研究目的
To demonstrate that a molecular design with hydrophilic oligo(ethylene glycol) chains and hydrophobic alkyl chains is effective for avoiding oxygen quenching in triplet-triplet annihilation-based photon upconversion in water.
研究成果
The study successfully demonstrated that a simple amphiphilic molecular design with oligo(ethylene glycol) and alkyl chains enables stable self-assembly in water, protecting against oxygen quenching and allowing TTA-UC emission in air-saturated conditions at low concentrations. This approach offers potential for applications in supramolecular chemistry and biological fields, with future work needed to generalize and optimize the system.
研究不足
The UC efficiency was modest (0.7%) and inferior to previous works, possibly due to partial aggregation of the donor and formation of quenching sites. The stability under continuous excitation in aerated conditions showed gradual decrease, and the assembly structure may require optimization for better oxygen blocking. Measurement sensitivity limited observations at concentrations below 40 μM.
1:Experimental Design and Method Selection:
The study involved synthesizing a non-ionic amphiphilic acceptor A1 and using Pt(II) octaethylporphyrin (PtOEP) as a donor. The experimental design focused on self-assembly in water to protect against oxygen quenching and enable photon upconversion. Methods included synthesis, characterization (NMR, DLS, TEM, UV-vis, fluorescence spectroscopy), and TTA-UC emission measurements under aerated and deaerated conditions.
2:Sample Selection and Data Sources:
Samples included A1 synthesized in the lab and commercial PtOEP. Aqueous dispersions were prepared by dissolving A1 and PtOEP in CHCl3, evaporating the solvent, adding water, and sonicating. Concentrations ranged from 40 μM to 400 μM for A1 and 0.1 μM to 1 μM for PtOEP.
3:1 μM to 1 μM for PtOEP. List of Experimental Equipment and Materials:
3. List of Experimental Equipment and Materials: Equipment included JNM-ECZ400S NMR spectrometer, Malvern Nano-ZS ZEN3600 for DLS, JASCO V-770 spectrophotometer for absorption, PerkinElmer LS 55 fluorescence spectrometer, HAMAMATSU multichannel analyzer C10027-01 for quantum yield, time-correlated single photon counting systems (C11367-02 and C11567-01) for lifetime measurements, diode laser (532 nm, 200 mW, RGB Photonics) for excitation, PD300-UV photodiode sensor (OPHIR Photonics) for power measurement, CCD beam profiler SP620 (OPHIR Photonics), multichannel detector MCPD-9800 (Otsuka Electronics), and absolute quantum yield measurement system C13534-01 (Hamamatsu Photonics). Materials included CHCl3, D2O, CDCl3, Milli-Q water, and various chemicals for synthesis.
4:Experimental Procedures and Operational Workflow:
A1 was synthesized and characterized. Aqueous dispersions were prepared by sonication. DLS and TEM were used to confirm assembly formation. Absorption and fluorescence spectra were recorded. For TTA-UC, samples were excited with a 532 nm laser, and emission was measured with notch filters to remove excitation light. Deaeration was done by freeze-pump-thaw cycles. Excitation intensity dependence and lifetime measurements were conducted.
5:Data Analysis Methods:
Data analysis included estimating assembly sizes from DLS, spectral analysis from UV-vis and fluorescence, calculation of quantum yields using integrating spheres, and fitting decay curves for triplet lifetimes. Excitation intensity plots were used to confirm TTA mechanism.
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NMR Spectrometer
JNM-ECZ400S
JEOL
Used for 1H-NMR and 13C-NMR measurements to confirm purity and self-assembly of A1.
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Dynamic Light Scattering Instrument
Nano-ZS ZEN3600
Malvern
Used to measure the size of molecular assemblies in aqueous dispersions.
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Spectrophotometer
V-770
JASCO
Used to record UV-vis absorption spectra of samples.
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Fluorescence Spectrometer
LS 55
PerkinElmer
Used to measure fluorescence spectra of samples.
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Multichannel Analyzer
C10027-01
Hamamatsu
Used for absolute quantum yield measurements in an integrating sphere.
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Time-Correlated Single Photon Counting System
C11367-02
Hamamatsu
Used for fluorescence lifetime measurements.
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Time-Correlated Single Photon Counting System
C11567-01
Hamamatsu
Used for delayed luminescence lifetime measurements.
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Diode Laser
200 mW, 532 nm
RGB Photonics
Used as an excitation source for TTA-UC emission measurements.
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Photodiode Sensor
PD300-UV
OPHIR Photonics
Used to measure laser power.
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CCD Beam Profiler
SP620
OPHIR Photonics
Used to measure the diameter of the laser beam.
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Absolute Quantum Yield Measurement System
C13534-01
Hamamatsu Photonics
Used to measure TTA-UC efficiency in an integrating sphere.
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Multichannel Detector
MCPD-9800
Otsuka Electronics
Used for detection of emitted light in TTA-UC measurements.
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Pt(II) Octaethylporphyrin
Aldrich
Used as the donor molecule in the TTA-UC system.
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