PMID- 22510068
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20120830
LR  - 20120510
IS  - 1520-5207 (Electronic)
IS  - 1520-5207 (Linking)
VI  - 116
IP  - 18
DP  - 2012 May 10
TI  - Tacticity influence on the electrochemical reactivity of group transfer 
      polymerization-synthesized PTMA.
PG  - 5542-50
LID - 10.1021/jp301207v [doi]
AB  - Spectroscopic, thermal, and electrochemical characterization results are 
      presented for the redox active polymer 
      poly(2,2,6,6-tetramethyl-1-piperinidyloxy-4-yl methacrylate) or PTMA, synthesized 
      by group transfer polymerization (GTP), and its precursors 
      4-hydroxy-tetramethylpiperidine-N-oxyl (HO-TEMPO) and 
      4-methacryloyloxy-tetramethylpiperidine-N-oxyl (MO-TEMPO). DSC analysis of 
      synthesized PTMA showed that the glass transition temperature (T(g)) of the 
      polymer structure occurs at 155  degrees C, corroborated by dynamic mechanical analysis 
      (DMA), which is higher when compared with T(g) data for PTMA synthesized by other 
      methods. Also, the amount of radical species present in PTMA synthesized by GTP 
      reactions (100%) is higher than the values typically upon synthesizing PTMA by 
      radical polymerization. Electrochemical and spectroelectrochemical-electron spin 
      resonance studies in acetonitrile revealed two redox events in the PTMA polymer, 
      one of which is reversible, accounting for ca. 80% of the spins in the polymer 
      and giving rise to the battery behavior. The other redox event is irreversible, 
      accounting for the remaining ca. 20% of spins, which has not previously been 
      reported. These two redox events are linked to a structural property associated 
      with the tacticity of the polymer, where the reversible feature (responsible for 
      cathode behavior) is the dominant species. This corresponds to a number of 
      isotactic domains of the polymer (determined by high temperature (1)H NMR). The 
      second feature accounts for the three-line impurity observed in the ESR, which 
      has been reported previously but poorly explained, associated to the number of 
      heterotactic/syndiotactic triads.
FAU - Lopez-Pena, Hugo A
AU  - Lopez-Pena HA
AD  - Universidad Autonoma Metropolitana-Iztapalapa Av., San Rafael Atlixco 186, Col. 
      Vicentina 09340, Mexico, DF, Mexico.
FAU - Hernandez-Munoz, Lindsay S
AU  - Hernandez-Munoz LS
FAU - Frontana-Uribe, Bernardo A
AU  - Frontana-Uribe BA
FAU - Gonzalez, Felipe J
AU  - Gonzalez FJ
FAU - Gonzalez, Ignacio
AU  - Gonzalez I
FAU - Frontana, Carlos
AU  - Frontana C
FAU - Cardoso, Judith
AU  - Cardoso J
LA  - eng
PT  - Journal Article
DEP - 20120430
PL  - United States
TA  - J Phys Chem B
JT  - The journal of physical chemistry. B
JID - 101157530
EDAT- 2012/04/19 06:00
MHDA- 2012/04/19 06:01
CRDT- 2012/04/19 06:00
PHST- 2012/04/19 06:00 [entrez]
PHST- 2012/04/19 06:00 [pubmed]
PHST- 2012/04/19 06:01 [medline]
AID - 10.1021/jp301207v [doi]
PST - ppublish
SO  - J Phys Chem B. 2012 May 10;116(18):5542-50. doi: 10.1021/jp301207v. Epub 2012 Apr 
      30.