The pH-switchable agglomeration and dispersion behavior of fluorescent Ag nanoclusters and its applications in urea and glucose biosensing
Source abstract
Abstract
Water-soluble fluorescent Ag nanoclusters (Ag NCs) with distinct pH-switchable agglomeration and spectral signal responses are prepared using a facile etching method. Increased and decreased pH cause the Ag NCs to switch between agglomeration and dispersion, accompanied by decreases in and recoveries of fluorescence intensity and absorbance. The pH switchable behavior of the Ag NCs is attributed to carboxyl groups on the nanocluster surface that are rich in the citrate and amido functional groups of ligands (glutathione), creating an easily formed, weak molecular interaction among Ag NCs (for example, hydrogen bonding) and maintaining a balance in the colloidal solution, whereas a change in pH will disrupt the balance, leading to the reversible agglomeration of Ag NCs and the switchable spectral signal response. In addition, because urea and glucose can change the pH of a solution by producing NH3 and gluconic acid in enzyme-catalyzed reactions, the pH-switchable behavior of the Ag NCs is used to develop them as an optical probe to establish a regenerated biosensing platform for the sensitive and selective detection of urea and glucose, and the test results are satisfactory. Fluorescent silver nanoclusters that reversibly form or break agglomerates on varying the pH are promising for sensing biological molecules. The ability to cause fluorescent nanoclusters to agglomerate and break up enables their fluorescence properties to be altered, but most systems studied to date do so only irreversibly. Now, Nian Bing Li and Hong Qun Luo of Southwest University in China and co-workers have produced water-soluble silver nanoclusters that agglomerate in basic and neutral solutions and disperse in acidic solutions in a reversible manner. The fluorescence intensity of the nanoclusters drops with increasing pH because aggregation quenches fluorescence. These nanoclusters are fabricated by straightforward etching of silver nanocrystals coated in citrate. The team demonstrated the potential of the nanoclusters for biosensing by using them to detect the biologically important molecules urea and glucose. Novel fluorescent Ag nanoclusters are prepared based on an etching method with citrate and GSH as the stabilizer of Ag nanocrystals and the etchant. The as-prepared Ag nanoclusters show good pH-switchable agglomeration and dispersion accompanied with the reversible agglomeration induced signal quenching. The pH-regulated behavior mechanism has been discussed, and the Ag nanoclusters is introduced as a probe to establish regenerable biosensing platform for urea and glucose detection.
Source: openalex_inverted_index · Quality: baseline
Research context
OpenAlex topics: Nanocluster Synthesis and Applications · Gold and Silver Nanoparticles Synthesis and Applications · Advanced Nanomaterials in Catalysis
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (42)
Show source-provided references
1. Zhang, Q., Xie, J., Yang, J. & Lee, J. Y. Monodisperse icosahedral Ag, Au, and Pd nanoparticles: Size control strategy and superlattice formation. ACS Nano 3, 139–148 (2008).10.1021/nn800531q ↗
2. 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 ↗
3. Qu, F., Li, N. B. & Luo, H. Q. Transition from nanoparticles to nanoclusters: microscopic and spectroscopic investigation of size-dependent physicochemical properties of polyamine-functionalized silver nanoclusters. J. Phys. Chem. C 117, 3548–3555 (2013).10.1021/jp3091792 ↗
4. Wu, Z. & Jin, R. Transition from nanoparticles to nanoclusters: microscopic and spectroscopic investigation of size-dependent physicochemical properties of polyamine-punctionalized silver nanoclusters. Nano Lett. 10, 2568–2573 (2010).10.1021/nl101225f ↗
5. Zheng, K., Yuan, X., Kuah, K., Luo, Z., Yao, Q., Zhang, Q. & Xie, J. Boiling water synthesis of ultrastable thiolated silver nanoclusters with aggregation-induced emission. Chem. Commun. 51, 15165–15168 (2015).10.1039/C5CC04858C ↗
6. Qu, F., Li, N. B. & Luo, H. Q. Highly sensitive fluorescent and colorimetric ph sensor based on polyethylenimine-capped silver nanoclusters. Langmuir 29, 1199–1205 (2013).10.1021/la304558r ↗
7. Ma, J. L., Yin, B. C., Le, H. N. & Ye, B. C. Label-free detection of sequence-specific dna based on fluorescent silver nanoclusters-assisted surface plasmon-enhanced energy transfer. ACS Appl. Mater. Interfaces 7, 12856–12863 (2015).10.1021/acsami.5b03837 ↗
8. Goswami, N., Yao, Q., Luo, Z., Li, J., Chen, T. & Xie, J. Luminescent metal nanoclusters with aggregation-induced emission. J. Phys. Chem. Lett. 7, 962–975 (2016).10.1021/acs.jpclett.5b02765 ↗
9. Song, X. R., Goswami, N., Yang, H. H. & Xie, J. Functionalization of metal nanoclusters for biomedical applications. Analyst 141, 3126–3140 (2016).10.1039/C6AN00773B ↗
10. Yao, Q., Yuan, X., Yu, Y., Yu, Y., Xie, J. & Lee, J. Y. Introducing amphiphilicity to noble metal nanoclusters via phase-transfer driven ion-pairing reaction. J. Am. Chem. Soc. 137, 2128–2136 (2015).10.1021/jacs.5b00090 ↗
11. Zheng, K., Yuan, X., Goswami, N., Zhang, Q. & Xie, J. Recent advances in the synthesis, characterization, and biomedical applications of ultrasmall thiolated silver nanoclusters. RSC Adv. 4, 60581–60596 (2014).10.1039/C4RA12054J ↗
12. 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 ↗
13. Balasubramanian, R., Guo, R., Mills, A. J. & Murray, R. W. Reaction of Au55(PPh3 12Cl6 with thiols yields thiolate monolayer protected Au75 clusters. J. Am. Chem. Soc. 127, 8126–8132 (2005).10.1021/ja050793v ↗
14. Qian, H., Zhu, Y. & Jin, R. Size-focusing synthesis, optical and electrochemical properties of monodisperse Au38(SC2H4Ph)24 nanoclusters. ACS Nano 3, 3795–3803 (2009).10.1021/nn901137h ↗
15. Muhammed, M. A. H., Aldeek, F., Palui, G., Trapiella-Alfonso, L. & Mattoussi, H. Growth of in situ functionalized luminescent silver nanoclusters by direct reduction and size focusing. ACS Nano 6, 8950–8961 (2012).10.1021/nn302954n ↗
16. Jeffrey, C. F. Simple and rapid colorimetric enzyme sensing assays using non-crosslinking gold nanoparticle aggregation. Chem. Commun. 36, 3729–3731 (2007).
17. Díez, I., Pusa, M., Kulmala, S., Jiang, H., Walther, A., Goldmann, A. S., Müller, A. H. E., Ikkala, O. & Ras, R. H. Color tunability and electrochemiluminescence of silver nanoclusters. Angew. Chem. Int. Ed. 48, 2122–2125 (2009).10.1002/anie.200806210 ↗
18. Albanese, A. & Chan, W. C. Effect of gold nanoparticle aggregation on cell uptake and toxicity. ACS Nano 5, 5478–5489 (2011).10.1021/nn2007496 ↗
19. Yao, Q., Yu, Y., Yuan, X., Yu, Y., Zhao, D., Xie, J. & Lee, J. Y. Counterion-assisted shaping of nanocluster supracrystals. Angew. Chem. Int. Ed. 54, 184–189 (2015).10.1002/anie.201408675 ↗
20. Jia, X., Li, J. & Wang, E. Cu nanoclusters with aggregation induced emission enhancement. Small 9, 3873–3879 (2013).10.1002/smll.201300896 ↗
21. Dou, X., Yuan, X., Yu, Y., Luo, Z., Yao, Q., Leong, D. T. & Xie, J. Lighting up thiolated Au@Ag nanoclusters via aggregation-induced emission. Nanoscale 6, 157–161 (2014).10.1039/C3NR04490D ↗
22. Zhang, L., He, N. & Lu, C. Aggregation-induced emission: a simple strategy to improve chemiluminescence resonance energy transfer. Anal. Chem. 87, 1351–1357 (2015).10.1021/ac5041605 ↗
23. 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 ↗
24. Yu, Y., Luo, Z., Chevrier, D. M., Leong, D. T., Zhang, P., Jiang, D. E. & Xie, J. Identification of a highly luminescent Au22(SG)18 nanocluster. J. Am. Chem. Soc. 136, 1246–1249 (2014).10.1021/ja411643u ↗
25. Chen, W., Tu, X. & Guo, X. Fluorescent gold nanoparticles-based fluorescence sensor for Cu2+ ions. Chem. Commun. 13, 1736–1738 (2009).10.1039/b820145e ↗
26. Chang, H. C., Chang, Y. F., Fan, N. C. & Ho, J. A. A. Facile preparation of high-quantum-yield gold nanoclusters: application to probing mercuric ions and biothiols. ACS Appl. Mater. Interfaces 6, 18824–18831 (2014).10.1021/am504546f ↗
27. García-Bosch, N., Liras, M., Quijada-Garrido, I. & García, O. Multiamino polymeric capping of fluorescent silver nanodots as an effective protective, amphiphilic and pH/thermo-responsive coating. RSC Adv. 6, 67643–67650 (2016).10.1039/C6RA12024E ↗
28. Wang, W., Leng, F., Zhan, L., Chang, Y., Yang, X. X., Lan, J. & Huang, C. Z. One-step prepared fluorescent copper nanoclusters for reversible ph-sensing. Analyst 139, 2990–2993 (2014).10.1039/C4AN00113C ↗
29. Chen, Z., Lu, D., Zhang, G., Yang, J., Dong, C. & Shuang, S. Glutathione capped silver nanoclusters-based fluorescent probe for highly sensitive detection of Fe3+. Sens. Actuators B Chem. 202, 631–637 (2014).10.1016/j.snb.2014.05.123 ↗
30. Tremey, E., Suraniti, E., Courjean, O., Gounel, S., Stines-Chaumeil, C., Louerat, F. & Mano, N. Switching an O2 sensitive glucose oxidase bioelectrode into an almost insensitive one by cofactor redesign. Chem. Commun. 50, 5912–5914 (2014).10.1039/C4CC01670J ↗
31. Tam, T. K., Strack, G., Pita, M. & Katz, E. Biofuel cell logically controlled by antigen-antibody recognition: Towards immune-regulated bioelectronic devices. J. Am. Chem. Soc. 131, 11670–11671 (2009).10.1021/ja9048459 ↗
32. 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 ↗
33. Zhou, T., Rong, M., Cai, Z., Yang, C. J. & Chen, X. Sonochemical synthesis of highly fluorescent glutathione-stabilized Ag nanoclusters and S2− sensing. Nanoscale 4, 4103–4106 (2012).10.1039/c2nr30718a ↗
34. Lu, W., Qin, X., Liu, S., Chang, G., Zhang, Y., Luo, Y., Asiri, A. M., Al-Youbi, A. O. & Sun, X. Economical, green synthesis of fluorescent carbon nanoparticles and their use as probes for sensitive and selective detection of mercury (II) ions. Anal. Chem. 84, 5351–5357 (2012).10.1021/ac3007939 ↗
35. Dong, J. X., Qu, F., Li, N. B. & Luo, H. Q. Aggregation, dissolution and cyclic regeneration of Ag nanoclusters based on ph-induced conformational changes of polyethyleneimine template in aqueous solutions. RSC Adv. 5, 6043–6050 (2015).10.1039/C4RA14812F ↗
36. Qin, Y., Ji, X., Jing, J., Liu, H., Wu, H. & Yang, W. Size control over spherical silver nanoparticles by ascorbic acid reduction. Colloid Surf. A 372, 172–176 (2010).10.1016/j.colsurfa.2010.10.013 ↗
37. Freitas, C. & Müller, R. H. Effect of light and temperature on zeta potential and physical stability in solid lipid nanoparticle (SLN) dispersions. Int. J. Phytoremdiat. 168, 221–229 (1998).
38. Sokolov, S. V., Tschulik, K., Batchelor-McAuley, C., Jurkschat, K. & Compton, R.G. Reversible or not? Distinguishing agglomeration and aggregation at the nanoscale. Anal. Chem. 87, 10033–10039 (2015).10.1021/acs.analchem.5b02639 ↗
39. Silverstein, R. M., Webster, F. X. Spectrometric Identification of Organic Compounds 6th edn (eds Silverstein, R. M. & Webster, F. X.) (Wiley: New York, NY, USA, 1998).
40. Solomons, T. W. G., Fryhle, C. Organic Chemistry 7th edn (eds Solomons, T. W. G. & Fryhle, C.) (Wiley: New York, NY, USA, 2001).
41. Qu, F., Li, N. B. & Luo, H. Q. Polyethyleneimine-templated Ag nanoclusters: a new fluorescent and colorimetric platform for sensitive and selective sensing halide ions and high disturbance-tolerant recognitions of iodide and bromide in coexistence with chloride under condition of high ionic strength. Anal. Chem. 84, 10373–10379 (2012).10.1021/ac3024526 ↗
42. Song, Y., Liu, H., Tan, H., Xu, F., Jia, J., Zhang, L., Zhuang, L. & Wang, L. pH-switchable electrochemical sensing platform based on chitosan reduced graphene oxide/concanavalin a layer for assay of glucose and urea. Anal. Chem. 86, 1980–1987 (2014).10.1021/ac402742m ↗