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Research Article

Super-assembled sandwich-like Au@MSN@Ag nanomatrices for high-throughput and efficient detection of small biomolecules

Dantong Zhao1,3,§, Chunxia Ma2,§( ), Meng Gao2, Yong Li2, Bo Yang2, Hui Li1, Runhao Zhang2, Minglu Hao2, Jing Huang2, Kang Liang4, Pu Chen5, Lei Xie6, Rong Rong1( ), Biao Kong6( )
College of Medicine, Shandong University of Traditional Chinese Medicine, Jinan 250355, China
Shandong Analysis and Test Center, National Supercomputer Research Center of Advanced Materials, Advanced Materials Institute, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250014, China
Heze Institute for Food and Drug Control, Heze 274000, China
School of Chemical Engineering and Graduate School of Biomedical Engineering, The University of New South Wales, NSW 2052, Australia
Department of Chemical Engineering, University of Waterloo, Waterloo, Ontario, N2L 3G1, Canada
Department of Chemistry, Shanghai Key Lab of Molecular Catalysis and Innovative Materials, iChEM, Fudan University, Shanghai 200032, China

§Dantong Zhao and Chunxia Ma contributed equally to this work.

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Graphical Abstract

Abstract

Small biomolecules (m/z < 500) are the material basis of organisms and participate in life activities, but their comprehensive and accurate detection in complex samples remains a challenge. Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is a powerful detection tool for molecular analysis with high throughput. The development of a new matrix is essential to improve the efficiency of the MALDI-MS for molecular compound detection. In this work, the sandwich-like gold nanoparticles@mesoporous silica nanocomposite@silver nanoparticles (Au@MSN@Ag) nanospheres were prepared by layer-by-layer super-assembly strategy, and can be used as a novel matrix for the quantitative detection and enrichment of small biomolecules by LDI-MS. The sandwich-like nanospheres form a unique plasma resonant cavity that effectively absorbs the laser energy, while the homogeneous mesoporous structure of MSN can lock the analyte, which is essential for efficient LDI of small molecules. Compared to traditional matrices, Au@MSN@Ag shows the advantages of low background, wide application range, high sensitivity, super high salt and protein tolerance, and good stability. For example, the detection limit of glucose was as low as 5 fmol, and showed a good linear relationship in the range of 1−750 μg/mL. Au@MSN@Ag assisted LDI-MS allows the enrichment and detection of small molecules in traditional Chinese medicine (TCM) without derivatization and purification, classification of herbs using the accurate quantitative results oligosaccharides, and identification of gelatin by amino acid content. This research could help in designing more efficient nanostructure matrices and further explored the application of LDI-MS.

Keywords

matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS)matrixsandwich-like nanostructuressmall biomoleculestraditional Chinese medicine (TCM)

References

1

Stockwell, B. R. Exploring biology with small organic molecules. Nature 2004, 432, 846–854.
Crossref Google Scholar
2

Scott, D. E.; Bayly, A. R.; Abell, C.; Skidmore, J. Small molecules, big targets: Drug discovery faces the protein-protein interaction challenge. Nat. Rev. Drug Discov. 2016, 15, 533–550.
Crossref Google Scholar
3

Li, N.; Li, S. M.; Li, T.; Yang, H.; Zhang, Y. Y.; Zhao, Z. W. Co-incorporated mesoporous carbon material-assisted laser desorption/ionization ion source as an online interface of in vivo microdialysis coupled with mass spectrometry. Anal. Chem. 2020, 92, 5482–5491.
Crossref Google Scholar
4

Schymanski, E. L.; Neumann, S. The critical assessment of small molecule identification (CASMI): Challenges and solutions. Metabolites 2013, 3, 517–538.
Crossref Google Scholar
5

He, H. X.; Qin, L.; Zhang, Y. W.; Han, M. M.; Li, J. M.; Liu, Y. Q.; Qiu, K. D.; Dai, X. Y.; Li, Y. Y.; Zeng, M. M. et al. 3,4-Dimethoxycinnamic acid as a novel matrix for enhanced in situ detection and imaging of low-molecular-weight compounds in biological tissues by MALDI-MSI. Anal. Chem. 2019, 91, 2634–2643.
Crossref Google Scholar
6

Xiao, H. M.; Liu, P.; Zheng, S. J.; Wang, X.; Ding, J.; Feng, Y. Q. Screening of amino acids in dried blood spots by stable isotope derivatization-liquid chromatography-electrospray ionization mass spectrometry. Chin. Chem. Lett. 2020, 31, 2423–2427.
Crossref Google Scholar
7

Tanaka, K.; Waki, H.; Ido, Y.; Akita, S.; Yoshida, Y.; Yoshida, T.; Matsuo, T. Protein and polymer analyses up to m/z 100 000 by laser ionization time-of-flight mass spectrometry. Rapid Commun. Mass Spectrom. 1988, 2, 151–153.
Crossref Google Scholar
8

Huang, L.; Wan, J. J.; Wei, X.; Liu, Y.; Huang, J. Y.; Sun, X. M.; Zhang, R.; Gurav, D. D.; Vedarethinam, V.; Li, Y. et al. Plasmonic silver nanoshells for drug and metabolite detection. Nat. Commun. 2017, 8, 220.
Crossref Google Scholar
9

Jiang, Y. M.; Sun, J.; Cui, Y.; Liu, H. H.; Zhang, X. Y.; Jiang, Y. R.; Nie, Z. X. Ti3C2 MXene as a novel substrate provides rapid differentiation and quantitation of glycan isomers with LDI-MS. Chem. Commun. 2019, 55, 10619–10622.
Crossref Google Scholar
10

van Kampen, J. J. A.; Burgers, P. C.; de Groot, R.; Gruters, R. A.; Luider, T. M. Biomedical application of MALDI mass spectrometry for small-molecule analysis. Mass Spectrom. Rev. 2011, 30, 101–120.
Crossref Google Scholar
11

Stopka, S. A.; Rong, C.; Korte, A. R.; Yadavilli, S.; Nazarian, J.; Razunguzwa, T. T.; Morris, N. J.; Vertes, A. Molecular imaging of biological samples on nanophotonic laser desorption ionization platforms. Angew. Chem., Int. Ed. 2016, 55, 4482–4486.
Crossref Google Scholar
12

Shi, R.; Dai, X.; Li, W. F.; Lu, F.; Liu, Y.; Qu, H. H.; Li, H.; Chen, Q. Y.; Tian, H.; Wu, E. H. et al. Hydroxyl-group-dominated graphite dots reshape laser desorption/ionization mass spectrometry for small biomolecular analysis and imaging. ACS Nano 2017, 11, 9500–9513.
Crossref Google Scholar
13

Fan, B. Y.; Zhou, H. Y.; Wang, Y. H.; Zhao, Z. Q.; Ren, S. Y.; Xu, L.; Wu, J.; Yan, H. Y.; Gao, Z. X. Surface siloxane-modified silica materials combined with metal-organic frameworks as novel MALDI matrixes for the detection of low-MW compounds. ACS Appl. Mater. Interfaces 2020, 12, 37793–37803.
Crossref Google Scholar
14

Sun, X. M.; Huang, L.; Zhang, R.; Xu, W.; Huang, J. Y.; Gurav, D. D.; Vedarethinam, V.; Chen, R. P.; Lou, J. T.; Wang, Q. et al. Metabolic fingerprinting on a plasmonic gold chip for mass spectrometry based in vitro diagnostics. ACS Cent. Sci. 2018, 4, 223–229.
Crossref Google Scholar
15

Wei, X.; Liu, Z. H.; Jin, X. L.; Huang, L.; Gurav, D. D.; Sun, X. M.; Liu, B. H.; Ye, J.; Qian, K. Plasmonic nanoshells enhanced laser desorption/ionization mass spectrometry for detection of serum metabolites. Anal. Chim. Acta 2017, 950, 147–155.
Crossref Google Scholar
16

Gao, M.; Zeng, J.; Liang, K.; Zhao, D. Y.; Kong, B. Mesoporous silica materials: Interfacial assembly of mesoporous silica-based optical heterostructures for sensing applications. Adv. Funct. Mater. 2020, 30, 1906950.
Crossref Google Scholar
17

Brongersma, M. L.; Halas, N. J.; Nordlander, P. Plasmon-induced hot carrier science and technology. Nat. Nanotechnol. 2015, 10, 25–34.
Crossref Google Scholar
18

Zhao, Q. Y.; Li, H.; Chen, H.; Wu, C.; Ei-Seedi, H.; Xu, X. B.; Du, M. High throughput analysis and quantitation of α-dicarbonyls in biofluid by plasmonic nanoshells enhanced laser desorption/ionization mass spectrometry. J. Hazard. Mater. 2021, 403, 123580.
Crossref Google Scholar
19
Wang, S. H.; Niu, H. Y.; Zeng, T.; Zhang, X. L.; Cao, D.; Cai, Y. Q. Rapid determination of small molecule pollutants using metal-organic frameworks as adsorbent and matrix of MALDI-TOF-MS. Micropor. Mesopor. Mat. 2017, 239, 390‒395.https://doi.org/10.1016/j.micromeso.2016.10.032
Crossref
20

Yang, B.; Zhou, S.; Zeng, J.; Zhang, L. P.; Zhang, R. H.; Liang, K.; Xie, L.; Shao, B.; Song, S. L.; Huang, G. et al. Super-assembled core-shell mesoporous silica-metal-phenolic network nanoparticles for combinatorial photothermal therapy and chemotherapy. Nano Res. 2020, 13, 1013–1019.
Crossref Google Scholar
21

Frens, G. Controlled nucleation for the regulation of the particle size in monodisperse gold suspensions. Nat. Phy. Sci. 1973, 241, 20–22.
Crossref Google Scholar
22

Shen, D. K.; Yang, J. P.; Li, X. M.; Zhou, L.; Zhang, R. Y.; Li, W.; Chen, L.; Wang, R.; Zhang, F.; Zhao, D. Y. Biphase stratification approach to three-dimensional dendritic biodegradable mesoporous silica nanospheres. Nano Lett. 2014, 14, 923–932.
Crossref Google Scholar
23

Xu, G. J.; Liu, S. J.; Peng, J. X.; Lv, W. P.; Wu, R. A. Facile synthesis of gold@graphitized mesoporous silica nanocomposite and its surface-assisted laser desorption/ionization for time-of-flight mass spectroscopy. ACS Appl. Mater. Interfaces 2015, 7, 2032–2038.
Crossref Google Scholar
24

Jiang, Z. J.; Liu, C. Y. Seed-mediated growth technique for the preparation of a silver nanoshell on a silica sphere. J. Phys. Chem. B 2003, 107, 12411–12415.
Crossref Google Scholar
25

Li, C. R.; Mei, J.; Li, S. W.; Lu, N. P.; Wang, L. N.; Chen, B. Y.; Dong, W. J. One-pot synthesis of Ag@SiO2@Ag sandwich nanostructures. Nanotechnology 2010, 21, 245602.
Crossref Google Scholar
26

Cai, Y. G.; Piao, X. Q.; Gao, W.; Zhang, Z. J.; Nie, E.; Sun, Z. Large-scale and facile synthesis of silver nanoparticles via a microwave method for a conductive pen. RSC Adv. 2017, 7, 34041–34048.
Crossref Google Scholar
27

Liu, J.; Yang, T. Y.; Wang, D. W.; Lu, G. Q.; Zhao, D. Y.; Qiao, S. Z. A facile soft-template synthesis of mesoporous polymeric and carbonaceous nanospheres. Nat. Commun. 2013, 4, 2798.
Crossref Google Scholar
28

Guo, Z.; Ganawi, A. A. A.; Liu, Q.; He, L. Nanomaterials in mass spectrometry ionization and prospects for biological application. Anal. Bioanal. Chem. 2006, 384, 584–592.
Crossref Google Scholar
29

Liz-Marzán, L. M.; Giersig, M.; Mulvaney, P. Synthesis of nanosized gold-silica core-shell particles. Langmuir 1996, 12, 4329–4335.
Crossref Google Scholar
30

Northen, T. R.; Yanes, O.; Northen, M. T.; Marrinucci, D.; Uritboonthai, W.; Apon, J.; Golledge, S. L.; Nordström, A.; Siuzdak, G. Clathrate nanostructures for mass spectrometry. Nature 2007, 449, 1033–1036.
Crossref Google Scholar
31

Chen, J. C.; Zhang, R. Y.; Han, L.; Tu, B.; Zhao, D. Y. One-pot synthesis of thermally stable gold@mesoporous silica core-shell nanospheres with catalytic activity. Nano Res. 2013, 6, 871–879.
Crossref Google Scholar
32

Gan, J. R.; Wei, X.; Li, Y. X.; Wu, J.; Qian, K.; Liu, B. H. Designer SiO2@Au nanoshells towards sensitive and selective detection of small molecules in laser desorption ionization mass spectrometry. Nanomed.: Nanotechnol., Biol. Med. 2015, 11, 1715–1723.
Crossref Google Scholar
33

Näsholm, T.; Ekblad, A.; Nordin, A.; Giesler, R.; Högberg, M.; Högberg, P. Boreal forest plants take up organic nitrogen. Nature 1998, 392, 914–916.
Crossref Google Scholar
34

Stone, T. W. Amino acids as neurotransmitters of corticofugal neurones in the rat: A comparison of glutamate and aspartate. Br. J. Pharmacol. 1979, 67, 545–551.
Crossref Google Scholar
35

Jackson, A. U.; Shum, T.; Sokol, E.; Dill, A.; Cooks, R. G. Enhanced detection of olefins using ambient ionization mass spectrometry: Ag+ adducts of biologically relevant alkenes. Anal. Bioanal. Chem. 2011, 399, 367–376.
Crossref Google Scholar
36

McLuckey, S. A.; Schoen, A. E.; Cooks, R. G. Silver ion affinities of alcohols as ordered by mass spectrometry/mass spectrometry. J. Am. Chem. Soc. 1982, 104, 848–850.
Crossref Google Scholar
37

Monroe, E. B.; Koszczuk, B. A.; Losh, J. L.; Jurchen, J. C.; Sweedler, J. V. Measuring salty samples without adducts with MALDI MS. Int. J. Mass Spectrom. 2007, 260, 237–242.
Crossref Google Scholar
38

Ropartz, D.; Bodet, P. E.; Przybylski, C.; Gonnet, F.; Daniel, R.; Fer, M.; Helbert, W.; Bertrand, D.; Rogniaux, H. Performance evaluation on a wide set of matrix-assisted laser desorption ionization matrices for the detection of oligosaccharides in a high-throughput mass spectrometric screening of carbohydrate depolymerizing enzymes. Rapid Commun. Mass Spectrom. 2011, 25, 2059–2070.
Crossref Google Scholar
39

Wan, D.; Gao, M. X.; Wang, Y. H.; Zhang, P.; Zhang, X. M. A rapid and simple separation and direct detection of glutathione by gold nanoparticles and graphene-based MALDI-TOF-MS. J. Sep. Sci. 2013, 36, 629–635.
Crossref Google Scholar
40
Chinese Pharmacopoeia Commission. Chinese Pharmacopoeia, 2020 Edition; Chinese Medicine Science and Technology Press: Beijing, 2020.
41

Wu, F. Q.; Zhang, Y.; Liu, W. J.; Zhu, N. N.; Chen, J. B.; Sun, Z. R. Comparison of torrefied and lyophilized Dendrobii Officinalis Caulis (Tiepishihu) by Fourier transform infrared spectroscopy and two-dimensional correlation spectroscopy. J. Mol. Struct. 2020, 1204, 127554.
Crossref Google Scholar
42

Zheng, X. Q.; Jin, C. S.; Zhang, Y. Z.; Liu, J. L.; Yu, N. J.; Ou, J. M. Content determination of 3 saccharides in 3 kinds of medicinal dendrobii caulis by HPLC-CAD. China Pharm. 2020, 31, 1185–1189.
Google Scholar
43

Li, L. F.; Yao, H.; Li, X. J.; Zhang, Q. W.; Wu, X. Y.; Wong, T.; Zheng, H. M.; Fung, H.; Yang, B. X.; Ma, D. et al. Destiny of Dendrobium officinale polysaccharide after oral administration: Indigestible and nonabsorbing, ends in modulating gut microbiota. J. Agric. Food Chem. 2019, 67, 5968–5977.
Crossref Google Scholar
44

Hanani, Z. A. N.; Roos, Y. H.; Kerry, J. P. Use and application of gelatin as potential biodegradable packaging materials for food products. Int. J. Biol. Macromol. 2014, 71, 94–102.
Crossref Google Scholar
45

Aykın-Dinçer, E.; Koç, A.; Erbaş, M. Extraction and physicochemical characterization of broiler (Gallus gallus domesticus) skin gelatin compared to commercial bovine gelatin. Poultry Sci. 2017, 96, 4124–4131.
Crossref Google Scholar
46

Cheng, X. L.; Wei, F.; Xiao, X. Y.; Zhao, Y. Y.; Shi, Y.; Liu, W.; Zhang, P.; Ma, S. C.; Tian, S. S.; Lin, R. C. Identification of five gelatins by ultra performance liquid chromatography/time-of-flight mass spectrometry (UPLC/Q-TOF-MS) using principal component analysis. J. Pharm. Biomed. Anal. 2012, 62, 191–195.
Crossref Google Scholar
47

Wang, D. L.; Ru, W. W.; Xu, Y. P.; Zhang, J. L.; He, X. X.; Fan, G. H.; Mao, B. B.; Zhou, X. S.; Qin, Y. F. Chemical constituents and bioactivities of Colla corii asini. Drug Discov. Ther. 2014, 8, 201–207.
Crossref Google Scholar
48

Azilawati, M. I.; Hashim, D. M.; Jamilah, B.; Amin, I. Validation of a reverse-phase high-performance liquid chromatography method for the determination of amino acids in gelatins by application of 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate reagent. J. Chromatogr. A 2014, 1353, 49–56.
Crossref Google Scholar
49

Jamilah, B.; Harvinder, K. G. Properties of gelatins from skins of fish—black tilapia (Oreochromis mossambicus) and red tilapia (Oreochromis nilotica). Food Chem. 2002, 77, 81–84.
Crossref Google Scholar
50

Kim, K.; Yoon, J. K. Raman scattering of 4-aminobenzenethiol sandwiched between Ag/Au nanoparticle and macroscopically smooth Au substrate. J. Phys. Chem. B 2005, 109, 20731–20736.
Crossref Google Scholar
51

Xu, S. P.; Zhao, B.; Xu, W. Q.; Fan, Y. G. Preparation of Au-Ag coreshell nanoparticles and application of bimetallic sandwich in surface-enhanced Raman scattering (SERS). Colloids Surf. A: Physicochem. Eng. Aspects 2005, 257-258, 313–317.
Crossref Google Scholar
52

Wang, M. Y.; Ye, M. D.; Iocozzia, J.; Lin, C. J.; Lin, Z. Q. Plasmon-mediated solar energy conversion via photocatalysis in noble metal/semiconductor composites. Adv. Sci. 2016, 3, 1600024.
Crossref Google Scholar
53

Wu, K.; Chen, J.; McBride, J. R.; Lian, T. Efficient hot-electron transfer by a plasmon-induced interfacial charge-transfer transition. Science 2015, 349, 632–635.
Crossref Google Scholar
54

Manjavacas, A.; Liu, J. G.; Kulkarni, V.; Nordlander, P. Plasmon-induced hot carriers in metallic nanoparticles. ACS Nano 2014, 8, 7630–7638.
Crossref Google Scholar
55

de Arquer, F. P. G.; Mihi, A.; Kufer, D.; Konstantatos, G. Photoelectric energy conversion of plasmon-generated hot carriers in metal-insulator-semiconductor structures. ACS Nano 2013, 7, 3581–3588.
Crossref Google Scholar
56

Lee, J.; Mubeen, S.; Ji, X. L.; Stucky, G. D.; Moskovits, M. Plasmonic photoanodes for solar water splitting with visible light. Nano Lett. 2012, 12, 5014–5019.
Crossref Google Scholar
57

Mubeen, S.; Lee, J.; Singh, N.; Krämer, S.; Stucky, G. D.; Moskovits, M. An autonomous photosynthetic device in which all charge carriers derive from surface plasmons. Nat. Nanotechnol. 2013, 8, 247–251.
Crossref Google Scholar
58

Enustun, B. V.; Turkevich, J. Coagulation of colloidal gold. J. Am. Chem. Soc. 1963, 85, 3317–3328.
Crossref Google Scholar
59

Deng, Z. W.; Chen, M.; Wu, L. M. Novel method to fabricate SiO2/Ag composite spheres and their catalytic, surface-enhanced Raman scattering properties. J. Phys. Chem. C 2007, 111, 11692–11698.
Crossref Google Scholar
60

Piraud, M.; Vianey-Saban, C.; Petritis, K.; Elfakir, C.; Steghens, J. P.; Morla, A.; Bouchu, D. ESI-MS/MS analysis of underivatised amino acids: A new tool for the diagnosis of inherited disorders of amino acid metabolism. Fragmentation study of 79 molecules of biological interest in positive and negative ionisation mode. Rapid Commun. Mass Spectrom. 2003, 17, 1297–1311.
Crossref Google Scholar
Nano Research
Volume 15 Issue 3,
March 2022
Pages 2722-2733
DOI: 10.1007/s12274-021-3741-0
Cite this article:
Zhao D, Ma C, Gao M, et al. Super-assembled sandwich-like Au@MSN@Ag nanomatrices for high-throughput and efficient detection of small biomolecules. Nano Research, 2022, 15(3): 2722-2733. https://doi.org/10.1007/s12274-021-3741-0
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Received: 03 May 2021
Revised: 29 June 2021
Accepted: 12 July 2021
Published: 12 August 2021
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021
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