Citation: FENG Yan-Lin, WANG Jian-Lin, NING Xin, CAO Ji-Min. Au@Ag Core-Shell Nanorods for Surface Enhanced Raman Scattering Imaging of Cancer Cells and in Vivo Cancer Spectroscopic Detection[J]. Chinese Journal of Analytical Chemistry, ;2022, 50(8): 1196-1204. doi: 10.19756/j.issn.0253-3820.221016 shu

Au@Ag Core-Shell Nanorods for Surface Enhanced Raman Scattering Imaging of Cancer Cells and in Vivo Cancer Spectroscopic Detection

Key Laboratory of Cellular Physiology, Ministry of Education, Department of Physiology, Shanxi Medical University, Taiyuan 030001, China

Corresponding author: CAO Ji-Min, caojimin@sxmu.edu.cn
Received Date: 11 January 2022
Revised Date: 13 April 2022

Fund Project: Supported by the National Natural Science Foundation of China (No.22007063) and the Shanxi Medical Key Science and Technology Project Plan, China (No.2020XM01).

Surface enhanced Raman scattering (SERS) is a molecular specific hypersensitive spectroscopy technique. However, the existing SERS are mainly limited to extracorporeal sensing. Silver (Ag) material has become the mostly used SERS substrate because of its excellent surface plasmon resonance (SPR) characteristics. However, poor chemical stability and biocompatibility limit its biomedical applications. Therefore, optimizing the SPR activity and stability of Ag materials has become the research focus to broaden its application in vivo. In this study, Au@Ag core-shell nanorods (Au@Ag NRs) were synthesized by chemical deposition. The detection results of transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), energy dispersive X-ray element mapping (EDX) and X-ray diffraction (XRD) proved that Au@Ag NRs were successfully synthesized. Then, the near infrared Raman molecules of diethylthioacridine carbonyl iodine (DTTC) and mercaptopolyethylene glycol (PEG-SH) were coupled to Au@Ag NRs (p_DAu@Ag NRs) to evaluate SERS properties both in vitro and in vivo. Ultraviolet visible spectrophotometer (UV-Vis) characterization revealed that p_DAu@Ag NRs had good SPR characteristics in the near infrared region, resulting in good SERS properties in vitro. Inductively coupled plasma optical emission spectroscopy (ICP-OES) showed little dissociation of Ag ions, which was not enough to cause biological toxicity. MTS (3-(4,5-dimethylthiazole-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H tetrazole) test further confirmed that p_DAu@Ag NRs had good biocompatibility, ensuring the safe application in vivo. Finally, p_DAu@Ag NRs was used for Raman imaging of human breast cancer (MCF-7) cells and Raman biosensing in MCF-7 tumor-bearing mice. The results showed that Au@Ag NRs had excellent SERS imaging ability in MCF-7 cells and maintained high SERS activity on the tumor site. This technique may be helpful for early monitoring and spectroscopic diagnosis of breast cancer.
1. [1]
  VENDRELL M, MAITI K K, DHALIWAL K, CHANG Y T. Trends Biotechnol., 2013, 31(4):249-257.
2. [2]
  CHAN S, KWON S, KOO T W, LEE L P, BERLIN A A. Adv. Mater., 2003, 15(19):1595-1598.
3. [3]
  DOERING W E, NIE S. Anal. Chem., 2003, 75(22):6171-6176.
4. [4]
  KIM H, BEACK S, HAN S, SHIN M, LEE T, PARK Y, KIM K S, YETISEN A K, YUN S H, KWON W, HAHN S K. Adv. Mater., 2018, 30(10):1701460.
5. [5]
  LISMONT M, DREESEN L. Mater. Sci. Eng., C, 2012, 32(6):1437-1442.
6. [6]
  BHARADWAJ P, NOVOTNY L. Opt. Express., 2007, 15(21):14266-14274.
7. [7]
  RYCENGA M, COBLEY C M, ZENG J, LI W Y, MORAN C H, ZHANG Q, XIA Y N. Chem. Rev., 2011, 111(6):3669-3712.
8. [8]
  YANG Y, LIU J Y, FU Z W, QIN D. J. Am. Chem. Soc., 2014, 136(23):8153-8156.
9. [9]
  MOTT D M, ANH D N, SINGH P, SHANKAR C, MAENOSONO S. Adv. Colloid Interface Sci., 2012, 185:14-33.
10. [10]
  SUN H Y, GUO X, YE W, KOU S F, YANG J. Nano Res., 2016, 9(4):1173-1181.
11. [11]
  WATSON R E, HUDIS J, PERLMAN M L. Phys. Rev. B, 1971, 4(12):4139-4144.
12. [12]
  DRUBE W, TREUSCH R, SHAM T K, BZOWSKI A, SOLDATOV A V. Phys. Rev. B, 1998, 58(11):6871-6876.
13. [13]
  TYSON C C, BZOWSKI A, KRISTOF P, KUHN M, SAMMYNAIKEN R, SHAM T K. Phys. Rev. B, 1992, 45(16):8924-8928.
14. [14]
  SINGH P, SHANKAR C, MOTT D, MAENOSONO S. Appl. Phys. Lett., 2011, 99(7):073107.
15. [15]
  FENG Y L, CHANG Y, SUN X J, CHENG Y, ZHENG R X, WU X Q, WANG L, MA X M, LI X, ZHANG H Y. Biomater. Sci., 2019, 7(4):1448-1462.
16. [16]
  GUO X, ZHANG Q, SUN Y H, ZHAO Q, YANG J. ACS Nano, 2012, 6(2):1165-1175.
17. [17]
  YANG Y, SHI J L, KAWAMURA G, NOGAMI M. Scr. Mater., 2008, 58(10):862-865.
18. [18]
  YIN Z, WANG Y, SONG C, ZHENG L, MA N, LIU X, LI S, LIN L, LI M, XU Y. J. Am. Chem. Soc., 2018, 140(3):864-867.
19. [19]
  SIVAPALAN S T, DEVETTER B M, YANG T K, VAN DIJK T, SCHULMERICH M V, CARNEY P S. ACS Nano, 2013, 7(3):2099-2105.
20. [20]
  FENG Y L, WANG G R, CHANG Y, CHENG Y, SUN B B, WANG L M, CHEN C Y, ZHANG H Y. Nano Lett., 2019, 19(7):4478-4489.
21. [21]
  WANG L M, ZHANG T L, LI P Y, HUANG W X, TANG J L, WANG P Y, LIU J, YUAN Q X, BAI R, LI B, ZHANG K, ZHAO Y L, CHEN C Y. ACS Nano, 2015, 9(6):6532-6547.
22. [22]
  CHOI O, CLEVENGER T E, DENG B, SURAMPALLI R Y, JR R L, HU Z. Water Res., 2009, 43(7):1879-1886.
23. [23]
  XIU Z M, MA J, ALVAREZ P J J. Environ. Sci., 2011, 45(20):9003-9008.
24. [24]
  GUO S T, HUANG L. J. Nanomater., 2011, 2011(1687):1-12.
25. [25]
  BODELON G, MONTES G V, LOPEZ P V, HILL E H, HAMON C, SANZ M N. Nat. Mater., 2016, 15(11):1203-1211.
26. [26]
  LI H, LIU H, QIN Y, MU Y, ZHANG X. Plasmonics, 2020, 15(6):2027-2032.
27. [27]
  NTZIACHRISTOS V, BREMER C,WEISSLEDER R. Eur. J. Radiol., 2003, 13(1):195-208.
28. [28]
  FANG J, NAKAMURA H, MAEDA H. Adv. Drug Delivery Rev., 2011, 63(3):136-151.
29. [29]
  MAEDA H, WU J, SAWA T, MATSUMURA Y, HORI K. J. Controlled Release., 2000, 65(1):271-284.
30. [30]
  WU N Z, DA D, RUDOLL T L, NEEDHAM D, WHORTON A R, DEWHIRST M W. Cancer Res., 1993, 53(16):3765-3770.
1. [1]
  Ruiqin Feng , Ye Fan , Yun Fang , Yongmei Xia . Strategy for Regulating Surface Protrusion of Gold Nanoflowers and Their Surface-Enhanced Raman Scattering. Acta Physico-Chimica Sinica, 2024, 40(4): 2304020-0. doi: 10.3866/PKU.WHXB202304020
2. [2]
  Liang MA , Honghua ZHANG , Weilu ZHENG , Aoqi YOU , Zhiyong OUYANG , Junjiang CAO . Construction of highly ordered ZIF-8/Au nanocomposite structure arrays and application of surface-enhanced Raman spectroscopy. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1743-1754. doi: 10.11862/CJIC.20240075
3. [3]
  Zhuomin Zhang , Hanbing Huang , Liangqiu Lin , Jingsong Liu , Gongke Li . Course Construction of Instrumental Analysis Experiment: Surface-Enhanced Raman Spectroscopy for Rapid Detection of Edible Pigments. University Chemistry, 2024, 39(2): 133-139. doi: 10.3866/PKU.DXHX202308034
4. [4]
  Wei Peng , Baoying Wen , Huamin Li , Yiru Wang , Jianfeng Li . Exploration and Practice on Raman Scattering Spectroscopy Experimental Teaching. University Chemistry, 2024, 39(8): 230-240. doi: 10.3866/PKU.DXHX202312062
5. [5]
  Yufan ZHAO , Jinglin YOU , Shixiang WANG , Guopeng LIU , Xiang XIA , Yingfang XIE , Meiqin SHENG , Feiyan XU , Kai TANG , Liming LU . Raman spectroscopic quantitative study of the melt microstructure in binary Li₂O-GeO₂ functional crystals. Chinese Journal of Inorganic Chemistry, 2025, 41(8): 1533-1544. doi: 10.11862/CJIC.20250063
6. [6]
  Jingyi Chen , Fu Liu , Tiejun Zhu , Kui Cheng . Practice of Integrating Ideological and Political Education into Raman Spectroscopy Analysis Experiment Course. University Chemistry, 2024, 39(2): 140-146. doi: 10.3866/PKU.DXHX202310111
7. [7]
  Zhaoyue Lü , Zhehao Chen , Yi Ni , Duanbin Luo , Xianfeng Hong . Multi-Level Teaching Design and Practice Exploration of Raman Spectroscopy Experiment. University Chemistry, 2024, 39(11): 304-312. doi: 10.12461/PKU.DXHX202402047
8. [8]
  Jiajie Li , Xiaocong Ma , Jufang Zheng , Qiang Wan , Xiaoshun Zhou , Yahao Wang . Recent Advances in In-Situ Raman Spectroscopy for Investigating Electrocatalytic Organic Reaction Mechanisms. University Chemistry, 2025, 40(4): 261-276. doi: 10.12461/PKU.DXHX202406117
9. [9]
  Kaifu Zhang , Shan Gao , Bin Yang . Application of Theoretical Calculation with Fun Practice in Raman Spectroscopy Experimental Teaching. University Chemistry, 2025, 40(3): 62-67. doi: 10.12461/PKU.DXHX202404045
10. [10]
  Huihui LIU , Baichuan ZHAO , Chuanhui WANG , Zhi WANG , Congyun ZHANG . Green synthesis of MIL-101/Au composite particles and their sensitivity to Raman detection of thiram. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 2021-2030. doi: 10.11862/CJIC.20240059
11. [11]
  Xue Wu , Yupeng Liu , Bingzhe Wang , Lingyun Li , Zhenjian Li , Qingcheng Wang , Quansheng Cheng , Guichuan Xing , Songnan Qu . Rationally assembling different surface functionalized carbon dots for enhanced near-infrared tumor photothermal therapy. Acta Physico-Chimica Sinica, 2025, 41(9): 100109-0. doi: 10.1016/j.actphy.2025.100109
12. [12]
  Hong LI , Xiaoying DING , Cihang LIU , Jinghan ZHANG , Yanying RAO . Detection of iron and copper ions based on gold nanorod etching colorimetry. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 953-962. doi: 10.11862/CJIC.20230370
13. [13]
  Hongpeng He , Mengmeng Zhang , Mengjiao Hao , Wei Du , Haibing Xia . Synthesis of Different Aspect-Ratios of Fixed Width Gold Nanorods. Acta Physico-Chimica Sinica, 2024, 40(5): 2304043-0. doi: 10.3866/PKU.WHXB202304043
14. [14]
  Siyi ZHONG , Xiaowen LIN , Jiaxin LIU , Ruyi WANG , Tao LIANG , Zhengfeng DENG , Ao ZHONG , Cuiping HAN . Targeting imaging and detection of ovarian cancer cells based on fluorescent magnetic carbon dots. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1483-1490. doi: 10.11862/CJIC.20240093
15. [15]
  Weihan Zhang , Menglu Wang , Ankang Jia , Wei Deng , Shuxing Bai . Surface Sulfur Species Influence Hydrogenation Performance of Palladium-Sulfur Nanosheets. Acta Physico-Chimica Sinica, 2024, 40(11): 2309043-0. doi: 10.3866/PKU.WHXB202309043
16. [16]
  Hong RAO , Yang HU , Yicong MA , Chunxin LÜ , Wei ZHONG , Lihua DU . Synthesis and in vitro anticancer activity of phenanthroline-functionalized nitrogen heterocyclic carbene homo- and heterobimetallic silver/gold complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2429-2437. doi: 10.11862/CJIC.20240275
17. [17]
  Di WU , Ruimeng SHI , Zhaoyang WANG , Yuehua SHI , Fan YANG , Leyong ZENG . Construction of pH/photothermal dual-responsive delivery nanosystem for combination therapy of drug-resistant bladder cancer cell. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1679-1688. doi: 10.11862/CJIC.20240135
18. [18]
  Endong YANG , Haoze TIAN , Ke ZHANG , Yongbing LOU . Efficient oxygen evolution reaction of CuCo₂O₄/NiFe-layered bimetallic hydroxide core-shell nanoflower sphere arrays. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 930-940. doi: 10.11862/CJIC.20230369
19. [19]
  Chen Pu , Daijie Deng , Henan Li , Li Xu . Fe_0.64Ni_0.36@Fe₃NiN Core-Shell Nanostructure Encapsulated in N-Doped Carbon Nanotubes for Rechargeable Zinc-Air Batteries with Ultralong Cycle Stability. Acta Physico-Chimica Sinica, 2024, 40(2): 2304021-0. doi: 10.3866/PKU.WHXB202304021
20. [20]
  Heng Chen , Longhui Nie , Kai Xu , Yiqiong Yang , Caihong Fang . Remarkable Photocatalytic H₂O₂ Production Efficiency over Ultrathin g-C₃N₄ Nanosheet with Large Surface Area and Enhanced Crystallinity by Two-Step Calcination. Acta Physico-Chimica Sinica, 2024, 40(11): 2406019-0. doi: 10.3866/PKU.WHXB202406019

Get Citation

PDF

XML

Metrics

PDF Downloads(12)
Abstract views(957)
HTML views(206)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142