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Title: Manganoporphyrin-Polyphenol Multilayer Capsules as Radical and Reactive Oxygen Species (ROS) Scavengers

Abstract

Local modulation of oxidative stress is crucial for a variety of biochemical events including cellular differentiation, apoptosis, and defense against pathogens. Currently employed natural and synthetic antioxidants exhibit a lack of biocompatibility, bioavailability, and chemical stability, resulting in limited capability to scavenge reactive oxygen species (ROS). To mediate these drawbacks, we have developed a synergistic manganoporphyrin-polyphenol polymeric nanothin coating and hollow microcapsules with efficient antioxidant activity and controllable ROS modulation. These materials are produced by multilayer assembly of a natural polyphenolic antioxidant, tannic acid (TA), with a synthesized copolymer of polyvinylpyrrolidone containing a manganoporphyrin modality (MnP-PVPON) which mimics the enzymatic antioxidant superoxide dismutase. The redox activity of the copolymer is demonstrated to dramatically increase the antioxidant response of MnP-PVPON/TA capsules versus unmodified PVPON/TA capsules through reduction of a radical cationic dye and to significantly suppress the proliferation of superoxide via cytochrome C competition. Inclusion of MnP-PVPON as an outer layer enhances radical-scavenging activity as compared to localization of the layer in the middle or inner part of the capsule shell. In addition, we demonstrate that TA is crucial for the synergistic radical-scavenging activity of the MnP-PVPON/TA system which exhibits a combined superoxide dismutase-like ability and catalase-like activity in response tomore » the free radical superoxide challenge. The MnP-PVPON/TA capsules exhibit a negligible, 8% loss of shell thickness upon free radical treatment, while PVPON/TA capsules lose 39% of their shell thickness due to the noncatalytic free-radical-scavenging of TA, as demonstrated by small angle neutron scattering (SANS). Finally, we have found the manganoporphyrin-polyphenol capsules to be nontoxic to splenocytes from NOD mice after 48 h incubation. In conclusion, our study illustrates the strong potential of combining catalytic activity of manganoporphyrins with natural polyphenolic antioxidants to design efficient free-radical-scavenging materials that may eventually be used in antioxidant therapies and as free radical dissipating protective carriers of biomolecules for biomedical or industrial applications.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [2]; ORCiD logo [3]; ORCiD logo [3];  [2]; ORCiD logo [1]
  1. Univ. of Alabama, Birmingham, AL (United States). Dept. of Chemistry
  2. Univ. of Alabama, Birmingham, AL (United States). Dept. of Microbiology
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); National Science Foundation (NSF)
OSTI Identifier:
1422484
Grant/Contract Number:  
AC05-00OR22725; DMR1608728
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 2; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; 60 APPLIED LIFE SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Alford, Aaron, Kozlovskaya, Veronika, Xue, Bing, Gupta, Nirzari, Higgins, William, Pham-Hua, Dana, He, Lilin, Urban, Volker S., Tse, Hubert M., and Kharlampieva, Eugenia. Manganoporphyrin-Polyphenol Multilayer Capsules as Radical and Reactive Oxygen Species (ROS) Scavengers. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.7b03502.
Alford, Aaron, Kozlovskaya, Veronika, Xue, Bing, Gupta, Nirzari, Higgins, William, Pham-Hua, Dana, He, Lilin, Urban, Volker S., Tse, Hubert M., & Kharlampieva, Eugenia. Manganoporphyrin-Polyphenol Multilayer Capsules as Radical and Reactive Oxygen Species (ROS) Scavengers. United States. doi:10.1021/acs.chemmater.7b03502.
Alford, Aaron, Kozlovskaya, Veronika, Xue, Bing, Gupta, Nirzari, Higgins, William, Pham-Hua, Dana, He, Lilin, Urban, Volker S., Tse, Hubert M., and Kharlampieva, Eugenia. Mon . "Manganoporphyrin-Polyphenol Multilayer Capsules as Radical and Reactive Oxygen Species (ROS) Scavengers". United States. doi:10.1021/acs.chemmater.7b03502. https://www.osti.gov/servlets/purl/1422484.
@article{osti_1422484,
title = {Manganoporphyrin-Polyphenol Multilayer Capsules as Radical and Reactive Oxygen Species (ROS) Scavengers},
author = {Alford, Aaron and Kozlovskaya, Veronika and Xue, Bing and Gupta, Nirzari and Higgins, William and Pham-Hua, Dana and He, Lilin and Urban, Volker S. and Tse, Hubert M. and Kharlampieva, Eugenia},
abstractNote = {Local modulation of oxidative stress is crucial for a variety of biochemical events including cellular differentiation, apoptosis, and defense against pathogens. Currently employed natural and synthetic antioxidants exhibit a lack of biocompatibility, bioavailability, and chemical stability, resulting in limited capability to scavenge reactive oxygen species (ROS). To mediate these drawbacks, we have developed a synergistic manganoporphyrin-polyphenol polymeric nanothin coating and hollow microcapsules with efficient antioxidant activity and controllable ROS modulation. These materials are produced by multilayer assembly of a natural polyphenolic antioxidant, tannic acid (TA), with a synthesized copolymer of polyvinylpyrrolidone containing a manganoporphyrin modality (MnP-PVPON) which mimics the enzymatic antioxidant superoxide dismutase. The redox activity of the copolymer is demonstrated to dramatically increase the antioxidant response of MnP-PVPON/TA capsules versus unmodified PVPON/TA capsules through reduction of a radical cationic dye and to significantly suppress the proliferation of superoxide via cytochrome C competition. Inclusion of MnP-PVPON as an outer layer enhances radical-scavenging activity as compared to localization of the layer in the middle or inner part of the capsule shell. In addition, we demonstrate that TA is crucial for the synergistic radical-scavenging activity of the MnP-PVPON/TA system which exhibits a combined superoxide dismutase-like ability and catalase-like activity in response to the free radical superoxide challenge. The MnP-PVPON/TA capsules exhibit a negligible, 8% loss of shell thickness upon free radical treatment, while PVPON/TA capsules lose 39% of their shell thickness due to the noncatalytic free-radical-scavenging of TA, as demonstrated by small angle neutron scattering (SANS). Finally, we have found the manganoporphyrin-polyphenol capsules to be nontoxic to splenocytes from NOD mice after 48 h incubation. In conclusion, our study illustrates the strong potential of combining catalytic activity of manganoporphyrins with natural polyphenolic antioxidants to design efficient free-radical-scavenging materials that may eventually be used in antioxidant therapies and as free radical dissipating protective carriers of biomolecules for biomedical or industrial applications.},
doi = {10.1021/acs.chemmater.7b03502},
journal = {Chemistry of Materials},
issn = {0897-4756},
number = 2,
volume = 30,
place = {United States},
year = {2017},
month = {12}
}

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Cited by: 5 works
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Figures / Tables:

Figure 1 Figure 1: Synthesis of carboxyl monofunctionalized tetrapyridyl Mnporphyrin (MnP).

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Works referencing / citing this record:

Layer‐by‐Layer Cerium Oxide Nanoparticle Coating for Antioxidant Protection of Encapsulated Beta Cells
journal, October 2018

  • Abuid, Nicholas J.; Gattás‐Asfura, Kerim M.; Schofield, Emily A.
  • Advanced Healthcare Materials, Vol. 8, Issue 12
  • DOI: 10.1002/adhm.201801493

Layer‐by‐Layer Cerium Oxide Nanoparticle Coating for Antioxidant Protection of Encapsulated Beta Cells
journal, October 2018

  • Abuid, Nicholas J.; Gattás‐Asfura, Kerim M.; Schofield, Emily A.
  • Advanced Healthcare Materials, Vol. 8, Issue 12
  • DOI: 10.1002/adhm.201801493