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Title: Redox Behavior of 2,3-Diamino-1,4-naphthoquinone and its N -Alkylated Derivatives

Authors:
 [1];  [2];  [1];  [3];  [4]
  1. Department of Chemistry and Biochemistry, University of Colorado, Boulder CO 80309-0215 U.S.A.
  2. J. Heyrovský Institute of Physical Chemistry AS CR, Dolejškova 3 18223 Prague Czech Republic
  3. J. Heyrovský Institute of Physical Chemistry AS CR, Dolejškova 3 18223 Prague Czech Republic, Institute of Organic Chemistry and Biochemistry AS CR, Flemingovo nám. 2 16610 Prague 6 Czech Republic
  4. Department of Chemistry and Biochemistry, University of Colorado, Boulder CO 80309-0215 U.S.A., Institute of Organic Chemistry and Biochemistry AS CR, Flemingovo nám. 2 16610 Prague 6 Czech Republic
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1400793
Grant/Contract Number:
SC0007004; 15-19143S; 16-03085S; RVO: 61388963
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Electroanalysis
Additional Journal Information:
Journal Volume: 28; Journal Issue: 11; Related Information: CHORUS Timestamp: 2017-10-20 15:54:05; Journal ID: ISSN 1040-0397
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Dron, Paul I., Ramešová, Šárka, Holloran, Nicholas P., Pospíšil, Lubomír, and Michl, Josef. Redox Behavior of 2,3-Diamino-1,4-naphthoquinone and its N -Alkylated Derivatives. Germany: N. p., 2016. Web. doi:10.1002/elan.201600356.
Dron, Paul I., Ramešová, Šárka, Holloran, Nicholas P., Pospíšil, Lubomír, & Michl, Josef. Redox Behavior of 2,3-Diamino-1,4-naphthoquinone and its N -Alkylated Derivatives. Germany. doi:10.1002/elan.201600356.
Dron, Paul I., Ramešová, Šárka, Holloran, Nicholas P., Pospíšil, Lubomír, and Michl, Josef. 2016. "Redox Behavior of 2,3-Diamino-1,4-naphthoquinone and its N -Alkylated Derivatives". Germany. doi:10.1002/elan.201600356.
@article{osti_1400793,
title = {Redox Behavior of 2,3-Diamino-1,4-naphthoquinone and its N -Alkylated Derivatives},
author = {Dron, Paul I. and Ramešová, Šárka and Holloran, Nicholas P. and Pospíšil, Lubomír and Michl, Josef},
abstractNote = {},
doi = {10.1002/elan.201600356},
journal = {Electroanalysis},
number = 11,
volume = 28,
place = {Germany},
year = 2016,
month = 9
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1002/elan.201600356

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  • Derivatives of 1,4-naphthoquinone, 2-chloro-3-((2-(dimethylpropylammonio)ethyl)amino)-1,4-naphthoquinone bromide, Ia, and 2-chloro-3-((2-(dimethyl(3-(trimethoxysilyl)propyl)ammonio)ethyl)amino)-1,4-naphthoquinone bromide, Ib, have been synthesized and used as solution and surface-bound catalysts, respectively, for the electrochemical and photoelectrochemical reduction of O/sub 2/ to H/sub 2/O/sub 2/. The surface derivatizing reagent Ib having the -Si(OCH/sub 3/)/sub 3/ functionality can be used to functionalize a variety of surfaces including electrode materials and high surface area oxides. The surface reagent, (Q/QH/sub 2/)/sub surf/, has the same E/sup 0/' as Ia in solution, approx. -0.4 V vs. SCE at pH 7. The (QH/sub 2/)/sub surf/ reacts with O/sub 2/ in aqueous electrolyte at pH 7 withmore » a rate constant > 10/sup 5/ M/sup -1/s/sup -1/ to form H/sub 2/O/sub 2/ and (Q)/sub surf/. High surface area oxides functionalized with Ib yield (M/sub x/O/sub y/)-(Q) that can be electrochemically reduced to (M/sub x/O/sub y/)-(QH/sub 2/) via mediation by a low concentration of Ia in solution. The (M/sub x/O/sub y/)-(QH/sub 2/) can be isolated from the electrolyte solution by filtration and reacted with O/sub 2//H/sub 2/O to yield up to 0.1 M H/sub 2/O/sub 2/ in H/sub 2/O free of electrolyte. Study of the reduction of Ia at rotating-W-disk electrodes derivatized with Ib shows that the redox equilibration of the solution quinone and surface quinone is rapid. Reduction of (Q)/sub surf/ or Ia at visible light illuminated p-WS/sub 2/ can be effected at an electrode potential approx. 0.8 V more positive than at a metallic electode. The overall energetics are such that light can be used to effect the uphill formation of H/sub 2/O/sub 2/ via the quinone-mediated reduction of O/sub 2/. The onset of O/sub 2/ reduction is up to 0.6 V more positive than E/sup 0/'(O/sub 2//H/sub 2/O/sub 2/). The sustained photoassisted reduction of O/sub 2/ to H/sub 2/O/sub 2/ has been demonstrated. 15 references, 8 figures, 2 tables.« less
  • This paper describes the electrochemical characterization of electrode-confined siloxane polymers that contain both naphthoquinone (NQ) and benzylviologen (BV{sup 2}{sup +}) subunits. These `homopolymers,` abbreviated (NQ-BV{sup 3+}){sub n} and (NQ-BV-BV{sup 5+}){sub n}, are derived from monomers, 2-chloro-3-[[2-(dimethyl[[[N`-[[4-(trimethoxysilyl)phenyl]methyl]-4, 4`-bipyridiniumyl]methyl]phenyl]methyl]ammonium)-ethyl]amino]-1,4-naphthoquinone, 1a, and 2-chloro-3-[[2-(dimethyl[[[[[[[[N`-[N`-[[4-(trimethoxysilyl)phenyl]methy]-4,4`-bipyridiniumyl]methyl]-phenyl]methyl]-4, 4`-bipyridiniumyl]methyl]phenyl]methyl]ammonium)ethyl]amino]-1,4-naphthoquinone, 2a, respectively. Particular to these types of surface-confined homopolymers is the ability to `trap` charge at low pH in the form of reduced quinone. The flexibility of these monolayers apparently allows direct contact of the NQ subunit with the electrode surface. Less flexible and more robust surface-confined polymers, abbreviated (NQ-BV{sup 3+}/siloxane){sub n} and (NQH{sub 2}-BV-BV{sup 5+}siloxane){sub n}, can bemore » prepared by copolymerization of 1a or 2a with 1,2-bis(trimethoxysilyl)ethane. Charge trapped in (NQH{sub 2}-BV{sup 3+}/siloxane){sub n} or (NQH{sub 2}-BV-BV{sup 5+}/siloxane){sub n} can be released and delivered to the surface of the electrode via chemical mediation or by an increase in solution pH. 26 refs., 13 figs.« less
  • Known O-alkylation procedures have been used to derivative the carboxyl and hydroxyl groups in the APCS coals Lewiston-Stockton, Wyodak-Anderson, Beulah-Zap, Illinois No. 6, Upper Freeport, and Pittsburgh No. 8. In general the resulting decrease in hydrogen bonding reduced the cyclical variation in nitroxide spin probe retention observed for nonalkylated coals when small amounts (<1%) of pyridine are present in the toluene swelling solvent. An increase in spin probe retention by the O-alkylated coals relative to the underivatized coals indicates a more open arrangement in the coal due to a decrease in attractive forces, confirming that microporosity increases with increasing rank.