PMID- 32652463
OWN - NLM
STAT- MEDLINE
DCOM- 20210607
LR  - 20210607
IS  - 1873-2682 (Electronic)
IS  - 1011-1344 (Linking)
VI  - 209
DP  - 2020 Aug
TI  - A general framework for non-exponential delayed fluorescence and phosphorescence 
      decay analysis, illustrated on Protoporphyrin IX.
PG  - 111887
LID - S1011-1344(20)30336-5 [pii]
LID - 10.1016/j.jphotobiol.2020.111887 [doi]
AB  - Delayed fluorescence (DF) is a long-lived luminescence process used in a variety 
      of applications ranging from oxygen sensing in biological tissues to organic 
      Light Emitting Diodes. In common cases, DF results from the de-excitation of the 
      first excited triplet state via the first excited singlet state of the 
      chromophore, which produces a mono-exponential light signal whose amplitude and 
      lifetime give an insight into the probed environment. However, non-linear 
      de-excitation reactions such as triplet-triplet annihilation, which can cause 
      decays to lose their mono-exponential nature, are often neglected. In this work, 
      we derive a global framework to properly interpret decays resulting from a 
      combination of linear and non-linear de-excitation processes. We show why the 
      standard method of using multi-exponential models when decays are not 
      mono-exponential is not always relevant, nor accurate. First, we explain why the 
      triplet de-excitation and light production processes should be analyzed 
      individually: we introduce novel concepts to precisely describe these two 
      processes, namely the deactivation pathway - the reaction which mainly 
      contributes to the triplet state de-excitation - and the measurement pathway - 
      the reaction which is responsible for light production. We derive explicit 
      fitting functions which allow the experimenter to estimate the reaction rates and 
      excited state concentrations in the system. To validate our formalism, we analyze 
      the in vitro Transient Triplet Absorption and DF of Protoporphyrin IX, a 
      well-known biological aromatic molecule used in photodynamic therapy, cancer 
      photodetection and oxygen sensing, which produces DF through various mechanisms 
      depending on concentration and excitation intensity. We also identify the precise 
      assumptions necessary to conclude that triplet-triplet annihilation DF should 
      follow a mono-exponential decay with a lifetime of half the triplet state 
      lifetime. Finally, we describe why the commonly used definitions of triplet / DF 
      lifetime are ill-defined in the case where second-order reactions contribute to 
      the deactivation process, and why the fitting of precise mixed-orders DF kinetics 
      should be preferred in this case. This work could allow the correct 
      interpretation of various long-lived luminescence processes and facilitate their 
      understanding.
CI  - Copyright (c) 2020 The Authors. Published by Elsevier B.V. All rights reserved.
FAU - Croizat, Gauthier
AU  - Croizat G
AD  - Laboratory for functional and metabolic imaging, LIFMET, Swiss Federal Institute 
      of Technology (EPFL), Lausanne, Switzerland. Electronic address: 
      g.croizat@gmail.com.
FAU - Gregor, Aurelien
AU  - Gregor A
AD  - Laboratory for functional and metabolic imaging, LIFMET, Swiss Federal Institute 
      of Technology (EPFL), Lausanne, Switzerland.
FAU - Gerelli, Emmanuel
AU  - Gerelli E
AD  - Laboratory for functional and metabolic imaging, LIFMET, Swiss Federal Institute 
      of Technology (EPFL), Lausanne, Switzerland.
FAU - Joniova, Jaroslava
AU  - Joniova J
AD  - Laboratory for functional and metabolic imaging, LIFMET, Swiss Federal Institute 
      of Technology (EPFL), Lausanne, Switzerland.
FAU - Scholz, Marek
AU  - Scholz M
AD  - Faculty of Science, University of South Bohemia, Ceske Budejovice, Czech 
      Republic. Electronic address: mara.scholz@gmail.com.
FAU - Wagnieres, Georges
AU  - Wagnieres G
AD  - Laboratory for functional and metabolic imaging, LIFMET, Swiss Federal Institute 
      of Technology (EPFL), Lausanne, Switzerland.
LA  - eng
PT  - Journal Article
DEP - 20200430
PL  - Switzerland
TA  - J Photochem Photobiol B
JT  - Journal of photochemistry and photobiology. B, Biology
JID - 8804966
RN  - 0 (Protoporphyrins)
RN  - C2K325S808 (protoporphyrin IX)
SB  - IM
MH  - Fluorescence
MH  - Kinetics
MH  - Models, Theoretical
MH  - Protoporphyrins/*chemistry
MH  - Spectrometry, Fluorescence
OTO - NOTNLM
OT  - Cancer photodetection
OT  - Delayed fluorescence
OT  - Oxygen sensing
OT  - Phosphorescence
OT  - Time-resolved spectroscopy
OT  - Triplet state kinetics
EDAT- 2020/07/12 06:00
MHDA- 2021/06/08 06:00
CRDT- 2020/07/12 06:00
PHST- 2020/02/12 00:00 [received]
PHST- 2020/04/14 00:00 [revised]
PHST- 2020/04/26 00:00 [accepted]
PHST- 2020/07/12 06:00 [pubmed]
PHST- 2021/06/08 06:00 [medline]
PHST- 2020/07/12 06:00 [entrez]
AID - S1011-1344(20)30336-5 [pii]
AID - 10.1016/j.jphotobiol.2020.111887 [doi]
PST - ppublish
SO  - J Photochem Photobiol B. 2020 Aug;209:111887. doi: 
      10.1016/j.jphotobiol.2020.111887. Epub 2020 Apr 30.