Application of novel nanomaterials labeled molecular imprinting technique in the detection and adsorptive removal of fluoroquinolones

doi:10.21203/rs.3.rs-1970637/v1

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Application of novel nanomaterials labeled molecular imprinting technique in the detection and adsorptive removal of fluoroquinolones

https://doi.org/10.21203/rs.3.rs-1970637/v1

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Fluoroquinolones are a new class of synthetic antimicrobials, which have been widely used in clinical treatment. However, their irrational use can lead to allergic reactions, adverse reactions of the heart system and damage of the liver system. Due to the urgency of the safety risk of fluoroquinolones, it is of great significance to establish rapid, sensitive and accurate detection methods for fluoroquinolones. Molecularly imprinted polymers with specific structures synthesized by molecular imprinting technology are widely used for the detection of fluoroquinolones due to their high specificity, high sensitivity and stable performance. Besides, new functional nanomaterials with different morphology and size can provide rich sites for surface chemical reactions, thus greatly promoting the sensitivity and innovation of molecular imprinted polymer. This review summarizes the application status and development prospects of molecular imprinting technology based on novel nanomaterials labeling in the adsorption and detection of fluoroquinolones, in order to provide references for the future research on the adsorption and removal of fluoroquinolones, analysis and detection fluoroquinolones.

Nano materials

Molecular imprinting technique

Fluoroquinolones

Adsorption and removal

Analysis and detection

Fluoroquinolones (FQs) are spectral antibiotics that are active against gram-negative and certain gram-positive bacteria (Ferreira et al. 2020). FQs is widely used in most types of animal husbandry, aquaculture and clinical treatment because of its wide antibacterial spectrum, low incidence of drug resistance, high tissue concentration and long half-life (Karp et al. 2018; Chen et al. 2019). FQs is used to treat human and animal infections, accounting for 18% of the international anti-infective drug market, and has become the largest anti-infective drug in the world after cephalosporins. However, adverse reactions caused by FQs, including joint disease, hepatorenal toxicity and hematological toxicity, have been reported (Chen et al. 2015; Wang et al. 2018). Therefore, the establishment of efficient and fast FQs detection methods has attracted more and more attention. At present, the commonly used detection methods for FQs include ultra-high performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) (Li et al. 2022), magnetic solid phase extraction (M-SPE) (Hong et al. 2022) and reversed phase thin layer chromatography (Urszula et al. 2015). Although these methods have the advantages of high separation efficiency, accurate quantification and high efficiency, they have not been widely used in FQs detection because of the need for expensive instruments and complex and cumbersome pretreatment procedures for the preparation of magnetic polymers. Immunoassay has the advantages of high sensitivity and fast detection, but it is expensive, physical and chemical stability is poor, and the experimental results are prone to false positive (Wang et al. 2019). Therefore, it is of great significance to apply the rapid detection method with low cost, high specificity and high sensitivity.

Molecularimprinting Technology (MIT) is a synthetic technology to recognize target molecules. In the presence of template molecules, MIT enables functional monomers to form reversible complexes with them, and then pre-polymerizes with cross-linking agents. Template molecules are eluted through certain physical or chemical methods, so that customized recognition cavities complementary to template molecules in shape, size and chemical function are formed in highly cross-linked polymer matrix, namely molecularly imprinted polymers (MIPs) (Chen et al. 2020). MIPs is a kind of synthetic material with three-dimensional cavity, which can specifically bind to target molecules to achieve high-efficiency and specific detection of subsequent substances to be tested (Lucci et al. 2020). MIPs have the advantages of low cost, rapid preparation, good stability, strong reproducibility and specific recognition, and their production does not need living animals, so they are widely used in the field of food safety (Benachio et al. 2020). The preparation process of MIPs is shown in Fig. 1.

Nano materials with different shapes and sizes can provide abundant sites for surface chemical reactions, showing great application potential (Jiang et al. 2021). Molecularly imprinted polymer sensors based on functional nanoparticles have become more and more popular in recent years. They have better stability and sensitivity than traditional MIPs, providing a more efficient, fast and accurate new method for the detection of fluoroquinolones, and also providing a new idea for the monitoring of food safety problems of veterinary drug residues. This paper reviews the application of molecular imprinting technology based on functional nanomaterials in fluoroquinolone detection, including gold nanoparticles, magnetic nanomaterials, quantum dots, metal-organic frameworks, magnetic heroxite nanotubes, carbon nanoparticles and silica nanoparticles, etc. In order to provide a reference for the application of molecular imprinting technology of novel functional nanomaterials in the field of fluoroquinolone adsorption removal and detection.

The preparation of MIPs has the characteristics of simple operation and low cost. At present, MIPs mainly have the following preparation methods: bulk polymerization, emulsion polymerization, suspension polymerization, sol-gel polymerization, surface molecular imprinting, precipitation polymerization, electropolymerization and thermal polymerization. The advantages and disadvantages of different preparation methods are compared in Table 1. Bulk polymerization (Mw et al. 2019; Zhang et al. 2020), sol-gel polymerization (Bagheri et al. 2018; Li et al. 2018) and precipitation polymerization (Lu et al. 2019; Wei et al. 2019) have obvious advantages of simple synthesis methods. The lotion polymerization (Dvorakova et al. 2010; Zhao et al. 2020), suspension polymerization (Rahangdale et al. 2018) and thermal polymerization (Tarannum et al. 2020) have the characteristics of fast polymerization reaction and synthesis speed. In addition, the MIPs synthesized by sol-gel polymerization and surface molecular imprinting(Dong et al. 2020) have the characteristics of uniform binding sites and strong affinity. The electropolymerization method (Gonalves 2021) can control the thickness of the film by current during polymerization, and has high repeatability. However, the reproducibility and selectivity of MIPs synthesized by bulk polymerization, thermal polymerization and electropolymerization are poor. The MIPs synthesized by emulsion polymerization and precipitation polymerization are susceptible to various reaction conditions and have poor stability. MIPs synthesized by sol-gel polymerization and surface molecular imprinting are toxic and easy to pollute the environment. However, the size of MIPs prepared by suspension polymerization is large, which limits its application scope. Therefore, it is of great research significance to look for a new method for preparing non-toxic, reproducible and selective MIPs, which can detect a variety of substances, simultaneously.

Table 1

Comparison of advantages and disadvantages of different preparation methods of MIPs
Preparation method	Advantages	Disadvantages
Bulk polymerization	Simple synthesis and good applicability	Poor reproducibility and selectivity
Lotion polymerization	Fast speed, stable dispersion system, continuous production without complex post-treatment process	Low imprinting efficiency and poor stability
Suspension polymerization	Regular shape, the binding site is not easy to be broken, and the synthesis is fast	Large particle size limits application,
Sol-gel polymerization	Strong affinity, large specific surface area, small particle size, strong adsorption, simple synthesis method, high chemical stability, good rigidity and uniform product	Polymerization time is long, most organic materials are toxic, susceptible to pH and different acid-base products
Surface molecular imprinting	High mass transfer efficiency, reduced "embedding" phenomenon, higher binding capacity, uniform binding sites	The required amount of organic reagent is large and toxic
Precipitation polymerization	Simple, low cost, no grinding required	Low productivity, susceptible to various reaction conditions
Electropolymerization	Current can control the thickness of the film, with high repeatability	The template is difficult to remove and the cavity selectivity is poor
Thermal polymerization	Fast polymerization	Low selectivity and reproducibility

2.1 Application of MIPs based on gold nanoparticles in the detection of FQs

Compared with bulk metals, gold nanoparticles (AuNPs) have many advantages in their own properties, such as stronger thermal stability, better conductivity, adsorption capacity and biocompatibility compared with bulk metals. Meanwhile, their preparation is not complicated, so they are widely used in the manufacture of various sensors (Essousi et al. 2019). Its average size is a key factor in determining physical and chemical properties (Yang et al. 2020). AuNPs combined with MIPs to detect template molecules can effectively amplify signals and shorten the binding time of identifying target molecules, which is of great research significance.

Surya et al. (Surya et al. 2020) creatively added glassy Carbon electrode (GCE) containing chitosan gold nanoparticles decorated MIPs (Ch-AuMIPs) into the sensor for detecting ciprofloxacin (CIP). Ch-AuMIPs investigated the sensitivity of the sensor in the range of 1-100 mmol/L, with a limit of detection (LOD) of 210 nmol/L, and successfully developed a sensor with a recovery rate of 94%-106% for the determination of CIP concentration. Li et al. (Li et al. 2022) developed a MIPs voltammetry sensor for the selective determination of Norfloxacin (NOR). The ultra-high sensitivity of this sensor is due to the manufacturing material of gold nanoparticles functionalized black phosphorus nanosheet nanocomposite (BPNS-AuNPs) covered by polypyrrole (Ppy) imprinted film. MIPs/BPNS-AuNPs/GCE is excellent for the determination of NOR, with a linear response range of 0.1–10 µmol/L and a LOD of 0.012 nmol/L. Ye et al. (Ye et al. 2021) prepared a three-dimensional CoFe metal organic framework (MIPs/CoFe-MOFs/AuNPs/GCE) with AuNPs using molecularly imprinted polymers (MIPs) supported on Ppy as coatings for electrochemical trace detection of nor. LOD reaches 0.131 pmol/l, and the linear range is 5-100, 100–1000 and 1000–6000 pmol/L. The recovery of NOR in pure milk ranged from 97.04–110.2%, and the relative standard deviation (RSD) was less than 5.7%. The results of MIPs/CoFe-MOFs/AuNPs/GCE were similar to those of NOR ELISA kit, indicating that it has a high potential for the detection of NOR trace in environmental and animal food.

2.2 Application of MIPs based on magnetic in the detection and adsorptive removal of FQs

MIT has been used with magnetic nanoparticles to develop magnetic molecularly imprinted polymers (MMIPs), and has been successfully used as adsorbent to identify and separate templates (Zhao et al. 2018). MMIPs combines the excellent magnetic properties of magnetic nanoparticles and the specific recognition characteristics of molecularly imprinted polymers. It has the advantages of easy separation, high selectivity, strong stability, simple preparation and short residence time. Under the condition of external magnetic field, it can directly and selectively separate and recognize template molecules, further expanding the application field of MIPs (Wang et al. 2020; Cui et al. 2021).

Fang et al. (Fang et al. 2021) developed a new magnetic MIPs (CoFe₂O₄@TiO₂-MMIPs) with a maximum adsorption capacity of 14.26 mg/g and an adsorption rate constant of 0.21 g/(mg min). This polymer adopts surface MIT combined with photocatalytic degradation and magnetic separation technology. The material has strong selective adsorption and high adsorption efficiency for FQs. These two properties determine that this material has great potential for removing FQs. He et al. (He et al. 2020) combined magnetic substrates, MIT and surface enhanced Raman scattering (SERS) to prepare core-shell magnetic MIPs (Fe₃O₄@SiO₂@Ag-MIPs) for quantitative determination of ofloxacin (OFX). The results show that the concentration of OFX in the range of 10^− 3-10^− 8 mol/L has a good linear relationship with the Raman peak intensity at 1416 cm^− 1. OFX shows strong Raman signal, while other drugs are difficult to generate Raman signal, indicating that Fe₃O₄@SiO₂@Ag-MIPs have good selectivity. The Raman detection of the commercial OFX eye drops shows that the recovery rate is good, which indicates that it can be used for the quantitative detection of actual samples. Zhao et al. (Zhao et al. 2021) prepared a surface MIPs based on dopamine coated magnetic nanoparticles. Under the optimal adsorption conditions, the final load of gatifloxacin on MMIPs was 51.9 mg/g, and the equilibrium adsorption time was 30 min. Through the spiked recoveries of three FQs aqueous solutions, it was found that their spiked recoveries, LOD and limits of quantitation (LOQ) were 84.1–91.9%, 6.4–9.9 ng/mL and 17.8–34.5 ng/mL respectively. Because of its adsorption selectivity and recoverability, this magnetic MIPs is a promising adsorbent for sample separation and pretreatment. Cao et al. (Cao et al. 2021) prepared magnetic MIPs nanoparticles (MMIPs NPs) for NOR extraction by self-polymerization of dopamine on the surface of Fe₃O₄ nanoparticles modified with triethoxysilane (APTES). The adsorption capacity of MMINs NPs for NOR was 14.2 mg/g, and 82.4-102.4% of the added NOR (20, 40, 60 µg/mL) was recovered from fortified milk samples with MMIPs NPs as adsorbent. The MMINs NPs remains stable after six cycles of use. Hu et al. (Hu et al. 2018) developed a new adsorbent (M-CCNs@MIPs), which is highly selective for FQs compounds, thanks to the surface functionalization of magnetic carboxylated cellulose nanocrystals (M-CCNs) and MIPs containing amine groups, as shown in Fig. 2. M-CCNs@MIPs has quite good performance for different FQs. In the experiment, the recovery rate of FQs is 81.2%-93.7%, and the LOD is 5.4 ng/mL-12.0 ng/mL.

2.3 Application of MIPs based on quantum dot in the detection of FQs

Quantum dot (QDs) is a new type of semiconductor fluorescent nanomaterial. Compared with traditional dyes, QDs has the advantages of high stability, high fluorescence efficiency, wide excitation spectrum, strong resistance to photobleached molecularly imprinted polymers, and narrow emission spectrum (Wang et al. 2019). Therefore, quantum dots are used in the fields of electronics, biology, medical diagnosis and so on because of their excellent electrical and optical properties (Zhou et al. 2020).

Liu et al. (Liu et al. 2022) developed a sensitive fluorescent sensor for detecting CIP by wrapping the surface of CdTe quantum dots with MIPs (MIPs@QDs). The linear calibration curve of CIP was obtained in the range of 0.5–24 µmol/L, with a LOD of 0.23 µmol/L (S/N = 3). The fluorescent probe was successfully applied to the determination of CIP in seawater samples. The recoveries were between 98.2% and 110.6%, and the RSD was less than 10.7%. MIPs@QDs is used for the separation and detection of CIP in seawater, and has obtained good specific recognition ability and potential practical value. Shi et al. (Shi et al. 2019) successfully developed a new probe for the determination of NOR in wastewater and seawater. This probe adopts fluorescent nanomaterial composed of CdTe quantum dots and coated with molecular imprinting layer, and LOD can reach 0.18 µmol/L, which has strong practicability. The method was used to analyze waste water and seawater samples mixed with NOR, and the recoveries were in the range of 96.2–106.0%. Gao et al. (Gao et al. 2014) introduced CdTe QDs and iron oxide nanoparticles into MIPs to detect CIP or its structural analog NOR in human urine, with the LOD is 130 ng/ml. The fluorescent probe is sensitive, convenient and has practical application potential. Cheng et al. (Cheng 2020) synthesized molecularly imprinted fluorescent sensor MIPs@SiO₂@CdTe (as shown in Fig. 3) is used for selective recognition and fluorescence detection of NOR. The specific recognition performance of MIPs@SiO₂@CdTe for NOR can accurately detect the linear concentration range of NOR from 3.82 nmol/L to 150 nmol/L, and the detection limit of NOR is 3.82 nmol/L, which has been successfully applied to the detection and analysis of actual samples. Chen et al. (Chen et al. 2021) developed a new probe for rapid detection of NOR residues in food substrates. Using magnetic room-temperature phosphorescent quantum dots and MIPs (MQD-MIPs) as raw materials, the detection limit of this new probe can reach 0.80 µg/L. At the same time, compared with the control HPLC-FLD, the recovery of NOR residues in fish and milk samples is 90.92-111.53%, with RSD < 7%.

2.4 Application of MIPs based on metal-organic frameworks in the detection and adsorptive removal of FQs

Metal-organic frameworks (MOFs) are supramolecular nanomaterials in which metal ions or clusters are linked by organic ligands to form lattices with highly ordered periodic porous network structures (Wang et al. 2021). MOFs have the advantages of large surface area, tunable porosity, simple and convenient synthesis, high chemical function, and open metal sites, and have been widely used in various fields such as adsorption materials, catalysts, sample preparation, and sensing (Sharabati et al. 2020).

Liu et al. (Liu et al. 2021) perfectly anchored the uniformly dispersed MOFs particles on the three-dimensional porous carbon foam (CF), and successfully prepared a new composite material for the efficient and selective removal of NOR from wastewater by combining MIT with in-situ growth strategy. The maximum capacity of MIT-MOFs/CF for NOR is 456 mg/g, which is much better than the original MOFs. This work effectively solved the bottleneck of MOFs in removing large antibiotic molecules, and provided a new direction for the design and synthesis of MOFs in the future. Zhao et al. (Zhao et al. 2020) successfully prepared a new type of restricted molecularly imprinted polymers (RAMIPs) on the surface of metal organic framework (NH₂-MIL-125) and used it as solid phase extraction (SPE) material to detect quinolones in bovine serum by high performance liquid chromatography. The recovery of gatifloxacin was 96.8%-105.6%, and the RSD was 1.7%-3.2% (n = 3). The results showed that the method was successfully applied to the selective enrichment of gatifloxacin in bovine serum, and provided a simple and effective method for the direct detection of gatifloxacin in bovine serum. Sun et al. (Sun et al. 2019) prepared RAMIPs on the surface of mesoporous UiO-66-NH2 metal organic framework, which can be crosslinked with bovine serum albumin (BSA), and filled with UiO-66-NH2@RAMIPs@BSA SPE column selectively enriched and analyzed OFX and enrofloxacin antibiotics from bovine serum. The RSD was 2.0-4.5%, the recovery was 93.7-104.2%, and the linear range was 0.1–100 µg/mL, the detection limit is 15.6 ng/ml, which indicates that UiO-66-NH2@RAMIPs@BSA can be used as a highly efficient pretreatment adsorbent for the analysis of biological samples.

2.5 Application of MIPs based on magnetic nanotube in the detection and adsorption of FQs

Halloysite nanotubes (HNTs) have many advantages, such as high adsorption capacity, biocompatibility, excellent water dispersion, hollow tubular structure and large specific surface area. As a new type of mineral nanomaterial with low cost, it has attracted extensive attention in the industry (Wang et al. 2020). Magnetic halloysite nanotubes (MHNTs) are composed of HNTs and magnetic nanomaterials. MIPs based on MHNTs have the characteristics of high surface-active sites and easy separation, which has good research significance (Sahar et al. 2020).

Meriem et al. (Meriem et al. 2018) used MHNTs-MIPs as adsorbent to establish a magnetic imprinted solid phase extraction high performance liquid chromatography method for the detection of NOR in serum and water samples. The recovery rate in water was 83.76%-103.30%, and that in serum was 90.46%-99.78%. In addition, MHNTs-MIPs also have good mechanical properties and specific recognition ability to template molecules, and can be reused for many times. The recoveries of water samples and serum samples were 83.25%-100.96% and 85.65%-100.33%, respectively. Therefore, MHNTs-MIPs can quickly and selectively extract therapeutic agents from environmental water and biological fluids. See Fig. 4 for the synthesis route of MHNTs-MIPs. Li et al. (Li et al. 2018) successfully developed three MHNTs-MIPs in order to extract NOR from lake water. MHNTs-MIPs have the highest adsorption capacity 312.08 µg/mg, the best selection coefficient is 5.41. Hydrochloric acid (9:1/v:v) can be used as the best eluent, and MHNTs-MIPs can be reused for at least 7 times. The LOD of NOR determined by this method was 0.005 µg/mL. The results showed that MHNTs-MIPs could be used to extract and detect NOR from wastewater.

2.6 Application of MIPs based on carbon nanoparticles in the detection and adsorptive removal of FQs

Carbon nanoparticles (CNPs) generally refer to several types of nanostructured carbon products based on product carbon black. As electrode sensing materials and adsorption material, they have the advantages of high conductivity, excellent water solubility, large surface area, good photostability, easy functionalization and good chemical stability (Liao et al. 2021; Porras et al. 2021). In addition, because of its high structural stability, low chemical reaction activity and non-toxicity, it is widely used in biological imaging, biosensor, ion detection, optoelectronic devices and photocatalysis, and has attracted much attention in recent years (Lai et al. 2020).

Tan et al. (Tan et al. 2013) prepared a novel MIPs (MCNs@MIPs) that covalent grafted OFX imprinted polymer to the surface of mesoporous carbon nanoparticles (MCNs) to remove FQs in environmental water. The adsorption capacity of ofloxacin (OFX) is 40.98 mg/g, which is similar to that of non-imprinted polymer nanoparticles (MCNs@NIPs) In contrast, the selectivity factor is 2.6. This MCNs@MIPs in addition to NOR, it can be reused for more than 5 times, with a removal rate of more than 90%. Tan et al. (Tan et al. 2014) used MCNs@MIPs formed by covalently grafted precipitated polymer onto the surface of MCNs to detect OFX and MCNs@MIPs as electrode sensing material. The peak current measured by cyclic voltammetry showed a linear relationship with the OFX concentration in the range of 0.5–100 µmol/L. The LOD is 80 nmol/L. Li et al. (Li et al. 2020) prepared MIPs films with binary functional monomers on the surface of iron doped porous carbon modified gold electrode by electropolymerization to detect lomefloxacin (LFX). Under the optimum conditions, the LOD is 0.2 nmol/L. In addition, the developed sensor has good repeatability and stability for LFX detection. It can be used to detect LFX in water and milk samples, and the recovery is between 86.6% and 105.0%.

2.7 Application of MIPs based on silica nanoparticles in the detection and adsorption removal of FQs

Silica nanoparticles (SiNPs) were synthesized from alcoholic solutions of silicon alkoxides in the presence of catalyst ammonia, which resulted in SiNPs of various sizes ranging from 50 nm to 1 µm (Jeelani et al. 2019). Among the numerous nanoparticles, SiNPs are a unique class of inorganic nanoparticles with a wide range of functional properties, such as large surface area, high chemical stability, low toxicity, easy functionalization, easy synthesis, good biocompatibility, key advantages such as modifiable surfaces and robust mechanical properties allow them to bind and functionalize with many compounds (functional species) or molecules, and can be used for adsorption removal of FQs (Nazri et al. 2020). SiNPs have been used as biomaterials for decades.

Tang et al. (Tang et al. 2014) used OFX as a template to synthesize porous hollow MIPs with SiNPs as sacrificial cores. When the initial concentration of OFX was 900 mg/mL, the theoretical adsorption capacity of MIPs to OFX was 147 mg/g, and the imprinting factor was 2.6. Combined with high performance liquid chromatography, the limit of determination of FQs in milk does not exceed 30 ng/mL. FQs in milk were enriched with SiNPs-MIPs as adsorbent, and good selectivity and enrichment rate were obtained. Ma et al. (Ma et al. 2020) mixed polyvinylidene fluoride powder with polyvinylidene imine (PEI) modified SiNPs under freezing condition by using organo-inorganic hybrid strategy to develop a simulated core-shell PEI@SiO₂ gienofloxacin molecularly imprinted nanocomposite film (SPEIMs), which has good selectivity for enoxacin. SPEIMs has good adsorption energy of 55.94 mg/g and regeneration performance of 90.31%. The significance of this experiment is to enrich the application of MIPs in pollution control and biochemical separation.

2.8 Application of MIPs based on graphene in the detection of FQs

Graphene is a two-dimensional network of carbon allotropes, containing a conjugated sp2 carbon honeycomb structure, which has a large specific surface area, high recombination ability, high electrical conductivity and almost no crystal defects, which is conducive to template completely removed (Adams et al. 2019). The small size and extremely high surface-to-volume ratio facilitate the localization of most template molecules on the surface, resulting in improved kinetics and accessibility of target molecules. Graphene oxide (GO) is a well-known carbon-based material that provides a two-dimensional environment with high specific surface area, excellent electrical conductivity, and high mechanical strength for electron transport, making it ideal for electrochemical sensors (Dehghani et al. 2019). At the same time, graphene can be reduced to reduced graphene oxide (rGO) by eliminating oxygen functional groups in order to improve its thermal and electrical conductivity. The two-dimensional honeycomb lattice of rGO has been reported to allow fast electronic displacement of different electroactive species in biosensor applications (Jaouhari et al. 2020). Binding GO or rGO to MIPs will result in higher affinity and exceptional sensitivity for specific detection molecules due to the uniform distribution of recognition sites.

Chen et al. (Chen et al. 2022) study GO MIPs were used as adsorbents to detect NOR in the Marine environment by solid-phase microextraction combined with high performance liquid chromatography. The method was applied to the analysis of NOR in seawater and fish with the recoveries of 90.1-102.7%. The LOD of seawater and fish were 0.15 µg/L and 0.10 µg/kg, respectively. Mujahid et al. (Mujahid et al. 2021) combined rGO with MIPs to develop a smart sensor device for direct detection of CIP. The sensor displacement of CIP, levofloxacin (LEV) and moxifloxacin (MOX) by rGO-MIPs in the concentration range of 10–50 mg/L shows that the sensor response sensitivity of CIP is at least 3 times higher than that of LEV and MOX. The results show that the addition of rGO not only improves the sensitivity of MIPs but also helps to improve the selectivity. Wang et al. (Wang et al. 2014) developed a new strategy for constructing highly sensitive LEV sensors based on the combination of MIPs with graphene-gold nanoparticles (G-AuNPs). Under the optimized conditions, the LOD is 0.53 µmol/L. The sensor based on MIPs/G-AuNPs has high sensitivity, excellent selectivity and good reproducibility, and can be used for the determination of LEV. Li et al. (Li et al. 2018) developed a molecularly imprinted electrochemical sensor that could selectively determine LFX in hydrochloric acid. The secret of the functionality of this molecularly imprinted electrochemical sensor lies in the use of gold electrode surface modification of rGO-AuNPs. The optimal differential pulse peak current of the redox probe showed a good linear relationship with the LFX concentration from 0.01 µmol/L to 1.0 µmol/L, and the LOD is 3.0 nmol/L. This method can perfectly detect LFX hydrochloride in Xijiang water and milk, with satisfactory precision (RSD ≤ 6.2%) and recovery (88.0%-102%).

In recent years, the residue of FQs has been highly concerned by people. MIT based on functional nanoparticle labeling combines nanoparticles with certain functional characteristics with MIPs, which greatly improves the sensitivity, reproducibility and selectivity of MIPs in identifying the substance to be tested, and makes it widely used in the detection and adsorption of FQs. In order to make the functional nanoparticle labeled MIPs better applied to the detection and adsorption removal of FQs in food and feed, future research directions may focus on the following areas: 1) Improved properties of existing materials: traditional quantum dots mostly contain heavy metals, such as mercury, cadmium, etc. to develop low toxic carbon quantum dots to solve the harm caused by traditional quantum dots; solve the problem of poor neutral energy of MOFs materials in humid environment and make them easier to store; 2) Improvements to existing MIPs: develop new functional monomers, cross-linking agents and initiators to make template molecules more easily eluted and synthesize a non-toxic MIPs; to develop a functional nanoparticle molecularly imprinted sensor that can simultaneously detect multiple analytes, in order to achieve rapid on-site screening of a large number of samples and expand its application scope; 3) To find other new nanomaterials to reduce the detection cost and improve the detection sensitivity.

Funding

This research was Funded by Science and Technology Project of Hebei Education Department (QN2020177), Hebei University of Science and Technology Graduate Innovation Funding Program (XJCXZZSS2022007).

Compliance with Ethical Standards

Conflict of Interest

The authors declare no competing financial interests.

Author Contribution

Tianqi Wu and Gaoshuang Hu wrote the main manuscript text, and Shan Gao and Jianxiong Hao prepared figures 1-4. All authors reviewed the manuscript.

Ethical Approval

This article does not contain any studies with human participants or animals performed by any of the authors.

Informed Consent

A statement regarding informed consent is not applicable for this study.

Data Availability Statement

The data that used in the study are available from the corresponding author upon reasonable request.

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Application of novel nanomaterials labeled molecular imprinting technique in the detection and adsorptive removal of fluoroquinolones

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Abstract

Figures

Introduction

1 Commonly Used Molecularly Imprinted Polymer Preparation Methods

2 Application Of Mit Based On Functional Nanoparticles In The Detection And Adsorption Of Fqs

2.1 Application of MIPs based on gold nanoparticles in the detection of FQs

2.2 Application of MIPs based on magnetic in the detection and adsorptive removal of FQs

2.3 Application of MIPs based on quantum dot in the detection of FQs

2.4 Application of MIPs based on metal-organic frameworks in the detection and adsorptive removal of FQs

2.5 Application of MIPs based on magnetic nanotube in the detection and adsorption of FQs

2.6 Application of MIPs based on carbon nanoparticles in the detection and adsorptive removal of FQs

2.7 Application of MIPs based on silica nanoparticles in the detection and adsorption removal of FQs

2.8 Application of MIPs based on graphene in the detection of FQs

3 Conclusions

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References

Additional Declarations

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