volume | PIER Journals

Abstract

Layered molybdenum disulphide (MoS₂) can efficiently emit photoluminescence (PL) excited by visible light. However, one-photon PL of MoS₂ for bioimaging purposes suffers from strong autofluorescence and ion-induced PL quenching. Herein, we report single layer chitosan decorated MoS₂ nanosheets as nonbleaching and nonblinking optical nanoprobes under near infrared femtosecond laser excitation and their applications for two photon luminescence (TPL) and second harmonic generation (SHG) bioimaging. The TPL can resist the ion-induced quenching by the cellular membrane. The proposed TPL and SHG of singlelayer MoS₂ show great potential for real-time, deep and multiphoton bioimaging.

1. Novoselov, K. S., A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, S. V. Dubonos, I. V. Grigorieva, and A. A. Firsov, "Electric field in atomically thin carbon films," Science, Vol. 306, No. 5696, 666-669, 2004, https://doi.org/10.1126/science.1102896.
doi:10.1126/science.1102896

2. Manzeli, S., D. Ovchinnikov, D. Pasquier, O. V. Yazyev, and A. Kis, "2D transition metal dichalcogenides," Nat. Rev. Mater., Vol. 2, Article number: 17033, 2017, https://doi.org/10.1038/natrevmats.2017.33.

3. Bhimanapati, G. R., Z. Lin, V. Meunier, Y. Jung, J. Cha, S. Das, D. Xiao, Y. Son, M. S. Strano, V. R. Cooper, L. Liang, S. G. Louie, E. Ringe, W. Zhou, S. S. Kim, R. R. Naik, B. G. Sumpter, H. Terrones, F. Xia, Y. Wang, J. Zhu, D. Akinwande, N. Alem, J. A. Schuller, R. E. Schaak, M. Terrones, and J. A. Robinson, "Recent advances in two-dimensional materials beyond graphene," ACS Nano, Vol. 9, No. 12, 11509-11539, 2015, https://doi.org/10.1021/acsnano.5b05556.
doi:10.1021/acsnano.5b05556

4. Dong, N., Y. Li, S. Zhang, X. Zhang, and J. Wang, "Optically induced transparency and extinction in dispersed MoS2, MoSe2, and graphene nanosheets," Adv. Opt. Mater., Vol. 5, No. 19, 1700543, 2017, https://doi.org/10.1002/adom.201700543.
doi:10.1002/adom.201700543

5. Wang, Q. H., K. Kalantar-Zadeh, A. Kis, J. N. Coleman, and M. S. Strano, "Electronics and optoelectronics of two-dimensional transition metal dichalcogenides," Nat. Nanotechnol., Vol. 7, 699-712, 2012, https://doi.org/10.1038/nnano.2012.193.
doi:10.1038/nnano.2012.193

6. Liu, T., C. Wang, X. Gu, H. Gong, L. Cheng, X. Shi, L. Feng, B. Sun, and Z. Liu, "Drug delivery with PEGylated MoS2 nano-sheets for combined photothermal and chemotherapy of cancer," Adv. Mater., Vol. 26, No. 21, 3433-3440, 2014, https://doi.org/10.1002/adma.201305256.
doi:10.1002/adma.201305256

7. Gao, W., Y. H. Lee, R. Jiang, J. Wang, T. Liu, and X. Y. Ling, "Localized and continuous tuning of monolayer MoS2 photoluminescence using a single shape-controlled Ag nanoantenna," Adv. Mater., Vol. 28, No. 4, 701-706, 2016, https://doi.org/10.1002/adma.201503905.
doi:10.1002/adma.201503905

8. Wang, H., B. H. Chen, X. Y. Zhang, S. Liu, B. Q. Zhu, J. Wang, K. Wu, and J. P. Chen, "Ethanol catalytic deposition of MoS2 on tapered fiber," Photonics Res., Vol. 3, No. 3, A102-A107, 2015, https://doi.org/10.1364/prj.3.00a102.
doi:10.1364/PRJ.3.00A102

9. Guan, G., S. Zhang, S. Liu, Y. Cai, M. Low, C. P. Teng, I. Y. Phang, Y. Cheng, K. L. Duei, B. M. Srinivasan, Y. Zheng, Y. W. Zhang, and M. Y. Han, "Protein induces layer-by-layer exfoliation of transition metal dichalcogenides," J. Am. Chem. Soc., Vol. 137, No. 19, 6152-6155, 2015, https://doi.org/10.1021/jacs.5b02780.
doi:10.1021/jacs.5b02780

10. Pi, Y., Z. Li, D. Xu, J. Liu, Y. Li, F. Zhang, G. Zhang, W. Peng, and X. Fan, "1T-phase MoS2 nanosheets on TiO2 nanorod arrays: 3D photoanode with extraordinary catalytic performance," ACS Sustain. Chem. Eng., Vol. 5, No. 6, 5175-5182, 2017, https://doi.org/10.1021/acssuschemeng.7b00518.
doi:10.1021/acssuschemeng.7b00518

11. Mak, K. F., C. Lee, J. Hone, J. Shan, and T. F. Heinz, "Atomically thin MoS2: A new direct-gap semiconductor," Phys. Rev. Lett., Vol. 105, 136805, 2010, https://doi.org/10.1103/PhysRevLett.105.136805.
doi:10.1103/PhysRevLett.105.136805

12. Ou, J. Z., A. F. Chrimes, Y. Wang, S. Y. Tang, M. S. Strano, and K. Kalantar-Zadeh, "Iondriven photoluminescence modulation of quasi-two-dimensional MoS2 nanoflakes for applications in biological systems," Nano Lett., Vol. 14, No. 2, 857-863, 2014, https://doi.org/10.1021/nl4042356.
doi:10.1021/nl4042356

13. Wang, N., F. Wei, Y. Qi, H. Li, X. Lu, G. Zhao, and Q. Xu, "Synthesis of strongly fluorescent molybdenum disulfide nanosheets for cell-targeted labeling," ACS Appl. Mater. Interfaces, Vol. 6, No. 22, 19888-19894, 2014, https://doi.org/10.1021/am505305g.
doi:10.1021/am505305g

14. Li, J. L., H. C. Bao, X. L. Hou, L. Sun, X. G. Wang, and M. Gu, "Graphene oxide nanoparticles as a nonbleaching optical probe for two-photon luminescence imaging and cell therapy," Angew. Chemie — Int. Ed., Vol. 51, No. 8, 1830-1834, 2012, https://doi.org/10.1002/anie.201106102.
doi:10.1002/anie.201106102

15. Qian, J., D.Wang, F. H. Cai, W. Xi, L. Peng, Z. F. Zhu, H. He, M. L. Hu, and S. He, "Observation of multiphoton-induced fluorescence from graphene oxide nanoparticles and applications in invivo functional bioimaging," Angew. Chemie — Int. Ed., Vol. 51, No. 42, 10570-10575, 2012, https://doi.org/10.1002/anie.201206107.
doi:10.1002/anie.201206107

16. Zhang, S., N. Dong, N. McEvoy, M. OBrien, S. Winters, N. C. Berner, C. Yim, Y. Li, X. Zhang, Z. Chen, L. Zhang, G. S. Duesberg, and J. Wang, "Direct observation of degenerate two-photon absorption and its saturation in WS2 and MoS2 monolayer and few-layer films," ACS Nano, Vol. 9, No. 7, 7142-7150, 2015, https://doi.org/10.1021/acsnano.5b03480.
doi:10.1021/acsnano.5b03480

17. Shi, L., L. A. Sordillo, A. Rodr´ıguez-Contreras, and R. Alfano, "Transmission in near-infrared optical windows for deep brain imaging," J. Biophotonics, Vol. 9, No. 1–2, 38-43, 2016, https://doi.org/10.1002/jbio.201500192.
doi:10.1002/jbio.201500192

18. Yin, W., L. Yan, J. Yu, G. Tian, L. Zhou, X. Zheng, X. Zhang, Y. Yong, J. Li, Z. Gu, and Y. Zhao, "High-throughput synthesis of single-layer MoS2 nanosheets as a near-infrared photothermaltriggered drug delivery for effective cancer therapy," ACS Nano, Vol. 8, No. 7, 6922-6933, 2014, https://doi.org/10.1021/nn501647j.
doi:10.1021/nn501647j

19. Chou, S. S., B. Kaehr, J. Kim, B. M. Foley, M. De, P. E. Hopkins, J. Huang, C. J. Brinker, and V. P. Dravid, "Chemically exfoliated MoS2 as near-infrared photothermal agents," Angew. Chemie — Int. Ed., Vol. 52, No. 15, 4160-4164, 2013, https://doi.org/10.1002/anie.201209229.
doi:10.1002/anie.201209229

20. Li, Y., N. Dong, S. Zhang, X. Zhang, Y. Feng, K. Wang, L. Zhang, and J. Wang, "Giant twophoton absorption in monolayer MoS2," Laser Photonics Rev., Vol. 9, No. 4, 427-434, 2015, https://doi.org/10.1002/lpor.201500052.
doi:10.1002/lpor.201500052

21. Malard, L. M., T. V. Alencar, A. P. M. Barboza, K. F. Mak, and A. M. De Paula, "Observation of intense second harmonic generation from MoS2 atomic crystals," Phys. Rev. B — Condens. Matter Mater. Phys., Vol. 87, 201401(R), 2013, https://doi.org/10.1103/PhysRevB.87.201401..
doi:10.1103/PhysRevB.87.201401

22. Zeng, J., M. Yuan, W. Yuan, Q. Dai, H. Fan, S. Lan, and S. Tie, "Enhanced second harmonic generation of MoS2 layers on a thin gold film," Nanoscale, Vol. 7, No. 32, 13547-13553, 2015, https://doi.org/10.1039/C5NR03133H.
doi:10.1039/C5NR03133H

23. Wang, R., H. C. Chien, J. Kumar, N. Kumar, H. Y. Chiu, and H. Zhao, "Third-harmonic generation in ultrathin films of MoS2," ACS Appl. Mater. Interfaces, Vol. 6, No. 1, 314-318, 2014, https://doi.org/10.1021/am4042542.
doi:10.1021/am4042542

24. Zhang, W., Y. Wang, D. Zhang, S. Yu, W. Zhu, J. Wang, F. Zheng, S. Wang, and J. Wang, "A onestep approach to the large-scale synthesis of functionalized MoS2 nanosheets by ionic liquid assisted grinding," Nanoscale, Vol. 7, No. 22, 10210-10217, 2015, https://doi.org/10.1039/c5nr02253c.
doi:10.1039/C5NR02253C

25. Eda, G., H. Yamaguchi, D. Voiry, T. Fujita, M. Chen, and M. Chhowalla, "Photoluminescence from chemically exfoliated MoS2," Nano Lett., Vol. 11, No. 12, 5111-5116, 2011, https://doi.org/10.1021/nl201874w.
doi:10.1021/nl201874w

26. Bao, H., Y. Pan, Y. Ping, N. G. Sahoo, T.Wu, L. Li, J. Li, and L. H. Gan, "Chitosan-functionalized graphene oxide as a nanocarrier for drug and gene delivery," Small, Vol. 7, No. 11, 1569-1578, 2011, https://doi.org/10.1002/smll.201100191.
doi:10.1002/smll.201100191

27. Shang, N. G., P. Papakonstantinou, S. Sharma, G. Lubarsky, M. Li, D. W. McNeill, A. J. Quinn, W. Zhou, and R. Blackley, "Controllable selective exfoliation of high-quality graphene nanosheets and nanodots by ionic liquid assisted grinding," Chem. Commun., Vol. 48, No. 13, 1877-1879, 2012, https://doi.org/10.1039/c2cc17185f.
doi:10.1039/c2cc17185f

28. Li, H., Q. Zhang, C. C. R. Yap, B. K. Tay, T. H. T. Edwin, A. Olivier, and D. Baillargeat, "From bulk to monolayer MoS2: Evolution of Raman scattering," Adv. Funct. Mater., Vol. 22, No. 7, 1385-1390, 2012, https://doi.org/10.1002/adfm.201102111.
doi:10.1002/adfm.201102111

29. Lee, C., H. Yan, L. E. Brus, T. F. Heinz, J. Hone, and S. Ryu, "Anomalous lattice vibrations of single- and few-layer MoS2," ACS Nano, Vol. 4, No. 5, 2695-2700, 2010, https://doi.org/10.1021/nn1003937.
doi:10.1021/nn1003937

30. Li, B. L., H. L. Zou, L. Lu, Y. Yang, J. L. Lei, H. Q. Luo, and N. B. Li, "Size-dependent optical absorption of layered MoS2 and DNA oligonucleotides induced dispersion behavior for label-free detection of single-nucleotide polymorphism," Adv. Funct. Mater., Vol. 25, No. 23, 3541-3550, 2015, https://doi.org/10.1002/adfm.201500180.
doi:10.1002/adfm.201500180

31. Splendiani, A., L. Sun, Y. Zhang, T. Li, J. Kim, C. Y. Chim, G. Galli, and F. Wang, "Emerging photoluminescence in monolayer MoS2," Nano Lett., Vol. 10, No. 4, 1271-1275, 2010, https://doi.org/10.1021/nl903868w.
doi:10.1021/nl903868w

32. Wang, Y., J. Z. Ou, S. Balendhran, A. F. Chrimes, M. Mortazavi, D. D. Yao, M. R. Field, K. Latham, V. Bansal, J. R. Friend, S. Zhuiykov, N. V. Medhekar, M. S. Strano, and K. Kalantar-Zadeh, "Electrochemical control of photoluminescence in two-dimensional MoS2 nanoflakes," ACS Nano, Vol. 7, No. 11, 10083-10093, 2013, https://doi.org/10.1021/nn4041987.
doi:10.1021/nn4041987

33. Zhan, Q., J. Qian, H. Liang, G. Somesfalean, D. Wang, S. He, Z. Zhang, and S. Andersson-Engels, "Using 915 nm laser excited Tm3+/Er3+/Ho33+-Doped NaYbF4 upconversion nanoparticles for in Vitro and deeper in Vivo bioimaging without overheating irradiation," ACS Nano, Vol. 5, No. 5, 3744-3757, 2011, https://doi.org/10.1021/nn200110j.
doi:10.1021/nn200110j

34. Wu, S., G. Han, D. J. Milliron, S. Aloni, V. Altoe, D. V. Talapin, B. E. Cohen, and P. J. Schuck, "Non-blinking and photostable upconverted luminescence from single lanthanidedoped nanocrystals," Journal Proceedings of the National Academy of Sciences of the United States of America, Vol. 106, No. 27, 10917-10921, 2014, https://doi.org/10.1073/pnas.0904792106.
doi:10.1073/pnas.0904792106

35. Wu, R., Q. Zhan, H. Liu, X. Wen, B. Wang, and S. He, "Optical depletion mechanism of upconverting luminescence and its potential for multi-photon STED-like microscopy," Opt. Express, Vol. 23, No. 25, 32401-32412, 2015, https://doi.org/10.1364/OE.23.032401.
doi:10.1364/OE.23.032401

36. Zhan, Q., H. Liu, B. Wang, Q. Wu, R. Pu, C. Zhou, B. Huang, X. Peng, H. Agren, and S. He, "Achieving high-efficiency emission depletion nanoscopy by employing cross relaxation in upconversion nanoparticles," Nat. Commun., Vol. 8, 1-11, 2017. https://doi.org/10.1038/s41467-017-01141-y.

Dr. Qiuqiang Zhan

Dr. Xin Zhang

Dr. Baoju Wang

Dr. Nana Li

Prof. Sailing He