Elsevier

Analytica Chimica Acta

Volume 1126, 22 August 2020, Pages 7-15
Analytica Chimica Acta

Masking quercetin: A simple strategy for selective detection of rutin by combination of bovine serum albumin and fluorescent silicon nanoparticles

https://doi.org/10.1016/j.aca.2020.06.002Get rights and content

Highlights

  • Water-dispersible fluorescent SiNPs was hydrothermally synthesized using ferulic acid as the reduction reagent.

  • Rutin but not its analogue quercetin can quench the fluorescence of SiNPs in the presence of BSA.

  • A new fluorescent method was established for recognition of rutin combining SiNPs with BSA.

  • This method can be used to assay rutin with high sensitivity and good selectivity.

Abstract

As a typical kind of bioactive flavonoid glycoside, rutin and its aglycone quercetin possess similar chemical structures and properties. It still remains a challenge to achieve reliably and accurately detection of rutin in the presence of quercetin. In this work, a simple fluorescent method combining water-dispersed silicon nanoparticles (SiNPs) with bovine serum albumin (BSA) were constructed for the selective detection of rutin in the presence of quercetin and other common compounds in traditional Chinese herbs. SiNPs with high fluorescent quantum yield and good thermostability were prepared by one-pot hydrothermal method using ferulic acid as the reduction reagent for the first time. The fluorescence of SiNPs could be obviously quenched both by rutin and quercetin in phosphate buffer solution. Interestingly, when the solution contained certain concentration of BSA, the fluorescence of the SiNPs can only be remarkably quenched by rutin. The innovative use of BSA to block the interference of quercetin make it possible to selectively detect of rutin by fluorescence spectrometry under the coexistence of quercetin. Under the optimum conditions, the fluorescence displayed a linear decrease response as the rutin concentration increased in the range of 0.33–33.30 μM with a detection limit of 0.04 μM (S/N = 3). The possible quenching mechanism of rutin to SiNPs has also explored and concluded to be mainly caused by inner filter effect. This work provides a novel methodology for the simple, low-cost and selective determination method for rutin.

Graphical abstract

(A) The preparation of SiNPs. (B) The sensing principle of rutin.A simple fluorescent method combining water-dispersed silicon nanoparticles (SiNPs) with bovine serum albumin (BSA) were constructed for the selective detection of rutin with low detection (4.2 × 10−8 mol/L). More importantly, its analogue quercetin could not bring obvious interference during the detection process.

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Introduction

Over the past decade, flavonoids, as a large family of polyphenolic compounds widely present in Chinese herbs, are verified to be an important class of antioxidants due to their radical-scavenging abilities. Rutin (3′, 4′, 5, 7-tetrahydroxy-flavone-3-rutinoside) is one of the most bioactive flavonoids. It has been investigated to have wide physiological functions including anti-tumor activity, anti-inflammatory, antibacterial and capability of reduce capillary impairment [1,2]. Rutin has been used clinically as a therapeutic drug to help patients to dilute blood, reduce capillary permeability, and stabilize platelets [3,4]. Hence, it is of great importance and considerable interest for the determination of rutin. Since now, numerous analytical techniques have been developed to quantify rutin, including high performance liquid chromatography (HPLC) [5], liquid chromatography-mass spectrometry (LC-MS) [6], chemiluminescence (CL), electrogenerated chemiluminescence (ECL) [7,8], electrochemistry [[9], [10], [11]], UV–vis spectrometry [12] and fluorescent methods [[13], [14], [15]]. Owing to their high sensitivity, good selectivity and operational simplicity, fluorescent methods have attracted intensive attention. However, it still remains a major challenge for selective fluorescent detection of rutin in the presence of other analogues, especially its aglycone quercetin. There have been few fluorescence based methods that can distinctive detection of rutin and quercetin until now.

As one of the most abundant carrier proteins, serum albumins (bovine serum albumin and human serum albumin) have been extensively studied in the drug-protein interaction. Since now, some researches have explored the interaction of rutin and quercetin with bovine serum albumin (BSA) [[16], [17], [18]]. It has been reported that BSA had obviously different binding ability toward rutin and quercetin [16]. However, till now rare reports use this protein to a detection system to distinguish these two compounds. In this work, we creatively introduce BSA to a fluorescent sensing system for rutin to block the signal interference of quercetin.

In recent years, fluorescent silicon nanomaterials (SiNPs) have been developed to meet the increasing demand of silicon materials and by taking advantages of their low cost, good biocompatibility and excellent optoelectronic properties [[19], [20], [21], [22], [23]]. The successful synthesis of excellent water-dispersed SiNPs by a rapid “bottom-up” microwave reaction by He’s group [23] greatly expands its wide-ranging optical applications [24,25]. It is worth noting that, most of the biomedical and bioanalytical applications of SiNPs were mainly about its synthesis and simple cell imaging [[26], [27], [28], [29], [30]], while lack of investigation on its interaction with intracellular matrix or drug molecules. Since the real-time monitoring of intracellular drug metabolism is also critical and the application of SiNPs are of great potential at this point, it is necessary to investigate the interaction between florescent SiNPs and small drug molecules.

Herein, a water-dispersible SiNPs was synthesized using APTMS as the Si source and FA (a hydroxycinnamic acid widely found in many plants and reported to be a powerful, plant-based antioxidant.) as the reduction reagent. Then the obtained SiNPs was used as the fluorescent probe to establish a fluorescent method for selective recognition of rutin with the assistant of BSA to mask the interference of quercetin. This method not only successfully detects rutin in samples with satisfactory results, but also provides a valuable platform for further fluorescent nanomaterials based intracellular drug metabolism.

Section snippets

Reagents

(3-Aminopropyl) trimethoxysilane (APTMS, 97%) was obtained from Sigma-Aldrich. Ferulic acid (99%), Na2HPO4·12H2O (≥98.0%) and NaH2PO4·2H2O (98–100.5%) were obtained from Shanghai Sinopharm (Shanghai, China). Rutin and other standard products were obtained from Shanghai Sinopharm (Shanghai, China). Bovine serum albumin (BSA, ≥98%) was obtained from Shanghai Sangon Biotechnology Co. (Shanghai, China). All chemicals were analytical grade and used without additional purification. All solutions were

Characterization of SiNPs

Firstly, the morphology of the synthesized SiNPs was studied by TEM. It is obviously observed that the prepared SiNPs are uniformly distributed with the average diameter of 10 nm (Fig. 1A and B). The SiNPs aqueous solution is colorless under sunlight (inset a in Fig. 1A), while shows bright blue fluorescence under UV light of 365 nm (inset b in Fig. 1A). The Fourier transform infrared (FT-IR) spectrum (Fig. 1C) was used to investigate the surface functional groups of the synthesized SiNPs. The

Conclusion

Water-dispersal SiNPs with high fluorescent quantum yield and good thermostability was synthesized by a facile one-pot method using ferulic acid as reducing agent and ATPMS as the silicon source. Then a new SiNPs-based fluorescent method was proposed for rapidly, selective and high sensitive determination of rutin using BSA to shield the interferences of its aglycone quercetin. The high bounding ability of BSA with quercetin make it suitable as a shielding agent to mask the interference of

CRediT authorship contribution statement

Lishuang Yu: Conceptualization, Methodology. Shiqi Zhang: Investigation, Data curation, Writing - original draft. Huifeng Xu: Investigation, Project administration. Lili Wang: Validation. Xi Zhu: Visualization, Writing - review & editing, Project administration. Xuzheng Chen: Formal analysis. Wen Xu: Resources. Wei Xu: Project administration. Hua Zhang: Validation. Yu Lin: Supervision, Funding acquisition.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgement

This project was financially supported by NSFC (81773894), the Natural Science Foundation of Fujian Province, China (2018J01871, 2019Y4009, 2017Y0047), and Key Subject of Ecology of Fujian Province (6112C0600). X. Zhu thanks the University Distinguished Young Research Talent Training Program of Fujian Province, and H. Xu also thanks the Natural Science Funds of Fujian Province for Distinguished Young Scholar (2019J06021).

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