DOCSLIB.ORG

The Selective Oxidation of Sulfides to Sulfoxides Or Sulfones with Hydrogen Peroxide Catalyzed by a Dendritic Phosphomolybdate H

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
The Selective Oxidation of Sulfides to Sulfoxides Or Sulfones with Hydrogen Peroxide Catalyzed by a Dendritic Phosphomolybdate H catalysts Article The Selective Oxidation of Sulfides to Sulfoxides or Sulfones with Hydrogen Peroxide Catalyzed by a Dendritic Phosphomolybdate Hybrid Qiao-Lin Tong y, Zhan-Fang Fan y, Jian-Wen Yang, Qi Li, Yi-Xuan Chen, Mao-Sheng Cheng and Yang Liu * Key Laboratory of Structure-Based Drug Design & Discovery of Ministry of Education, School of Pharmaceutical Engineering, Shenyang Pharmaceutical University, Shenyang 110016, China; [email protected] (Q.-L.T.); [email protected] (Z.-F.F.); [email protected] (J.-W.Y.); [email protected] (Q.L.); [email protected] (Y.-X.C.); [email protected] (M.-S.C.) * Correspondence: [email protected] Qiao-Lin Tong and Zhan-Fang Fan contributed equally to this work. y Received: 6 September 2019; Accepted: 20 September 2019; Published: 22 September 2019 Abstract: The oxidation of sulfides to their corresponding sulfoxides or sulfones has been achieved using a low-cost poly(amidoamine) with a first-generation coupled phosphomolybdate hybrid as the catalyst and aqueous hydrogen peroxide as the oxidant. The reusability of the catalyst was revealed in extensive experiments. The practice of this method in the preparation of a smart drug Modafinil has proved its good applicability. Keywords: dendritic phosphomolybdate hybrid; sulfides; selective oxidation; hydrogen peroxide; reusability 1. Introduction Many biologically and chemically active molecules are constructed from sulfoxides and sulfones [1–5]. The oxidation of sulfides is a fundamental reaction as one of the most straightforward methods to afford sulfoxides and sulfones [6]. Many reagents, including peracids and halogen derivatives, are used in the common approaches of sulfoxidation reactions [7,8]. However, these common reactions often suffer from the formation of many environmentally unfriendly byproducts and low oxygen atom efficiency [6,9]. The development of environmentally benign catalysts and oxidants has become a research hotspot in recent green chemistry pursuits. Among various oxidants, aqueous hydrogen peroxide, which is inexpensive, is readily available, has a high effective oxygen content, is safe in operation and storage, and yields stoichiometric amounts of environmentally friendly water as a byproduct, is generally considered one of the most environmentally benign “green oxidants”. These characteristics of aqueous hydrogen peroxide have led to the development of many valuable methods for the oxidation of sulfides to sulfoxides and sulfones with various transition metal catalysts, including Ti(SO4)2/GOF [10], PDDA-SiV2W10 [11], the cobalt(III)–salen ion [12], TiO /AA/MoO [13], a copper–Schiff base complex [14], (C H N) [MoO(O ) (C O )] H O[6], 2 2 19 42 2 2 2 2 4 · 2 vanadium Schiff base complexes [15], and so on [16–19]. Polyoxometalates (POMs), which are composed of anionic transition metal–oxygen clusters [20–23], have been widely studied in the field of catalysis due to their excellent catalytic characteristics, including efficient catalytic activity and selectivity, controllable redox potential and acidity through the choice of the countercations and constituent elements [24,25]. Among these POMs, Keggin-type phosphomolybdic acid (H3Mo12O40, HPMo) has shown excellent catalytic performance in oxidation reactions with aqueous hydrogen peroxide [26–29]. Catalysts 2019, 9, 791; doi:10.3390/catal9100791 www.mdpi.com/journal/catalysts Catalysts 2019, 9, x FOR PEER REVIEW 2 of 10 Catalysts 2019, 9, 791 2 of 10 Dendritic poly(amidoamine) (PAMAM), which contains many amino groups, is an excellent organicDendritic modifier poly(amidoamine) for POMs [30–32]. (PAMAM), PAMAMs can which be functionalized contains many to amino couple groups, to various is an POMs, excellent and theorganic dendritic modifier structure, for POMs which [30 –is32 different]. PAMAMs from can the be common functionalized organic to modifier, couple to can various provide POMs, a local and microenvironmentthe dendritic structure, for the which POMs, is diwhichfferent may from result the commonin a help organicful “dendritic modifier, effect” can on provide the reaction a local [microenvironment33,34]. PAMAM-G for1 (poly(amidoamine) the POMs, which may with result the in first a helpful generation) “dendritic dendrimers effect” on have the reaction been used [33,34 in]. industrialPAMAM-G1 production (poly(amidoamine) and are relatively with the inexpensive. first generation) Moreover, dendrimers the amino have groups been used of the in PAMAM industrial- G1production dendrimer and can are be relatively protonated inexpensive. by HPMo, Moreover, and the PMo the amino anions groups and PAMAM of the PAMAM-G1-G1 can strongly dendrimer bond togethercan be protonated through electrostatic by HPMo, and interactions the PMo anions [35]. and PAMAM-G1 can strongly bond together through electrostaticHerein, interactionswe report a [35 heterogeneous,]. simple, recyclable, efficient, and green protocol for the oxidationHerein, of sulfides we report to sulfoxides a heterogeneous, and sulfones simple, with recyclable, 30 wt% H2 eOffi2 undercient, andmild greenconditions protocol in excellent for the yield, catalyzed by a composite based on PAMAM-G1 and HPMo (denoted as PAMAM-G1-PMo). To oxidation of sulfides to sulfoxides and sulfones with 30 wt% H2O2 under mild conditions in excellent theyield, best catalyzed of our knowledge, by a composite this basedis the first on PAMAM-G1 report of PAMAM and HPMo-G1-PMo (denoted as the as catalyst PAMAM-G1-PMo). used in the Tooxidation the best of of sulfides our knowledge, to sulfoxides this and is the sulfones. first report of PAMAM-G1-PMo as the catalyst used in the oxidation of sulfides to sulfoxides and sulfones. 2. Results and Discussion 2. Results and Discussion In this oxidation system, PAMAM-G1-PMo is utilized as the catalyst, and 30 wt% H2O2 is used as theIn oxidant. this oxidation We selected system, thioanisole PAMAM-G1-PMo (1a) as a ismodel utilized substrate as the catalyst,and found and that 30 less wt% than H2O 5%2 is of used 1a couldas the be oxidant. directly We oxidized selected by thioanisole 30 wt% H2O (1a)2 alone as a, even model when substrate the reaction and found time lasted that less to 6 than hours 5% (Table of 1a 1could, entry be 1) directly. However, oxidized when by 50 30 mg wt% of HPAMAM2O2 alone,-G1PMo even whenwas added the reaction to the timeabove lasted mixture, to 6 hsulfoxide (Table1, (entry1b) was 1). generated However, whensoon as 50 the mg oxidation of PAMAM-G1PMo product. In wasaddition, added control to the experiments above mixture, were sulfoxide performed (1b) wasto assess generated the individually soon as the catalytic oxidation activity product. of HPMo In addition, and PAMAM control-G1 experiments dendrimer. were Regrettably, performed only to 8%assess of starting the individually material could catalytic be activityoxidized of by HPMo 30 wt% and H PAMAM-G12O2 catalyzing dendrimer. by HPMo alone Regrettably, (Table only1, entry 8% 2),of startingand much material less yield could was be oxidizedobtained bywhen 30 wt% catalyzing H2O2 catalyzing by PAMAM by- HPMoG1 dendrimer alone (Table alone1, ( entryTable 2), 1, entryand much 3). When less yield the reaction was obtained was carried when catalyzing out in the by presence PAMAM-G1 of PAMAM dendrimer-G1- alonePMo, (Tableup to 185%, entry of 3).1a Whencould be the oxidized reaction within was carried 4 hours out (Table in the 1, presenceentry 4), indicating of PAMAM-G1-PMo, that PAMAM up-G1 to- 85%PMo ofpla 1ayed could a very be significantoxidized within role in 4 prompting h (Table1, entry the process 4), indicating of this thatoxidation PAMAM-G1-PMo effectively. played a very significant role in prompting the process of this oxidation effectively. Table 1. Control experiments with different components as catalyst a. Table 1. Control experiments with different components as catalyst a. b Entry Catalyst Time (h) Temperature (◦C) Yield (%) Entry Catalyst Time (h) Temperature (°C ) Yield b (%) 1 — 6.0 25 4 1 — 6.0 25 4 2 HPMo 8.0 25 8 32 PAMAM-G1HPMo 8.0 8.0 25 258 0.5 43 PAMAM-G1-PMoPAMAM-G1 8.0 4.0 25 250.5 85 4 PAMAM-G1-PMo 4.0 25 85 a a Reaction conditions: 1a (62 mg, 0.5 mmol), solvent (8 mL), catalyst (50 mg), 30 wt% H2O2 (63 mg, 0.55 mmol); bReactionIsolated yield.conditions: HPMo: 1a Keggin-type (62 mg, 0.5 phosphomolybdicmmol), solvent (8 acid. mL), PAMAM-G1:catalyst (50 mg), poly(amidoamine) 30 wt% H2O2 with(63 mg, the 0.55 first mmol);generation. b Isolated PAMAM-G1-PMo: yield. HPM compositeo: Keggin based-type on phosphomolybdic PAMAM-G1 and HPMo. acid. PAMAM-G1: poly(amidoamine) with the first generation. PAMAM-G1-PMo: composite based on PAMAM-G1 and HPMo. TToo optimize the conditions for the oxidation of sulfides sulfides to sulfoxides,sulfoxides, we firstfirst investigated the effectseffects of the solvent in thethe PAMAM-G1-PMo-catalyzedPAMAM-G1-PMo-catalyzed reactionreaction system.system. The The results results are listed in Table1 1.. After screening different di fferent solvents, solvents, we we observed observed that that when when MeOH MeOH or or95% 95% EtOH EtOH was was used used as theas the solvent solvent in the in the presence presence of PAMAM of PAMAM-G1-PMo,-G1-PMo, we we obtained obtained the the desired desired sulfoxide sulfoxide products products (1b (1b)) in relativelyin relatively high high yields yields of 85 of– 85–90%90% and and a minor a minor amount amount of starting of starting material material (1a) (1a)remained remained,, without without any sulfonesany sulfones (Table (Table 2, entries2, entries 1–2). 1–2). However, However, the conversion the conversion was wasrelatively relatively poor poor when when the reaction the reaction was was carried out in other solvents, including EtOH, CH COCH , CH COOC H and i-PrOH (Table2, carried out in other solvents, including EtOH, CH3COCH3 3, 3CH3COOC3 2H25, 5,and i-PrOH (Table 2, entries 3–6).3–6).
Load more

Recommended publications
  • Dimethyl Sulfoxide MSDS
    He a lt h 1 2 Fire 2 2 0 Re a c t iv it y 0 Pe rs o n a l Pro t e c t io n F Material Safety Data Sheet Dimethyl sulfoxide MSDS Section 1: Chemical Product and Company Identification Product Name: Dimethyl sulfoxide Contact Information: Catalog Codes: SLD3139, SLD1015 Sciencelab.com, Inc. 14025 Smith Rd. CAS#: 67-68-5 Houston, Texas 77396 RTECS: PV6210000 US Sales: 1-800-901-7247 International Sales: 1-281-441-4400 TSCA: TSCA 8(b) inventory: Dimethyl sulfoxide Order Online: ScienceLab.com CI#: Not applicable. CHEMTREC (24HR Emergency Telephone), call: Synonym: Methyl Sulfoxide; DMSO 1-800-424-9300 Chemical Name: Dimethyl Sulfoxide International CHEMTREC, call: 1-703-527-3887 Chemical Formula: (CH3)2SO For non-emergency assistance, call: 1-281-441-4400 Section 2: Composition and Information on Ingredients Composition: Name CAS # % by Weight Dimethyl sulfoxide 67-68-5 100 Toxicological Data on Ingredients: Dimethyl sulfoxide: ORAL (LD50): Acute: 14500 mg/kg [Rat]. 7920 mg/kg [Mouse]. DERMAL (LD50): Acute: 40000 mg/kg [Rat]. Section 3: Hazards Identification Potential Acute Health Effects: Slightly hazardous in case of inhalation (lung irritant). Slightly hazardous in case of skin contact (irritant, permeator), of eye contact (irritant), of ingestion, . Potential Chronic Health Effects: Slightly hazardous in case of skin contact (irritant, sensitizer, permeator), of ingestion. CARCINOGENIC EFFECTS: Not available. MUTAGENIC EFFECTS: Mutagenic for mammalian somatic cells. Mutagenic for bacteria and/or yeast. TERATOGENIC EFFECTS: Not available. DEVELOPMENTAL TOXICITY: Not available. The substance may be toxic to blood, kidneys, liver, mucous membranes, skin, eyes.
    [Show full text]
  • A Flexible All-Atom Model of Dimethyl Sulfoxide for Molecular Dynamics Simulations
    1074 J. Phys. Chem. A 2002, 106, 1074-1080 A Flexible All-Atom Model of Dimethyl Sulfoxide for Molecular Dynamics Simulations Matthew L. Strader and Scott E. Feller* Department of Chemistry, Wabash College, CrawfordsVille, Indiana 47933 ReceiVed: October 1, 2001 An all-atom, flexible dimethyl sulfoxide model has been created for molecular dynamics simulations. The new model was tested against experiment for an array of thermodynamic, structural, and dynamic properties. Interactions with water were compared with previous simulations and experimental studies, and the unusual changes exhibited by dimethyl sulfoxide/water mixtures, such as the enhanced structure of the solution, were reproduced by the new model. Particular attention was given to the design of the electrostatic component of the force field and to providing compatibility with the CHARMM parameter sets for biomolecules. Introduction mixtures,14,17,18 and its interaction with a phospholipid bi- Theoretical methods for the investigation of biological layer.19,20 Simulations published to date have utilized a rigid, molecules have become commonplace in biochemistry and united-atom model where each methyl group is represented by biophysics.1 These approaches provide detailed atomic models a single atomic center and all bond lengths and angles are fixed of biological systems, from which structure-function relation- at their equilibrium values. Another feature common to most ships can be elucidated. Methods based on empirical force fields, of these models is the use of the same charge distribution, such as molecular dynamics (MD) simulations, allow for namely that obtained by Rao and Singh from a Hartree-Fock calculations on relatively large systems, e.g., complete biomol- 6-31G* ab initio quantum mechanical calculation.21 ecules or assemblies of biomolecules in their aqueous environ- Recent advances in computer hardware now allow a flexible, ment.
    [Show full text]
  • The Hydrolysis of Carbonyl Sulfide at Low Temperature: a Review
    Hindawi Publishing Corporation The Scientific World Journal Volume 2013, Article ID 739501, 8 pages http://dx.doi.org/10.1155/2013/739501 Review Article The Hydrolysis of Carbonyl Sulfide at Low Temperature: A Review Shunzheng Zhao, Honghong Yi, Xiaolong Tang, Shanxue Jiang, Fengyu Gao, Bowen Zhang, Yanran Zuo, and Zhixiang Wang Department of Environmental Engineering, College of Civil and Environmental Engineering, University of Science and Technology Beijing, Beijing 100083, China Correspondence should be addressed to Honghong Yi; [email protected] Received 16 May 2013; Accepted 19 June 2013 Academic Editors: S. Niranjan, L. Wang, and Q. Wang Copyright © 2013 Shunzheng Zhao et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Catalytic hydrolysis technology of carbonyl sulfide (COS) at low temperature was reviewed, including the development of catalysts, reaction kinetics, and reaction mechanism of COS hydrolysis. It was indicated that the catalysts are mainly involved metal oxide and activated carbon. The active ingredients which can load on COS hydrolysis catalyst include alkali metal, alkaline earth metal, transition metal oxides, rare earth metal oxides, mixed metal oxides, and nanometal oxides. The catalytic hydrolysis of COS isa first-order reaction with respect to carbonyl sulfide, while the reaction order of water changes as the reaction conditions change. The controlling steps are also different because the reaction conditions such as concentration of carbonyl sulfide, reaction temperature, water-air ratio, and reaction atmosphere are different. The hydrolysis of carbonyl sulfide is base-catalyzed reaction, and the forceof thebasesitehasanimportanteffectonthehydrolysisofcarbonylsulfide.
    [Show full text]
  • Dimethyl Sulfoxide Oxidation of Primary Alcohols
    Western Michigan University ScholarWorks at WMU Master's Theses Graduate College 8-1966 Dimethyl Sulfoxide Oxidation of Primary Alcohols Carmen Vargas Zenarosa Follow this and additional works at: https://scholarworks.wmich.edu/masters_theses Part of the Chemistry Commons Recommended Citation Zenarosa, Carmen Vargas, "Dimethyl Sulfoxide Oxidation of Primary Alcohols" (1966). Master's Theses. 4374. https://scholarworks.wmich.edu/masters_theses/4374 This Masters Thesis-Open Access is brought to you for free and open access by the Graduate College at ScholarWorks at WMU. It has been accepted for inclusion in Master's Theses by an authorized administrator of ScholarWorks at WMU. For more information, please contact [email protected]. DIMETHYL SULFOXIDE OXIDATION OF PRIMARY ALCOHOLS by Carmen Vargas Zenarosa A thesis presented to the Faculty of the School of Graduate Studies in partial fulfillment of the Degree of Master of Arts Western Michigan University Kalamazoo, Michigan August, 1966 ACKNOWLEDGMENTS The author wishes to express her appreciation to the members of her committee, Dr, Don C. Iffland and Dr. Donald C, Berndt, for their helpful suggestions and most especially to Dr, Robert E, Harmon for his patience, understanding, and generous amount of time given to insure the completion of this work. Appreciation is also expressed for the assistance given by her. colleagues. The author acknowledges the assistance given by the National Institutes 0f Health for this research project. Carmen Vargas Zenarosa ii TABLE OF CONTENTS Page
    [Show full text]
  • In This Handout, All of Our Functional Groups Are Presented As Condensed Line Formulas, 2D and 3D Formulas and with Nomenclature Prefixes and Suffixes (If Present)
    In this handout, all of our functional groups are presented as condensed line formulas, 2D and 3D formulas and with nomenclature prefixes and suffixes (if present). Organic names are built on a foundation of alkanes, alkenes and alkynes. Those examples are presented first and you need to know those rules. The strategies can be found in Chapter 4 of our textbook (alkanes: pages 93-98, cycloalkanes 102-104, alkenes: pages 104-110, alkynes: pages 112-113 and combinations of all of them 113-115). After introducing examples of alkanes, alkenes, alkynes and combinations of them, the functional groups are presented in order of priority. A few nomenclature examples are provided for each of the functional groups. Examples of the various functional groups are presented on pages 115-135 in the textbook. Two overview pages are on pages 136-137. Some functional groups have a suffix name when they are the highest priority functional group and a prefix name when they are not the highest priority group, and these are added to the skeletal names with identifying numbers and stereochemistry terms (E and Z for alkenes, R and S for chiral centers and cis and trans for rings). Several low priority functional groups only have a prefix name. A few additional special patterns are shown on pages 98-102. The only way to learn this topic is practice (over and over). The best practice approach is to actually write out the names (on an extra piece of paper or on a white board, and then do it again). The same functional groups are used throughout the entire course.
    [Show full text]
  • Synthesis and Characterization of Functionalized Poly(Arylene Ether Sulfone)S Using Click Chemistry
    Wright State University CORE Scholar Browse all Theses and Dissertations Theses and Dissertations 2016 Synthesis and Characterization of Functionalized Poly(arylene ether sulfone)s using Click Chemistry Kavitha Neithikunta Wright State University Follow this and additional works at: https://corescholar.libraries.wright.edu/etd_all Part of the Chemistry Commons Repository Citation Neithikunta, Kavitha, "Synthesis and Characterization of Functionalized Poly(arylene ether sulfone)s using Click Chemistry" (2016). Browse all Theses and Dissertations. 1650. https://corescholar.libraries.wright.edu/etd_all/1650 This Thesis is brought to you for free and open access by the Theses and Dissertations at CORE Scholar. It has been accepted for inclusion in Browse all Theses and Dissertations by an authorized administrator of CORE Scholar. For more information, please contact [email protected]. SYNTHESIS AND CHARACTERIZATION OF FUNCTIONALIZED POLY (ARYLENE ETHER SULFONE)S USING CLICK CHEMSITRY A thesis submitted in partial fulfilment of the requirements for the degree of Master of Science By Kavitha Neithikunta B.sc Osmania University, 2010 2016 Wright State University WRIGHT STATE UNIVERSITY GRADUATE SCHOOL August 26, 2016 I HEREBY RECOMMEND THAT THE THESIS PREPARED UNDER MYSUPERVISION BY Kavitha Neithikunta ENTITLED Synthesis and Characterization of Functionalized Poly(arylene ether sulfone)s using Click chemistry BE ACCEPTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF Master of Science __________________________ Eric Fossum, Ph.D. Thesis Advisor ___________________________ David Grossie, Ph.D. Chair, Department of Chemistry Committee on Final Examination ____________________________ Eric Fossum, Ph.D. _____________________________ Daniel M. Ketcha, Ph.D. _____________________________ William A. Feld, Ph.D. _______________________________ Robert E. W. Fyffe, Ph.D Vice President for Research and Dean of the Graduate School ABSTRACT Neithikunta, Kavitha M.S., Department of Chemistry, Wright State University, 2016.
    [Show full text]
  • Removal of Hydrogen Sulfide, Benzene and Toluene by a Fluidized Bed Bioreactor
    Korean J. Chem. Eng., 23(1), 148-152 (2006) Removal of hydrogen sulfide, benzene and toluene by a fluidized bed bioreactor Kwang Joong Oh†, Ki Chul Cho, Young Hean Choung, Suk Kyong Park*, Sung Ki Cho* and Donguk Kim* Department of Environmental Engineering, Pusan National University, Busan 609-735, Korea *Department of Pharmaceutical Engineering, Inje University, Gimhae, Gyongnam 621-749, Korea (Received 11 May 2005 • accepted 5 September 2005) Abstract−The dominant off gases from publicly owned treatment works include hydrogen sulfide, benzene, and toluene. In this research, hydrogen sulfide oxidized by Bacillus cereus, and benzene with toluene were removed by VOC-degrading microbial consortium. The optimum operating condition of the fluidized bed bioreactor including both microorganisms was 30 oC, pH 6-8, and 150 cm of liquid bed height. The critical loading rate of hydrogen sulfide, benzene and toluene in the bioreactor was about 15 g/m3 h, 10 g/m3 h and 12 g/m3 h, respectively. The fluidized bed bioreactor showed an excellent elimination capacity for 580 hours of continuous operation, and maintained stable removal efficiency at sudden inlet concentration changes. Key words: Hydrogen Sulfide, Benzene, Toluene, Fluidized Bed Bioreactor, Microbial Consortium INTRODUCTION EXPERIMENTAL The major odorous compounds of off-gases from publicly owned 1. Cells 2− treatment works (POTWs) include hydrogen sulfide and VOCs such H2S was oxidized to SO4 by Bacillus cereus which was sepa- as benzene and toluene [Cox and Deshusses, 2001]. Odorous gases rated from closed coal mines in Hwasoon, Korea. Concentration of have been conventionally treated by physical and chemical treat- sulfate in solution was measured by absorbance at 460 nm after reac- ments like absorption, adsorption and catalytic oxidation [Cooper tion with BaCl2·H2O [Cha et al., 1994].
    [Show full text]
  • Provisional Peer-Reviewed Toxicity Values for Carbonyl Sulfide (Carbon Oxide Sulfide; Casrn 463 58 1)
    EPA/690/R-15/002F l Final 9-29-2015 Provisional Peer-Reviewed Toxicity Values for Carbonyl Sulfide (Carbon Oxide Sulfide) (CASRN 463-58-1) Superfund Health Risk Technical Support Center National Center for Environmental Assessment Office of Research and Development U.S. Environmental Protection Agency Cincinnati, OH 45268 AUTHORS, CONTRIBUTORS, AND REVIEWERS CHEMICAL MANAGER John C. Lipscomb, PhD, DABT, Fellow ATS National Center for Environmental Assessment, Cincinnati, OH DRAFT DOCUMENT PREPARED BY SRC, Inc. 7502 Round Pond Road North Syracuse, NY 13212 PRIMARY INTERNAL REVIEWERS Jeff Swartout National Center for Environmental Assessment, Cincinnati, OH This document was externally peer reviewed under contract to Eastern Research Group, Inc. 110 Hartwell Avenue Lexington, MA 02421-3136 Questions regarding the contents of this document may be directed to the U.S. EPA Office of Research and Development’s National Center for Environmental Assessment, Superfund Health Risk Technical Support Center (513-569-7300). ii Carbonyl Sulfide TABLE OF CONTENTS COMMONLY USED ABBREVIATIONS AND ACRONYMS .................................................. iv BACKGROUND .............................................................................................................................1 DISCLAIMERS ...............................................................................................................................1 QUESTIONS REGARDING PPRTVs ............................................................................................1
    [Show full text]
  • Ethyl Methyl Sulfone-Based Electrolytes for Lithium Ion Battery Applications
    energies Article Ethyl Methyl Sulfone-Based Electrolytes for Lithium Ion Battery Applications Peter Hilbig 1, Lukas Ibing 2, Ralf Wagner 2, Martin Winter 1,2 and Isidora Cekic-Laskovic 1,2,* 1 Helmholtz-Institute Münster, IEK-12, Forschungszentrum Jülich GmbH, Corrensstrasse 46, 48149 Münster, Germany; [email protected] (P.H.); [email protected] (M.W.) 2 MEET Battery Research Center/Institute of Physical Chemistry, University of Münster, Corrensstrasse 46, 48149 Münster, Germany; [email protected] (L.I.); [email protected] (R.W.) * Correspondence: [email protected]; Tel.: +49-251-83-36805 Received: 20 July 2017; Accepted: 28 August 2017; Published: 1 September 2017 Abstract: Sulfone-based electrolytes, known for their higher oxidative stability compared to the typically used organic carbonate-based electrolytes, are considered promising electrolytes for high voltage cathode materials towards the objective of obtaining increased energy density in lithium ion batteries. Nevertheless, sulfones suffer from high viscosity as well as incompatibility with highly graphitic anode materials, which limit their application. In this paper, the effect of fluoroethylene carbonate (FEC) as an electrolyte additive for the application of ethyl methyl sulfone (EMS) electrolytes containing LiPF6 as conducting salt, is studied in graphite-based cells by means of selected electrochemical and spectroscopic methods. In addition, influence of ethylene acetate (EA) as co-solvent on the electrolyte viscosity and conductivity of the EMS-based electrolytes is discussed, revealing improved overall nickel cobalt manganese oxide (NMC)/graphite cell performance. X-ray photoelectron spectroscopy (XPS) measurements provide information about the surface chemistry of the graphite electrodes after galvanostatic cycling.
    [Show full text]
  • Photoredox Α‑Vinylation of Α‑Amino Acids and N‑Aryl Amines Adam Noble and David W
    Communication pubs.acs.org/JACS Open Access on 07/14/2015 Photoredox α‑Vinylation of α‑Amino Acids and N‑Aryl Amines Adam Noble and David W. C. MacMillan* Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, United States *S Supporting Information radicals to the direct synthesis of allylic amines from N-aryl ABSTRACT: A new coupling protocol has been amines or α-amino acids. Specifically, we hypothesized that allyl developed that allows the union of vinyl sulfones with amines should be accessible via exposure of α-amino radicals to photoredox-generated α-amino radicals to provide allylic olefins that can generically participate in radical-based vinylation amines of broad diversity. Direct C−H vinylations of N- mechanisms (i.e., incorporate leaving groups that are susceptible aryl tertiary amines, as well as decarboxylative vinylations to single-electron β-elimination pathways). As an overarching of N-Boc α-amino acids, proceed in high yield and with goal of this work we hoped to demonstrate that photoredox- excellent olefin geometry control. The utility of this new generated α-amino radicals provide a complementary approach allyl amine forming reaction has been demonstrated via the to allyl amine production in comparison to stoichiometric metal- syntheses of several natural products and a number of based technologies. Herein, we describe the successful execution established pharmacophores. of these ideals and present the first direct C−H vinylation of N- aryl tertiary amines and the first decarboxylative olefination of N- Boc α-amino acids using vinyl sulfones in the presence of isible light photoredox catalysis has recently emerged as a iridium-based MLCT catalysts.
    [Show full text]
  • Thiol–Disulfide Exchange Is Involved in the Catalytic Mechanism of Peptide Methionine Sulfoxide Reductase
    Thiol–disulfide exchange is involved in the catalytic mechanism of peptide methionine sulfoxide reductase W. Todd Lowther*, Nathan Brot†, Herbert Weissbach‡, John F. Honek¶, and Brian W. Matthews*§ *Institute of Molecular Biology, Howard Hughes Medical Institute and Department of Physics, 1229 University of Oregon, Eugene, OR 97403-1229; †Hospital for Special Surgery, Cornell University Medical Center, New York, NY 10021; ‡Center for Molecular Biology and Biotechnology, Florida Atlantic University, Boca Raton, FL 33431; and ¶Department of Chemistry, University of Waterloo, Waterloo, ON, Canada N2L 3G1 Contributed by Herbert Weissbach, April 6, 2000 Peptide methionine sulfoxide reductase (MsrA; EC 1.8.4.6) re- L-Met(O), D-Met(O), N-Ac-L-Met(O), dimethyl sulfoxide, and verses the inactivation of many proteins due to the oxidation of L-ethionine sulfoxide (12, 17). However, the most important critical methionine residues by reducing methionine sulfoxide, physiological role of MsrAs is to reduce Met(O) residues in Met(O), to methionine. MsrA activity is independent of bound proteins (12, 17, 18). The enzymatic activity of MsrAs depends metal and cofactors but does require reducing equivalents from on the reducing equivalents from DTT or a thioredoxin- either DTT or a thioredoxin-regenerating system. In an effort to regenerating system (12, 17), suggesting the potential involve- understand these observations, the four cysteine residues of ment of one or more cysteine residues. To test this involve- bovine MsrA were mutated to serine in a series of permutations. ment, the four cysteine residues of bovine MsrA (bMsrA, Fig. An analysis of the enzymatic activity of the variants and their 1) were mutated to serine in a series of permutations.
    [Show full text]
  • Converting Copper Sulfide to Copper with Surface Sulfur For
    ARTICLE https://doi.org/10.1038/s41467-021-24059-y OPEN Converting copper sulfide to copper with surface sulfur for electrocatalytic alkyne semi- hydrogenation with water ✉ Yongmeng Wu 1,3, Cuibo Liu 1,3, Changhong Wang 1,3, Yifu Yu 1, Yanmei Shi 1 & Bin Zhang 1,2 Electrocatalytic alkyne semi-hydrogenation to alkenes with water as the hydrogen source using a low-cost noble-metal-free catalyst is highly desirable but challenging because of their 1234567890():,; over-hydrogenation to undesired alkanes. Here, we propose that an ideal catalyst should have the appropriate binding energy with active atomic hydrogen (H*) from water electrolysis and a weaker adsorption with an alkene, thus promoting alkyne semi-hydrogenation and avoiding over-hydrogenation. So, surface sulfur-doped and -adsorbed low-coordinated copper nano- wire sponges are designedly synthesized via in situ electroreduction of copper sulfide and enable electrocatalytic alkyne semi-hydrogenation with over 99% selectivity using water as the hydrogen source, outperforming a copper counterpart without surface sulfur. Sulfur 2− + 2− + anion-hydrated cation (S -K (H2O)n) networks between the surface adsorbed S and K in the KOH electrolyte boost the production of active H* from water electrolysis. And the trace doping of sulfur weakens the alkene adsorption, avoiding over-hydrogenation. Our catalyst also shows wide substrate scopes, up to 99% alkenes selectivity, good reducible groups compatibility, and easily synthesized deuterated alkenes, highlighting the promising potential of this method. 1 Department of Chemistry, Institute of Molecular Plus, School of Science, Tianjin University, Tianjin, China. 2 Tianjin Key Laboratory of Molecular Optoelectronic Science, Collaborative Innovation Center of Chemical Science and Engineering, Tianjin, China.
    [Show full text]