Abstract
Surface enhanced Raman scattering (SERS) is a rapid and nondestructive technique that is capable of detecting and identifying chemical or biological compounds. Sensitive SERS quantification is vital for practical applications, particularly for portable detection of biomolecules such as amino acids and nucleotides. However, few approaches can achieve sensitive and quantitative Raman detection of these most fundamental components in biology. Herein, a noble-metal-free single-atom site on a chip strategy was applied to modify single tungsten atom oxide on a lead halide perovskite, which provides sensitive SERS quantification for various analytes, including rhodamine, tyrosine and cytosine. The single-atom site on a chip can enable quantitative linear SERS responses of rhodamine (10−6−1 mmol L−1), tyrosine (0.06–1 mmol L−1) and cytosine (0.2–45 mmol L−1), respectively, which all achieve record-high enhancement factors among plasmonic-free semiconductors. The experimental test and theoretical simulation both reveal that the enhanced mechanism can be ascribed to the controllable single-atom site, which can not only trap photoinduced electrons from the perovskite substrate but also enhance the highly efficient and quantitative charge transfer to analytes. Furthermore, the label-free strategy of single-atom sites on a chip can be applied in a portable Raman platform to obtain a sensitivity similar to that on a benchtop instrument, which can be readily extended to various biomolecules for low-cost, widely demanded and more precise point-of-care testing or in-vitro detection.
摘要
表面增**拉曼散射(SERS)是一种快速且无损的化学和生物分子检测技术. 高灵敏且定量化的SERS检测技术对其在实际中的应用至关重要, 尤其是对生物分子如氨基酸和碱基的便携化检测. 但是鲜有技术手段能够实现对这些最基本的生物分子进行高灵敏且定量化的拉曼检测. 我们提出了一种无需贵金属的单原子位点修饰芯片策略, 用钨单原子氧化物修饰铅卤钙钛矿芯片, 实现了多种检测物的高灵敏定量化识别, 包括罗丹明、 酪氨酸和胞嘧啶. 芯片上单原子位点技术能够实现对罗丹明、 酪氨酸和胞嘧啶的线性检测, 相应的定量化区间分别为: 10−6–1 mmol L−1, 0.06–1 mmol L−1和0.2–45 mmol L−1, 同时我们的拉曼增**芯片对这三种分子的增**因子在非等离子激元半导体中是最高的. 我们通过实验测试结合理论模拟揭示了由可控单原子位点实现拉曼增**的机理: 束缚由钙钛矿基底产生的光生电子, 同时高效且定量地将这些电子转移到待测分子上. 不仅如此, 芯片上单原子位点技术可以在便携式拉曼设备下得到与台式拉曼设备类似的增**效果, 这意味着这项技术有机会应用于多种生物分子的低成本、 广谱、 即时检测和体外检测.
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References
Cardinal MF, Vander Ende E, Hackler RA, et al. Expanding applications of SERS through versatile nanomaterials engineering. Chem Soc Rev, 2017, 46: 3886–3903
Garcia-Rico E, Alvarez-Puebla RA, Guerrini L. Direct surface-enhanced Raman scattering (SERS) spectroscopy of nucleic acids: From fundamental studies to real-life applications. Chem Soc Rev, 2018, 47: 4909–4923
Bell SEJ, Charron G, Cortés E, et al. Towards reliable and quantitative surface-enhanced Raman scattering (SERS): From key parameters to good analytical practice. Angew Chem Int Ed, 2020, 59: 5454–5462
Wang X, Huang SC, Hu S, et al. Fundamental understanding and applications of plasmon-enhanced Raman spectroscopy. Nat Rev Phys, 2020, 2: 253–271
Langer J, Jimenez de Aberasturi D, Aizpurua J, et al. Present and future of surface-enhanced Raman scattering. ACS Nano, 2020, 14: 28–117
Li D, Yao D, Li C, et al. Nanosol SERS quantitative analytical method: A review. TrAC Trends Anal Chem, 2020, 127: 115885
** Y, **e Y, Wu K, et al. Probing the dynamic interaction between damaged DNA and a cellular responsive protein using a piezoelectric mass biosensor. ACS Appl Mater Interfaces, 2017, 9: 8490–8497
Perales-Rondon JV, Colina A, González MC, et al. Roughened silver microtubes for reproducible and quantitative SERS using a templateassisted electrosynthesis approach. Appl Mater Today, 2020, 20: 100710
Pilot R. SERS detection of food contaminants by means of portable Raman instruments. J Raman Spectrosc, 2018, 49: 954–981
Huang JA, Mousavi MZ, Giovannini G, et al. Multiplexed discrimination of single amino acid residues in polypeptides in a single SERS hot spot. Angew Chem Int Ed, 2020, 59: 11423–11431
Kim M, Ko SM, Lee C, et al. Hierarchic interfacial nanocube assembly for sensitive, selective, and quantitative DNA detection with surface-enhanced Raman scattering. Anal Chem, 2019, 91: 10467–10476
Yan W, Yang L, Chen J, et al. In situ two-step photoreduced SERS materials for on-chip single-molecule spectroscopy with high re-producibility. Adv Mater, 2017, 29: 1702893
Chen G, Dai Z, Ji B, et al. Dynamic enrichment of plasmonic hot-spots and analytes on superhydrophobic and magnetically functionalized platform for surface-enhanced Raman scattering. Sens Actuat B-Chem, 2020, 319: 128297
Wu Y, Bennett D, Tilley RD, et al. How nanoparticles transform single molecule measurements into quantitative sensors. Adv Mater, 2020, 32: 1904339
Li JF, Zhang YJ, Ding SY, et al. Core-shell nanoparticle-enhanced Raman spectroscopy. Chem Rev, 2017, 117: 5002–5069
Xu D, Teng F, Wang Z, et al. Droplet-confined electroless deposition of silver nanoparticles on ordered superhydrophobic structures for high uniform SERS measurements. ACS Appl Mater Interfaces, 2017, 9: 21548–21553
Kim N, Thomas MR, Bergholt MS, et al. Surface enhanced Raman scattering artificial nose for high dimensionality fingerprinting. Nat Commun, 2020, 11: 207
Lee HK, Lee YH, Koh CSL, et al. Designing surface-enhanced Raman scattering (SERS) platforms beyond hotspot engineering: Emerging opportunities in analyte manipulations and hybrid materials. Chem Soc Rev, 2019, 48: 731–756
Yang L, Peng Y, Yang Y, et al. A novel ultra-sensitive semiconductor SERS substrate boosted by the coupled resonance effect. Adv Sci, 2019, 6: 1900310
Cong S, Yuan Y, Chen Z, et al. Noble metal-comparable SERS enhancement from semiconducting metal oxides by making oxygen vacancies. Nat Commun, 2015, 6: 7800
Shan Y, Zheng Z, Liu J, et al. Niobium pentoxide: A promising surface-enhanced Raman scattering active semiconductor substrate. npj Comput Mater, 2017, 3: 11
Guan H, Yi W, Li T, et al. Low temperature synthesis of plasmonic molybdenum nitride nanosheets for surface enhanced Raman scattering. Nat Commun, 2020, 11: 3889
Wang X, Shi W, Wang S, et al. Two-dimensional amorphous TiO2 nanosheets enabling high-efficiency photoinduced charge transfer for excellent SERS activity. J Am Chem Soc, 2019, 141: 5856–5862
Ye Y, Yi W, Liu W, et al. Remarkable surface-enhanced Raman scattering of highly crystalline monolayer Ti3C2 nanosheets. Sci China Mater, 2020, 63: 794–805
Yilmaz M, Babur E, Ozdemir M, et al. Nanostructured organic semiconductor films for molecular detection with surface-enhanced Raman spectroscopy. Nat Mater, 2017, 16: 918–924
Zheng Z, Cong S, Gong W, et al. Semiconductor SERS enhancement enabled by oxygen incorporation. Nat Commun, 2017, 8: 1993
Song G, Gong W, Cong S, et al. Ultrathin two-dimensional nanostructures: Surface defects for morphology-driven enhanced semiconductor SERS. Angew Chem Int Ed, 2021, 60: 5505–5511
Huang C, Li A, Chen X, et al. Understanding the role of metal-organic frameworks in surface-enhanced Raman scattering application. Small, 2020, 16: 2004802
Sun H, Cong S, Zheng Z, et al. Metal-organic frameworks as surface enhanced Raman scattering substrates with high tailorability. J Am Chem Soc, 2019, 141: 870–878
Lin J, Yu J, Akakuru OU, et al. Low temperature-boosted high efficiency photo-induced charge transfer for remarkable SERS activity of ZnO nanosheets. Chem Sci, 2020, 11: 9414–9420
Lin J, Hao W, Shang Y, et al. Direct experimental observation of facet-dependent SERS of Cu2O polyhedra. Small, 2018, 14: 1703274
Liu H, Yang Z, Meng L, et al. Three-dimensional and time-ordered surface-enhanced Raman scattering hotspot matrix. J Am Chem Soc, 2014, 136: 5332–5341
Wang X, Guo L. SERS activity of semiconductors: Crystalline and amorphous nanomaterials. Angew Chem Int Ed, 2020, 59: 4231–4239
Sun J, Hu H, Zheng D, et al. Light-emitting plexciton: Exploiting plasmon-exciton interaction in the intermediate coupling regime. ACS Nano, 2018, 12: 10393–10402
Yang S, Yao J, Quan Y, et al. Monitoring the charge-transfer process in a Nd-doped semiconductor based on photoluminescence and SERS technology. Light Sci Appl, 2020, 9: 117
Feng E, Zheng T, He X, et al. A novel ternary heterostructure with dramatic SERS activity for evaluation of PD-L1 expression at the single-cell level. Sci Adv, 2018, 4: eaau3494
Liu P, Zhao Y, Qin R, et al. Photochemical route for synthesizing atomically dispersed palladium catalysts. Science, 2016, 352: 797–800
Wang J, Li Z, Wu Y, et al. Fabrication of single-atom catalysts with precise structure and high metal loading. Adv Mater, 2018, 30: 1801649
Yang J, Li W, Wang D, et al. Electronic metal-support interaction of single-atom catalysts and applications in electrocatalysis. Adv Mater, 2020, 32: 2003300
Wang C, Li A, Li C, et al. Ultrahigh photocatalytic rate at a single-metal-atom-oxide. Adv Mater, 2019, 31: 1903491
Hsu HC, Huang BC, Chin SC, et al. Photodriven dipole reordering: Key to carrier separation in metalorganic halide perovskites. ACS Nano, 2019, 13: 4402–4409
Caicedo-Dávila S, Gunder R, Márquez JA, et al. Effects of postdeposition annealing on the luminescence of mixed-phase CsPb2Br5/CsPbBr3 thin films. J Phys Chem C, 2020, 124: 19514–19521
Su X, Ma H, Wang H, et al. Surface-enhanced Raman scattering on organic-inorganic hybrid perovskites. Chem Commun, 2018, 54: 2134–2137
Hewitt RW, Winograd N. Investigation of the oxidation of polycrystalline lead by XPS and SIMS. Surf Sci, 1978, 78: 1–14
Le Ru EC, Etchegoin PG. Single-molecule surface-enhanced Raman spectroscopy. Annu Rev Phys Chem, 2012, 63: 65–87
Cook C, Farber-Eger E, Wang T, et al. Prevalence of clinically apparent hypertrophic cardiomyopathy in 32 patients with the gla a143t mutation: Implications for genetic screening for fabry disease in patients with hypertrophic cardiomyopathy. J Am College Cardiol, 2015, 65: A953
Kim JY, Lee JW, Jung HS, et al. High-efficiency perovskite solar cells. Chem Rev, 2020, 120: 7867–7918
Li Y, Xu M, **a Y, et al. Multilayer assembly of electrospun/electrosprayed PVDF-based nanofibers and beads with enhanced piezoelectricity and high sensitivity. Chem Eng J, 2020, 388: 124205
Osticioli I, Mencaglia AA, Siano S. Temperature-controlled portable Raman spectroscopy of photothermally sensitive pigments. Sens Actuat B-Chem, 2017, 238: 772–778
Yu Z, Yu W, **ng J, et al. Charge transfer effects on resonance-enhanced Raman scattering for molecules adsorbed on single-crystalline perovskite. ACS Photonics, 2018, 5: 1619–1627
Cañamares MV, Lombardi JR. Raman, SERS, and DFT of mauve dye: Adsorption on Ag nanoparticles. J Phys Chem C, 2015, 119: 14297–14303
Granold M, Hajieva P, Tosa MI, et al. Modern diversification of the amino acid repertoire driven by oxygen. Proc Natl Acad Sci USA, 2018, 115: 41–46
Yang L, Jiang X, Ruan W, et al. Observation of enhanced Raman scattering for molecules adsorbed on TiO2 nanoparticles: Chargetransfer contribution. J Phys Chem C, 2008, 112: 20095–20098
Saunders SR, Eden MR, Roberts CB. Modeling the precipitation of polydisperse nanoparticles using a total interaction energy model. J Phys Chem C, 2011, 115: 4603–4610
Demirel G, Gieseking RLM, Ozdemir R, et al. Molecular engineering of organic semiconductors enables noble metal-comparable SERS enhancement and sensitivity. Nat Commun, 2019, 10: 5502
Acknowledgements
This work was supported by the Natural Science Foundation of Bei**g Municipality (Z180014). We thank Dr. Chen Qian and Dr. Yingying Wang for providing measurement support, and we also thank Taifeng Lin, Prof. Yiyang Sun and Prof. Shengbai Zhang for discussions.
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Author contributions Feng R designed and performed the experiments; Miao Q analyzed TAS data; Zhang X calculated the electronic structure; Cui P analyzed the XANES data; Wang C wrote the paper; Han X discussed partial experimental data. All authors contributed to the general discussion.
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Supplementary information Experimental details and supporting data are available in the online version of the paper.
Ran Feng received his BSc degree in 2020 from Nan**g Normal University, China. He is currently an MSc candidate in physics under the supervision of Prof. Cong Wang at Bei**g Key Laboratory of Microstructure and Properties of Solids, Bei**g University of Technology. His research centers on develo** the single-site decorated SERS substrate for ultrasensitive molecule detection.
Qing Miao received his BSc degree in engineering from Baicheng Normal University in 2014 and MSc degree in physics from North China Electric Power University in 2017. He is currently pursuing his PhD degree in optical engineering under the supervision of Prof. Dawei He at Bei**g Jiaotong University. His research focuses on ultrafast laser spectroscopy of nanoscale materials, such as photocarrier dynamics, charge transfer, and its potential applications in optoelectronics and photonics.
**ang Zhang received his BSc degree in 2020 from Sichuan University of Science & Engineering. Then, he joined the Institute of Structure & Function, Chongqing University as a master student. His research centers on Schottky barrier heights in two-dimensional field-effect transistors.
Peixin Cui received his PhD degree from the University of Science and Technology of China in 2013, followed by working as a postdoc at the same university. He joined the Institute of Soil Science, Chinese Academy of Sciences in 2016. His research focuses on the study of local structures of nano and single-atom materials by synchrotron radiation techniques.
Cong Wang received his BSc degree in 2009 and MSc degree in 2012 from the University of Science and Technology Bei**g, respectively. In 2015, he received his PhD degree from Hong Kong University of Science and Technology. Then, he joined Bei**g University of Technology and became an associate professor in 2016. His research interests focus on the single-atom sites rational design and synthesis, single-sites catalysis, and single-sites SERS in energy, environment and biology.
**aodong Han received his BSc degree in 1989 and MSc degree in 1992 from Harbin Institute of Technology. In 1996, he received his PhD degree from Dalian University of Technology. Then, he joined City University of Hong Kong and the University of Pittsburgh as postdoc. In 2001, he joined HKL Technology (Oxford Instruments Group), and in 2004, he joined Bei**g University of Technology. His research interests focus on in-situ transmission electron microscopy, and physical and chemical properties of materials in catalytic, optical, and mechanical communities.
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Feng, R., Miao, Q., Zhang, X. et al. Single-atom sites on perovskite chips for record-high sensitivity and quantification in SERS. Sci. China Mater. 65, 1601–1614 (2022). https://doi.org/10.1007/s40843-022-1968-5
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DOI: https://doi.org/10.1007/s40843-022-1968-5