- Full Organic Aqueous Battery Based on TEMPO Small Molecule with Millimeter-Thick Electrodes
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Thick electrodes with sodium and even anion intercalation organic compounds integrated in a neutral-pH aqueous battery offer unique advantages in terms of round trip efficiency, environmental impact, and scalability for off- or on-grid renewable energy st
- Perticarari, Sofia,Grange, Elodie,Doizy, Tom,Pellegrin, Yann,Quarez, Eric,Oyaizu, Kenichi,Fernandez-Ropero, Antonio Jesus,Guyomard, Dominique,Poizot, Philippe,Odobel, Fabrice,Gaubicher, Jo?l
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Read Online
- The Photodynamic Covalent Bond: Sensitized Alkoxyamines as a Tool to Shift Reaction Networks Out-of-Equilibrium Using Light Energy
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We implement sensitized alkoxyamines as "photodynamic covalent bonds" - bonds that, while being stable in the dark at ambient temperatures, upon photoexcitation efficiently dissociate and recombine to the bound state in a fast thermal reaction. This type of bond allows for the photochemically induced exchange of molecular building blocks and resulting constitutional variation within dynamic reaction networks. To this end, alkoxyamines are coupled to a xanthone unit as triplet sensitizer enabling their reversible photodissociation into two radical species. By studying the photochemical properties of three generations of sensitized alkoxyamines it became clear that the nature and efficiency of triplet energy transfer from the sensitizer to the alkoxyamine bond as well as the reversibility of photodissociation crucially depends on the structure of the nitroxide terminus. By employing the thus designed photodynamic covalent bonding motif, we demonstrate how to use light energy to shift a dynamic covalent reaction network away from its thermodynamic minimum into a photostationary state. The network could be repeatedly switched between its minimum and kinetically trapped out-of-equilibrium state by thermal scrambling and selective photoactivation of sensitized alkoxyamines, respectively.
- Herder, Martin,Lehn, Jean-Marie
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supporting information
p. 7647 - 7657
(2018/06/26)
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- METHOD OF PRODUCING N-OXYL COMPOUND
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PROBLEM TO BE SOLVED: To provide a safe and convenient method of producing an N-oxyl compound without using a special reaction device. SOLUTION: A compound represented by a following formula is obtained by the reaction between 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl and aromatic acid chloride in the presence of tertiary amine (where at least one of R1 and R2 is a group represented by a following formula). COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0063; 0064
(2016/12/16)
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- Iron chloride/4-acetamido-TEMPO/sodium nitrite-catalyzed aerobic oxidation of primary alcohols to the aldehydes
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A variety of 4-substituted 2,2,6,6-tetramethylpiperidyl-1-oxy (TEMPO) derivatives has been screened for their ability in the oxidation of primary alcohols to the aldehydes with dioxygen under mild conditions. An evaluation of the efficiency of these 4-substituted TEMPO derivatives in the alcohol oxidation may allow an insight into the effect of the structural variations of TEMPO on the oxidation of alcohols, which should facilitate catalyst design and screening efforts. Based on the screening results of 4-substituted TEMPO derivatives, the catalyst comprised of 4-acetamidoTEMPO, iron chloride and sodium nitrite, has been developed for the highly efficient oxidation of a wide range of primary alcohols including primary aliphatic alcohols to the corresponding aldehydes under mild conditions.
- Yin, Weili,Chu, Changhu,Lu, Qiongqiong,Tao, Jianwei,Liang, Xinmiao,Liu, Renhua
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supporting information; experimental part
p. 113 - 118
(2010/07/03)
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- Inhibiting polymerization of vinyl aromatic monomers
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When a nitroxyl compound is heated in an oxygen-free atmosphere with a vinyl aromatic monomer at 50-140 DEG C. for up to 60 days, it forms an activated inhibitor mixture which is superior to the nitroxyl compound itself in preventing the premature polymerization of a vinyl aromatic monomer during its processing and purification.
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- Polymerization inhibition of acrylates using blends of nitroxides
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Ethylenically unsaturated carboxyl monomers, such as acrylic or methacrylic acid or their esters, are protected from premature polymerization during manufacture and storage in the presence or absence of water by the incorporation therein of an effective stabilizing amount of a blend two or more nitroxides. Some of these blends provide synergistic stabilization efficacy much superior to the stabilization results obtained by use of either nitroxide alone.
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- Method for inhibiting premature polymerization of vinyl aromatic monomers
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Nitroxyl inhibitors in combination with some oxygen reduce the premature polymerization of vinyl aromatic monomers during the manufacturing processes for such monomers. Even small quantities of air used in combination with the nitroxyl inhibitors result in vastly prolonged inhibition times for said monomers.
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- Inhibiting polymerization of vinyl aromatic monomers
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The polymerization of a vinyl aromatic compound, such as styrene, during distillation or purification is very effectively inhibited by the presence of at least one stable nitroxyl compound together with at least one aromatic nitro compound.
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- Prevention of oxidation in petrochemical extraction solvents
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A wide variety of hindered amine compounds are effective as antioxidant stabilizers to prevent the oxidation of liquid hydrocarbons and of oxygenated compounds, such as sulfolane or tetraethylene glycol, used as extraction solvents in the petroleum industry.
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- A Reaction of Nitroxides with Ethyl Mercaptane: A Mild Method for the Conversion of Nitroxides into Their Corresponding Amines
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The mild reduction of the nitroxides 1a-j to the corresponding sterically hindered amines 2a-j by means of ethyl mercaptane is reported.The reaction mixtures of 1a,b,g were analyzed by glc/ms.
- Zakrzewski, Jerzy
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p. 803 - 808
(2007/10/02)
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- 13. Photofragmentation of Dibenzyl Ketone in the Presence of Tetramethylpiperidine Derivatives. Studies on Light Stabilizer Mechanisms
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The interaction of selected tetramethylpiperidine derivatives with radicals arising from the Norrish-type I cleavage of dibenzyl ketone under oxygen was studied.Product analyses and kinetic studies showed that the investigated sterically hindered piperidine derivatives have a pronounced effect on both the nature and distribution of the products of photolysis of dibenzyl ketone in the presence of oxygen.Observations indicated that the phenylperacetoxyl radical is formed as an intermediate during irradiation and that is interacts with additives used.Possible mechanism of the reactions studied are discussed.The observation that oxidation of an isolated duoble bond by radicals formed in dibenzyl ketone photolysis under oxygen is strongly inhibited in the presence of the studied sterically hindered amines is discussed in the light of the results presented. the findings are considered in realtion to the problem of polymer stabilization.
- Felder, Bruno,Schumacher, Rolf,Sitek, Franciszek
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p. 132 - 147
(2007/10/02)
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