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CURRENT CONTENTS/Chemistry

Chemistry – An Asian Journal v.7 n.1 2012

seoulfric 2012. 7. 26. 15:03

ISSN 0009-2665

 

 

  1. Cover Picture

Cover Picture: Seed-mediated Growth of Gold inside Hollow Silica Nanospheres for Sensing Peroxide and Glucose Concentrations (Chem. Asian J. 1/2012) (page 1)

Tae-Lin Ha, Jongmin Shin, Choon Woo Lim and Prof. In Su Lee

Article first published online: 22 DEC 2011 | DOI: 10.1002/asia.201190055

 

Inside Cover

Inside Cover: Dual Roles of Polyhydroxy Matrices in the Homocoupling of Arylboronic Acids Catalyzed by Gold Nanoclusters under Acidic Conditions (Chem. Asian J. 1/2012) (page 2)

Raghu Nath Dhital, Dr. Arumugum Murugadoss and Prof. Dr. Hidehiro Sakurai

Article first published online: 22 DEC 2011 | DOI: 10.1002/asia.201190057

 

The chitosan matrix plays dual roles as a stabilizer of nanogold and as an activator of arylboronic acids in homocoupling reactions in acidic aqueous media. In their Communication on page 55 ff., H. Sakurai et al. demonstrate, by using 11B NMR spectroscopy, that the tetra-coordinated boronate species are generated inside the chitosan (or starch) matrix even under acidic conditions, resulting in a high reactivity and selectivity for aerobic homocoupling of arylboronic acid. The result could expedite the development of designer catalysts consisting of combinations of functionalized polymers and metal nanoclusters.

Editorial

Ring In the New (pages 4–5)

Dr. Theresa Kueckmann

Article first published online: 22 DEC 2011 | DOI: 10.1002/asia.201100973

Graphical Abstract

Graphical Abstract: Chem. Asian J. 1/2012 (pages 7–15)

Article first published online: 22 DEC 2011 | DOI: 10.1002/asia.201190059

News

Spotlights on our sister journals: Chem. Asian J. 1/2012 (pages 18–20)

Article first published online: 22 DEC 2011 | DOI: 10.1002/asia.201190056

Focus Review

    1. Total Synthesis

Chemical Synthesis of the Englerins (pages 22–35)

Dr. Rebecca H. Pouwer, Dr. Jean-Alexandre Richard, Dr. Chih-Chung Tseng and Prof. Dr. David Y.-K. Chen

Article first published online: 8 DEC 2011 | DOI: 10.1002/asia.201100780

 

Total Englerin of the Heart: In this focus review, the total syntheses and synthetic approaches towards englerin A and B are presented, showcasing the creative synthetic designs and method development for the preparation of these promising therapeutic agents.

Communications

    1. Sensors

Seed-mediated Growth of Gold inside Hollow Silica Nanospheres for Sensing Peroxide and Glucose Concentrations (pages 36–39)

Tae-Lin Ha, Jongmin Shin, Choon Woo Lim and Prof. In Su Lee

Article first published online: 5 SEP 2011 | DOI: 10.1002/asia.201100501

A growth spurt: Catalytic growth of Au NPs inside a cavity protected by hollow silica nanoshells, which is accompanied by an SPR spectroscopic enhancement, allows for the quantitative detection of H2O2 and glucose concentrations, even in the presence of interfering BSA proteins.

    1. Palladium Catalysis

Palladium-Catalyzed Carbonylative Negishi-type Coupling of Aryl Iodides with Benzyl Chlorides (pages 40–44)

Xiao-Feng Wu, Johannes Schranck, Dr. Helfried Neumann and Prof. Dr. Matthias Beller

Article first published online: 11 OCT 2011 | DOI: 10.1002/asia.201100627

 

Do the competition: The synthesis of 1,2-diarylethanones has been accomplished using the palladium-catalyzed coupling of aryl iodides and CO/benzyl chlorides or benzoyl chlorides. These reactions proceed smoothly in the presence of zinc powder to afford the products in moderate to excellent yields.

Microwave-Promoted “One-Pot” Synthesis of 4-Nitrobenzylthioinosine Analogues Using Thiourea as a Sulfur Precursor (pages 45–49)

Dr. Hong-Ying Niu, Dr. Chao Xia, Prof. Gui-Rong Qu, Shan Wu, Yi Jiang, Xin Jin and Prof. Dr. Hai-Ming Guo

Article first published online: 14 OCT 2011 | DOI: 10.1002/asia.201100699

 

An efficient one-pot method for the synthesis of various C6-alkylthio-substituted purine nucleosides has been developed under microwave irradiation with good to excellent yields without any metal catalyst (see scheme). This process expands the scope of existing synthetic methodologies and was further successfully applied for synthesis of the biologically important compound 4-nitrobenzylthioinosine (NBTI).

    1. Calixarenes

Reversible Molecular Motion of a Bis-calix[5]arene Host Driven by a Photoresponsive Guest (pages 50–54)

Dr. Giovanna Brancatelli, Dr. Calogero Capici, Dr. Giuseppe Gattuso, Prof. Silvano Geremia, Dr. Anna Notti, Prof. Sebastiano Pappalardo, Prof. Melchiorre F. Parisi, Prof. Salvatore Sortino and Dr. Elisa Vittorino

Article first published online: 31 OCT 2011 | DOI: 10.1002/asia.201100738

 

Control by light: Reversible switching between closed and open conformations of a calix[5]arene-based receptor was conveniently controlled, at the supramolecular level, exclusively through light inputs by exploiting the photoisomerization of a tailor-made azobenzene guest.

    1. Matrices

Dual Roles of Polyhydroxy Matrices in the Homocoupling of Arylboronic Acids Catalyzed by Gold Nanoclusters under Acidic Conditions (pages 55–59)

Raghu Nath Dhital, Dr. Arumugum Murugadoss and Prof. Dr. Hidehiro Sakurai

Article first published online: 7 OCT 2011 | DOI: 10.1002/asia.201100478

 

Polyhydroxy biopolymers play dual roles in the stabilization of gold clusters as well as the activation of arylboronic acids through reversible binding. In acidic pH (4.57), the electronic state of boron is changed into that observed at pH 9 in the vicinity of Au/chit or Au/starch, which favors the transmetalation process; this change is why homocoupling product was observed even in acidic solutions.

    1. Fluorescence

PyA-Modified Oligodeoxyadenylates: Expanded Fluorescence Phenomena and Structural Formation (pages 60–63)

Jeong Wu Yi and Prof. Byeang Hyean Kim

Article first published online: 18 NOV 2011 | DOI: 10.1002/asia.201100674

 

PyA-modified oligodeoxyadenylates exhibit blue, white, or reddish-orange fluorescence emission depending on the number of incorporated PyA units. These results expand the number of building blocks available for constructing DNA-based nanoarchitectures and might be applicable to the development of new fluorescent devices (PyA=8-(1-pyrenyl ethynyl)-2′-deoxyadenosine).

Full Papers

    1. Aldol Reactions

One-pot Chemoenzymatic Synthesis of Chiral 1,3-Diols Using an Enantioselective Aldol Reaction with Chiral Zn2+ Complex Catalysts and Enzymatic Reduction Using Oxidoreductases with Cofactor Regeneration (pages 64–74)

Shotaro Sonoike, Toshinari Itakura, Dr. Masanori Kitamura and Prof. Shin Aoki

Article first published online: 15 DEC 2011 | DOI: 10.1002/asia.201100584

 

Which stereoisomer do you want? The one-pot chemoenzymatic synthesis of all possible stereoisomers of 1,3-diols in a water system by an enantioselective aldol reaction catalyzed by chiral Zn2+-complexes combined with a successive enantioselective reduction of the aldol product using oxidoreductase with regeneration of the NADH cofactor is described.

    1. Oligothiophenes

Synthesis of Self-Threading Bithiophenes and their Structure–Property Relationships Regarding Cyclic Side-Chains with Atomic Precision (pages 75–84)

Yuki Ouchi, Dr. Kazunori Sugiyasu, Dr. Soichiro Ogi, Akira Sato and Prof. Dr. Masayuki Takeuchi

Article first published online: 16 NOV 2011 | DOI: 10.1002/asia.201100524

 

Through the eye of a needle: The influence of the size and flexibility of the cyclic side-chains on the photophysical properties of bithiophene monomers have been examined by using UV absorption, fluorescence and NMR spectroscopic methods.

    1. Nanoparticles

Decoration of Diatom Biosilica with Noble Metal and Semiconductor Nanoparticles (<10 nm): Assembly, Characterization, and Applications (pages 85–90)

Anne Jantschke, Anne-Kristin Herrmann, Dr. Vladimir Lesnyak, Prof. Alexander Eychmüller and Prof. Eike Brunner

Article first published online: 18 NOV 2011 | DOI: 10.1002/asia.201100563

 

Midas touch: Diatom-templated noble metal (Ag, Pt, Au) and semiconductor (CdTe) nanoparticle arrays were synthesized by the attachment of prefabricated nanoparticles of defined size. The synthesized arrays were useful for surface-enhanced Raman spectroscopy (SERS) of components, for catalysis, and for the improvement of image quality in SEM.

    1. Gene Delivery

Cyclic RGD–Polyethylene Glycol–Polyethylenimine for Intracranial Glioblastoma-Targeted Gene Delivery (pages 91–96)

Dr. Changyou Zhan, Dr. Qinggang Meng, Dr. Qinghua Li, Dr. Linglin Feng, Prof. Jianhua Zhu and Prof. Weiyue Lu

Article first published online: 9 NOV 2011 | DOI: 10.1002/asia.201100570

 

A polymeric nonviral gene carrier composed of polyethylene glycol–polyethylenimine (PEG–PEI) conjugated with a cyclic tripeptide, RGD, can facilitate gene delivery targeted against intracranial U87 tumor xenografts, resulting in higher gene transfection efficiency in intracranial glioblastoma and prolonging the median survival of intracranial U87 tumor-bearing nude mice when complexed with plasmid DNA carrying the TRAIL gene.

    1. Oligosaccharides

Degradation of Target Oligosaccharides by Anthraquinone–Lectin Hybrids with Light Switching (pages 97–104)

Yukari Imai, Shingo Hirono, Haruka Matsuba, Dr. Tomohiro Suzuki, Dr. Yuka Kobayashi, Prof. Dr. Hirokazu Kawagishi, Dr. Daisuke Takahashi and Prof. Dr. Kazunobu Toshima

Article first published online: 13 OCT 2011 | DOI: 10.1002/asia.201100586

 

Ray of light: An efficient method for target-selective degradation of oligosaccharides induced by a light-activated hybrid molecule consisting of anthraquinone and lectin has been developed. The reaction takes place under neutral conditions and no additives are required.

    1. Semiconductors

Tetracene Dicarboxylic Imide and Its Disulfide: Synthesis of Ambipolar Organic Semiconductors for Organic Photovoltaic Cells (pages 105–111)

Dr. Toshihiro Okamoto, Tsuyoshi Suzuki, Dr. Hideyuki Tanaka, Dr. Daisuke Hashizume and Prof. Yutaka Matsuo

Article first published online: 26 OCT 2011 | DOI: 10.1002/asia.201100590

 

Time and TIDS wait for no man: A new donor/acceptor-type tetracene derivative, TIDS, which contains dicarboxylic imide and disulfide groups as electron-withdrawing and -donating units was synthesized. TIDS showed long-wavelength absorption up to 886 nm in thin film, and exhibited ambipolar transport of both holes and electrons in p–nand p–i–n heterojunction organic thin-film photovoltaic devices.

    1. Organometallic Complexes

Selective, Cytotoxic Organoruthenium(II) Full-Sandwich Complexes: A Structural, Computational and In Vitro Biological Study (pages 112–121)

Dr. Bradley T. Loughrey, Benjamin V. Cunning, Prof. Peter C. Healy, Prof. Christopher L. Brown, Prof. Peter G. Parsons and Dr. Michael L. Williams

Article first published online: 17 NOV 2011 | DOI: 10.1002/asia.201100637

 

Ru positive? A diverse range of lipophilic, cationic full-sandwich complexes of ruthenium(II) have been prepared and structurally characterized. Computational experiments predict each molecule to possess a delocalized δ+ electrostatic potential, and in vitro cytotoxicity studies demonstrate these lipophilic cations to be potent and selective growth inhibitors of tumorigenic cells lines.

    1. Host–Guest Complexes

Abnormal Thermal Expansion of Clathrate Hydrates Induced by Asymmetric Guest Molecules (pages 122–126)

Minjun Cha, Yeobum Youn, Minchul Kwon, Dr. Kyuchul Shin, Dr. Seongsu Lee and Prof. Dr. Huen Lee

Article first published online: 27 OCT 2011 | DOI: 10.1002/asia.201100645

 

Unusual doughnut-like motion! Through structure refinement processes, it was found that THF+HD hydrate exhibits an abnormal thermal expansion behavior. This peculiar expansion of a clathrate hydrate is clearly due to the asymmetric structure of the HD guest and might be one of the important physical properties necessary to understand the unique unrevealed properties of clathrate hydrates.

    1. Nanostructures

An Anticoagulant Activity System Using Nanoengineered Autofluorescent Heparin Nanotubes (pages 127–132)

Wei Cui, Dr. Yue Cui, Dr. Pengli Zhu, Dr. Jie Zhao, Dr. Ying Su, Dr. Yang Yang and Prof. Dr. Junbai Li

Article first published online: 26 OCT 2011 | DOI: 10.1002/asia.201100425

 

The bleeding edge: Periodate-oxidized heparin (O-HEP) and chitosan (CHI) were assembled alternatively into the pore of polycarbonate membranes to form nanotube structures through a layer-by-layer method (see graphic). O-HEP/CHI nanotubes display an autofluorescent property without the addition of any fluorescent dye. They also have a lower anticoagulant activity.

    1. OLEDs

Spiro-Configured Bipolar Host Materials for Highly Efficient Electrophosphorescent Devices (pages 133–142)

Dr. Sung-Yu Ku, Prof. Wen-Yi Hung, Chung-Wen Chen, Shih-Wei Yang, Ejabul Mondal, Prof. Yun Chi and Prof. Ken-Tsung Wong

Article first published online: 13 OCT 2011 | DOI: 10.1002/asia.201100467

 

Bipolar personalities: Spiro-configured bipolar compounds are excellent host materials for iridium- and osmium-based green and red electrophosphorescent devices. The device incorporating D2 ACN doped with the red osmium emitter gave a saturated red electrophosphorescence with CIE coordinates of (0.65, 0.35) and remarkably high efficiencies of 20.3 % (21 cd A−1) and 13.5 Lm W−1 at a practical brightness of 1000 cd m−2.

    1. Dendrons

Synthesis of Polyisoprene Terpenoid Dendrons and their Applications in Oligo(phenylene ethynylene)s as “Shells” (pages 143–155)

Wen-Yu Chai, Dr. Zi-Fa Shi, Peng An, Wei Wang, Lu-Feng Wang and Prof. Xiao-Ping Cao

Article first published online: 27 OCT 2011 | DOI: 10.1002/asia.201100480

 

Core of the matter! Polyisoprene terpenoid (PIPTP) dendrons, which bear a highly branched aliphatic hydrocarbon skeleton and a hydrophilic hydroxy focal point functionality, have been synthesized for the first time. They have the specific formula C(5×2G+1-5)H(5×2G+2-8)O, and each dendritic layer is constructed from an isoprene unit. The number of polyisoprene monomers incorporated is N=2G+1−1 (G represents the generation of the dendron).

    1. Solar Cells

Effects of Dye-Adsorption Solvent on the Performances of the Dye-Sensitized Solar Cells Based on Black Dye (pages 156–162)

Dr. Hironobu Ozawa, Megumi Awa, Dr. Takahiko Ono and Prof. Dr. Hironori Arakawa

Article first published online: 23 NOV 2011 | DOI: 10.1002/asia.201100484

 

Black power: The conversion efficiency of the dye-sensitized solar cell based on black dye (see figure) strongly depends on the dielectric constant of the dye-adsorption solvent. The highest conversion efficiency (10.6 %) was obtained for 1-propanol under AM 1.5 (100 mW cm−2) irradiation.

    1. Lithium Batteries

LiCoxMn1-xPO4/C: A High Performing Nanocomposite Cathode Material for Lithium Rechargeable Batteries (pages 163–168)

Chandrasekaran Nithya, Dr. Ramasamy Thirunakaran, Dr. Arumugam Sivashanmugam and Dr. Sukumaran Gopukumar

Article first published online: 14 OCT 2011 | DOI: 10.1002/asia.201100485

 

Better batteries! Pristine and Co-doped LiMnPO4 cathode materials have been synthesized by the sol-gel method using glycine as a chelating agent. The corresponding carbon composites are prepared by the wet ball mill method. Carbon particles appear as a coating layer over the active materials (see picture).

    1. Catalysis

An Efficient Zinc-Catalyzed Dehydration of Primary Amides to Nitriles (pages 169–175)

Dr. Stephan Enthaler and Prof. Dr. Shigeyoshi Inoue

Article first published online: 29 SEP 2011 | DOI: 10.1002/asia.201100493

 

Zincing about catalysis: A straightforward method for the dehydration of primary amides using zinc catalysts is presented. Excellent performance is demonstrated by a system composed of Zn(OTf)2 as the catalyst and N-methyl-N-(trimethylsilyl)trifluoroacetamide as the dehydration reagent under ambient conditions. The applicability of this procedure is shown by the dehydration of various substrates with excellent yields and functional-group tolerance (see scheme).

    1. Self-Assembly

Light-Induced Electron Transfer over Distances of 5, 10, and 15 Å within Water-Filled Yoctowells (pages 176–182)

Dr. Sheshanath V. Bhosale, Dr. Steffen Hackbarth, Prof. Steven J. Langford and Dr. Sidhanath V. Bhosale

Article first published online: 28 OCT 2011 | DOI: 10.1002/asia.201100533

 

All′s well that yoctowells: Two different dyes (porphyrin 1 and quinone 2) have been immobilized in a yoctoliter-sized cavity at defined subnanometer distances of 5, 10, and 15 Å in an aqueous medium. Upon photoexcitation of the bottom porphyrin, electron transfer occurred with varying amplitudes in the range of 60–70 %.

    1. Calix[4]arenes

Metal-Ion-Promoted Electron Transfer between Tetrathiafulvalene and Quinone Units Within a Calix[4]arene Framework and Tuning through Coordination of the Neighboring Crown Ether with a Sodium Cation (pages 183–189)

Fei Sun, Fang Hu, Dr. Guanxin Zhang and Prof. Dr. Deqing Zhang

Article first published online: 4 OCT 2011 | DOI: 10.1002/asia.201100560

 

Turn on/switch off: The intramolecular electron transfer between tetrathiafulvalene (TTF) and quinone units within calix[4]arene 1occurs efficiently in the presence of Zn2+/Sc3+/Pb2+, and moreover the electron transfer within 1 triggered by Zn2+ can be switched off upon addition of Na+ and further turned on by further addition of either Sc3+ or Pb2+ (see scheme).

    1. Carbon Nanotubes

Chitosan-Functionalized Carbon Nanotubes as Support for the High Dispersion of PtRu Nanoparticles and their Electrocatalytic Oxidation of Methanol (pages 190–195)

Bohua Wu, Yunsong Zhang, Yinjie Kuang, Yaming Yu, Xiaohua Zhang and Prof. Dr. Jinhua Chen

Article first published online: 11 OCT 2011 | DOI: 10.1002/asia.201100564

 

Chit Chit Bang Bang: An alternative strategy for the synthesis of noble metal nanoparticle/CNT nanohybrids was developed based on the functionalization of carbon nanotubes (CNTs) with chitosan (Chit). Owing to high dispersion of PtRu nanoparticles with small particle size, and the excellent proton conductivity of Chit, the obtained PtRu NPs/CNT-Chit nanohybrids show superb performance for methanol electro-oxidation.

    1. Sensors

A Highly Selective Colorimetric and Fluorescent Probe for Cu2+ and Hg2+ Ions Based on a Distyryl BODIPY with Two Bis(1,2,3-triazole)amino Receptors (pages 196–200)

Wen-Jing Shi, Dr. Jian-Yong Liu and Prof. Dennis K. P. Ng

Article first published online: 26 OCT 2011 | DOI: 10.1002/asia.201100598

 

Mark of distinction: A click-derived probe has been developed that can selectively detect Cu2+ and Hg2+ ions in CH3CN/H2O, and this gives remarkable color changes that can be detected by the naked eye (see picture).

    1. Nanostructures

Human Serum Albumin Nanotubes with Esterase Activity (pages 201–206)

Prof. Dr. Teruyuki Komatsu, Dr. Takaaki Sato and Dr. Christoph Boettcher

Article first published online: 4 NOV 2011 | DOI: 10.1002/asia.201100606

 

Blood protein nanotubes: A nanocylindrical wall structure made by layer-by-layer assembly of poly-L-arginine and human serum albumin (HSA) was characterized by direct imaging methods. SEM and SFM measurements yielded images of round, chimney-like architectures. Cryo-TEM pictures revealed that the tube walls are composed of densely packed HSA molecules. The protein cylinders are considerably swollen in water and showed esterase activity.

    1. Rotaxanes

Organometallic Rotaxanes with a Triazole Group in the Axle Component and Their Behavior as Ligands of PtII Complexes (pages 207–213)

Gilbert Yu, Dr. Yuji Suzaki, Tomoko Abe and Prof. Kohtaro Osakada

Article first published online: 27 OCT 2011 | DOI: 10.1002/asia.201100617

 

A crowning achievement: A copper-catalyzed Huisgen coupling reaction was employed for the synthesis of [2]rotaxanes composed of dibenzo[24]crown-8 (DB24C8) and dialkylammonium, and their triazole units were applied as the ligands for platinum(II) complexes (see scheme).

    1. Nitrogen Heterocycles

New Azidotetrazoles: Structurally Interesting and Extremely Sensitive (pages 214–224)

Prof. Dr. Thomas M. Klapötke, Dr. Burkhard Krumm, Franz A. Martin and Dr. Jörg Stierstorfer

Article first published online: 9 NOV 2011 | DOI: 10.1002/asia.201100632

 

Hypersensitivity: 1-Amino-5-azidotetrazole (1), 5-azido-1-diazido-carbamoyltetrazole (2), and 1-(amino-azidocarbamoyl)-5-azidotetrazole (3) were formed by the diazotation of triaminoguanidinium chloride and separated by short-column chromatography. Their high nitrogen content results in extremely high sensitivity, therefore handling and characterization were very challenging.

    1. Oligothiophenes

Synthesis, Electronic, and Morphological Properties of Tetrahedral Oligothiophenes with n-Hexyl Terminal Groups (pages 225–232)

Dr. Kouzou Matsumoto, Sota Kugo, Dr. Daisuke Takajo, Prof. Dr. Akira Inaba, Dr. Yasukazu Hirao, Dr. Hiroyuki Kurata, Prof. Dr. Takeshi Kawase and Prof. Dr. Takashi Kubo

Article first published online: 12 OCT 2011 | DOI: 10.1002/asia.201100639

 

Avenged fourfold: A series of tetrahedral oligothiophenes with n-hexyl groups have been synthesized, using the fourfold Kosugi–Migita–Stille coupling as the key step. The terminal n-hexyl groups affect the morphological properties of this tetrahedral π-electron system; namely, thiophene and bithiophene derivatives are obtained as liquid substances and the terthiophene derivative can take both the crystal and the stable glassy state.

    1. Friedel–Crafts Reaction

A Highly Efficient Friedel–Crafts Reaction of 3-Hydroxyoxindoles and Aromatic Compounds to 3,3-Diaryl and 3-Alkyl-3-aryloxindoles Catalyzed by Hg(ClO4)2⋅3 H2O(pages 233–241)

Feng Zhou, Zhong-Yan Cao, Jing Zhang, Prof. Dr. Hai-Bo Yang and Prof. Dr. Jian Zhou

Article first published online: 28 NOV 2011 | DOI: 10.1002/asia.201100773

 

Back to nature: A highly efficient catalytic Friedel–Crafts reaction of 3-substituted 3-hydroxyoxindoles with a variety of (hetero)aromatic compounds is reported. It allowed the facile synthesis of 3,3-diaryloxindoles and 3-alkyl-3-aryloxindoles (see scheme), which are useful building blocks for natural products and interesting medicinal targets. Hg(ClO4)2⋅3 H2O is identified as a powerful catalyst.

Preview

Preview: Chem. Asian J. 2/2012 (page 243)

Article first published online: 22 DEC 2011 | DOI: 10.1002/asia.201190058

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