The storage and controlled release of singlet oxygen (1O2) have attracted increasing attention due to the wide application and microsecond lifetime of 1O2 in water. Herein we provide an integrated nanoplatform consisting of a diphenylanthracene derivative, a water-soluble pillar[5]arene and a photosensitizer tetrakis(4-hydroxyphenyl)porphyrin (TPP), that may provide the controlled generation, storage and release of singlet oxygen. We design a new diphenylanthracene derivative with two trimethylammonium bromide groups on both ends that can be well recognized by the pillar[5]arene. The formed nanocarriers can be used to load TPP through their supramolecular self-assembly. The resulting nanoparticles show good water-solubility and uniform spherical morphology. After laser irradiation (660 nm), the nanoparticles exhibit excellent ability for the generation and storage of 1O2. When the irradiated nanoparticles are heated above 80 °C, 1O2 can be released from the system. Therefore, in this paper we pioneer the use of noncovalent interaction to integrate the diphenylanthracene derivatives and photosensitizers into one functional system, which provides a new strategy for the controlled generation, storage and release of singlet oxygen. We believe this groundbreaking strategy will have a great potential in providing necessary amounts of 1O2 for the photodynamic therapy of tumors in dark.
. [J]. Frontiers of Chemical Science and Engineering, 2023, 17(3): 307-313.
Bing Lu, Zhecheng Zhang, Meiyu Qi, Yuehua Zhang, Hualing Yang, Jin Wang, Yue Ding, Yang Wang, Yong Yao. All-in-one functional supramolecular nanoparticles based on pillar[5]arene for controlled generation, storage and release of singlet oxygen. Front. Chem. Sci. Eng., 2023, 17(3): 307-313.
D B Ushakov, K Gilmore, D Kopetzki, D T McQuade, P H Seeberger. Continuous-flow oxidative cyanation of primary and secondary amines using singlet oxygen. Angewandte Chemie International Edition, 2014, 53(2): 557–561 https://doi.org/10.1002/anie.201307778
2
S Nonell, C Flors. Singlet Oxygen: Applications in Biosciences and Nanosciences. Cambridge: Royal Society of Chemistry, 2016,
3
Z Zhou, J Song, L Nie, X Chen. Reactive oxygen species generating systems meeting challenges of photodynamic cancer therapy. Chemical Society Reviews, 2016, 45(23): 6597–6626 https://doi.org/10.1039/C6CS00271D
4
Y Liu, P Bhattarai, Z Dai, X Chen. Photothermal therapy and photoacoustic imaging via nanotheranostics in fighting cancer. Chemical Society Reviews, 2019, 48(7): 2053–2108 https://doi.org/10.1039/C8CS00618K
5
D Lu, R Tao, Z Wang. Carbon-based materials for photodynamic therapy: a mini-review. Frontiers of Chemical Science and Engineering, 2019, 13(2): 310–323 https://doi.org/10.1007/s11705-018-1750-7
6
H Wang, S Jiang, W Liu, X Zhang, Q Zhang, Y Luo, Y Xie. Ketones as molecular Co-catalysts for boosting exciton-based photocatalytic molecular oxygen activation. Angewandte Chemie International Edition, 2020, 59(27): 11093–11100 https://doi.org/10.1002/anie.202003042
7
B Lu, Z Zhang, D Jin, X Yuan, J Wang, Y Ding, Y Wang, Y Yao. A–DA′D–A fused-ring small molecule-based nanoparticles for combined photothermal and photodynamic therapy of cancer. Chemical Communications, 2021, 57(90): 12020–12023 https://doi.org/10.1039/D1CC04629B
8
H H Wasserman, J R Scheffer. Singlet oxygen reactions from photoperoxides. Journal of the American Chemical Society, 1967, 89(12): 3073–3075 https://doi.org/10.1021/ja00988a064
9
M A Filatov, M O Senge. Molecular devices based on reversible singlet oxygen binding in optical and photomedical applications. Molecular Systems Design & Engineering, 2016, 1(3): 258–272 https://doi.org/10.1039/C6ME00042H
10
S Kolemen, T Ozdemir, D Lee, G M Kim, T Karatas, J Yoon, E U Akkaya. Remote-controlled release of singlet oxygen by the plasmonic heating of endoperoxide-modified gold nanorods: towards a paradigm change in photodynamic therapy. Angewandte Chemie International Edition, 2016, 55(11): 3606–3610 https://doi.org/10.1002/anie.201510064
11
W Lv, H Xia, K Y Zhang, Z Chen, S Liu, W Huang, Q Zhao. Photothermal-triggered release of singlet oxygen from an endoperoxide-containing polymeric carrier for killing cancer cells. Materials Horizons, 2017, 4(6): 1185–1189 https://doi.org/10.1039/C7MH00726D
12
W Fudickar, T Linker. Release of singlet oxygen from aromatic endoperoxides by chemical triggers. Angewandte Chemie International Edition, 2018, 57(39): 12971–12975 https://doi.org/10.1002/anie.201806881
13
Y You. Chemical tools for the generation and detection of singlet oxygen. Organic & Biomolecular Chemistry, 2018, 16(22): 4044–4060 https://doi.org/10.1039/C8OB00504D
14
K Liu, R A Lalancette, F Jäkle. Tuning the structure and electronic properties of B-N fused dipyridylanthracene and implications on the self-sensitized reactivity with singlet oxygen. Journal of the American Chemical Society, 2019, 141(18): 7453–7462 https://doi.org/10.1021/jacs.9b01958
15
V Brega, Y Yan, S W I Thomas. Acenes beyond organic electronics: sensing of singlet oxygen and stimuli-responsive materials. Organic & Biomolecular Chemistry, 2020, 18(45): 189191–189209 https://doi.org/10.1039/D0OB01744B
16
Y Q He, W Fudickar, J H Tang, H Wang, X Li, J Han, Z Wang, M Liu, Y W Zhong, T Linker, P J Stang. Capture and release of singlet oxygen in coordination-driven self-assembled organoplatinum(II) metallacycles. Journal of the American Chemical Society, 2020, 142(5): 2601–2608 https://doi.org/10.1021/jacs.9b12693
17
C Yang, M Su, P Luo, Y Liu, F Yang, C Li. A photosensitive polymeric carrier with a renewable singlet oxygen reservoir regulated by two NIR beams for enhanced antitumor phototherapy. Small, 2021, 17(29): 2101180 https://doi.org/10.1002/smll.202101180
18
H Lai, J Yan, S Liu, Q Yang, F Xing, P Xiao. Peripheral RAFT polymerization on a covalent organic polymer with enhanced aqueous compatibility for controlled generation of singlet oxygen. Angewandte Chemie International Edition, 2020, 59(26): 10431–10435 https://doi.org/10.1002/anie.202002446
19
B R Xie, C X Li, Y Yu, J Y Zeng, M K Zhang, X S Wang, X Zeng, X Z Zhang. A singlet oxygen reservoir based on poly-pyridone and porphyrin nanoscale metal−organic framework for cancer therapy. CCS Chemistry, 2021, 3(5): 1187–1202 https://doi.org/10.31635/ccschem.020.202000201
20
C Mongin, A M Ardoy, R Méreau, D M Bassani, B Bibal. Singlet oxygen stimulus for switchable functional organic cages. Chemical Science, 2020, 11(6): 1478–1484 https://doi.org/10.1039/C9SC05354A
21
D Yan, E Lin, F Jin, S Qiao, Y Yang, Z Wang, F Xiong, Y Chen, P Cheng, Z Zhang. Engineering COFs as smart triggers for rapid capture and controlled release of singlet oxygen. Journal of Materials Chemistry A, 2021, 9(48): 27434–27441 https://doi.org/10.1039/D1TA07810K
22
J Zou, L Li, J Zhu, X Li, Z Yang, W Huang, X Chen. Singlet oxygen “afterglow” therapy with NIR-II fluorescent molecules. Advanced Materials, 2021, 33(44): 2103627 https://doi.org/10.1002/adma.202103627
23
S Martins, J P S Farinha, C Baleizão, M N Berberan-Santos. Controlled release of singlet oxygen using diphenylanthracene functionalized polymer nanoparticles. Chemical Communications, 2014, 50(25): 3317–3320 https://doi.org/10.1039/c3cc48293f
24
Z Yuan, S Yu, F Cao, Z Mao, C Gao, J Ling. Near-infrared light triggered photothermal and photodynamic therapy with an oxygen-shuttle endoperoxide of anthracene against tumor hypoxia. Polymer Chemistry, 2018, 9(16): 2124–2133 https://doi.org/10.1039/C8PY00289D
25
G Yu, K Jie, F Huang. Supramolecular amphiphiles based on host−guest molecular recognition motifs. Chemical Reviews, 2015, 115(15): 7240–7303 https://doi.org/10.1021/cr5005315
26
S Wang, W Gao, X Y Hu, Y Z Shen, L Wang. Supramolecular strategy for smart windows. Chemical Communications, 2019, 55(29): 4137–4149 https://doi.org/10.1039/C9CC00273A
27
Y Zhou, K Jie, R Zhao, F Huang. Supramolecular-macrocycle-based crystalline organic materials. Advanced Materials, 2019, 32(20): 1904824 https://doi.org/10.1002/adma.201904824
28
T Hashimoto, M Kumai, M Maeda, K Miyoshi, Y Tsuchido, S Fujiwara, T Hayashita. Structural effect of fluorophore on phenylboronic acid fluorophore/cyclodextrin complex for selective glucose recognition. Frontiers of Chemical Science and Engineering, 2019, 14(1): 53–60 https://doi.org/10.1007/s11705-019-1851-y
29
T Xiao, L Qi, W Zhong, C Lin, R Wang, L Wang. Stimuli-responsive nanocarriers constructed from pillar[n]arene-based supra-amphiphiles. Materials Chemistry Frontiers, 2019, 3(10): 1973–1993 https://doi.org/10.1039/C9QM00428A
30
H Zhang, Z Liu, Y Zhao. Pillararene-based self-assembled amphiphiles. Chemical Society Reviews, 2018, 47(14): 5491–5528 https://doi.org/10.1039/C8CS00037A
31
T Ogoshi, T A Yamagishi, Y Nakamoto. Pillar-shaped macrocyclic hosts pillar[n]arenes: new key players for supramolecular chemistry. Chemical Reviews, 2016, 116(14): 7937–8002 https://doi.org/10.1021/acs.chemrev.5b00765
32
X Wu, Y Yu, L Gao, X Y Hu, L Wang. Stimuli-responsive supramolecular gel constructed by pillar[5]arene-based pseudo[2]rotaxanes via orthogonal metal−ligand coordination and hydrogen bonding interaction. Organic Chemistry Frontiers, 2016, 3(8): 966–970 https://doi.org/10.1039/C6QO00197A
33
Y F Li, Z Li, Q Lin, Y W Yang. Functional supramolecular gels based on pillar[n]arene macrocycles. Nanoscale, 2020, 12(4): 2180–2200 https://doi.org/10.1039/C9NR09532B
34
D Dai, Z Li, J Yang, C Wang, J R Wu, Y Wang, D Zhang, Y W Yang. Supramolecular assembly-induced emission enhancement for efficient mercury(II) detection and removal. Journal of the American Chemical Society, 2019, 141(11): 1414756–1414763 https://doi.org/10.1021/jacs.9b01546
35
J Wang, L Zhou, J Bei, Q Zhao, X Li, J He, Y Cai, T Chen, Y Du, Y Yao. An enhanced photo-electrochemical sensor constructed from pillar[5]arene functionalized au nps for ultrasensitive detection of caffeic acid. Talanta, 2022, 243: 243123322 https://doi.org/10.1016/j.talanta.2022.123322
36
H Zhu, H Wang, B Shi, L Shangguan, W Tong, G Yu, Z Mao, F Huang. Supramolecular peptide constructed by molecular lego allowing programmable self-assembly for photodynamic therapy. Nature Communications, 2019, 10(1): 2412 https://doi.org/10.1038/s41467-019-10385-9
37
M Cen, Y Ding, J Wang, X Yuan, B Lu, Y Wang, Y Yao. Cationic water-soluble pillar[5]arene-modified Cu2–xSe nanoparticles: supramolecular trap for atp and application in targeted photothermal therapy in the NIR-II window. ACS Macro Letters, 2020, 9(11): 1558–1562 https://doi.org/10.1021/acsmacrolett.0c00714
38
Y Wang, M Z Lv, N Song, Z J Liu, C Wang, Y W Yang. Dual-stimuli-responsive fluorescent supramolecular polymer based on a diselenium-bridged pillar[5]arene dimer and an AIE-active tetraphenylethylene guest. Macromolecules, 2017, 50(15): 5759–5766 https://doi.org/10.1021/acs.macromol.7b01010
39
H Guo, X Yan, B Lu, J Wang, X Yuan, Y Han, Y Ding, Y Wang, C Yan, Y Yao. Pillar[5]arene-based supramolecular assemblies with two-step sequential fluorescence enhancement for mitochondria-targeted cell imaging. Journal of Materials Chemistry C, 2020, 8(44): 15622–15625 https://doi.org/10.1039/D0TC04343E
40
Y Li, J Wen, J Li, Z Wu, W Li, K Yang. Recent applications of pillar[n]arene-based host–guest recognition in chemosensing and imaging. ACS Sensors, 2021, 6(11): 3882–3897 https://doi.org/10.1021/acssensors.1c01510
41
W X Feng, Z Sun, M Barboiu. Pillar[n]arenes for construction of artificial transmembrane channels. Israel Journal of Chemistry, 2018, 58(11): 1209–1218 https://doi.org/10.1002/ijch.201800017
42
P Xin, H Kong, Y Sun, L Zhao, H Fang, H Zhu, T Jiang, J Guo, Q Zhang, W Dong, C P Chen. Artificial K+ channels formed by pillararene-cyclodextrin hybrid molecules: tuning cation selectivity and generating membrane potential. Angewandte Chemie International Edition, 2019, 58(9): 2779–2784 https://doi.org/10.1002/anie.201813797
