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An artificial metalloenzyme with the kinetics of native enzymes

P. Dydio, 1,2 * H. M. Key, 1,2 * A. Nazarenko, 1 J. Y.-E. Rha, 1 V. Seyedkazemi, 1 D. S. Clark, 3,4 J. F. Hartwig 1,2 †  Department of Chemistry, University of California, Berkeley, CA 94720, USA. 2 Chemical Sciences Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, CA 94720, USA. 3 Department of Chemical and Biomolecular Engineering, University of California, Berkeley, CA 94720, USA. 4 Molecular Biophysics and Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, CA 94720, USA.  28 June 2016; accepted 12 September 2016   Science  07 Oct 2016: Vol. 354, Issue 6308, pp. 102-106 DOI: 10.1126/science.aah4427   http://science.sciencemag.org/content/sci/354/6308/102.full.pdf Abstract Natural enzymes contain highly evo...

One-pot room-temperature conversion of cyclohexane to adipic acid by ozone and UV light

Kuo Chu Hwang*, Arunachalam Sagadevan National Tsing Hua University, Republic of China. Science, 2014, 346, 149 DOI: 10.1126/science.1259684 http://www.sciencemag.org/content/346/6216/1495.full Abstract Nitric acid oxidation of cyclohexane accounts for ~95% of the worldwide adipic acid production and is also responsible for ~5 to 8% of the annual worldwide anthropogenic emission of the ozone-depleting greenhouse gas nitrous oxide (N2O). Here we report a N2O-free process for adipic acid synthesis. Treatment of neat cyclohexane, cyclohexanol, or cyclohexanone with ozone at room temperature and 1 atmosphere of pressure affords adipic acid as a solid precipitate. Addition of acidic water or exposure to ultraviolet (UV) light irradiation (or a combination of both) dramatically enhances the oxidative conversion of cyclohexane to adipic acid. 少し古いですが、興味深い報告なので、紹介させていただきます。 シクロアルカンを基質として、オゾンガスを吹き込み、水銀灯(かなり強いUVがでる)を当てると工業的に重要なジカルボン酸がでるという報告です。 従来法だと、酸化剤に強烈な地球温暖化ガスであ...

Hydrogenation of carboxylic acids with a homogeneous cobalt catalyst

Ties J. Korstanje, Jarl Ivar van der Vlugt, Cornelis J. Elsevier,* Bas de Bruin* University of Amsterdam, Netherlands Science 2015 , 350 ,   6258 http://www.sciencemag.org/content/350/6258/298.full.pdf Abstract The reduction of esters and carboxylic acids to alcohols is a highly relevant conversion for the pharmaceutical and fine-chemical industries and for biomass conversion. It is commonly performed using stoichiometric reagents, and the catalytic hydrogenation of the acids previously required precious metals. Here we report the homogeneously catalyzed hydrogenation of carboxylic acids to alcohols using earth-abundant cobalt . This system, which pairs Co(BF4)2·6H2O with a tridentate phosphine ligand, can reduce a wide range of esters and carboxylic acids under relatively mild conditions (100°C, 80 bar H2) and reaches turnover numbers of up to 8000. プロポーズドメカニズムで、カルボキシル基の酸素とコバルト中心で、それぞれプロトンとヒドリドを受け取っていますが、このような遷移状態を取りやすそうなフェイシャル三配位、低原子価を安定化しそうなトリフォスフィン配位子がポイントでしょうか。 ...

Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water

Song Lin, 1,2 * Christian S. Diercks, 1,3 * Yue-Biao Zhang, 1,3,4 * Nikolay Kornienko, 1 Eva M. Nichols, 1,2 Yingbo Zhao, 1 Aubrey R. Paris, 1 Dohyung Kim, 5 Peidong Yang, 1,3,5,6 Omar M. Yaghi, 1,3,6,7 † Christopher J. Chang 1,2,8,9 † Science  11 September 2015:  Vol. 349  no. 6253  pp. 1208-1213  DOI:  10.1126/science.aac8343 http://www.sciencemag.org/content/349/6253/1208.short Abstract Conversion of carbon dioxide (CO 2 ) to carbon monoxide (CO) and other value-added carbon products is an important challenge for clean energy research. Here we report modular optimization of covalent organic frameworks (COFs), in which the building units are cobalt porphyrin catalysts linked by organic struts through imine bonds, to prepare a catalytic material for aqueous electrochemical reduction of CO 2 to CO. The catalysts exhibit high Faradaic efficiency (90%) and turnover numbers (up to 290,000, with initial turnover frequency of 9400 h...

Catalytic asymmetric hydroamination of unactivated internal olefins to aliphatic amines

Yang Yang, 1 * Shi-Liang Shi, 1 * Dawen Niu, 1 Peng Liu, 2 Stephen L. Buchwald 1 † Catalytic assembly of enantiopure aliphatic amines from abundant and readily available precursors has long been recognized as a paramount challenge in synthetic chemistry. Here, we describe a mild and general copper-catalyzed hydroamination that effectively converts unactivated internal olefins — an important yet unexploited class of abundant feedstock chemicals — into highly enantioenriched a -branched amines ( ≥ 96% enantiomeric excess) featuring two minimally differentiated aliphatic substituents. This method provides a powerful means to access a broad range of advanced, highly functionalized enantioenriched amines of interest in pharmaceutical research and other areas.  1 Depart ment of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.  2 Department of Chemis...

A synthetic Mn4Ca-cluster mimicking the oxygen-evolving center of photosynthesis

Chunxi Zhang 1 , * ,  Changhui Chen 2 ,  Hongxing Dong 2 , * ,  Jian-Ren Shen 3 ,  Holger Dau 4 , * ,  Jingquan Zhao 1 + Author Affiliations 1 Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China. 2 College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China. 3 Photosynthesis Research Center, Graduate School of Natural Science and Technology, Okayama University, Okayama 700-8530, Japan. 4 Department of Physics, Free University Berlin, Arnimallee 14, 14195 Berlin, Germany. ↵ * Corresponding author. E-mail:  chunxizhang@iccas.ac.cn  (C.Z.);  dhongxing@hrbeu.edu.cn  (H.D.);  holger.dau@fu-berlin.de  (H.D.) ABSTRACT EDITOR'S SUMMARY Photosynthetic splitting of water into oxygen by plants, algae, and cyanobacteria is catalyzed by the oxygen-evolving center (OEC). Synthetic mimics of the OEC, which is c...

Electronic structure of the oxygen-evolving complex in photosystem II prior to O-O bond formation

Nicholas Cox 1 , * ,  Marius Retegan 1 ,  Frank Neese 1 ,  Dimitrios A. Pantazis 1 ,  Alain Boussac 2 , Wolfgang Lubitz 1 , * + Author Affiliations 1 Max Planck Institute for Chemical Energy Conversion, Stiftstrasse 34-36, D-45470 Mülheim an der Ruhr, Germany. 2 Institut de Biologie et de Technologies de Saclay, CNRS UMR 8221, Commissariat à l’Énergie Atomique (CEA) Saclay, 91191 Gif-sur-Yvette, France. ↵ * Corresponding author. E-mail:  nicholas.cox@cec.mpg.de  (N.C.);  wolfgang.lubitz@cec.mpg.de  (W.L.) ABSTRACT EDITOR'S SUMMARY The photosynthetic protein complex photosystem II oxidizes water to molecular oxygen at an embedded tetramanganese-calcium cluster. Resolving the geometric and electronic structure of this cluster in its highest metastable catalytic state (designated S 3 ) is a prerequisite for understanding the mechanism of O-O bond formation. Here, multifrequency, multidimensional magnetic resonance spectr...
Imaging the Absolute Configuration of a Chiral Epoxide in the Gas Phase Philipp Herwig 1 , * ,  Kerstin Zawatzky 2 , * ,  Manfred Grieser 1 ,  Oded Heber 3 ,  Brandon Jordon-Thaden 1 , Claude Krantz 1 ,  Oldřich Novotný 1 , 4 ,  Roland Repnow 1 ,  Volker Schurig 5 ,  Dirk Schwalm 1 , 3 ,  Zeev Vager 3 , Andreas Wolf 1 ,  Oliver Trapp 2 , † ,  Holger Kreckel 1 , † + Author Affiliations 1 Max-Planck-Institut für Kernphysik, 69117 Heidelberg, Germany. 2 Organisch-Chemisches Institut, Ruprecht-Karls Universität Heidelberg, 69120 Heidelberg, Germany. 3 Department of Particle Physics and Astrophysics, Weizmann Institute, 76100 Rehovot, Israel. 4 Columbia Astrophysics Laboratory, Columbia University, New York, NY 10027, USA. 5 Institut für Organische Chemie, Eberhard Karls Universität Tübingen, 72076 Tübingen, Germany. ↵ † Corresponding author. E-mail:  holger.kreckel@mpi-hd.mpg.de  (H.K.);...