Among the many peculiarities of elemental metallic mercury, its liquid form at room temperature, and low melting temperature at -38.83 °C, has eluded fundamental understanding so far. Special relativity has been speculated as a possible cause for this unique state, but never was proven. Using Monte Carlo simulations, together with a diatomic-in-molecule method to simulate the many-body interactions in bulk mercury, was the key to solve this challenging problem. Relativistic and nonrelativistic calculations show that the melting temperature in bulk mercury is lowered by 105 °C due to relativistic effects. Thus, hypothetical nonrelativistic mercury remains solid under normal conditions.

Graphene nanoribbons are commonly synthesized using carbon nanotubes (CNTs) as a precursor through the oxidative opening of the nanotubes into elongated ribbons. However, CNTs contain significant amounts of metallic impurities even after purification. Herein, we show that these impurities persist at parts-per-billion levels after oxidative opening of CNTs to graphene oxide nanoribbons and heavily influence the electrochemical behavior of the resulting material. This may have negative impacts on the range and effectiveness of potential applications suitable for graphene materials.

The standard model for molecular electrical p-doping of organic semiconductors (OSCs) assumes integer charge transfer between OSC and dopant. Here, it is contrasted to an alternative model based on intermolecular complex formation between OSC and dopant. Systematically varying the acceptor strength of prototypical dopants in a matrix of a solution processible OSC allowed discriminating the two models. Determining the actual structure of intermolecular complexes and correlating it with the optical and electronic properties of p-doped samples clearly favored the alternative model. Consequences for chemical design strategies of more efficient molecular dopants are deduced.

Coming soon.

Robert Kretschmer, Zhe-Chen Wang, Maria Schlangen, Drs. h. c. Helmut Schwarz*

Crime scene: N–H bond activation. When ammonia gets in the crosshairs of [Al₂O₃]·⁺ the reaction is not limited to a single hydrogen-atom transfer, double hydrogen abstraction takes place as well and free nitrene is liberated at room temperature. These results are confirmed by mass spectrometric and theoretical investigations.

Published online, DOI: 10.1002/anie.201302506 – Read now

A synthesis of the sesquiterpenoid antibiotic (+)-hongoquercin A using sequential site-specific C–H methylation and oxidation reactions is described. A key advancement toward this goal was the development of a ligand-accelerated C–H methylation reaction. This unique strategic disconnection enables the generation of a library of eight structurally diverse analogs, highlighting the utility of these reactions in the synthesis and modification of structurally complex molecules.

Coming soon.

Enantioselective isomerization of γ-substituted primary allylic alcohols into the β-substituted aldehydes is catalyzed by the [RuCl₂{(S)-tol-binap}{(R)-dbapen}]–KOH system. The reaction is conducted with a substrate-to-catalyst molar ratio in the range of 100–2000 at 25°C for 0.5–1 h. A turnover number of about 1550 is achieved in the best case. A series of (E)- and (Z)-configurated aromatic and aliphatic allylic alcohols, including a simple primary alkyl-substituted compound (E)-3-methyl-2-hepten-1-ol, is transformed to the aldehydes in at least 99% ee. The plausible mechanism for this reaction, which is promoted by the hemilability of the dbapen–Ru chelate structure, is also discussed.

Coming soon.

Gregor Kiefer, Lo[iuml]c Jeanbourquin, Kay Severin*

Catalysis with laughing gas: N₂O in combination with transition-metal catalysts allow the oxidative homo- and cross-coupling of Grignard reagents. The reactions can be performed under mild conditions despite the inert character of N₂O.

Published online, DOI: 10.1002/anie.201302471 – Read now

André Nadler, Gregor Reither, Suihan Feng, Frank Stein, Sabine Reither, Rainer Müller, Carsten Schultz*

Caged compounds are designed to release biologically active signaling molecules with temporal, spatial, and even subcellular resolution. But how localized does the signal stay? Using the example of diacylglycerol, some signal responses (PKC) are shown to remain spatially distinct while other signals ([Ca²⁺]_i) spread across the entire cell. Surprisingly, this distribution patterns depend on the fatty acid composition of the lipid species.

Coming soon.

Because of the higher electronegativity of hydrogen (2.20) compared to boron (2.04), hydrogen atoms bonded to boron are regarded as hydrides, and thus deprotonation does not seem feasible. The use of both an electrophilic cyclic (alkyl)(amino)carbene (CAAC) and of two electron-withdrawing nitrile groups, makes a neutral carbene-borohydride adduct acidic enough to be deprotonated by a strong base. The resulting (CAAC)-B(CN)₂^- anion is stable in the absence of air and moisture, and reacts with carbon and metal electrophiles at the boron center.

Coming soon.

A conceptually novel method for performing in situ separation and recycling of submicrometer-sized solid catalysts has been explored, which is based on the pH-triggered Pickering emulsion inversion. This method enables solid catalysts to be recycled 36 times without significant loss of activity. The developed method is distinguished from the conventional methods in respect of time and energy consumption, catalyst separation, and recycling effectiveness.

Coming soon.

Alexander C. Filippou*, Yury N. Lebedev, Oleg Chernov, Martin Straßmann, Gregor Schnakenburg

Ligand swap: The exchange of N-heterocyclic carbene (NHC) ligands at Si^II centers is shown to provide access to a dicationic NHC complex of silicon(II), and an NHC adduct of the iodosilyliumylidene cation SiI⁺, [SiI(IiPr₂Me₂)(IDipp)]⁺ (see picture). Characterization studies led to the discovery of an unprecedented C–H···Si anagostic interaction for [SiI(IiPr₂Me₂)(IDipp)]⁺.

Coming soon.

Yusuke Kawanaka, Akihiro Shimizu, Tetsuro Shinada, Rika Tanaka, Yoshio Teki*

A radical solution: The photochemical instability and insolubility in organic solvents of pentacene derivatives prevent their use in molecular electronics. These issues were solved by using pentacene derivatives with stable radicals (Y=radical moiety, 2 and 4) that have a lifetime of 2077 min in organic solvents under ambient light. The corresponding nonradical pentacene derivatives (Y=radical precursor, 1 and 3) decay on exposure to light.

Coming soon.

Photoswitchable inhibitors of protein–protein interactions have been applied to photoregulate clathrin-mediated endocytosis (CME) in living cells. These peptides, named traffic lights because they act as "stop" and "go" signals for membrane traffic, constitute a novel tool to control cell signaling in spatiotemporally defined patterns. Traffic light peptides can be used to dissect the role of CME in receptor internalization and in cell growth, division, and differentiation.

Coming soon.

Despite over a century of numerous investigations on the very important hydrophobic effect, direct observation of the evolving roles of the different related contributions during multi-step hydrophobic assembly processes has remained experimentally inaccessible. This challenging problem was now addressed by using an unprecedented type of experiment based on the step-wise growth of a structurally well-defined organic aggregate within a water-soluble porous metal-oxide nanocapsule. Detailed thermodynamic data obtained reveal an evolving spectrum of different types of hydrophobic effects acting in context with sequential growth steps, which finally lead to the formation of a beautiful "micelle"-like n-butyrate-ion assembly with a practically water-free central cavity.

Coming soon.

Molecular crystal nanowires composed of an anthracene-9-(1,3-butadiene) derivative exhibit a rapid transition from straight to highly coiled structures when exposed to a pulse of visible light. The curling does not depend on the direction of the light illumination and occurs for nanowires composed of either the (E) or (Z) isomer. The shape change is driven by an E⇌Z photoisomerization reaction that generates a mixture of isomers within a single nanowire.

Received March 19, 2013, published online May 16, 2013, DOI: 10.1002/anie.201302323 – read now.

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Chiral bis(diimine) ligands (derived from chiral diamines and pyridine-2-aldehyde) enantioselectively self-assemble with iron(II) sulfate to form the new enantiopure tetrahedral cage molecule ΔΔΔΔ-[Fe₄L₆] or its enantiomer, ΛΛΛΛ-[Fe₄L₆]. These versatile water-soluble capsules are capable of binding a wide range of organic guests in their large hydrophobic cavities and, additionally, are able to distinguish between the enantiomers of chiral organic guests. Furthermore, the ΔΔΔΔ-[Fe₄L₆] coordination capsule also serves as a competent supramolecular catalyst for the hydrolysis of the neurotoxic organophosphate dichlorvos.

Coming soon.

A general way is reported to synthesize novel self-supported one-dimensional mesoporous Pt nanorods with high density of mesopores by using electrochemical micelle assembly in confined space of polycarbonate membrane. The mesoporous structures with around 6–8 nm pore size and thin wall thickness are well developed over the entire area. The obtained 1D motifs show high activity and CO tolerance in the methanol oxidation reaction and also exhibit superior electrochemical activity in the oxygen reduction reaction. The all-wet approach is highly reproducible and widely applicable to other metal and alloy systems, which will be very useful for the development of future electrocatalysts.

Coming soon.

Umar Farid, Florence Malmedy, Romain Claveau, Lena Albers, Thomas Wirth*

I likes rearrangements: Hypervalent iodine compounds can be used as environmentally friendly, mild, and selective reagents for highly enantioselective rearrangements of alkenes. For the first time, rearrangements to α-arylated ketones can be performed enantioselectively using lactic acid-based iodine(III) reagents.

Published online, DOI: 10.1002/anie.201302358 – Read now

Joseph J. Richardson, Hirotaka Ejima, Samuel L. Lörcher, Kang Liang, Philipp Senn, Jiwei Cui, Frank Caruso*

Slipping into a comfortable routine: Multilayered polymer thin films were assembled on particles immobilized in agarose by electrophoresis on the basis of various interactions. Core removal then led to robust capsules with different polymer compositions (see fluorescence image). This approach enables the versatile and routine assembly of nanometer- and micron-sized capsules and coated particles with very few processing steps.

Published online, DOI: 10.1002/anie.201302092 – Read now

Christoph Sämann, Matthias A. Schade, Shigeyuki Yamada, Paul Knochel*

Highly functionalized cyclic and acyclic alkenylzinc reagents bearing functional groups such as aldehyde, keto, and ester groups were readily prepared by either direct zinc insertion in the presence of LiCl or by magnesium insertion in the presence of LiCl and ZnCl₂. Subsequent functionalization reactions like Negishi cross-couplings, acylations, and allylations were performed, furnishing polyfunctional compounds in excellent yields.

Published online, DOI: 10.1002/anie.201302058 – Read now

Kazuhiko Maeda*, Daling Lu, Kazunari Domen*

Water splitting: In heterogeneous photocatalysis, it has been believed that doping transition-metal cations having partly filled d orbitals into semiconductor photocatalysts results in a significant drop in photocatalytic activity. Nevertheless, it was found that the activity for the water oxidation of BaTaO₂N could be improved by seven times upon modification by pentavalent W species (see picture).

Published online, DOI: 10.1002/anie.201301357 – Read now

Hélio Faustino, Isaac Alonso, José L. Mascareñas*, Fernando López*

Gold standard: Allenamides react with aldehydes or ketones having γ, δ, or [epsiv] alkenyl groups, upon activation with suitable gold catalysts, to provide oxa-bridged systems containing seven- to nine-membered carbocycles, in a formal cascade cycloaddition. By using chiral phosphoramidite/gold or bisphosphine/gold catalysts it is possible to obtain the oxa-bridged seven- and eight-membered rings with good to high enantioselectivities.

Published online, DOI: 10.1002/anie.201302713 – Read now

Birju Shah, Perry T. Yin, Shraboni Ghoshal, Ki-Bum Lee*

Special delivery! The title system, composed of a highly magnetic core surrounded by a thin uniform gold shell, has been synthesized and applied to the magnetically facilitated delivery of genetic material (siRNA or plasmid DNA) into neural stem cells (NSCs) for controlling their neural differentiation in a spatiotemporally controlled, biocompatible manner.

Published online, DOI: 10.1002/anie.201302245 – Read now

By using a neutral bidentate bis-NHC ligand (NHC=1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene), an unprecedented bis-carbene chlorosilyliumylidene complex could be isolated, in which both HOMO and LUMO are mainly represented on the silicon(II) atom according to DFT calculations. Remarkably, dechlorination of the latter complex by sodium naphthalenide led to the first isolable cyclic siladicarbene with a bent geometry (C–Si–C angle: 89.1°) and average Si–C distances of 1.869 Å. According to the DFT calculations, the latter compound bears a single Si(0) atom with strikingly high basicity as predicted by the calculated first and second proton affinities and is hence best described as a silylone.

Coming soon.

Larysa Baraban, Stefan M. Harazim, Samuel Sanchez*, Oliver G. Schmidt

Chemotaxis in practice: Two different artificial catalytic micromotors (tubular and spherical, see scheme) show chemotactic behavior in microfluidic channels demonstrating that catalytic micromotors can sense the gradient of chemical fuel in their environment and be directed towards desired locations.

Published online, DOI: 10.1002/anie.201301460 – Read now No. 21/2013.

Hyungki Kim, Yoonkook Son, Chibeom Park, Jaephil Cho*, Hee Cheul Choi*

Direct growth of a single to a few layers of graphene on a germanium nanowire (Gr/Ge NW; see picture) was achieved by a metal-catalyst-free chemical vapor deposition (CVD) process. The Gr/Ge NW was used as anode in a lithium ion battery. This material has a specific capacity of 1059 mA h g⁻¹ at 4.0 C, a long cycle life over 200 cycles, and a high capacity retention of 90 %.

Published online, DOI: 10.1002/anie.201300896 – Read now

Strongly emissive gold(III) complexes which display phosphorescence in the visible region and with emission quantum yields and lifetimes up to 58% and 305 µs, respectively, could be achieved using chelating cyclometalated ligands having fluorene substituent(s). These gold(III) complexes can sensitize energy up-conversion with a quantum yield Φ_UC up to 9.8% and display rich two-photon absorption properties.

Received February 08, 2013, published online May 16, 2013, DOI: 10.1002/anie.201301149 – read now.

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Adel M. ElSohly, Daniel A. Wespe, Tyler J. Poore, Scott A. Snyder*

Folding it all together: Most of the syntheses developed for the securinega alkaloid class require lengthy sequences to create their bridging butenolide domains. A novel approach uses
N-heterocyclic carbenes (NHCs) and Lewis acids to forge the entire domain in a single step from appropriate precursors, showing that ynal-derived homoenolates can participate as nucleophiles in intramolecular settings (see scheme).

Published online, DOI: 10.1002/anie.201301849 – Read now No. 22/2013.

See the list now.

Coming soon.

The pyridine heterocycle is an important structural motif that can be found in many natural products, drugs, herbicides, and fungicides. Here, a sustainable iridium-catalyzed pyridine synthesis is introduced. Alcohols and γ-amino alcohols are deoxygenated and selectively linked through C–N and C–C bond formation steps. The starting materials can be obtained from renewable resources. Three equivalents of hydrogen gas are eliminated in the course of the reaction. The synthesis protocol tolerates a large variety of functional groups and significantly extents the scope of existing pyridine syntheses. The new chemistry is not just sustainable it also can be impressive in scope.

Coming soon.

Yoshitsune Sugano, Yasuhiro Shiraishi*, Daijiro Tsukamoto, Satoshi Ichikawa, Shunsuke Tanaka, Takayuki Hirai

Rejuvenating sunlight: Supported Au–Cu bimetallic alloy nanoparticles promote aerobic oxidation at room temperature under visible light ([lambda]>450 nm) irradiation with little deactivation by the oxidation of surface Cu atoms by oxygen. This is achieved through the reduction of oxidized surface Cu atoms by the surface Au atoms, a process which is activated by visible-light irradiation, even by sunlight.

Published online, DOI: 10.1002/anie.201301669 – Read now No. 20/2013.

An interesting feature of (6–4) photoproducts is their relatively long-wavelength absorption, which could extend the active fraction of sunlight. Surprisingly, their potential role as intrinsic DNA photosensitizers has not been addressed yet. This appealing question has been tackled here by model studies with a 5-methyl-2-pyrimidone deoxyribonucleoside, the main chromophore of (6–4) photoproducts. The results reveal photosensitized formation of oxidation products and cyclobutane thymine dimers. Overall, this raises the issue of a possible aggravation of the photomutagenicity of (6–4) lesions, acting as Trojan horses.

Received March 14, 2013, published online May 09, 2013, DOI: 10.1002/anie.201302176 – read now.

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Wei Liu, John T. Groves*

An efficient protocol for the selective fluorination of benzylic C–H bonds is described. The process is catalyzed by manganese salen complexes and uses nucleophilic fluorine sources, such as triethylamine trihydrofluoride and KF. Reaction rates are sufficiently high (30 min) to allow adoption for the incorporation of ¹⁸F fluoride sources for PET imaging applications.

Published online, DOI: 10.1002/anie.201301097 – Read now

Muhammad K. Kashif, Michael Nippe, Noel. W. Duffy, Craig M. Forsyth, Christopher J. Chang*, Jeffrey R. Long*, Leone Spiccia*, Udo Bach*

Energy conversion: A cobalt redox mediator, [Co(bpyPY4)]^2+/3+, based on a hexadentate polypyridyl ligand, was developed. Dye-sensitized solar cells (DSCs) made with this redox mediator showed improved stability and slightly higher efficiencies compared to [Co(bpy)₃]^2+/3+-based devices. Long-term stability evaluation of DSCs based on [Co(bpyPY4)]^2+/3+ revealed excellent stability under full irradiation conditions (see picture).

Published online, DOI: 10.1002/anie.201300070 – Read now No. 21/2013.

Masashi Hayashi, Masahide Sano, Yasuhiro Funahashi, Shuichi Nakamura*

Managing the Mannich: The first enantioselective vinylogous Mannich reaction of siloxyfurans with ketimines derived from unactivated ketones has been developed. Excellent yields and enantioselectivities were obtained using a new class of readily accessible cinchona alkaloid amide/Cu(OAc)₂ catalysts on a range of substrates.

Published online, DOI: 10.1002/anie.201301917 – Read now No. 21/2013.

Julia R. Khusnutdinova, Yehoshoa Ben-David, David Milstein*

Just add water! The title reaction is catalyzed by an acridine-based pincer complex (1, see scheme). This one-step transformation uses water as the only reagent in the absence of additional bases, oxidants, or reductants. Cyclization of 1,4-diaminobutane and 1,6-diaminohexane catalyzed by 1 leads to the formation of pyrrolidine and azepane, respectively.

Published online, DOI: 10.1002/anie.201301000 – Read now

The one-pot synthesis of a molecular Solomon link assembles four iron(II) cations, four bis-aldehyde and four bis-amine building blocks to generate two interwoven 68-membered-ring macrocycles with four crossings in 75 % isolated yield. The synthesis of the Solomon link, and an earlier pentafoil knot, demonstrate that cyclic helicates of different sizes can act as highly efficient and effective scaffolds for intricate molecular topologies.

Received March 29, 2013, published online May 06, 2013, DOI: 10.1002/anie.201302634 – read now.

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Using the 3D structural depiction of the environment around the absorbing atom provided by X-ray absorption near-edge structure (XANES) spectroscopy and DFT calculations, the molecular-scale structure of the TiO₂-supported molybdenum oxide catalysts has been unraveled and it consists of Mo octahedra arranged in a six-membered ring structure.

Received January 21, 2013, published online May 07, 2013, DOI: 10.1002/anie.201300538 – read now.

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Ken Mukai, Daisuke Urabe, Satoshi Kasuya, Naoto Aoki, Masayuki Inoue*

19 in 19: A convergent total synthesis of 19-hydroxysarmentogenin has been achieved, starting from three simple fragments. The desired product was synthesized in 19 steps from the AB ring with the installation of six stereocenters and the formation of three C–C bonds.

Published online, DOI: 10.1002/anie.201302067 – Read now No. 20/2013.

Haiyin Liu, Angus P. R. Johnston*

A molecular sensor has been developed to probe the internalization of proteins and nanoparticles into live cells. This simple, high-throughput technique is compatible with cell phenotyping and is independent of the cellular fate of the material.

Published online, DOI: 10.1002/anie.201301243 – Read now No. 22/2013.

Tao Shen, Teng Wang, Chong Qin, Ning Jiao*

Three in one blow! A novel direct transformation of alkynes into nitriles by a silver-catalyzed nitrogenation reaction through C≡C bond cleavage has been developed. This research provides both a new application for alkynes in organic synthesis, and valuable mechanistic insights into nitrogenation chemistry.

Published online, DOI: 10.1002/anie.201300193 – Read now

Akira Ueda, Shuichi Suzuki, Kenta Yoshida, Kozo Fukui, Kazunobu Sato, Takeji Takui*, Kazuhiro Nakasuji, Yasushi Morita*

A phenalenyl radical with six methoxy groups, which were introduced symmetrically, has been synthesized. The extensively delocalized and highly symmetric electronic-spin system was studied with advanced cw-/pulsed-ESR techniques, thereby giving an experimental model to explore molecular quantum spin simulators with novel quantum coherence attributable to the extremely high degeneracy of the nuclear spin states owing to the eighteen equivalent protons.

Published online, DOI: 10.1002/anie.201301435 – Read now

A novel silver-catalyzed click synthesis of pyrroles by the co-cyclization of terminal alkynes and isocyanides has been developed. From the synthetic point of view, this protocol represents an extremely simple, efficient, and atom-economic way to construct substituted pyrroles in good yields with high selectivity, which complements the click method for the rapid construction of multifunctional heterocycles.

Received March 28, 2013, published online April 29, 2013, DOI: 10.1002/anie.201302604 – read now.

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Yuehui Li, Xianjie Fang, Kathrin Junge, Matthias Beller*

Putting CO₂ to work: Carbon dioxide is shown to be a general and selective methylating reagent for secondary and primary, aromatic and aliphatic amines under reductive conditions. A variety of tertiary amines are obtained from CO₂ and commercially available silanes in high yields with good tolerance to nitrile, olefin, ether, ester, and hydroxy groups.

Published online, DOI: 10.1002/anie.201301349 – Read now

Jun Wang, Hai-xia Zhong, Yu-ling Qin, Xin-bo Zhang*

Oxygen evolution: A 3D nickel foam/porous carbon/anodized nickel electrode was designed for the oxygen evolution reaction (see picture). The conductive porous carbon membrane plays a key role, which is derived from zeolite imidazolate framework and subsequently employed as interlayer to both protect the inner instable Ni foam and support the outermost oxygen-evolving Ni catalyst layer.

Published online, DOI: 10.1002/anie.201301066 – Read now No. 20/2013.

Electron diffraction measurements on a set of homonuclear 55-atom transition-metal clusters covering essentially all 3d and 4d elements are reported. The diffraction data obtained for cluster anions in gas phase at 95K show four main structure types. Elements with the same bulk lattice morphology generally have a common cluster structure type. To rationalize this, cluster geometries have been determined by fitting structural models from density functional theory calculations to the diffraction data. The four structure types differ in maximum atomic coordination numbers in analogy to the coordination numbers in the corresponding bulk lattices.

Received March 14, 2013, published online May 09, 2013, DOI: 10.1002/anie.201302165 – read now.

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The solid-phase synthesis of the potent antitumoral thiocoraline is accomplished for the first time by a combined approach involving chemical and enzymatic methods. With a sequence highly rich in Cys, consecutive NMe amino acids, and a bicyclic structure formed by a disulfide bridge flanked by two thioester moieties, an orchestrated protection group scheme becomes the cornerstone for the successful synthesis for thiocoraline. One-pot cleavage of the phenylacetamidomethyl moiety by the immobilized penicillin G acylase and disulfide formation are the key steps of the synthetic strategy.

Received February 27, 2013, published online April 25, 2013, DOI: 10.1002/anie.201301708 – read now. No. 22/2013.

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The first transition-metal-catalyzed cycloaddition of isocyanides and unactivated terminal alkynes has been realized by the discovery of silver carbonate (Ag₂CO₃) as a unique and robust catalyst. This protocol for silver-catalyzed reaction is highly efficient allowing a broad range of terminal and internal alkynes to react with isocyanides under base- and ligand-free conditions, regioselectively generating synthetically useful 2,3-disubstituted and 2,3,4-trisubstituted pyrroles in good to high yields.

Received March 11, 2013, published online May 06, 2013, DOI: 10.1002/anie.201302024 – read now.

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Combining the classical cobalt carbonyl hydride configuration with the question of how, mechanistically, cobalt hydrides effect the formation of H₂, a specific, structurally protecting and potentially electronically active ferrocenyldiphosphane co-ligand at Co(CO)₂H was used to characterize the native metal hydride, the one-electron oxidized form, and the sensitive, metal hydride-free byproduct of H₂ formation by structure analysis and low-temperature spectroelectrochemistry. The first identification of all elementary steps in the homolytic pathway for oxidative carbonylmetal hydride conversion is reported.

Received February 27, 2013, published online May 10, 2013, DOI: 10.1002/anie.201301706 – read now.

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A dual-responsive block-statistical copolymer was synthesized by integrated ring-opening and atom transfer radical polymerizations. This copolymer condenses nucleic acids into self-assembled nanoparticles that undergo triggered changes in response to intracellular microenvironments. Under acidifying conditions such as in endosomes after intracellular uptake, the materials increase their protonation state, facilitating endosomal escape. Under the reducing conditions of cell cytosol, polyplexes are cleaved to release a stabilizing hydrophobic domain, prompting nucleic acid cargo release. Effective plasmid and siRNA delivery to cultured mammalian cells and mouse brain is demonstrated using this optimized formulation that combines reversible hydrophobization with statistical hydrophilization.

Received March 06, 2013, published online April 16, 2013, DOI: 10.1002/anie.201301896 – read now. No. 20/2013.

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CdS-based visible-light photocatalysts have intrinsic photocorrosion problems. Another great concern is the toxicity of leached Cd²⁺ ions. In this work, we show that by simply coating the CdS particles with a thin layer of amorphous carbon, the above problems can be largely solved. We demonstrate the concept by synthesizing novel carbon-coated CdS petalous particles using a one-pot solvothermal method. The carbon nanocoating serves multifold functions including surface protection of CdS, visible-light absorption enhancement and facilitated separation of photogenerated charges. As a result, this CdS–C nanohybrid photocatalyst exhibits significantly enhanced photostability and photocatalytic activity.

Received February 27, 2013, published online April 05, 2013, DOI: 10.1002/anie.201301709 – read now. No. 21/2013.

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A method of forming tetrameric aggregates with an ααββ structure is developed using stereoisomeric bidomain oligomers for the α and β subunits. The α subunit contains a (M)-amidohelicene tetramer domain and a (M)-ethynylhelicene pentamer domain, and the β subunit contains a (M)-amidohelicene tetramer domain and a (P)-ethynylhelicene pentamer domain. Each bidomain oligomers was dimeric in chloroform, and mixing of the two solutions gave a tetrameric ααββ aggregate by heteroaggregation at the ethynyl domain. The tetrameric aggregate reversibly changed its structure between the dimeric homoaggregates on heating and cooling. Gelation occurred in toluene by the polymerization of the tetrameric aggregate.

Received February 19, 2013, published online April 09, 2013, DOI: 10.1002/anie.201301463 – read now. No. 20/2013.

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A heterobimetallic high-valent CuNi bis(µ–oxo) complex is prepared by the reduction of a nickel superoxo complex with a Cu(I) reductant, and characterized by low–temperature UV/Vis, resonance Raman, electron paramagnetic resonance, and X–ray absorption spectroscopy in conjunction with reactivity and DFT studies. Unlike typical homodinuclear high–valent [M₂(µ–O)₂]ⁿ⁺ cores, which have electrophilic oxo groups, the oxo groups in [Cu(µ–O)₂Ni]²⁺ behave as nucleophiles, and can initiate deformylation of aldehydes. Mixed–metal bis(µ–oxo) cores are, therefore, viable intermediates during the deformylation of fatty aldehydes by cyanobacterial aldehyde decarbonylase, where a heterodinuclear cofactor has been suggested.

Received January 31, 2013, published online April 15, 2013, DOI: 10.1002/anie.201300861 – read now. No. 21/2013.

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Peptide self-assemblies have great potential for applications in nanotechnology. However, atomic-scale structure determination is not straightforward, which is essentially due to the difficulty associated with using X-ray crystallography. Dynamic nuclear polarization (DNP) enhanced solid-state NMR was performed on self-assembled peptide nanotubes prepared with a new DNP-friendly method. This approach achieves uniform distribution of polarizing agents around the sample without sample dilution and yields significant experimental time-savings of five orders of magnitude. This super-sensitivity was used to exemplify the feasibility of supramolecular structural studies of organic nanoassemblies using multidimensional ¹³C NMR at natural isotopic abundance.

Received December 18, 2012, published online April 05, 2013, DOI: 10.1002/anie.201210093 – read now.

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Silke Gandor, Stephanie Reisewitz, Muthukumaran Venkatachalapathy, Giuseppe Arrabito, Martina Reibner, Hendrik Schröder, Katharina Ruf, Christof M. Niemeyer, Philippe I. H. Bastiaens*, Leif Dehmelt*

Taking the bait: Protein interaction arrays were generated in living cells by the interaction of bait-presenting artificial receptor constructs (bait-PARCs) with micrometer-scaled antibody surface patterns (see figure). This method was applied to simultaneously monitor the interaction kinetics of a prey protein with two distinct bait proteins in individual living cells.

Published online, DOI: 10.1002/anie.201209127 – Read now

A meta-terphenyl-based achiral conjugated polymer bearing carboxy groups self-associated to form a racemic double helix in the solid state, whereas with chiral amines the polymer formed a unique one-handed double helix in solution, in which each strand sandwiched a pair of chiral amines through a cyclic hydrogen-bonding network. The chiral information of the amines is transferred to the polymer backbones with remarkable amplification of the helical chirality.

Received February 04, 2013, published online April 05, 2013, DOI: 10.1002/anie.201301005 – read now. No. 20/2013.

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Photocatalysts active under near-infrared (NIR) light have been unknown. The libethenite Cu₂(OH)PO₄ absorbs strongly in the NIR light region and is an effective photocatalyst under NIR light irradiation, which decomposes 2,4-dichlorophenol in aqueous solution. Cu₂(OH)PO₄ consists of distorted CuO₄(OH)₂ octahedra sharing their corners with distorted CuO₄(OH) trigonal bipyramids. The NIR-light-driven photocatalytic ability of Cu₂(OH)PO₄ is due to a facile transfer of the photogenerated electrons from the trigonal bipyramidal Cu(II) sites to the adjacent octahedral Cu(II) sites.

Received February 14, 2013, published online March 28, 2013, DOI: 10.1002/anie.201301306 – read now.

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An efficient and general synthetic route to the elusive epoxyisoprostanoid phospholipids PECPC and PEIPC, along with the isoprostanoids EC and EI is reported, relying on a number of stereo- and chemoselective steps, including a C–H insertion for rapid construction of the cyclopentanone ring. The synthesized compounds display unprecedented biological activity in reducing the secretion of pro-inflammatory cytokines.

Received January 28, 2013, published online April 16, 2013, DOI: 10.1002/anie.201300739 – read now. No. 20/2013.

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A general strategy for producing recombinant histones with site-specific serine phosphorylation is developed through engineering phosphoseryl-tRNA synthetase and an elongation factor. Serine-phosphorylated nucleosomes provide the first direct evidence for crosstalk between phosphorylation and acetylation in histone. This strategy should facilitate the study of histone phosphorylation and cross-regulatory mechanisms.

Received January 21, 2013, published online March 26, 2013, DOI: 10.1002/anie.201300531 – read now. No. 22/2013.

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Cucurbit[14]uril, the largest cucurbit[n]uril member with 14 normal glycoluril units linked by 28 methylene bridges using the traditional synthetic routes. However, it seems to be formed from 14 units of the –glycoluril-(CH₂)₂– moiety with a 360° twist. As a consequence, it does not have a normal cavity like the most cucubit[n]urils, and looks to have a folded, figure-of-eight conformation. We are naming it twisted cucurbit[14]uril (tQ[14]).

Coming soon.