4.8 Article

Molecular Planarization of Raman Probes to Avoid Background Interference for High-Precision Intraoperative Imaging of Tumor Micrometastases and Lymph Nodes

Journal

NANO LETTERS
Volume 22, Issue 23, Pages 9424-9433

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.nanolett.2c03416

Keywords

Raman imaging; polymeric Raman nanoprobes; molecular planarization; polythiophene; intraoperative imaging; background interference

Funding

  1. National Key R&D Program of China [2020YFA0210800]
  2. National Natural Science Foundation of China [52161160307, 21874092]
  3. Excellent Academic Leader Programme by Shanghai Health Commission [2022XD033]
  4. Science and Technology Commission of Shanghai Municipality [19ZR1428800]
  5. Startup Fund for Young Faculty at Shanghai Jiao Tong University [21X010501069]

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This study presents a molecular planarization strategy for adjusting the signal shift of Raman probes. By modifying the backbone of P3HT polymer, we obtained a PCPDT probe with a blueshifted characteristic signal. The PCPDT probe successfully avoids interference with lipid signals in tissue and enables high-precision intraoperative imaging.
The intraoperative imaging applications of a large number of Raman probes are hampered by the overlap of their signals with the background Raman signals generated by biological tissues. Here, we describe a molecular planarization strategy for adjusting the Raman shift of these Raman probes to avoid interference. Using this strategy, we modify the backbone of thiophene polymer-poly(3-hexylthiophene) (P3HT), and obtain the adjacent thiophene units planarized polycyclopenta[2,1-b;3,4-b']dithiophene (PCPDT). Compared with P3HT whose signal is disturbed by the Raman signal of lipids in tissues, PCPDT exhibits a 60 cm(-1) blueshift in its characteristic signal. Therefore, the PCPDT probe successfully avoids the signal of lipids, and achieves intraoperative imaging of lymph nodes and tumor micrometastasis as small as 0.30 x 0.36 mm. In summary, our study presents a concise molecular planarization strategy for regulating the signal shift of Raman probes, and brings a tunable thiophene polymer probe for high-precision intraoperative Raman imaging.

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