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Vol. 14 (2022)

Visualized SERS Imaging of Single Molecule by Ag/Black Phosphorus Nanosheets

https://doi.org/10.1007/s40820-022-00803-x
Chenglong Lin
State Key Laboratory of High‑Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, People’s Republic of China
Shunshun Liang
State Key Laboratory of Oncogenes and Related Genes, Shanghai Cancer Institute, Renji Hospital, Shanghai Jiaotong University School of Medicine, 200032 Shanghai, People’s Republic of China
Yusi Peng
State Key Laboratory of High‑Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, People’s Republic of China
Li Long
School of Physics and Optoelectronics, South China University of Technology, Guangzhou 510641, People’s Republic of China
Yanyan Li
State Key Laboratory of High‑Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, People’s Republic of China
Zhengren Huang
State Key Laboratory of High‑Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, People’s Republic of China
Nguyen Viet Long
Department of Electronics and Telecommunications, Saigon University, Hochiminh City, Vietnam
Xiaoying Luo
State Key Laboratory of Oncogenes and Related Genes, Shanghai Cancer Institute, Renji Hospital, Shanghai Jiaotong University School of Medicine, 200032 Shanghai, People’s Republic of China
Jianjun Liu
State Key Laboratory of High‑Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, People’s Republic of China
Zhiyuan Li
School of Physics and Optoelectronics, South China University of Technology, Guangzhou 510641, People’s Republic of China
Yong Yang
State Key Laboratory of High‑Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, People’s Republic of China

Corresponding Author: Yong Yang

yangyong@mail.sic.ac.cn

Nano-Micro Letters, Vol. 14 (2022), Article Number: 75

Abstract

Single-molecule detection and imaging are of great value in chemical analysis, biomarker identification and other trace detection fields. However, the localization and visualization of single molecule are still quite a challenge. Here, we report a special-engineered nanostructure of Ag nanoparticles embedded in multi-layer black phosphorus nanosheets (Ag/BP-NS) synthesized by a unique photoreduction method as a surface-enhanced Raman scattering (SERS) sensor. Such a SERS substrate features the lowest detection limit of 10–20 mol L−1 for R6G, which is due to the three synergistic resonance enhancement of molecular resonance, photo-induced charge transfer resonance and electromagnetic resonance. We propose a polarization-mapping strategy to realize the detection and visualization of single molecule. In addition, combined with machine learning, Ag/BP-NS substrates are capable of recognition of different tumor exosomes, which is meaningful for monitoring and early warning of the cancer. This work provides a reliable strategy for the detection of single molecule and a potential candidate for the practical bio-application of SERS technology.


Highlights:


1 Ag/BP-NS exhibit remarkable surface-enhanced Raman scattering performance with single-molecule detection ability. This remarkable enhancement can be attributed to the synergistic resonance enhancement of R6G molecular resonance, photo-induced charge transfer resonance and electromagnetic resonance.
2 A new polarization-mapping method was proposed, which can quickly screen out single-molecule signals and prove that the obtained spectra are emitted by single molecule.
3 The recognition of different tumor exosomes can be realized combining the method of machine learning.

Keywords

Black phosphorus Single molecule SERS Exosome Machine learning
Lin, Chenglong, Shunshun Liang, Yusi Peng, Li Long, Yanyan Li, Zhengren Huang, Nguyen Viet Long, Xiaoying Luo, Jianjun Liu, Zhiyuan Li, and Yong Yang. 2022. “Visualized SERS Imaging of Single Molecule by Ag/Black Phosphorus Nanosheets”. Nano-Micro Letters 14 (March):75. https://doi.org/10.1007/s40820-022-00803-x.
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References
  1. R.A. Halvorson, P.J. Vikesland, Surface-enhanced Raman spectroscopy (SERS) for environmental analyses. Environ. Sci. Technol. 44(20), 7749–7755 (2010). https://doi.org/10.1021/es101228z
  2. Z. Han, H. Liu, J. Meng, L. Yang, J. Liu et al., Portable kit for identification and detection of drugs in human urine using surface-enhanced Raman spectroscopy. Anal. Chem. 87(18), 9500–9506 (2015). https://doi.org/10.1021/acs.analchem.5b02899
  3. Y. Yang, Y. Peng, C. Lin, L. Long, J. Hu et al., Human ACE2-functionalized gold “virus-trap” nanostructures for accurate capture of SARS-CoV-2 and single-virus SERS detection. Nano-Micro Lett. 13, 109 (2021). https://doi.org/10.1007/s40820-021-00620-8
  4. B.Y. Wen, A. Wang, J.S. Lin, P.C. Guan, P.M. Radjenovic et al., A new approach for quantitative surface-enhanced Raman spectroscopy through the kinetics of chemisorption. Small Methods 5(3), 2000993 (2021). https://doi.org/10.1002/smtd.202000993
  5. X. Jiang, Z.Y. Tan, L. Lin, J. He, C. He et al., Surface-enhanced Raman nanoprobes with embedded standards for quantitative cholesterol detection. Small Methods 2(11), 1800182 (2018). https://doi.org/10.1002/smtd.201800182
  6. J.D. Spitzberg, A. Zrehen, X.F. Kooten, A. Meller, Plasmonic-nanopore biosensors for superior single-molecule detection. Adv. Mater. 31(23), 1900422 (2019). https://doi.org/10.1002/adma.201900422
  7. E. Anastasiadou, F.J. Slack, Malicious exosomes. Science 346(6216), 1459–1460 (2014). https://doi.org/10.1126/science.aaa4024
  8. L. Zhao, W.T. Liu, J. Xiao, B.W. Cao, The role of exosomes and “exosomal shuttle microrna” in tumorigenesis and drug resistance. Cancer Lett. 356(2), 339–346 (2015). https://doi.org/10.1016/j.canlet.2014.10.027
  9. J.C. Fraire, S. Stremersch, D. Bouckaert, T. Monteyne, T.D. Beer et al., Improved label-free identification of individual exosome-like vesicles with au@ag nanops as SERS substrate. ACS Appl. Mater. Interfaces 11(43), 39424–39435 (2019). https://doi.org/10.1021/acsami.9b11473
  10. J. Langer, D.J. Aberasturi, J. Aizpurua, R.A. Alvarez-Puebla, B. Auguie et al., Present and future of surface-enhanced Raman scattering. ACS Nano 14(1), 28–117 (2020). https://doi.org/10.1021/acsnano.9b04224
  11. M.G. Albrecht, J.A. Creighton, Anomalously intense Raman spectra of pyridine at a silver electrod. J. Am. Chem. Soc. 99(15), 5215–5217 (1977). https://doi.org/10.1021/ja00457a071
  12. D.L. Jeanmaire, R.P. Vanduyne, Surface Raman spectroelectrochemistry: part I. heterocyclic, aromatic, and aliphatic-amines adsorbed on anodized silver electrode. J. Electroanal. Chem. 84(1), 1–20 (1977). https://doi.org/10.1016/s0022-0728(77)80224-6
  13. A.B. Zrimsek, N.H. Chiang, M. Mattei, S. Zaleski, M.O. McAnally et al., Single-molecule chemistry with surface- and tip-enhanced Raman spectroscopy. Chem. Rev. 117(11), 7583–7613 (2017). https://doi.org/10.1021/acs.chemrev.6b00552
  14. Y. Peng, C. Lin, Y. Li, Y. Gao, J. Wang et al., Identifying infectiousness of SARS-CoV-2 by ultra-sensitive SnS2 SERS biosensors with capillary effect. Matter 5, 694–709 (2022). https://doi.org/10.1016/j.matt.2021.11.028
  15. R. Haldavnekar, K. Venkatakrishnan, B. Tan, Non plasmonic semiconductor quantum SERS probe as a pathway for in vitro cancer detection. Nat. Commun. 9(1), 3065 (2018). https://doi.org/10.1038/s41467-018-05237-x
  16. F. Yu, M. Su, L. Tian, H. Wang, H. Liu, Organic solvent as internal standards for quantitative and high-throughput liquid interfacial SERS analysis in complex media. Anal. Chem. 90(8), 5232–5238 (2018). https://doi.org/10.1021/acs.analchem.8b00008
  17. J.F. Li, Y.F. Huang, Y. Ding, Z.L. Yang, S.B. Li et al., Shell-isolated nanop-enhanced Raman spectroscopy. Nature 464(7287), 392–395 (2010). https://doi.org/10.1038/nature08907
  18. Z. Liu, H. Chen, Y. Jia, W. Zhang, H. Zhao et al., A two-dimensional fingerprint nanoprobe based on black phosphorus for bio-SERS analysis and chemo-photothermal therapy. Nanoscale 10(39), 18795–18804 (2018). https://doi.org/10.1039/c8nr05300f
  19. X. Luo, R. Pan, M. Cai, W. Liu, C. Chen et al., Atto-molar Raman detection on patterned superhydrophilic-superhydrophobic platform via localizable evaporation enrichment. Sens. Actuat. B Chem. 326, 128826 (2021). https://doi.org/10.1016/j.snb.2020.128826
  20. C. Yang, Y. Xu, M. Wang, T. Li, Y. Huo et al., Multifunctional paper strip based on GO-veiled Ag nanops with highly SERS sensitive and deliverable properties for high-performance molecular detection. Opt. Express 26(8), 10023–10037 (2018). https://doi.org/10.1364/OE.26.010023
  21. P. Etchegoin, R.C. Maher, L.F. Cohen, H. Hartigan, R.J.C. Brown et al., New limits in ultrasensitive trace detection by surface enhanced Raman scattering (SERS). Chem. Phys. Lett. 375(1–2), 84–90 (2003). https://doi.org/10.1016/s0009-2614(03)00821-2
  22. S.M. Nie, S.R. Emery, Probing single molecules and single nanops by surface-enhanced Raman scattering. Science 275(5303), 1102–1106 (1997). https://doi.org/10.1126/science.275.5303.1102
  23. M. Keshavarz, P. Kassanos, B. Tan, K. Venkatakrishnan, Metal-oxide surface-enhanced Raman biosensor template towards point-of-care EGFR detection and cancer diagnostics. Nanoscale Horiz. 5(2), 294–307 (2020). https://doi.org/10.1039/c9nh00590k
  24. P.K. Kannan, P. Shankar, C. Blackman, C.H. Chung, Recent advances in 2D inorganic nanomaterials for SERS sensing. Adv. Mater. 31(34), 1803432 (2019). https://doi.org/10.1002/adma.201803432
  25. H.H. Tian, N. Zhang, L.M. Tong, J. Zhang, In situ quantitative graphene-based surface-enhanced Raman spectroscopy. Small Methods 1(6), 1700126 (2017). https://doi.org/10.1002/smtd.201700126
  26. L. Li, Y. Yu, G.J. Ye, Q. Ge, X. Ou et al., Black phosphorus field-effect transistors. Nat. Nanotechnol. 9(5), 372–377 (2014). https://doi.org/10.1038/nnano.2014.35
  27. L.C. Bai, X. Wang, S.B. Tang, Y.H. Kang, J.H. Wang et al., Black phosphorus/platinum heterostructure: a highly efficient photocatalyst for solar-driven chemical reactions. Adv. Mater. 30(40), 1803641 (2018). https://doi.org/10.1002/adma.201803641
  28. D. Huang, Z. Zhuang, Z. Wang, S. Li, H. Zhong et al., Black phosphorus-Au filter paper-based three-dimensional SERS substrate for rapid detection of foodborne bacteria. Appl. Surf. Sci. 497, 143825 (2019). https://doi.org/10.1016/j.apsusc.2019.143825
  29. F. Liu, R. Shi, Z. Wang, Y. Weng, C.M. Che et al., Direct Z-scheme hetero-phase junction of black/red phosphorus for photocatalytic water splitting. Angew. Chem. Int. Ed. 58(34), 11791–11795 (2019). https://doi.org/10.1002/anie.201906416
  30. J. Qiao, X. Kong, Z.X. Hu, F. Yang, W. Ji, High-mobility transport anisotropy and linear dichroism in few-layer black phosphorus. Nat. Commun. 5, 4475 (2014). https://doi.org/10.1038/ncomms5475
  31. L. Li, G.J. Ye, V. Tran, R. Fei, G. Chen et al., Quantum oscillations in a two-dimensional electron gas in black phosphorus thin films. Nat. Nanotechnol. 10(7), 608–613 (2015). https://doi.org/10.1038/nnano.2015.91
  32. H. Wang, X. Yang, W. Shao, S. Chen, J. Xie et al., Ultrathin black phosphorus nanosheets for efficient singlet oxygen generation. J. Am. Chem. Soc. 137(35), 11376–11382 (2015). https://doi.org/10.1021/jacs.5b06025
  33. A. Kundu, R. Rani, K.S. Hazra, Controlled nanofabrication of metal-free SERS substrate on few layered black phosphorus by low power focused laser irradiation. Nanoscale 11(35), 16245–16252 (2019). https://doi.org/10.1039/c9nr02615k
  34. P. Li, W. Chen, D. Liu, H. Huang, K. Dan et al., Template growth of Au/Ag nanocomposites on phosphorene for sensitive SERS detection of pesticides. Nanotechnology 30(27), 275604 (2019). https://doi.org/10.1088/1361-6528/ab12fb
  35. T. Zhang, Y. Wan, H. Xie, Y. Mu, P. Du et al., Degradation chemistry and stabilization of exfoliated few-layer black phosphorus in water. J. Am. Chem. Soc. 140(24), 7561–7567 (2018). https://doi.org/10.1021/jacs.8b02156
  36. X.H. Niu, Y.H. Li, Y.H. Zhang, Q. Li, Q.H. Zhou et al., Photo-oxidative degradation and protection mechanism of black phosphorus: insights from ultrafast dynamics. J. Phys. Chem. Lett. 9(17), 5034–5039 (2018). https://doi.org/10.1021/acs.jpclett.8b02060
  37. Y.T. Lei, D.W. Li, T.C. Zhang, X. Huang, L. Liu et al., One-step selective formation of silver nanops on atomic layered MoS2 by laser-induced defect engineering and photoreduction. J. Mater. Chem. C 5(34), 8883–8892 (2017). https://doi.org/10.1039/c7tc01863k
  38. P. Hildebrandt, M. Stockburger, Surface-enhanced resonance Raman spectroscopy of rhodamine 6G adsorbed on colloidal silver. J. Phys. Chem. 88(24), 5935–5944 (1984). https://doi.org/10.1021/j150668a038
  39. Y. Yang, Z.Y. Li, K. Yamaguchi, M. Tanemura, Z.R. Huang et al., Controlled fabrication of silver nanoneedles array for SERS and their application in rapid detection of narcotics. Nanoscale 4(8), 2663–2669 (2012). https://doi.org/10.1039/c2nr12110g
  40. L. Yang, Y. Peng, Y. Yang, J. Liu, Z. Li et al., Green and sensitive flexible semiconductor SERS substrates: hydrogenated black TiO2 nanowires. ACS Appl. Nano Mater. 1(9), 4516–4527 (2018). https://doi.org/10.1021/acsanm.8b00796
  41. A. Kudelski, Analytical applications of Raman spectroscopy. Talanta 76(1), 1–8 (2008). https://doi.org/10.1016/j.talanta.2008.02.042
  42. S. Yadav, J. Satija, The current state of the art of plasmonic nanofibrous mats as SERS substrates: design, fabrication and sensor applications. J. Mater. Chem. B 9(2), 267–282 (2021). https://doi.org/10.1039/d0tb02137g
  43. J.E. Kim, J.H. Choi, M. Colas, D.H. Kim, H. Lee, Gold-based hybrid nanomaterials for biosensing and molecular diagnostic applications. Biosens. Bioelectron. 80, 543–559 (2016). https://doi.org/10.1016/j.bios.2016.02.015
  44. Z.H. Zhou, L. Liu, G.Y. Wang, Z.Z. Xu, Surface-enhanced resonance Raman scattering spectroscopy of single R6G molecules. Chinese Phys. 15(1), 126–131 (2006). https://doi.org/10.1088/1009-1963/15/1/020
  45. K. Kneipp, Y. Wang, H. Kneipp, I. Itzkan, R.R. Dasari et al., Population pumping of excited vibrational states by spontaneous surface-enhanced Raman scattering. Phys. Rev. Lett. 76(14), 2444–2447 (1996). https://doi.org/10.1103/PhysRevLett.76.2444
  46. M. Hashimoto, K. Yoshiki, M. Kurihara, N. Hashimoto, T. Araki, Orientation detection of a single molecule using pupil filter with electrically controllable polarization pattern. Opt. Rev. 22(6), 875–881 (2015). https://doi.org/10.1007/s10043-015-0143-0
  47. K. Kneipp, H. Kneipp, I. Itzkan, R.R. Dasari, M.S. Feld, Surface-enhanced Raman scattering and biophysics. J. Phys. Condes. Matter 14(18), R597–R624 (2002). https://doi.org/10.1088/0953-8984/14/18/202
  48. J.R. Lombardi, R.L. Birke, A unified approach to surface-enhanced Raman spectroscopy. J. Phys. Chem. C 112(14), 5605–5617 (2008). https://doi.org/10.1021/jp800167v
  49. J.R. Lombardi, R.L. Birke, A unified view of surface-enhanced Raman scattering. Acc. Chem. Res. 42(6), 734–742 (2009). https://doi.org/10.1021/ar800249y
  50. Y.S. Peng, C.L. Lin, L. Long, T. Masaki, M. Tang et al., Charge-transfer resonance and electromagnetic enhancement synergistically enabling mxenes with excellent SERS sensitivity for SARS-CoV-2 S protein detection. Nano-Micro Lett. 13, 52 (2021). https://doi.org/10.1007/s40820-020-00565-4
  51. W.Y. Lei, T.T. Zhang, P. Liu, J.A. Rodriguez, G. Liu et al., Bandgap- and local field-dependent photoactivity of Ag/black phosphorus nanohybrids. ACS Catal. 6(12), 8009–8020 (2016). https://doi.org/10.1021/acscatal.6b02520
  52. R.J. Simpson, J.W.E. Lim, R.L. Moritz, S. Mathivanan, Exosomes: proteomic insights and diagnostic potential. Expert Rev. Proteomic. 6(3), 267–283 (2009). https://doi.org/10.1586/epr.09.17
  53. S. Mathivanan, H. Ji, R.J. Simpson, Exosomes: extracellular organelles important in intercellular communication. J. Proteomic. 73(10), 1907–1920 (2010). https://doi.org/10.1016/j.jprot.2010.06.006
  54. Y.F. Pang, J.M. Shi, X.S. Yang, C.W. Wang, Z.W. Sun et al., Personalized detection of circling exosomal PD-L1 based on Fe3O4@TiO2 isolation and SERS immunoassay. Biosens. Bioelectron. 148, 111800 (2020). https://doi.org/10.1016/j.bios.2019.111800
  55. R. Kalluri, V.S. Lebleu, The biology, function, and biomedical applications of exosomes. Science 367(6478), aau6977 (2020). https://doi.org/10.1126/science.aau6977
  56. A.V. Vlassov, S. Magdaleno, R. Setterquist, R. Conrad, Exosomes: current knowledge of their composition, biological functions, and diagnostic and therapeutic potentials. Biochim. Biophys. Acta Gen. Subj. 1820(7), 940–948 (2012). https://doi.org/10.1016/j.bbagen.2012.03.017
  57. A.J. Massey, D.S. Williamson, H. Browne, J.B. Murray, P. Dokurno et al., A novel, small molecule inhibitor of Hsc70/Hsp70 potentiates Hsp90 inhibitor induced apoptosis in Hct116 colon carcinoma cells. Cancer Chemother. Pharmacol. 66(3), 535–545 (2010). https://doi.org/10.1007/s00280-009-1194-3
  58. Y.L. Chang, S.T. Yang, J.H. Liu, E. Dong, Y.W. Wang et al., In vitro toxicity evaluation of graphene oxide on A549 cells. Toxicol. Lett. 200(3), 201–210 (2011). https://doi.org/10.1016/j.toxlet.2010.11.016
  59. H. Cui, B. Seubert, E. Stahl, H. Dietz, U. Reuning et al., Tissue inhibitor of metalloproteinases-1 induces a pro-tumourigenic increase of miR-210 in lung adenocarcinoma cells and their exosomes. Oncogene 34(28), 3640–3650 (2015). https://doi.org/10.1038/onc.2014.300
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