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News

Editorials: New Developments

Theresa Kueckmann
All in the Family
Chem. Asian J. 2013 8, 4.

Richard Threlfall
But First, This
Asian J. Org. Chem. 2013 2, 4.

 

Research of the DayEditors' Choice: Spotlights

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Light-Induced Click Reactions

Shine a light: Owing to their ease of implementation and the availability of inexpensive light sources, light-induced click reactions (see picture) have become a powerful methodology for the synthesis of materials and the modification of biomaterials. Fundamental aspects of these reactions and their application in surface and materials science, as well as their potential in the study of biomolecular systems are highlighted.

[Minireview]
Mehmet Atilla Tasdelen, Yusuf Yagci
Angew. Chem. Int. Ed. 2013, 52, No. 23, 5930. Read article.

Molecular Understanding of Reactivity and Selectivity for Methanol Oxidation at the Au/TiO₂ Interface

Gold catalysis: Experimental and theoretical data demonstrated consistently that the interfacial sites on a Au/TiO₂ catalyst show both high reactivity and selectivity for low-temperature methanol oxidation with O₂ to give formaldehyde. The microscopic mechanism of this complex reaction has been unraveled in full molecular detail (see picture, gold cluster on TiO₂ surface).

[Communication]
Matteo Farnesi Camellone, Jianli Zhao, Lanying Jin, Yuemin Wang, Martin Muhler, Dominik Marx
Angew. Chem. Int. Ed. 2013, 52, No. 22, 5780. Read article.

Palladium-catalyzed Asymmetric 1,4-Addition of Diarylphosphines to α,β-Unsaturated Carboxylic Esters

Pincer my ride: A highly stereoselective asymmetric 1,4-addition of diarylphosphines to α,β-unsaturated carboxylic esters catalyzed by a PCP pincer–Pd complex has been developed for the synthesis of chiral phosphines in up to 99 % ee.

[Communication]
Dan Du, Zi-Qi Lin, Jun-Zhu Lu, Chun Li, Wei-Liang Duan
Asian J. Org. Chem. 2013, 2, No. 5, 392. Read article.

Biocatalytic and Structural Properties of a Highly Engineered Halohydrin Dehalogenase

Synergistic mutations: A halohydrin dehalogenase with 37 mutations and improved catalytic properties for statin side chain synthesis has been biochemically characterized. Crystal structures with different ligands in the active site give insight into the way in which individual mutations contribute to enhanced stability and faster cyanolysis of epoxides and illustrate the importance of synergistic mutations in directed evolution.

[Full Paper]
Marcus Schallmey, Robert J. Floor, Bernhard Hauer, Michael Breuer, Peter A. Jekel, Hein J. Wijma, Bauke W. Dijkstra, Dick B. Janssen
ChemBioChem 2013, 14, No. 7, 870. Read article.

Reversible Dimerization of Mononuclear Models of [Fe]-Hydrogenase

Enzyme models on the catwalk! A series of new model complexes of the active site of [Fe]-hydrogenase have been synthesized and characterized. These complexes are monomeric in solution, but dimeric in the solid state.

[Communication]
Bowen Hu, Dafa Chen, Xile Hu
Chem. Eur. J. 2013, 19, No. 20, 6221. Read article.

Negative Thermal Expansion in LnCo(CN)₆ (Ln=La, Pr, Sm, Ho, Lu, Y): Mechanisms and Compositional Trends

RUM with a twist: The magnitude of negative thermal expansion (NTE) in the LnCo(CN)₆ coordination frameworks increases with Ln ion radius r_Ln. The framework structure contains an unusual locally unstable trigonal prismatic LnN₆ unit that participates in an NTE-contributing vibrational mode by twisting about its axis at low energies. This contrasts with the rigid unit modes (RUMs) prevalent in other systems.

[Communication]
Samuel G. Duyker, Vanessa K. Peterson, Gordon J. Kearley, Anibal J. Ramirez-Cuesta, Cameron J. Kepert
Angew. Chem. Int. Ed. 2013, 52, No. 20, 5266. Read article.

Carboxylate-Assisted Formation of Alkylcarbonate Species from CO₂ and Tetramethylammonium Salts with a β-Amino Acid Anion

Catch me if you can: Tetramethylammonium salts bearing a β-amino acid anion (TMAAs) are synthesized through Michael addition reactions of amines with methyl acrylate, subsequent hydrolysis, and neutralization with aqueous tetramethylammonium hydroxide. These TMAAs interact with CO₂ in a 1:1 mode in ethylene glycol, which forms hydroxyethylcarbonate species. The driving force for the 1:1 bonding appears to be the intramolecular hydrogen bonding network exerted through the carboxylate group.

[Full Paper]
Sung Yun Hong, Youngeun Cheon, Seung Hoon Shin, Hyunjoo Lee, Minserk Cheong, Hoon Sik Kim
ChemSusChem 2013, 6, No. 5, 890. Read article.

A Gel-Based Trihybrid System Containing Nanofibers, Nanosheets, and Nanoparticles: Modulation of the Rheological Property and Catalysis

Wonderful gels: A trihybrid gel was prepared by incorporating graphene oxide and in situ synthesized gold nanoparticles (AuNPs) into an amino-acid-based native gel matrix (see pict). The morphology of this system indicates the presence of three distinctly different nanostructures: nanofibers, nanosheets, and nanoparticles. The catalytic efficiency of this trihybrid system is enhanced relative to that of AuNPs in a dihybrid system.

[Communication]
Jayanta Nanda, Abhijit Biswas, Bimalendu Adhikari, Arindam Banerjee
Angew. Chem. Int. Ed. 2013, 52, No. 19, 5041. Read article.

Design and Synthesis of Camphor-derived Chiral [1,2,4]Triazolo[4,3-a]tetrahydroquinoline N-Heterocyclic Carbene Precursors by Pd-Catalyzed Coupling Reactions of Aryl Hydrazides with a Pyridyl Triflate Derivative

Which came first? A Pd-catalyzed coupling reaction of N-tert-butyloxycarbonyl (Boc) aryl hydrazines with a camphor-derived pyridyl triflate derivative has been developed by using bulky electron-rich phosphine or N-heterocyclic carbene as the ligand. With this C-N coupling reaction as the key step, camphor-derived chiral [1,2,4]triazolo[4,3-a]tetrahydroquinoline N-heterocyclic carbene precursors were synthesized. Tf=trifluoromethanesulfonyl.

[Communication]
Liang-An Chen, Chuan-Fei Wang, Ming-Gui Lin, Jin-Long Zhang, Pei-Qiang Huang, Ai-E Wang
Asian J. Org. Chem. 2013, 2, No. 4, 294. Read article.

Molecular Tweezers with Freely Rotating Linker and Porphyrin Moieties

Usually molecular tweezers possess a high degree of preorganisation, but we have found that the introduction of several rotational degrees of freedom has little impact on association constant strength.

[Full Paper]
Rhys B. Murphy, Duc-Truc Pham, Stephen F. Lincoln, Martin R. Johnston
Eur. J. Org. Chem. 2013, No. 15, 2985. Read article.

Porphyrin Analogues That Consist of Indole, Benzofuran, and Benzothiophene Subunits

Switching to analogue: We have designed and synthesized porphyrin analogues that consist of benzofuran, benzothiophene, and indole subunits. These cyclic benzoheterole tetramers were more stable in air and have more planar structures than the corresponding cyclic tetraindole. Photophysical and theoretical investigations revealed effective π-conjugation over the macrocyclic systems.

[Full Paper]
Shoichi Nakamura, Takeshi Kondo, Satoru Hiroto, Hiroshi Shinokubo
Asian J. Org. Chem. 2013, 2, No. 4, 312. Read article.

Metal-Free Coupling of 3-Alkenyl Oxoindoles by Nucleophilic Vinylic Substitution of Nitroolefins

The fuge-es: A metal-free coupling reaction for the synthesis of oxindoles by nucleophilic vinylic substitution (S_NV) of nitroolefins is described. By using the nitro group as a nucleofuge, the reaction proceeds through a Michael addition/1,2-cis-elimination process. Alcohols, phenols, amines, thiols, and even a β-ketoester worked as nucleophiles to form C-O, C-N, C-S, and C-C bonds and afford the corresponding oxindoles.

[Communication]
Hongrui Zhang, Yun Liu, Rui Chen, Jijun Xue, Ying Li, Yu Tang
Asian J. Org. Chem. 2013, 2, No. 4, 307. Read article.

Direct Water Splitting into Hydrogen and Oxygen under Visible Light by using Modified TaON Photocatalysts with d⁰ Electronic Configuration

Parting water! Direct splitting of pure water into H₂ and O₂ under visible light (λ>400 nm) was achieved by using a modified TaON photocatalyst with d⁰ electronic configuration. Modification of a less-defective TaON (ZrO₂/TaON) with core/shell-structured RuO_x/Cr₂O₃ nanoparticles and colloidal IrO₂ was found to be indispensable to achieving the reaction (see figure).

[Communication]
Kazuhiko Maeda, Daling Lu, Kazunari Domen
Chem. Eur. J. 2013, 19, No. 16, 4986. Read article.

Highly Efficient F�rster Resonance Energy Transfer in a Fast, Serum-Compatible Immunoassay

Highly efficient FRET leads to important enhancements for homogeneous immunoassays. By using the novel phosphorescent dye EuLH and BHQ-10 as a donor–acceptor pair, the FRET efficiency increases to >99.5 %, leading to significantly improved signal-to-background ratio, precision and linear range. The phosphorescence detection enabled full compatibility to serum samples for this fast-responding immunoassay.

[Communication]
Thomas Kreisig, Ralf Hoffmann, Thole Zuchner
ChemBioChem 2013, 14, No. 6, 699. Read article.

The Minimum Activation Peptide from ilvH Can Activate the Catalytic Subunit of AHAS from Different Species

Small but active: The minimum-length activation peptide Δ_N14–Δ_C89 from ilvH can activate the catalytic subunit of acetohydroxyacid synthases (AHASs) from E. coli, A. thaliana , S. cerevisiae, and N. plumbaginifolia. The high sequence similarity between Δ_N14–Δ_C89 and the regulatory subunits (RSUs) of AHAS across various species hints that this peptide represents the minimum activation motif in the RSU.

[Full Paper]
Yuefang Zhao, Congwei Niu, Xin Wen, Zhen Xi
ChemBioChem 2013, 14, No. 6, 746. Read article.

Silicateins—A Novel Paradigm in Bioinorganic Chemistry: Enzymatic Synthesis of Inorganic Polymeric Silica

From gene to enzyme to inorganic polymer: The elucidation of bioinorganic reactions that catalyze the formation of an inorganic polymer from inorganic monomeric substrates, here the synthesis of the biosilica matrix of the sponge skeleton by the enzyme silicatein, resulted in a paradigm shift. This progress opened new horizons in the application field of bionanotechnology (opto-electronics) and even in biomedicine (bone/tissue engineering).

[Review]
Werner E. G. Müller, Heinz C. Schröder, Zaklina Burghard, Dario Pisignano, Xiaohong Wang
Chem. Eur. J. 2013, 19, No. 19, 5790. Read article.

Aromatic Claisen Rearrangements of O-Prenylated Tyrosine and Model Prenyl Aryl Ethers: Computational Study of the Role of Water on Acceleration of Claisen Rearrangements

LynF, an enzyme from the TruF family, O-prenylates tyrosines in proteins, with subsequent Claisen rearrangements giving C-prenylated tyrosine products. These reactions in tyrosines and model phenolic systems have been explored with DFT and SCS-MP2 calculations. Solvent effects from water were considered using implicit and explicit models.

[Full Paper]
Sílvia Osuna, Seonah Kim, Guillaume Bollot, Kendall N. Houk
Eur. J. Org. Chem. 2013, No. 14, 2823. Read article.

Mo₃Q₇ (Q = S, Se) Clusters Containing Dithiolate/Diselenolate Ligands: Synthesis, Structures, and Their Use as Precursors of Magnetic Single-Component Molecular Conductors

Scrambling between the chalcogen atoms of the Mo₃Se₇ cluster unit and the sulfur atoms of dithiolene ligands can be avoided by appropriate selection of the reaction conditions (solvent, temperature) to afford well-defined dithiolene Mo₃Se₇ anions that could serve as precursors of magnetic molecular conductors.

[Full Paper]
Artem L. Gushchin, Rosa Llusar, Cristian Vicent, Pavel A. Abramov, Carlos J. Gómez-Garcia
Eur. J. Inorg. Chem. 2013, No. 14, 2615. Read article.

Optical/Magnetic Multimodal Bioprobes Based on Lanthanide-Doped Inorganic Nanocrystals

Must-see attractions: Lanthanide-doped inorganic nanoparticles have great potential as optical/magnetic multimodal bioprobes. Recent advances, from their design strategies to biomedical applications, are presented, with an emphasis on multimodal detection, in vitro and in vivo imaging, and medical diagnostics and therapeutics.

[Concept]
Datao Tu, Yongsheng Liu, Haomiao Zhu, Xueyuan Chen
Chem. Eur. J. 2013, 19, No. 18, 5516. Read article.

Self-Assembly of Arylboronate Esters with Pyridyl Side Chains

Dioxaborinanes and benzodioxaboroles containing pyridyl side chains were synthesized. The boronate esters can aggregate through dative boron–nitrogen bonds to give trimeric and tetrameric macrocycles as well as polymeric structures. The assembly process was found to depend to a large extent on electronic effects.

[Full Paper]
Erin Sheepwash, Kai Zhou, Rosario Scopelliti, Kay Severin
Eur. J. Inorg. Chem. 2013, No. 14, 2558. Read article.

Highly Fluorescent, π-Extended Indenopyrido[2,1-a]isoindolone Derivatives Prepared by a Palladium-Catalysed Cascade Reaction

Highly fluorescent pentacyclic compounds have been synthesized by a palladium-catalysed cascade reaction. The fluorescence quantum yields and lifetimes of the luminescent excited states of these compounds are strongly influenced by the electronic nature and position of the substituents. These effects have been rationalized on the basis of photophysical, electrochemical and computational studies.

[Full Paper]
Zein el abidine Chamas, Enrico Marchi, Alberto Modelli, Yves Fort, Paola Ceroni, Victor Mamane
Eur. J. Org. Chem. 2013, No. 12, 2316. Read article.

Capping α-Cyclodextrin with Cyclotriveratrylene by Triple Disulfide-Bridge Formation

Hemicryptophanes based on permethylated -cyclodextrin (PM -CDX) were obtained as a diastereomeric mixture in a 5:3 ratio and 11 % yield by reacting a C₃-symmetric trithiol PM -CDX derivative with the known chiral cyclotrithiophenolene under conditions (I₂/KI, Et₃N) that promote disulfide-bridge formation.

[Full Paper]
Frédérique Brégier, Juliette Lavalle, Jean-Claude Chambron
Eur. J. Org. Chem. 2013, No. 13, 2666. Read article.

Unbiased Photoelectrochemical Water Splitting in Z-Scheme Device Using W/Mo-Doped BiVO₄ and Zn_xCd_1−xSe

Water splitting to generate H₂ and O₂ using only photon energy (with no added electrical energy) is demonstrated with dual n-type-semiconductor (or Z-scheme) systems. The authors investigate two different Z-scheme systems; one is comprised of two cells with the same metal-oxide semiconductor, and the other is comprised of the metal oxide and a chalcogenide semiconductor.

[Article]
Hyun S. Park, Heung Chan Lee, Kevin C. Leonard, Guanjie Liu, Allen J. Bard
ChemPhysChem, March 12, 2013, DOI: 10.1002/cphc.201201044. Read article.

Structure, Optical, and Magnetic Properties of (PPN⁺)₂(C₇₀²⁻)·2 C₆H₄Cl₂, which Contains Dianionic Polymeric (C₇₀²⁻)_n Chains

The cocoon chain: A new salt, (PPN⁺)₂(C₇₀²⁻)·2 C₆H₄Cl₂ (1), which contains polymeric zigzag (C₇₀²⁻)_n chains, was obtained; the fullerene C₇₀²⁻ units are bonded in the polymer through single C-C bonds of length 1.581(5)–1.586(6) Å. Salt 1 shows broad absorption in the NIR region, with maxima at 890, 1200, and 1550 nm. The (C₇₀²⁻)_n polymer is diamagnetic and EPR silent, with a negative molar magnetic susceptibility of −3.82×10⁻⁴ emu mol⁻¹.

[Full Paper]
Dmitri V. Konarev, Sergey I. Troyanov, Salavat S. Khasanov, Akihiro Otsuka, Hideki Yamochi, Gunzi Saito, Rimma N. Lyubovskaya
Chem. Asian J. 2013, 8, No. 6, 1139. Read article.

Synthesis and Structure–Activity Relationship Studies of Derivatives of the Dual Aromatase–Sulfatase Inhibitor 4-{[(4-Cyanophenyl)(4H-1,2,4-triazol-4-yl)amino]methyl}phenyl sulfamate

A new head! Derivatives of dual steroid sulfatase and aromatase inhibitor 4-{[(4-cyanophenyl)(4H-1,2,4-triazol-4-yl)amino]methyl}phenyl sulfamate were prepared, leading to a range of SAR information and a highly potent (in vitro) imidazole congener which can be further developed for potential use in treating hormone-dependent diseases.

[Full Paper]
L. W. Lawrence Woo, Paul M. Wood, Christian Bubert, Mark P. Thomas, Atul Purohit, Barry V. L. Potter
ChemMedChem 2013, 8, No. 5, 779. Read article.

Emulsion-Templated Macroporous Carbons Synthesized By Hydrothermal Carbonization and their Application for the Enzymatic Oxidation of Glucose

Baking biomass! Highly porous carbonaceous monoliths are designed and synthesized from a sustainable saccharide derivative. With furfural as the carbon precursor and using a carbonization method that is based on using a concentrated direct emulsion as a soft-template, a graphitized carbon framework was produced. As a proof of principle, these new carbons are successfully used as electrodes for enzymatic biofuel cells.

[Full Paper]
Nicolas Brun, Lise Edembe, Sébastien Gounel, Nicolas Mano, Magdalena M. Titirici
ChemSusChem 2013, 6, No. 4, 701. Read article.

Pd-modified Au on Carbon as an Effective and Durable Catalyst for the Direct Oxidation of HMF to 2,5-Furandicarboxylic Acid

Mixed noblility: We show that the modification of a gold/carbon catalyst with platinum or palladium produces stable and recyclable catalysts for the selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA): the support and nanoparticle chemistry directly mediate the selective oxidation of terminal hydroxyl groups in bio-derived HMF. This finding is a significant advance over current conversion technology because of the technological importance of FDCA.

[Communication]
Alberto Villa, Marco Schiavoni, Sebastiano Campisi, Gabriel M. Veith, Laura Prati
ChemSusChem 2013, 6, No. 4, 609. Read article.

Selective Electrochemical Recognition of the α-Naphthol Isomer and In Situ Immobilization of Naphthoquinones for Tunable Electrocatalysis

Fits like a glove: Separationless and selective electrochemical oxidation of the α-naphthol (α-NAP) isomer yields naphthoquinone species on the surface of multiwalled carbon nanotubes, which can further catalyze the electro-oxidation of NADH and hydrazine at different potentials. The β-NAP isomer failed to show any such electro-oxidation.

[Communication]
Puchakayala Swetha, Annamalai Senthil Kumar
Chem. Asian J. 2013, 8, No. 5, 896. Read article.

Photocatalytic CO₂ Reduction using Non-Titanium Metal Oxides and Sulfides

No need for TiO₂: By far the most widely used photocatalyst both for the degradation of pollutants and in the field of renewable energies for producing solar fuels is TiO₂. However, TiO₂ has limitations when applied to photocatalytic CO₂ reduction, particularly under visible light irradiation, and therefore, development of alternative materials seems appropriate. Here, we focus on alternatives with photocatalytic activity and describe the state of the art.

[Review]
Sergio Navalón, Amarajothi Dhakshinamoorthy, Mercedes Alvaro, Hermenegildo Garcia
ChemSusChem 2013, 6, No. 4, 562. Read article.

Cooperative Behaviour of Pt Microelectrodes during CO Bulk Electrooxidation

Cooperative behaviour of an array of microelectrodes: The interplay of bistable reaction kinetics with global coupling results in a spontaneous sequential activation of electrodes when the applied current is increased.

[Communication]
D. Alfonso Crespo-Yapur, Antoine Bonnefont, Rolf Schuster, Katharina Krischer, Elena R. Savinova
ChemPhysChem 2013, 14, No. 6, 1117. Read article.

Luminescent Conjugated Oligothiophenes for Sensitive Fluorescent Assignment of Protein Inclusion Bodies

Bright bodies! The unique optical properties of luminescent conjugated oligothiophenes have been utilized in fluorescent probes for rapid and accurate detection and spectral assignment of protein inclusion bodies in sporadic inclusion-body myositis.

[Full Paper]
Therése Klingstedt, Cristiane Blechschmidt, Anna Nogalska, Stefan Prokop, Bo Häggqvist, Olof Danielsson, W. King Engel, Valerie Askanas, Frank L. Heppner, K. Peter R. Nilsson
ChemBioChem 2013, 14, No. 5, 607. Read article.

A Conductive Polypyrrole-Coated, Sulfur–Carbon Nanotube Composite for Use in Lithium–Sulfur Batteries

Battery powered: The title composite (see figure) was prepared and investigated as a cathode material for Li–S batteries. The conducting polypyrrole coating serves to confine polysulfides and prevent them from dissolving into the electrolyte. The capacity of S-CNT-PPy is about 600 mAh g⁻¹ after 40 cycles, which is much higher than for the S-CNT composite (430 mAh g⁻¹)

[Full Paper]
Jiazhao Wang, Lin Lu, Dongqi Shi, Richard Tandiono, Zhaoxiang Wang, Konstantin Konstantinov, Huakun Liu
ChemPlusChem 2013, 78, No. 4, 318. Read article.

Light Energy Collection in a Porphyrin–Imide–Corrole Ensemble

Let's get (co)rolling: Light absorption in an assembly consisting of a free-base corrole and a Zn porphyrin connected by 1,8 naphthaleneimide results in a sequence of electronic energy transfer processes, ultimately concentrating the energy at the corrole extremity with a yield higher than 90 %.

[Full Paper]
Adina I. Ciuciu, Lucia Flamigni, Roman Voloshchuk, Daniel T. Gryko
Chem. Asian J. 2013, 8, No. 5, 1004. Read article.

Chemical Regulation of Carbon Quantum Dots from Synthesis to Photocatalytic Activity

Outer beauty: The sizes and surface states of carbon quantum dots (CQDs) were tuned by chemical methods. The photoluminescent behavior is related to both the sizes and surface states of the CQDs, but the photocatalytic activities are determined by the surface states alone. The separation and recombination of electron–hole pairs are determined by the degree of upward band bending induced by oxygen-containing groups on the surface of CQDs.

[Full Paper]
Shengliang Hu, Ruixue Tian, Lingling Wu, Qing Zhao, Jinlong Yang, Jun Liu, Shirui Cao
Chem. Asian J. 2013, 8, No. 5, 1035. Read article.

Understanding Photophysical Effects of Cucurbituril Encapsulation: A Model Study with Acridine Orange in the Gas Phase

CB, or not CB: How the confined, hydrophobic environment offered by the interior of cucurbiturils (CBs) in some ways resembles the gas phase, and in other ways does not.

[Article]
Martin F. Czar, Rebecca A. Jockusch
ChemPhysChem 2013, 14, No. 6, 1138. Read article.

Electron Transfer between Hydrogen-Bonded Pyridylphenols and a Photoexcited Rhenium(I) Complex

A concerted effort: Two pyridylphenols with intramolecular hydrogen bonds react with a metal complex through concerted proton transfer (PT)–electron transfer (ET). Upon photoexcitation of the complex, ET occurs from the phenol to the metal, and the phenolic proton is transferred to the pyridine moiety (see picture; MLCT=metal-to-ligand charge transfer).

[Article]
William Herzog, Catherine Bronner, Susanne Löffler, Bice He, Daniel Kratzert, Dietmar Stalke, Andreas Hauser, Oliver S. Wenger
ChemPhysChem 2013, 14, No. 6, 1168. Read article.

The Discovery of Novel Human Androgen Receptor Antagonist Chemotypes Using a Combined Pharmacophore Screening Procedure

A new tack altogether: Using structural information for human androgen receptor (hAR) antagonists in an agonistic conformation, a pharmacophore query was constructed for the agonistic and antagonistic conformations. A homology model of hAR in an antagonistic conformation was created. These models were combined for virtual screening to identify pure antagonists, which were experimentally confirmed.

[Full Paper]
Arnout Voet, Christine Helsen, Kam Y. J. Zhang, Frank Claessens
ChemMedChem 2013, 8, No. 4, 644. Read article.

A Concise Synthesis of Pyrazole Analogues of Combretastatin A1 as Potent Anti-Tubulin Agents

(Combreta)statin' the facts: A series of 3,4-diaryl pyrazole analogues of combretastatin A1 were concisely synthesized, one of which proved to be a cytotoxic anti-tubulin agent with low nanomolar potency. It retains the ability to form ortho-quinone species, which are assumed to be directly cytotoxic in tumor cells, while the pyrazole ring shows high metabolic stability, suggesting that this compound might give better pharmacokinetic profiles than the parent compound, with similar pharmacodynamic properties and clinical potential.

[Full Paper]
Roberta Zaninetti, Salvatore V. Cortese, Silvio Aprile, Alberto Massarotti, Pier Luigi Canonico, Giovanni Sorba, Giorgio Grosa, Armando A. Genazzani, Tracey Pirali
ChemMedChem 2013, 8, No. 4, 633. Read article.

Enantioselective Ir-Catalyzed Hydrogenation of Minimally Functionalized Olefins Using Pyranoside Phosphinite-Oxazoline Ligands

Pyranoside phosphinite-oxazoline ligands were successfully applied in the asymmetric Ir-catalyzed hydrogenation of a wide range of minimally functionalized olefins (ee up to 99 %). The introduction of a bulky ortho-tolyl phosphinite moiety was crucial to achieving the highest enantioselectivities with some of the most challenging substrate types.

[Full Paper]
Javier Mazuela, Oscar Pàmies, Montserrat Diéguez
Eur. J. Inorg. Chem. 2013, No. 12, 2139. Read article.

Metal-Conjugated Affinity Labels: A New Concept to Create Enantioselective Artificial Metalloenzymes

How to train a protein: Metal-conjugated affinity labels were used to selectively position catalytically active metal centers in the binding pocket of proteases. The resulting artificial metalloenzymes achieve up to 82 % e.r. in the hydrogenation of ketones. The modular setup enables a rapid generation of artificial metalloenzyme libraries, which can be adapted to a broad range of catalytic conditions.

[Communication]
Thomas Reiner, Dominik Jantke, Alexander N. Marziale, Andreas Raba, Jörg Eppinger
ChemistryOpen 2013, 2, No. 2, 50. Read article.

Direct Fluorination of Cyclic Carbonates and closo-K₂[B₁₂H₁₂] in a Slug-Flow Ministructured Reactor

A novel multiphase minireactor was used for direct fluorination of ethylene carbonate, propylene carbonate, and closo-K₂[B₁₂H₁₂]. The results of the direct fluorination reactions are presented and calculated Gibbs free energies for the cyclic carbonates are discussed. It followed that cyclic carbonates are also possible solvents for the fluorination of ionic substrates, for example closo-K₂[B₁₂H₁₂]. The figure shows a schematic view of the reactor and its function.

[Full Paper]
Mathias Hill, Patrick Baron, Keith Cobry, Sascha K. Goll, Philipp Lang, Carsten Knapp, Harald Scherer, Peter Woias, Pengcheng Zhang, Ingo Krossing
ChemPlusChem 2013, 78, No. 4, 292. Read article.

AgBr Nanocrystals from Plates to Cubes and Their Photocatalytic Properties

Crystal evolution: AgBr nanocrystals, evolving from plates through truncated cubes and finally to regular cubes, corresponding to a progressive shrinkage of exposed {1 1 1} facets and enlargement of exposed {1 0 0} facets, are prepared and their growth mechanism investigated. These nanocrystals exhibit facet-dependent photocatalytic properties.

[Full Paper]
Hua Wang, Yang Liu, Pengfei Hu, Liang He, Jinghong Li, Lin Guo
ChemCatChem 2013, 5, No. 6, 1426. Read article.

Application of Bismuth-Impregnated Mesoporous Silica to the Photochemical Oxidation of Methylene Blue: An Example of Nanoparticle Autocatalysis

Less is sometimes more: The irradiation of a series of bismuth-impregnated mesoporous silicas (Bi-TUD-1) in the presence of peroxide show increasing degradation activity of methylene blue with decreasing bismuth loadings. Kinetic studies reveal that the active sites of the catalyst are generated autocatalytically.

[Full Paper]
Antony J. Ward, Cameron C. Weber, Anthony F. Masters, Thomas Maschmeyer
ChemCatChem 2013, 5, No. 4, 959. Read article.

Practical and Efficient Organocatalytic Enantioselective α-Hydroxyamination Reactions of β-Ketoamides

Constrained chiral center: The first general, efficient and highly enantioselective α-hydroxyamination reactions of carbonyl compounds are described, securing a practical synthetic access to conformationally constrained α-amino acid derivatives exhibiting a quaternary chiral center at the α-position.

[Full Paper]
Damien Mailhol, Juan-Carlos Castillo, Kishor Mohanan, Rodrigo Abonia, Yoann Coquerel, Jean Rodriguez
ChemCatChem 2013, 5, No. 5, 1192. Read article.

An Experimental and Theoretical Approach to the Photophysical Properties of Some Rh and Ir Complexes Incorporating the Dipyrromethene Ligand

The spectroscopic properties of Rh and Ir complexes that contain meso-p-methoxyphenyldipyrromethene (dipyH) and phenylpyridine (ppy) ligands, [Rh(dipy)₃], [Rh(ppy)₂(dipy)] and [Ir(ppy)₂(dipy)], are described and discussed from experimental and theoretical approaches.

[Full Paper]
Diane Ramlot, Mateusz Rebarz, Leen Volker, Margriet Ovaere, David Beljonne, Wim Dehaen, Luc Van Meervelt, Cécile Moucheron, Andrée Kirsch-De Mesmaeker
Eur. J. Inorg. Chem. 2013, No. 12, 2031. Read article.

Direct Nucleophilic Substitution of Free Allylic Alcohols in Water Catalyzed by FeCl₃�6 H₂O: Which is the Real Catalyst?

Taking a leaf out of the green book: The use of FeCl₃·6 H₂O as an efficient water-compatible catalyst for the allylic substitution of free alcohols is disclosed. This inexpensive, low-toxic, and easily accessible Fe^III salt used as the catalyst in a process conducted in pure water as the solvent represents an environmentally friendly alternative to previously reported methods and allows the introduction of a broad range of nitrogenated and carbon nucleophiles.

[Full Paper]
Paz Trillo, Alejandro Baeza, Carmen Nájera
ChemCatChem 2013, 5, No. 6, 1538. Read article.

Optimization of Marine Triterpene Sipholenols as Inhibitors of Breast Cancer Migration and Invasion

Sipholenol A, a sipholane triterpene from Callyspongia siphonella, and its analogues are shown to have antimigratory activity in metastatic human breast cancer cells, while exhibiting no cytotoxicity towards normal epithelial cells. Evaluation of 19,20-anhydrosipholenol A 4β-benzoate ester against 451 human protein kinases identified protein tyrosine kinase 6 as a potential target. Sipholane triterpenoids represent novel antimigratory marine natural products with potential for development against metastatic malignancies.

[Full Paper]
Ahmed I. Foudah, Sandeep Jain, Belnaser A. Busnena, Khalid A. El Sayed
ChemMedChem 2013, 8, No. 3, 497. Read article.

Fluoride as Ligand: Chemistry of Some New Terminal and Bridged Systems

Fluorine is unique! A synthesis method for polynuclear systems with bridging fluorido ligands has been developed. The method is based on anchoring and protection of the fluorido ligand by initial coordination to a robust metal center (e.g., Cr^III) and subsequent use of the robust fluoride complex for construction of more complicated polynuclear structures.

[Thesis Treasury]
Torben Birk
ChemistryOpen 2013, 2, No. 1, 13. Read article.

Synthesis of Anatase Se/Te-TiO₂ Nanorods with Dominant {100} Facets: Photocatalytic and Antibacterial Activity Induced by Visible Light

Antibacterial agents: Te–TiO₂ and Se_n/Te–TiO₂ nanorods (NRs) with exposed {100} facets are efficient photocatalysts and antibacterial agents against E. coli and S. aureus (see graph; background of red fluorescent stains represents dead or compromised cells). The activity mainly results from the generation of ·OH, TeO₃²⁻, and SeO₃²⁻ ions.

[Full Paper]
Zong-Hong Lin, Prathik Roy, Zih-Yu Shih, Chung-Mao Ou, Huan-Tsung Chang
ChemPlusChem 2013, 78, No. 4, 302. Read article.

Catalytic Oxidation of Benzene on Liquid Ion-Exchanged Cu,H(Na)/ZSM-5 and Cu,H(Na)/Y Zeolites: Spin Trapping of Transient Radical Intermediates

The zeolites ZSM-5 and Y were exchanged with copper ions, with the aim to oxidize benzene with molecular oxygen at ambient temperature in cyclohexane solution. Transient radical intermediates were detected in high yield using the spin trap technique. The Cu,H/ZSM-5 acts as a redox/Brønsted acid bifunctional catalyst and shows high activity for radical formation. Remarkably over 30 % of the benzene was converted into radicals (DMPO=5,5-dimethyl-1-pyrroline-N-oxide).

[Full Paper]
Alexander Kromer, Emil Roduner
ChemPlusChem 2013, 78, No. 3, 268. Read article.

Carbon Dioxide Adsorption in Betulin-Based Micro- and Macroporous Polyurethanes

Separation of CO₂. Microporous polyurethane networks were prepared based on a renewable resource. Betulin, extracted from birch bark, is used as a structure-directing diol monomer in A₃-B₂ monomers. The resulting microporous networks show very promising CO₂/N₂ selectivities. The state of adsorbed CO₂ is analyzed by in situ NMR spectroscopy, and pure physisorption is proven. The preparation of monolithic materials is demonstrated as well.

[Communication]
Jekaterina Jeromenok, Winfried Böhlmann, Christian Jäger, Jens Weber
ChemistryOpen 2013, 2, No. 1, 17. Read article.

Embedded Palladium Activation as a Facile Method for TiO₂-Nanotube Nanoparticle Decoration: Cu₂O-Induced Visible-Light Photoactivity

Highly decorated! A direct and efficient way to decorate TiO₂ nanotubes with copper, Cu₂O and CuO particles is shown. Active palladium species embedded in the TiO₂ nanotube walls allow specific initiation sites to be triggered for electroless copper deposition. These Cu₂O-decorated TiO₂ nanotubes could be used for water splitting.

[Communication]
Anca Mazare, Ning Liu, Kiyoung Lee, Manuela S. Killian, Patrik Schmuki
ChemistryOpen 2013, 2, No. 1, 21. Read article.