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Para-aminohippuric acid (PAH) serves as a pivotal marker widely employed for accurately estimating effective renal plasma flow, playing a crucial role in the diagnosis and determination of various PAH-related diseases. Consequently, it arises a necessity to devise an advanced quantitative spectrofluorometric technique utilizing fluorescence detection methods for the precise detection of PAH. Therefore, the present work achieved the detection of PAH through a meticulously designed On-Off-On fluorescent nano-system, incorporating graphene quantum dots (CE-GQDs) into cobalt–hemin metal–organic frameworks (Co–hemin MOF). Briefly, the one-pot green synthesis of CE-GQDs was accomplished using the natural precursor derived from the Colocasia Esculenta stem through the hydrothermal method. Subsequently, the synthesized CE-GQD was encapsulated within the Co–hemin MOF, composed of cobalt nitrate hexahydrate as the metal and hemin as a linker. The outcome revealed a wide linear range (20–400 ng/mL) and the lowest detection limit (2.75 ng/mL). CE-GQD exhibited remarkable photoluminescence quenching kinetics towards the metal–organic framework and demonstrated recovery post-sensing. The amino group of PAH readily donates an electron pair to metal ions, facilitating the formation of a coordination bond between PAH and cobalt ions. Consequently, the interaction between carboxyl-enriched CE-GQDs within the designed Co–hemin MOF weakens upon the introduction of PAH. This weakening effect results in the recovery of the quenched fluorescence of CE-GQDs, termed fluorescence “Turn-On”. In conclusion, the preference for CE-GQDs@Co–hemin MOF underscores its high sensitivity and stability for the detection of PAH. Looking ahead, the utilization of CE-GQDs@Co–hemin MOF holds promise for ushering in a new era in PAH sensing.


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Graphene Quantum Dots Decorated Cobalt–Hemin Metal–Organic Frameworks Mediated Fluorescent Sensor for Para-aminohippuric Acid Sensing

Show Author's information Sopan NangareMinal PatilPravin Patil( )
Department of Pharmaceutical Chemistry, H. R. Patel Institute of Pharmaceutical Education and Research, Shirpur 425405, Dhule, Maharashtra, India

Abstract

Para-aminohippuric acid (PAH) serves as a pivotal marker widely employed for accurately estimating effective renal plasma flow, playing a crucial role in the diagnosis and determination of various PAH-related diseases. Consequently, it arises a necessity to devise an advanced quantitative spectrofluorometric technique utilizing fluorescence detection methods for the precise detection of PAH. Therefore, the present work achieved the detection of PAH through a meticulously designed On-Off-On fluorescent nano-system, incorporating graphene quantum dots (CE-GQDs) into cobalt–hemin metal–organic frameworks (Co–hemin MOF). Briefly, the one-pot green synthesis of CE-GQDs was accomplished using the natural precursor derived from the Colocasia Esculenta stem through the hydrothermal method. Subsequently, the synthesized CE-GQD was encapsulated within the Co–hemin MOF, composed of cobalt nitrate hexahydrate as the metal and hemin as a linker. The outcome revealed a wide linear range (20–400 ng/mL) and the lowest detection limit (2.75 ng/mL). CE-GQD exhibited remarkable photoluminescence quenching kinetics towards the metal–organic framework and demonstrated recovery post-sensing. The amino group of PAH readily donates an electron pair to metal ions, facilitating the formation of a coordination bond between PAH and cobalt ions. Consequently, the interaction between carboxyl-enriched CE-GQDs within the designed Co–hemin MOF weakens upon the introduction of PAH. This weakening effect results in the recovery of the quenched fluorescence of CE-GQDs, termed fluorescence “Turn-On”. In conclusion, the preference for CE-GQDs@Co–hemin MOF underscores its high sensitivity and stability for the detection of PAH. Looking ahead, the utilization of CE-GQDs@Co–hemin MOF holds promise for ushering in a new era in PAH sensing.

Keywords: fluorescence, sensitivity, graphene quantum dots (GQDs), para-aminohippuric acid, cobalt–hemin metal–organic framework (MOF)

References(25)

[1]

A. Pandey, N. Dhas, P. Deshmukh, et al. Heterogeneous surface architectured metal-organic frameworks for cancer therapy, imaging, and biosensing: A state-of-the-art review. Coordination Chemistry Reviews, 2020, 409: 213212. https://doi.org/10.1016/j.ccr.2020.213212

[2]

T. Anusha, K.S. Bhavani, J.V. Shanmukha Kumar, et al. Synthesis and characterization of novel lanthanum nanoparticles-graphene quantum dots coupled with zeolitic imidazolate framework and its electrochemical sensing application towards vitamin D3 deficiency. Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2021, 611: 125854. https://doi.org/10.1016/j.colsurfa.2020.125854

[3]

S.N. Nangare, S.R. Patil, A.G. Patil, et al. Structural design of nanosize-metal–organic framework-based sensors for detection of organophosphorus pesticides in food and water samples: Current challenges and future prospects. Journal of Nanostructure in Chemistry, 2022, 12(5): 729−764. https://doi.org/10.1007/s40097-021-00449-y

[4]

C.L. Dai, Y.J. Gan, J.C. Qin, et al. An ultrasensitive solid-state ECL biosensor based on synergistic effect between Zn-NGQDs and porphyrin-based MOF as “on-off-on” platform. Colloids and Surfaces B:Biointerfaces, 2023, 226: 113322. https://doi.org/10.1016/j.colsurfb.2023.113322

[5]

S.N. Nangare, P.M. Sangale, A.G. Patil, et al. Surface architectured metal organic frameworks-based biosensor for ultrasensitive detection of uric acid: Recent advancement and future perspectives. Microchemical Journal, 2021, 169: 106567. https://doi.org/10.1016/j.microc.2021.106567

[6]

S.N. Nangare, A.G. Patil, S.M. Chandankar, et al. Nanostructured metal–organic framework-based luminescent sensor for chemical sensing: current challenges and future prospects. Journal of Nanostructure in Chemistry, 2023, 13(2): 197−242. https://doi.org/10.1007/s40097-022-00479-0

[7]

Y.-C. Chen, W.-H. Chiang, D. Kurniawan, et al. Impregnation of graphene quantum dots into a metal–organic framework to render increased electrical conductivity and activity for electrochemical sensing. ACS Applied Materials &Interfaces, 2019, 11(38): 35319−35326. https://doi.org/10.1021/acsami.9b11447

[8]
S. Nangare, S. Chandankar, P. Patil, Design of carbon and graphene quantum dots based nanotheranostics applications for glioblastoma management: Recent advanced and future prospects. Journal of Drug Delivery Science and Technology,2023, 89: 105060.
DOI
[9]
S. Nangare, S. Patil, K. Chaudhari, et al. Graphene quantum dots incorporated UiO-66-NH2 based fluorescent nanocomposite for highly sensitive detection of quercetin. Nano Biomedicine and Engineering, 2023, 15(1): 1–13.
DOI
[10]

M. Li, T. Chen, J.J. Gooding, et al. Review of carbon and graphene quantum dots for sensing. ACS sensors, 2019, 4(7): 1732−1748. https://doi.org/10.1021/acssensors.9b00514

[11]
J. Pantwalawalkar, S. Chandankar, R. Tade, et al. Graphene quantum dot based ultrasensitive probe for biosensing of prostate cancer biomarkers: Current updates and future challenges. Advances in Natural Sciences: Nanoscience and Nanotechnology, 2022, 13(1): 013001.
DOI
[12]

S. Nangare, S. Patil, S. Patil, Z. Khan, et al. Design of graphene quantum dots decorated MnO2 nanosheet based fluorescence turn “On-Off-On” nanoprobe for highly sensitive detection of lactoferrin. Inorganic Chemistry Communications, 2022, 143: 109751. https://doi.org/10.1016/j.inoche.2022.109751

[13]
S. Nangare, K. Chaudhari, P. Patil, Poly-L-lysine functionalized graphene quantum dots embedded zirconium metal–organic framework-based fluorescence switch on-off-on nanoprobe for highly sensitive and selective detection of taurine. Journal of Photochemistry and Photobiology A: Chemistry, 2024, 446: 115158.
DOI
[14]

Y. Guo, G. Yuan, X. Hu, et al. A high-luminescence biomimetic nanosensor based on N, S-GQDs-embedded zinc-based metal–organic framework@molecularly imprinted polymer for sensitive detection of octopamine in fermented foods. Foods, 2022, 11(9): 1348. https://doi.org/10.3390/foods11091348

[15]
Y. Guan, T. Wu, J. Ye, Determination of uric acid and p-aminohippuric acid in human saliva and urine using capillary electrophoresis with electrochemical detection: Potential application in fast diagnosis of renal disease. Journal of Chromatography B, 2005, 821(2): 229–234.
DOI
[16]
S. Anitta, C. Sekar, HAP-TiO2 nanocomposites based electrochemical sensor for selective and simultaneous detection of para-aminohippuric acid and uric acid. Microchemical Journal, 2022, 181: 107704.
DOI
[17]

S. Nangare, S. Patil, A. Patil, et al. Bovine serum albumin-derived poly-l-glutamic acid-functionalized graphene quantum dots embedded UiO-66-NH2 MOFs as a fluorescence ‘On-Off-On’ magic gate for para-aminohippuric acid sensing. Journal of Photochemistry and Photobiology A:Chemistry, 2023, 438: 114532. https://doi.org/10.1016/j.jphotochem.2022.114532

[18]

R. Marsilio, R. Dall'Amico, G. Montini, et al. Rapid determination of p-aminohippuric acid in serum and urine by high-performance liquid chromatography. Journal of Chromatography B:Biomedical Sciences and Applications, 1997, 704(1-2): 359−364. https://doi.org/10.1016/s0378-4347(97)00467-2

[19]
G. Dryhurst. Electrochemistry of Biological Molecules. New York: Elsevier, 1977.
DOI
[20]

P.Y. Han, P.N. Shaw, C.M. Kirkpatrick. Determination of para-aminohippuric acid (PAH) in human plasma and urine by liquid chromatography–tandem mass spectrometry. Journal of Chromatography B, 2009, 877(27): 3215−3220. https://doi.org/10.1016/j.jchromb.2009.08.037

[21]

R.H. Alremeithi, M.A. Meetani, K.M. Mu'ath, et al. Determination of p-aminohippuric acid with β-cyclodextrin sensitized fluorescence spectrometry. RSC Advances, 2016, 6(115): 114296−114303. https://doi.org/10.1039/C6RA11742B

[22]

S. Nangare, S. Baviskar, A. Patil, et al. Design of" turn-off" fluorescent nanoprobe for highly sensitive detection of uric acid using green synthesized nitrogen-doped graphene quantum dots. Acta Chimica Slovenica, 2022, 69(2): 437−447. https://doi.org/10.17344/acsi.2022.7333

[23]

H.S. Choi, X. Yang, G. Liu, et al. Development of Co–hemin MOF/chitosan composite based biosensor for rapid detection of lactose. Journal of the Taiwan Institute of Chemical Engineers, 2020, 113: 1−7. https://doi.org/10.1016/j.jtice.2020.07.021

[24]

M.P. More, P.H. Lohar, A.G. Patil, et al. Controlled synthesis of blue luminescent graphene quantum dots from carbonized citric acid: Assessment of methodology, stability, and fluorescence in an aqueous environment. Materials Chemistry and Physics, 2018, 220: 11−22. https://doi.org/10.1016/j.matchemphys.2018.08.046

[25]

J.B. Raoof, R. Ojani, M. Baghayeri, et al. Fabrication of a fast, simple and sensitive voltammetric sensor for the simultaneous determination of 4-aminohippuric acid and uric acid using a functionalized multi-walled carbon nanotube modified glassy carbon electrode. Analytical Methods, 2012, 4(6): 1825−1832. https://doi.org/10.1039/C2AY05900B

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Publication history

Received: 30 November 2023
Revised: 24 December 2023
Accepted: 10 January 2024
Published: 28 February 2024

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© The Author(s) 2024.

Acknowledgements

Acknowledgements

The authors would like to acknowledge the Sophisticated Test and Instrumentation Centre (STIC) in Cochin, India, for providing access to an HRTEM analytical facility.

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