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Fluorescent Carbon Dots: Aggregation-Induced Emission Enhancement, Application as Probe for CN and Cr2O7−2, Sensing Strips and Bio-imaging Agent

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Abstract

Fluorescent carbon dots (Trp-CDs) were prepared using tryptophan as precursor and were characterized on the basis of elemental analysis, powder-XRD, IR, Raman spectroscopy, 13C-NMR, UV–Vis, fluorescence and TEM. Trp-CDs exhibit poor fluorescence in 100% water but showed strong Aggregation Induced Emission (AIE) in ethanol and higher alcohols. The anion sensing study of Trp-CD revealed that it selectively detects CN and Cr2O7−2 and from fluorescence quenching titration study, quenching constant, LOD and range of detection were evaluated. The emission life-time of Trp-CD before and after addition of CN and Cr2O7−2 were measured, the decay curve before addition of anion was best fitted with a bi-exponential function with life-time of τ1 2.79 ns (10.74%) and τ2 18.93 ns (89.26%). The mechanistic study revealed that for CN, the fluorescence quenching is due to its interaction with protons attached to surface functional groups and for Cr2O7−2, it is due to inner filter effect (IFE). Sensing strips were prepared by coating Trp-CDs onto various solid surfaces including agarose films and were used for detection of CN and Cr2O7. Trp-CD was found to be nontoxic and biocompatible and used as staining agent for Artemia and Bacteria (Bacillus Subtilis, Pseudomonas) and detection of CN and Cr2O7.

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References

  1. Rajamanikandan R, Sasikumar K, Kosame S, Ju H (2023) Optical sensing of toxic cyanide anions using noble metal. Nanomaterials 13:290

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  2. Zhu M, Sun L, Liu X, Pang X, Fan F, Yang X, Hua R, Wang Y (2023) A reversible CHEF-based NIR fluorescent probe for sensing Hg2+ and its multiple application in environmental media and biological systems. Sci Total Env 874:162460

    Article  CAS  Google Scholar 

  3. Kongsanan N, Pimsin N, Keawprom C, Sricharoen P, Areerob Y, Nuengmatcha P, Oh W-C, Saksit C (2021) Limchoowong N (2021) A fluorescence switching sensor for sensitive and selective detections of cyanide and ferricyanide using mercuric cation-graphene quantum dots. ACS Omega 6:14379–14393

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  4. Zhu M, Zhao Z, Liu X, Chen P, Fan F, Wu X, Hua R, Wang Y (2021) A novel near-infrared fluorimetric method for point-of-care monitoring of Fe2+ and its application in bioimaging. J Hazard Mat 406:124767

    Article  CAS  Google Scholar 

  5. Ji C, Zhou Y, Leblanc RM, Peng Z (2020) Recent developments of carbon dots in biosensing: a review. ACS Sens 5:2724–2741

    Article  CAS  PubMed  Google Scholar 

  6. Sharma A, Das J (2019) Small molecules derived carbon dots: synthesis and applications in sensing, catalysis, imaging, and biomedicine. Nanobiotechnol 17:Article No 92

  7. Sharma V, Singh SK, Mobin SM (2019) Bioinspired carbon dots: from rose petals to tunable emissive nanodots. Nanoscale Adv 1:1290–1296

    Article  ADS  CAS  PubMed  PubMed Central  Google Scholar 

  8. Bhatt M, Bhatt S, Vyas G, Raval IH, Haldar S, Paul P (2020) Water-dispersible fluorescent carbon dots as bioimaging agents and probes for Hg2+ and Cu2+ ions. ACS Appl Nano Mater 3:7096–7104

    Article  CAS  Google Scholar 

  9. Li P, Li SFY (2020) Recent advances in fluorescence probes based on carbon dots for sensing and speciation of heavy metals. Nanophotonics 10:877–908

    Article  CAS  Google Scholar 

  10. Arshad F, Pal A, Md Palashuddin SK (2021) Review—aggregation-induced emission in carbon dots for potential applications. ECS J Solid State Sci Techno 10:021001

    Article  ADS  CAS  Google Scholar 

  11. Juang RS, Fu CC, Hsieh CT, Gu S, Gandomi YA, Liu SH (2020) Highly luminescent aggregate-induced emission from polyethylene glycol-coated carbon quantum dot clusters under blue light illumination. J Mater Chem C 8:16569

    Article  CAS  Google Scholar 

  12. Liu ZX, Wu ZL, Gao MX, Liu H, Huang CZ (2016) Carbon dots with aggregation induced emission enhancement for visual permittivity detection. Chem Commun 52:2063

    Article  CAS  Google Scholar 

  13. Mei J, Leung NLC, Kwok RTK, Lam JWY, Tang BZ (2015) Aggregation-induced emission: together we shine, united we soar. Chem Rev 115:11718–11940

    Article  CAS  PubMed  Google Scholar 

  14. Chen Y, Lam JWY, Kwok RTK, Liu B, Tang BZ (2019) Aggregation-induced emission: fundamental understanding and future developments. Mater Horiz 6:428–433

    Article  CAS  Google Scholar 

  15. Wurthner F (2020) Aggregation-induced emission (AIE): a historical perspective. Angew Chem Int Ed 59:14192–14196

    Article  Google Scholar 

  16. Wu Z, Yao Q, Zang SQ, Xie J (2021) Aggregation-induced emission in luminescent metal nanoclusters. Natl Sci Rev 8:nwaa208

    Article  PubMed  Google Scholar 

  17. Wang C, Jiang K, Xu Z, Lin H, Zhang C (2016) Glutathione modified carbon-dots: from aggregation-induced emission enhancement properties to a “turn-on” sensing of temperature/Fe3+ ions in cells. Inorg Chem Front 3:514–522

    Article  CAS  Google Scholar 

  18. Singh VD, Singh RS, Paitandi RP, Dwivedi BK, Maiti B, Pandey DS (2018) Solvent-dependent self-Assembly and aggregation-induced emission in Zn(II) complexes containing phenothiazine-based terpyridine ligand and its efficacy in pyrophosphate sensing. J Phys Chem C 122:5178–5187

    Article  CAS  Google Scholar 

  19. Wang F, Wang L, Chen X, Yoon J (2014) Recent progress in the development of fluorometric and colorimetric chemosensors for detection of cyanide ions. Chem Soc Rev 43:4312–4324

    Article  CAS  PubMed  Google Scholar 

  20. Xu Z, Chen X, Kim HN, Yoon J (2010) Sensors for the optical detection of cyanide ion. Chem Soc Rev 39:127–137

    Article  CAS  PubMed  Google Scholar 

  21. Kulig W (1991) Cyanide Toxicity; U.S. Department of Health and Human Services. LAND WA30 no.15 Atlanta GA 30333

  22. Vennesland B, Comm EE, Knownles CJ, Westly J, Wissing F (1981) Cyanide in Biology. Academic Press, London

    Google Scholar 

  23. Acheampong MA, Meulepas RJW, Lens PNL (2010) Removal of heavy metals and cyanide from gold mine wastewater. J Chem Technol Biotechnol 85:590–613

    Article  CAS  Google Scholar 

  24. Khairnar N, Tayade K, Bothra S, Sahoo SK, Singh J, Singh N, Bendre R, Kuwar A (2014) Novel fluorescent chemosensing of CN− anions with nanomolar detection using the Zn2+–isonicotinohydrazide metal complex. RSC Adv 4:41802–41806

    Article  ADS  CAS  Google Scholar 

  25. Kumar A, Maity D, Vyas G, Bhatt M, Bhatt S, Paul P (2021) Polyacrylic acid@zeolitic imidazolate framework-8 nanoparticles for detection and absorptive removal of cyanide from aqueous media with high efficiency. Colloids Surf A: Physicochem Eng Aspects 617:126358

    Article  CAS  Google Scholar 

  26. Bolarinwa F, Orfila C, Morgan MRA (2014) Amygdalin content of seeds, kernels and food products commercially-available in the UK. Food Chem 152:133–139

    Article  CAS  PubMed  Google Scholar 

  27. Dagiliene M, Martynaitis V, Krisciuniene V, Ktolaityte S, Ackus AS (2015) Colorimetric cyanide chemosensor based on 1′,3,3′,4-tetrahydrospiro[chromene-2,2′-indole]. ChemistryOpen 4:363–369

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  28. Dinker MK, Kulkarni PS (2015) Recent advances in silica-based materials for the removal of hexavalent chromium: a review. J Chem Eng Data 60:2521–2540

    Article  CAS  Google Scholar 

  29. Rathi BS, Kumar PS, Show PL (2021) A review on effective removal of emerging contaminants from aquatic systems: Current trends and scope for further research. J Hazard Mater 409:124413–124492

    Article  CAS  PubMed  Google Scholar 

  30. Dakiky M, Khamis M, Manassra A, Mereb M (2002) Selective adsorption of chromium (VI) in industrial wastewater using low-cost abundantly available adsorbents. Advan Environ Res 6:533–540

    Article  CAS  Google Scholar 

  31. U. S. EPA (2018) Edition of the drinking water standards and health advisories tables, Office of Water, Washington DC EPA 822-F-18-001: March 2018

  32. Hagendorfer H, Goessler W (2008) Separation of chromium(III) and chromium(VI) by ion chromatography and an inductively coupled plasma mass spectrometer as element-selective detector. Talanta 76:656–661

    Article  CAS  PubMed  Google Scholar 

  33. Desharnais B, Huppé G, Lamarche M, Mireault P, Skinner CD (2012) Cyanide quantification in post-mortem biological matrices by headspace GC-MS. Forensic Sci Int 222:346–351

    Article  CAS  PubMed  Google Scholar 

  34. Sulistyarti H, Kolev SD (2013) Online ligand exchange in the determination of weak acid dissociable cyanide by gas diffusion-flow injection analysis. Microchem J 111:103–107

    Article  CAS  Google Scholar 

  35. Balamurugan G, Velmathi S (2016) Novel chromogenic selective sensors for aqueous cyanide ions under high water content and real sample analysis. Anal Methods 8:1705–1710

    Article  CAS  Google Scholar 

  36. Sukato R, Sangpetch N, Palaga T, Jantra S, Vchirawongkwin V, Jongwohan C, Sukwattanasinitt M, Wacharasindhu S (2016) New turn-on fluorescent and colorimetric probe for cyanide detection based on BODIPY-salicylaldehyde and its application in cell imaging. J Hazard Mater 314:277–285

    Article  CAS  PubMed  Google Scholar 

  37. Long L, Yuan X, Cao S, Han Y, Liu W, Chen Q, Han A, Wang K (2019) Determination of cyanide in water and food samples using an efficient naphthalene-based ratiometric fluorescent probe. ACS Omega 4:10784–10790

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  38. Maity D, Vyas G, Bhatta M, Paul P (2015) Detection of NaCN in aqueous media using a calixarene-based fluoroionophore containing ruthenium(II)-bipyridine as the fluorogenic unit. RSC Adv 5:6151–6159

    Article  ADS  CAS  Google Scholar 

  39. Nhien PQ, Chou WL, Cuc TTK, Khang TM, Wu CH, Thirumalaivasan N, Hue BTB, Wu TJI, Wu SP, Lin HC (2020) Multi-stimuli responsive FRET processes of bifluorophoric AIEgens in an amphiphilic copolymer and Its application to cyanide detection in aqueous media. ACS Appl Mater Interfaces 12:10959–10972

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  40. Oh J, Jeon I, Kim D, You Baek D, Kang SJ, Lee J (2020) Highly stable upconverting nanocrystal–polydiacetylenes nanoplates for orthogonal dual signaling-based detection of cyanide. ACS Appl Mater Interfaces 12:4934–4943

    Article  CAS  PubMed  Google Scholar 

  41. Hajizadeh S, Farhadi K, Forough M, Sabzi RE (2011) Silver nanoparticles as a cyanide colorimetric sensor in aqueous media. Anal Methods 3:2599–2603

    Article  CAS  Google Scholar 

  42. Zeng J, Cao Y, Chen J, Wang X, Yua J, Yu B, Yan Z, Chend X (2014) Au@Ag core/shell nanoparticles as colorimetric probes for cyanide sensing. Nanoscale 6:9939–9943

    Article  ADS  CAS  PubMed  Google Scholar 

  43. Bhatt S, Vyas G, Paul P (2022) Rosmarinic acid-capped silver nanoparticles for colorimetric detection of CN– and redox-modulated surface reaction-aided detection of Cr(VI) in water. ACS Omega 7:1318–1328

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  44. Kumar A, Maity D, Vyas G, Bhatt M, Bhatt S, Paul P (2021) Polyacrylic acid@zeolitic imidazolate framework-8 nanoparticles for detection and absorptive removal of cyanide from aqueous media with high efficiency. Colloids Surf A: Physico Eng Aspects 617:126358

    Article  CAS  Google Scholar 

  45. Ensafi AA, Kazemifard N, Rezaei B (2015) Label-free and turn-on fluorescent cyanide sensor based on CdTe quantum dots using silver nanoparticles. RSC Adv 5:40088–40093

    Article  ADS  CAS  Google Scholar 

  46. Molaei MJ (2020) Principles, mechanisms, and application of carbon quantum dots in sensors: a review. Anal Methods 12:1266–1287

    Article  CAS  Google Scholar 

  47. Bhatt S, Vyas G, Paul P (2022) Microwave-assisted synthesis of nitrogen-doped carbon dots using prickly pear as the carbon source and its application as a highly selective sensor for Cr(VI) and as a patterning agent. Anal Methods 14:269–277

    Article  CAS  PubMed  Google Scholar 

  48. Bhatt S, Bhatt M, Kumar A, Vyas G, Gajaria T, Paul P (2018) Green route for synthesis of multifunctional fluorescent carbon dots from Tulsi leaves and its application as Cr(VI) sensors, bio-imaging and patterning agents. Colloids Surf, B 167:126–133

    Article  CAS  Google Scholar 

  49. Grabolle M, Spieles M, Lesnyak V, Gaponik N, Eychmuller A, Genger UR (2009) Determination of the fluorescence quantum yield of quantum dots: suitable procedures and achievable uncertainties. Anal Chem 81:6285–6294

    Article  CAS  Google Scholar 

  50. Kwon W, Do S, Lee J, Hwang S, Kim JK, Rhee SW (2013) Freestanding luminescent films of nitrogen-rich carbon nanodots toward large-scale phosphor-based white-light-emitting devices. Chem Mater 25:1893–1899

    Article  CAS  Google Scholar 

  51. Peng H, Sejdic JT (2009) Simple aqueous solution route to luminescent carbogenic dots from carbohydrates. Chem Mater 21:5563–5565

    Article  CAS  Google Scholar 

  52. Ding H, Yu SB, Xiong WJS, HM, (2016) Full-color light-emitting carbon dots with a surface-state-controlled luminescence mechanism. ACS Nano 10:484–491

    Article  CAS  PubMed  Google Scholar 

  53. Fileti EE, Chaudhuri P, Canuto S (2004) Relative strength of hydrogen bond interaction in alcohol–water complexes. Chem Phys Lett 400:494–499

    Article  ADS  CAS  Google Scholar 

  54. Zhu S, Meng Q, Wang L, Zhang J, Song Y, Jin H, Zhang K, Sun H, Wang H, Yang B (2013) Highly photoluminescent carbon dots for multicolor patterning, sensors, and bioimaging. Angew Chem 125:4045–4049

    Article  ADS  Google Scholar 

  55. Li W, Zhang Z, Kong B, Feng S, Wang J, Wang L, Yang J, Zhang F, Wu P, Zhao D (2013) Simple and green synthesis of nitrogen-doped photoluminescent carbonaceous nanospheres for bioimaging. Angew Chem 52:8151–8155

    Article  CAS  Google Scholar 

  56. Qian Z, Ma J, Shan X, Feng H, Shao L, Chen J (2014) Highly luminescent N-doped carbon quantum dots as an effective multifunctional fluorescence sensing platform. Chem Eur J 20:2254–2263

    Article  CAS  PubMed  Google Scholar 

  57. Chen Y, Rosenzweig Z (2002) Luminescent CdS quantum dots as selective ion probes. Anal Chem 74:5132–5138

    Article  CAS  PubMed  Google Scholar 

  58. Jia X, Li J, Wang E (2012) One-pot green synthesis of optically pH-sensitive carbon dots with upconversion luminescence. Nanoscale 4:5572–5575

    Article  ADS  CAS  PubMed  Google Scholar 

  59. Qu S, Chen H, Zheng X, Cao J, Liu X (2013) Ratiometric fluorescent nanosensor based on water soluble carbon nanodots with multiple sensing capacities. Nanoscale 5:5514–5518

    Article  ADS  CAS  PubMed  Google Scholar 

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Acknowledgements

CSIR-CSMCRI Registration No. is 217/2021. P. P. Gratefully acknowledges CSIR for the financial support in the form of CSIR-Emeritus Scientist Scheme (CSIR-ES Scheme No. 21(1046)/18/EMR-II). S. Bhatt (CSIR Award No.: 31/28(0240)/2018-EMR-I) and G. Vyas (CSIR- Award No.: 31/28(0238)/2018-EMR-I) acknowledge CSIR for awarding the Senior Research Fellowship. A. Kumar (Award No. 19-06/2011(i)EU-IV) gratefully acknowledges UGC for awarding the Research Fellowship (JRF and SRF). All the authors acknowledge CSIR-CSMCRI for providing research facilities and partial research expense related to this work. We thank Dr. G. R. Bhadu, for recording TEM and Laiya Riddhi P. for XRD, V. Agrawal for recording IR spectra, V. Bakani for elemental analysis and Raman spectra. We thank AESD&CIF for additional analytical support.

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M.B. Conceptualization of work, methodology and wrote draft of the manuscript. S.B. Data curation and formal analysis. G.V. Data analysis and validation. I.R. Toxicity study, imaging and prepared Figures 11 and 12. A.K. Application study with sensing strips. P.P. Conceptualization, funding acquisition, supervision and writing – review and editing of manuscript.

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Correspondence to Parimal Paul.

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Bhatt, M., Bhatt, S., Vyas, G. et al. Fluorescent Carbon Dots: Aggregation-Induced Emission Enhancement, Application as Probe for CN and Cr2O7−2, Sensing Strips and Bio-imaging Agent. J Fluoresc (2024). https://doi.org/10.1007/s10895-024-03602-2

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