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Title: Chlorophyll-Inspired Red-Region Fluorophores: Building Block Synthesis and Studies in Aqueous Media

Abstract

Fluorophores that absorb and emit in the red spectral region (600–700 nm) are of great interest in photochemistry and photomedicine. Eight new target chlorins (and 19 new chlorins altogether)—analogues of chlorophyll—of different polarities have been designed and synthesized for various applications; seven of the chlorins are equipped with a bioconjugatable tether. Hydrophobic or amphiphilic chlorins in a non-polar organic solvent (toluene), polar organic solvent (DMF), and aqueous or aqueous micellar media show a sharp emission band in the red region and modest fluorescence quantum yield (Φ f = 0.2–0.3). A Poisson analysis implies most micelles are empty and few contain >1 chlorin. Water-soluble chlorins each bearing three PEG (oligoethyleneglycol) groups exhibit narrow emission bands (full-width-at-half maximum <25 nm). The lifetime of the lowest singlet excited state and the corresponding yields and rate constants for depopulation pathways (fluorescence, intersystem crossing, internal conversion) are generally little affected by the PEG groups or dissolution in aqueous or organic media. A set of chlorin–avidin conjugates revealed a 2-fold increase in Φ f with increased average chlorin/avidin ratio (2.3–12). In summary, the chlorins of various polarities described herein are well suited as red-emitting fluorophores for applications in aqueous or organic media.

Authors:
 [1];  [1];  [2];  [3];  [3];  [2]; ORCiD logo [1]
  1. North Carolina State Univ., Raleigh, NC (United States)
  2. Washington Univ., St. Louis, MO (United States)
  3. NIRvana Sciences, Inc., Research Triangle Park, NC
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Photosynthetic Antenna Research Center (PARC); Washington Univ., St. Louis, MO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1470069
Grant/Contract Number:  
SC0001035
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Molecules
Additional Journal Information:
Journal Volume: 23; Journal Issue: 1; Related Information: PARC partners with Washington University in St. Louis (lead); University of California, Riverside; University of Glasgow, UK; Los Alamos National Laboratory; University of New Mexico; New Mexico Corsortium; North Carolina State University; Northwestern University; Oak Ridge National Laboratory; University of Pennsylvania; Sandia National Laboratories; University of Sheffield, UK; Journal ID: ISSN 1420-3049
Publisher:
MDPI
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; amphiphilic; bioconjugation; chlorin; fluorescence; micelle; Poisson; PEG; protein

Citation Formats

Liu, Rui, Liu, Mengran, Hood, Don, Chen, Chih-Yuan, MacNevin, Christopher, Holten, Dewey, and Lindsey, Jonathan. Chlorophyll-Inspired Red-Region Fluorophores: Building Block Synthesis and Studies in Aqueous Media. United States: N. p., 2018. Web. doi:10.3390/molecules23010130.
Liu, Rui, Liu, Mengran, Hood, Don, Chen, Chih-Yuan, MacNevin, Christopher, Holten, Dewey, & Lindsey, Jonathan. Chlorophyll-Inspired Red-Region Fluorophores: Building Block Synthesis and Studies in Aqueous Media. United States. doi:10.3390/molecules23010130.
Liu, Rui, Liu, Mengran, Hood, Don, Chen, Chih-Yuan, MacNevin, Christopher, Holten, Dewey, and Lindsey, Jonathan. Wed . "Chlorophyll-Inspired Red-Region Fluorophores: Building Block Synthesis and Studies in Aqueous Media". United States. doi:10.3390/molecules23010130. https://www.osti.gov/servlets/purl/1470069.
@article{osti_1470069,
title = {Chlorophyll-Inspired Red-Region Fluorophores: Building Block Synthesis and Studies in Aqueous Media},
author = {Liu, Rui and Liu, Mengran and Hood, Don and Chen, Chih-Yuan and MacNevin, Christopher and Holten, Dewey and Lindsey, Jonathan},
abstractNote = {Fluorophores that absorb and emit in the red spectral region (600–700 nm) are of great interest in photochemistry and photomedicine. Eight new target chlorins (and 19 new chlorins altogether)—analogues of chlorophyll—of different polarities have been designed and synthesized for various applications; seven of the chlorins are equipped with a bioconjugatable tether. Hydrophobic or amphiphilic chlorins in a non-polar organic solvent (toluene), polar organic solvent (DMF), and aqueous or aqueous micellar media show a sharp emission band in the red region and modest fluorescence quantum yield (Φf = 0.2–0.3). A Poisson analysis implies most micelles are empty and few contain >1 chlorin. Water-soluble chlorins each bearing three PEG (oligoethyleneglycol) groups exhibit narrow emission bands (full-width-at-half maximum <25 nm). The lifetime of the lowest singlet excited state and the corresponding yields and rate constants for depopulation pathways (fluorescence, intersystem crossing, internal conversion) are generally little affected by the PEG groups or dissolution in aqueous or organic media. A set of chlorin–avidin conjugates revealed a 2-fold increase in Φf with increased average chlorin/avidin ratio (2.3–12). In summary, the chlorins of various polarities described herein are well suited as red-emitting fluorophores for applications in aqueous or organic media.},
doi = {10.3390/molecules23010130},
journal = {Molecules},
issn = {1420-3049},
number = 1,
volume = 23,
place = {United States},
year = {2018},
month = {1}
}

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Works referenced in this record:

Click Chemistry: Diverse Chemical Function from a Few Good Reactions
journal, June 2001