ChemSusChem

Cover image for Vol. 1 Issue 3

March 25, 2008

Volume 1, Issue 3

Pages 161–266

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Highlight
    6. Communications
    7. Articles
    8. Book Review
    9. Preview
    1. Cover Picture: Highly Active Catalysts for the Telomerization of Crude Glycerol with 1,3-Butadiene (ChemSusChem 3/2008) (page 161)

      Regina Palkovits, Ilenia Nieddu, Robertus J. M. Klein Gebbink and Bert M. Weckhuysen

      Article first published online: 18 MAR 2008 | DOI: 10.1002/cssc.200890004

      Thumbnail image of graphical abstract

      The cover picture shows a palladium-based molecular catalyst for the direct telomerization of glycerol with 1,3-butadiene, which presents a promising technology allowing direct access to C8-chain mono-, di-, and triethers of glycerol as useful chemical building blocks. Crude glycerol is obtained as a by-product of biodiesel manufacturing, for example, from rapeseed or sunflowers. In their Communication on page 193 ff., B. M. Weckhuysen et al. report how palladium complexes with methoxy-substituted triphenylphosphine ligands entail superior catalytic activity in the telomerization of not only pure glycerol but also crude glycerol. The resulting C8-chain ethers can potentially be applied in the production of surfactant or detergent molecules, as illustrated by the structures set against the foam-like background.

  2. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Highlight
    6. Communications
    7. Articles
    8. Book Review
    9. Preview
    1. Graphical Abstract: ChemSusChem 3/2008 (pages 163–169)

      Article first published online: 18 MAR 2008 | DOI: 10.1002/cssc.200890005

  3. News

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Highlight
    6. Communications
    7. Articles
    8. Book Review
    9. Preview
    1. Spotlights on our sister journals: ChemSusChem 3/2008 (pages 170–171)

      Article first published online: 18 MAR 2008 | DOI: 10.1002/cssc.200890006

  4. Highlight

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Highlight
    6. Communications
    7. Articles
    8. Book Review
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    1. Powered by Nanowires (pages 173–174)

      Ralf Wehrspohn

      Article first published online: 19 FEB 2008 | DOI: 10.1002/cssc.200800002

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      Wired up to the sun: The first solar cells based on silicon nanowires have been prepared using the p–i–n core–shell concept adopted from amorphous silicon solar cells. These solar cells produce power in the nanowatt range, which is sufficient to drive self-sustaining nanoelectronic circuits.

  5. Communications

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Highlight
    6. Communications
    7. Articles
    8. Book Review
    9. Preview
    1. Oxidation of 1,4-Dioxane over Ti-MWW in the Presence of H2O2 (pages 175–178)

      Weibin Fan, Yoshihiro Kubota and Takashi Tatsumi

      Article first published online: 12 FEB 2008 | DOI: 10.1002/cssc.200700003

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      Ti time for dioxane: Oxidation of 1,4-dioxane with aqueous H2O2 over various titanosilicates was investigated. Use of Ti-MWW as catalyst leads to much higher conversions than with TS-1 and Ti-Beta under solvent-free conditions and is accounted for by a radical mechanism. The number of active intermediate Ti species is highly dependent on the substrate, solvent, and titanosilicate used.

    2. Coprocessing of Oxygenated Biomass Compounds and Hydrocarbons for the Production of Sustainable Fuel (pages 179–181)

      Marcelo E. Domine, Andre C. van Veen, Yves Schuurman and Claude Mirodatos

      Article first published online: 4 FEB 2008 | DOI: 10.1002/cssc.200700049

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      From biomass to tomorrow's biofuels: Pyrolysis oils, obtained by fast pyrolysis of solid biomass, comprise a wide range of oxygenated compounds. It is proposed that after adequate upgrading, these oils may be fed into large-scale refinery units to obtain fuels. Thus, the co-feeding of a model hydrocarbon (C8) and model oxygenated molecules was studied in a fixed-bed catalytic reactor using an industrial fluid catalytic cracking catalyst.

    3. Kinetics and Mechanism of 9H-Fluorene Oxidation Catalyzed by Manganese Oxide Octahedral Molecular Sieves (pages 182–185)

      Naftali N. Opembe, Young-Chan Son, Thamayanthy Sriskandakumar and Steven L. Suib

      Article first published online: 5 FEB 2008 | DOI: 10.1002/cssc.200700094

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      Sift fluorene into a bowl: Manganese oxide octahedral molecular sieves (OMS-2), with the overall composition KMn8O16n H2O, catalyze the mild, green, and efficient oxidation of 9H-fluorene to 9-fluorenone. The involvement of lattice oxygen species has been implicated in a free-radical chain mechanism. In terms of reaction kinetics, the breaking of the C[BOND]H bond is rate controlling.

    4. Synthesis of Dimethyl Carbonate from Carbon Dioxide Catalyzed by Titanium Alkoxides with Polyether-type Ligands (pages 186–188)

      Kazufumi Kohno, Jun-Chul Choi, Yoshihiro Ohshima, Hiroyuki Yasuda and Toshiyasu Sakakura

      Article first published online: 21 JAN 2008 | DOI: 10.1002/cssc.200700113

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      Run DMC: Homogeneous catalysts based on titanium alkoxides and polyethers were studied for the production of the industrially important intermediate dimethyl carbonate (DMC) from carbon dioxide and methanol (see scheme). The reaction proceeds in the presence of 2,2-dimethoxypropane as a recyclable organic dehydrating agent under supercritical CO2 conditions.

    5. ε-Caprolactamium Hydrogen Sulfate: An Ionic Liquid Used for Decades in the Large-Scale Production of ε-Caprolactam (pages 189–192)

      Viktória Fábos, Diána Lantos, Andrea Bodor, Ana-Maria Bálint, László T. Mika, Ot E. Sielcken, Agnes Cuiper and István T. Horváth

      Article first published online: 12 FEB 2008 | DOI: 10.1002/cssc.200700135

      Thumbnail image of graphical abstract

      An iconic liquid: Investigation of the mechanism of the Beckmann rearrangement of cyclohexanone oxime to ε-caprolactam (1) in sulfuric acid or oleum has led to the conclusion that the manufacturing process for ε-caprolactam is in fact the largest-scale industrial technology that has been using an ionic liquid, caprolactamium hydrogen sulfate (2), as the reaction medium for decades.

    6. Highly Active Catalysts for the Telomerization of Crude Glycerol with 1,3-Butadiene (pages 193–196)

      Regina Palkovits, Ilenia Nieddu, Robertus J. M. Klein Gebbink and Bert M. Weckhuysen

      Article first published online: 21 JAN 2008 | DOI: 10.1002/cssc.200700147

      Thumbnail image of graphical abstract

      The chain gang: Crude glycerol, a by-product in the production of biodiesel, can be telomerized with 1,3-butadiene to form C8-chain ethers. The development of suitable catalyst systems for the direct telomerization of crude glycerol at the biodiesel plant provides a route to useful building blocks from cheap starting materials for commercially valuable products such as detergents and surfactants.

  6. Articles

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Highlight
    6. Communications
    7. Articles
    8. Book Review
    9. Preview
    1. Formation of Organobrominated Compounds in the Presence of Bromide under Simulated Atmospheric Aerosol Conditions (pages 197–204)

      Davide Vione, Valter Maurino, Simona Cucu Man, Swapan Khanra, Cecilia Arsene, Romeo-Iulian Olariu and Claudio Minero

      Article first published online: 5 FEB 2008 | DOI: 10.1002/cssc.200700031

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      Bromine, bromine, everywhere: Bromination of phenol to 2- and 4-bromophenol takes place upon photolysis of FeBr2+ with visible light, under UV irradiation in the presence of NaNO3/Br, and upon dark reaction in the presence of H2O2/Br. Therefore, brominated compounds from abiotic natural sources can be present in the environment, besides those from biotic and anthropic sources.

    2. Fixation of CO2 by Electrocatalytic Reduction and Electropolymerization in Ionic Liquid–H2O Solution (pages 205–209)

      Daobao Chu, Guoxu Qin, Ximei Yuan, Mai Xu, Peng Zheng and Jia Lu

      Article first published online: 18 JAN 2008 | DOI: 10.1002/cssc.200700052

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      Making polymers out of thin air: The electrosynthesis of low-density polyethylene from CO2 on a nanostructured TiO2 film electrode was investigated by controlled potential electrolysis in an ionic liquid–water solvent mixture at room temperature. The TiO2 film is remarkably efficient and selective for the electrochemical reduction of CO2.

    3. Sulfonation of Phenols Extracted from the Pyrolysis Oil of Oil Palm Shells for Enhanced Oil Recovery (pages 210–214)

      Mariyamni Awang and Goh Meng Seng

      Article first published online: 10 MAR 2008 | DOI: 10.1002/cssc.200700083

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      Shell oil: In the oil industry, water flooding is conducted to enhance oil recovery from low-pressure, depleted reservoirs before other types of flooding are conducted. To this end, surfactants are useful in the oil field. Phenols and phenolic compounds extracted from the pyrolysis oil from oil palm shells were sulfonated to produce surfactants with minimal processing and at low cost for such applications.

    4. Exclusive Production of Chloroaniline from Chloronitrobenzene over Au/TiO2 and Au/Al2O3 (pages 215–221)

      Fernando Cárdenas-Lizana, Santiago Gómez-Quero and Mark A. Keane

      Article first published online: 10 JAN 2008 | DOI: 10.1002/cssc.200700105

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      An untarnished halo: Nanoscale Au particles supported on Al2O3 (see TEM image) and TiO2 promote a 100 % selective gas-phase hydrogenation of p-chloronitrobenzene to commercially important p-chloroaniline. The results can serve as the basis for a sustainable alternative route to haloamines.

    5. Energetic N,N,N′,N′-Tetraaminopiperazinium Salts (pages 222–227)

      Haixiang Gao, Yangen Huang, Brendan Twamley, Chengfeng Ye and Jean'ne M. Shreeve

      Article first published online: 10 JAN 2008 | DOI: 10.1002/cssc.200700114

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      High in N-ergy: Several new nitrogen-rich materials with the N,N,N′,N′-tetraaminopiperazinium cation, such as that with the 5,5-azotetrazolate anion (see structure; N blue, O red, C black), have been prepared in water and characterized. A combination of theoretical and empirical calculations shows that all the salts have high molar enthalpies of formation.

    6. The Role of Zinc(II) in the Absorption–Desorption of CO2 by Aqueous NH3, a Potentially Cost-Effective Method for CO2 Capture and Recycling (pages 228–235)

      Fabrizio Mani, Maurizio Peruzzini and Francesco Barzagli

      Article first published online: 18 MAR 2008 | DOI: 10.1002/cssc.200700124

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      Basic in-zinc: The CO2-absorption capacity of aqueous NH3 is substantially increased (20–30 %) by the presence of dissolved zinc(II) salts. The speciation of NH2CO2 (•), CO32− (▴) and HCO3 (▪) was investigated by 13C NMR spectroscopy. The addition at room temperature of a zinc salt to the NH3 solution at the end of the absorption process releases one-third of the absorbed CO2 and produces basic zinc carbonates containing the remaining two-thirds of the captured CO2.

    7. Bifunctional Metal-Salen Complexes as Efficient Catalysts for the Fixation of CO2 with Epoxides under Solvent-Free Conditions (pages 236–241)

      Cheng-Xia Miao, Jin-Quan Wang, Ying Wu, Ya Du and Liang-Nian He

      Article first published online: 18 MAR 2008 | DOI: 10.1002/cssc.200700133

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      A Co catalyst with no co-catalyst: A bifunctional cobalt-salen complex that contains a Lewis acidic metal center and a quaternary phosphonium salt unit anchored on the ligand has been developed as an active and recyclable homogeneous catalyst for the cycloaddition of CO2 to epoxides. The catalyst can be easily recovered and reused at least four times without any significant loss in catalytic activity.

    8. Oxidation of Citronellal to Citronellic Acid by Molecular Oxygen Using Supported Gold Catalysts (pages 242–248)

      A. Martin, U. Armbruster, D. Decker, T. Gedig and A. Köckritz

      Article first published online: 12 FEB 2008 | DOI: 10.1002/cssc.200700140

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      A hint of citrus in the air: The oxidation of citronellal to citronellic acid was studied using molecular oxygen in the presence of gold-containing supported catalysts (see image). Detailed studies on the influence of reaction time, pH value, reactant concentration and amount of catalyst show that citronellic acid can be obtained in over 90 % yield at pH 12 and a temperature of 80 °C.

    9. Organic Carbonates as Alternative Solvents for Palladium-Catalyzed Substitution Reactions (pages 249–253)

      Benjamin Schäffner, Jens Holz, Sergey P. Verevkin and Armin Börner

      Article first published online: 20 FEB 2008 | DOI: 10.1002/cssc.200700142

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      An alternative solution: Organic carbonates such as propylene carbonate can be used as alternative solvents to CH2Cl2 in palladium-catalyzed asymmetric allylic alkylation and amination reactions. With an appropriate ligand (L*), the enantioselectivity of the reaction can be improved in organic carbonates as compared to those obtained in standard organic solvents.

    10. Light Harvesting and Energy Transfer in Multiporphyrin-Modified CdSe Nanoparticles (pages 254–261)

      Soonchul Kang, Masakazu Yasuda, Hiroshi Miyasaka, Hironobu Hayashi, Mitsuo Kawasaki, Tomokazu Umeyama, Yoshihiro Matano, Kaname Yoshida, Seiji Isoda and Hiroshi Imahori

      Article first published online: 19 FEB 2008 | DOI: 10.1002/cssc.200700138

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      Array of sunshine: CdSe nanoparticles modified with multiple porphyrin units have been developed as light-harvesting molecules. The CdSe nanoparticle absorbs UV/Vis light and transfers the energy efficiently to the porphyrin moieties. Importantly, the porphyrin excited singlet state is not quenched by the CdSe core, in sharp contrast to the rapid quenching observed for the same porphyrin unit by the metal surface in porphyrin-modified metal nanoparticles.

  7. Book Review

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Highlight
    6. Communications
    7. Articles
    8. Book Review
    9. Preview
  8. Preview

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Highlight
    6. Communications
    7. Articles
    8. Book Review
    9. Preview
    1. Preview: ChemSusChem 4/2008 (page 266)

      Article first published online: 18 MAR 2008 | DOI: 10.1002/cssc.200890007

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