Smart control of nitroxide-mediated polymerization initiators' reactivity by p H , complexation with metals, and chemical transformations

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Smart control of nitroxide-mediated polymerization initiators' reactivity by p ^H , complexation with metals, and chemical transformations. / Edeleva, Mariya; Audran, Gerard; Marque, Sylvain et al.

In: Materials, Vol. 12, No. 5, 688, 01.03.2019.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{8f8b165f27504795b95a41c1af1e367c,

title = "Smart control of nitroxide-mediated polymerization initiators' reactivity by p H , complexation with metals, and chemical transformations",

abstract = "Because alkoxyamines are employed in a number of important applications, such as nitroxide-mediated polymerization, radical chemistry, redox chemistry, and catalysis, research into their reactivity is especially important. Typically, the rate of alkoxyamine homolysis is strongly dependent on temperature. Nonetheless, thermal regulation of such reactions is not always optimal. This review describes various ways to reversibly change the rate of C-ON bond homolysis of alkoxyamines at constant temperature. The major methods influencing C-ON bond homolysis without alteration of temperature are protonation of functional groups in an alkoxyamine, formation of metal-alkoxyamine complexes, and chemical transformation of alkoxyamines. Depending on the structure of an alkoxyamine, these approaches can have a significant effect on the homolysis rate constant, by a factor of up to 30, and can shorten the half-lifetime from days to seconds. These methods open new prospects for the application of alkoxyamines in biology and increase the safety of (and control over) the nitroxide-mediated polymerization method.",

keywords = "Alkoxyamine, Complexation, Nitroxide mediated polymerization, Protonation, Tunable rate constants, nitroxide mediated polymerization, protonation, METHYL-METHACRYLATE, QUATERNIZATION, STYRENE, IMIDAZOLINE SERIES, ALKOXYAMINES, tunable rate constants, ON BOND HOMOLYSIS, alkoxyamine, LIVING RADICAL POLYMERIZATION, AGENTS, complexation, CATION",

author = "Mariya Edeleva and Gerard Audran and Sylvain Marque and Elena Bagryanskaya",

note = "Publisher Copyright: {\textcopyright} 2019 by the authors.",

year = "2019",

month = mar,

day = "1",

doi = "10.3390/ma12050688",

language = "English",

volume = "12",

journal = "Materials",

issn = "1996-1944",

publisher = "MDPI AG",

number = "5",

}

RIS

TY - JOUR

T1 - Smart control of nitroxide-mediated polymerization initiators' reactivity by p H , complexation with metals, and chemical transformations

AU - Edeleva, Mariya

AU - Audran, Gerard

AU - Marque, Sylvain

AU - Bagryanskaya, Elena

PY - 2019/3/1

Y1 - 2019/3/1

N2 - Because alkoxyamines are employed in a number of important applications, such as nitroxide-mediated polymerization, radical chemistry, redox chemistry, and catalysis, research into their reactivity is especially important. Typically, the rate of alkoxyamine homolysis is strongly dependent on temperature. Nonetheless, thermal regulation of such reactions is not always optimal. This review describes various ways to reversibly change the rate of C-ON bond homolysis of alkoxyamines at constant temperature. The major methods influencing C-ON bond homolysis without alteration of temperature are protonation of functional groups in an alkoxyamine, formation of metal-alkoxyamine complexes, and chemical transformation of alkoxyamines. Depending on the structure of an alkoxyamine, these approaches can have a significant effect on the homolysis rate constant, by a factor of up to 30, and can shorten the half-lifetime from days to seconds. These methods open new prospects for the application of alkoxyamines in biology and increase the safety of (and control over) the nitroxide-mediated polymerization method.

AB - Because alkoxyamines are employed in a number of important applications, such as nitroxide-mediated polymerization, radical chemistry, redox chemistry, and catalysis, research into their reactivity is especially important. Typically, the rate of alkoxyamine homolysis is strongly dependent on temperature. Nonetheless, thermal regulation of such reactions is not always optimal. This review describes various ways to reversibly change the rate of C-ON bond homolysis of alkoxyamines at constant temperature. The major methods influencing C-ON bond homolysis without alteration of temperature are protonation of functional groups in an alkoxyamine, formation of metal-alkoxyamine complexes, and chemical transformation of alkoxyamines. Depending on the structure of an alkoxyamine, these approaches can have a significant effect on the homolysis rate constant, by a factor of up to 30, and can shorten the half-lifetime from days to seconds. These methods open new prospects for the application of alkoxyamines in biology and increase the safety of (and control over) the nitroxide-mediated polymerization method.

KW - Alkoxyamine

KW - Complexation

KW - Nitroxide mediated polymerization

KW - Protonation

KW - Tunable rate constants

KW - nitroxide mediated polymerization

KW - protonation

KW - METHYL-METHACRYLATE

KW - QUATERNIZATION

KW - STYRENE

KW - IMIDAZOLINE SERIES

KW - ALKOXYAMINES

KW - tunable rate constants

KW - ON BOND HOMOLYSIS

KW - alkoxyamine

KW - LIVING RADICAL POLYMERIZATION

KW - AGENTS

KW - complexation

KW - CATION

UR - http://www.scopus.com/inward/record.url?scp=85063001246&partnerID=8YFLogxK

U2 - 10.3390/ma12050688

DO - 10.3390/ma12050688

M3 - Article

C2 - 30813542

AN - SCOPUS:85063001246

VL - 12

JO - Materials

JF - Materials

SN - 1996-1944

IS - 5

M1 - 688

ER -

ID: 18860959