Abstract
This article reports the fluorometric detection of toxic hexavalent chromium Cr (VI)) in wastewater and Cr (VI) contaminated living cells using in-situ grown carbon quantum dots into the goethite (α-FeOOH) nano-matrix. The synthesized nano-hybrid shows enormous potential in determining the chromium contamination levels in various types of water samples. This selective fluorometric probe is enormously sensitive (LOD 81 nM) toward hexavalent chromium, which makes it a dedicated chromium sensor. Moreover, the sensing mechanism has been assessed using Stern–Volmer’s equation and fluorescence lifetime experiments showing the simultaneous occurrence of photoinduced electron transfer and the inner filter effect. This chromium sensor has also been employed to assess the contamination level in real-life industrial wastewater. The performance of this probe in a real-life wastewater sample is quite commendable. Further, this biocompatible fluorometric probe has been used to demonstrate the in-vitro sensing of Cr (VI) in HeLa cells. The rapid detection mechanism of hexavalent chromium in living cells has been validated using theoretical docking simulations. Henceforth, this fluorometric sensor material could open new avenues not only in wastewater monitoring but also in biomedical applications.
Similar content being viewed by others
Data Availability Statement
The data will be available at the reasonable request.
References
Hazrat A, Khan E, Ilahi I (2019) Environmental Chemistry & Ecotoxicology of Hazardous Heavy Metals: Environmental Persistence Toxicity & Bioaccumulation. J Chem 4:1–14
Jarup L (2003) Hazards of Heavy Metal Contamination. Br Med Bull 68(1):167–182
Jayshankar M et al (2014) Toxicity mechanism and health effects of some heavy metals. Interdiscip Toxicol 7(2):60–72
Rahman Z, Singh VP (2019) The relative impact of toxic heavy metals (THMs) arsenic (As), cadmium (Cd), chromium (Cr VI), mercury (Hg) and lead (Pb) on the total environment. Environ Monit Assess 191(7):1–11
Mitra S, Sarkar A, Sen S (2017) Removal of Chromium from industrial effluents using nanotechnology: a review. Nanotechnology Environmental Engineering 2(11):1–14
Guo Q (1997) Increase of lead and chromium in drinking water from using cement-mortar lined pipes: initial modelling and assessment. J Hazard Mater 56(1–2):181–213
Ray RR (2016) Adverse hematological effects of hexavalent chromium: an overview. Interdiscip Toxicol 9(2):55–65
Turskewycz AR, Shukla R, Ball AS (2018) Pndhytofabrication of Iron nanoparticles for hexavalent chromium remediation. ACS Omega 3(9):10781–10790
Tall A et al (2021) Green emitting N, P- doped Carbon dots as efficient fluorescent nanoprobes for determination of Cr (VI) in water and soil samples. Microchem J 166:1–11
Alford R et al (2009) Toxicity of Organic Fluorophores Used in Molecular Imaging: Literature Review. Mol Imaging 8(6):341–354
Roy S et al (2020) In situ Grown C-dot Wrapped Boehmite Nanoparticles for Cr (VI) Sensing in Waste water and a Theoretical Probe for Chromium-Induced Carcinogen Detection. ACS Applied Material Interfaces 12(39):43833–43843
Ryu HJ et al (2014) Evaluation of silica nanoparticle toxicity after topical exposure for 90 days. Int J Nanomed 9(2):127–136
Forest V et al (2014) Toxicity of boehmite nanoparticles: Impact of the ultrafine fraction and of the agglomerates size on cytotoxicity and proinflammatory response. Inhalation Toxicol 26(9):545–553
Pauluhn J (2009) Pulmonary Toxicity and Fate of Agglomerated 10 and 40nm Aluminium oxyhydroxides following 4 week Inhalation exposure of Rats: Toxic Effects are Determined by Agglomerated, not primary particle size. Toxicol Sci 109(1):152–167
Darehnaranji MK et al (2021) Bio Assisted Food Grade FeOOH Nanoellipsoids as Promising Iron Supplements For Food Fortification. Applied Food Biotechnology 8:71–77
Novin D et al (2020) A functional dairy product rich in Menaquinone-7 and FeOOH nanoparticles. Food Sci Technol 129:1–18
Saffari F et al (2015) Effects of Co-substitution on the structural and magnetic properties of Ni CoxFe2-xO4 ferrite nanoparticles. Ceramic International 41(6):7352–7358
Momma K, Izumi F (2008) VESTA: A Three-Dimensional Visualization System for Electronic and Structural Analysis. J Appl Crystallogr 41:653–658
Siroha P et al (2006) Comparative Study on crystallographic representation of transition metal oxides polymorphs nanomaterials using VESTA software: Case Study of Fe2O3 and TiO2. AIP Conference Proceedings
Goodsell DS, Morris GM, Olson AJ (1996) Automated docking of flexible ligands: applications of Auto dock. J Mol Recognit 9(1):1–5
Muzio ED, Toti D, Polticelli F (2017) DockingApp: a user-friendly interface for facilitated simulations with Autodock Vina. J Comput Aided Mol Des 31(2):213–218
Trott O, Olson AJ (2010) Autodock Vina: Improving the speed and accuracy of docking with a new scoring function, efficient optimization and multithreading. J Comput Chem 31(2):455–461
Delano WL et al (2002) An open- source molecular graphics tool. CCP4 Newsletter Protein Crystallography 40:82–92
Seeliger D, Groot BL (2010) Ligand Docking and binding site analysis with PyMOL and Autodock/Vina. Computer- Aided Molecular Design 24(5):417–422
Ji TH et al (2020) Electron/ energy co-transfer behaviour and reducibility of Cu-Chlorophyllin bonded carbon dots. RSC Advance 10(52):31495–31501
Varotsis C, Vamvouka M (1998) Resonance Raman and FTIR studies of Carbon Monoxide-bound Cytochrome aa3-600 Oxidase of Bacillus subtilis. J Phys Chem B 102(39):7670–7673
Verneker D, Jagadeesan D (2015) Tunable acid base bifunctional catalytic activity of FeOOH in an orthogonal tandem reaction. Cat Sci Technol 5(8):4029–4038
Su Y et al (2018) Immobilization of horse peroxidase on amino functionalized carbon dots for the sensitive detection of hydrogen peroxide. Microchim Acta 185(2):1–8
Wu Y, Remcho VT (2016) A capillary electrophoretic method for separation and characterization of carbon dots and carbon antibody bioconjugates. Talanta 161:854–859
Zhao Y et al (2015) Carbon dots: From Intense Absorption in Visible Range to Excitation Independent and Excitation dependant Fluorescence. Fullerene Nanotubes Carbon Nanostructures 23(11):922–929
Tadesse A et al (2020) Fluorescent Nitrogen Doped Carbon Quantum dots Derived from Citrus Lemon Juice: Green Synthesis, Mercury (II) Ion Sensing and Live Cell Imaging. ACS Omega 5(8):3889–3898
Sherman DM, Waite TD (1985) Electronic spectra of Fe3+ oxide and oxide hydroxides in the near IR to UV. Am Miner 70(11–12):1262–1269
Tang X, Yu H, Bui B (2021) Nitrogen Doped Fluorescent Carbon dots as multi mechanism detection for iodide and curcumin in biological and food sample. Bioactive Materials 6(6):1541–1554
Yan F et al (2019) The fluorescence mechanism of carbon dots and methods for tuning their emission color: a review. Microchim Acta 186(8):1–37
Lu F (2017) Fluorescent Carbon dots with tunable negative charges for bioimaging in bacterial viability assessment. Carbon 120:95–102
Bardhan S et al (2020) Nitrogenous Carbon dot decorated natural microcline: an ameliorative dual probe for Fe3+ and Cr6+ detection. Dalton Trans 49(30):10554–10556
Roy S et al (2019) Gd (III) Doped Boehmite Nanoparticle: An Emergent Material for Fluorescent sensing of Cr (VI) in Waste Water and Live cells. Inorg Chem 58(13):8369–8378
Malkondu S (2014) A highly selective and sensitive perylenebisimide based fluorescent PET sensor for Al3+ determination in MeCN. Tetrahedron 70(35):5580–5584
Mohandoss S, Stalin T (2017) A new fluorescent PET sensor probe for Co2+ ion detection: computational, logic device and living cell imaging applications. RSC Advance 7(27):16581–16593
Fegade U, Attarde S, Kuwar A (2013) Fluorescent recognition of Fe3+ ion with photoinduced electron transfer (PET) sensor. Chem Phys Lett 584:165–171
Bhatt S et al (2018) Green route for synthesis of multifunctional fluorescent carbon dots from Tulsi leaves and its application as Cr (VI) sensors, bioimaging and patterning agents. Colloids Surf, B 167:126–133
Mao M et al (2018) Inner filter effect based fluorometric determination of the activity of alkaline phosphatase by using carbon dots codoped with boron and nitrogen. Microchim Acta 185(1):1–6
Huang D et al (2021) Fluorescent Nitrogen doped Ti3C2 Mxene quantum dots as unique on off on nanoprobe for chromium (VI) and ascorbic acid based on inner filter effect. Sensors and Actuators B: Chemistry 342
Mattia GD et al (2004) Impairment of cell and plasma redox state in subjects professionally exposed to chromium. Am J Ind Med 46(2):120–125
Chiu A et al (2010) Review of chromium (VI) apoptosis, cell cycle arrest and carcinogenesis. J Environ Sci Health C Environ Carcinog Ecotoxicol Rev 28(3):188–230
Wang S et al (2020) The role of hydroxyl radical as a messenger in Cr (VI) induced p53 activation. American Journal of Physiology- Cell- Physiology 279(3):868–875
Myers CR (2012) The effect of chromium (VI) on the thioredoxin system: Implications for redox regulation. Free Radical Biol Med 52(10):2091–2107
Des Marias TL, Costa DL (2019) Mechanisms of chromium induced toxicity. Curr Opin Toxicol 14:1–7
Fang Z et al (2014) Genotoxicity of Tri and Hexavalent Chromium Compounds In Vivo and Their mode of action on DNA damage In Vitro. PLoS ONE 9(8):1–9
Zhang XH et al (2011) Chronic occupational exposure to hexavalent chromium causes DNA damage in electroplating workers. BMC Public Health 11:1–8
Huang Q et al (2021) Carbon dots derived from Poria cocos polysaccharide as an effective “’on off” fluorescent sensor for chromium (VI) detection. J Pharm Anal p. 1–9
Lu KH et al (2019) A fluorometric paper test for chromium (VI) based on the use of N doped carbon dots. Mirochimica Acta 186(227):1–7
Gao Y et al (2018) Carbon dots with red emission as a fluorescence and colorimetric dual readout probe for the detection of chromium (VI) and cysteine and its logic gate operation. J Mater Chem B 6(38):6099–6107
Sakaew C et al (2020) Green and facile synthesis of water soluble carbon dots from ethanolic shallot extract for chromium ion sensing in milk, fruit juices and waste water samples. RSC Adv 10(35):20638–20645
Acknowledgements
The authors would like to thank the Department of Physics, Jadavpur University, for extending experimental facilities.
Funding
S.D and D.M would like to acknowledge DST-SERB (Grant No. EEQ/2018/000747) for.
funding. S.R and B.G would like to acknowledge the Dept. of Higher Education, Govt. of West.
Bengal for providing them with the SVMCM fellowship.
Author information
Authors and Affiliations
Contributions
Bidisha Ghosh: Data curation, Writing- Original draft preparation. Shubham Roy: Conceptualization, Software, Writing- Reviewing and Editing. Souravi Bardhan: Data curation, Investigation, Writing- Assistance. Dhananjoy Mondal: Data curation, Investigation, Software. Ishita Saha: Investigation. Saheli Ghosh: Data curation, Investigation. Ruma Basu: Writing- Reviewing and Editing. Parimal Karmakar: Writing- Reviewing and Editing, Resources. Kaustuv Das: Supervision, Funding acquisition. Sukhen Das: Supervision, Funding acquisition.
Corresponding authors
Ethics declarations
Ethics Approval
Not applicable.
Consent to Participate
Not applicable.
Consent for Publication
Not applicable.
Competing Interests
The authors declare that they have no competing interests.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Ghosh, B., Roy, S., Bardhan, S. et al. Biocompatible Carbon Dot Decorated α-FeOOH Nanohybrid for an Effective Fluorometric Sensing of Cr (VI) in Wastewater and Living Cells. J Fluoresc 32, 1489–1500 (2022). https://doi.org/10.1007/s10895-022-02962-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10895-022-02962-x