.1002/anie. Cyclic polymer brushes: The cyclic polymer topology strongly alters the interfacial properties of polymer brushes. The smaller hydrodynamic volume coupled with the distinctive cyclic architecture generates surface assemblies with increased grafting density, augmented steric stabilization, improved antifouling and lubrication properties with respect to linear brush counterparts. Drug DeliverySebastian H&rner, Sascha Knauer, Christina Uth, Marina J&st, Dr. Volker Schmidts, Dr. Holm Frauendorf, Prof. Dr. Christina Marie Thiele, Dr. Olga Avrutina and Prof. Dr. Harald KolmarVersion of Record online: 24 OCT 2016 | DOI: 10.1002/anie. COSS and effect: New-generation molecular transporters are based on cell-penetrating cube-octameric silsesquioxanes (COSS). These nanoscale hybrid carriers are biodegradable, low-toxic, and show efficient uptake in living cells of all three domains of life. H2S DonorsDr. Yu Zhao and Prof. Dr. Michael D. PluthVersion of Record online: 24 OCT 2016 | DOI: 10.1002/anie. Release and protection: H2S is an important biomolecule and H2S donors are valuable research and pharmacological tools. An H2S donor is prepared that is stable in aqueous solution and is triggered to release H2S on exposure to reactive oxygen species (ROS), such as hydrogen peroxide. It also provides live cells protection against H2O2-induced oxidative damage. PolymersDr. Xiaochao Shi, Dr. Masayoshi Nishiura and Prof. Dr. Zhaomin HouVersion of Record online: 24 OCT 2016 | DOI: 10.1002/anie. Growth spurt: Both continuous C=C bond insertion and C&H addition of anisole units to vinyl groups took place in the polymerization of para- and meta-methoxystyrenes when catalyzed by a half-sandwich rare-earth catalyst, thus affording novel macromolecules containing multiple branches of alternating anisole-ethylene sequences. In contrast, the polymerization of ortho-methoxystyrene occurred exclusively through continuous C=C insertion without involving C&H activation. Prof. Fran&ois TerrierVersion of Record online: 24 OCT 2016 | DOI: 10.1002/anie. Joseph F. Bunnett, professor emeritus at the University of California, Santa Cruz, passed away on May 22, 2015. Bunnett, who was Founding Editor of Acc. Chem. Res., was an internationally renowned physical organic chemist, who demonstrated that a physical organic approach to reactivity is of fundamental importance in determining the mechanisms of organic reactions, and who published an original paper in verse. Metal&Organic FrameworksKeumnam Cho, Prof. Sung-Hwan Han and Prof. Myunghyun Paik SuhVersion of Record online: 24 OCT 2016 | DOI: 10.1002/anie. A new method for fabricating CuS nanoparticles in/on a Cu-MOF was developed. The conductivity of the composites is up to 109-fold higher than that of the pristine MOF. They also show excellent activities for the oxygen reduction reaction, affording more positive onset potentials, higher electron transfer numbers, and greater kinetic current densities than the pristine MOF. Medicinal ChemistryDr. Khaled El Cheikh, Dr. Ilaria Basile, Afitz Da Silva, Dr. Coralie Bernon, Dr. Pierre C&rutti, Dr. Fr&d&ric Salgues, Marc Perez, Dr. Marie Maynadier, Dr. Magali Gary-Bobo, Dr. Catherine Caillaud, Dr. Martine C&rutti, Dr. Marcel Garcia and Prof. Alain Mor&reVersion of Record online: 24 OCT 2016 | DOI: 10.1002/anie. Crafty grafting: Mannose 6-phosphate (M6P) derivatives functionalized at the anomeric position (AMFAs) were designed to target recombinant enzymes to lysosomes. When one such AMFA was grafted on human acid &-glucosidase, the therapeutic activity of the modified enzyme against Pompe disease was remarkably improved in adult mice as compared to that of the enzyme (containing natural M6P) authorized for the treatment of Pompe disease. Two-Dimensional MaterialsJinnan Xuan, Zhiqiang Wang, Yuyan Chen, Dujuan Liang, Liang Cheng, Xiaojing Yang, Zhuang Liu, Renzhi Ma, Takayoshi Sasaki and Fengxia GengVersion of Record online: 24 OCT 2016 | DOI: 10.1002/anie. Slimming down: The treatment of Ti3AlC2 with the organic base tetramethylammonium hydroxide (TMAOH) led to Al(OH)4&-modified and TMA+-intercalated titanium carbide (TC), which underwent facile delamination to give extremely thin TC sheets terminated with Al(OH)4& (see picture). In preliminary studies, the resulting TC nanosheets served as efficient photothermal agents against tumor cells as a result of their unusually high NIR absorption. Surface ChemistryZijie Wang, Prof. Dr. Guojun Liu and Shuaishuai HuangVersion of Record online: 24 OCT 2016 | DOI: 10.1002/anie. A Janus fabric is generated in situ from a fabric filter used to separate oil-in-water emulsions. The asymmetric environment of the filter pulls different components to the surface of a switchable coating, generating a Janus fabric. One side of his easy-to-prepare Janus fabric destabilizes emulsions, while the other separates the coagulated oil from water. FLP HydrogenationDaniel J. Scott, Dr. Nicholas A. Phillips, Joshua S. Sapsford, Arron C. Deacy, Dr. Matthew J. Fuchter and Dr. Andrew E. AshleyVersion of Record online: 24 OCT 2016 | DOI: 10.1002/anie. Less frustration with new FLP: The simple Lewis acid iPr3SnOTf can be used to activate H2 in conjunction with common N-centered Lewis bases via a frustrated Lewis pair (FLP) mechanism. These FLP systems are effective for the catalytic hydrogenation of a variety of C=C, C=N, and even C=O bonds and display an unprecedented level of tolerance to moisture. Optical Microscopy | Very Important PaperYou have full text access to this OnlineOpen articleDr. Beno&t Roubinet, Dr. Mariano L. Bossi, Dipl.-Biophys. Philipp Alt, Dr. Marcel Leutenegger, Dr. Heydar Shojaei, M. Sc. Sebastian Schnorrenberg, Dr. Shamil Nizamov, Prof. Dr. Masahiro Irie, Dr. Vladimir N. Belov and Prof. Dr. Stefan W. HellVersion of Record online: 21 OCT 2016 | DOI: 10.1002/anie. Glow the distance: Diarylethenes with a fluorescent &closed& form and carboxylic groups reversibly switch between &dark& and green-emitting states. In aqueous buffers their antibody conjugates specifically stain cellular structures. RESOLFT microscopy based on reversible saturable (switchable) optically linear fluorescence transitions (induced by UV and blue light) demonstrated optical resolution of 75 nm. CO2 CaptureBenjamin S. Gelfand, Racheal P. S. Huynh, Roger K. Mah and Prof. George K. H. ShimizuVersion of Record online: 21 OCT 2016 | DOI: 10.1002/anie. Fine tuning of porosity: Controlled in situ ester hydrolysis during metal complexation enables the formation of isostructural phosphonate monoester and phosphonate MOFs with very different gas sorption properties. By tuning of the synthetic conditions, it is possible to selectively remove some of the monoesters lining the pore to form a hydrogen phosphonate with increased affinity for CO2. Spin Crossover | Very Important PaperDr. John E. Clements, Dr. Jason R. Price, Dr. Suzanne M. Neville and Prof. Cameron J. KepertVersion of Record online: 21 OCT 2016 | DOI: 10.1002/anie. Four-step SCO: A porous 3D spin crossover (SCO) framework material that displays a four-step transition with long-range ordering of FeII sites is reported. From only one unique site in the high-spin state, three intermediate phases with individual high-spin/low-spin patterns are produced upon cooling to the fully low-spin state. C&H ActivationAgostino Biafora, Thilo Krause, Dagmar Hackenberger, Florian Belitz and Prof. Dr. Lukas J. Goo&enVersion of Record online: 21 OCT 2016 | DOI: 10.1002/anie. Bromides and chlorides: A system consisting of [(p-cym)RuCl2]2/PEt3&HBF4 as the catalyst, K2CO3 as the base, and NMP as the solvent efficiently mediates the ortho-C&H arylation of benzoic acids with aryl bromides at 100&&C. Replacing the phosphine ligand with the amino acid dl-pipecolinic acid enables the analogous transformation with aryl chlorides. Organometallic CompoundsLiang Liu, Dr. Junnian Wei, Yue Chi, Prof. Dr. Wen-Xiong Zhang and Prof. Dr. Zhenfeng XiVersion of Record online: 21 OCT 2016 | DOI: 10.1002/anie. Cut and Paste: A series of unprecedented alkenyl magnesium organocuprates and organoargentates were synthesized and structurally characterized. Unique structural characteristics and bonding situations were revealed. The ligand-exchange reaction was realized through the synergistic activation of M&X bonds by reactive magnesiacyclopentadienes. Hybrid PerovskitesYingxia Zong, Dr. Yuanyuan Zhou, Dr. Minggang Ju, Dr. Hector F. Garces, Dr. Amanda R. Krause, Fuxiang Ji, Dr. Guanglei Cui, Prof. Xiao Cheng Zeng, Prof. Nitin P. Padture and Dr. Shuping PangVersion of Record online: 21 OCT 2016 | DOI: 10.1002/anie. Smooth transformation: A photo-inactive thin-film material (porous, rough, polycrystalline NH4PbI3 non-perovskite) is converted stepwise to an excellent photovoltaic material (dense, smooth, textured MAPbI3 perovskite) in an methylamine-induced transformation process. The chemical origins of this transformation are studied at various length scales. Two-Dimensional MaterialsDr. Gonzalo Abell&n, Vicent Lloret, Udo Mundloch, Mario Marcia, Dr. Christian Neiss, Prof. Andreas G&rling, Dr. Maria Varela, Dr. Frank Hauke and Prof. Andreas HirschVersion of Record online: 20 OCT 2016 | DOI: 10.1002/anie. Patterned is the new black: Black phosphorus (BP) underwent organic functionalization based on liquid exfoliation (see picture). The treatment of BP with electron-withdrawing 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) led to electron transfer from BP to the organic dopant, whereas the noncovalent interaction of BP with a perylene diimide (PDI) was mainly due to van der Waals interactions and dramatically improved the stability of the flakes. Protein NMR SpectroscopyDr. Christoph G&bl, Moritz Resch, Dr. Madeleine Strickland, Christoph Hartlm&ller, Martin Viertler, Dr. Nico Tjandra and Prof. Dr. Tobias MadlVersion of Record online: 20 OCT 2016 | DOI: 10.1002/anie. Widespread shift: A covalent paramagnetic lanthanide-binding tag (LBT) was used to increase the chemical-shift dispersion in protein NMR and thus facilitating the chemical-shift assignment of challenging intrinsically disordered proteins. Linkage of the DOTA-based LBT to a cysteine residue induces pseudo-contact shifts (PCS) for resonances more than 20 residues from the spin-labeling site (DOTA=1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid). NanomotorsDr. Deliang Yi, Qian Zhang, Yinghua Liu, Jiaying Song, Prof. Yi Tang, Prof. Frank Caruso and Prof. Yajun WangVersion of Record online: 20 OCT 2016 | DOI: 10.1002/anie. A nanoscopic engine: Chemically asymmetric silica nanobottles (NBs) with a hydrophobic exterior surface and a hydrophilic interior surface are prepared for spatially selective cargo loading, and for application as nanoreactors and nanomotors. A nanomotor is constructed by loading hydrophilic Pt nanoparticles inside the NBs, self-propelling in solution in the presence of H2O2. DiradicalsProf. Dr. Curt Wentrup, Dr. Mich&le J. Regimbald-Krnel, Dr. Dennis M&ller and Prof. Dr. Peter CombaVersion of Record online: 20 OCT 2016 | DOI: 10.1002/anie. Twist of fate: Bis(dibenzo[a,i&]fluorenylidene) (see scheme) has a closed-shell singlet ground state, but the amount of the 90& twisted, antiferromagnetic triplet diradical increases in the temperature range 300&500 K. The exchange coupling Jex/h&c was determined to be 3551 cm&1, which corresponds to a singlet&triplet energy splitting of 9.6 kcal&mol&1. Structure ElucidationDr. David Gau, Raphael Nougu&, Dr. Nathalie Saffon-Merceron, Dr. Antoine Baceiredo, Dr. Abel De C&zar, Prof. Fernando P. Coss&o, Dr. Daisuke Hashizume and Dr. Tsuyoshi KatoVersion of Record online: 20 OCT 2016 | DOI: 10.1002/anie. Squeeze out: A donor-stabilized 1,3-disila-2,4-diazacyclobutadiene presents a surprisingly short nonbonded Si&&&Si distance (2.23 &A) which is as short as Si=Si double bonds. Theoretical investigations indicate that the unusual geometry results from a deformation of the four-membered ring as result of significant repulsion between the two ring N atoms. This phenomenon can be regarded as a chemical pressure, and can provide an alternative way of squeezing out van der Waals space in highly strained structures. Bioorthogonal LabelingDr. Bruno L. Oliveira, Zijian Guo, Dr. Omar Boutureira, Ana Guerreiro, Dr. Gonzalo Jim&nez-Os&s and Dr. Gon&alo J. L. BernardesVersion of Record online: 20 OCT 2016 | DOI: 10.1002/anie. Minimal handle, maximal output: The site-specific chemical incorporation of a small-sized, unstrained S-allyl handle into an apoptosis biomarker enables efficient inverse-electron-demand Diels&Alder labeling in live cells using a fluorogenic tetrazine. Fluorescent ProbesAlina Tirla and Prof. Dr. Pablo Rivera-FuentesVersion of Record online: 20 OCT 2016 | DOI: 10.1002/anie. Photoactivatable phosphines: Reductive stress is triggered in live cells employing a photoactivatable phosphine probe. This probe releases tributylphosphine, an efficient reducing agent, and a cyanine reporter fluorophore. Reductive stress induced by this probe ultimately leads to formation of intracellular protein aggregates. ExcimersDr. Zhuolei Zhang and Prof. Shenqiang RenVersion of Record online: 20 OCT 2016 | DOI: 10.1002/anie. Luminescent network: Colloidal excimer superstructures with unique optical and electronic properties have recently been described. Ground-state gold cluster cores were held together by the hydrogen-bonding network formed by their capping ligands, which enabled excimer formation. Molecular MachinesProf. David A. LeighVersion of Record online: 20 OCT 2016 | DOI: 10.1002/anie. In the beginning&: The Nobel Prize in Chemistry 2016 goes to three of the pioneers of the field of synthetic molecular machines, Jean-Pierre Sauvage, Sir J. Fraser Stoddart, and Ben L. Feringa. Their work has led from the reliable synthesis of rotaxanes and catenanes (see picture) to molecular rotary motors, shuttles, muscles, and other devices. Polymorphic Materials | Hot PaperFranziska Fischer, Sebastian Greiser, Dr. Dietmar Pfeifer, Prof. Dr. Christian J&ger, Prof. Dr. Klaus Rademann and Dr. Franziska EmmerlingVersion of Record online: 20 OCT 2016 | DOI: 10.1002/anie. Shapeshifter: Complete transformation of benzamide polymorph form I into the metastable form III by mechanochemical treatment is presented. Catalytic amounts of nicotinamide seeds activate conversion by mechanochemical seeding. Cooperative CatalysisDr. Michael H. Wang and Prof. Karl A. ScheidtVersion of Record online: 20 OCT 2016 | DOI: 10.1002/anie. N-Heterocyclic carbene (NHC) catalysis is a versatile and powerful strategy to construct complex molecules. To extend and enhance the reactivity of these nucleophiles, cooperative catalysis and related activation approaches have been developed by integrating complementary modes (Lewis/Br&nsted acidity, transition-metal processes, photoredox). Recent contributions are summarized in this Minireview. Main-Group CompoundsChenting Yan, Prof. Zhifang Li, Dr. Xu-Qiong Xiao, Ningka Wei, Qiong Lu and Prof. Mitsuo KiraVersion of Record online: 20 OCT 2016 | DOI: 10.1002/anie. A fluorostannylenoid was prepared by reacting a dialkylstannylene with CsF at room temperature in THF. While the fluorostannylenoid is stable in THF and DME, removal of the solvent leads to the regeneration of the dialkylstannylene. Addition of dibenzo-21-crown-7 to the THF solution of the stannylenoid affords the corresponding crystalline stannylenoid crown ether complex, which exhibits a fluorine-bridged contact ion-pair structure. BiomassProf. Eero Kontturi, Anne Meriluoto, Dr. Paavo A. Penttil&, Dr. Niki Baccile, Dr. Jani-Markus Malho, Prof. Antje Potthast, Prof. Thomas Rosenau, Prof. Janne Ruokolainen, Prof. Ritva Serimaa, Prof. Janne Laine and Prof. Herbert SixtaVersion of Record online: 20 OCT 2016 | DOI: 10.1002/anie. Vapor over the cracks: The adsorption of hydrogen chloride vapor on water-covered cellulose microfibrils results in rapid degradation and increased crystallinity without a change in fiber morphology. This process constitutes an example of supramolecular tuning of native biological materials directly in the solid state. Bioorthogonal ReactionsMan Kyu Shim, Dr. Hong Yeol Yoon, Dr. Ju Hee Ryu, Dr. Heebeom Koo, Dr. Sangmin Lee, Dr. Jae Hyung Park, Dr. Jong-Ho Kim, Dr. Seulki Lee, Dr. Martin G. Pomper, Dr. Ick Chan Kwon and Dr. Kwangmeyung KimVersion of Record online: 20 OCT 2016 | DOI: 10.1002/anie. A cathepsin B-specific metabolic precursor can incorporate azide molecules as chemical receptors onto the tumor-cell surface. The generated azide groups enable tumor-specific fluorescence imaging through a bioorthogonal click reaction both in vitro and in vivo. Anti-Inflammatory CompoundsXiaohui Liu, Ting Dong, Yu Zhou, Prof. Dr. Niu Huang and Prof. Dr. Xiaoguang LeiVersion of Record online: 20 OCT 2016 | DOI: 10.1002/anie. Search and find: A bifunctional probe design based on monogalactosyldiacylglycerol (MGDG) for mechanistic studies of glycolipids in living system was developed. A typical MGDG probe enabled the identification of TLR4 as its cellular target. In combination with biochemical studies and molecular modeling, it was demonstrated that binding of MGDG to TLR4/MD-2 leads to its anti-inflammatory activity. MetallacyclesBenjamin J. Frogley and Prof. L. James WrightVersion of Record online: 20 OCT 2016 | DOI: 10.1002/anie. Metalla as anything: Metalla-analogues of the linear polycyclic aromatic hydrocarbons have been extended to include metallaanthracenes with a rational synthesis of an iridaanthracene. In analogues of classic anthracene reactions, the iridaanthracene forms a Diels&Alder adduct with maleic anhydride and oxidation leads to an unprecedented fused-ring metallaanthraquinone. Responsive BatteriesXiaopeng Wang, Jian Gao, Zhihua Cheng, Dr. Nan Chen and Prof. Liangti QuVersion of Record online: 20 OCT 2016 | DOI: 10.1002/anie. Press to turn on the light: A new type of responsive battery was developed enabling the spontaneous control of its power output in response to pressure changes (see picture). The battery design is based on the Zn&air battery with a graphene-coated sponge serving as pressure-sensitive air cathode that endows the whole system with the capability of self-controlled energy release. OrganocatalysisClaire M. Young, Dr. Daniel G. Stark, Thomas H. West, Dr. James E. Taylor and Prof. Andrew D. SmithVersion of Record online: 20 OCT 2016 | DOI: 10.1002/anie. Drop the Base: N-Acyl imidazoles act as ammonium enolate precursors in the presence of catalytic isothiourea hydrochloride salts in the absence of base. Subsequent reactions with various Michael acceptors proceed with high stereoselectivity. Mechanistic investigations have revealed the importance of the &imidazolium effect& during enolate formation and highlight key differences with traditional base-mediated processes. Sequence ControlProf. Makoto Ouchi, Marina Nakano, Tomoya Nakanishi and Prof. Mitsuo SawamotoVersion of Record online: 20 OCT 2016 | DOI: 10.1002/anie. The vinyl cut: Controlled cyclopolymerization of a hemiacetal ester (HAE) bond-connected divinyl monomer and subsequent cleavage of the HAE in the cyclo-pendant led to alternating copolymers consisting of methacrylic acid and 2-hydroxyethyl acrylate units. The copolymer showed a lower critical solution temperature (LCST) in DME, which is a result of the alternating sequence. VIEW1 - 100 Select All