Abstract
In this work, L-Histidine-protected copper nanoclusters synthesized by changing the pH levels of precursor solution have been shown to display different emission wavelengths and intensities. As determined by mass spectrometry, nanoclusters Cu3L2 synthesized at acidic pH have 3 atoms in their core and emit in the greenish-yellow region, and nanoclusters Cu2L2, synthesized in the basic conditions have 2 atoms in their core and emit in the blue-green region. They are expected to have coordination through the carboxylate group and nitrogen of the imidazole ring of histidine ligand, respectively. Metal ions Mg2+, Mn2+, Zn2+, and Pb2+ selectively enhance the interaction between carboxylate – copper metal core and increase the emission intensity of Cu3L2. These metal ions weaken the interaction between imidazole nitrogen and copper metal core and quench the emission intensity of Cu2L2. As synthesized, nanoclusters exhibit good water solubility and photostability, they can act as fluorescent probes to sense the metal ions, therefore, they were utilized for the optical sensing of the mentioned metal ions. Fluorescent nanoclusters were found to sense even a very low concentration of metal ions with a limit of detection (3 σ/slope) in nanomolar range.
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26 September 2023
To correct the placements of the floats of the figures and schemes in the PDF version as well as their corresponding captions. Also, to captured ‘2+’ as superscript of metal ion (Pb, Zn, Hg, Mn) in references number 23, 25, 31, 32 respectively.
References
Kang X, Zhu M (2019) Tailoring the photoluminescence of atomically precise nanoclusters. Chem Soc Rev 48:2422–2457. https://doi.org/10.1039/C8CS00800K
Ou G, Zhao J, Chen P et al (2018) Fabrication and application of noble metal nanoclusters as optical sensors for toxic metal ions. Anal Bioanal Chem 410:2485–2498. https://doi.org/10.1007/s00216-017-0808-6
Mittal R, Gupta N (2023) Towards green synthesis of fluorescent metal nanoclusters. J Fluoresc. https://doi.org/10.1007/s10895-023-03229-9
Salvadori MR, Ando RA, Oller Do Nascimento CA, Corrêa B (2014) Intracellular biosynthesis and removal of copper nanoparticles by dead biomass of yeast isolated from the wastewater of a mine in the brazilian Amazonia. PLOS ONE 9:1–9. https://doi.org/10.1371/journal.pone.0087968
Chakraborty S, Mukherjee S (2022) Effects of protecting groups on luminescent metal nanoclusters: spectroscopic signatures and applications. Chem Commun 58:29–47. https://doi.org/10.1039/D1CC05396E
Liu Z, Zu Y, Fu Y et al (2010) Hydrothermal synthesis of histidine-functionalized single-crystalline gold nanoparticles and their pH-dependent UV absorption characteristic. Colloids Surf B Biointerfaces 76:311–316. https://doi.org/10.1016/j.colsurfb.2009.11.010
Guevel X, Le, Tagit O, Rodríguez CE et al (2014) Ligand effect on the size, valence state and red/near infrared photoluminescence of bidentate thiol gold nanoclusters. Nanoscale 6:8091–8099. https://doi.org/10.1039/c4nr01130a
Feng J, Chen Y, Han Y, Liu J, Ma S, Zhang H, Chen X (2017) pH-Regulated synthesis of trypsin-templated copper nanoclusters with blue and yellow fluorescent emission. ACS Omega 2:9109–9117. https://doi.org/10.1021/acsomega.7b01052
Kawasaki H, Hamaguchi K, Osaka I, Arakawa R (2011) pH-dependent synthesis of pepsin-mediated gold nanoclusters with blue green and red fluorescent emission. Adv Funct Mater 21:3508–3515. https://doi.org/10.1002/adfm.201100886
Kennedy TAC, MacLean JL, Liu J (2012) Blue emitting gold nanoclusters templated by poly-cytosine DNA at low pH and poly-adenine DNA at neutral pH. Chem Commun 48:6845–6847. https://doi.org/10.1039/c2cc32841k
Yuan X, Luo Z, Yu Y et al (2013) Luminescent noble metal nanoclusters as an emerging optical probe for sensor development. Chem - An Asian J 8:858–871. https://doi.org/10.1002/asia.201201236
Shang L, Xu J, Nienhaus GU (2019) Recent advances in synthesizing metal nanocluster-based nanocomposites for application in sensing, imaging and catalysis. Nano Today 28:100767. https://doi.org/10.1016/j.nantod.2019.100767
Rötzschke O, Lau JM, Hofstätter M et al (2002) A pH-sensitive histidine residue as control element for ligand release from HLA-DR molecules. Proc Natl Acad Sci U S A 99:16946–16950. https://doi.org/10.1073/pnas.212643999
Wu N-N, Chen L-G, Xiao M-Z et al (2023) Determination of trypsin using protamine mediated fluorescent enhancement of DNA templated au nanoclusters. Microchim Acta 190:158. https://doi.org/10.1007/s00604-023-05754-7
Pandit S, Kundu S (2020) pH-Dependent reversible emission behaviour of lysozyme coated fluorescent copper nanoclusters. J Lumin 228:117607. https://doi.org/10.1016/j.jlumin.2020.117607
Karimi A, Kirk KA, Andreescu S (2017) Electrochemical investigation of pH-Dependent activity of polyethylenimine-capped silver nanoparticles. ChemElectroChem 4:2801–2806. https://doi.org/10.1002/celc.201700460
Liu Y, Bryantsev VS, Diallo MS, Goddard WA III (2009) PAMAM dendrimers undergo pH responsive conformational changes without swelling. J Am Chem Soc 131:2798–2799. https://doi.org/10.1021/ja8100227
Wang HB, Li Y, Bai HY, Liu YM (2018) DNA-templated Au nanoclusters and MnO2 sheets: a label-free and universal fluorescence biosensing platform. Sens Actuators B Chem 259:204–210. https://doi.org/10.1016/j.snb.2017.12.048
Saurabh S, Kalonia C, Li Z et al (2022) Understanding the stabilizing effect of histidine on mAb aggregation: a Molecular Dynamics Study. Mol Pharm 19:3288–3303. https://doi.org/10.1021/acs.molpharmaceut.2c00453
An Y, Ren Y, Bick M et al (2020) Highly fluorescent copper nanoclusters for sensing and bioimaging. Biosens Bioelectron 154:112078. https://doi.org/10.1016/j.bios.2020.112078.
Das NK, Ghosh S, Priya A et al (2015) Luminescent copper nanoclusters as a specific cell-imaging probe and a selective metal ion sensor. J Phys Chem C 119:24657–24664. https://doi.org/10.1021/acs.jpcc.5b08123
Deibert BJ, Li J (2014) A distinct reversible colorimetric and fluorescent low pH response on a water-stable zirconium–porphyrin metal–organic framework. Chem Commun 50:9636–9639. https://doi.org/10.1039/C4CC01938E
Das S, Rakshit S, Datta A (2021) Mechanistic insights into selective sensing of Pb2+ in water by photoluminescent CdS quantum dots. J Phys Chem C 125:15396–15404. https://doi.org/10.1021/acs.jpcc.1c02357
Wang H-B, Tao B-B, Wu N-N et al (2022) Glutathione-stabilized copper nanoclusters mediated-inner filter effect for sensitive and selective determination of p-nitrophenol and alkaline phosphatase activity. Spectrochim Acta Part A Mol Biomol Spectrosc 271:120948. https://doi.org/10.1016/j.saa.2022.120948
Kotha S, Goyal D, Banerjee S, Datta A (2012) A novel di-triazole based peptide as a highly sensitive and selective fluorescent chemosensor for Zn2+ ions. Analyst 137:2871–2875. https://doi.org/10.1039/c2an35222b
Chen X, Zhou Y, Peng X, Yoon J (2010) Fluorescent and colorimetric probes for detection of thiols. Chem Soc Rev 39:2120–2135. https://doi.org/10.1039/B925092A
Li X, Yang C, Yang S, Li G (2012) Fiber-optical sensors: basics and applications in multiphase reactors. Sens 12:12519–12544. https://doi.org/10.3390/s120912519
Lin SM, Geng S, Li N et al (2017) L-Histidine-protected copper nanoparticles as a fluorescent probe for sensing ferric ions. Sens Actuators B Chem 252:912–918. https://doi.org/10.1016/j.snb.2017.06.079
Guévela XL, Trouilletb V, Spiesc C, Lia K, Laaksonend T, Auerbachc D, Gregor Jungc MS (2012) High photostability and enhanced fluorescence of gold nanoclusters by silver doping. Nanoscale 4:7624–7631. https://doi.org/10.1039/b000000x
Mott D, Galkowski J, Wang L et al (2007) Synthesis of size-controlled and shaped copper nanoparticles. Langmuir 23:5740–5745. https://doi.org/10.1021/la0635092
Zhong Y, Deng C, He Y et al (2015) Glutathione-protected silver nanoclusters for sensing trace-level Hg2+ in a wide pH range. Anal Methods 7:1558–1562. https://doi.org/10.1039/c4ay02561j
Han B, Xiang R, Hou X et al (2017) One-step rapid synthesis of single thymine-templated fluorescent copper nanoclusters for turn on detection of Mn2+. Anal Methods 9:2590–2595. https://doi.org/10.1039/c7ay00625j
Ding W, Huang S, Guan L et al (2015) Furthering the chemosensing of silver nanoclusters for ion detection. RSC Adv 5:64138–64145. https://doi.org/10.1039/c5ra11124b
Naaz S, Chowdhury P (2017) Sunlight and ultrasound-assisted synthesis of photoluminescent silver nanoclusters: a unique ‘Knock out’ sensor for thiophilic metal ions. Sens Actuators B Chem 241:840–848. https://doi.org/10.1016/j.snb.2016.10.116
Acknowledgements
For the stipend R.M. thank the Council of Scientific & Industrial Research (CSIR), India. R. M. and N. G. thank the Department of Chemistry at Netaji Subash University of Technology (NSUT) for providing the facilities.
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Author R.M. has received research support from the Council of Scientific & Industrial Research (CSIR), India (Grant number -CSIRAWARD/JRF-NET2021/113630). The authors declare that no funds, grants, or other support were received during the preparation of this manuscript.
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Ritika Mittal has performed the literature search, experimental, data analysis, drafted and critically revised the work. Nancy Gupta has contributed to the conceptualization and critical revision of the work. All authors read and approved the final manuscript.
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Mittal, R., Gupta, N. pH-dependent Synthesis and Interactions of Fluorescent L-Histidine Capped Copper Nanoclusters with Metal Ions. J Fluoresc (2023). https://doi.org/10.1007/s10895-023-03433-7
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DOI: https://doi.org/10.1007/s10895-023-03433-7