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Frontiers of Environmental Science & Engineering

ISSN 2095-2201

ISSN 2095-221X(Online)

CN 10-1013/X

Postal Subscription Code 80-973

2018 Impact Factor: 3.883

Front. Environ. Sci. Eng.    2022, Vol. 16 Issue (3) : 27    https://doi.org/10.1007/s11783-021-1461-z
RESEARCH ARTICLE
Valorization of agro-industrial fruit peel waste to fluorescent nanocarbon sensor: Ultrasensitive detection of potentially hazardous tropane alkaloid
Athiyanam Venkatesan Ramya(), Manoj Balachandran
Nanocarbon Research Group, Materials Science Research Laboratory, Department of Physics and Electronics, CHRIST (Deemed to be University), Bengaluru- 560029, Karnataka, India
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Abstract

• Transformation of agro-industrial waste to value-added material via green chemistry.

• Orange peel is valorized into fluorescent nanodiamond-like carbon (fNDC) sensor.

• fNDC detects potentially hazardous drug atropine sulfate (AS).

• fNDC recognizes AS in biological fluids and pharmaceuticals.

• fNDC assures applications in clinical and forensic toxicology.

Millions of tonnes of agro-industrial waste are generated each year globally, with the vast majority of it going untreated, underutilized, and disposed of by burning or landfilling, causing severe environmental distress and economic downturn. A practical solution to this global issue is to use green chemistry to convert this waste into value-added products. Accordingly, in the present study, agro-industrial orange peel waste was valorized into fluorescent nanodiamond-like carbon sensor via a green route involving hydrothermal treatment of microwave carbonized orange peel waste. The developed sensor, used for the fluorescence detection of potentially hazardous drug atropine sulfate, exhibits unique dual linearity over concentration ranges of 300 nM to 1 M and from 1 M to 10 M, as well as ultra-low sensitivity of 34.42 nM and 356.46 nM, respectively. Additionally, the sensor demonstrates excellent reproducibility, high stability, and satisfactory recovery when used to identify and quantify atropine sulfate in biological samples and commercially available pharmaceuticals, indicating promising multidisciplinary applications.

Keywords Agro-industrial waste      Orange peel      Valorization      Nanodiamond-like carbon      Atropine sulphate      Fluorescence sensing     
Corresponding Author(s): Athiyanam Venkatesan Ramya   
Issue Date: 08 June 2021
 Cite this article:   
Athiyanam Venkatesan Ramya,Manoj Balachandran. Valorization of agro-industrial fruit peel waste to fluorescent nanocarbon sensor: Ultrasensitive detection of potentially hazardous tropane alkaloid[J]. Front. Environ. Sci. Eng., 2022, 16(3): 27.
 URL:  
https://academic.hep.com.cn/fese/EN/10.1007/s11783-021-1461-z
https://academic.hep.com.cn/fese/EN/Y2022/V16/I3/27
Fig.1  HRTEM images of carbon nanostructures derived from agro-industrial orange peel waste. (a) HRTEM image exhibiting agglomerated polyhedral nanostructures, (b) Polyhedral structures similar to diamond-like carbon is observed in the encircled portion of the image, (c) An enhanced image of (b) depicting the formation of diamond-like carbon nanostructures, and (d) The selected area diffraction pattern of (b) showing reflections corresponding to nanodiamond phase.
Fig.2  (a) UV-Visible absorption spectrum of the synthesized nanodiamond-like carbon material, displaying bands corresponding to σ-σ* transition of nanodiamonds and n-Π* transition of C= O functionalities, (b) Steady-state excitation wavelength dependant fluorescence emission spectra of the synthesized fNDC material excited at wavelengths ranging between 300 nm and 500 nm, exhibiting a characteristic red shift.
Fig.3  First-Order Raman spectrum of the synthesized fNDC deconvoluted with peaks corresponding to different moieties. The line interconnected by tiny circles represents the original experimental spectrum, and the colored solid lines represent the deconvoluted peaks. The dotted line represents the sum of the deconvoluted peaks.
Fig.4  FTIR transmission spectrum of the synthesized fNDC material displaying the presence of different surface functional groups.
Fig.5  High-Resolution (a) C 1s and (b) O 1s XPS spectra of fNDC fitted by Voigt line shapes after applying Shirley background. The line interconnected by circular symbols indicates the original experimental spectra, and the colored solid lines represent the deconvoluted peaks. The red dotted line represents the sum of the deconvoluted peaks.
Chemical group Chemical group content (in at %)
C 1s C sp3 C sp2 C-OH C-O-C C= O COOH
41.01 6.71 13.04 8.22 5.23 3.84
O 1s Carboxyl C= O and C-O C= O C-O-C C-OH H2O
2.75 3.05 4.14 10.61 1.40
Tab.1  Atomic content of C and O chemical groups in fNDC determined from C 1s and O 1s XPS spectra of fNDC
Fig.6  (a) Fluorescence emission spectra of 25 µg/mL fNDC (λexc = 440 nm and λem = 520 nm) for increasing concentrations of AS in PBS (pH= 7). (b) The relative intensity (F0/F) plot of fluorescence quenching of fNDC for varying concentrations of AS, exhibiting dynamic linear range (F0 and F, represent the fluorescence intensity of fNDC in the absence and presence of AS).
Fig.7  Fluorescence intensity ratio response of fNDC to AS and other potential interferents in PBS (λexc = 440 nm and λem = 525 nm; interferents= 10 μM; fNDC= 25 µg/mL; pH= 7).
Sample Atropine sulfate (μM) Recovery (%) *RSD (%) (n = 3)
Spiked Found
Human Blood Serum 0.30 0.28 96.06 0.39
0.60 0.62 103.01 0.36
0.90 0.88 97.78 0.29
Human Urine 0.30 0.32 103.68 0.39
0.60 0.59 97.33 0.30
0.90 0.89 98.49 0.25
Atropine sulfate
1 mL ampoules
(0.6 mg/mL)
0.30 0.29 97.83 0.33
0.60 0.62 102.18 0.39
0.90 0.88 97.33 0.28
Atropine 1% 5 mL eye drop
(10 mg/mL)
0.30 0.31 103.45 0.38
0.60 0.58 98.68 0.31
0.90 0.91 101.56 0.35
Tab.2  Analytical performance of fNDC sensor for various concentrations of AS in biological fluids and pharmaceutical formulations
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