Singlet Oxygen Generation from Polyaminoglycerol by Spin-Flip-Based Electron Transfer

Jung Seung Nam; Youngjoo Hong; Chae Gyu Lee; Tae In Kim; Chaiheon Lee; Deok Ho Roh; In Seong Lee; Songa Kweon; Gyunhyeok Ahn; Seung Kyu Min; Byeong Su Kim; Tae Hyuk Kwon

doi:10.1021/jacsau.2c00050

Singlet Oxygen Generation from Polyaminoglycerol by Spin-Flip-Based Electron Transfer

Jung Seung Nam, Youngjoo Hong, Chae Gyu Lee, Tae In Kim, Chaiheon Lee, Deok Ho Roh, In Seong Lee, Songa Kweon, Gyunhyeok Ahn, Seung Kyu Min, Byeong Su Kim, Tae Hyuk Kwon

Department of Chemistry

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

2 Citations (Scopus)

Abstract

Reactive oxygen species have drawn attention owing to their strong oxidation ability. In particular, the singlet oxygen (¹O₂) produced by energy transfer is the predominant species for controlling oxidation reactions efficiently. However, conventional ¹O₂generators, which rely on enhanced energy transfer, frequently suffer from poor solubility, low stability, and low biocompatibility. Herein, we introduce a hyperbranched aliphatic polyaminoglycerol (hPAG) as a ¹O₂generator, which relies on spin-flip-based electron transfer. The coexistence of a lone pair electron on the nitrogen atom and a hydrogen-bonding donor (the protonated form of nitrogen and hydroxyl group) affords proximity between hPAG and O₂. Subsequent direct electron transfer after photo-irradiation induces hPAG^•+-O₂^•-formation, and the following spin-flip process generates ¹O₂. The spin-flip-based electron transfer pathway is analyzed by a series of photophysical, electrochemical, and computational studies. The ¹O₂generator, hPAG, is successfully employed in photodynamic therapy and as an antimicrobial reagent.

Original language	English
Pages (from-to)	933-942
Number of pages	10
Journal	JACS Au
Volume	2
Issue number	4
DOIs	https://doi.org/10.1021/jacsau.2c00050
Publication status	Published - 2022 Apr 25

Bibliographical note

Funding Information:
This work was supported by the Ulsan National Institute of Science & Technology (UNIST) (Research Fund 1.220026.01), and the National Research Foundation of Korea (NRF) (Grant 2016M1A2A2940910, 2017M3A7B4052802, 2017R1A2B3012148, 2018R1A5A1025208, 2019R1A2C1007744, 2021M3H4A1A0305139011, 2021R1A2C3004978, and 2021R1A2C2009504). C.G.L. and I.S.L. acknowledge support from the Global Ph.D. Fellowship Program through the NRF funded by the Ministry of Education (NRF-2018H1A2A1061237 and NRF-2017H1A2A1043792).

Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.

All Science Journal Classification (ASJC) codes

Chemistry (miscellaneous)
Analytical Chemistry
Organic Chemistry
Physical and Theoretical Chemistry

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10.1021/jacsau.2c00050

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@article{1e215d8727e246bdb96ed8047fca0aa3,

title = "Singlet Oxygen Generation from Polyaminoglycerol by Spin-Flip-Based Electron Transfer",

abstract = "Reactive oxygen species have drawn attention owing to their strong oxidation ability. In particular, the singlet oxygen (1O2) produced by energy transfer is the predominant species for controlling oxidation reactions efficiently. However, conventional 1O2generators, which rely on enhanced energy transfer, frequently suffer from poor solubility, low stability, and low biocompatibility. Herein, we introduce a hyperbranched aliphatic polyaminoglycerol (hPAG) as a 1O2generator, which relies on spin-flip-based electron transfer. The coexistence of a lone pair electron on the nitrogen atom and a hydrogen-bonding donor (the protonated form of nitrogen and hydroxyl group) affords proximity between hPAG and O2. Subsequent direct electron transfer after photo-irradiation induces hPAG•+-O2•-formation, and the following spin-flip process generates 1O2. The spin-flip-based electron transfer pathway is analyzed by a series of photophysical, electrochemical, and computational studies. The 1O2generator, hPAG, is successfully employed in photodynamic therapy and as an antimicrobial reagent.",

author = "Nam, {Jung Seung} and Youngjoo Hong and Lee, {Chae Gyu} and Kim, {Tae In} and Chaiheon Lee and Roh, {Deok Ho} and Lee, {In Seong} and Songa Kweon and Gyunhyeok Ahn and Min, {Seung Kyu} and Kim, {Byeong Su} and Kwon, {Tae Hyuk}",

note = "Funding Information: This work was supported by the Ulsan National Institute of Science & Technology (UNIST) (Research Fund 1.220026.01), and the National Research Foundation of Korea (NRF) (Grant 2016M1A2A2940910, 2017M3A7B4052802, 2017R1A2B3012148, 2018R1A5A1025208, 2019R1A2C1007744, 2021M3H4A1A0305139011, 2021R1A2C3004978, and 2021R1A2C2009504). C.G.L. and I.S.L. acknowledge support from the Global Ph.D. Fellowship Program through the NRF funded by the Ministry of Education (NRF-2018H1A2A1061237 and NRF-2017H1A2A1043792). Publisher Copyright: {\textcopyright} 2022 American Chemical Society. All rights reserved.",

year = "2022",

month = apr,

day = "25",

doi = "10.1021/jacsau.2c00050",

language = "English",

volume = "2",

pages = "933--942",

journal = "JACS Au",

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T1 - Singlet Oxygen Generation from Polyaminoglycerol by Spin-Flip-Based Electron Transfer

AU - Nam, Jung Seung

AU - Hong, Youngjoo

AU - Lee, Chae Gyu

AU - Kim, Tae In

AU - Lee, Chaiheon

AU - Roh, Deok Ho

AU - Lee, In Seong

AU - Kweon, Songa

AU - Ahn, Gyunhyeok

AU - Min, Seung Kyu

AU - Kim, Byeong Su

AU - Kwon, Tae Hyuk

N1 - Funding Information: This work was supported by the Ulsan National Institute of Science & Technology (UNIST) (Research Fund 1.220026.01), and the National Research Foundation of Korea (NRF) (Grant 2016M1A2A2940910, 2017M3A7B4052802, 2017R1A2B3012148, 2018R1A5A1025208, 2019R1A2C1007744, 2021M3H4A1A0305139011, 2021R1A2C3004978, and 2021R1A2C2009504). C.G.L. and I.S.L. acknowledge support from the Global Ph.D. Fellowship Program through the NRF funded by the Ministry of Education (NRF-2018H1A2A1061237 and NRF-2017H1A2A1043792). Publisher Copyright: © 2022 American Chemical Society. All rights reserved.

PY - 2022/4/25

Y1 - 2022/4/25

N2 - Reactive oxygen species have drawn attention owing to their strong oxidation ability. In particular, the singlet oxygen (1O2) produced by energy transfer is the predominant species for controlling oxidation reactions efficiently. However, conventional 1O2generators, which rely on enhanced energy transfer, frequently suffer from poor solubility, low stability, and low biocompatibility. Herein, we introduce a hyperbranched aliphatic polyaminoglycerol (hPAG) as a 1O2generator, which relies on spin-flip-based electron transfer. The coexistence of a lone pair electron on the nitrogen atom and a hydrogen-bonding donor (the protonated form of nitrogen and hydroxyl group) affords proximity between hPAG and O2. Subsequent direct electron transfer after photo-irradiation induces hPAG•+-O2•-formation, and the following spin-flip process generates 1O2. The spin-flip-based electron transfer pathway is analyzed by a series of photophysical, electrochemical, and computational studies. The 1O2generator, hPAG, is successfully employed in photodynamic therapy and as an antimicrobial reagent.

AB - Reactive oxygen species have drawn attention owing to their strong oxidation ability. In particular, the singlet oxygen (1O2) produced by energy transfer is the predominant species for controlling oxidation reactions efficiently. However, conventional 1O2generators, which rely on enhanced energy transfer, frequently suffer from poor solubility, low stability, and low biocompatibility. Herein, we introduce a hyperbranched aliphatic polyaminoglycerol (hPAG) as a 1O2generator, which relies on spin-flip-based electron transfer. The coexistence of a lone pair electron on the nitrogen atom and a hydrogen-bonding donor (the protonated form of nitrogen and hydroxyl group) affords proximity between hPAG and O2. Subsequent direct electron transfer after photo-irradiation induces hPAG•+-O2•-formation, and the following spin-flip process generates 1O2. The spin-flip-based electron transfer pathway is analyzed by a series of photophysical, electrochemical, and computational studies. The 1O2generator, hPAG, is successfully employed in photodynamic therapy and as an antimicrobial reagent.

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U2 - 10.1021/jacsau.2c00050

DO - 10.1021/jacsau.2c00050

M3 - Article

AN - SCOPUS:85129332045

SN - 2691-3704

VL - 2

SP - 933

EP - 942

JO - JACS Au

JF - JACS Au

IS - 4

ER -

Singlet Oxygen Generation from Polyaminoglycerol by Spin-Flip-Based Electron Transfer

Abstract

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