An Electrochemical-Fluorescence Dual-Mode Chemosensor for Berberine Detection in Biological Samples

doi:10.19894/j.issn.1000-0518.240417

Chinese Journal of Applied Chemistry ›› 2025, Vol. 42 ›› Issue (4): 522-532.DOI: 10.19894/j.issn.1000-0518.240417

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An Electrochemical-Fluorescence Dual-Mode Chemosensor for Berberine Detection in Biological Samples

Wen-Qi PENG, Rui ZHOU, Wang-Xin CHENG, Zi-Pin ZHANG()

Department of Pharmacy，Anhui University of Chinese Medicine，Hefei 230012，China

Received:2024-12-17 Accepted:2025-03-17 Published:2025-04-01 Online:2025-05-14
Contact: Zi-Pin ZHANG
Supported by:
the Natural Science Foundation of Anhui Province of China(2008085MH293);the Key Projects of Natural Scientific Research Programs of Universities in Anhui Province(2022AH050459);Anhui Province 2020 Provincial-Level Quality Engineering Project-Analytical Chemistry Massive Open Online Caurse （MOOC） Demonstration Project(2020MOOC265)

Abstract

Abstract:

By taking advantage of the non-covalent interactions between 1，3，6-tri-sulfonate 8-aminonaphthalene （ANTS） and berberine， we have reported a novel electrochemical-fluorescent dual-mode chemosensor for berberine based on using ANTS as both the recognition element for berberine and a dual-mode probe for electrochemical and fluorescent responses. ANTS was immobilized onto the glass carbon （GC） electrode surface via single-walled carbon nanotubes （SWNTs） through π-π interactions to generate the ANTS/SWNTs/GC electrode. Upon being immersed in berberine solution， the ANTS/SWNTs-modified GC electrode shows current decreases in the oxidation peaks at both -0.003 V and +0.074 V（vs.Ag/AgCl） due to the interaction-driven adsorption of berberine on the electrode surface， which validates berberine detection using the sum of the ratios of current decreases in two oxidation peaks as the electrochemical signal readout. Upon addition of berberine into ANTS solution， ANTS emission shows a turn-off signal at 517 nm， which enables the berberine quantification using the decrease in ANTS emission at 517 nm as the fluorescent readout. Under the optimized conditions， the ANTS-based electrochemical sensor shows current decrease response to berberine in the dynamic range from 0.05 to 1000 μmol/L with a detection limit of 0.013 μmol/L， and the fluorescent sensor shows linear fluorescent response to berbeine within a concentration range of 1~100 μmol/L with a detection limit of 0.325 μmol/L. In the animal experiments， the dual-mode chemsensor has demonstrated a high selectivity against the endogenous species coexisting in rat plasma and liver homogenerates. Moreover， the electrochemical sensor is remarkably sensitive for berberine level quantification in rat plasma and liver homogenates， wherein the relative standard deviations （RSDs） for the plasma and liver homogenates measurements are 3.0% （n=3） and 4.0% （n=3）， respectively. The fluorescent sensor has achieved satisfactory spike-and-recoveries within 99.8%~100.2% （n=3） for plasma and 95.5%~99.9% （n=3） for liver homogenates. The dual-mode chemosensor reported here is readily accessible， simple， robust， and cost-effective and offers a promising tool for rapid detection of berberine in biological samples with less technically demanding and simple operating procedures.

Key words: 1, 3, 6-Tri-sulfonate 8-aminonaphthalene, Berberine, Dual-readout sensor, Fluorescence, Electrochemical sensor

CLC Number:

O657

Wen-Qi PENG, Rui ZHOU, Wang-Xin CHENG, Zi-Pin ZHANG. An Electrochemical-Fluorescence Dual-Mode Chemosensor for Berberine Detection in Biological Samples[J]. Chinese Journal of Applied Chemistry, 2025, 42(4): 522-532.

Figures/Tables 8

Fig.1 （A） Typical 8-cycle repetitive CV obtained at the ANTS/SWNTs/GC electrode in 0.1 mol/L Tris-HCL at pH=7.4. The dashed curve represent the first cycles of the CV. Inset， CVs obtained at the ANTS/SWNTs-modified GC electrode in 0.1 mol/L Tris-HCL of pH=7.4 for 50 cycles. Scan rate， 50 mV/s. （B） Typical CVs obtained at the ANTS/SWNTs/GC electrode in 0.1 mol/L Tris-HCL at pH=7.4 in the absence （a） and presence （b） of 500 μmol/L berberine after 10 min incubation， Scan rate， 50 mV/s. （C） Typical Nyquist plots obtained in 0.1 mol/L KCl containing an equimolar （5.0×10-3 mol/L） mixture of K3［Fe（CN）6］ and K4［Fe（CN）6］ for SWNTs/GC electrode （a）， ANTS/SWNT/GC electrode before （b）， and after 10-min of incubation with 500 μmol/L berberine （c）

Fig.2 Emission spectra of 1 μmol/L ANTS in 0.01 mol/L Tris-HCL （pH=7.4） after addition of berberine （10~200 μmol/L）

Fig.3 （A） Linear plots of the current decrease ratio for peak 1 （a） and peak 2 （b） of the ANTS/SWNTs/GC electrode in 0.1 mol/L Tris-HCL （pH=7.4） after immersing into 500 μmol/L berberine versus incubation time；（B） 50-Cycle repetitive CVs obtained at ANTS/SWNTs/GC electrode in 0.1 mol/L B-R solution at pH=6.0 （a）， pH=7.4 （b）， and pH=10.0 （c）；（C） The linear relationships between ΔI1/I10 （a），ΔI2/I20 （b） and ΔI1/I10+ΔI2/I20 （c） andberberine concentration；（D） The linear relationships between ΔI1/I10+ΔI2/I20 of ANTS/SWNTs/GC electrode in responses to berberine in 0.1 mol/L of Tris-HCL （a） and PBS （b） at pH=7.4

Fig.4 （A） Typical DPVs of the ANTS/SWNTs-modified GC electrode in 0.1 mol/L Tris-HCL （pH=7.4） after immersing with 0.05~1000 μmol/L berberine for 10 min. Inset： Linear plots of current response versus concentration of berberine from 0.05 to 2 μmol/L and 2 to 1000 μmol/L；（B） Emission spectra of 1 μmol/L ANTS in 0.01 mol/L Tris-HCL （pH=7.4） upon addition of 1~400 μmol/L berberine. Inset： Linear plot of the ratio of fluorescence intensity decrease versus concentration of berberine from 1 to 100 μmol/L. In Fig.4A and 4B， the arrows indicate the direction of increase in berberine concentration

Fig.5 Typical DPVs recorded at the ANTS/SWNTs/GC electrode （a） in 2 mL of 0.1 mol/L Tris-HCL （pH=7.4） upon the addition of 10 μL rat plasma （b）（A） and 10 μL liver homogenates （b）（B）； The Emission spectra of 2 mL of 0.01 mol/L Tris-HCL （pH=7.4） containing 1 μmol/L ANTS （a） upon addition of 2 μL rat plasma （b）（C） and 2 μL liver homogenates （b）（D）

Fig.6 （A） Typical DPVs recorded at the ANTS/SWNTs/GC electrode in 2 mL of 0.1 mol/L Tris-HCL （pH=7.4）（a） upon the addition of 10 μL model plasma of rats after dosing of berberine for 1 h （b） and 2 h （c）；（B） Typical DPVs recorded at the ANTS/SWNTs/GC electrode in 2 mL of 0.1 mol/L Tris-HCL （pH=7.4）（a） upon the addition of 10 μL model liver homogenate after dosing of berberine for 3 h （b）

Table 1 Spike-and-recovery in rat plasma and liver homogenate（n=3）

Sample	Spiked/（μmol·L^-1）	Found/（μmol·L^-1）	Recovery/%	RSD/%
Liver homogenate	2	1.997	99.8	0.54
	15	14.46	96.4	2.6
	80	76.40	95.5	3.2
Plasma	2	2.004	100.2	1.06
	15	14.54	96.9	2.11
	80	79.84	99.8	3.17

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An Electrochemical-Fluorescence Dual-Mode Chemosensor for Berberine Detection in Biological Samples

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