Room‐Temperature‐Phosphorescence‐Based Dissolved Oxygen Detection by Core‐Shell Polymer Nanoparticles Containing Metal‐Free Organic Phosphors

Yu, Young Chang; Kwon, Min Sang; Jung, Jaehun; Zeng, Yingying; Kim, Mounggon; Chung, Kyeongwoon; Gierschner, Johannes; Youk, Ji Ho; Borisov, Sergey; Kim, Dong Ha

doi:10.1002/ange.201708606

Cited by 40 publications

(9 citation statements)

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“…The host–guest recognition with an inclusion effect can also induce RTP signals reversibly as a supramolecular polymer system . Main‐chain or side‐chain polymers with RTP property can be formed by covalent linkage between phosphors and polymer matrices, and the crosslinking of organic phosphors into core‐shell nanoparticles affords a new versatile platform that allows the realization of bright RTP …”

Section: The Formation Of a Stable Excited State To Generate Photolummentioning

confidence: 99%

Fluorescence of Nonaromatic Organic Systems and Room Temperature Phosphorescence of Organic Luminogens: The Intrinsic Principle and Recent Progress

Tang

et al. 2018

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Following the development of photoluminescence systems with various compositions, some nontraditional structures, including nonaromatic organic systems as fluorophores and organic luminogens as the source of phosphorescence emission at room temperature, have attracted considerable attention for their advantages in biological and medical applications, and for the updated photophysical understandings in science. In this Review, the recent progress in understanding these organic compounds or polymers for fluorescence and phosphorescence is briefly summarized, with the aim of exploring the intrinsic principle of these novel photoluminescence systems and providing reasonable constructs for molecular design. Finally, some prospects are suggested for further development of this continually expanding area of research, with the coined concept of Molecular Uniting Set Identified Characteristic (MUSIC).

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Section: The Formation Of a Stable Excited State To Generate Photolummentioning

confidence: 99%

Fluorescence of Nonaromatic Organic Systems and Room Temperature Phosphorescence of Organic Luminogens: The Intrinsic Principle and Recent Progress

Tang

et al. 2018

Small

215

117

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“…Though the molecule emission was not as strong as that in the air condition, there was still an enhancement effect for the emitters in the presence of O 2 . Thereby, the acceleration of radiative emission could be diminished by the quenching effect, and overall, it leads to an obvious enhancement under quenching conditions to provide a novel and effective approach for trace detection of oxygen in surface analysis …”

Section: Resultsmentioning

confidence: 99%

“…Thereby, the acceleration of radiative emission could be diminished by the quenching effect, and overall, it leads to an obvious enhancement under quenching conditions to provide a novel and effective approach for trace detection of oxygen in surface analysis. 45…”

Section: Analytical Chemistrymentioning

confidence: 99%

Shell-Isolated Nanoparticle-Enhanced Phosphorescence

Meng

Zhang

et al. 2018

Anal. Chem.

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The emerging field of plasmonics has promoted applications of optical technology, especially in plasmon-enhanced spectroscopy (PES). However, in plasmon-enhanced fluorescence (PEF), "metal loss" could significantly quench the fluorescence during the process, which dramatically limits its applications in analysis and high-resolution imaging. In this report, silver core silica shell-isolated nanoparticles (Ag@SiO NPs or SHINs) with a tunable thickness of shell are used to investigate the interactions between NPs and emitters by constructing coupling and noncoupling modes. The plasmonic coupling mode between Ag@SiO NPs and Ag film reveals an exceeding integrating spectral intensity enhancement of 330 and about 124 times that of the radiative emission rate acceleration for shell-isolated nanoparticle enhanced phosphorescence (SHINEP). The experimental findings are supported by theoretical calculations using the finite-element method (FEM). Hence, the SHINEP may provide a novel approach for understanding the interaction of plasmon and phosphorescence, and it holds great potential in surface detection analysis and singlet-oxygen-based clinical therapy.

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“…Because of its triplet ground state ( 3 Σ g – ), molecular oxygen is a strong phosphorescence quencher. Although this characteristic has incited facile oxygen sensors, − POPs usually require oxygen-impermeable matrices to prevent oxygen quenching. , …”

Section: Factors Regulating the Performances Of Pops And Insights On ...mentioning

confidence: 99%

“…In this regard, the sensitivity of triplet emission to molecular motion has envisioned solid-state POP-based sensors to organic solvent penetration (Figure e) and temperature (Figure f) . Their sensitivity to oxygen has inspired us to develop dissolved oxygen sensors for oxygen quantification in aqueous environments by embedding hydrophobic POPs in oxygen-permeable water-soluble core–shell nanoparticles (Figure a), which was further explored in biodetection platforms with a subpicomolar detection limit by combining lipid-polymer hybrid POP-based nanoparticles with a signal-amplifying enzymatic oxygen-scavenging reaction (Figure b) . Phosphorescent bioimaging agents have also been devised to map the hypoxia in tumors (Figure d) or living tissues .…”

Section: Application Merits Of Popsmentioning

confidence: 99%

Metal-Free Organic Phosphors toward Fast and Efficient Room-Temperature Phosphorescence

Shao

J²

2022

Acc. Chem. Res.

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Conspectus Metal-free purely organic phosphors (POPs) are promising materials for display technologies, solid-state lighting, and sensors platforms because of their advantageous properties such as large design windows, easy processability, and economic material cost. Unlike inorganic semiconductors, creating the conditions for triplet excitons to produce light in organic materials is a demanding task because of the presence of electron spin configurations that undergo spin-forbidden transitions, which is usually facilitated by spin–orbit coupling (SOC). In the absence of heavy metals, however, the SOC efficiency in POPs remains low, and consequently, external nonradiative photophysical processes will also severely affect triplet excitons. Addressing these challenges requires the development of rational molecular design principles to accurately account for how all conceivable structural, electronic, chemical, compositional factors affect materials performance. This Account summarizes important molecular design and matrix engineering strategies to tackle the two key challenges for POPsboosting SOC efficiencies and suppressing nonradiative decays. We start by reviewing the fundamental understanding of internal and external factors affecting the emission efficiencies of POPs, including the theory behind SOC and the origin of nonradiative decays. Subsequently, we discuss the design of contemporary POP systems on the basis of research insights from our group and others, where SOC is mostly promoted by heavy atom effects and the El-Sayed rule. On one hand, nonmetal heavy atoms including Br, I, or Se provide the heavy atom effects to boost SOC. On the other hand, the El-Sayed rule addresses the necessity of orbital angular momentum change in SOC and the general utilization of carbonyl, heterocyclic rings, and other moieties with rich nonbonding electrons. Because of the slow-decaying nature of triplet excitons, engineering the matrices of POPs is critical to effectively suppress collisional quenching as the major nonradiative decay route, thus achieving POPs with decent room temperature quantum efficiency. For that purpose, crystalline or rigid amorphous matrices have been implemented along with specific intermolecular forces between POPs and their environment. Despite the great efforts made in the past decade, the intrinsic SOC efficiencies of POPs remain low, and their emission lifetimes are pinned in the millisecond to second regime. While this is beneficial for POPs with ultralong emission, designing high-SOC POPs with simultaneous fast decay and high quantum efficiencies is particularly advantageous for display systems. Following the design of contemporary POPs, we will discuss molecular design descriptors that could potentially break the current limit to boost internal SOC in purely organic materials. Our recently developed concept of “heavy atom oriented orbital angular momentum manipulation” will be discussed, accompanied by a rich and expanded library of fast and efficient POP molecules, which serves as a stepp...

show abstract

Room‐Temperature‐Phosphorescence‐Based Dissolved Oxygen Detection by Core‐Shell Polymer Nanoparticles Containing Metal‐Free Organic Phosphors

Cited by 40 publications

References 65 publications

Fluorescence of Nonaromatic Organic Systems and Room Temperature Phosphorescence of Organic Luminogens: The Intrinsic Principle and Recent Progress

Fluorescence of Nonaromatic Organic Systems and Room Temperature Phosphorescence of Organic Luminogens: The Intrinsic Principle and Recent Progress

Shell-Isolated Nanoparticle-Enhanced Phosphorescence

Metal-Free Organic Phosphors toward Fast and Efficient Room-Temperature Phosphorescence

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