NiO@Ni-MOF nanoarrays modified Ti mesh as ultrasensitive electrochemical sensing platform for luteolin detection
Graphical abstract
An ultrasensitive electrochemical sensor based on NiO@Ni-MOF nanoarrays modified Ti mesh was fabricated for luteolin detection.
Introduction
Luteolin is a representative natural flavonoid [1]. With the deepening of the research, luteolin is found to inhibit the proliferation of cancer cells, induce apoptosis of cancer cells, and enhance the activity of anticancer drugs [2,3]. In addition, luteolin has been used to treat some serious diseases, such as cough, expectoration, inflammation, cardiovascular disease and amyotrophic lateral sclerosis [4,5]. Therefore, the development of a facile and sensitive strategy to detect luteolin has gained growing research attention. At present, various analytical strategies have been established for the quantitative and qualitative detection of luteolin, including spectrophotometry [6], capillary electrophoresis [7], high-performance liquid chromatography [8,9], and electrochemical sensor [10]. Among them, electrochemical sensing technology stands out owing to its fast response, portable feasibility, convenient operation and low cost. Over the past years, some nanomaterials such as Ni/graphene oxide-MWCNTs [11], Au/Pd/reduced graphene oxide [12] modified electrodes have been used for luteolin determination. However, some major problem such as narrow linear range and low sensitivity still remains. Thence, it is necessary to prepare novel electrocatalysts with high catalytic activity.
Metal-organic frameworks (MOFs) are ascendant crystalline porous structural materials with unique features of huge surface area, enormous pore volume as well as easy functionalization [[13], [14], [15]]. Accordingly, MOFs have received great attention as potential electrochemical sensing materials. The high specific surface area and porosity of MOFs increase the concentration and capture of analytes with suitable configuration and size, thus detection signal is amplified [16,17]. In fact, the direct utilization of MOFs in electrochemical sensors is limited for their poor conductivity. Thus, combining MOFs with highly conductive nano-carbon materials including graphene, carbon nanotubes and activated carbon [[18], [19], [20]], is expected to further achieve improved electrochemical performance. However, owing to the weak force between MOFs and these carriers, the obtained MOFs composites usually manifest agglomerated and disordered structure, leading to inferior catalytic ability and poor stability. Therefore, the design of uniform and orderly MOF composites for fabricating high-performance electrochemical biosensors is still urgent.
Self-template strategy based on metal oxide nanostructure is one of the most effective methods for ordered MOFs synthesis [21]. Metal oxide templates offer metal ions at the expense of themselves, and then MOF are directly grown on the surface of metal oxides, forming heterogeneous metal oxides@MOFs. In comparison to pure MOFs, the core-shell MOF heterostructures display great advantages by virtue of their synergism effect. For example, Chen et al. synthesized Fe3O4@MIL-100 (Fe) core-shell composite using Fe3O4 nanosphere as the core [22]. The Fe3O4@MIL-100 modified electrode as electrochemical sensor showed high sensitivity for chlorogenic acid detection with low LOD of 0.05 μM. Zhang et al. reported the utilization of MoO3 nanorods as core for the fabrication of MoO3@ZIF-8 core-shell nanorods [23]. The MoO3@ZIF-8 composite was applied to photocatalytic detection of hexavalent chromium (Cr(VI)) in wastewater. In addition, directly growing electroactive materials on conductive substrates can effectively improve the electron transfer by reducing the contact resistance relative to powder samples assistance with binders [24,25], resulting in significantly improved electrochemical performance. Additionally, different from traditional 2D planar architecture, electrodes with 3D nanoarrays exhibit many inherent advantages in terms of high specific surface area, fast electron transport, and enhanced electrolyte penetration [[26], [27], [28]]. However, the fabrication of NiO@MOF nanoarrays electrode for electrochemical sensing applications has not yet been reported.
Considering the good redox properties of Ni based compounds, in this work, we developed a NiO nanosheet arrays on TM by a facile hydrothermal method, followed by in-situ growth of Ni-MOF on NiO arrays surface (NiO@Ni-MOF/TM). The NiO@Ni-MOF/TM was directly used as free-standing electrode for electrochemical sensing of luteolin. The NiO@Ni-MOF/TM integrates the remarkable electrical and catalytic properties of NiO/TM and high enrichment ability of Ni-MOF, which effectively improved the electron-transfer kinetics and accumulated more luteolin on the electrode. Under the optimum conditions, the luteolin sensor showed a low LOD of 3 pM, and wide linear ranges of 0.01 nM–1 nM and 1 nM −50 μM. The method was successfully applied to the detection of luteolin contents in Duyiwei capsule sample.
Section snippets
Materials and apparatuses
Luteolin was acquired from XF Nano Co. Ltd. (Nanjing, China). Duyiwei capsules were purchased from Gansu Duyiwei biopharmaceutical Co. Ltd. (China). Ti mesh was provided by Kangwei wire mesh (Hengshui, China). Alcohol (95%), Nickel nitrate hexahydrate (Ni(NO3)2·6H2O), NH4F, urea, 2-methylimidazole (2-MeIM), Na2HPO4 and NaH2PO4 were gotten from Ganyi Technology Co. Ltd. (Jiangxi, China). Luteolin solution was dispersed with alcohol. Phosphate buffer solution (PBS) with pH from 3.0 to 7.0 was
Characterization of structure and morphology
The morphologies of NiO/TM nanosheet arrays and NiO@Ni-MOF/TM nanosheet arrays were observed by scanning electron microscope (SEM). As shown in Fig. 1A, it was found that the surface of TM was uniformly covered by NiO nanosheet arrays. After chemical bath treatment in MIM solution, the granular Ni-MOF was grown on the surface of the NiO nanosheet arrays (Fig. 1B). Meanwhile, we can see that the morphology and structure of the nanosheet arrays were maintained, endowing it with enormous
Conclusion
In this work, 3D hierarchical NiO@MOF nanoarrays were successfully synthesized on TM and developed as a novel electrochemical sensing platform for luteolin determination. The obtained NiO@Ni-MOF/TM possessed large surface area, more active sites, fast electron transport, and good electrolyte penetration, leading to excellent electrocatalytic activity toward the oxidation-reduction of luteolin. As electrochemical sensor, the resulting electrode showed superior sensing performances with linear
CRediT authorship contribution statement
Feng Gao: Conceptualization, Methodology, Writing - original draft, Funding acquisition. Xiaolong Tu: Methodology, Investigation, Validation. Xue Ma: Methodology, Formal analysis, Writing - review & editing. Yu Xie: Methodology, Writing - review & editing. Jin Zou: Writing - review & editing, Investigation, Visualization. Xigen Huang: Investigation, Visualization. Fengli Qu: Supervision, Project administration, Funding acquisition, Writing - review & editing. Yongfang Yu: Investigation,
Declaration of competing interest
The authors declare that there are no conflicts of interest.
Acknowledgements
We are grateful to the National Natural Science Foundation of China (51862014, 31741103, 21665010, 21563014 and 51302117), the outstanding youth fund of Jiangxi Province (20162BCB23027), the Natural Science Foundation of Jiangxi Province (20171BAB203015), Provincial Projects for Postgraduate Innovation in Jiangxi (YC2019–S182) and National College Students' innovation and entrepreneurship training program (201810410013) for their financial support of this work.
References (34)
- et al.
Gas chromatographic/mass spectrometric profiling of luteolin and its metabolites in rat urine and bile
J. Pharmaceut. Biomed. Anal.
(1995) - et al.
Luteolin suppresses inflammation-associated gene expression by blocking NF-κB and AP-1 activation pathway in mouse alveolar macrophages
Life Sci.
(2007) - et al.
Application of derivative spectrophotometry to determination of flavonoid mixtures
Talanta
(2001) - et al.
Simultaneous determination of flavonoid analogs in Scutellariae Barbatae Herba by β-cyclodextrin and acetonitrile modified capillary zone electrophoresis
Talanta
(2013) - et al.
Metabolic profiling of four South African herbal teas using high resolution liquid chromatography-mass spectrometry and nuclear magnetic resonance
Food Chem.
(2018) - et al.
Extraction efficiency and validation of an HPLC method for flavonoid analysis in peppers
Food Chem.
(2012) - et al.
An ultrasensitive luteolin sensor based on MOFs derived CuCo coated nitrogen-doped porous carbon polyhedron
Sensor. Actuator. B Chem.
(2019) - et al.
Synthesis, structure and photocatalysis properties of two 3D Isostructural Ln (III)-MOFs based 2, 6-Pyridinedicarboxylic acid
J. Mater. Sci. Technol.
(2018) - et al.
Metal-organic frameworks for direct electrochemical applications
Coord. Chem. Rev.
(2018) - et al.
Synthesis and electrochemical characterization of nanostructured Ni-Co-MOF/graphene oxide composites as capacitor electrodes
Electrochim. Acta
(2019)
Enzyme immobilization on ZIF-67/MWCNT composite engenders high sensitivity electrochemical sensing
J. Electroanal. Chem.
Synthesis and hydrogen-storage performance of interpenetrated MOF-5/MWCNTs hybrid composite with high mesoporosity
Int. J. Hydrogen Energy
Template strategies with MOFs
Coord. Chem. Rev.
Facile construction of MoO3@ ZIF-8 core-shell nanorods for efficient photoreduction of aqueous Cr(VI)
Appl. Catal. B Environ.
Core-shell copper oxide@ nickel/nickel–iron hydroxides nanoarrays enabled efficient bifunctional electrode for overall water splitting
Electrochim. Acta
CoP/WS2 nanoflake heterostructures as efficient electrocatalysts for significant improvement in hydrogen evolution activity
Appl. Surf. Sci.
One-pot synthesis of heterogeneous Co3O4-nanocube/Co(OH)2-nanosheet hybrids for high-performance flexible asymmetric all-solid-state supercapacitors
Nanomater. Energy
Cited by (67)
A donor-acceptor-type photoactive material based cathode molecularly imprinted photoelectrochemical sensor for luteolin
2024, Sensors and Actuators B: ChemicalExpanded interlayer spacing of SnO<inf>2</inf> QDs-Decorated MXene for highly selective luteolin detection with Ultra-Low limit of detection
2024, Journal of Colloid and Interface ScienceA novel dopamine electrochemical sensor based on a β-cyclodextrin/Ni-MOF/glassy carbon electrode
2023, Microchemical JournalTin dioxide quantum Dots-Modified sensing electrode for selective detection of luteolin
2023, Microchemical JournalEnhanced colorimetric strategy: Aptamer-triggered assembly of Ni-Fe layered double oxide/DNA networks for ultrasensitive detection of chloramphenicol
2023, Journal of Food Composition and Analysis