pH-Sensitive C–ON Bond Homolysis of Alkoxyamines of Imidazoline Series with Multiple Ionizable Groups As an Approach for Control of Nitroxide Mediated Polymerization

2011 ◽  
Vol 76 (14) ◽  
pp. 5558-5573 ◽  
Author(s):  
Mariya V. Edeleva ◽  
Igor A. Kirilyuk ◽  
Irina F. Zhurko ◽  
Dmitry A. Parkhomenko ◽  
Yuri P. Tsentalovich ◽  
...  
Keyword(s):  
Ph Sensitive ◽  
Bond Homolysis ◽  
Nitroxide Mediated Polymerization ◽  
Ionizable Groups

pH-Sensitive C–ON Bond Homolysis of Alkoxyamines of Imidazoline Series: A Theoretical Study

2014 ◽  
Vol 118 (20) ◽  
pp. 5542-5550 ◽  
Author(s):  
Dmitriy A. Parkhomenko ◽  
Mariya V. Edeleva ◽  
Vitaly G. Kiselev ◽  
Elena G. Bagryanskaya
Keyword(s):  
Theoretical Study ◽  
Ph Sensitive ◽  
Bond Homolysis

Versatile approach to activation of alkoxyamine homolysis by 1,3-dipolar cycloaddition for efficient and safe nitroxide mediated polymerization

2019 ◽  
Vol 55 (2) ◽  
pp. 190-193 ◽  
Author(s):  
Mariya Edeleva ◽  
Denis Morozov ◽  
Dmitriy Parkhomenko ◽  
Yulia Polienko ◽  
Anna Iurchenkova ◽  
...  
Keyword(s):  
Dipolar Cycloaddition ◽  
Bond Homolysis ◽  
Nitroxide Mediated Polymerization

In situ activation of alkoxyamine towards C–ON bond homolysis by 1,3-dipolar cycloaddition with monomers is reported.

scholarly journals Smart Control of Nitroxide-Mediated Polymerization Initiators’ Reactivity by pH, Complexation with Metals, and Chemical Transformations

Materials ◽  
2019 ◽  
Vol 12 (5) ◽  
pp. 688 ◽  
Author(s):  
Mariya Edeleva ◽  
Gerard Audran ◽  
Sylvain Marque ◽  
Elena Bagryanskaya
Keyword(s):  
Functional Groups ◽  
Chemical Transformation ◽  
Constant Temperature ◽  
Thermal Regulation ◽  
Chemical Transformations ◽  
Smart Control ◽  
Bond Homolysis ◽  
And Control ◽  
Nitroxide Mediated Polymerization ◽  
Polymerization Method

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.

C–ON bond homolysis in alkoxyamines. Part 12: the effect of the para-substituent in the 1-phenylethyl fragment

2016 ◽  
Vol 14 (14) ◽  
pp. 3574-3583 ◽  
Author(s):  
Gérard Audran ◽  
Paul Brémond ◽  
Jean-Patrick Joly ◽  
Sylvain R. A. Marque ◽  
Toshihide Yamasaki
Keyword(s):  
Bond Homolysis ◽  
Nitroxide Mediated Polymerization

The application of alkoxyamines as initiators/controllers in nitroxide mediated polymerization and as agents for theranostics requires the development of switchable (from stable one to labile one) alkoxyamines.

A Mechanism for Reversibly Pausing a Self-Immolation Cascade in Response to pH Changes

2019 ◽  
Author(s):  
Derrick Roberts ◽  
Ben S. Pilgrim ◽  
Tristan Dell ◽  
Molly Stevens
Keyword(s):  
Local Environment ◽  
Chemical Signals ◽  
Ph Sensitive ◽  
First Report ◽  
Ph Changes ◽  
Self Immolation

We describe the first report of a self-immolation cascade that can be reversibly paused and reactivated in response to pH changes. This system employs a triazole-based self-immolative linker, which expresses a pH-sensitive intermediate during its elimination sequence. This allows the system to respond to pH cues within its local environment, thus establishing a new way to gate self-immolative release using fluctuating or transient chemical signals.<br>

BODIPY Fluorophores for Membrane Potential Imaging

2019 ◽  
Author(s):  
Jenna Franke ◽  
Benjamin Raliski ◽  
Steven Boggess ◽  
Divya Natesan ◽  
Evan Koretsky ◽  
...  
Keyword(s):  
Mammalian Cells ◽  
Water Solubility ◽  
Water Soluble ◽  
Voltage Sensitivity ◽  
Chemical Transformations ◽  
Direct Modification ◽  
Biological Compatibility ◽  
Meso Position ◽  
Ionizable Groups ◽  
Boron Center

Fluorophores based on the BODIPY scaffold are prized for their tunable excitation and emission profiles, mild syntheses, and biological compatibility. Improving the water-solubility of BODIPY dyes remains an outstanding challenge. The development of water-soluble BODIPY dyes usually involves direct modification of the BODIPY fluorophore core with ionizable groups or substitution at the boron center. While these strategies are effective for the generation of water-soluble fluorophores, they are challenging to implement when developing BODIPY-based indicators: direct modification of BODIPY core can disrupt the electronics of the dye, complicating the design of functional indicators; and substitution at the boron center often renders the resultant BODIPY incompatible with the chemical transformations required to generate fluorescent sensors. In this study, we show that BODIPYs bearing a sulfonated aromatic group at the meso position provide a general solution for water-soluble BODIPYs. We outline the route to a suite of 5 new sulfonated BODIPYs with 2,6-disubstitution patterns spanning a range of electron-donating and -withdrawing propensities. To highlight the utility of these new, sulfonated BODIPYs, we further functionalize them to access 13 new, BODIPY-based voltage-sensitive fluorophores. The most sensitive of these BODIPY VF dyes displays a 48% ΔF/F per 100 mV in mammalian cells. Two additional BODIPY VFs show good voltage sensitivity (≥24% ΔF/F) and excellent brightness in cells. These compounds can report on action potential dynamics in both mammalian neurons and human stem cell-derived cardiomyocytes. Accessing a range of substituents in the context of a water soluble BODIPY fluorophore provides opportunities to tune the electronic properties of water-soluble BODIPY dyes for functional indicators.

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