Fluorometric assay of iron(II) lactate hydrate and ammonium ferric citrate in food and medicine based on poly(sodium-p-styrenesulfonate)-enhanced Ag nanoclusters

doi:10.1016/j.saa.2019.117519

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Volume 225, 15 January 2020, 117519

https://doi.org/10.1016/j.saa.2019.117519 Get rights and content

Highlights

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A multifunctional probe (PSS-DPA-AgNCs) was developed.
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Effect of polymer and energy supplier on the synthesis of AgNCs was studied.
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The action mechanism of PSS-DPA-AgNCs-ILH/AFC system was discussed.
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The probe was utilized to indirectly test Fe²⁺/Fe³⁺ from ILH/AFC in real samples.
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The AgNCs could be used as a temperature sensor.

Abstract

Poly(sodium-p-styrenesulfonate)-enhanced and D-penicillamine stabilized Ag nanoclusters (PSS-DPA-AgNCs) were prepared using one-step ultraviolet irradiation combined with microwave heating method, and the effects of the AgNCs photo-luminescence performance based on different types of polyelectrolytes and energy suppliers were studied detailedly. The as-prepared AgNCs can be used as a viable fluorescent probe for monitoring indirectly iron(II) lactate hydrate (ILH) and ammonium ferric citrate (AFC), respectively. The fluorescence (FL) quenching of PSS-DPA-AgNCs by Fe³⁺ (it is obtained from oxidized ILH/ionized AFC) mainly derives from a dynamic quenching process. Excellent linear relationships exist between the FL quenching degree of the AgNCs and the concentrations of ILH/AFC in the range of 0.17–6.00/0.067–3.33 μmol·L⁻¹, and corresponding limit of detection (at 3σ/slope) is 12.4/6.04 nmol·L⁻¹. Moreover, the AgNCs probe was extended to the assays of ILH in tablets, solid beverage or ILH additive and AFC in two kinds of edible salts or syrup with satisfactory results compared with the standard 1, 10-phenanthroline method. In addition, the AgNCs probe reveals a good temperature sensing capability.

Graphical abstract

The introduction of PSS and UV irradiation could enhance remarkably the FL intensity and stability of PSS-DPA-AgNCs due to the electrostatic interaction of PSS with the DPA-AgNCs and the formation of smaller AgNCs in the presence of PSS. The as-prepared PSS-DPA-AgNCs could monitor indirectly iron(II) lactate hydrate (ILH) or ammonium ferric citrate (AFC) with a low limit of detection (12.4 or 6.04 nmol·L⁻¹). Besides, the probe was extended to the assay of ILH/AFC in real samples.

Introduction

Iron is particularly important for oxygen transport, DNA and neurotransmitter synthesis, electron transport in the respiratory chain and various enzymatic reactions, so it is absolutely required for mammals [1,2]. Nevertheless, many people in the world, especially for over 2 billion people including infants, young children and women of childbearing age, are suffering from serious iron deficiency problem due to poor utilization of iron from ingested food, and/or insufficient dietary intake of iron [3,4]. Fortunately, two strategies of increasing the iron intake, pharmacological supplementation and food fortification regularly consumed by the groups at risk, have greatly relieved pathema caused by iron deficiency [5]. Among of them, some food fortifications including iron(II) lactate hydrate (ILH), ammonium ferric citrate (AFC), ferrous sulphate (FS), sodium iron(III) ethylenediaminetetraacetate, ferrous ammonium phosphate, or ferric pyrophosphate are selected to add into foods [[6], [7], [8]], which have been widely admitted all over the world. What's more, excess intake of iron has been linked with severe problems like liver damage, kidney failure, Parkinson's and Alzheimer's diseases and other neurogenerative disease [9,10]. Except as an iron enhancer, AFC as an anticaking agent is often added into edible salt in china, and its maximum dosage is set at 0.025 g/kg [11]. Currently, a few common techniques such as colorimetric analysis, flow injection spectrophotometric analysis and atomic absorption spectroscopy (AAS) have been employed to monitor the concentration of Fe³⁺ [[12], [13], [14]]. While only the papain-AgNCs probe with a ratiometric fluorescent was used for monitoring ILH (Fe²⁺) in the ferrous lactate oral solution and a high limit of detection (LOD) (500 nmol/L) was obtained [15]. However, the methods require obsolete instrumentation, complex sample preparation, high LOD, or poor accuracy, which will limit the sensitivity and accuracy of the assays. Therefore, it is still of great challenge to develop a facile method for the assay of ILH/AFC in food and medicine.

In recent years, a new class of fluorescence materials metal nanoclusters (MNCs) should be acted as promising alternatives to organic dyes (relatively poor photo-stability) and semiconductor quantum dots (toxicity concerns) [[16], [17], [18]], because they are prepared with easily controlled size and excellent chemical properties (such as small size, low toxicity, good photo-stability and large stokes displacement) [[19], [20], [21]]. Among of the MNCs, Ag nanoclusters (AgNCs) have attracted attention owing to advantages in cost over gold or platinum and excellent sensitivity compared with copper nanoclusters. Thus, the AgNCs as a chemical sensor have been used for monitoring Hg²⁺ [22], DNaseIactivity and HIV (human immunodeficiency virus) [23], folic acid [24], cytochrome c [25], melamine [26] and multiple DNAs and MicroRNAs [27]. However, the AgNCs have low FL quantum yields and poor stability compared with carbon quantum dots (CQDs), which will limit their applications [28]. Happily, a few methods like doping, aggregation-induced emission (AIE) and Förster resonance energy transfer (FRET) were developed for enhancing the FL intensities of MNCs [[29], [30], [31]], and the strong stability of MNCs could be obtained by photo-reduction approach [32]. For example, the study of Jin's group discovered that the FL intensity and photo-stability of AgNCs-NFR/LDH UTFs ((AgNCs-nuclear fast red)/(Mg₂Al-layered double hydroxide) UTFs) enhanced obviously in comparing with that of AgNCs-NFR by the AIE mechanism, and the probe could be used successfully to determine guanine with a LOD of 1.85 μM [33]. Liu et al. [34] have also applied the same method to heightening the FL of AgNCs/GSH (glutathion) because zinc ion can coordinate with AgNCs/GSH to cause the AgNCs aggregation. And the AgNCs/GSH sensor can be used for the mensuration of adenosine 5′-triphosphate (ATP). Up to now, PSS-enhanced Ag nanoclusters have not yet been reported. Therefore, PSS was adopted to improve the FL of AgNCs based on the method of UV irradiation combined with microwave heating.

In the study, a facile one-pot approach was employed to prepare stable AgNCs by DPA as both the stabilizer and reductant. Importantly, PSS was introduced to increase markedly the FL of DPA-AgNCs and their stability. Meanwhile, the synthesis conditions (m_PSS, T, t, pH and n_DPA:n_AgNO3) of the AgNCs were optimized. On this basis, we have exploited a simple probe (PSS-DPA-AgNCs) for monitoring indirectly ILH/AFC (Scheme 1), and corresponding quenching mechanism was also investigated in detail. Moreover, the probe was successfully utilized to analyze ILH in ILH tablets, solid beverage with reinforced iron or ILH additive, and AFC in two kinds of edible salts or AFC syrup with VB1 (vitamin B1), respectively.

Section snippets

Materials and instruments

Silver nitrate (AgNO₃, AR) was bought from Aladdin Chemistry Co., Ltd. (Shanghai, China). Iron(II) lactate hydrate (ILH, 98%) was purchased from Sigma-Aldrich Chemical Co., Inc. (Milwaukee, USA). D-penicillamine (DPA, 98%) was obtained from Shanghai Civi Chemical Technology Co., Ltd. (Shanghai, China). Poly(sodium-p-styrenesulfonate) (PSS, Mw = 80,000) and ammonium ferric citrate (AFC, AR) were purchased from Shanghai Macklin Biochemical Co., Ltd. (Shanghai, China). Other reagents (see

Effect of types of polyelectrolytes and energy suppliers

When a suitable dose of DPA was added into the solution of AgNO₃, no luminescent Ag(I)-DPA complexes were formed. And then under UV irradiation (UVI), DPA-AgNCs were formed by ligand (DPA) to metal charge transfer (LMCT; S → Ag metal) process [37,38]. To enhance the FL intensity and stability of AgNCs, a polyelectrolyte PSS was introduced in the preparation process using UV irradiation method at 60 °C. The study discovered that the FL intensity of PSS-DPA-AgNCs at 665 nm was about eight times

Conclusion

In summary, for the first time, water solubility and long preservation time PSS-DPA-AgNCs were synthesized by a facile and one-step UVI combined with MWH method, and their properties were characterized and analyzed by TEM, XPS, FTIR, fluorescence and UV–vis spectroscopy, and zeta potential measurement, respectively. The optimized preparation conditions of PSS-DPA-AgNCs and the detection conditions of ILH/AFC by the as-prepared probe were discussed. The FL intensity of PSS-DPA-AgNCs was quenched

Acknowledgements

The authors gratefully acknowledge financial support from Sichuan Provincial Science & Technology Fund for Applied Fundamental Research (2016JY0080), Doctor Start-up Fund (15E006) of China West Normal University, and Talent research fund of China West Normal University (17YC012).

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Fluorometric assay of iron(II) lactate hydrate and ammonium ferric citrate in food and medicine based on poly(sodium-p-styrenesulfonate)-enhanced Ag nanoclusters

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Materials and instruments

Effect of types of polyelectrolytes and energy suppliers

Conclusion

Acknowledgements

Cell Discov

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Anal. Chim. Acta

Anal. Chim. Acta

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