Tuning the singlet-triplet energy gap: a unique approach to efficient photosensitizers with aggregation-induced emission (AIE) characteristics.
Tuning the singlet-triplet energy gap: a unique approach to efficient photosensitizers with aggregation-induced emission (AIE) characteristics.
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DOI:
10.1039/c5sc01733e
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发表时间:
2015-10-01
期刊:
影响因子:
8.4
通讯作者:
Liu B
中科院分区:
文献类型:
--
作者:
Xu S;Yuan Y;Cai X;Zhang CJ;Hu F;Liang J;Zhang G;Zhang D;Liu B
The efficiency of the intersystem crossing process can be improved by reducing the energy gap between the singlet and triplet excited states (ΔE ST), which offers the opportunity to improve the yield of the triplet excited state. The efficiency of the intersystem crossing process can be improved by reducing the energy gap between the singlet and triplet excited states (ΔE ST), which offers the opportunity to improve the yield of the triplet excited state. Herein, we demonstrate that modulation of the excited states is also an effective strategy to regulate the singlet oxygen generation of photosensitizers. Based on our previous studies that photosensitizers with aggregation-induced emission characteristics (AIE) showed enhanced fluorescence and efficient singlet oxygen production in the aggregated state, a series of AIE fluorogens such as TPDC, TPPDC and PPDC were synthesized, which showed ΔE ST values of 0.48, 0.35 and 0.27 eV, respectively. A detailed study revealed that PPDC exhibited the highest singlet oxygen efficiency (0.89) as nanoaggregates, while TPDC exhibited the lowest efficiency (0.28), inversely correlated with their ΔE ST values. Due to their similar optical properties, TPDC and PPDC were further encapsulated into nanoparticles (NPs). Subsequent surface modification with cell penetrating peptide (TAT) yielded TAT–TPDC NPs and TAT–PPDC NPs. As a result of the stronger singlet oxygen generation, TAT–PPDC NPs showed enhanced cancer cell ablation as compared to TAT–TPDC NPs. Fine-tuning of the singlet-triplet energy gap is thus proven to be an effective new strategy to generate efficient photosensitizers for photodynamic therapy.
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