Société Chimique de France

Playing it cool: Almost all of the constituent parts of the complex [Ln^III₄M^II₈(OH)₈(L)₈(O₂CR)₈]X₄, namely the lanthanide ions Ln³⁺, the transition-metal ions M²⁺, the bridging ligand L, the carboxylates, and the counterions X can be exchanged, thus allowing a thorough understanding of the individual contributions to the magnetocaloric effect. Example in picture: Gd purple, Cu green, O red, N blue.

[Communication]
Thomas N. Hooper, Jürgen Schnack, Stergios Piligkos, Marco Evangelisti, Euan K. Brechin
Angew. Chem. Int. Ed. 2012, 51, No. 19, 4633. Read article.

A convenient and low-cost immunosensor was designed by using a polyethylene-glycol-film-modified screen-printed carbon electrode combined with a self-synthesized carbon sphere/gold nanoparticle composite as an electrochemical label for signal amplification (see scheme). This efficient method provides a potential application for clinical detection of protein markers.

[Full Paper]
Qiunan Xu, Feng Yan, Jianping Lei, Chuan Leng, Huangxian Ju
Chem. Eur. J. 2012, 18, No. 16, 4994. Read article.

Strychnine thrillers beyond Agatha Christie: The complex indole alkaloid strychnine has engaged the chemical community since the 19th century. This Review examines why strychnine has been and still remains an important target for directed synthesis efforts. Selected syntheses of strychnine are discussed with the aim of identifying their influence on the evolution of the strategy and tactics of organic synthesis.

[Review]
Jeffrey S. Cannon, Larry E. Overman
Angew. Chem. Int. Ed. 2012, 51, No. 18, 4288. Read article.

Vertically aligned ZnO single-crystal nanotube/nanorod array films have been concurrently fabricated, respectively, on the top and bottom surfaces of a zinc foil substrate by a facile vapor-phase hydrothermal method, due to the unique vapor-phase reaction environment (see figure).

[Communication]
Haimin Zhang, Yibing Li, Porun Liu, Ying Li, Dongjiang Yang, Huagui Yang, Huijun Zhao
Chem. Eur. J. 2012, 18, No. 17, 5165. Read article.

Dream team: Heterogeneous inorganic semiconductors and chiral organocatalysts team up for the stereoselective photocatalytic formation of carbon–carbon bonds. However, the connection between the organic and inorganic catalysts should not be too tight: Covalent immobilization inactivates the system.

[Communication]
Maria Cherevatskaya, Matthias Neumann, Stefan Füldner, Christoph Harlander, Susanne Kümmel, Stephan Dankesreiter, Arno Pfitzner, Kirsten Zeitler, Burkhard König
Angew. Chem. Int. Ed. 2012, 51, No. 17, 4062. Read article.

Flip a switch: A nanoswitch uses chemical inputs to turn an organocatalytic Knoevenagel reaction on and off (see scheme: R=reactant, P=product). To stop catalysis the chemical input (pink and green) wraps around the inhibitory segment of the nanoswitch to effect release or unlocking of the switch. The process can run reversibly over three cycles without loss of activity.

[Communication]
Michael Schmittel, Soumen De, Susnata Pramanik
Angew. Chem. Int. Ed. 2012, 51, No. 16, 3832. Read article.

Any which way but loose: DNA has become a fascinating construction material for nanosized objects (see figure); these are beginning to play an important role in nanotechnology due to their ability to form structures with function. This article highlights the recent developments in the field of DNA architectonics, including 2D and 3D structures, nanoparticle complexes, chemical modification and DNA-based nanodevices.

[Concept]
Eugen Stulz
Chem. Eur. J. 2012, 18, No. 15, 4456. Read article.

Salty water! Lithium salts (LiCl, LiNO₃, and LiClO₄) at very high concentrations in water form lyotropic liquid crystalline (LLC) mesophases with a nonionic surfactant (10-lauryl ether) and display high ionic conductivities (10⁻²–10⁻⁴ S cm⁻¹) over a broad temperature range (−10 to 80 °C) with excellent behavior as gel electrolytes in electrochemical applications.

[Communication]
Cemal Albayrak, Atilla Cihaner, Ömer Dag
Chem. Eur. J. 2012, 18, No. 14, 4190. Read article.

Squeezing out the energy: Macroscopically reversible deformation of polymers in contact with water produces H₂O₂ in quantities that are sufficient to drive small-scale chemical syntheses. The amount of mechanosynthesized H₂O₂ scales with the polymer–water interfacial area, and the efficiency of the mechanical-to-chemical energy transduction can be as high as 30 % for soft, porous polymer “sponges”.

[Communication]
H. Tarik Baytekin, Bilge Baytekin, Bartosz A. Grzybowski
Angew. Chem. Int. Ed. 2012, 51, No. 15, 3596. Read article.

Catalytic asymmetric formal synthesis of (−)-cephalotaxine has been accomplished based on an efficient tandem intramolecular hydroamination/asymmetric semipinacol rearrangement reaction catalyzed by chiral silver phosphate. During the course of the study it was observed that an advanced intermediate could be obtained in enantiopure form by enantiomer separation on silica gel.

[Communication]
Qing-Wei Zhang, Kai Xiang, Yong-Qiang Tu, Shu-Yu Zhang, Xiao-Ming Zhang, Yu-Ming Zhao, Tian-Cai Zhang
Chem. Asian J. 2012, 7, No. 5, 894. Read article.

Making sense of sensitization: A systematic series of heteroleptic bis(tridentate) ruthenium(II) complexes of 1,3-bis(1,2,3-triazol-4-yl)benzene N C N-coordinating ligands and 2,2':6',2''-terpyridine was synthesized, analyzed by single-crystal X-ray diffraction, investigated photophysically and electrochemically, and studied by computational methods (see figure) revealing great potential for application in dye-sensitized solar cells.

[Full Paper]
Benjamin Schulze, Daniel Escudero, Christian Friebe, Ronald Siebert, Helmar Görls, Stephan Sinn, Martin Thomas, Sebastian Mai, Jürgen Popp, Benjamin Dietzek, Leticia González, Ulrich S. Schubert
Chem. Eur. J. 2012, 18, No. 13, 4010. Read article.

Cheers for titania: An N-doped composite of carbon nanotubes (CNTs) and mesoporous TiO₂ is used as support for Pt nanoparticles applied in the oxygen reduction reaction. The composite Pt/N-TiO₂-CNT shows a higher stability than Pt particles on carbon black or N-doped CNTs, as indicated by accelerated stress tests of up to 2000 cycles. The enhanced stability is attributed to strong interactions between TiO₂ and Pt and a higher corrosion resistance of TiO₂ as well as CNTs.

[Communication]
Justus Masa, Ankur Bordoloi, Martin Muhler, Wolfgang Schuhmann, Wei Xia
ChemSusChem 2012, 5, No. 3, 523. Read article.

AHA Erlebnis: CaC₂, used to produce acetylene until several decades ago, is re-emerging as a cheap, sustainable resource synthesized from coal and lignocellulosic biomass. We report efficient catalytic protocols for the synthesis of functional acetylene derivatives from CaC₂ through aldehyde, alkyne, and amine (AAA) as well as alkyne, haloalkane, and amine (AHA) couplings, and in addition demonstrate its use in click and Sonogashira chemistry, showing that calcium carbide is a sustainable and cost-efficient carbon source.

[Communication]
Zhewang Lin, Dingyi Yu, Yin Ngai Sum, Yugen Zhang
ChemSusChem 2012, 5, No. 4, 625. Read article.

The new 1,2: The feeding of fluorine-labelled precursors together with mutagenesis experiments revealed that the rare 3-amino-salicylate moiety of antimycins is produced by a particular multicomponent oxidation complex.

[Communication]
Ilka Schoenian, Christian Paetz, Jeroen S. Dickschat, Bertrand Aigle, Pierre Leblond, Dieter Spiteller
ChemBioChem 2012, 13, No. 6, 769. Read article.

One-pot stew of sugars: The steam reforming of sugars, such as sorbitol and glucose, with an integrated CO₂ capture using a calcium-based acceptor is demonstrated to give hydrogen of very high purity and improved yield in a single step, while the risk of coke formation compared to conventional steam reforming is reduced. However, there is a trade-off between hydrogen selectivity and yield. High temperatures lead to high hydrogen yields with relatively low purity.

[Full Paper]
Li He, De Chen
ChemSusChem 2012, 5, No. 3, 587. Read article.

A color change: X-ray-induced photochromic species are rare and can be used for detection of X-rays. A highly robust X-ray-sensitive material with the discrete structure of a metal–organic complex has been found to show both soft and hard X-ray-induced photochromism at room temperature (see picture). A new ligand-to-ligand electron-transfer mechanism was proposed to elucidate this photochromic phenomenon.

[Communication]
Ming-Sheng Wang, Chen Yang, Guan-E. Wang, Gang Xu, Xiang-Ying Lv, Zhong-Ning Xu, Rong-Guang Lin, Li-Zhen Cai, Guo-Cong Guo
Angew. Chem. Int. Ed. 2012, 51, No. 14, 3432. Read article.

Watch out for water! The stereoselective diarylation of three different metal-coordinating, cyclic methylamino vinyl ethers is described. The reaction proceeds via a chelation-controlled Heck/Suzuki diarylation pathway, and represents the first example of a stereoselective, oxidative Heck/Suzuki domino reaction.

[Full Paper]
Alejandro Trejos, Luke R. Odell, Mats Larhed
ChemistryOpen 2012, 1, No. 1, 49. Read article.

Hear O'YE, hear O'YE! The combination of the in situ substrate feeding product removal technology with a multienzymatic cascade system (old yellow enzyme and horse liver alcohol dehydrogenase) increased both the yields and enantioselectivities in the reduction of α-substituted cinnamaldehydes.

[Full Paper]
Elisabetta Brenna, Francesco G. Gatti, Daniela Monti, Fabio Parmeggiani, Alessandro Sacchetti
ChemCatChem 2012, 4, No. 5, 653. Read article.

The basicities of a number of important phosphanes and diphosphanes have been determined in the solvent acetonitrile. The relationship between basicity and structure was examined and compared with amines and diamines.

[Full Paper]
Kristjan Haav, Jaan Saame, Agnes Kütt, Ivo Leito
Eur. J. Org. Chem. 2012, No. 11, 2167. Read article.

Relative acidities were determined spectrophotometrically for twenty partially methylated methyl α-D-glycopyranosides. It was proven that the more adjacent hydroxy groups a sugar displays, the more acidic is the corresponding hydroxy system, apparently caused by extended hydrogen bonding. A first estimation of the pK_a of partially methylated methyl α-D-glycopyranosides was obtained.

[Full Paper]
Martin Matwiejuk, Joachim Thiem
Eur. J. Org. Chem. 2012, No. 11, 2180. Read article.

The combination of macrocycles with fluorescent dyes affords supramolecular reporter pairs, which can be employed for the monitoring of catalytic, particularly biocatalytic, reactions. The resulting assays are unselective time-resolved variants of indicator displacement and uptake sensing systems. They are applicable to a large range of analytes and allow direct real-time monitoring in homogeneous solution, with the possibility of performing inhibitor and catalyst screening.

[Concept]
Roy N. Dsouza, Andreas Hennig, Werner M. Nau
Chem. Eur. J. 2012, 18, No. 12, 3444. Read article.

One to enhance them all: Spiked gold beads are efficient optical enhancers for single-particle SERS ultradetection (see picture), due to the localization of high electric fields at the apex of the tips and the antenna effect displayed by the core.

[Article]
Paula Aldeanueva-Potel, Enrique Carbó-Argibay, Nicolás Pazos-Pérez, Silvia Barbosa, Isabel Pastoriza-Santos, Ramón A. Alvarez-Puebla, Luis M. Liz-Marzán
ChemPhysChem, February 22, 2012, DOI: 10.1002/cphc.201101014. Read article.

The one-pot solvothermal reactions of mixtures of zinc and copper salts and H₂bdc and dabco linkers have led to the formation of novel mixed-metal [Zn_1–xCu_x(bdc)(dabco)_0.5] MOFs. The prepared materials are isostructural with the known layer-pillared monometallic [M(bdc)(dabco)_0.5] (M = Zn or Cu) frameworks and exhibit permanent porosity.

[Full Paper]
Olesia Kozachuk, Kira Khaletskaya, Markus Halbherr, Angélique Bétard, Mikhail Meilikhov, Rüdiger W. Seidel, Bettina Jee, Andreas Pöppl, Roland A. Fischer
Eur. J. Inorg. Chem. 2012, No. 10, 1688. Read article.

Rare and precious: Following the lead taken by the EU in energy and climate policy, a shift from fossil fuels to regenerative energy will have occurred globally by the second half of this century. This will be accompanied by a strong demand for other exhaustible raw materials, in particular metals. The terms “sustainability”, “depletion” and “scarcity” are examined in the context of mineral supply and the situation with regard to some rare metals is discussed.

[Full Paper]
Alex M. Bradshaw, Thomas Hamacher
ChemSusChem 2012, 5, No. 3, 550. Read article.

Prenylation probes: Eukaryotic protein prenyltransferases modify polypeptides with isoprenoid lipids. Modification of isoprenoids with reporter groups allows the creation of probes for the analysis of protein prenylation in vitro and in vivo. An amine-derivatized isoprenoid scaffold was used as a novel starting point for the synthesis of functionalized phosphoisoprenoid libraries.

[Full Paper]
Debapratim Das, Zakir Tnimov, Uyen T. T. Nguyen, Govindaraju Thimmaiah, Harriet Lo, Daniel Abankwa, Yaowen Wu, Roger S. Goody, Herbert Waldmann, Kirill Alexandrov
ChemBioChem 2012, 13, No. 5, 674. Read article.

A third twin: Homopolymers are formed by the copolymerization of two twin monomers. Using the new method of simultaneous twin polymerization, complex hybrid materials can be synthesized in a targeted manner (see scheme), in which, depending upon the combination of twin monomers used, nanostructured hybrid materials with different compositions and properties can be obtained.

[Communication]
Tina Löschner, Alexander Mehner, Silke Grund, Andreas Seifert, Andreas Pohlers, Arno Lange, Gerhard Cox, Hans-Joachim Hähnle, Stefan Spange
Angew. Chem. Int. Ed. 2012, 51, No. 13, 3258. Read article.

Complementary toxicity: Phosphonium salts with halogen anions are several times more cytotoxic against HeLa and K562 cancer cells than the clinically used reference compound cisplatin and show unusual complementary anticancer selectivity, which has not previously been reported in the literature.

[Full Paper]
Barbara Bachowska, Julia Kazmierczak-Baranska, Marcin Cieslak, Barbara Nawrot, Dorota Szczęsna, Joanna Skalik, Piotr Bałczewski
ChemistryOpen 2012, 1, No. 1, 33. Read article.

Nuclease activation: The HNH motif characterizes many nucleases, among them EndA from Streptococcus pneumoniae. One of the His residues is responsible for activating a water molecule for phosphodiester bond cleavage. Its replacement by other amino acids leads to inactive enzymes. However, subsequent addition of imidazole can rescue catalytic activity in vitro and in vivo.

[Full Paper]
Marika Midon, Oleg Gimadutdinow, Gregor Meiss, Peter Friedhoff, Alfred Pingoud
ChemBioChem 2012, 13, No. 5, 713. Read article.

The state of the art of force-field parametrization for ionic liquids is reviewed and an overview of the advantages and disadvantages of the various available force fields is provided. Insight obtained from recent electronic density functional results into the parametrization of partial charges and on the influence of polarization effects in bulk ionic liquids is highlighted.

[Minireview]
Florian Dommert, Katharina Wendler, Robert Berger, Luigi Delle Site, Christian Holm
ChemPhysChem 2012, 13, No. 7, 1625. Read article.

Please release me: Mesoporous silica nanoparticles capped with bulky organic moieties containing amide and urea linkages were able to release their cargo upon addition of amidase and urease. Amidase induced an immediate, yet not complete, release of the cargo. On the other hand, urease allowed a near total cargo release that was delayed in time (see graph).

[Communication]
Alessandro Agostini, Laura Mondragón, Carmen Coll, Elena Aznar, M. Dolores Marcos, Ramón Martínez-Máñez, Félix Sancenón, Juan Soto, Enrique Pérez-Payá, Pedro Amorós
ChemistryOpen 2012, 1, No. 1, 17. Read article.

Responsive carriers: Autofluorescent microcapsules were assembled by covalent cross-linking of polysaccharide derivative alginate dialdehyde (ADA) and cystamine dihydrochloride (CM) through a layer-by-layer technique. The formulated Schiff base and disulfide bonds render capsules with pH- and redox-responsive properties for pinpointed intracellular delivery.

[Full Paper]
Liang Gao, Jinbo Fei, Jie Zhao, Wei Cui, Yue Cui, Junbai Li
Chem. Eur. J. 2012, 18, No. 11, 3185. Read article.

Chirality transfer: In large chiral plasmonic structures, a new electrodynamic mechanism of plasmonic CD that is qualitatively different to near-field, dipolar mechanism of plasmonic chirality is described. The models presented also show that anisotropic nanocrystals have strongly enhanced CD at the plasmonic frequency.

[Article]
Alexander O. Govorov, Zhiyuan Fan
ChemPhysChem, February 16, 2012, DOI: 10.1002/cphc.201100958. Read article.

Switch 'em up: Two-electron oxidation and reduction switches the title complexes between aromatic and antiaromatic character (see picture). The switching is confirmed by ¹H NMR and UV/Vis/NIR absorption spectroscopy and by cyclic voltammetry. The structure of the porphyrin–[26]hexaphyrin hybrid tape was elucidated by X-ray diffraction analysis.

[Communication]
Takayuki Tanaka, Naoki Aratani, Atsuhiro Osuka
Chem. Asian J. 2012, 7, No. 5, 889. Read article.

Strong as an Ox: Chemical oxidation of the thiophene ring of fused thiophenes and their derivatives could significantly improve their semiconductor properties, which suggests it may be a promising way to convert p-type semiconductors into ambipolar or n-type semiconductors.

[Full Paper]
Jin-Dou Huang, Shu-Hao Wen, Ke-Li Han
Chem. Asian J. 2012, 7, No. 5, 1032. Read article.

Nortropine opens up: A reaction mechanism for the ring opening of the bicyclic amine, nortropine, is proposed on the basis of a combined experimental and DFT computational analysis of the associated ²H and ¹⁵N isotope effects. The metabolism by cytochrome P450 monooxygenase leads to a labile product, and the C-N bond cleavage involves a molecule of water.

[Full Paper]
Renata A. Kwiecień, Katarzyna Kosieradzka, Jean-Yves Le Questel, Jacques Lebreton, Anaïs Fournial, Emmanuel Gentil, Marcel Delaforge, Piotr Paneth, Richard J. Robins
ChemCatChem 2012, 4, No. 4, 530. Read article.

Depending on the concentration, the reagents can form different supramers with distinct chemical properties. The changes in supramer structure (indicated by the red vertical arrows) correlate with the glycosylation yield (1) and stereoselectivity (2) and can be detected by physical methods.

[Full Paper]
Leonid O. Kononov, Nelly N. Malysheva, Anna V. Orlova, Alexander I. Zinin, Tatiana V. Laptinskaya, Elena G. Kononova, Natalya G. Kolotyrkina
Eur. J. Org. Chem. 2012, No. 10, 1926. Read article.

A homogeneous and disordered assembly of densely packed titanium oxides nanocrystals 2–3 nm in size is formed by means of aqueous-solution processes at room temperature. The assembled nanocrystals form macroscopic transparent objects 2–5 mm in size. Formation of the hydrated layer on the surface of nanocrystals facilitates the generation of macroscopic objects through the inhibition of inhomogeneous and disordered aggregates.

[Full Paper]
Yuya Oaki, Keisuke Nakamura, Hiroaki Imai
Chem. Eur. J. 2012, 18, No. 10, 2825. Read article.

Leaky layers: Several 10 μm-thick, highly aligned, porous structures of titanium dioxide, niobium pentoxide and mixed oxides can be grown anodically in nitrate-containing electrolytes with channel diameters in the range of 10–20 nm. Depending on the substrate, the electrochemical growth parameters need to be optimized to achieve a high degree of long-range order.

[Communication]
Robin Kirchgeorg, Wei Wei, Kiyoung Lee, Seugli So, Patrik Schmuki
ChemistryOpen 2012, 1, No. 1, 21. Read article.

Turning on the power: Irradiating metal–solvent mixtures with microwaves produces electric discharges that are critically dependent on microwave power, solvent, metal type, size and morphology.

[Full Paper]
Wen Chen, Bernhard Gutmann, C. Oliver Kappe
ChemistryOpen 2012, 1, No. 1, 39. Read article.

A rare find: Two types of organic–inorganic hybrid monovacant Keggin silicotungstates with both rare-earth–transition-metal heterometals and mixed ligands (H₂pzda and ethylenediamine; pzda=pyrazine-2,3-dicarboxylate) were separated and characterized.

[Full Paper]
Shaowei Zhang, Junwei Zhao, Pengtao Ma, Jingyang Niu, Jingping Wang
Chem. Asian J. 2012, 7, No. 5, 966. Read article.

Cobalt crowds crack it up: The catalytic activity of a cobalt-oxido film for water oxidation may be inversely proportional to atomic order, determined by the size of contiguous Co_xO_y clusters in the amorphous material. The redox-inert cations and anions in CoCat modulate redox properties and catalytic activity without modifying the basic structural motif of Co-oxido clusters.

[Full Paper]
Marcel Risch, Katharina Klingan, Franziska Ringleb, Petko Chernev, Ivelina Zaharieva, Anna Fischer, Holger Dau
ChemSusChem 2012, 5, No. 3, 542. Read article.

Four new EuDOTA-tetraamides with variable alkyl chains lengths were synthesized and their CEST properties were extensively studied. Three of these complexes werefound to spontaneously form micelles due to their long alkyl chains which resulted in a dramatic increase in their CEST sensitivities.

[Full Paper]
Osasere M. Evbuomwan, Garry Kiefer, A. Dean Sherry
Eur. J. Inorg. Chem. 2012, No. 12, 2126. Read article.

A model chromophore set consisting of four fluorene/oxadiazole-based analogues was synthesized, and its members were shown to display ascending two-photon absorptivities with increasing size of their π systems. The observed nanosecond excited-state lifetimes suggested that these model compounds could be potential candidates as broad-band optical power limiters for laser pulses of long duration.

[Full Paper]
Tzu-Chau Lin, Ying-Hsuan Lee, Chia-Ling Hu, Yu-Kai Li, Yu-Jhen Huang
Eur. J. Org. Chem. 2012, No. 9, 1737. Read article.

A series of (η³-allyl)palladium complexes bearing 1,2,3-triazole carbene (tzNHC) ligands has been prepared and characterized. The donor properties of tzNHC ligands are stronger than those of imidazole carbene ligands. The [1,4-bis(2,6-diisopropylphenyl)-3-methyl-1,2,3-triazol-5-ylidene](cinnamyl)PdCl complex shows high activity in the room-temperature Suzuki–Miyaura coupling reaction with aryl chlorides.

[Full Paper]
Takahiro Terashima, Sayuri Inomata, Kenichi Ogata, Shin-ichi Fukuzawa
Eur. J. Inorg. Chem. 2012, No. 9, 1387. Read article.

The magic key for dopamine D₂ receptor agonism was studied by using a combined receptor and pharmacophore modeling approach. All available experimental data, including a set of carefully selected active and inactive ligands, were used to identify the reasons behind selectivity and to pinpoint the specific ligand–receptor interactions made by D₂ agonists.

[Full Paper]
Marcus Malo, Lars Brive, Kristina Luthman, Peder Svensson
ChemMedChem 2012, 7, No. 3, 471. Read article.

Nuked catalysts! Nanosized platinum particles loaded on TiO₂ (Pt–TiO₂) were synthesized by using a microwave-assisted deposition method with the aim of developing a highly efficient photocatalyst for the decomposition of aqueous NH₃ into H₂ and N₂ in a stoichiometric molar ratio under inert conditions (see picture).

[Full Paper]
Kojirou Fuku, Takashi Kamegawa, Kohsuke Mori, Hiromi Yamashita
Chem. Asian J., February 7, 2012, DOI: 10.1002/asia.201100984. Read article.

In vivo miRNA assassination: We designed and employed a strategy with locked nucleic acid enzyme (LNAzyme) for in vivo knockdown of microRNA (miRNA) in zebrafish embryos. We demonstrate that LNAzyme can efficiently knockdown miRNAs with minimal toxicity to the zebrafish embryos.

[Full Paper]
Hemant Suryawanshi, Mukesh Kumar Lalwani, Soundhar Ramasamy, Rajiv Rana, Vinod Scaria, Sridhar Sivasubbu, Souvik Maiti
ChemBioChem 2012, 13, No. 4, 584. Read article.

Hold your P's: Phosphorylated tyrosine and serine residues in peptides have been modified selectively by DNA catalysts (see graphic). These deoxyribozymes catalyze covalent attachment of an RNA tag to a range of peptide sequences, thus a proof of principle for a new approach to phosphopeptide analysis is established.

[Communication]
Amit Sachdeva, Madhavaiah Chandra, Jagadeeswaran Chandrasekar, Scott K. Silverman
ChemBioChem 2012, 13, No. 5, 654. Read article.

Meet me at the symmetry gates: A supramolecular approach using chlorides as structure-directing ligands gives high-nuclearity, mixed-valent Mn coordination clusters with {Mn^IIMn^III₁₂}, {Mn^II₃Mn^III₁₀}, and {Mn^II₃Mn^III₁₁} core structures that have supramolecular chirality. The {Mn^IIMn^III₁₂} complex (see structure: Mn blue, Cl green, O red) is the first structurally characterized Mn-based Keplerate and has one of the highest symmetries reported for a high-nuclearity Mn coordination cluster.

[Communication]
Lei Zhang, Rodolphe Clérac, Pierre Heijboer, Wolfgang Schmitt
Angew. Chem. Int. Ed. 2012, 51, No. 12, 3007. Read article.

Oligonucleotide conjugates exhibiting two or three thio-linkers, ferrocene moieties, or up to four carbohydrate residues were synthesized by poly click chemistry by using new bis- or tris-alkyne phosphoramidites

[Full Paper]
Caroline Ligeour, Albert Meyer, Jean-Jacques Vasseur, François Morvan
Eur. J. Org. Chem. 2012, No. 9, 1851. Read article.

Binding it soft but strong: Resorcinarene bis-thiacrowns containing soft sulfur donor atoms are shown to be ideal host molecules for high-affinity encapsulation of silver inside the resorcinarene cavity. A 1:2 host–guest binding was observed both in solution and in the solid state.

[Full Paper]
Kirsi Salorinne, Elisa Nauha, Maija Nissinen
Chem. Asian J. 2012, 7, No. 4, 809. Read article.

All that glitters is gold: Highly phosphorescent gold(III) complexes (see picture) with extended π-conjugated cyclometalating ligands exhibit rich photophysical and photochemical properties. They act as efficient photocatalysts/photosensitizers for oxidative functionalizations of secondary and tertiary benzylic amines and homogeneous hydrogen production from a water/acetonitrile mixture.

[Communication]
Wai-Pong To, Glenna So-Ming Tong, Wei Lu, Chensheng Ma, Jia Liu, Andy Lok-Fung Chow, Chi-Ming Che
Angew. Chem. Int. Ed. 2012, 51, No. 11, 2654. Read article.

Peripheral cannabinoid: Chromenopyrazoles were identified as cannabinoid receptor ligands, and some compounds in the series were found to be selective agonists of the CB₁ receptor. Results of molecular modeling studies support this finding. Behavioral tests and peripheral pain assays carried out with the most effective agonist show peripheral analgesia without CNS-mediated effects.

[Full Paper]
Jose Cumella, Laura Hernández-Folgado, Rocio Girón, Eva Sánchez, Paula Morales, Dow P. Hurst, Maria Gómez-Cañas, Maria Gómez-Ruiz, Diana C. G. A. Pinto, Pilar Goya, Patricia H. Reggio, María Isabel Martin, Javier Fernández-Ruiz, Artur M. S. Silva, Nadine Jagerovic
ChemMedChem 2012, 7, No. 3, 452. Read article.

Pt precursor promotes performance: The use of H₂PtCl₆ as metal precursor affects the observed activity of γ-Al₂O₃ supported catalysts in aqueous phase conversion of cellulose to sugar alcohols. The precursor changes the point of zero charge and leads to leaching. These two phenomena shift the dissociation equilibrium of water and enhance acid-catalyzed hydrolysis of cellulose.

[Communication]
Ryan M. Ravenelle, Fatoumata Z. Diallo, John C. Crittenden, Carsten Sievers
ChemCatChem 2012, 4, No. 4, 492. Read article.

Out of the woods: Considerable advances have been made for the synthesis of furan-based polyester building blocks, especially 2,5-furandicarboxylic acid (FDCA), by using nanoparticulate gold catalysts. This Minireview discuss the fundamental aspects of using nanoparticulate catalysts for the aerobic oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) into FDCA and selective transformation of HMF into potential biofuels (DMF=2,5-dimethylfuran).

[Minireview]
Saikat Dutta, Sudipta De, Basudeb Saha
ChemPlusChem 2012, 77, No. 4, 259. Read article.

An organoimido-substituted monovacant hexamolybdate containing additional multidentate ligands and its phenylphosphonate derivative were both synthesized directly from an aromatic amine by using an N,N-dicyclohexylcarbodiimide (DCC) protocol. The inherent chirality of these compounds and their hydrophobic shells are pictured.

[Communication]
Jian Hao, Jin Zhang, Panchao Yin, Zicheng Xiao, Fengping Xiao, Yongge Wei
Chem. Eur. J. 2012, 18, No. 9, 2503. Read article.

Amidoborane ammoniate formation is investigated by using isotopic labeling techniques. The formation of Ca(NH₂BH₃)₂·2 NH₃ is initiated by proton transfer from NH₃BH₃ to NH₂⁻ (amide), forming Ca(NH₃)²⁺ and anionic [NH₂BH₃]⁻ groups. The dehydrogenation of the ammoniate, which occurs at lower temperatures, is a result of the participation of NH₃ in the dehydrogenation process via the combination of (NH₃)H^δ+···H^δ−(NH₂BH₃⁻).

[Full Paper]
Yong Shen Chua, Wen Li, Wendy J. Shaw, Guotao Wu, Tom Autrey, Zhitao Xiong, Ming Wah Wong, Ping Chen
ChemSusChem, January 31, 2012, DOI: 10.1002/cssc.201100523. Read article.

On the dot: A water-soluble single-source precursor has been used in the synthesis of CdS quantum dots passivated with a nucleotide in an aqueous one-pot reaction (see figure). The crystal structure of the decomposition product of a single-source precursor, 3-methyl-5-(1,2,3,4-tetrahydroxybutyl)oxazolidine-2-thione is also presented. A new decomposition mechanism is suggested that compliments existing routes.

[Communication]
Mark Green, Lydia Sandiford, Kirsty M. Anderson, Yongmin Ma
ChemPlusChem 2012, 77, No. 3, 192. Read article.

An eye on thrombin: A series of fluorogenic peptidyl-AMC substrates were synthesized and subjected to a biological evaluation to determine their suitability in the thrombin generation test (TGT). Evaluation of the acquired thrombin generation curves showed that several of these substrates have excellent potential for replacement of the substrate in current use.

[Full Paper]
Sander S. van Berkel, Bas van der Lee, Floris L. van Delft, Rob Wagenvoord, H. Coenraad Hemker, Floris P. J. T. Rutjes
ChemMedChem 2012, 7, No. 4, 606. Read article.

Double whammy! Small molecules that inhibit Staphylococcus aureus dehydrosqualene synthase (CrtM) or host squalene synthase (SQS) are of interest as novel, innate immunity-based therapeutics, blocking virulence or stimulating antibacterial neutrophil extracellular trap (NET) formation. The discovery of leads that do both represents a new route to treating staph infections.

[Communication]
Fu-Yang Lin, Yonghui Zhang, Mary Hensler, Yi-Liang Liu, Ohn A. Chow, Wei Zhu, Ke Wang, Ran Pang, Wdee Thienphrapa, Victor Nizet, Eric Oldfield
ChemMedChem 2012, 7, No. 4, 561. Read article.

A novel sugar prenyltansferase, PAPT, from the fungus Phomopsis amygdali has been cloned and characterized. This enzyme transfers dimethylallyl diphosphate to the 6'-hydroxy group of the glucose moiety of fusicoccin (FC) A, a diterpene glucoside. To the best of our knowledge, this is the first enzyme to catalyze prenylation of a hydroxyl group in a glucose moiety.

[Full Paper]
Motoyoshi Noike, Chengwei Liu, Yusuke Ono, Yoshimitsu Hamano, Tomonobu Toyomasu, Takeshi Sassa, Nobuo Kato, Tohru Dairi
ChemBioChem 2012, 13, No. 4, 566. Read article.

Two for the price of one: The imidazolium cation serves both as part of the ionic liquid (IL) and as an NMR probe. Hydrogen-bond-accepting (HBA) and donating (HBD) abilities of ILs with halogeno complex anions (X⁻) are determined by means of ¹H NMR spectroscopy (see picture). The chemical shift of the H(2) atom is a function of the HBA strength of the anion.

[Article]
Ralf Lungwitz, Stefan Spange
ChemPhysChem 2012, 13, No. 7, 1910. Read article.

Reactive molecular dynamics (RMD) simulations are used to investigate the time evolution, governed by empirical potential energy functions, of reactive systems (see graphic). RMD approaches are the only methods that allow the study of chemical reactions in large condensed-phase systems. Exciting microscopic insights into chemical reactions in condensed phases are discussed in this review.

[Minireview]
Karim Farah, Florian Müller-Plathe, Michael C. Böhm
ChemPhysChem 2012, 13, No. 5, 1127. Read article.

Clean catalysts: A facile and novel chemical method is introduced for cleaning Pt nanoparticles with preferential orientation. The method is based on the idea that the decomposition of hydrogen peroxide may aid in removing organic components from the Pt-nanoparticle surface, and does not introduce any major loss of superficial structure.

[Article]
J. Monzó, M. T. M. Koper, P. Rodriguez
ChemPhysChem 2012, 13, No. 3, 709. Read article.

The chirality of molecular building units has been efficiently transferred to themacroscopic level, leading to chiral bulk materials of opposite handedness.

[Full Paper]
Gunther Hennrich, Belén Nieto-Ortega, Berta Gómez-Lor, Entique Gutierrez, Laura de Vega, Emma Cavero, Francisco J. Ramírez, Juan T. López Navarrete, Juan Casado
Eur. J. Org. Chem. 2012, No. 8, 1577. Read article.

α- and γ-Fe₂O₃ nanorods were obtained by proper dehydration of a rod-shaped β-FeOOH precursor. The Fe₂O₃ nanorods showed a distinct crystal-phase effect in the reduction of NO by CO on the basis of their exposed surface facets.

[Full Paper]
Xiaoling Mou, Yong Li, Bingsen Zhang, Lide Yao, Xuejiao Wei, Dang Sheng Su, Wenjie Shen
Eur. J. Inorg. Chem. 2012, No. 16, 2684. Read article.

Let's twist again: A “clean reaction” strategy based on thermally eliminating lactam bridges from a soluble acene precursor through a retro-Diels–Alder reaction gives a new, stable, green heptatwistacene (see structure). The molecule has a twist angle of 23.49°, is very stable even in air, and has an optical band gap of 1.82 eV.

[Communication]
Jinchong Xiao, Christos D. Malliakas, Yi Liu, Feng Zhou, Gang Li, Haibin Su, Mercouri G. Kanatzidis, Fred Wudl, Qichun Zhang
Chem. Asian J. 2012, 7, No. 4, 672. Read article.

Go on, liver little: NaGdF₄:Yb,Er/NaGdF₄ nanoparticles with a carboxy aluminum phthalocyanine (AlC₄Pc) photosensitizer incorporated inside silica shells were used in photodynamic therapy and magnetic resonance imaging (MRI) of liver cancer cells. In vitro studies indicated that these nanoparticles effectively killed cancer cells upon near-infrared excitation. This work has potential applications in imaging-guided therapy.

[Full Paper]
Zengxia Zhao, Yuning Han, Chenghong Lin, Dong Hu, Fang Wang, Xiaolan Chen, Zhong Chen, Nanfeng Zheng
Chem. Asian J. 2012, 7, No. 4, 830. Read article.

Affinity and selectivity: The online detection of the explosive triacetone triperoxide (TATP) is an utmost challenge in security research. The great number of events wherein TATP was involved underlines the significance of solutions to trace that particular explosive material. New optimized functionalized polyphenylene dendrimers (see structure) have been synthesized that can be used as powerful affinity systems to trace TATP on a ppb level.

[Communication]
Daniel Lubczyk, Matthias Grill, Martin Baumgarten, Siegfried R. Waldvogel, Klaus Müllen
ChemPlusChem 2012, 77, No. 2, 102. Read article.

Upconverting DNA: Upconversion nanoparticles are ligated to oligonucleotides by using “click”-type cycloaddition (see figure). Excitation in the near-infrared region yields bright luminescence of the DNA conjugates in the visible range.

[Full Paper]
Moritz M. Rubner, Daniela E. Achatz, Heike S. Mader, Judith A. Stolwijk, Joachim Wegener, Gregory S. Harms, Otto S. Wolfbeis, Hans-Achim Wagenknecht
ChemPlusChem 2012, 77, No. 2, 129. Read article.

Getting to the core: The role of the central nucleus in the diarylheterocycle COX-1 inhibitor class was investigated. We identified 5-(furan-2-yl)-1-(4-methoxyphenyl)-3-(trifluoromethyl)-1H-pyrazole (17) as a selective inhibitor of COX-1 activity. The results of molecular docking studies shed light the binding mode of 17 into the catalytic site of COX-1.

[Full Paper]
Maria Grazia Perrone, Paola Vitale, Paola Malerba, Angela Altomare, Rosanna Rizzi, Antonio Lavecchia, Carmen Di Giovanni, Ettore Novellino, Antonio Scilimati
ChemMedChem 2012, 7, No. 4, 629. Read article.

Cast your net widely: Three distinct structure types of porous frameworks based on carborane–Ln₂(CO₂)₆ (structure type I with Schläfli symbol of 4⁴·6², structure type II with Schläfli symbol of (4⁸·6⁶·8)(4⁸·6⁶·8), and structure type III with Schläfli symbol of 4¹²·6³) have been synthesized and structurally characterized (see figure). Gas sorption was studied and selective CO₂ capture over CH₄ and N₂ was observed.

[Full Paper]
Sheng-Li Huang, Yue-Jian Lin, Wei-Bin Yu, Guo-Xin Jin
ChemPlusChem 2012, 77, No. 2, 141. Read article.

The perfect combination: The combination of functionalized mesoporous materials such as MCM-41 with betulinic acid, a potent anticancer drug, led to novel drug delivery systems which may be useful in the future as adjuvant agents to avoid the recurrence of bone tumors on local implantations.

[Full Paper]
Sergio Sánchez-Muñoz, Santiago Gómez-Ruiz, Damián Pérez-Quintanilla, Sonia Morante-Zarcero, Isabel Sierra, Sanjiv Prashar, Reinhard Paschke, Goran N. Kaluđerović
ChemMedChem 2012, 7, No. 4, 670. Read article.

It's all about performance: ZnO/SnO₂ heterojunction nanocatalysts (see the formation of a ZnO/SnO₂ heterojunction in the TEM image) with excellent photocatalytic performances have been synthesized through a simple one-pot solvothermal method. The relationship between their structure and photocatalytic performances, especially antiphotocorrosion property, has been systematically studied.

[Full Paper]
Lirong Zheng, Yuanhui Zheng, Chongqi Chen, Yingying Zhan, Xinyi Lin, Qi Zheng, Kemei Wei
ChemPlusChem 2012, 77, No. 3, 217. Read article.

Glycotyping of KO mice: Glycotyping analysis of serum N-glycomes from gene-knockout mice that show no significant phenotype or abnormality can provide highly informative data to facilitate further comprehensive discussion of functions of cell surface C-type lectins in the maintenance of homeostatic balance of general immune system.

[Full Paper]
Maho Amano, Ryo Hashimoto, Shin-Ichiro Nishimura
ChemBioChem 2012, 13, No. 3, 451. Read article.

A flexible polymer for selective seawater splitting: Incorporation of a monomeric Mn-porphyrin that is normally catalytically inactive, into a flexible poly(terthiophene) film yields a remarkable light-assisted water oxidation catalyst with an apparent overpotential for water oxidation of a mere 0.09 V. The catalyst generates exclusively O₂ and no Cl₂ in seawater at 0.9 V versus Ag/AgCl.

[Communication]
Jun Chen, Pawel Wagner, Lei Tong, Gordon G. Wallace, David L. Officer, Gerhard F. Swiegers
Angew. Chem. Int. Ed. 2012, 51, No. 8, 1907. Read article.

Enantioselect-DeFluor: Carbon–fluorine bond cleavage by a chiral zirconium complex allows the synthesis of optically active 1,3-difluoroallene for the first time. Its absolute configuration was established by gas-phase vibrational circular dichroism spectroscopy (see picture).

[Communication]
Moritz F. Kuehnel, Tobias Schlöder, Sebastian Riedel, Belén Nieto-Ortega, Francisco J. Ramírez, Juan T. López Navarrete, Juan Casado, Dieter Lentz
Angew. Chem. Int. Ed. 2012, 51, No. 9, 2218. Read article.

Game over—structure solved: A combination of labeling experiments with mass spectrometry results in the reliable determination of the sum formula, the nature of the building blocks, and (for peptide natural products) also the determination of the absolute configuration as exemplified for the novel natural products GameXPeptide A–D (see scheme).

[Full Paper]
Helge B. Bode, Daniela Reimer, Sebastian W. Fuchs, Ferdinand Kirchner, Christina Dauth, Carsten Kegler, Wolfram Lorenzen, Alexander O. Brachmann, Peter Grün
Chem. Eur. J. 2012, 18, No. 8, 2342. Read article.

Strike while the iron is hot: Stable core/shell nanoparticles of single-crystal iron core are shown to produce much greater contrast enhancement in magnetic resonance imaging of cells, compared to that produced by pure iron oxides without increase in cytotoxicity (see TEM image of iron/iron oxide nanoparticles).

[Full Paper]
Soshan Cheong, Peter Ferguson, Ian F. Hermans, Guy N. L. Jameson, Sujay Prabakar, David A. J. Herman, Richard D. Tilley
ChemPlusChem 2012, 77, No. 2, 135. Read article.

From ANNs to NAMs! Data from an experimental metabotropic glutamate receptor 5 (mGlu₅) high-throughput screen (HTS) were employed to train artificial neural networks (ANNs) based on 345 confirmed negative allosteric modulators (NAMs) and 155 774 inactive compounds. This effort identified two potent mGlu₅ NAMs with a unique chemotype. Optimization afforded a tool compound (shown), active in mouse models of anxiety and addiction.

[Communication]
Ralf Mueller, Eric S. Dawson, Jens Meiler, Alice L. Rodriguez, Brian A. Chauder, Brittney S. Bates, Andrew S. Felts, Jeffrey P. Lamb, Usha N. Menon, Sataywan B. Jadhav, Alexander S. Kane, Carrie K. Jones, Karen J. Gregory, Colleen M. Niswender, P. Jeffrey Conn, Christopher M. Olsen, Danny G. Winder, Kyle A. Emmitte, Craig W. Lindsley
ChemMedChem 2012, 7, No. 3, 406. Read article.

Get a load of this! The purification of lactic dehydrogenase (LHD) using an affinity column of TiO₂ functionalized with Cibacron blue dye is illustrated. The large capacity of the TiO₂–CB NP microtip column for proteins, its stability at room temperature, and low cost of preparation suggest that TiO₂–CB NPs are useful for rapid protein purification. The two-step procedure results in the recovery of over 90 % of the protein loaded.

[Full Paper]
Chilukuri Subbalakshmi, Manaswita Nag, Sunkara V. Manorama
ChemPlusChem 2012, 77, No. 2, 113. Read article.

The sialome comprises sialylated glycoproteins and glycolipids that play essential roles in cell–cell communication. Using azide-modified molecular precursors of sialic acids and copper-free click chemistry, we visualized the spatiotemporal dynamics of the sialome in live zebrafish embryos.

[Communication]
Karen W. Dehnert, Jeremy M. Baskin, Scott T. Laughlin, Brendan J. Beahm, Natasha N. Naidu, Sharon L. Amacher, Carolyn R. Bertozzi
ChemBioChem 2012, 13, No. 3, 353. Read article.

Go with the flow: A flow-through microfluidic reactor system was developed that contains the three enzymes, β-galactosidase (β-Gal), glucose oxidase (GOD), and peroxidase (HRP), immobilized with a polycationic dendronized polymer in a predetermined sequence on a single chip for the conduction of an enzymatic cascade reaction. The desired enzyme localization within the microchannels of the chip could be achieved with a micromechanical valve system.

[Communication]
Sara Fornera, Phillip Kuhn, Dario Lombardi, A. Dieter Schlüter, Petra S. Dittrich, Peter Walde
ChemPlusChem 2012, 77, No. 2, 98. Read article.

On all fours: Recent work has used quadruplet codons to encode unnatural amino acids. Multiple unnatural amino acids have been incorporated into proteins through orthogonal protein translation using a quadruplet decoding ribosome (see figure; mutations to ribosome are shown in red).

[Minireview]
Kaihang Wang, Wolfgang H. Schmied, Jason W. Chin
Angew. Chem. Int. Ed. 2012, 51, No. 10, 2288. Read article.

Spontaneous spores: Spore-coat morphogenetic proteins are chemically bound to an AFM tip and silicon substrate, respectively, through a flexible cross-linker, and by using single-molecule recognition force spectroscopy (SMRFS) the piconewton forces and a series of dynamic kinetic data related to spore-coat morphogenetic proteins are obtained (see picture).

[Full Paper]
Haiyan Qiao, Daniela Krajcikova, Caisheng Liu, Yongjun Li, Hongda Wang, Imrich Barak, Jilin Tang
Chem. Asian J. 2012, 7, No. 4, 725. Read article.

Zn and the Art of Battery Development: A zinc/polyhalide redox flow battery employs Br⁻/ClBr²⁻ and Zn/Zn²⁺ redox couples in its positive and negative half-cells, respectively. The performance of the battery is evaluated by charge–discharge cycling tests and reveals a high energy efficiency of 81%, based on a Coulombic efficiency of 96% and voltage efficiency of 84%. The new battery technology can provide high performance and energy density at an acceptable cost.

[Communication]
Liqun Zhang , Qinzhi Lai, Jianlu Zhang, Huamin Zhang
ChemSusChem, January 19, 2012, DOI: 10.1002/cssc.201100530. Read article.

Two macrocycles that incorporate the redox-active ferrocene motif for anion sensing are presented. The urea macrocycle binds anions more strongly than the amide macrocycle and exhibits greater shifts of the ferrocene/ferrocenium redox couple upon the addition of anions.

[Full Paper]
Nicholas H. Evans, Christopher J. Serpell, Kirsten E. Christensen, Paul D. Beer
Eur. J. Inorg. Chem. 2012, No. 6, 939. Read article.

Fluorescent nanorods: Donor–acceptor dyads based on novel unsymmetrically disubstituted closo-1,12-dicarbadecaboranes have been prepared in a completely controlled manner by using a three-step procedure. Dyads with different donor–acceptor spacing were thereby obtained. Efficient energy transfer from the donor to the acceptor was determined in fluid solution at room temperature.

[Communication]
Delphine Hablot, Alexandra Sutter, Pascal Retailleau, Raymond Ziessel
Chem. Eur. J. 2012, 18, No. 7, 1890. Read article.

A 3D hierarchical flower-like MgO microsphere was formed by a new assembly process from 1D to 3D. The highly crystalline product has cubic symmetry and is assembled from close-packed nanoflakes. Its large surface area makes it highly favourable for heterogeneous catalysis, particularly in the Claisen–Schmidt condensation reactions for preparing chalcones with benzaldehyde and acetophenone.

[Full Paper]
Yang Qu, Wei Zhou, Zhiyu Ren, Kai Pan, Chungui Tian, Yang Liu, Shanshan Feng, Youzhen Dong, Honggang Fu
Eur. J. Inorg. Chem. 2012, No. 6, 954. Read article.

Nature bestows many gifts upon us, among which countless biomolecules have the ability to bridge metal ions and exert important functions in biology. By taking advantage of specific interactions between metal ions and biomolecules, this article highlights a novel concept for the construction of nanoscale biocoordination polymers through replacement of synthetic organic molecules with natural biomolecules as building blocks. The most recent advances are summarized and future challenges are discussed.

[Concept]
Yaling Liu, Zhiyong Tang
Chem. Eur. J. 2012, 18, No. 4, 1030. Read article.

Photon manipulation: The interaction efficiency between photons and molecules can be enhanced by a transformation between free-propagating massless photons and “heavy” photons. Although such photon manipulation is realized by metallic optical antennas, chemical interactions at metal–molecule interfaces have to be controlled to increase the overall photochemical reaction efficiency.

[Concept]
Katsuyoshi Ikeda, Kohei Uosaki
Chem. Eur. J. 2012, 18, No. 6, 1564. Read article.

Paramagnetic metal ions are important for the development of MRI contrast agents that function through chemical exchange saturation transfer (CEST or paraCEST). Recent work shows that Fe^II paraCEST MRI contrast agents are promising new candidates to add to the current repertoire of lanthanide(III) complex contrast agents.

[Microreview]
Sarina J. Dorazio, Janet R. Morrow
Eur. J. Inorg. Chem. 2012, No. 12, 2006. Read article.

Uracil is a common form of DNA damage resulting from hydrolysis of cytosine, and cellular uracil DNA glycosylases (UDG) have evolved to remove it specifically. The use of nonnatural pyrene deoxyriboside in short DNA oligomers to directly report on UDG enzymatic activity is described. The mechanism relies on the use of uracil as a strong quencher of pyrene, and enzyme repair activity can be directly imaged with bacterial cells in real time.

[Communication]
Toshikazu Ono, Shenliang Wang, Chi-Kin Koo, Lisa Engstrom, Sheila S. David, Eric T. Kool
Angew. Chem. Int. Ed. 2012, 51, No. 7, 1689. Read article.

Four lipophilic alkyl-substituted 6,6'-bis(1,2,4-triazin-3-yl)-2,2'-bipyridine (BTBP) ligands have been synthesized and the effects of the additional alkyl substitution on their extraction properties in nuclear waste treatment have been studied by Am^III/Eu^III solvent extraction experiments and lanthanide NMR spectroscopic titrations.

[Full Paper]
Frank W. Lewis, Laurence M. Harwood, Michael J. Hudson, Petr Distler, Jan John, Karel Stamberg, Ana Núñez, Hitos Galán, Amparo G. Espartero
Eur. J. Org. Chem. 2012, No. 8, 1509. Read article.

The wonderful world of graphene! A simple one-step fabrication of biomimetic graphene surfaces that possess both superhydrophobicity and bright structural color is presented. By using two-beam laser interference, construction of periodic grating microstructures and removal of hydrophilic oxygen groups were realized at the same time.

[Communication]
Jian-Nan Wang, Rui-Qiang Shao, Yong-Lai Zhang, Li Guo, Hao-Bo Jiang, Dong-Xiao Lu, Hong-Bo Sun
Chem. Asian J. 2012, 7, No. 2, 301. Read article.

Divide and organize: Exfoliation and dispersion of hexagonal boron nitride (h-BN) was achieved through reaction with a range of inorganic reagents (see picture). The product exists in the form of stable colloids in water or N,N-dimethylformamide (DMF) as thin platelets of functionalized h-BN. Highlights of this method are high yields of soluble h-BN and increased concentrations of dispersions.

[Full Paper]
Albert S. Nazarov, Viktor N. Demin, Ekaterina D. Grayfer, Alexander I. Bulavchenko, Aida T. Arymbaeva, Hyeon-Jin Shin, Jae-Young Choi, Vladimir E. Fedorov
Chem. Asian J. 2012, 7, No. 3, 554. Read article.

Isoform-selective histone deacetylase (HDAC) inhibitors containing mercaptoacetamide zinc binding groups are known to be viable alternatives to the more traditional hydroxamic acid based inhibitors. Herein we demonstrate the HDAC6 enantioselectivity of α-methyl-substituted mercaptoacetamides and provide evidence to support their use as neuroprotective agents.

[Full Paper]
Jay H. Kalin, Hankun Zhang, Sophie Gaudrel-Grosay, Giulio Vistoli, Alan P. Kozikowski
ChemMedChem 2012, 7, No. 3, 425. Read article.

Layer upon layer: Pure V₂O₅ nanosheets (see figure; C) have been successfully synthesized by a novel and facile dissolution–splitting method using low-cost raw materials (A). The as-prepared product exhibits enhanced lithium storage properties including good cycling and rate performance, 144 mAh g⁻¹ at 10 C and 95 mAh g⁻¹ at 20 C, as well as high reversible capacity, 290 mAh g⁻¹.

[Full Paper]
Zhong-li Wang, Dan Xu, Li-min Wang, Xin-bo Zhang
ChemPlusChem 2012, 77, No. 2, 124. Read article.

Tetrazine–triphenylamine bichromophores linked by an oxygen atom were designed and synthesized. Their photophysical and electrochemical properties were investigated. These dyads are nonfluorescent compounds in their neutral state because of phoinduced electron transfer. However, tetrazine fluorescence was restored by chemical oxidation (cation radical formation).

[Full Paper]
Cassandre Quinton, Valérie Alain-Rizzo, Cécile Dumas-Verdes, Gilles Clavier, Fabien Miomandre, Pierre Audebert
Eur. J. Org. Chem. 2012, No. 7, 1394. Read article.

Step by step: The stepwise nucleophilic addition of amidoximes to nitrile ligands in platinum(IV) complexes leads to coordinated O-imidoylamidoximines. These newly formed species after decoordination undergo cyclization (see scheme) to furnish 1,2,4-oxadiazoles. The cyclization is promoted by strong acceptor substituents R' and is not affected by a metal center.

[Full Paper]
Dmitrii S. Bolotin, Nadezhda A. Bokach, Matti Haukka, Vadim Yu. Kukushkin
ChemPlusChem 2012, 77, No. 1, 31. Read article.

Lock up your valuables: Receptor 1 acts as a “molecular lock” and anions act as “keys”; H₂PO₄⁻ can “lock” 1 by switching it from its “unlocked” conformation, however, the structurally similar HSO₄⁻ cannot “lock” receptor 1 as evidenced by single-crystal X-ray analysis (see scheme). The “unlocked–locked” conformational switching of 1 was investigated by monitoring changes in fluorescence intensity in the presence of different anions.

[Communication]
Sasanka Dalapati, Md. Akhtarul Alam, Sankar Jana, Rajat Saha, Saptarshi Biswas, Nikhil Guchhait
ChemPlusChem 2012, 77, No. 2, 93. Read article.

Occupy TiO₂: Co-grafting dyes with amphiphilic molecules containing phosphinic or phosphonic acid end groups can form a more compact monolayer than the adsorption of dye alone. This insulating molecular layer can effectively shield the back electron transfer from the conduction band of TiO₂ to redox electrolytes. Herein coadsorbents are found to not only influence the dye loading, but also the geometry and electronic properties of the system.

[Full Paper]
Mingkui Wang, Stefan Plogmaker, Robin Humphry-Baker, Peter Pechy, Håkan Rensmo, Shaik. M. Zakeeruddin, Michael Grätzel
ChemSusChem 2012, 5, No. 1, 181. Read article.

The entire zinc-finger domain of Zif268 was synthesized by a semi-synthetic pathway using the expressed protein ligation approach. Despite several modifications, for example, attachment of a fluorophore and introduction of a metal-chelating amino acid within the sequence of the third zinc finger, circular dichroism spectroscopic measurements confirmed zinc-induced folding and intact DNA binding ability.

[Full Paper]
Friederike Fehr, André Nadler, Florian Brodhun, Ivo Feussner, Ulf Diederichsen
ChemistryOpen 2012, 1, No. 1, 26. Read article.

Saturation transfer difference (STD) NMR spectroscopy was used to study the role of aromatic moieties in the inhibition of α-glucosidases by N-arylmethyl ent-conduramine F-1. STD epitope mapping and molecular docking simulations provide new insights into the structure-based design of drugs targeting this enzyme (see figure).

[Communication]
Antonio Hernández Daranas, Sonia Koteich Khatib, Robert Lysek, Pierre Vogel, José A. Gavín
ChemistryOpen 2012, 1, No. 1, 13. Read article.

Go with the flow! A novel 4-(1-triazolyl)proline immobilized onto 8 % DVB-PS catalyzes highly stereoselective aldol reactions under continuous flow conditions with very low catalyst loading (TON up to 61). Up to four different enantiomerically pure aldol products can be sequentially produced in gram amounts with the same catalyst sample.

[Full Paper]
Carles Ayats, Andrea H. Henseler, Miquel A. Pericàs
ChemSusChem 2012, 5, No. 2, 320. Read article.

One for all, all for one: A self-assembled M₄L₆ cage, incorporating small amounts of enantiopure subcomponents at the peripheries, forms predominantly with a one-handed twist at all metal centers. Strong stereochemical coupling between metal centers in the cage amplifies energy differences between the ΔΔΔΔ and ΛΛΛΛ diastereomers as compared to analogous mononuclear metal complexes (see picture; red and gray bars denote chiral and achiral subcomponents, respectively).

[Communication]
Naoki Ousaka, Jack K. Clegg, Jonathan R. Nitschke
Angew. Chem. Int. Ed. 2012, 51, No. 6, 1464. Read article.

Three phases are a charm: The electroactive nature of Ce and its renowned Ce^III/IV couple make it the keystone of this investigation at the intersection of separation science and electrochemistry. The Ce^III/IV couple has been probed to disclose its physical and spectroscopic behaviors in organic phases of relevance to solvent extraction, thus affording original insights into third phase phenomena and ion transfer across the aqueous–organic liquid interface in the title system (see figure).

[Full Paper]
Ross J. Ellis, Mark R. Antonio
ChemPlusChem 2012, 77, No. 1, 41. Read article.

Tailored foam bed: Cerium oxide with a foam morphology is used as a support for gold nanoparticles. The foams are synthesized using L-asparagine to produce a cerium coordination polymer foam, which is calcined to give the oxide foam. The activity of the Au/foamCeO₂ for solvent-free benzyl alcohol oxidation is superior to standard Au/CeO₂ catalysts.

[Full Paper]
Mosaed Alhumaimess, Zhongjie Lin, Weihao Weng, Nikolaos Dimitratos, Nicholas F. Dummer, Stuart H. Taylor, Jonathan K. Bartley, Christopher J. Kiely, Graham J. Hutchings
ChemSusChem 2012, 5, No. 1, 125. Read article.

We have implemented the super-resolution method of direct stochastic optical reconstruction microscopy (dSTORM) to image nuclear and mitochondrial DNA in living cells. We also demonstrate time-lapse imaging, all using a dye that associates directly with cellular DNA: the commercially available dye Picogreen (see figure).

[Communication]
Alexander Benke, Suliana Manley
ChemBioChem 2012, 13, No. 2, 298. Read article.

Unwritten tales of isosorbide: Isosorbide is a versatile platform chemical that can be derived from cellulosic biomass as a sustainable resource. Numerous derivatives can be obtained by using various chemical, chemocatalytic, and biotechnological processes to enable the replacement of products in numerous applications that are currently based on fossil resources.

[Minireview]
Marcus Rose, Regina Palkovits
ChemSusChem 2012, 5, No. 1, 167. Read article.

A mechanically interlocked antenna: Two rotaxanes consisting of six naphthyl units appended to the stoppers and a pyrene chromophore attached to the wheel perform as light-harvesting antennae (see figure). Upon excitation of the naphthyl units energy transfer to the pyrene acceptor takes place with an efficiency higher than 90 %.

[Full Paper]
Maria E. Gallina, Bilge Baytekin, Christoph Schalley, Paola Ceroni
Chem. Eur. J. 2012, 18, No. 5, 1528. Read article.

Hunter/Vögtle-type tetralactam macrocycles are equipped with metal coordination sites through Suzuki cross-coupling. The same bromo-substituted macrocycle can be used irrespective of the individual binding site, which provides versatile access to different complexes. The complexes represent multivalent hosts that are potentially useful for the formation of multiply interlocked molecules.

[Full Paper]
Egor V. Dzyuba, Bilge Baytekin, Dominik Sattler, Christoph A. Schalley
Eur. J. Org. Chem. 2012, No. 6, 1171. Read article.

A mild and efficient enzymatic method for the aza-Michael addition of mono- and bifunctional amines to acrylates was developed. The high substrate specificity showed by Rhizomucor miehei lipase as the catalyst for this reaction was a key feature for obtaining various N-substituted β-amino esters in high yield and purity.

[Full Paper]
Leandro N. Monsalve, Florencia Gillanders, Alicia Baldessari
Eur. J. Org. Chem. 2012, No. 6, 1164. Read article.

Quite materialistic: The dye CB-PSP exhibited J_sc (14.63 mA cm⁻²), V_oc (0.685 V), and FF values (0.67), which corresponded to a conversion efficiency of 6.70 %. The overall performance was reduced by about 16–18 % with addition of chenodeoxycholic acid (CDCA). This result indicated that the presence of tert-butylphenyl substituents can effectively inhibit self-aggregation, even without CDCA.

[Full Paper]
Yuan Jay Chang, Po-Ting Chou, Szu-Yu Lin, Motonori Watanabe, Zhi-Qian Liu, Ju-Ling Lin, Kew-Yu Chen, Shih-Sheng Sun, Ching-Yang Liu, Tahsin J. Chow
Chem. Asian J. 2012, 7, No. 3, 572. Read article.

Small but smart: Miniproteins are scaffolds for the development of alternative non-immunoglobin binding entities. Their structural characteristics and excellent stability support the use of this peptide format for the engineering of novel diagnostic agents. Herein we present the total chemical synthesis of the disulfide-constrained scaffold Min-23 and its functionalization for in vitro and in vivo application.

[Full Paper]
Frederic Zoller, Thimon Schwaebel, Annette Markert, Uwe Haberkorn, Walter Mier
ChemMedChem 2012, 7, No. 2, 237. Read article.

The volatiles from 35 bacteria with sequenced genomes, most of them actinomycetes, have been analysed. In the genomes of 34 species, one or several sesquiterpene cyclase homologues were encoded. The diversity of volatile terpenes emitted by these strains was correlated to the available genetic information, giving interesting new insights into bacterial terpene biosynthesis.

[Full Paper]
Christian A. Citron, Julia Gleitzmann, Gianfranco Laurenzano, Rüdiger Pukall, Jeroen S. Dickschat
ChemBioChem 2012, 13, No. 2, 202. Read article.

An appraisal of copper: This review highlights the general features of nanoparticles as catalyst with particular reference to copper and the recent developments in the copper(0) nanoparticle-catalyzed bond formations and related reactions. The mechanisms of the reactions have been outlined and discussed with respect to the active catalytic species and possible intermediates. The scope, limitations, and green aspects of the reactions are also highlighted.

[Review]
Brindaban C. Ranu, Raju Dey, Tanmay Chatterjee, Sabir Ahammed
ChemSusChem 2012, 5, No. 1, 22. Read article.

Hyping up the iodines: The discovery and development of oxidative coupling reactions catalyzed by inorganic iodine species (i.e., hypoiodite or iodite), which are generated in situ from an iodide ion and hydrogen peroxide or tert-butyl hydroperoxide as an environmentally benign oxidant is highlighted.

[Concept]
Muhammet Uyanik, Kazuaki Ishihara
ChemCatChem 2012, 4, No. 2, 177. Read article.

Going mobile: Based on screening hit 1, a novel class of polyamine compounds, as represented by compound 8, were identified as potent and selective CXCR4 antagonists. CXCR4-targeted molecules, as demonstrated by the marketed AMD3100 and 8, are able to mobilize stem cells from bone marrow effectively and are expected to have broad utility in cell therapy and regenerative medicine.

[Communication]
Chien-Huang Wu, Chun-Ping Chang, Jen-Shin Song, Jiing-Jyh Jan, Ming-Chen Chou, Szu-Huei Wu, Kai-Chia Yeh, Ying-Chieh Wong, Chieh-Jui Hsieh, Chiung-Tong Chen, Tzu-Ting Kao, Su-Ying Wu, Ching-Fang Yeh, Chen-Tso Tseng, Yu-Sheng Chao, Kak-Shan Shia
ChemMedChem 2012, 7, No. 2, 209. Read article.

The most stable IPR isomer of C₈₈ fullerene, C₈₈ (17), has been captured by chlorination as C₈₈(17)Cl₁₆ and C₈₈(17)Cl₂₂. X-ray crystallography revealed C_s-symmetrical molecular structures of both compounds, with the former being a substructure of the latter (see picture; C grey, Cl green). The chlorination patterns are characterized by the formation of isolated double C-C bonds, benzenoid rings, and, in C₈₈(17)Cl₂₂, a long chain of Cl additions in adjacent positions on the C₈₈ fullerene cage.

[Communication]
Shangfeng Yang, Tao Wei, Erhard Kemnitz, Sergey I. Troyanov
Chem. Asian J. 2012, 7, No. 2, 290. Read article.

Molecule-by-molecule arrangement of proteins, for example, in enzymatic networks of predefined composition and proximity, is a major goal that may be accomplished by the single-molecule cut-and-paste technique (SMC&P). For this purpose, co-expressed anchors and handles as protein tags should be employed. As a first step in this direction, the authors develop an SMC&P design which exploits an antibody–peptide complex as a molecular handle.

[Communication]
Mathias Strackharn, Stefan W. Stahl, Philip M. D. Severin, Thomas Nicolaus, Hermann E. Gaub
ChemPhysChem 2012, 13, No. 4, 914. Read article.

Labyrinthine: Quantitative insight into phototphysics of organic dye nanoparticles and the dewetting induced patterns formed from a push–pull triarylamine dye is obtained by using simultaneous absorption and fluorescence microscopy (see picture). The quantum yield of organic nanoparticles and the number of molecules forming the nanoparticles and patterns are deduced.

[Article]
Alexander Gaiduk, Mustafa Yorulmaz, Eléna Ishow, Michel Orrit
ChemPhysChem 2012, 13, No. 4, 946. Read article.

We prepared a V–Nb octacyano-bridged bimetal assembly, K_0.59V^II_1.59V^III_0.41[Nb^IV(CN)₈]·(SO₄)_0.50·6.9H₂O, with a high Curie temperature (T_C) of 210 K, which is the highest T_C among those of other octacyanometalate-based compounds. The high coordination number of octacyanoniobate and the strong superexchange interaction between V^II (S = 3/2) and Nb^IV (S = 1/2) through the CN groups are the reasons for such a high value.

[Short Communication]
Kenta Imoto, Miho Takemura, Hiroko Tokoro, Shin-ichi Ohkoshi
Eur. J. Inorg. Chem., December 19, 2011, DOI: 10.1002/ejic.201101219. Read article.

Maps on metals: Photoactivation localization microscopy (PALM) is applied to study suface-enhanced fluorescence (SEF) on metal nanostructures (SEF-PALM), see picture. The detection of fluorescence from individual single molecules can be used to image the point-spread function and spatial distribution of the fluorescence emitted in the vicinity of a metal surface.

[Article]
Hongzhen Lin, Silvia P. Centeno, Liang Su, Bart Kenens, Susana Rocha, Michel Sliwa, Johan Hofkens, Hiroshi Uji-i
ChemPhysChem 2012, 13, No. 4, 973. Read article.

Make the switch: Poly(N-vinylcarbazole) derivatives with pendant donor–trap–acceptor structures exhibit electrical effects. The origin of the electrical bistability, which arises from the intramolecular charge transfer, trapping, and conformational relaxation of the electrostatic energy of the Al/polymer/indium tin oxide sandwich structure (see figure), was established by spectroscopic, microscopic, and molecular computational techniques.

[Full Paper]
Bin Zhang, Gang Liu, Yu Chen, Cheng Wang, Koon-Gee Neoh, Ting Bai, En-Tang Kang
ChemPlusChem 2012, 77, No. 1, 74. Read article.

Capacity management: Gold nanoparticle (AuNP) spacers have been used to increase the capacitance of electrochemically reduced graphene (ER-GO) to values of approximately 174 F g⁻¹. By the careful and systematic optimization of nanospacers loadings, the capacitance can be dramatically enhanced because these spacers prevent the graphene sheets from stacking (see picture: yellow=AuNP, green=purple=ER-GO).

[Full Paper]
Lucia Buglione, Alessandra Bonanni, Adriano Ambrosi, Martin Pumera
ChemPlusChem 2012, 77, No. 1, 71. Read article.

A series of core/shell magnetic mesoporous silica nanoparticle (MMSN) materials were prepared. The loading and release of anticancer drugs, 9-aminoacridine (9AA) and camptothecin (CPT), as well as cytotoxic activity of drug loaded materials, is influenced by the presence of phenylethyl functionalization inside the MMSN mesopores (see figure). An externally applied magnetic field accelerates the drug release from the materials.

[Full Paper]
Nikola Ž. Knežević, Igor I. Slowing, Victor S.-Y. Lin
ChemPlusChem 2012, 77, No. 1, 48. Read article.

It's all under control: High-yield production of Fe₃O₄ (10–15 nm) was realized by using a simple solution-phase method at room temperature. The Fe₃O₄ nanocrystals were continually synthesized by controlling the pH value of the reaction solution. The SEM, TEM, and XRD studies reveal the particles to be single nanocrystals. New adsorbents of FNBC are better at removing Cd²⁺ than BC and Fe₃O₄ nanocrystals.

[Full Paper]
Xiao-Hui Guan, Bo-Tian Zheng, Min Lu, Xin Guan, Guang-Sheng Wang, Lin Guo
ChemPlusChem 2012, 77, No. 1, 56. Read article.

What shape is it? Single-molecule and ensemble time-resolved studies support the notion that the π-bond in large macromolecules, such as conjugated polymers, is remarkably persistent in space: even individual chromophores can be bent and twisted, so that caution is warranted when interpreting a wide range of polarization-based spectroscopies.

[Concept]
John M. Lupton
ChemPhysChem 2012, 13, No. 4, 901. Read article.

Nanopods functionalized with anti-HER2 antibodies (ImmunoPods, see scheme) have been synthesized by adsorbing the proteins onto gold nanoparticles and catalytically cross-linking them with a coadsorbed polymer through pendant propargyl ether groups. Upon dissolution of the gold template, the hollow polymer nanopod–protein conjugates remain. ImmunoPods are bioactive and can target cancer cells that express the HER2 antigen.

[Communication]
Ke Zhang, Dan Zheng, Liangliang Hao, Joshua I. Cutler, Evelyn Auyeung, Chad A. Mirkin
Angew. Chem. Int. Ed. 2012, 51, No. 5, 1169. Read article.

Tracing the infection: The binding of human norovirus particles to blood group antigens was investigated using NMR spectroscopy. Binding epitopes were determined at atomic resolution, information on the binding specificity was obtained, and the bioactive conformation of various sugars was revealed. This provides valuable information for the design of entry inhibitors against this important class of human pathogenic viruses.

[Communication]
Brigitte Fiege, Christoph Rademacher, Jonathan Cartmell, Pavel I. Kitov, Francisco Parra, Thomas Peters
Angew. Chem. Int. Ed. 2012, 51, No. 4, 928. Read article.

A great sense of achievement! The performance of nanoporous carbon as an electrode material was investigated and compared with that of bare glassy carbon, graphite microparticles, and carbon nanotubes. Nanoporous carbon was found to exhibit the highest heterogeneous electron transfer (HET) rate among these materials, thus sensing analytes such as NADH, DNA bases, and 2,4,6-trinitrotoluene (TNT) with an improved electrochemical response.

[Full Paper]
Hwee Ling Poh, Martin Pumera
Chem. Asian J. 2012, 7, No. 2, 412. Read article.

The reactions of the metallocene alkyne complexes [Cp₂Ti(η²-Me₃SiC₂SiMe₃)] and [Cp₂Zr(pyridine)(η²-Me₃SiC₂SiMe₃)] with the sulfurdiimide Me₃SiN=S=NSiMe₃yields metallacyclic metallocene sulfurdiimide complexes. The molecular structure and DFT analysis of the titanocene product revealed the presence of a butterfly coordination of the diimide along with two Ti–N σ-bonds.

[Full Paper]
Katharina Kaleta, Martin Ruhmann, Oliver Theilmann, Subhendu Roy, Torsten Beweries, Perdita Arndt, Alexander Villinger, Eluvathingal D. Jemmis, Axel Schulz, Uwe Rosenthal
Eur. J. Inorg. Chem. 2012, No. 4, 611. Read article.

Clusters of color: Three type II PKS gene clusters (msn, mec, and rsl) in Streptomyces bottropensis were screened. Heterologous expression of the msn and rsl clusters in Streptomyces albus led to the production of didesmethylmensacarcin (DDMM), and of rishirilide A and B, respectively. No product was isolated from mec (a putative spore pigment biosynthesis gene cluster).

[Full Paper]
Xiaohui Yan, Katharina Probst, Anton Linnenbrink, Moritz Arnold, Thomas Paululat, Axel Zeeck, Andreas Bechthold
ChemBioChem 2012, 13, No. 2, 224. Read article.

Onkel Fritz: In his lecture at the Centennial Celebration of The Fritz Haber Institute, Fritz Stern reflects on the strengths and flaws of the Institute's founder. Can we judge a person without considering the historical and cultural context? In a sense, Haber's life encompassing triumph and tragedy is a reflection of his country at that time.

[Essay]
Fritz Stern
Angew. Chem. Int. Ed. 2012, 51, No. 1, 50. Read article.

Bridging inhibition: A series of 12- to 22-membered bicyclic bridged β-lactams were synthesized with the aim of developing new inhibitors of penicillin-binding proteins and feature a planar amide function and no carboxy group (see picture; Boc=tert-butyloxycarbonyl).

[Full Paper]
Aline Sliwa, Georges Dive, Jacqueline Marchand-Brynaert
Chem. Asian J. 2012, 7, No. 2, 425. Read article.

Nanofilaments: The B4 liquid crystal phase of bent-core molecules is one of the most complex hierarchical self-assemblies in soft materials. Near the glass substrate, the formation of twisted nanofilaments is suppressed and the chiral smectic layers self-assemble into parabolic focal conic arrays. Further from the substrate, homochiral helical nanofilaments nucleate smoothly on top of the underlying layers (see picture).

[Article]
Dong Chen, Michael-Scott Heberling, Michi Nakata, Loren E. Hough, Joseph E. Maclennan, Matthew A. Glaser, Eva Korblova, David M. Walba, Junji Watanabe, Noel A. Clark
ChemPhysChem 2012, 13, No. 1, 155. Read article.

The quest for the etiology of a biomolecular structure acquires special significance when the questions asked refer to molecules, the existence of which are fundamental to life, and in particular to the origin of life. In a search for the chemistry of the emergence of life, one needs to pay strict heed to molecular guides—nucleic acids, proteins, cofactors—that all carry a message, which is our job to decipher.

[Review]
Albert Eschenmoser
Angew. Chem. Int. Ed. 2011, 50, No. 52, 12412. Read article.

Select your size: The size evolution of gold nanoparticles in a millifluidic reactor (see picture) is investigated through spatially resolved transmission electron microscopy. The experimental data supported by numerical simulations suggests that size and size distributions of the particles formed within the channels are influenced by the mixing zone as well as the residence-time distribution.

[Article]
Yuehao Li, Ashwin Sanampudi, Vanga Raji Reddy, Sanchita Biswas, Krishnaswamy Nandakumar, Dawit Yemane, Jost Goettert, Challa S. S. R. Kumar
ChemPhysChem 2012, 13, No. 1, 177. Read article.

Build a base in your base: The synergistic effect of Sr and Mg species acting as heterogeneous catalysts is observed in biodiesel production as it enhances the activity, which is attributable to new strong basic sites as evidenced by using CO₂-TPD measurements and DFT calculations.

[Full Paper]
Kajornsak Faungnawakij, Boonyawan Yoosuk, Supawadee Namuangruk, Pawnprapa Krasae, Nawin Viriya-empikul, Buppa Puttasawat
ChemCatChem 2012, 4, No. 2, 209. Read article.

An addiction to rhodium: A nicotinamide-independent regeneration approach for enoate reductases is proposed. The transition metal complex [Cp*Rh(bpy)(H₂O)]²⁺ can replace both the nicotinamide cofactor and a corresponding enzymatic regeneration system, which results in a simplified reaction system. This system is characterized and applied to the chemoenzymatic reduction of various conjugated C=C double bonds.

[Communication]
Julie Bernard, Esta van Heerden, Isabel W. C. E. Arends, Diederik J. Opperman, Frank Hollmann
ChemCatChem 2012, 4, No. 2, 196. Read article.

Step by step: Due to its extraordinary potential, N-H bond activation and C-N coupling processes have formed the focus of broad research activities. This Minireview will describe examples of these processes mediated by gaseous “bare” or ligated ions and provide detailed insights into the underlying mechanisms and elementary steps.

[Minireview]
Robert Kretschmer, Maria Schlangen, Helmut Schwarz
Chem. Eur. J. 2012, 18, No. 1, 40. Read article.

A galacturonic acid based macrocycle containing an amide group and a triazole ring has been synthesized by a procedure involving a copper-catalysed intramolecular cycloaddition reaction as the key step. The results of a preliminary study of the complexation properties of this macrocycle towards Cu^II cations are described.

[Full Paper]
Anas Allam, Laurent Dupont, Jean-Bernard Behr, Richard Plantier-Royon
Eur. J. Org. Chem. 2012, No. 4, 817. Read article.

A life RAFT! A series of well-defined polymer–drug conjugates have been prepared to increase the bioavailability of the known cytotoxic drug 7-ethyl-10-hydroxycamptothecin (SN-38). Reversible addition–fragmentation chain transfer (RAFT) polymerisation was used to covalently and site-specifically append an N-(2-hydroxypropyl)methacrylamide (HPMA) polymer to SN-38. The poly-HPMA–SN-38 conjugates displayed excellent aqueous solubility, cytotoxic activity, and specificity for cancer cells.

[Full Paper]
Charlotte C. Williams, San H. Thang, Tina Hantke, Uwe Vogel, Peter H. Seeberger, John Tsanaktsidis, Bernd Lepenies
ChemMedChem 2012, 7, No. 2, 281. Read article.

The importance of being SBA-16: Co/SBA-16 catalysts are prepared by means of the incipient wetness impregnation method for Fischer–Tropsch synthesis (FTS). Most of the Co₃O₄ nanoparticles are introduced into the SBA-16 cages. High FTS activity and stability are observed on the SBA-16-supported catalyst. SBA-16 support can efficiently prevent the aggregation and sintering of cobalt nanoparticles.

[Full Paper]
Yanxi Zhao, Yuhua Zhang, Jian Chen, Jinlin Li, Kongyong Liew, Mohd Ridzuan Bin Nordin
ChemCatChem 2012, 4, No. 2, 265. Read article.

Photopolymerized micelles obtained from the self-assembly of diacetylene-containing amphiphiles have been developed for biomedical applications in the fields of imaging and drug delivery (see figure).

[Concept]
Edmond Gravel, Julien Ogier, Thomas Arnauld, Nicolas Mackiewicz, Frédéric Ducongé, Eric Doris
Chem. Eur. J. 2012, 18, No. 2, 400. Read article.

The sincerest form of flattery! A novel, symmetric lipid A mimetic (D1) formed by two glucose units linked through a 6-6' succinic diamide linker is active in modulating the activity of human TLR4. D1 inhibits endotoxin-stimulated TLR4 activation by inhibiting interaction of endotoxin with both receptors CD14 and MD-2 (associated to TLR4). D1 also has weak TLR4 agonist activity that makes it a promising lead compound for development as a vaccine adjuvant.

[Communication]
Matteo Piazza, Valentina Calabrese, Gaetana Damore, Roberto Cighetti, Theresa Gioannini, Jerrold Weiss, Francesco Peri
ChemMedChem 2012, 7, No. 2, 213. Read article.

The substitution of N₂Py₂ ligands with carboxylic functionalities affects the catalytic properties of a series of iron complexes. Selective epoxidation catalysis with H₂O₂ was obtained only when one carboxylic group was present in the ligand. The moderate (up to 40 %) enantioselectivity of the reaction with electron-rich/poor alkenes was also tuned by the presence of exogenous acids.

[Full Paper]
Frédéric Oddon, Elodie Girgenti, Colette Lebrun, Caroline Marchi-Delapierre, Jacques Pécaut, Stéphane Ménage
Eur. J. Inorg. Chem. 2012, No. 1, 85. Read article.

Finest selection: Side-chain selective, end-group selective, diastereoselective, and RNA- vs. DNA-selective interactions have been revealed between multiturn helical aromatic amide foldamers having cationic side chains and G-quadruplex aptamers.

[Communication]
Laurence Delaurière, Zeyuan Dong, Katta Laxmi-Reddy, Frédéric Godde, Jean-Jacques Toulmé, Ivan Huc
Angew. Chem. Int. Ed. 2012, 51, No. 2, 473. Read article.

Perylene diimides make excellent building blocks for the formation of [2]-rotaxanes. The rich electrochemistry of the perylene-based recognition site facilitates a pathway to different oxidation states and properties and allows a mechanism for electrochemically driven de-treading of the interlocked species (see figure).

[Full Paper]
Benjamin J. Slater, E. Stephen Davies, Stephen P. Argent, Harriott Nowell, William Lewis, Alexander J. Blake, Neil R. Champness
Chem. Eur. J. 2011, 17, No. 52, 14746. Read article.

Immobilized for crimes of pyrolysis: Quaternary ammonium- and amino-functionalized silica catalysts promote the cycloaddition of sulfur dioxide to epoxides to produce cyclic sulfites in high yields (79–96 %) that are comparable to those with the homogeneous catalysts. Separation of the functionalized silica catalyst from the product solution by filtration avoids pyrolysis of the cyclic sulfites during purification by distillation.

[Full Paper]
Yasumasa Takenaka, Takahiro Kiyosu, Goro Mori, Jun-Chul Choi, Norihisa Fukaya, Toshiyasu Sakakura, Hiroyuki Yasuda
ChemSusChem 2012, 5, No. 1, 194. Read article.

Nanotubes say goodbye to H₂S: Nitrogen-doped carbon nanotubes (N-CNTs) are synthesized by using a chemical vapor deposition method under a mixture of C₂H₆/NH₃/Ar with Fe/Al₂O₃ as a growth catalyst. N-CNTs can be used as a metal-free catalyst for the selective oxidation of H₂S into elemental sulfur. The desulfurization activity can be further improved by supporting the N-CNT on a macroscopic host structure such as SiC foam.

[Full Paper]
Kambiz Chizari, Adrien Deneuve, Ovidiu Ersen, Ileana Florea, Yu Liu, David Edouard, Izabela Janowska, Dominique Begin, Cuong Pham-Huu
ChemSusChem 2012, 5, No. 1, 102. Read article.

Invasion of the strand snatchers: We have synthesized chiral γ-peptide nucleic acids containing miniPEG side chains. Using gel shift assays we show that this particular type of nucleic acid mimic can invade any sequence of double helical B-form DNA (see figure), and this recognition occurs through direct Watson–Crick base pairing.

[Communication]
Raman Bahal, Bichismita Sahu, Srinivas Rapireddy, Chong-Min Lee, Danith H. Ly
ChemBioChem 2012, 13, No. 1, 56. Read article.

We have studied the oxidation of electron deficient [Au(C₆F₅)(PPh₃)] in the presence of PhI(Cl)₂, PhI(OAc)₂, and Selectfluor. cis-[Au(C₆F₅)₂Cl(PPh₃)] was obtained in the reaction with PhI(OAc)₂, which points towards the oxidation of the starting complex to gold(III) followed by gold(I)/gold(III) transmetalation or a ligand exchange pathway.

[Short Communication]
Manuel Hofer, Cristina Nevado
Eur. J. Inorg. Chem. 2012, No. 9, 1338. Read article.

Turning up the stereo: An efficient three-step strategy for synthesizing chiral biobased dideoxy-diamino isoidide and dideoxy-diamino isosorbide in high yield with absolute stereo control is described. These highly interesting chiral building blocks are presently the subject of several investigations due to their application in high-performance biobased polymers such as polyamides and polyurethanes.

[Full Paper]
Shanmugam Thiyagarajan, Linda Gootjes, Willem Vogelzang, Jacco van Haveren, Martin Lutz, Daan S. van Es
ChemSusChem 2011, 4, No. 12, 1823. Read article.

Topoisomerase inhibition: Nogalamycin is an anthracycline antibiotic with an unusual structure and significant cytotoxicity. In this work the nogalamycin biosynthetic gene cluster has been expressed in a heterologous host, late-stage tailoring steps of nogalamycin biosynthesis have been investigated and new compounds have been isolated.

[Full Paper]
Vilja Siitonen, Magnus Claesson, Pekka Patrikainen, Maria Aromaa, Pekka Mäntsälä, Gunter Schneider, Mikko Metsä-Ketelä
ChemBioChem 2012, 13, No. 1, 120. Read article.

Bridge not required: The disulfide bridge in the antibacterial peptide leucocin A was replaced with two Ser or two Leu residues. The double leucine mutant was found to be active, and elucidation of its 3D structure showed that the two leucines interact to hold the N- and C-terminal domains together.

[Communication]
Clarissa S. Sit, Christopher T. Lohans, Marco J. van Belkum, Chantel D. Campbell, Mark Miskolzie, John C. Vederas
ChemBioChem 2012, 13, No. 1, 35. Read article.

The best of two worlds! Both heterogeneous and homogeneous catalyses by gold have well-known advantages. The heterogenization of gold complexes through anchoring on porous solid materials is a way to have “the best of two worlds.” This work reviews the attempts made so far on this important topic. The results obtained show that these hybrid materials can have improved activity and selectivity and are potential choice candidates for several catalytic processes.

[Review]
Miguel Peixoto de Almeida, Sónia A. C. Carabineiro
ChemCatChem 2012, 4, No. 1, 18. Read article.

A variety of new titanium imido complexes with different pendant groups have been synthesized from Ti(NMe₂)₄. The nature of the donor atom in the pendant group and the length of the side arm influence the coordination to the metal center. These compounds were evaluated as ethylene polymerization precatalysts.

[Full Paper]
Viet-Hoang Nguyen, Laure Vendier, Michel Etienne, Emmanuelle Despagnet-Ayoub, Pierre-Alain R. Breuil, Lionel Magna, David Proriol, Hélène Olivier-Bourbigou, Christian Lorber
Eur. J. Inorg. Chem. 2012, No. 1, 97. Read article.

The capacity of oxorhenium(V) anions with redox-active catecholate ligands to homolyze O₂ and generate dioxorhenium(VII) products is utilized for oxidase-type alcohol oxidations. Formation of the active oxidant requires both the dioxo and monooxo species. The scope and limitations of this redox-active ligand-mediated catalysis are discussed.

[Full Paper]
Cameron A. Lippert, Korbinian Riener, Jake D. Soper
Eur. J. Inorg. Chem. 2012, No. 3, 554. Read article.