Highly luminescent silver nanoclusters with tunable emissions: cyclic reduction–decomposition synthesis and antimicrobial properties
Source abstract
Abstract
This paper reports a facile aqueous-based synthesis method for highly luminescent Ag nanoclusters (NCs) with tunable emissions. The key strategy was to use a reduction–decomposition–reduction cycle to modify the Ag NC intermediates that were further subjected to size/structure focusing. The as-modified Ag NC intermediates were more robust in water against the subsequent etching by thiol ligands, making a mild size-/structure-focusing environment possible, which produced highly luminescent Ag NCs with a well-defined size and structure. Ag NCs with intense red and green emission were successfully synthesized by this method. These Ag NCs possessed a well-defined size and structure (Ag16(SG)9 and Ag9(SG)6), and exhibited excellent stability in the aqueous phase. Our highly luminescent Ag NCs also possessed superior antimicrobial properties against the multidrug-resistant bacteria Pseudomonas aeruginosa, via generating a high concentration of intracellular reactive oxygen species. Jianping Xie, David Tai Leong and co-workers from the National University of Singapore have devised a method to prepare silver nanoclusters that exhibit interesting luminescence and antimicrobial properties. Small metallic clusters of sizes between single atoms and nanoparticles show properties different from both of these, and have been attracting increasing attention. Gold and silver clusters, for example, are investigated as optical probes in bioimaging and biosensing. The researchers used a two-step process — a reduction–decomposition–reduction cycle then an etching step — to assemble well-defined silver clusters stabilized by glutathione ligands through a thiol linkage. The clusters, which comprise Ag16 and Ag9 cores, are stable in aqueous solutions and show intense red and green luminescence, respectively. Furthermore, they efficiently inhibited the growth of multidrug resistant Pseudomonas aeruginosa in cell culture. This antimicrobial activity arises through the intracellular generation of reactive oxygen species. This paper reports a facile cyclic reduction–decomposition method for the aqueous-based synthesis of highly luminescent Ag nanoclusters (NCs) with tunable emissions. A reduction–decomposition–reduction cycle was used to modify the non-luminescent Ag NC intermediates with improved stability against subsequent etching by thiol ligands, which created a mild size-/structure-focusing (or etching) environment and produced highly luminescent Ag NCs with intense red (Ag16(SG)9) and green (Ag9(SG)6) emission. The highly luminescent Ag NCs also possessed superior antimicrobial properties against the multidrug-resistant bacteria Pseudomonas aeruginosa via generating a high concentration of intracellular reactive oxygen species.
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Research context
OpenAlex topics: Nanocluster Synthesis and Applications · Advanced Nanomaterials in Catalysis · Gold and Silver Nanoparticles Synthesis and Applications
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (76)
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1. Jin, R. C. Quantum sized, thiolate-protected gold nanoclusters. Nanoscale 2, 343–362 (2010).10.1039/B9NR00160C ↗
2. Diez, I. & Ras, R. H. A. Fluorescent silver nanoclusters. Nanoscale 3, 1963–1970 (2011).10.1039/c1nr00006c ↗
3. Zhang, Q. B., Xie, J. P., Yu, Y. & Lee, J. Y. Monodispersity control in the synthesis of monometallic and bimetallic quasi-spherical gold and silver nanoparticles. Nanoscale 2, 1962–1975 (2010).10.1039/c0nr00155d ↗
4. Shang, L., Dong, S. & Nienhaus, G. U. Ultra-small fluorescent metal nanoclusters: synthesis and biological applications. Nano Today 6, 401–418 (2011).10.1016/j.nantod.2011.06.004 ↗
5. Laaksonen, T., Ruiz, V., Liljeroth, P. & Quinn, B. M. Quantised charging of monolayer-protected nanoparticles. Chem. Soc. Rev. 37, 1836–1846 (2008).10.1039/b713681c ↗
6. González, B. S., Rodriáguez, M. A. J., Blanco, C., Rivas, J., Loápez-Quintela, M. A. & Martinho, J. M. G. One step synthesis of the smallest photoluminescent and paramagnetic PVP-protected gold atomic clusters. Nano Lett. 10, 4217–4221 (2010).10.1021/nl1026716 ↗
7. Xie, J. P., Zheng, Y. G. & Ying, J. Y. Protein-directed synthesis of highly fluorescent gold nanoclusters. J. Am. Chem. Soc. 131, 888–889 (2009).10.1021/ja806804u ↗
8. Xu, H. & Suslick, K. S. Water-soluble fluorescent silver nanoclusters. Adv. Mater. 22, 1078–1082 (2010).10.1002/adma.200904199 ↗
9. Choi, S., Dickson, R. M. & Yu, J. Developing luminescent silver nanodots for biological applications. Chem. Soc. Rev. 41, 1867–1891 (2012).10.1039/C1CS15226B ↗
10. Tanaka, S.-I., Miyazaki, J., Tiwari, D. K., Jin, T. & Inouye, Y. Fluorescent platinum nanoclusters: synthesis, purification, characterization, and application to bioimaging. Angew. Chem. Int. Ed. 50, 431–435 (2011).10.1002/anie.201004907 ↗
11. Wei, W., Lu, Y., Chen, W. & Chen, S. One-pot synthesis, photoluminescence, and electrocatalytic properties of subnanometer-sized copper clusters. J. Am. Chem. Soc. 133, 2060–2063 (2011).10.1021/ja109303z ↗
12. Yu, J., Patel, S. A. & Dickson, R. M. In vitro and intracellular production of peptide-encapsulated fluorescent silver nanoclusters. Angew. Chem. Int. Ed. 46, 2028–2030 (2007).10.1002/anie.200604253 ↗
13. Zhou, C., Long, M., Qin, Y., Sun, X. & Zheng, J. Luminescent gold nanoparticles with efficient renal clearance. Angew. Chem. Int. Ed. 50, 3168–3172 (2011).10.1002/anie.201007321 ↗
14. Resch-Genger, U., Grabolle, M., Cavaliere-Jaricot, S., Nitschke, R. & Nann, T. Quantum dots versus organic dyes as fluorescent labels. Nat. Meth. 5, 763–775 (2008).10.1038/nmeth.1248 ↗
15. Bottrill, M. & Green, M. Some aspects of quantum dot toxicity. Chem. Commun. 47, 7039–7050 (2011).10.1039/c1cc10692a ↗
16. Shang, L., Azadfar, N., Stockmar, F., Send, W., Trouillet, V., Bruns, M., Gerthsen, D. & Nienhaus, G. U. One-pot synthesis of near-infrared fluorescent gold clusters for cellular fluorescence lifetime imaging. Small 7, 2614–2620 (2011).10.1002/smll.201100746 ↗
17. Yeh, H.-C., Sharma, J., Han, J. J., Martinez, J. S. & Werner, J. H. A DNA-silver nanocluster probe that fluoresces upon hybridization. Nano Lett. 10, 3106–3110 (2010).10.1021/nl101773c ↗
18. Guo, W., Yuan, J., Dong, Q. & Wang, E. Highly sequence-dependent formation of fluorescent silver nanoclusters in hybridized DNA duplexes for single nucleotide mutation identification. J. Am. Chem. Soc. 132, 932–934 (2009).10.1021/ja907075s ↗
19. Yang, S. W. & Vosch, T. Rapid detection of microrna by a silver nanocluster DNA probe. Anal. Chem. 83, 6935–6939 (2011).10.1021/ac201903n ↗
20. Yu, J., Choi, S. & Dickson, R. M. Shuttle-based fluorogenic silver-cluster biolabels. Angew. Chem. Int. Ed. 48, 318–320 (2009).10.1002/anie.200804137 ↗
21. Lu, Y. & Chen, W. Sub-nanometre sized metal clusters: from synthetic challenges to the unique property discoveries. Chem. Soc. Rev. 41, 3594–3623 (2012).10.1039/c2cs15325d ↗
22. Project on Emerging Nanotechnologies. Silver Nanotechnology: A database of silver nanotechnology in commercial products (2011).
23. Chen, M. W., Yang, Z. W., Wu, H. M., Pan, X., Xie, X. B. & Wu, C. B. Antimicrobial activity and the mechanism of silver nanoparticle thermosensitive gel. Int. J. Nanomed. 6, 2873–2877 (2011).
24. Fisher, J. F., Meroueh, S. O. & Mobashery, S. Bacterial resistance to β-lactam antibiotics: compelling opportunism, compelling opportunity. Chem. Rev. 105, 395–424 (2005).10.1021/cr030102i ↗
25. Kim, J. S., Kuk, E., Yu, K. N., Kim, J. H., Park, S. J., Lee, H. J., Kim, S. H., Park, Y. K., Park, Y. H., Hwang, C. Y., Kim, Y. K., Lee, Y. S., Jeong, D. H. & Cho, M. H. Antimicrobial effects of silver nanoparticles. Nanomed. Nanotechnol. 3, 95–101 (2007).10.1016/j.nano.2006.12.001 ↗
26. Morones, J. R., Elechiguerra, J. L., Camacho, A., Holt, K., Kouri, J. B., Ramirez, J. T. & Yacaman, M. J. The bactericidal effect of silver nanoparticles. Nanotechnology 16, 2346–2353 (2005).10.1088/0957-4484/16/10/059 ↗
27. Maity, D., Kanti Bain, M., Bhowmick, B., Sarkar, J., Saha, S., Acharya, K., Chakraborty, M. & Chattopadhyay, D. In situ synthesis, characterization, and antimicrobial activity of silver nanoparticles using water soluble polymer. J. Appl. Polym. Sci. 122, 2189–2196 (2011).10.1002/app.34266 ↗
28. Pal, S., Tak, Y. K. & Song, J. M. Does the antibacterial activity of silver nanoparticles depend on the shape of the nanoparticle? A study of the gram-negative bacterium Escherichia coli. Appl. Environ. Microbiol. 73, 1712–1720 (2007).10.1128/AEM.02218-06 ↗
29. Shahverdi, A. R., Fakhimi, A., Shahverdi, H. R. & Minaian, S. Synthesis and effect of silver nanoparticles on the antibacterial activity of different antibiotics against Staphylococcus aureus and Escherichia coli. Nanomed.: Nanotechnol. 3, 168–171 (2007).10.1016/j.nano.2007.02.001 ↗
30. Martínez-Castañón, G., Niño-Martínez, N., Martínez-Gutierrez, F., Martínez-Mendoza, J. & Ruiz, F. Synthesis and antibacterial activity of silver nanoparticles with different sizes. J. Nanopart. Res. 10, 1343–1348 (2008).10.1007/s11051-008-9428-6 ↗
31. Wu, Z., Wang, M., Yang, J., Zheng, X., Cai, W., Meng, G., Qian, H., Wang, H. & Jin, R. Well-defined nanoclusters as fluorescent nanosensors: a case study on Au25(SG)18 . Small 8, 2028–2035 (2012).10.1002/smll.201102590 ↗
32. Duan, H. & Nie, S. Etching colloidal gold nanocrystals with hyperbranched and multivalent polymers: a new route to fluorescent and water-soluble atomic clusters. J. Am. Chem. Soc. 129, 2412–2413 (2007).10.1021/ja067727t ↗
33. Lin, C. A. J., Yang, T. Y., Lee, C. H., Huang, S. H., Sperling, R. A., Zanella, M., Li, J. K., Shen, J. L., Wang, H. H., Yeh, H. I., Parak, W. J. & Chang, W. H. Synthesis, characterization, and bioconjugation of fluorescent gold nanoclusters toward biological labeling applications. ACS Nano 3, 395–401 (2009).10.1021/nn800632j ↗
34. Liu, Y. L., Ai, K. L., Cheng, X. L., Huo, L. H. & Lu, L. H. Gold-nanocluster-based fluorescent sensors for highly sensitive and selective detection of cyanide in water. Adv. Funct. Mater. 20, 951–956 (2010).10.1002/adfm.200902062 ↗
35. Huang, C. -C., Yang, Z., Lee, K.-H. & Chang, H.-T. Synthesis of highly fluorescent gold nanoparticles for sensing mercury(II). Angew. Chem. Int. Ed. 46, 6824–6828 (2007).10.1002/anie.200700803 ↗
36. Luo, Z., Yuan, X., Yu, Y., Zhang, Q., Leong, D. T., Lee, J. Y. & Xie, J. From aggregation-induced emission of Au(I)–thiolate complexes to ultrabright Au(0)@Au(I)–thiolate core–shell nanoclusters. J. Am. Chem. Soc. 134, 16662–16670 (2012).10.1021/ja306199p ↗
37. Xu, H. X. & Suslick, K. S. Sonochemical synthesis of highly fluorescent Ag nanoclusters. ACS Nano 4, 3209–3214 (2010).10.1021/nn100987k ↗
38. Shen, Z., Duan, H. & Frey, H. Water-soluble fluorescent Ag nanoclusters obtained from multiarm star poly(acrylic acid) as “molecular hydrogel” templates. Adv. Mater. 19, 349–352 (2007).10.1002/adma.200601740 ↗
39. Shang, L. & Dong, S. J. Facile preparation of water-soluble fluorescent silver nanoclusters using a polyelectrolyte template. Chem. Commun. 1088–1090 (2008).10.1039/b717728c ↗
40. Zheng, J. & Dickson, R. M. Individual water-soluble dendrimer-encapsulated silver nanodot fluorescence. J. Am. Chem. Soc. 124, 13982–13983 (2002).10.1021/ja028282l ↗
41. Petty, J. T., Zheng, J., Hud, N. V. & Dickson, R. M. DNA-templated Ag nanocluster formation. J. Am. Chem. Soc. 126, 5207–5212 (2004).10.1021/ja031931o ↗
42. Richards, C. I., Choi, S., Hsiang, J.-C., Antoku, Y., Vosch, T., Bongiorno, A., Tzeng, Y.-L. & Dickson, R. M. Oligonucleotide-stabilized Ag nanocluster fluorophores. J. Am. Chem. Soc. 130, 5038–5039 (2008).10.1021/ja8005644 ↗
43. Gwinn, E. G., O'Neill, P., Guerrero, A. J., Bouwmeester, D. & Fygenson, D. K. Sequence-dependent fluorescence of DNA-hosted silver nanoclusters. Adv. Mater. 20, 279–283 (2008).10.1002/adma.200702380 ↗
44. Narayanan, S. S. & Pal, S. K. Structural and functional characterization of luminescent silver-protein nanobioconjugates. J. Phys. Chem. C 112, 4874–4879 (2008).10.1021/jp709999x ↗
45. Guo, C. & Irudayaraj, J. Fluorescent Ag clusters via a protein-directed approach as a Hg(II) ion sensor. Anal. Chem. 83, 2883–2889 (2011).10.1021/ac1032403 ↗
46. Bakr, O. M., Amendola, V., Aikens, C. M., Wenseleers, W., Li, R., Dal Negro, L., Schatz, G. C. & Stellacci, F. Silver nanoparticles with broad multiband linear optical absorption. Angew. Chem. Int. Ed. 48, 5921–5926 (2009).10.1002/anie.200900298 ↗
47. Udaya Bhaskara Rao, T. & Pradeep, T. Luminescent Ag7 and Ag8 clusters by interfacial synthesis. Angew. Chem. Int. Ed. 49, 3925–3929 (2010).10.1002/anie.200907120 ↗
48. Yuan, X., Luo, Z., Zhang, Q., Zhang, X., Zheng, Y., Lee, J. Y. & Xie, J. Synthesis of highly fluorescent metal (Ag, Au, Pt, and Cu) nanoclusters by electrostatically induced reversible phase transfer. ACS Nano 5, 8800–8808 (2011).10.1021/nn202860s ↗
49. Yuan, X., Yeow, T. J., Zhang, Q., Lee, J. Y. & Xie, J. Highly luminescent Ag+ nanoclusters for Hg2+ ion detection. Nanoscale 4, 1968–1971 (2012).10.1039/c2nr11999d ↗
50. Wang, C., Xu, L., Wang, Y., Zhang, D., Shi, X., Dong, F., Yu, K., Lin, Q. & Yang, B. Fluorescent silver nanoclusters as effective probes for highly selective detection of mercury(II) at parts-per-billion levels. Chem. Asian J. 7, 1652–1656 (2012).10.1002/asia.201200033 ↗
51. Le Guével, X., Spies, C., Daum, N., Jung, G. & Schneider, M. Highly fluorescent silver nanoclusters stabilized by glutathione: a promising fluorescent label for bioimaging. Nano Res. 5, 379–387 (2012).10.1007/s12274-012-0218-1 ↗
52. Huang, S., Pfeiffer, C., Hollmann, J., Friede, S., Chen, J. J. -C., Beyer, A., Haas, B., Volz, K., Heimbrodt, W., Montenegro Martos, J. M., Chang, W. & Parak, W. J. Synthesis and characterization of colloidal fluorescent silver nanoclusters. Langmuir 28, 8915–8919 (2012).10.1021/la300346t ↗
53. Dhanalakshmi, L., Udayabhaskararao, T. & Pradeep, T. Conversion of double layer charge-stabilized Ag@citrate colloids to thiol passivated luminescent quantum clusters. Chem. Commun. 48, 859–861 (2012).10.1039/C1CC15604G ↗
54. Jin, R., Qian, H., Wu, Z., Zhu, Y., Zhu, M., Mohanty, A. & Garg, N. Size focusing: a methodology for synthesizing atomically precise gold nanoclusters. J. Phys. Chem. Lett. 1, 2903–2910 (2010).10.1021/jz100944k ↗
55. Qian, H. & Jin, R. Ambient synthesis of Au144(SR)60 nanoclusters in methanol. Chem. Mater. 23, 2209–2217 (2011).10.1021/cm200143s ↗
56. Wu, Z., MacDonald, M. A., Chen, J., Zhang, P. & Jin, R. Kinetic control and thermodynamic selection in the synthesis of atomically precise gold nanoclusters. J. Am. Chem. Soc. 133, 9670–9673 (2011).10.1021/ja2028102 ↗
57. Zhu, M., Lanni, E., Garg, N., Bier, M. E. & Jin, R. Kinetically controlled, high-yield synthesis of Au25 clusters. J. Am. Chem. Soc. 130, 1138–1139 (2008).10.1021/ja0782448 ↗
58. Zhu, M., Qian, H. & Jin, R. Thiolate-protected Au20 clusters with a large energy gap of 2.1 ev. J. Am. Chem. Soc. 131, 7220–7221 (2009).10.1021/ja902208h ↗
59. Zhu, M., Qian, H. & Jin, R. Thiolate-protected Au24(SC2H4Ph)20 nanoclusters: superatoms or not? J. Phys. Chem. Lett. 1, 1003–1007 (2010).10.1021/jz100133n ↗
60. Tzeng, B. -C., Yeh, H. -T., Huang, Y. -C., Chao, H. -Y., Lee, G. -H. & Peng, S. -M. A luminescent supermolecule with gold(I) quinoline-8-thiolate: crystal structure, spectroscopic and photophysical properties. Inorg. Chem. 42, 6008–6014 (2003).10.1021/ic034041i ↗
61. Yu, S. -Y., Zhang, Z. -X., Cheng, E. C. -C., Li, Y. -Z., Yam, V. W. -W., Huang, H.-P. & Zhang, R. A chiral luminescent Au16 ring self-assembled from achiral components. J. Am. Chem. Soc. 127, 17994–17995 (2005).10.1021/ja0565727 ↗
62. Kristiansson, O. Unusual manifestation of closed-shell interactions in silver(I) complexes: crystal structure of catena-bis(4-aminobenzoato)disilver(I) acetone solvate with ligand unsupported chains of repeated rhombohedral Ag4 units. Inorg. Chem. 40, 5058–5059 (2001).10.1021/ic015534v ↗
63. Angel, L. A., Majors, L. T., Dharmaratne, A. C. & Dass, A. Ion mobility mass spectrometry of Au25(SCH2CH2Ph)18 nanoclusters. ACS Nano 4, 4691–4700 (2010).10.1021/nn1012447 ↗
64. Shichibu, Y., Negishi, Y., Tsunoyama, H., Kanehara, M., Teranishi, T. & Tsukuda, T. Extremely high stability of glutathionate-protected Au25 clusters against core etching. Small 3, 835–839 (2007).10.1002/smll.200600611 ↗
65. Zheng, J., Nicovich, P. R. & Dickson, R. M. Highly fluorescent noble-metal quantum dots. Annu. Rev. Phys. Chem. 58, 409–431 (2007).10.1146/annurev.physchem.58.032806.104546 ↗
66. Jiang, D.-e., Whetten, R. L., Luo, W. & Dai, S. The smallest thiolated gold superatom complexes. J. Phys. Chem. C 113, 17291–17295 (2009).10.1021/jp9035937 ↗
67. Walter, M., Akola, J., Lopez-Acevedo, O., Jadzinsky, P. D., Calero, G., Ackerson, C. J., Whetten, R. L., Grönbeck, H. & Häkkinen, H. A unified view of ligand-protected gold clusters as superatom complexes. Proc. Natl Acad. Sci. USA 105, 9157–9162 (2008).10.1073/pnas.0801001105 ↗
68. Sacha, P., Wieczorek, P., Hauschild, T., Zorawski, M., Olszanska, D. & Tryniszewska, E. Metallo-beta-lactamases of Pseudomonas aeruginosa—a novel mechanism resistance to beta-lactam antibiotics. Folia Histochem. Cytobiol. 46, 137–142 (2008).10.2478/v10042-008-0020-9 ↗
69. Mittal, R., Aggarwal, S., Sharma, S., Chhibber, S. & Harjai, K. Urinary tract infections caused by Pseudomonas aeruginosa: a minireview. J. Infect. Public Health 2, 101–111 (2009).10.1016/j.jiph.2009.08.003 ↗
70. Bjarnsholt, T., Jensen, P. Ø., Fiandaca, M. J., Pedersen, J., Hansen, C. R., Andersen, C. B., Pressler, T., Givskov, M. & Høiby, N. Pseudomonas aeruginosa biofilms in the respiratory tract of cystic fibrosis patients. Pediatr. Pulmonol. 44, 547–558 (2009).10.1002/ppul.21011 ↗
71. Shepp, D. H., Tang, I. T. L., Ramundo, M. B. & Kaplan, M. H. Serious Pseudomonas aeruginosa infection in AIDS. J. Acquir. Immune Defic. Syndr. Hum. Retrovirol. 7, 823–831 (1994).
72. Lara, H. H., Ayala-Nunez, N. V., Turrent, L. D. I. & Padilla, C. R. Bactericidal effect of silver nanoparticles against multidrug-resistant bacteria. World J. Microbiol. Biotechnol. 26, 615–621 (2010).10.1007/s11274-009-0211-3 ↗
73. Singh, N., Manshian, B., Jenkins, G. J. S., Griffiths, S. M., Williams, P. M., Maffeis, T. G. G., Wright, C. J. & Doak, S. H. Nanogenotoxicology: the DNA damaging potential of engineered nanomaterials. Biomaterials 30, 3891–3914 (2009).10.1016/j.biomaterials.2009.04.009 ↗
74. Kim, S., Choi, J. E., Choi, J., Chung, K. -H., Park, K., Yi, J. & Ryu, D. -Y. Oxidative stress-dependent toxicity of silver nanoparticles in human hepatoma cells. Toxicol. In Vitro 23, 1076–1084 (2009).10.1016/j.tiv.2009.06.001 ↗
75. Foldbjerg, R., Olesen, P., Hougaard, M., Dang, D. A., Hoffmann, H. J. & Autrup, H. PVP-coated silver nanoparticles and silver ions induce reactive oxygen species, apoptosis and necrosis in THP-1 monocytes. Toxicol. Lett. 190, 156–162 (2009).10.1016/j.toxlet.2009.07.009 ↗
76. Park, H.-J., Kim, J. Y., Kim, J., Lee, J.-H., Hahn, J.-S., Gu, M. B. & Yoon, J. Silver-ion-mediated reactive oxygen species generation affecting bactericidal activity. Water Res. 43, 1027–1032 (2009).10.1016/j.watres.2008.12.002 ↗